US3885912A - Method of rendering textiles flame retardant with phosphorus containing melamine - Google Patents

Abstract

New compounds are disclosed of the formula

WHEREIN R is independently selected from the group consisting of

AND WHEREIN R'' is lower alkyl. The compounds of this invention serve as flame retarding agents for textiles and as additives to render polymers and copolymers flame retardant.

Description

United States Patent 91 Golborn et al.

[451 May 27, 1975 METHOD OF RENDERING TEXTILES FLAME RETARDANT WITH PHOSPHORUS CONTAINING MELAMINE [75] Inventors: Peter Golborn, Lewiston; James J.

Duffy, Buffalo, both of NY.

[73] Assignee: Hooker Chemicals & Plastics Corp., Niagara Falls, NY.

221 Filed: Sept. 28, 1973 21 Appl. No.: 401,767

Related U.S. Application Data [62] Division of Ser. No. 239,797, March 30, 1972,

Primary Examiner-Stephen J. Lechert, Jr. Attorney, Agent, or Firm-Peter F. Casella; Donald C. Studley; William .1. Crossetta, Jr.

[57] ABSTRACT New compounds are disclosed of the formula RCH when New NYN NHCHZR wherein R is independently selected from the group consisting of and wherein R is lower alkyl. The compounds of this invention serve as flame retarding agents for textiles and as additives to render polymers and copolymers flame retardant.

16 Claims, No Drawings METHOD OF RENDERING TEXTILES FLAME RETARDANT WITH PHOSPHORUS CONTAINING MELAMINE This is a division of application Ser. No. 239,797, filed Mar. 30, 1972, now abandoned.

FIELD OF INVENTION This invention relates to novel compounds of the formula N Rcn HN NHCH R II NHCHZPIOR' wherein R is independently selected from the group consisting of BACKGROUND OF THE INVENTION Many flame retarding agents and methods of application have been developed in attempts to obtain flame resistant textile materials and thermoplastic and thermosetting resin compositions.

Flame retardant textiles have been produced by depositing metal oxides, within or on the textile fibers, by the successive precipitation of ferric oxides and a mixture of tungstic acid and stannic oxide or by successive deposition of antimony trioxide and titanium dioxide. Such processes require plural treatment baths in which strongly acidic solutions are employed thus posing the problem of possible textile degradation. Furthermore, metal oxide coatings on textile materials create difficulties in subsequent dyeing processes which deleteriously affect the hand of the finished product. Another process involves the use of a single processing bath wherein a dispersion of a chlorinated hydrocarbon and finely divided antimony oxide is padded on the textile material. Near the textile combustion temperature antimony oxide will react with hydrogen chloride. generated by degradation of the chlorinated hydrocarbon, to form antimony oxychloride which acts to suppress flame. This combination of a chlorinated hydrocarbon and finely divided antimony oxide are not acceptable finishes for closely woven textiles as they deleteriously affect the hand of the finished product. A further process for imparting flame resistance to cellulosic materials is by the esterification of the cellulose with diammonium hydrogen orthophosphate. Textile products so treated however are subjected to metathesis reaction with cations during washing, and must be regenerated by reacting the wash product with an ammonium chloride solution.

The production of thermoplastic and thermosetting resin compositions which are flame retardant is of considerable commercial importance. For example, such articles as castings, moldings, foamed 0r laminated structures and the like are required, or are at least desired, to be resistant to fire and flame and to possess the ability to endure heat without deterioration. The use of various materials incorporated into thermoplastic and thermosetting resins so as to improve the flame retardance thereof has ben known. Many compounds have been commercially available for such use, among them being chlorostyrene copolymers, chlorinated paraffin wax in admixture with triphenyl styrene, chlorinated paraffins and aliphatic antimonical compounds, as well as antimony oxide-chlorinated hydrocarbon mixtures. A problem associated with these compounds has been however, the fact that generally a large amount, i.e. up-

wards of 35 percent of additive, must be incorporated into the resin in order to make it sufficiently flame retardant. Such large amounts of additive may deliteriously affect the physical characteristics of the thermoplastic resin, as well as substantially complicating and increasing the cost of preparation thereof. A further problem is that these prior art additives tend to crystallize or oil out of the resin after a relatively short time of incorporation. The present invention relates to a group of compounds which may be added to thermoplastic and thermosetting resins in relatively small amounts and still produce satisfactory flame retardant compositions which will not crystallize nor oil out of the resin after incorporation therein.

