as previously noted , the additive employed according to the invention , i . e . the polymeric phosphorylated amide , can be employed in an amount ranging from about 5 to about 40 parts , per 100 parts of resin or resin solids , by weight , but preferably is employed in an amount ranging from about 10 to about 40 parts , per 100 parts of resin or resin solids , by weight . the additive employed can be either a homopolymer or a copolymer . for the homopolymer , the general formula is : ## str1 ## where y is o or s ; r is h , alkyl , with straight chain or branched chain , and generally containing from about 1 to about 6 carbon atoms , e . g ., methyl , ethyl , propyl , isopropyl , butyl , isobutyl , pentyl , hexyl , and isohexyl ; cycloalkyl , generally containing from about 5 to about 7 carbon atoms , such as , for example , cyclopentyl , cyclohexyl , methylcyclohexyl ; aryl , generally containing from about 6 to about 14 carbon atoms , such as phenyl , xylyl , tolyl , naphthyl , methylnaphthyl and ethylnaphthyl ; the corresponding halogenated alkyl and aryl groups including , for example , the chlorinated , brominated and fluorinated derivatives , e . g . trichloromethyl and chlorophenyl , nitroaryl containing about 6 to about 14 carbon atoms such as nitrophenyl , nitrotolyl , and the like ; heterocyclic containing 5 to 6 members in the heterocyclic nucleus , and o , n or s as hetero atoms , e . g ., furanyl , pyridyl , pyrrolyl , quinolyl and thiophene ; amino , alkylamino containing from about 1 to about 8 carbon atoms in the alkyl group , e . g ., methylamino , ethylamino , dimethylamino , diethylamino , arylamino containing from about 6 to about 14 carbon atoms such as phenylamino and naphthylamino , oxyalkyl containing from 1 to about 4 carbon atoms such as oxymethyl , oxyethyl , oxypropyl , and oxyaryl containing about 6 to about 14 carbon atoms such as oxyphenyl , oxytolyl and oxynaphthyl , and the like ; x is -- nr 1 -- r 2 ) c nr 1 --, where r 1 is h , alkyl , cycloalkyl , aryl , all as described above , acyl containing about 1 to about 7 carbon atoms such as formyl , acetyl , propionyl , and including cycloalkylacyl such as cyclohexylacyl , aroyl containing about 7 to about 11 carbon atoms such as benzoyl , naphthoyl and the like ; and r 2 is alkylene of from about 2 to about 14 atoms , such as ethylene , propylene , and the like , arylene of from about 6 to about 14 carbon atoms , such as divalent phenylene , biphenylene , naphthylene and anthracene ; divalent carbonyl and thiocarbonyl , & gt ; c ═ nh , cycloalkylene of from about 6 to about 8 carbon atoms , such as cyclohexylene ; and where c is 0 to 2 ; n is 1 to about 1 , 000 , usually 1 to about 100 ; and a is the terminal group -- nr 1 r 3 where r 3 has the same values as r 1 , and r 1 and r 3 can be the same or different . for the copolymers the general formula is : ## str2 ## where a and y are the same as for the homopolymer ; r 4 can have any of the values described above for r , and r and r 4 can be the same or different , and x &# 39 ; and x &# 34 ; can have any of the values described above for x , and x &# 39 ; and x &# 34 ; can be the same or different , and where the relationship between r and r 4 , and x &# 39 ; and x &# 34 ; is such that when r and r 4 are different , x &# 39 ; and x &# 34 ; are the same , and when r and r 4 are the same , x &# 39 ; and x &# 34 ; are different ; s and t can be the same or different and where s and t are from about 1 to about 10 , and n has the same values noted above for the homopolymer . preferred additives are those wherein r is hydrogen , alkyl , aryl or the chlorinated derivatives thereof . another preferred class of polymers according to the invention are the poly phosphinohydrazides , poly phosphinoguanides and their thio analogs . such polymers have the following recurring structural units : ## str3 ## where y and r have the values defined above . examples of specific polymeric additives and their recurring structural units , according to the invention are : table__________________________________________________________________________polymeric phosporylated amides__________________________________________________________________________ ( 1 )## str4 ## poly ( phenyl phosphonic polyamide )( 2 )## str5 ## poly ( p - phenylenediamine phenyl hosphonic acid amide )( 3 )## str6 ## poly ( m - phenylene diamine phenyl phosphonic acid amide )( 4 )## str7 ## poly ( 1 , 8 - naphthalene diamine phenyl phosphonic amide )( 5 )## str8 ## poly ( p - phenylene diamine phenylthiophosphonic amide )( 6 )## str9 ## poly ( p - phenylene diamine amido ethyl phosphonate )( 7 )## str10 ## poly ( urea phosphinate )( 8 )## str11 ## poly ( biuret phosphinate )( 9 )## str12 ## poly ( urea methyl phosphonate )( 10 )## str13 ## poly ( biuret methyl phosphonate )( 11 )## str14 ## poly ( urea trichloromethyl phosphonate )( 12 )## str15 ## poly ( biuret trichloromethyl phosphonate )( 13 )## str16 ## poly ( ethylenediamine phosphinate )( 14 )## str17 ## poly ( ethylenediamine methyl phosphonate )( 15 )## str18 ## poly ( ethylenediamine trichloro - methyl phosphonate )( 16 )## str19 ## poly ( guanidine methyl phosphonate )( 17 )## str20 ## poly ( phosphorylated melamine )( 18 )## str21 ## poly ( hydrazyl phosphinate )( 19 )## str22 ## poly ( hydrazyl methyl phosphonate )( 20 )## str23 ## poly ( hydrazyl trichloromethyl phosphonate )( 21 )## str24 ## poly ( 2 , 6 - diaminopyridyl trichloromethyl phosphonate )( 22 )## str25 ## poly ( co - hydrazyl methyl phosphonate phosphinate )( 23 )## str26 ## poly ( co - ethylenediamine hydrazyl trichloromethyl phosphonate )( 24 )## str27 ## copolymer from dimethyl methyl hosphonate plus ethylenediamine and hydrazine ( hydrate ) __________________________________________________________________________ the compounds of the invention above can be prepared in various ways , as illustrated in the examples below . the 1 : 1 molar reaction of phosphonic dichlorides with diamines is given in the representative reaction of phenylphosphonic dichloride with para - phenylene diamine , below . two methods were used . one involved use of triethylamine as the acid acceptor and the other a high boiling solvent , such as bromobenzene , to decompose the amine hydrochloride formed . in the first case , one mole of para - phenylenediamine and two moles of triethylamine were mixed in one liter of methylene chloride . one mole of phenylphosphonic dichloride was then added dropwise . an exothermic reaction occurred , and after the addition was complete , the mixture was heated to reflux for two hours . the solvent was evaporated and the resultant solid slurried in about two liters of warm water to remove the triethylamine hydrochloride . the polymer was filtered under vacuum and the dried polymer had a softening point around 240 ° c . the second method used the same ratios of reactants , but bromobenzene was used as a solvent , with no triethylamine . in this system , the mixture was heated to reflux for about 40 hours to remove the hcl . this product had a softening point around 225 ° c . other substituted diamides were also prepared , and representative of this type of reaction are the reactions of phosphonic acid esters with various diamines , e . g . urea , guanidine , hydrazine and ethylene diamine , among others . thus , one mole of dimethyl methylphosphonate [ ch 3 p ( o )( och 3 ) 2 ] and one mole of urea were mixed in 130 mls of xylene . the reaction was heated to 130 ° c . for 48 hours and the xylene decanted off to leave behind an extremely viscous polymer . another similar reaction was that between 0 . 5 moles of the dimethyl methylphosphonate and 0 . 5 moles of ethylene diamine in 250 mls of methylene chloride . after all the diamine had been added dropwise , the reaction mixture was allowed to stand 72 hours at room temperature . the methylene chloride was evaporated off and the reaction mixture heated first to 65 ° c . for 4 hours , then 120 ° c . for 4 hours . a viscous polymer resulted . dimethylphosphite , in the amount of 336 . 5 g ( 3 . 04 moles ), was dissolved in 1 liter of xylene in a 2 - liter resin kettle fitted with a stirrer , claisen takeoff head , and a condenser . the mixture was cooled with a dry ice - ethylene glycol bath and 155 g ( 3 . 1 moles ) of hydrazine hydrate were added slowly . the mixture was allowed to warm to room temperature and left to stir overnight . it was then heated to reflux ( 60 ° c .) for 48 hours , at which time alcohol and water were distilled off until the temperature rose to 140 ° c . it was refluxed at this temperature for two hours and then about 600 mls of xylene were distilled off . the remaining solution was transferred to a beaker , cooled , and the excess xylene was decanted off . the beaker was heated in a vacuum oven to remove the last trace of xylene to yield a viscous , slightly yellow poly ( phosphinohydrazide ), where y is o and r is h in formula ( c ) above . dimethyl methylphosphonate , in the amount of 620 . 4 g ( 5 moles ), was placed in a 2 - liter resin kettle , equipped as above . it was cooled in a dry ice - ethylene glycol bath and 251 g ( 5 moles ) hydrazine hydrate were slowly added . the mixture was left to stir overnight and then heated to distill off the alcohol and water . the residue was a very viscous , light yellow product , poly ( methylphosphinohydrazide ), where y is o and r is ch 3 in formula ( c ) above . the phosphorylated amide additives can be added to the resin , e . g . polyimide , in the required amount , and the resulting mixture applied to the substrate such as graphite fabric or glass fabric , to form a composite or laminate utilizing , e . g . a plurality of fiberglass or graphite cloth plies . the composite is heated at elevated temperature ranging from about 200 ° to about 350 ° f . for curing , usually , although not necessarily , followed by a post curing operation at higher