United States Patent (19) 11) 4,177,300 Walsh et al. 45) Dec. 4, 1979

54 PHOSPHONOXYCARBOXAMIDE FLAME RETARDING COMPOSITIONS OTHER PUBLICATIONS Shiskin et al., "Methylphosphonic Acid Esters Contain 75 Inventors: Edward N. Walsh, New City; Ralph ing the Carbamoyl Group', C.A. 13602v, vol. 81, 1974. B. Fearing, Bardonia, both of N.Y. Shiskin et al., "Dialkyl Methylphosphonates with a Carboximidic Ester Hydrochloride Grouping in One of 73) Assignee: Stauffer Chemical Company, the C-Alkyl Groups', Journal of General Chemistry of Westport, Conn. USSR, vol. 46, No. 10, PL 1, pp. 2143 to 2146 (transla tion) (1976). (21) Appl. No.: 905,307 Primary Examiner-John D. Smith (22 Filed: May 12, 1978 Attorney, Agent, or Firm-William C. Gerstenzang 57 ABSTRACT Related U.S. Application Data Novel phosphonxycarboxamides of the formula: 62 Division of Ser. No. 837,072, Sep. 28, 1977. O O 3 51) Int. Cl?...... COTF 9/11; CO7F 9/40 Rl-P-O-R-C-NC R ) 52 U.S. C...... 427/390 D; 252/8.1; NR4 260/943; 427/394; 106/18.15 (RO)2- 58 Field of Search ...... 427/390 D, 394; 260/943; 252/8.1; 106/18 FP wherein R and R2 are selected from the group consist ing of aryl and alkyl having from 1-6 carbon atoms and 56 References Cited may be the same or different; R3 represents hydrogen or U.S. PATENT DOCUMENTS -CH2OH.; R represents hydrogen, -CH3, -CH2OH, or -C2H4OH, R represents an alkyl group having 2,494,283 1/1950 Cassaday et al...... 260/943 3,644,140 2/1972 Weisz et al...... 427/390 D from 1-5 carbon atoms; and n represents 1 or 2 are 3,669,725 6/1972 Nachbur et al...... 427/390 D useful as flame retardant agents for textile materials. 3,763,283 10/1973 Curgan ...... 260/938 4,028,053 6/1977 Duke ...... 427/390 D 7 Claims, No Drawings

4,177,300 1. 2 PHOSPHONOXYCARBOXAMIDE FLAME O O RETARDING COMPOSTIONS R' This is a division of application Ser. No. 837,072 filed 5 R!--O-R-C-N-(RO)2- R n Sept. 28, 1977. This invention relates to new and useful phosphonox wherein R and R2 are selected from the group consist ycarboxamides and their method of preparation. More ing of aryl and alkyl having from 1-6 carbon atoms and particularly, this invention relates to new phosphonox may be the same or different; R represents hydrogen or ycarboxamide compounds which are useful as agents O -CH2OH; R represents hydrogen, -CH3, -CH2OH, for imparting flame retardance to textile materials such or -C2H4OH, R represents an alkyl group having as cotton fabric or yarn. from 1-5 carbon atoms; and n represents 1 r 2; (2) an It has long been known that flame retardant proper aminoplast; and (3) an acid catalyst. In preferred em ties may be incorporated into textile materials such as bodiments, the flame-retardant composition is an aque cotton fabric or yarn by treatment with phosphorus 15 ous formulation wherein the aminoplast is present at a containing compounds. Such compounds are usually in concentration ranging from about 10 to about 600 per the form of organophosphorus compounds which are cent by weight of the phosphonoxycarboxamide com relatively harmless to the material being treated as well pound, the acid catalyst is present at a concentration as resistant to laundering. ranging from about 0.01 to about 5 percent by weight of 20 the phosphonoxycarboxamide, and the total concentra More recently, it has been discovered that organic tion (i.e., the "solids' content) of the phosphonoxycar nitrogen is a synergist for phosphorus-induced flame boxamide, aminoplast, and catalyst is adjusted to pro retardance in cellulosic fabrics, and its presence in the vide a phosphorus uptake of 1 to 5% by weight on the flame-retardant compound permits a reduction in the fabric being treated. amount of flame retardant which is required to achieve 25 In accordance with a further aspect of this invention, an acceptable degree of flame retardance. Exemplary of there is provided a process for imparting flame retard flame-retardant compounds which contain both nitro ance to textile materials comprising the steps of impreg gen and phosphorus are those disclosed in U.S. Pat. nating the textile material with a flame-retardant com Nos. 3,268,292; 3,374,292; 3,556,840; 3,634,422; position comprising: 3,763,283; and 3,835,204. 