OBJECTS OF THE INVENTION It is, therefore, a principal object of this invention to provide novel compounds of the formula:

0 RcH -HN L HCH R consisting of mi and (R' oi and wherein R is lower alkyl.

It is also an object of this invention to provide flame retarding textile materials comprising normally flammable cellulosic, proteinaceous or analogous manmade materials. Another object is to provide a method for treating normally flammable cellulosic, proteinaceous or analogous man-made materials to render them flame retardant. Another object is to provide flame retarding thermoplastic and thermosetting resin compositions comprising normally flammable thermoplastic and thermosetting resin materials. A further object is to provide a process for treating normally flammable thermoplastic and thermosetting resin compositions to render them flame retardant. A particular object is to devise a composition comprising normally flammable cellulosic, proteinaceous or analogous manmade materials and an effective flame retardant amount of the compound represented by the formula RCHZHN N uucu pma' NHCH. R

DESCRIPTION OF THE INVENTION In accordance with this invention there are provided novel compounds, for imparting flame retardancy to textiles and thermoplastic and thermosetting resin materials, of the formula 0 N\ n RCH -NH I 2 f NHCHZNOR NHCH R wherein R is independently selected from the group consisting of N H HO-CH -NH "f Wl"'NHCH -P(OCH CH CH CH CH The synthesis of the compositions of the present invention is accomplished by reacting a N- hydroxymethylated melamine of the formula NHCH OH with a trialkyl phosphite of the formula (R'O) P R is as previously described in a suitable solvent, excess phosphite or neat Typically, the reaction occurs at elevated temperatures and is continued for about 1 to about 12 hours. Temperatures are generally about 50 to about 160C. Preferably reaction is continued from about 3 to about 6 hours at a temperature of about to about C. The solvent and other volatiles are thereafter stripped, or otherwise removed from the product. Suitable solvents include alcohols, glymes, dimethyl formamide or mixtures of the previous solvents with aliphatic or aromatic hydrocarbons.

One or more of the novel compounds of this invention may be applied to textile materials by conventional finishing techniques such as by thermal induced pad curing so as to incorporate into the textile a flame retardant amount thereof. The compounds of this invention have advantages over the flame retardant agents of the prior art in that they may be used on a variety of textile materials of different chemical composition, and they may be applied by a variety of methods. They may be applied to materials in either the fiber or fabric form to give flame retarding materials with minimum detectable physical changes in the quality or hand of the textile material.

The products of this invention may be applied to cellulosic materials in several ways to give a durable flame retardant treatment. For example, the products of this invention may be reacted with formaldehyde to give N- hydroxymethyl derivatives which can react with cellulosic materials in a known manner. Alternatively aqueous mixtures of the products with formaldehyde, urea, trimethylol melamine or other known cellulose crosslinking agents may be applied to a cellulose substrate with the aid of an acidic catalyst by a pad dry process. A further method is to mix the invention with an acid catalyst in aqueous solution and apply directly.

More preferably the Nhydroxymethyl derivative of the products of this invention prepared by the condensation of the products with formaldehyde, are mixed in an aqueous medium with trimethylol malamine and a Lewis acid catalyst such as NH Cl or Zn(NO -6H O. The cellulosic material is immersed in an aqueous solution of the methylol derivative, trimethylol melamine, and Zn(NO -6H O and squeezed on a two roll padder to 7090% wet weight pick-up. The material is dried at 220270F for 1-3 minutes and cured at 300370F for l6 minutes in a circulating air oven. The samples are then washed in hot water and dried. The finished samples have a flame retardant add-on of about 5 to about 40 percent and preferably about 10 to about 25% by weight.

The flame retardant agents of this invention may be applied to various textiles such as cellulosic material, proteinaceous materials and blends of cellulosic or proteinaceous materials and analogous man-made fibers. By cellulosic materials, applicant intends to embrace cotton, rayon, paper, regenerated cellulose and cellulose derivatives which retain a cellulose backbone of at least one hydroxy substituent per repeating glucose unit. By proteinaceous material applicant intends to embrace those textile materials comprising the functional groups of proteins such as the various animal wools, hairs and furs.