temperatures , e . g . ranging from about 400 ° to about 600 ° f . the polymeric phosphorylated amide additive is added to the resin , e . g . polyimide , or such additive can be first incorporated in a solvent such as n - methyl pyrrolidone , and the resulting solution is then employed to impregnate the substrate such as graphite fabric or glass cloth , to form a composite or laminate , which is then cured as noted above . the cured composites or laminates are subjected to flame tests employing a burner flame at a temperature of 2 , 000 ° f . in these tests the sample composite is mounted vertically , and the flame is impinged on the front face of the composite or laminate , and the temperature of the front face at 2 , 000 ° f . is monitored by a thermocouple . under such conditions samples with substantially reduced burn - off areas on the back face of the composite or laminate after exposure to the 2 , 000 ° f . flame for 15 minutes show stabilization and thermal stability of the resin char and reduced thermal conductivity of the char , due to the presence of the polymeric phosphorylated amide additive . 30 grams of the product prepared in example i , viz , the polymer obtained from the reaction of phenylphosphonic dichloride with para - phenylene diamine , was dissolved in 135 grams of skybond 703 polyimide varnish ( a condensation type polyimide marketed by monsanto as a 67 percent solids solution ). the resulting solution was used to impregnate 8 plies of a 9 - inch square 181 fiberglass cloth ( marketed by owens corning ). the resulting resin impregnated glass cloth laminate was vacuum bagged and maintained at 28 inches of mercury vacuum , and initially heated for one hour at 175 ° f . the temperature was then increased over a period of 3 hours to 350 ° f . and maintained at that temperature for about 21 / 2 hours . the laminate was then removed from the vacuum bag and post - cured at a temperature of 550 ° f . for 4 hours . skybond 703 is usually sold as a polyamic acid varnish which is converted to a polyimide during heating and curing . however , skybond 703 is usually referred to as the &# 34 ; polyimide varnish ,&# 34 ; even though it requires curing to convert it to the polyimide . samples of the resulting cured polyimide glass fabric laminate , and samples of a polyimide - impregnated glass laminate control employing the same amount of polyimide and using the same number of plies of 181 fiberglass cloth , as for producing the polyimide glass fabric laminate above containing the additive of the invention , and cured by the procedure described above , were subjected to a meeker burner flame maintained at 2 , 000 ° f . by means of a thermocouple , for a period of 15 minutes . for the polyimide - glass fabric laminate control a large burn - off area was observed on the back , or rear face , of the laminate resulting from almost complete volatilization of resin and showed considerable delamination . additionally , the backside temperature was around 1 , 200 ° f . on the other hand , for the polyimide impregnated glass fabric laminate containing the phenylphosphonic para - phenylene diamine polymer of the present example , essentially no burn - off areas on the back face of such polyimide glass laminate were observed , and the backside temperature was around 500 ° f . this example accordingly shows that the resin char formed at the 2 , 000 ° f . flame temperature with the polyimide glass laminate of the invention containing the polymeric phosphorylated amide additive can be stabilized , and the resin char has reduced thermal conductivity . thus , it can be seen that the presence of the polymeric phosphorylated amide additive in the resin stabilizes the char formed , and reduces the resin burn - off on the back face of the laminate as well as reducing the thermal conductivity of the char . the procedure of example iii was repeated except that 30 grams of poly phenylphosphonic polyamide was used in place of the polymer obtained from the reaction of phenylphosphonic dichloride with para - phenylene diamine . the polyphenylphosphonic polyamide is obtained from a reaction of phenyl phosphonic dichloride with ammonia followed by heating this product to split out ammonia to form the polyphenylphosphonic polyamide having the recurring structural unit ## str28 ## there is essentially no resin burn - off on the rear side of polyimide - glass cloth laminate treated with this compound , as opposed to the untreated polyimide control of example iii , and the backside temperature was around 450 ° f . the procedure of example iv was repeated using 30 grams of the polymeric phosphorylated amide of example iv in 100 grams of epon 828 epoxy resin . the procedure of example iii was followed , except that 30 grams of a polymeric 1 : 1 reaction product of meta phenylenediamine and phenyl phosphonic dichloride was used in place of the 1 : 1 reaction product of phenylphosphonic dichoride and para - phenylene diamine of example i . a product was obtained that showed no resin burn - off in the rear , and the backside temperature was around 600 ° f . the procedure of example iii was repeated using 30 grams of the same polymer in 100 grams of epon 828 epoxy resin . the results were similar to example vi . 