30 (a) at least one compound represented by the formula: It is an object of this invention to provide a novel class of phosphonoxycarboxamide compounds which are effective in imparting flame retardance to textile materials. It is another object of this invention to pro f R: vide novel compositions which may be used at rela 35 Rl-e-o-R5-3-NC), tively low add-on weights to impart flame retardance to R4 textile compositions. It is a further object of this inven tion to provide a novel process by which flame retard wherein R1 and R2 are selected from the group consist ancy may be imparted to textile materials. ing of aryl and alkyl having from 1-6 carbon atoms and In accordance with one aspect of this invention, there may be the same or different; R3 represents hydrogen or is provided a compound of the formula: -CH2OH.; R represents hydrogen, -CH3, -CH2OH, or -C2H4OH; R represents an alkyl group having O O R3 (1) from 1-5 carbon atoms; and n represents 1 or 2; (b) an I 45 aminoplast; and (c) an acid catalyst and heating the impregnated textile material to a temperature sufficient to cure the flame-retardant composition. (rib- Y. The phosphonoxycarboxamides of this invention may wherein R1 and R2 are selected from the group consist be prepared by a variety of techniques known in the art. ing of aryl and alkyl having from 1-6 carbon atoms and 50 For example, when n=1, they may be prepared by may be the same or different; R3 represents hydrogen or reacting a carbalkoxyalkyl phosphonate such as a carb -CH2OH.; R“represents hydrogen, -CH3, -CH2OH, alkoxy methyl phosphonate, i.e., or -C2H4OH, R5 represents an alkyl group having from 1-5 carbon atoms, provided that only one of R: O O (II); and R may be hydrogen; and n represents 1 or 2. 55 RI-P-O-CH-C-OR6 Within the broad class of compounds encompassed by this invention, a particularly preferred subclass com prises those compounds wherein R represents an alkyl wherein R and R2 are as defined hereinabove, and R6 radical of from 1-4 carbon atoms; R2 represents an alkyl 60 represents an alkyl group having from 1 to 2 carbon radical of from 1-2 carbon atoms; R3 represents hydro atoms; with ammonia, i.e., NH3 to form an N- unsubsti gen or -CH2OH.; R represents hydrogen, -CH3, tuted phosphonoxycarboxamide -CH2OH, or -CH2CH2OH, R5 represents -CH2; and n represents 1 or 2. O O H (III); In accordance with another aspect of this invention, 65 / Rl-P-O-CH2-C-N there is provided a flame-retardant composition com N prising: (1) at least one compound represented by the R2O H formula: 4,177,300 3. 4. or with a primary amine such as, for example, methyl amine, ethanolamine, or the like to form a partially -continued N-substituted phosphonoxycarboxamide, e.g., ch,--och, + 2C1-CH2-C-OC2H5-Ge. 5 O O H (IVA); CH3O / O O I (IIA) R-i-o-CH-C-NR2O CH3 or O O H 10 The N- unsubstituted or partially substituted phos / phonoxycarboxamides which are prepared by reacting R!--o-ch-c-N the precursor phosphonates with either ammonia or a R2O C2H4OH primary amine may then be condensed with an alde hyde to form the alkyloamides. Aldehydes which may This reaction may be conducted in a solvent which is 15 be used for this purpose include, but are not limited to, nonreactive towards either the starting reagents or the formaldehyde, acetaldehyde, and glyoxal. the alkylol resulting phosphonoxycarboxamide. Suitable solvents amides may then be reacted with an aminoplast to form include, but are not limited to water, methanol, ethanol, a water-insoluble resin. Aminoplasts which may be used ethylene glycol, diethyl ether, acetone, toluene, and the for this purpose include, but are not limited to, me like. The reaction is conducted at a temperature ranging 20 thylol- and methoxymethylmelamines, methylolated from about 0° C. to about 40 C. and generally requires ureas, and cyclic ureas such as dimethyloldihydroxye a reaction time ranging from about 2 to 20 hours. thyleneurea. The phosphonoxy-bix-carboxamide compounds (i.e., For example, Compound III may be methylolated by Compound I wherein n=2) of this invention may be reaction with formaldehyde, which can be in gaseous, prepared using the same procedures as described above 25 liquid solution, or solid form, over a period of from except that a bis-carbalkoxyalkyl phosphonate, i.e., about 0.5 to about 2 hours at a temperature ranging from about 55 to about 85°C. while maintaining the O O (IIA) system at an alkaline pH, preferably in the range of I about 7.5 to about 8.5. The product of this reaction 30 using Compound III will be a mixture of the monometh ylol substituted derivative (V) and the dimethylol deriv is used as a starting material instead of a carbalkox ymethyl phosphonate (II). ative (VI): The precursor phosphonates (Compounds II and 35 O O H (V) IIA) used in preparing the novel phosphonoxyaceta | M. RI-P-O-CH-C-N mides of this invention may be prepared by reacting an R2O alkyl, aryl, alkylaryl, or arylalkyl phosphonate with an CH2OH alkyl halo alkanoate at a temperature ranging from and about 125° C. to about 175 C. in the presence of an O O CH2OH (VI) anionic catalyst such as sodium carbonate at a concen I / tration ranging from about 0.2 percent to about 0.5 R!