The flame retardant compounds or additives of the invention may be incorporated into thermoplastic or thermosetting resin compositions by any known method. That is to say, the flame retardant additive may be added to the resin by milling the resin and the additive on, for example, a two-roll mill, or in a Banbury mixer etc., or it may be added by molding or extruding the additive and resin simultaneously, or by merely blending it with the resin in powder form and thereafter forming the desired article. Additionally, the flame-retardant may be added during the resin manufacture, i.e., during the polymerization procedure by which the resin is made, provided the catalysts etc. and other ingredients of the polymerization system are inert thereto. Generally, the compounds of this invention may be incorporated into the thermoplastic and thermosetting resin in flame-retarding amounts, i.e. generally amounts ranging from about 5 percent by weight, to about 50 percent by weight, preferably from about percent by weight, to about 40 percent by weight, based on the weight of the polymer, have been found sufficient.

The thermoplastic and thermosetting resins embraced within the scope of this invention include the homopolymers and copolymers of unsaturated aliphatic, alicyclic, and aromatic hydrocarbons. Suitable monomers are ethylene, propylene, butene, pentene, hexane, heptene, octene, 2-methylpropene-l, 3- methylbutenel, 4-methylpentene-l ,4-methyl-hexene- 1,5-methylhexenel bicyclo-( 2.2.1 )-2-heptene, butadiene, pentadiene, hexadiene, isoprene, 2,3-dimethylbutadiene-1,3 2-methylpentadienel ,3, 4- vinylcyclohexene, vinylcyclohexene, cyclopentadiene, styrene and methylstyrene, and the like.

Other polymers in addition to the above-described olefin polymers that are useful in the invention include polyindene, idenecoumarone resins; polymers of acrylate esters and polymers of methacrylate esters, acrylate and methacrylate resins such as ethyl acrylate, nbutyl methacrylate, isobutyl methacrylate, ethyl methacrylate and methyl methacrylate; alkyd resins and paint vehicles, such as bodied linseed oil; cellulose derivatives such as cellulose acetate, cellulose acetate butyrate, cellulose nitrate, ethyl cellulose, hydroxyethyl cellulose, methyl cellulose and sodium carboxymethyl cellulose; epoxy resins; furan resins (furfuryl alcohol or furfuralketone); hydrocarbon resins from petroleum; isobutylene resins (polyisobutylene); isocyanate resins (polyurethanes); melamine resins such as melamineformaldehyde and melamine-urea-formaldehyde; oleoresins; phenolic resins such as phenol-formaldehyde, phenolic-elastomer, phenolic-epoxy, phenolicpolyamide, and phenolic-vinyl acetals; polyamide polymers, such as polyamides, polyamide-epoxy and particularly long chain synthetic polymeric amides containing recurring carbonamide groups as an integral part of the main polymer chain; polyester resins such as unsaturated polyesters of dibasic acids and dihydroxy compounds, and polyester elastomer and resorcinol resins such as resorcinolformaldehyde, resorcinol-furfural, resorcinol-phenol-formaldehyde, resorcinol-polyamide and resorcinol-urea; rubbers such as natural rubber, synthetic polyisoprene, reclaimed rubber, chlorinated rubber, polybutadiene, cyclized rubber, butadiene acrylonitrile rubber, butadiene-styrene rubber, and butyl rubber; neoprene rubber (polychloroprene); polysulfides (Thiokol); terpene resins; urea resins; vinyl resins such as polymers of vinyl acetal, vinyl acetate or vinyl alcohol-acetate copolymer, vinyl alcohol. vinyl chloride, vinyl butyral, vinyl chloride-acetate copolymer, vinyl pyrrolidone and vinylidene chloride copolymers; polyformaldehyde; polyphenylene oxide; polymers of diallyl phthalates and phthalates; polycarbonates of phosgene or thiophosgene and dihydroxy compounds such as bisphenols, phosgene, thermoplastic polymers of bisphenols and epichlorohydrin (trade named Phenoxy polymers); graft copolymers and polymers of unsaturated hydrocarbons and unsaturated monomer, such as graft copolymers of polybutadiene, styrene and acrylonitrile, commonly called ABS resins; ABS polyvinyl chloride polymers, recently introduced under the trade name of Cycovin; and acrylic polyvinyl chloride polymers, known by the trade name Kydex 100.

The polymers of the invention can be in various physical forms, such as shaped articles, for example, moldings, sheets, rods, and the like; fibers, coatings, films and fabrics, and the like.