30 grams of the polymer obtained from a 1 : 1 reaction between para phenylenediamine and phenyl thiophosphonic dichloride was added to 135 grams of the polyimide ( skybond 703 ), followed by impregnating the composition into 8 plies of a 9 - inch square of 181 fiberglass cloth ( marketed by owens corning ), and curing the laminate as in example iii . the resulting cured laminate was subjected to a 2 , 000 ° f . meeker burner flame for 15 minutes . there was essentially no resin burn - off , and the backside temperature was around 500 ° f . the procedure of example iii was repeated using 30 grams of the polymer prepared by reacting one mole of urea with one mole of dimethylphosphite , in place of the polymeric phosphorylated amide of example iii . there was essentially no resin burn - off , and the backside temperature was around 490 ° f . the procedure of example ix was repeated except that 30 grams of the urea / dimethylphosphite polymer was used with 90 grams of epon 828 epoxy . the results obtained were similar to example ix . the procedure of example ix was repeated , but using 15 grams of the polymer prepared by reacting one mole of urea with one mole of dimethyl methylphosphonate , in place of the urea / dimethylphosphite polymer of example ix . the results obtained were essentially the same as those of example ix . the procedure of example ix was repeated , but using 40 grams of the polymer prepared by reacting one mole of urea with one mole of diethyl trichlorophosphonate , in place of the urea / dimethylphosphite polymer of example ix . the results obtained were similar to those obtained in example ix . the procedure of example ix was repeated , but using 10 grams of the polymer prepared in example iia in place of the urea / dimethylphosphite polymer of example ix . the results obtained were similar to those obtained in example ix . the procedure of example xiii was repeated , but using 40 grams of a product obtained from the reaction of two moles of hydrazine hydrate with one mole of dimethylphosphite , in place of the hydrazine / dimethylphosphite polymer of example iia . it should be noted that heating the reaction product of two moles of hydrazine hydrate with one mole of dimethylphosphite results in the elimination of hydrazine and / or ammonia to form a polymeric derivative . the results obtained were similar to those obtained in example xiii . the procedure of example xiii was repeated except that 40 grams of the hydrazine / dimethylphosphite polymer was used with 135 grams of a phenolic polymer of 100 percent solids ( plyophen 23 - 169 , a product of reichold chemical co .) the results obtained were similar to example xiii . the procedure of example xiii was repeated except that 32 grams of the hydrazine / dimethylphosphite polymer was used with 90 grams of epon 828 epoxy . the results obtained were similar to example xiii . the procedure of example xiii was repeated except that 40 grams of a copolymer prepared from the reaction of one mole of hydrazine hydrate with 0 . 5 mole of dimethylphosphite and 0 . 5 mole of dimethylmethyl phosphonate was used in place of the hydrazine / dimethylphosphite polymer of example xiii . the results obtained were similar to example xiii . the procedure of example xiii was repeated except that 40 grams of a polymer prepared by reacting one mole of guanidine with one mole of dimethylmethylphosphonate was used in place of the hydrazine / dimethylphosphite polymer of example xiii . the results obtained were similar to those obtained in example xiii . the procedure of example xiii was repeated except that 40 grams of a polymer prepared by reacting one mole of ethylenediamine with one mole of diethylaminophosphonic dichloride was used in place of the hydrazine / dimethylphosphite polymer of example xiii . the results obtained were similar to those obtained in example xiii . from the foregoing , it is seen that the invention provides a fire barrier composition and composite having high fire resistance and low thermal conductivity , by incorporating therein additives in the form of certain polymeric phosphorylated amides , and which function to stabilize the char formed from the resin at high temperatures , e . g . a 2 , 000 ° f . flame temperature , thereby permitting the char to hold the glass or graphite fibers of a fibrous substrate , such as fiberglass cloth , together and maintain the structural stability and integrity of the composite or laminate . since various modifications and changes will occur to those skilled in the art within the spirit of the invention , the invention is not to be taken as limited except by the scope of the appended claims .