--o-ch-c-N percent by weight of total reaction mixture. This reac R2O CH2OH tion is generally conducted without a solvent and re quires from about 8 to about 12 hours at the stated 45 wherein the specific proportions of the mono- and temperature range. Typical alkyl phosphonates which dimenthylol derivatives within the mixture depends, in may be used in preparing these precursor phosphonates part, upon the molar ratio of the formaldehyde relative include, but are not limited to, dimethyl methylphos to the unsubstituted phosphonoxycarboxamide present phonate, diethyl methyphosphonate, dimethyl ethyl in the initial reaction mixture. Although completely phosphonate, diethyl ethylphosphonate, dimethyl 50 satisfactory in this form for most applications, it is un butylphosphonate, dipropyl butylphosphonate, dibutyl derstood that, if desired, the reaction product may be butylphosphonate, and the like. further refined by techniques well-known in the art to Exemplary of the alkyl halo alkanoates which may be obtain the desired compound in a more pure form such used to form the precursor phosphonate compounds are as, for example, by crystallization. methyl chloroacetate, ethyl chloroacetate, ethylbrom 55 The partially substituted phosphonoxycarboxamides oacetate, and the like. (i.e., Compounds IVA, IVB) may also be reacted with Thus, the formation of precursor phosphonates II and formaldehyde to form N-methylol substituted deriva IIA may be illustrated schematically as follows. tives, i.e., 60 O O O O CH2OH (VIIA) I | M. RI-P-O-CH2-C-N CH-i-och, + CICH2-C-OC2H5-Ge. N CH3O R2O CH3 (II) O O CH2OH (VIIB) I / 65 Rl-P-O-CH-C-N CH-i-o-ch-c-och, + CH3Cl R2O N CH3O C2H4OH and 4,177,300 5 6 Exemplary phosphonoxycarboxamides of this inven tion are: * ... O O H (9) O-methyl methylphosphonoxyacetamide: I. M. r. CH-Peo-CH-C-N, ); . . . 5 H O O H (1) M CH-i-o-CH-C-N Bis (carbamidomethyl)ethyl phosphonate: CH3O H O O (10) 10 N-methyl, O-methyl methylphosphonoxyacetamide: H O O 2-2CH2OH (2) Bisi (dimethylol carbamidomethyl) ethyl phospho CH-i-o-ch-c-N 15 nate: CH3O H O CH2OH (11) N-methyl-N-methylol. O-methyl methylphosphonox yacetamide: 20

O O CH2OH (3) Bis (N-methyl-N-methylol carbamidomethyl) me / CH3-P-O-CH2-C-N thylphosphonate: N 25 CH3O CH3 O O (12) II M N,N-dimethylol, O-methyl methylphosphonox CH3-P--O-CH2-C-N yacetamide: CH3 30 The unsubstituted phosphonoxycarboxamides of OI O --"CH2OH. (4) structure (III) and the partially substituted phosphonox CH-i-o-ch-c-N s ycarboxamides of structure (IV) are useful in their own CH3O CH2OH right since they can be bonded to a textile by means of 35 a reaction with an aminoplast. Thus, for example, a compound of structure (III) such as is illustrated by O-methyl ethylphosphonoxyacetamide: O-methyl methylphosphonoxyacetamide can be ad mixed with about 0.2 to 5 parts by weight of tri-, tetra-, O o H (5) or pentamethylolated melamine, or a partially etherified / 40 derivative thereof, and cured in the presence of an acid ch-i-o-ch-c-N s catalyst such as those hereinabove described so as to CH3O H yield durable flame retardant finishes on cellulosic, cellulosepolyester, or other textiles. Methylolation of O-ethyl ethylphosphonoxyacetamide: the phosphonoxycarboxamide does, however, offer the 45 advantage of making it reactive with cellulose as well as with the aminoplast and thus generally minimizes the O O H (6) amount of aminoplast which is required. CHpris- O CH--n,2 N The phosphonoxycarboxamides of this invention may C2H5O . H be applied to normally flammable substrates in the form 50 of an aqueous flame retardant formulation or as a liquid formulation in any of the organic solvents commonly N-methylol, O-ethyl ethylphosphonoxyacetamide: used in the solvent finishing of textiles including, for example, ethanol, methanol, chloroform, water and mixtures thereof. Preferably, these formulations also include an aminoplast and an acid catalyst. The term "aminoplast' is here meant to denote a nitrogen-containing resin which is capable of reacting with itself, with the phosphonoxycarboxamide, and/or L-hydroxyethyl, O-ethyl ethylphosphonoxyaceta with the textile or other substrate, and which is pre pared by the polycondensation of