The compounds of this invention have been found to have particular utility in ABS resins and in elastomeric materials such as acrylic rubber; acrylonitrilebutadiene styrene terpolymers; butadieneacrylonitrile copolymers; butyl rubber; chlorinated rubbers, e.g., polyvinyl chloride resins, chloroprene rubber, chlorosulfonated polyethylene; ethylene polymers, e.g., ethylene-propylene copolymers, ethylene-propylene terpolymers; fluorinated rubbers, butadiene rubbers, e.g., styrene-butadiene rubber, isobutylene polymers, polybutadiene polymers, polyisobutylene rubbers, polyisoprene rubbers; polysulfide rubbers; silicon rubbers; urethane rubbers; high styrene resins latices, high styrene resins, vinyl resins; sponge rubber; and the like.

It should be noted that it is also within the scope of the present invention to incorporate such ingredients as plasticizers, dyes, pigments, stabilizers, antioxidants, antistatic agents and the like to the novel composition.

ASTM Test D2863-70, used in accordance with the following examples, generally provides for the comparison of relative flammability of self-supporting plastics by measuring the minimum concentration of oxygen in a slowly rising mixture of oxygen and nitrogen that will support combustion. The procedure encompasses supporting cylindrical test specimens -150 mm X 8.0 mm vertically in a glass tube fitted with controlled upward oxygen/nitrogen gas flow. The top of the specimen is ignited and oxygen flow is adjusted until it reaches that minimum rate which the specimen is extinguished before burning 3 minutes or 50 mm whichever happens first. The oxygen index(n) is then calculated as follows:

wherein O is the volumetric flow of oxygen, at the minimal rate and N is the corresponding volumetric flow rate of nitrogen.

A modification of ASTM Test D635-68 used in accordance with the following examples, generally provides for the comparison of burning rates, selfextinguishment and non-burning characteristics of plastics in the form of sheets, bars, plates or panels. The procedure encompasses preparing 150-200 mm X 8 mm plastic samples with and without the subject flame retardant additive. Each sample is marked at points 1 inch and 4 inches from its end and held, marked end in the flame, at a 45 angle in a controlled burner flame (1 inch flame length) for two 30 second attempt. The movement of the flame up the length of the sample through the two points is measured for rate of burning, non-burning or self-extinguishing characteristics. A sample is rated SE(self-extinguishing) if the flame burns through the first point but extinguishes before reaching the second point. A sample is rated NB(nonburning) if, upon ignition it does not burn to the first point.

AATCC test method 34-1969, The Vertical Char Test, used in accordance with the following examples, generally provides for the comparison of relative flammability of 2% inch X 10 inch fabric test specimens when exposed to a controlled burner flame, under controlled conditions, for periods of 12.0 and 3.0 seconds. Charred specimens are thereafter subjected to controlled tearing tests, using tabulated weights, to determine the average tear length as representing the char length of the fabric. In addition, samples which are wholly consumed by the flame are rated (B) and samples which do not burn are rated (NB). For comparison purposes, it should be noted that untreated samples of the fabrics used in the examples of this case would be consumed for this test.

In all the examples of the application, the following general procedure was used except when otherwise specifically noted. Padding was done on a standard two roll laboratory padder at a gauge pressure of about 60 pounds per square inch in all cases. Drying and curing during processing were done with a standard laboratory textile circulating air oven. Washing and drying was done in a standard, home, top loading, automatic washer and dryer. A Hooker Boil (HE) is done in a standard, center post, wringer washer fitted with internal steam coils. The sample to be treated is washed and agitated therein for 45 minutes in a solution containing 88 pounds of water, 100 grams of sodium carbonate, 100 grams oflvory" soap and 10 grams ofTide" detergent at a temperature of about 200 to about 210 Fahrenheit. The washer is then drained, the sample squeezed through the wringer and again washed and agitated therein for minutes in about 88 pounds of water at about 140 to about 160 Fahrenheit.

The following examples are set forth for purposes of illustration only and are not to be construed as limitations of the present invention except as set forth in the appended claims. All parts and percentages are by weight unless otherwise specified.

EXAMPLE I Preparation of ll HOCH NH /N 2 written H001 NHCH OH 216g. of trimethylol melamine (1.0 mole) was dissolved in 1 liter of N,N-dimethylforamide, using a 2 liter, round bottom, three necked flask, fitted with mechanical stirrer, thermometer, and condenser with a take off. The mixture was then heated to and maintained at l 10C. while 124g. of trimethylphosphite was slowly dropped into the reaction mixture over a period of 1.5 hours. Methanol was recovered from the condenser take off during the course of the reaction. After the addition was complete the mixture was heated for an additional one half hour at 115120C and the solvent was then removed on a rotary evaporator, at C under 2 mm Hg, to give the desired product in quantitative yield.

