BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     Fireproofing. 
     2. Description of the Prior Art 
     One of the older patents in this art is U.S. Pat. No. 2,782,133 teaching aminocyclophosphazene as a fireproofing agent for cellulosic fibers such as cotton. A recent patent is U.S. Pat. No. 3,711,542 teaching certain new N-methylol phosphazene compounds as flame retardants on cotton, and this patent under Background of the Invention contains a summary of certain phosphazene prior art on flameproofing. 
     SUMMARY OF THE INVENTION 
     Mixtures comprising compounds of the formula ##STR1## wherein A is either NH 2  or N=P (NH 2 ) 3 , provided at least one A is N=P (NH 2 ) 3 , have been found to be good flameretardants for material made from cotton or polyester-cotton having about 30 to 70% by weight cotton. Conveniently the material can be treated with an aqueous solution containing a sufficient amount of said mixtures and the material dried to make the material self extinguishing. Then the treated and dried material is cured at a sufficient temperature to bond said compounds to the materials. Alternatively and usually preferably the drying and curing can be accomplished as a single operation. 
     DESCRIPTION OF THE PREFERRED EMBODIMENTS 
     Preparation of the flame-proofing reagents -- Melamine and phosphorus pentachloride were allowed to react in molar ratios of 1/3; 1/2; 1/1. After reaction with ammonia, three materials were obtained having different solubilities, although their infrared spectra were quite similar. Elemental analyses showed that these materials were not pure compounds nor were they the simple materials expected by the reaction of the trihalophosphazenes with excess ammonia. ##SPC1## 
     n = 1, 2, or 3, but n = 1 in the above reaction. 
     A reference to the tris-trichlorophosphazene was found in the literature (I. Derkash, USSR 168,693, C.A. 63, 1700g; C.A. 69, 36082s); however, no reference to any of the ammoniated compounds from melamine +PCl 5  + NH 3  has been found. All of the ammoniated products were water soluble and contained chlorine. Recrystallization from water resulted in losses of chlorine and significant changes in the phosphorus analyses. These products flame retarded cotton and 65/35 polyester-cotton. 
     The reaction of 3 moles of phosphorus pentachloride and a mole of melamine will be used to represent all of the reactions between these two reagents in varying stoichiometries. ##SPC2## 
     A mixture of 30.0 g (0.24 m) of melamine (MCB) and 177.5 g (0.85 m) of PCl 5  with 200 ml of CHCl 3  was heated at gentle reflux with stirring, until the evolution of HCl had ceased (44 hours). The top of the condenser was protected by a Drierite tube. The mixture was allowed to cool, and the solvent and trapped HCl were removed on a rotary evaporator leaving 190.7 g of a white solid which smelled of CHCl 3 . The solid was reactive to water but was not as reactive as PCl 5 . 
     The solid was placed in a 3-liter flask with 500 ml of toluene. Eight hundred ml of liquid ammonia was added in portions. A Dry Ice condenser was used to contain the ammonia. This mixture was stirred overnight. The copious white solid that had formed was filtered to remove the toluene. Twelve hundred ml of ammonia was poured cautiously over the filter cake. The solid left on the filter and the solid left after evaporation of the ammonia from the filtrate had identical infrared spectra indicating the presence of both product and ammonium chloride and that the product was soluble in ammonia. The residue from evaporation of the ammonia filtrate was added to the filter cake giving a combined weight of product of 230 g. The product was soluble in water. The mixture was also soluble in methanol and ethanol and formed a salt with acetic acid. There was no apparent solubility in acetone, acetonitrile, THF, benzene, toluene, chloroform or methylene chloride. 
     The 230 g of solids product was slurried in 1200 ml of chloroform and 315 ml (3 m) of diethylamine. The mixture was heated slowly to reflux. (This method, see below, affords a chloroform soluble amine hydrochloride from the ammonium chloride, thus enabling separation of the phosphazene.) 
     