formaldehyde with a mide: - compound having at least two reactive amino or amido hydrogen atoms. Exemplary of the aminoplasts which o O C2H5OH (8) may be used are methylolureas which may be either C2H O-CH n^ straight chained or cyclic, methylolmelamines, me 25 2 N 65 thylolcarbamates, methylolurons, methylolamides, the C2H5O CH3 methyl ethers of the above listed methylol compounds, methylolated acid amides, urea glyoxal condensation Bis (carbamidomethyl) methylphosphonate: products, urea-glyoxaliformaldehyde condensation 4,177,300 7 products, N-methylolated or N,N-dimenthylolated O about 180 C. with temperatures in the range of from alkyl, O-alkoxy, or O-hydroxyalkyl carbamates. Pre about 150 to 160" C. being preferred. Curing time may ferred aminoplasts include tris(methoxymethyl) mela vary from about 1 minute to about 20 minutes depend mine as sold by the American Cyanamid Company ing on the nature of the substrate being treated. The under the trademark "AEROTEX M-3”; partially effect of the curing operation is to cause the alkylolated methylated melamine as sold by the American Cyana phosphonoxycarboxamide and aminoplast to react with mid Company under the trademark "AEROTEX 23 the cellulose or with each other so as to form a cross SPECIAL'; demethylolethylene urea; dimethylol dihy linked, insoluble finish in and/or on the individual fibers droxyethylene urea, dimethylol methyl carbamate, di comprising the textile or other flammable substrate. methylol hydroxyethyl/hydroxypropyl carbamate, and 10 As used herein, the term "flame retardant' is in dimethoxymethyl uron. For most purposes, the use of tended to refer to that particular property of a material one or more of the above-described aminoplasts at a which provides it with a degree of resistance to ignition concentration ranging from 10 to 600 percent and pref and burning. Thus, a fire or flame retardant textile, erably from about 25 to 300 percent by weight of the paper, or other solid substrate is one which has a low phosphonoxyacetamide will be satisfactory. 15 level of flammability and flame spread. This property Suitable acidic catalysts for use in the flame-retardant may be conveniently evaluated by means of any of the compositions of this invention include mineral acids standard flame retardancy tests such as for example, the such as phosphoric acid; organic acids such as oxalic, vertical char length tests described in the federal Flam citric, succinic, maleic, glycolic, chloroacetic, and tolu mability Standard of July 27, 1971 (35 Federal Register enesulfonic acids; alkyl acid phosphates, and the like. 20 146). Also included are the salts of strong acids with rela As used herein, the term "textile' or "textiles' is tively weak bases such as, for example, zinc nitrate, zinc meant to encompass woven or knitted fabrics as well as chloride, magnesium chloride, ammonium chloride, non-woven fabrics which consist of continuous or dis ammonium phosphates, and amine hydrochlorides. continuous fibers bonded so as to form a fabric by me Some typical amine hydrochlorides include 2-amino-2- 25 chanical entanglement, thermal interfiber bonding, or methylpropanol hydrochloride sold under the trade by use of adhesive or bonding substances. Such non name "Catalyst AC' by the Monsanto Company, and woven fabrics may contain a certain percentage, up to the alkanolamine hydrochloride sold as "Catalyst 100 percent, of wood pulp as well as conventional tex XRF" by the Millmaster Onyx Corporation. The use of tile fibers in which case part of the bonding process is one or more of these catalysts in a concentration of from 30 achieved by means of hydrogen bonding between the about 0.01 to 5 percent based on the weight of the phos cellulosic pulp fibers. In non-woven fabrics, the com phonoxyacetamide will be suitable for most purposes. pounds of this invention can serve not only as flame The concentration (i.e., the "solids' content) of the retardant finishes but can also contribute to the interfi phosphonoxycarboxanide/aminoplast/catalyst compo ber bonding mechanism by serving as all or part of the sition used may vary in accordance with several factors 35 adhesive or bonding resin component. This dual role such as the nature of the substrate or fabric to which it can also be played by the phosphonoxycarboxamides of is being applied, the amount of phosphonoxycarboxa this invention in fabric laminates where they can at the mide resin desired in or on the final product, and the same time serve as the interlaminar bonding agent and