Infrared, nuclear magnetic resonance and elemental analyses showed the product to be essentially pure.

EXAMPLE II Preparation of H (ocH cH A mixture of 0.5 mole of triethylphosphite and 0.5 liter of diglyme was heated to 120 in a three necked, round bottom, flask with thermometer, stirrer, and condenser. To this mixture was added 0.25 mole of trimethylomelamine in small portions over 0.5 hour time period. After the addition was complete, the mixture was stirred for 1 hour and the solvent and other volatiles were then removed on a rotary evaporator, at 80C and 2 mm Hg. The resulting clear viscous liquid, when tested by elemental, infrared and nuclear magnetic resonance spectroscopy, analysis was shown to be essentially pure desired product.

EXAMPLE III Preparation of NHCH P(OCl-l Trimethylol melamine (54g, 0.25 mole) was mixed with trimethyl phosphite (496g, 4.0 mole) in a 1 liter, round bottom, three necked flask fitted with a mechanical stirrer, condenser and thermometer. The mixture was slowly warmed to about 1 10C and distillate, identified as methanol diluted with a small amount of trimethyl phosphite, was continuously collected in the take off. Heating was continued until the distillate subsided and thereafter for one additional hour at C. Excess phosphite was then removed by a rotary evaporator, under reduced pressure at 80C, yield; the desired product, a clear colorless liquid. The desired product was found to be essentially pure by infrared and nuclear magnetic resonance analyses.

EXAMPLE IV In the first stage 5.0 oz. sq. yd. of cotton fabric was padded with an aqueous solution containing 40 parts of Bis (N-dimethyl phosphonomethyl) N-hydroxymethyl melamine, 50 parts of water and parts of Zn(NO '6- H O.

The fabric was then squeezed to 80 percent wet pickup on a laboratory padder, dried for about 2 minutes at about 250F and cured for about 4 minutes at about 350F in a circulating air oven. The fabric was then washed with tide detergent, for one wash cycle in a standard, home type, automatic washer and tumble dried. The thus treated and washed fabric was found to have an initial resin add-on of about 16.2 percent and when tested by AATCC method 34-1969, had an initial calculated char length of 5.5 inches.

In the second stage the thus treated and washed fabric was subjected to 4 more cycles (total=5 and when tested by AATCC method 34-1969, had a calculated char length of 6.1 inches. Data, pertaining to Example 4 has been tabulated in Table 1 for comparison.

EXAMPLE VIX 5 oz. per square yard of cotton fabric was padded, with an aqueous solution containing the components as described in Table l, and thereafter treated and tested in accordance with the first stage procedure of Example IV. Thereafter, samples were individually subjected to 4 additional wash cycles (total=5), 14 additional washes (total 15), one Hooker boil (as above described) or three Hooker boils. Each of the individually subjected samples were then tested by AATCC method 34-1969 and char length calculated therefore. Data, pertaining to Examples V-IX, has been tabulated in Table l for comparison.

TABLE EXAMPLE x grams of tris-N-diethylphosphone0methyl melamine was dissolved in 100 ml of 40 percent formalin solution and stirred at C for three hours at a pH of 9.5-10.0. The mixture was cooled to room temperature and the pH adjusted to 7.0 with hydrochloric acid.

5.0 02. sq. yd. cotton fabric was padded through this solution and squeezed on a two roll laboratory padder to about 85 percent wet pickup. The fabric was then dried at about 250F for about 2 minutes and cured at about 330F for about 5 minutes in a circulating air oven. The fabric was then washed with tide detergent for one wash cycle in a standard home type, automatic washer. and tumble dried. The thus treated fabric was found to have an initial resin add-on of about 20.2 percent and when tested by AATCC method 34-1969 had an initial char length of 4.3 inches. The thus treated and washed fabric was subjected to 9 more wash cycles and, when tested by AATCC method 34-1969 had a calculated char length of 5.0 inches.

EXAMPLE Xl A padding solution was prepared by the process of Example X utilizing tris-Ndimethylphosphonomethyl melamine. 5.0 ounce per square yard cotton fabric was padded through this above solution and thereafter treated and tested in accordance with Example X. The results of testing indicated an initial vertical char of 3.8 inches with a 4.9 inch vertical char after 10 wash cy cles.

EXAMPLE Xll A solution was prepared, as in Example X, to which was added 25g of a 50 percent methylolated melamine solution and 7.5g of Zn(NO '6H O.