         (C.sub.2 H.sub.5).sub.2 NH + NH.sub.4 Cl → (C.sub.2 H.sub.5).sub.2 NH.sub.2 Cl + NH.sub.3 
    
     the ammonia was detected at the top of the condenser. The mixture was refluxed overnight. The cooled solution was filtered to remove the red chloroform solution of the amine hydrochloride. The filter cake product was washed with chloroform and air dried, wt. 89.9 g. The infrared spectrum of this product showed no ammonium chloride. An aqueous solution of the product was neutral; however, there was a slight indication of chloride ion using a silver nitrate test. 
     When heated in a capillary tube, gas was evolved at 113° C to form a foam; at 260° C, more expansion occurred and at 280°-300° C, the material softened to a thick syrup with more gas evolution. A thermogravimetric analysis on this material in air from room temperature to 980° C left 18% residue. At 300° C, only 20% of the material had decomposed. Another 30% was lost between 300° and 500° C. There was slightly less weight loss in helium. An elemental analysis of the product was as follows: 
     
         ______________________________________      %   Found______________________________________   C         10.17   H         5.61   N         41.04   P         19.06   Cl        1.70______________________________________ 
    
     Treatment of Fabrics -- A solution containing the desired weight percent of the flameproofing reagent in sufficient water to just saturate the cloth was poured on a weighed piece of cloth lying flat in a plastic bag. The solution was worked over the surface of the cloth, until it was uniformly wet. After standing for about 15 minutes, the cloth was placed in an oven at the desired temperature and cured. After curing and drying, the cloth was allowed to equilibrate before being weighed. 
     Cure Conditions -- Cure was effected at 140° C or as shown in the following table using the one operation to also dry the wet sample. Formaldehyde or trimethylolmelamine and quarternary base, sodium hydroxide or magnesium chloride were included as auxiliary treatments in some instances attempting to make the material more durable to washing, and these auxiliary agents are present in the same aqueous solution as the primary reagent when it is applied to the material. 
     Flammability Tests -- Samples of cloth 10 in. × 31/2 in. were clamped in a metal stand and tested according to AATCC Test Method 34-1969 using a propane torch in place of the special gas mixture. This flammability test is described in J. Amer. Assoc. Text. Chem. and Colorists 2 (3), 49/19 (1970). 
     Tabulation of Data -- The test data are tabulated in the following table. The table is divided into three main sections: Fabric Treatment, Flammability Tests and Miscellaneous Conditions. The following column headings are used. The added notes are for explanation of their meanings where not self explanatory. 
     
         ______________________________________Column Heading     Explanation______________________________________1     Cloth Type2     Reagent     *Melamine/PCl.sub.5 + NH.sub.3 product3     Auxiliary   material used to bind to             cloth such as formaldehyde             and catalyst; QB = quarternary             base, TMM = trimethylolmelamine4     % Final     weight percent of product added Add-On      to the cloth after all processes             including laundering if indicated             in column 95     Distance    this represents the length of Burned, in. the sample that was burned             out, charred or scorched from             the ignited edge6     Time, Sec   time from ignition to removal             of flame even though self             extinguishment had already             occurred7     (SE)        answers question -- Did the Self        fire self extinguish before Extinguish  burning the entire sample             length? Y = yes; N = no8     Cure        temperature at which the Temperature wet cloth was dried and cured             in a single operation9     Post        indicates treatment of sample Treatment   after curing but before             flammability test. L = Laundered,             detergent wash and dried;             NL = Not Laundered______________________________________ 
    
     
         __________________________________________________________________________                                  MiscellaneousFabric Treatment          Flammability Test                                  Conditions                %    Distance     Cure                Final                     Burned,                          Time,   Temp                                      PostCloth Type    Reagent         Auxiliary                Add-On                     in.  Sec  SE ° C                                      Treatment__________________________________________________________________________cotton   --   --     0.00 10   1    N  --  NL65/35polyester/cotton    --   --     0.00 10   1    N  --  NLcotton   *    --     5.27 31/2 3, 15                               Y  120 NLcotton   *    --     5.27 10   3    N  120 L65/35    *    --     15.2 4    3    Y  140 NLpolyester/cotton65/35    *    --     15.2 10   3    N  140 Lpolyester/cottoncotton   *    --     2.5  51/2 12   Y  150 NLcotton   *    --     2.5  10   15   N  150 L65/35    *    --     9.3  6    15   Y  150 NLpolyester/cotton65/35    *    --     9.3  10   15   N  150 Lpolyester/cotton65/35    *    CH.sub.2 O                4.45 10   8    N  120 Lpolyester/cottoncotton   *    CH.sub.2 O, Q.B..sup.1                20.3 3    20   Y  130 NLcotton   *    CH.sub.2 O, Q.B.                14.7 6    15   Y  130 L65/35    *    CH.sub.2 O, Q.B.                30.7 3    20   Y  130 NLpolyester/cotton65/35polyester/cotton    *    CH.sub.2 O, Q.B.                0    10   15   N  130 Lcotton   *    CH.sub.2 O, NaOH                7.7  10   10   N  140 L65/35    *    CH.sub.2 O, NaOH                6.45 8    8    N  140 Lpolyester/cottoncotton   *    Q.B.   5.7  10   5    N  140 L65/35    *    Q.B.   6.25 10   5    N  140 Lpolyester/cottoncotton   *    TMM.sup.2,Q.B.                6.4  4    5-30 Y  140 L65/35    *    TMM, Q.B.                8.9  10   5    N  140 Lpolyester/cotton65/35    *    TMM, Q.B.                9.5  10   10   N  140 Lpolyester/cotton50/50    *    TMM, Q.B.                20.0 41/2 3    Y  140 NLpolyester/cotton50/50    *    TMM, Q.B.                7.6  10   10   N  140 Lpolyester/cotton65/35    *    CH.sub.2 O, Q.B.                3.85 10   8    N  140 Lpolyester/cotton65/35    *    TMM, Q.B.                10.7 10   15   N  140 Lpolyester/cotton65/35    *    CH.sub.2 O, MgCl.sub.2                4.86 10   10   N  140 Lpolyester/cottoncotton   *    CH.sub.2 O, MgCl.sub.2                7.1  10   10   N  140 L__________________________________________________________________________ .sup.1 Quarternary base .sup.a Trimethylol melamine *Melamine/PCl.sub.5 + NH.sub.3 SE = Self Extinguishing Y = Yes NL = Not Laundered N = No L = Laundered Note: Untreated cotton and polyester/cotton cloth are not self extinguishing in the flammability test and data for these materials are given for comparison purposes. 
    
     Although the invention has been described in terms of specified embodiments which are set forth in considerable detail, it should be understood that this is by way of illustration only and that the invention is not necessarily limited thereto, since alternative embodiments and operating techniques will become apparent to those skilled in the art in view of the disclosure. For example, although mixtures of compounds of the invention were used for flameproofing, each individual compound is a flameproofing agent, i.e. each compound whether one, two or all three A&#39;s of the general formula is N=P(NH 2 ) 3 . Accordingly, modifications are contemplated which can be made without departing from the spirit of the described invention.
Mixtures comprising compounds of the formula ##EQU1## wherein A is either NH 2  or N=P(NH 2 ) 3 , provided at least one A is N=P(NH 2 ) 3 , have been found to be good flame-retardants for material made from cotton or polyester-cotton having about 30 to 70% by weight cotton. Conveniently the material can be treated with an aqueous solution containing a sufficient amount of said mixtures and the material dried to make the material self extinguishing. Then the treated and dried material is cured at a sufficient temperature to bond said compounds to the material. Alternatively and usually preferably the drying and curing can be accomplished as a single operation.