like. It is generally desirable, however, to achieve a as the flame retardant. In both of these systems, i.e., phosphorous uptake on the textile or other substrate 40 non-woven fabrics and laminated fabrics, the com ranging from about 1 to about 5 percent by weight of pounds of this invention can also be blended with the the dry untreated fabric or substrate. Thus, the concen usual bonding agents such as, for example, acrylic enul tration of the flame-retardant composition will be ad sion polymers, vinyl acetate homo- and copolymer justed to a solids level which will produce the desired emulsions, styrenebutadiene rubber emulsions, urethane amount of phosphorous uptake with the anticipated 45 resin emulsions, polyvinyl chloride emulsions, vinyl amount of wet-pickup. The ranges given, of course, are chloride-alkyl acrylate copolymer emulsions, poly merely illustrative and may be varied in accordance acrylates modified by vinyl carboxylic acid comono with the particular needs of the user. mers, and the like. The flame-retardant composition containing the The preparation and use of the novel phosphonox phosphonoxycarboxamide, aminoplast, and catalyst 50 ycarboxamide compounds of this invention is further may be applied to textiles or other substrates by the use illustrated by the following nonlimiting examples, all of any of those techniques known in the art for this parts and percentages given being by weight unless purpose such as dipping, spraying, painting, padding, otherwise stated. etc. A preferred method for applying the composition to a fabric is that known as "padding' wherein the 55 EXAMPLE 1. fabric is passed or "padded' through the composition This example illustrates the preparation of O-methyl while the latter is being held in a tank or other suitable carbomethoxymethyl methylphosphonate to be used as container. For most applications, it is desirable to main a precursor in preparing the phosphonoxycarboxamides tain the pH of the padding bath in the range of from of this invention. about 4.5 to about 5.5. 18 grams (9 moles) of dimethyl methylphosphonate The thus applied flame-retardant composition may was mixed with 653.5 grams (6 moles) methyl chloroac then be dried and cured. Drying may be accomplished etate and 4.0 grams sodium carbonate (catalyst) in a by various techniques including heating at a tempera flask equipped with a stirrer, an overhead condenser, ture ranging from room temperature up to about 120° C. and a condensate trap. The reaction mixture was heated or higher. It is, of course, entirely possible to eliminate over several hours to a temperature of 128 C. during drying as a separate step and accomplish the drying as a which period some methyl chloride was collected in the part of the curing step. Curing may be accomplished by condensate trap. The reaction mixture was brought to a heating at a temperature ranging from about 130 C. to temperature of 130-131 C. and held there for several 4,177,300 9 10 hours during which time 239 grams of methyl chloride was collected in the distillate trap. Increasing the tem EXAMPLE 4 perature to 138 C. for one hour produced an additional This example illustrates the preparation of a bis car 28 grams of methyl chloride. balkoxymethyl phosphonate precursor used in prepar The reaction product was then stripped in a 1-foot 5 ing the bis(carbamidomethyl) phosphonates of this in vigreux column to remove excess dimethyl methylphos vention. phonate. A first distillate fraction, weighing 509.5 167.5 grams of dimethyl methyl phosphonate was grams, was taken off at a column pressure of 24 mm. heated to 125 C. in a flask equipped with a stirrer, an Hg. abs., a base temperature of up to 119 C., and an overhead condenser, and a condensate trap. 0.5 gram of overhead vapor temperature of up to 87 C.; and a 10 tetraethylammonium chloride was stirred in, and then second distillate fraction, weighing 150 grams, was 457 grams of ethyl bromoacetate was added over a taken off at a column pressure of 0.1 mm. Hg. abs., a period of about 23 hours. As the ethyl bromoacetate base temperature up to 100° C., and an overhead vapor was being added, the reaction temperature increased to a maximum of 170 C., and methyl bromide vapors were temperature up to 40° C. The total amount of distillate 15 condensed in the overhead condenser and collected in collected, 659.5 grams, exceeded the theoretical amount the condensate trap. Upon completion of the addition of by 123.5 grams. This excess was attributed to unsubsti the ethyl bromoacetate to the