5.0 oz. cotton fabric was immersed in this solution 40 and squeezed on a two roll laboratory padder to 85 per- Trimethylol VerticaT Char (inzhs) H 0 Zn(NO CH 0 Urea Melamine Percent Fzer After Arter- Fiame Retardant P rts by Pa i b Pans b Parts by Resin 1 Home 5 Home 15 Ham 1 3 Examph 50 Parts by Weight Hei ht Height Weight Height Add-on Hash Hashes dashes H8 H3 0 (cm 1 H HN NHCH -P 11! Hot 2 I 2 3 2 5 16.1 5.5 6.1

1111c11 -Pu1c11 V ditto $0 5 5 13.8 5.1 3.9 3.8 7.9 8.

VI ditto I0 S 15 26.1 3.8 5.8 3.1 3.1 5.7

N m llmc"ZM'I/ WHNCHZDH s5 5 17.9 5.1 4.1 7.1 8.8 7.1

N\ N o NHCH -P(OCH3) 'vm ditto so 5 5 1 .1 11.2 7.1 u.9 7.1

U1 ditto IO S 15 28.2 2.7 5.2 6-1 5.2, 4.8

cent wet pickup. The fabric was then dried at about 240F for about 2.5 minutes and cured at about 330F for about minutes in a circulating air oven. The fabric was washed, with tide detergent in a standard home type automatic washer for one complete wash cycle and tumble dried. The thus treated fabric was subjected to testing by AATCC method 34-1969 and had a calculated char length of 4.2 inches. The treated and washed fabric was thereafter subjected to nine more wash cycles and, when tested by AATCC method 34-1969 had a calculated char length of 5.1 inches.

EXAMPLES XIIIXV Solutions were prepared at 5 ounces per square yard cotton fabric treated and tested by the procedure of Example '12 using the phosphorus containing melamine derivatives denoted in Table II. The results of testing are as indicated therein.

EXAMPLE XVI 8 oz. per sq. yd. Bedford wool cord was padded with an aqueous solution containing 20 parts of N- dimethylphosphonomethyl-bis-hydroxymethyl melamine, 5 parts of Zn(NO '6I-I O and 75 parts of water.

The fabric was squeezed to about 65 percent wet pick-up on a laboratory padder and cured for about 4 minutes at 350F in a circulating air oven. The fabric was then washed by rinsing with water for about 10 minutes and thereafter air dried. Resin add on was calculated to be about 10.7 percent by weight. This fabric was then subjected to testing under AATCC test method 34-1969 and had a calculated char length of 2.3 inches. The fabric was then subjected to four additional water wash cycles and tested by AATC test method 34-1969 to have a 2.5 inch char length.

EXAMPLE xvn grams of tris-N-dimethylphosphonomethyl melamine was dissolved in 40 percent formalin solution (g) and stirred over nightat pH 10. The pH was adjusted to 7.0 with hydrochloric acid and 5g of ammonium chloride and thereafter 23 g of a 50 percent solution of trimethylol melamine was added. 6.0 oz. per square yard wool fabric was padded through the solution and squeezed to about percent wet pick-up. The fabric was dried at about 250F for about 2 minutes and cured for about 5 minutes at about 350F in a circulating air oven. The fabric was washed by hand for about 5 minutes in a water-detergent (tide) mixture and tumbled dried. Resin add on was calculated to be 29 percent. The fabric was then subjected to AATCC test method 34-1969 and had a calculated char length of 3.3 inches. The fabric was then subjected to 4 additional wash and dry cycles as above described and when subjected to testing had a char length of 3.5 inches.

EXAMPLE XVIII Rayon staple fiber was immersed in the padding solution of Example XVII, and thereafter squeezed on a laboratory padder to percent wet pick-up. The fiber was then dried in a circulating air oven at about 250F for about 5 minutes and cured at about 350F for about 10 minutes. The fabric was then washed by hand in running water for about 5 minutes and air dried. Untreated rayon staple fiber and the treated fiber were tested when ASTM test D2863-70 and found to have an oxygen index of 18.9 and 29.0 respectively. Both the untreated and treated rayon fiber were placed in a burner flame for 3 seconds. The untreated fiber was 'r A a L e n Verucnl Cha (inches) Examplg Compound lnirial After l0 Hash CyzleS o o N a 5.\ XII tocu cuy vcn nnf/ m nu CH P(0CH CH u IM-CH2-P(OCH2CH3)2 o o H N u 3 9 xlrr tocn rcn uu n-un cu M001 3 7 NH-CR2-P(0H3)2 2. 5.0 XIV noca ua-f T an cn New 9 NH-CHZ-V (04:11

N 9. m8 6.1 xv mac" ran- NH cn Maur NH-CHZOH consumed, the treated fiber self-extinguished upon rewherein R is independently selected from the group moval. consisting of OH and EXAMPLE XIX Thirty parts of tris-Ndimethylphosphonomethyl melamine was dry blended with 70 parts of nylon for about 5 minutes. The mixture was then brought to a melt, mixed thoroughly for about 15 minutes, and then cooled to room temperature. After cooling the mixture was cut into small pieces which were added continuously to a 9 mm diameter glass tube immersed in a hot salt bath (above the melt temperature of the plastic composition). Addition was continued until a depth of 9 i plastlc of about 2 mmhad been reached At 3. A process of rendering thermoplastic resin compothls a metal wlth a welght attached was put 15 sitions flame retardant which comprises applying to and wherein R is lower alkyl.

2. The process of claim 1 wherein said textile is selected from the group consisting of cellulosic fibers, proteinoceous fibers and blends thereof.

into the opening in the glass rod and the rod allowed to Said resin about 5 to about 50 percent by weight of a cool to room temperature. The cooled plastic composition was then removed from the glass and tested by Compound of the formula ASTM tests D2863-70 and D635-68. 0 The results of these tests are set forth in Table Ill. N

EXAMPLE XX-XXXI 2 "f l- 2 2 Using the same procedure as Example XIX, various additions are mixed with various resin compounds and tested by ASTM test method D2863-70 and D635-68. NHCHZR The components, additions and test results are tabulated in Table III.

TABLE III Percent Flammabil .y Test in Example Plastic Additive Additive 0.535

0 0 II N I XIX Nylon (CH3O)2P-CH2HN(/ flmncu -flocufi 26.8 MB N\ N o NHCH P (OCH XX Polyethylene ditto 30 N5 Terephthalate XXI Polypropylene ditto +0 2M7 XXII Epoxy ditto 40 26.0

n 9. mm ABS OH-CHflN-f/ FM-ICH2-P(OCHB)Z "0 SE uncn -on XXIV Polystyrene ditto 30 7 SE XXV Polyethylene ditto 30 29.2 NB

Terephthalate XXVI Polypropylene 17. 4 XXVI! Polystyrene 18.0 xxvm A85 i9.n xiux Nylon 22.1 XXX Polyethylene 22.7

Terepntholate XXX! Epoxy 22.5

We claim: wherein R is independently selected from the group 1. A process for rendering textiles flame retardant consisting of -OH and which comprises applying to said textile, in an amount 60 of from about 5 to about 40 percent by weight, a com- (W0) 2 pound of the formula N NHcllzpwk' (,5 and wherein R is lower alkyl.

N l 4, process for rendering thermosetting resin compositlons flame retardant which comprises applying to N R said resin about 5 to about percent by weight of a compound of the formula I NHCH NHCl-l R 2 2 l 8. The article of claim 5 wherein the compound is of wherein R is independently selected from the group the ula:

consisting of OH and 0 II 9 NHCH -P(0CH CH N o I II and wherein R is lower alkyl. HQCH HN I l NHCH P OCH c H 5. An article comprising a textile selected from the 2 N 2 2 3 )2 group consisting of cellulosic fibers, proteinaceous fihers and blends thereof and about 5 to about 50 P 9. The article of claim 5 wherein the compound is of cent by weight of a compound of the formula the formua]:

O O O II N u N (H CO)PCH NH NHCH P(0CH 3 2 2 2 RCHZHN *{4 T uncn pwn 2 f F 3 N 0 i 3O NHCHZR NHCH2P(OCH3)2 10. The article of claim 5 wherein the compound is wherein R is independently selected from the group 0f the formula! consisting of OH and 0 N H ll HOCH HN NHCH p o R'o 2 2 ,F 2 (CH and wherein R is lower alkyl.