flask, the reaction mixture tuted dimethyl methylphosphate remaining in the reac was allowed to cool to room temperature. At this time, tion mixture due to the disubstitution of a correspond the condensate trap was found to contain 217.3 grams of ing amount of the desired product by an extra mole of 20 methyl bromide. The flask contents were then reheated methyl chloroacetate. to a temperature ranging from about 162 C. to about The crude reaction product remaining after distilla 165 C. for about 1 hours during which time an addi tion had an acidity to bromothynol blue equivalent to tional 14 grams of methyl bromide was collected in the 0.18 milliequivalents acid per gram. condensate trap. Upon cooling, the flask was found to EXAMPLE 2. 25 contain 394 grams of product in the form of a yellow fluid. This compares to a calculated (theoretical) yield This example illustrates the preparation of the N of 368 grams. unsubstituted phosphonoxycarboxamides of this inven tion from the O-methyl carbomethoxymethyl methyl EXAMPLE 5 phosphonate prepared in Example 1. 30 This example illustrates the preparation of bis(car Fifty grams of anhydrous ammonia was dissolved in bamidomethyl) phosphonate from the bis carbalkox 700 ml. of methanol to prepare a 4.43 normal solution. ymethyl phosphonate precursor prepared in Example 4. 125 ml. of this solution was slowly added to the O Forty-seven grams of anhydrous ammonia was dis methyl carbomethoxymethyl methylphosphonate pre solved in ethanol to prepare 660 ml. of a 4.15 molar pared in Example 1 at a temperature of 10-15 C. This 35 solution. This solution was then added at room tempera reaction mixture was then allowed to stand overnight at ture to the product of Example 4, with no observable room temperature. exotherm resulting. The reaction mixture was allowed The next day, an additional 545 ml. of the 4.43 normal to stand in an ice bath for three days. When subse ammonia solution was added to the reaction mixture at quently heated to 65 C. under a dry-ice dephlegmator, reduced temperature followed by 220 ml. of a similarly 0 no ammonia condensed out; this was taken as an indica prepared 9.3 molar ammonia solution. Following this tion that the reaction had been completed. The reaction addition, a 1.0 ml. sample of the reaction product was mixture was then stripped of ethanol under vacuum to a found to have 0.21 meq. ammonia (to bromothymol weight of 394 grams and then Hivac stripped to a final blue). The reaction mixture was heated to 46' C. for weight of 366 grams (compared to a theoretical weight two hours after which it was found to contain 0.18 meq 45 of 290 grams). Infrared analysis indicated the presence ammonia/ml. and 0.4 med. RNH3/ml. The reaction of some remaining ester functionality. A sample of the product was then stripped of methanol to a final weight reaction mixture was titrated to the thymolphthalein of 781 grams. end point which indicated the presence of about 0.4 275 ml. of tetrahydrofuran and a few seed crystals mole of NH4+. Seven grams of ammonia in 35 ml. of 50 methanol was then added and the reaction mixture al were added to 760 grams of the stripped product. The lowed to stand overnight at 43' C. Titration of a sample resulting precipitate was filtered out and washed three of the reaction mixture with acid indicated that the times with butanol to yield 375 grams of crystalline entire reaction mixture contained about 70 meq NH3. product having a melting point of 40-48 C. This prod The reaction mixture was then heated for 29 hours at a uct was recrystallized in 200 grams of ethanol and then 55 temperature ranging from 40-45° C. Subsequent analy washed with methyl-ethyl ketone to yield 210.5 grams sis indicated the presence of 25 meq. of ammonia. of a crystalline product having a melting point of The reaction mixture was then stripped of methanol 50-55° C. Infrared analysis of this product indicated at a temperature of 62 C. and a pressure of 0.1 mm. abs. that C-O and P-O were present in a 1:1 ratio. to a final product weight of 345 grams. EXAMPLE 3 60 EXAMPLE 6 This example illustrates the N- substitution of the This example illustrates the preparation of a flame phosphonoxycarboxamide prepared in Example 2. retardant textile finish with the phosphonoxycarboxa 200 grams of the phosphonoxycarboxamide prepared mides of this invention. in Example 2 and 42 grams of paraformaldehyde (95 65 An aqueous padding bath was prepared containing percent formaldehyde) were heated to 80 C. and 54.9 percent by weight of water, 0.1 percent by weight stirred for one hour. All of the paraformaldehyde dis of "TRITON X-100', an ethoxylated tertiary-octyl solved, indicating that reaction had taken place. phenol condensate wetting agent sold by the Rohm and 4,177,300 2. Haas Company, 30 percent by weight of O-methyl me thylphosphonoxyacetamide (i.e., Compound (I), 10 per -continued cent by weight of tris (methoxymethyl) melamine, an Vertical aminoplast obtained from the American Cyanamid Char (inches) Hand Color Company under the tradename “AEROTEX 23 SPE- 5 After Washing B.E.L. l Tan CIAL', and 5 percent by weight of ammonium chloride *Burned entire length. (as catalyst). A sample of cotton flannel cloth having a weight of 3.8 oz./sq. yard was padded through the It was found that the flame retardancy "before wash aqueous padding bath and then dried at 250' F. (121.1 ing' produced by the bis (carbamidomethyl) methyl C.) for 1 hours and cured at 350 F. (176.7° C) for two 10 phosphonate was roughly equivalent to that of the hours. Dry add-on weight was found to be 24.2 percent monocarbamidomethyl methyl phosphonate of Exam by weight of untreated cloth. ple 6. The flame retardancy after washing 10 times was The treated flannel cloth was then subjected to a judged to be unacceptable. thus, either compound may series often hot water, i.e., 60' C., detergent washes in be used to achieve effective flame retardancy in applica 15 tions which are not subject to laundering; but for those a home washing machine containing 50 grams of “Tide applications subject to laundering, the mono-car XK', a strong laundry detergent sold by the Proctor bamidomethyl methyl-phosphonate should be used. and Gamble Company, and 200 parts per million of It may thus be seen that the novel phosphonoxycar water hardness (calculated as CaCO3 using Mig. boxamide compounds of this invention are effective in (NO3)2.6H2O and Ca(NO3)2.4H2O) and eight bath tow 20 imparting flame retardance to textile materials. The els as ballast. novel flame-retardant compositions of this invention The flammability of the cloth was evaluated before impart flame retardance to textile materials at reason and after washing by means of the vertical char length able add-on weights, thereby making them highly desir test. In the vertical char length test, the complete details able for use in textiles from which light weight articles of which are described in the Federal Flammability 25 of clothing are to be manufactured. The textiles to be Standard of July 27, 1971, (35 Federal Register 146), a made flame retardant may be effectively and conve 10-inch strip of the finished cloth is suspended vertically niently treated to impart flame retardance to them by so that its lower edge is maintained inch (1.9 CH) the process of this invention. The objects set forth above the top of a Bunsen burner having a 1.5-inch (3.81 above, among those made apparent from the preceding cm) high flame for a period of three seconds. The length 30 description, are therefore effectively attained. of the resulting char, in inches, is then measured upward Since certain changes may be made in the above from the base of the strip. Thus, a shorter char length of compounds, compositions, and process without depart about 3 to 5 (7.6 to 12.7 cm) is indicative of a greater ing from the scope of this invention, it is intended that degree of fire retardancy while a char length of about all matter contained in the above description shall be 10 inches (25.4 cm) (burned its entire length) is unac- 35 interpreted as illustrative and not in a limiting sense. ceptable for most applications. The hand and color of What is claimed is: the cloth samples were also evaluated before and after 1. A flame-retardant composition comprising: washing. The results of these evaluations were as fol (1) at least one compound represented by the formula: lows: 40 O O 3 Vertical 1- -R Char (inches) Hand Color R --O-R-C-N- )n Before Washing 4.25"(10.8cm) 2.0 Light Yellow (RO)2. After Washing 6.5 '(16.5cm) 1.5 White 45 wherein R and R2 are selected from the group consisting of aryl and alkyl having from 1-6 carbon EXAMPLE 7 atoms and may be the same or different; R3 repre This example illustrates the preparation of a flame sents hydrogen or -CH2OH.; R4 represents hy retardant finish with a bis-phosphonoxycarboxamide of 50 drogen, -CH3, -CH2OH, or -C2H4OH, R5 rep this invention. resents an alkyl group having 1-5 carbon atoms An aqueous padding bath was prepared as in Exam and n represents 1 or 2; ple 6 except that the O-methyl methylphosphonox (2) an aminoplast; and yacetamide of Example 7 was replaced by the bis(car (3) an acid catalyst. bamidomethyl) methylphosphonate prepared in Exam 55 2. A flame-retardant composition in accordance with ple 5, i.e., compound (9). A sample of the same cotton claim 1 wherein R represents an alkyl radical of from flannel cloth as was used in Example 6 was padded 1-4 carbon atoms, R2 represents an alkyl radical of from through the aqueous padding bath, dried, and cured as 1-2 carbon atoms, and Rs is -CH2-. in Example 6. Dry add-on weight was found to be 21.8 3. A flame-retardant composition in accordance with percent by weight of untreated cloth. 60 claim 1 wherein said aminoplast is selected from the The treated cloth was washed and evaluated for flam group consisting of straight chained or cyclic, methylol mability, hand, and color as in Example 6 with the melamines, methylolcarbamates, methylolurons, me following results: thylolamides, the methyl ethers of the above listed methylol compounds, methylolated acid amines, urea 65 glyoxal condensation products, urea-glyoxalformalde Vertical hyde condensation product, N-methylolated or N,N- Char (inches) Hand Color dimethylolated O-alkyl, O-alkoxy, or O-hydroxyalkyl Before Washing 4.5"(11.4 cm) 2.0 Brown carbamates or mixtures thereof. 13 4,177,300 14 4. A flame-retardant composition in accordance with (a) at least one compound represented by the for claim 1 wherein said acid catalyst is selected from the mula: group consisting of phosphoric acid, oxalic acid, citric acid, succinic acid, maleic acid, glycolic acid, chloro O O 3 acetic acid, toluenesulfonic acid, zinc nitrate, zinc chlo 5 R1 Oa-R N1 R ride, magnesium chloride, ammonium chloride, ammo 5 Sr. nium phosphates, and amine hydrochlorides. (RO)2. 5. A flame-retardant composition in accordance with wherein R and R2 are selected from the group claim 6 wherein said composition is an aqueous compo 10 consisting of aryl and alkyl having from 1-6 sition and the concentration of said aminoplast ranges carbon atoms and may be the same or different; from about 10 to about 60 percent by weight of said at R3 represents hydrogen or -CH2OH.; R4 repre least one compound, the concentration of said catalyst sents hydrogen, -CH3, -CH2OH, or -C2 ranges from about 0.01 to about 5 percent by weight of H4OH; R5 represents an alkyl group having from said at least one compound, and the total concentration 15 1-5 carbon atoms and n represents 1 or 2; of said at least one compound, said aminoplast and said (b) an aminoplast; and catalyst is adjusted to a value which will achieve a (c) an acid; and phosphorous uptake on the substrate being treated rang (2) heating said impregnated textile material suffi ing from about 1 to about 5% by weight. ciently to cure said flame-retardant composition. 6. A process for imparting flame retardance to textile 20 7. A process in accordance with claim 6 wherein said materials comprising the steps of heating takes place at a temperature ranging from about (1) impregnating the textile material with a flame 130 C, to about 180 C. retardant composition comprising; it is 25

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UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. : 4, 177,300 Page 1 of 2 DATED December 4, 1979

INVENTOR(S) : Edward N. Walsh and Ralph B. Fearing it is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below: In the Abstract, the word "phosphonxycarboxamides" should read -- phosphonoxycarboxamides --. Column 2, line l2 - "Il r 2" should read -- l or 2 --.

Column 3, line 24, - "phosphonoxy-bix-carboxamide" should read -- phosphonoxy-bis-carboxamide --. Column 4, line 36, - In Formula V there should be a single bond down to R*O from the P. Column 4, line 65, - In Formula VIIB there should be a single bond down to RO from the P. Column 8 line 43, the word "enulsion" should read -- emulsion --. Column 8, line 60, "18 grams" should read "ll18 grams". Column 12 line l3, "thus" should read -- Thus --.

UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. : 4, l77,300 Page 2 of 2 DATED December 4, 1979 INVENTOR(S) : Edward N. Walsh and Ralph B. Fearing It is certif ed that error appears in the above-identified patent and that said Letters Patent are hereby Corrected as shown below:

Column 13 line 9, "claim 6" should read -- claim 4 -- . Column 13 line 12, "60" should read -- 600 --. signed and sealed this Twenty-fifth Day of March 1980 SEAL Attest:

SIDNEY A. DAMOND Attesting Officer Commissioner of Patents and Trademarks