6. An article comprising a resin compound and a HCH -P(0CH flame retardant amount of a compound of the formula 11. The article of claim 5 wherein the compound is of the formula:

N ll

wherein R is independently selected from the group 12. The article of claim 6 wherein the compound is consisting of OH and of the formula:

N O Q n HO CH NH (R'O) p 2 NHCH -P(OCH and wherein R is lower alkyl. Y

7. The article of claim 5 wherein the compound is of C the formula:

13. The article of claim 6 wherein the compound is of the formula:

0 i N ll HOCHZHN N} NHCHZ-P (0CH2CH3 14. The article of claim 6 wherein the compound is of the formual:

15. The article of claim 6 wherein the compound is of the formula:

N u HOCHZHN NHCH2-P(0CH3 10 NHCH --P(OCH 16. The article of claim 6 wherein the compound is of the formula:

U 0 n N 1| 0 H H c c 3 )ZPCHZNH f T NH CH2P (ocH cH Ni N E)! NH-CH -HOCH CH v UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT NO. 3,885,912

DATED May 27, 1975 INVENTOR(S) Peter Golborn and James J. Duffy Itis certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 4, line 51, "invention with" should read -invention product with-;

Column 5, line 40, "hexane" should read ---hexene; line 49, "idenecoumarone" should read -indenecoumarone-. Column 6, line 65, "rate which" should read -rate at which---. Column 7, line 16, "attempt" should read -attempts. Column 8, line 39, "trimethylomelamine" should read --trimethylolmelamine. Column 9, line 19, "16.2%" should read -;--l6.l'%--; line 23, "more cycles" should read more wash .cycles Column 10, line 3, "phosphoneomethyl" should read --phosphonomethyl--. Column 11, line 34, "AATC" should read -AATCC-. Claim 2, line 12, "proteinoceous" should read -proteinaceous-.

' Claim 14, line 15, "formual" should read --formula'--. Column 14, lines 5 and 63 and Column 15, lines 15 and 37 and 63 the formula should read 0 I (R O) P Signed and Scaled this Nineteenth Day of April 1977 [SEAL] Attest:

RUTH C. MASON C. MARSHALL DANN Arresting Officer Commissioner of Patents and Trademarks UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION- PATENT NO. 3,885,912

DATED May 27, 1975 |NVENTOR(S) Peter Golborn and James J. Duffy It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown b8|0WI O Column 4, line 51, "invention with" should read invention product with-;

Column 5, line 40, "hexane" should read hexene--; line 49, "idenecoumarone" should read indenecoumarone--. Column 6, line 65, "rate which" should read rate at which. Column 7, line 16, "attempt" should read attempts. Column 8, line 39, "trimethylomelamine" should read trimethylolmelamine. Column 9, line 19, "16.2%" should read --l6.l'%-; line 23, "more cycles" should read more wash cycles Column 10, line 3, "phosphoneomethyl" should read phosphonomethyl--. Column 11, line 34, "AA'I'C" should read ---AATCC-. Claim 2, line l2,"prot einoceous" should read -proteinaceous---.

' Claim 14, line 15, "formual" should read --formula'-. Column 14, lines 5 and 63 and Colunm 15, lines 15 and 37 and 63 the formula should read 0 I (R O) P I I Signed and Scaled this Nineteenth Of April 1977 [SEAL] Arrest:

RUTH C. MASON C. MARSHALL DANN Arres ing Officer Commissioner of Patents and Trademarks

Claims (16)

1. A PROCESS FOR RENDERING TEXTILES FLAME RETARDANT WHICH COMPRISES APPLYING TO SAID TEXTILE, IN AN AMOUNT OF FROM ABOUT 5 TO ABOUT 40 PERCENT BY WEIGHT, A COMPOUND OF THE FORMULA

2. The process of claim 1 wherein said textile is selected from the group consisting of cellulosic fibers, proteinoceous fibers and blends thereof.

3. A process of rendering thermoplastic resin compositions flame retardant which comprises applying to said resin about 5 to about 50 percent by weight of a compound of the formula

4. A process for rendering thermosetting resin compositions flame retardant which comprises applying to said resin about 5 to about 50 percent by weight of a compound of the formula

5. An article comprising a textile selected from the group consisting of cellulosic fibers, proteinaceous fibers and blends thereof and about 5 to about 50 percent by weight of a compound of the formula

6. An article comprising a resin compound and a flame retardant amount of a compound of the formula

7. The article of claim 5 wherein the compound is of the formula:

8. The article of claim 5 wherein the compound is of the formula:

9. The article of claim 5 wherein the compound is of the formual:

10. The article of claim 5 wherein the compound is of the formula:

11. The article of claim 5 wherein the compound is of the formula:

12. The article of claim 6 wherein the compound is of the formula:

13. The article of claim 6 wherein the compound is of the formula:

14. The article of claim 6 wherein the compound is of the formual:

15. The article of claim 6 wherein the compound is of the formula:

16. The article of claim 6 wherein the compound is of the formula: