Compounds of the formulas ##STR1## WHEREIN: X represents oxygen or sulfur; PA1 Z represents the residue of a hydroxyl-containing moiety; PA1 R.sub.1 and R.sub.2 in formula (1) may be the same or different and individually represent alkyl, cycloalkyl or aryl and, together with the common nitrogen atom, represent a 5 or 6 member ring containing oxygen, sulfur or nitrogen or combination thereof; PA1 Nr.sub.1 r.sub.2 in formula (2) represents a 5 or 6 member ring containing oxygen, sulfur or nitrogen or combination thereof; PA1 n represents an integer having a value of 2 or greater and is equal to the number of hydroxyl groups on the orginal hydroxyl-containing moiety, the residue of which is now represented by Z. are prepared by reacting a phosphorohalidate with an amine in an organic solvent containing aqueous alkali metal or ammonium hydroxide. The compounds are useful as flame retardants for natural and synthetic materials.

BACKGROUND OF THE INVENTION 
This invention relates to (a) a novel process for preparing 
phosphoroamidates, (b) novel flame retardant polymer compositions 
containing certain known phosphoroamidates, (c) novel phosphoroamidates 
and (d) novel flame retardant polymer compositions containing novel 
phosphoroamidates. 
(a) Process 
In the past, one method of preparing phosphoroamidates has been carried out 
by reacting a corresponding phosphorohalidate with an excess of an 
appropriate amine in an organic diluent. This method is disadvantageous 
since salts are formed during the reaction which precipite from the 
organic solution and must be separated and since the only means of 
scavenging hydrogen chloride formed during the reaction is by the use of 
excess amine which is quite expensive. 
It was also known, of course, that aqueous caustic is a hydrogen chloride 
scavenger but that knowledge was not believed adaptable to the preparation 
of phosphoroamidates since it appeared obvious that aqueous caustic would 
hydrolyze the intermediate phosphorohalidate to phosphoric acid. 
(b) Known Phosphoroamidates 
The following patents disclose phosphoroamidates prepared from simple 
aliphatic and aromatic alcohols, phosphorus oxyhalide or thiohalide and an 
amine: 
U.s. pat. No. 2,385,713 U.S. Pat. No. 3,531,550 
U.s. pat. No. 2,912,451 U.S. Pat. No. 3,584,085 
U.s. pat. No. 3,328,494 
U.S. Pat. No. 2,385,713 discloses compounds of the formula (Phenyl-O).sub.m 
P(O)(NX.sub.2).sub.n wherein X .dbd. H or hydrocarbon and m + n = 3. The 
compounds are esters of amidophosphoric acids with substituted phenols and 
have utility as germicides and bactericides. With regard to the present 
invention, the patent indicates no distinction between the use of primary 
and secondary amines, contains an enabling disclosure directed only to 
"diamidophosphates" and, while disclosing certain compounds within the 
scope of formula (1) of this invention, does not teach the use of 
phosphorodiamidates as flame retardants. 
U.S. Pat. No. 2,912,451 discloses acyclic tetramethylphosphorodiamidates 
having utility as weed killers. With regard to the present invention, the 
patent discloses amidation only with dimethylamine, makes only 
tetramethylphosphoroamidates and does not teach the use of 
phosphordiamidates as flame retardants, although disclosing certain 
compounds falling within the scope of formula (1) of this invention. 
U.S. Pat. No. 3,328,494 discloses O-(2-naphthyl)phosphorothionates, which 
may be mono- or diamido substituted, having utility as herbicides. With 
regard to the present invention, the patent does not disclose a process 
suing an alkali metal hydroxide and, while disclosing certain 
N,N'-di-lower alkylamido compounds falling within the scope of formula (1) 
of this invention, does not distinguish between those compounds the the 
disclosed diamido compounds and does not teach the use of 
phosphorodiamidates as flame retardants. 
U.S. Pat. No. 3,531,550 discloses certain phosphorus ester mono- and 
diamides having utility as functional fluids. With regard to the present 
invention, the patent does not use a process involving alkali metal 
hydroxide and, while disclosing certain compounds within the scope of 
formula (1) of this invention, does not teach the use of 
phosphorodiamidates as flame retardants. 
U.S. Pat. No. 3,584,085 discloses the use of certain phosphoromonoamidates 
as flame retardants for polyurethanes. With regard to the present 
invention, the patent does not disclose the use of an alkali metal 
hydroxide and prepares hydroxyalkyl, halophenyl, hydrogen and 
alkyl-substituted amides which are not within the scope of formula (1) of 
this invention. 
(c) Novel Phosphoroamidates 
The following patents disclose phosphoroamidates which are relevant to the 
compounds of formula (2) of this invention: 
U.s. pat. No. 3,254,050 
U.s. pat. No. 3,335,129 
W. german Pat. No. 2,104,569 
U.S. Pat. No. 3,254,050 discloses certain bisphenol biphosphites as flame 
retardants for various resin systems. With regard to the present 
invention, the patent does not prepare amidates from bisphenol compounds 
as defined in formula (2) of the present invention. 
U.S. Pat. No. 3,335,129 discloses certain phosphoromono- and diamidates 
having utility as flame retardants for various resin systems. With regard 
to the present invention, the patented compounds must contain free 
hydroxyl groups to provide a reactive site so the compounds may be reacted 
with the resin systems which they are intended to flame retard. In 
contrast thereto, the compounds of formula (2) of this invention contain 
no free hydroxyl groups. 
W. German Pat. No. 2,104,569 discloses certain haloalkylamides as flame 
retardants for polyurethanes. The compounds of formulas (II) and (III) of 
the patent are distinguished from the compounds of formula (2) of this 
invention since the compounds of this invention are not 
haloalkylamide-substituted phosphorus compounds. 
(d) Novel Polymer Compositions 
The following patents disclose phosphoramidate/resin compositions which are 
relevant to the polymer compositions containing compounds as defined in 
formula (2): 
U.s. pat. No. 3,256,249 
W. german Pat. No. 2,104,569 
U.S. Pat. No. 3,256,249 is relevant to the polymer compositions of this 
invention which contain compounds of formula (2). The patent discloses 
hydroxylated phosphoromono- and diamides as flame retardants in various 
resin systems. In contrast thereto, the polymer compositions of this 
invention do not contain hydroxylated phosphoroamidate flame retardants. 
W. German Pat. No. 2,104,569 discloses haloalkylamide-substituted 
phosphorus compounds as flame retardants for polyurethanes. With regard to 
the present invention, the compounds of formulas (II) and (III) of the 
patent are haloalkylamide-substituted compounds while those of formula (2) 
of this invention contain no haloalkylamide substituents. 
SUMMARY OF THE INVENTION 
It has been found that certain phosphoroamidates are useful as flame 
retardant additives and that such compounds may be prepared by the 
reaction of a phosphorus halidate with an amine in an organic diluent 
containing an aqueous solution of an alkali metal or ammonium hydroxide. 
DESCRIPTION OF THE PREFERRED EMBODIMENT 
The compounds of this invention are prepared by reaction of a 
hydroxyl-containing moiety with a phosphorus oxyhalide or phosphorus 
thiohalide to afford a phosphorohalidate which is then reacted with a 
secondary amine in an organic diluent containing an aqueous solution of an 
alkali metal hydroxide. 
The compound of this invention are represented by the formulas 
##STR2## 
wherein X represents oxygen or sulfur; 
Z-represents the residue of a hydroxyl-containing moiety; 
R.sub.1 and R.sub.2 in formula (1) individually represent alkyl, cycloalkyl 
or aryl, and may be the same or different and, together with their common 
nitrogen atom represent a 5 or 6 member ring containing oxygen, sulfur or 
nitrogen or combination thereof; 
Nr.sub.1 r.sub.2 in formula (2) represents a 5 or 6-member ring containing 
oxygen, sulfur or nitrogen or combination thereof; 
n represents an integer having a value of 2 or greater and is equal to the 
number of hydroxyl groups on the original hydroxyl-containing moiety, the 
residue of which is herein-represented by Z. 
It is understood that the acid and alkaline and ammonium salts of compounds 
of formulas (1) and (2) are within the scope of the invention, i.e., 
hydrochlorides, sulfates, toluenesulfonates and the like. Accordingly, 
reference hereinafter to a group of compounds or to a specific compound 
within a group is intended to include the acid and alkaline and ammonium 
slat thereof. 
Generalized reaction schemes for preparing the compounds of formulas (1) 
and (2) of the invention are as follows: 
##STR3## 
wherein X, Z, R.sub.1, R.sub.2 and n are identified above. 
Hydroxyl-containing compounds which are reacted with a phosphorus oxyhalide 
or thiohalide to obtain phosphorohalidates or thiophosphorohalides are 
represented by the formulas 
EQU ZOH and 
EQU (4) Z--OH).sub.n 
where n represents an integer having a value of 2 or greater. 
The particular hydroxyl-containing compound used is not critical, insofar 
as the preparation of the phosphorohalidate intermediate is concerned, 
since any hydroxyl-containing material which will react with a phosphorus 
oxyhalide or phosphorus thiohalide may be utilized. Additionally, the 
hydroxyl-containing compound may be the reaction product of a 
hydroxyl-containing compound and an alkylene oxide. 
Illustrative examples of hydroxyl-containing compounds represented by ZOH 
and Z--OH).sub.n include substituted and nonsubstituted hydrocarbon chains 
which may be aliphatic or branched-chain, saturated or unsaturated, 
aromatic or mixed aliphatic/aromatic or cyclic in character, e.g., 
aliphatic and aromatic alcohols such as mono- and poly-hydroxy aliphatic 
or aromatic alcohols and phenols, carbohydrates and hydroxyl-containing 
higher polymers whether natural or synthetic in origin. 
Exemplary aliphatic alcohols which are used include methanol, ethanol, 
propanol, isopropanol, butanol, isobutanol, nonanol, isononanol, decanol, 
octadecanol, allyl alcohol, phytol, ethylene glycol, farnesol, propylene 
glycol, trimethylene glycol, glycerol, .beta.-chloroethanol, glycol methyl 
ether, glycol ethyl ether, citronellol, ethylene chlorohydrin, diethylene 
glycol, carbitol, 1,2-butanediol, 2,3-butanediol, pentamethylene glycol, 
geraniol, xanthyl alcohol, naphthyl alcohol, erythritol, arabitol, 
sorbitol, mixtures of C.sub.7, C.sub.9 and C.sub.11 alcohols, and mixtures 
of C.sub.6, C.sub.8, C.sub.10 and C.sub.12 alcohols. 
Cyclic alcohols include cyclopentanol, cyclohexanol, 
pentahydroxycyclohexane, terpineol, hexahydroxycyclohexane, 
cyclopropylcarbinol, borneol, cyclohexanediol, cyclohexanedimethanol. 
Aromatic alcohols include trimellitic alcohol, benzyl alcohol, 
.beta.-phenylethanol, .beta.-phenoxyethanol, .alpha.-phenylethanol, 
phenylallyl alcohol, diphenylcarbinol, triphenylcarbinol, salicyl alcohol 
Phenols include phenol, bis(alkylidene)phenols such as 4,4'-isopropylidene 
diphenol, allylphenol, nitrosophenol, cresol, methyl phenol, ethyl phenol, 
thymol, carvacrol, p-.alpha.-propenylphenol, resorcinol, aminophenol, 
catechol, quinol, adrenaline, hexylresorcinol, hydroquinone, 
trihydroxybenzene, pyrogallol. 
Carbohydrates include the aldotetroses, the aldopentoses, e.g., xylose, 
ribose, the aldohexoses, e.g., glucose, the disaccharides, e.g., sucrose, 
lactose, maltose, the trisaccharides, e.g., raffinose, sorbitol, rahmnose, 
fructose, glycosides, cellobiose, polysaccharides, e.g., starch, 
cellulose. 
Higher polymer materials include the polyalkylene glycols, polyvinyl 
alcohol, hydrolyzed vinyl acetate/vinyl alcohol copolymers, phenolic 
resins. 
Other hydroxyl-containing materials, such as dihydroxyacetone, glyceryl 
monostearate, glyceraldehyde, cellosolve acetate and hydroxyacetophenone 
may be used. 
Primary or secondary alcohols or phenols are the preferred 
hydroxyl-containing material. Tertiary alcohols are unsuitable since 
reaction thereof with a phosphoryl halide affords an alkyl halide rather 
than a phosphorohalidate. 
A preferred class of hydroxyl-containing compounds are represented by 
phenol, o, m, p-cresol, o-ethylphenol, o, m, p-isopropylphenol, 
p-tert-butylphenol, p-tert-amylphenol, nonylphenol, xylenol, o, m, 
p-chlorophenol, p-bromophenol, p-iodophenol, dichlorophenol, 
trichlorophenol, pentachlorophenol, p-cumylphenol, o-cyclohexylphenol, 
naphthol, methoxyphenol, ethoxyphenol, phenoxyphenol, p-nitrophenol, 
trifluoromethylphenol, allylphenol, benzylphenol, vanillin, 
4-chloro-3,5-dimethylphenol, 4-chloro-1-naphthol, 2-chloro-4-nitrophenol, 
cyanophenol, di-tert-butylphenol, dimethoxyphenol, methylsalicylate, 
fluorophenol. Especially preferred of this group are phenol, cresol, 
cumylphenol, nonylphenol, chlorophenol, xylenol, tert-butylphenol, 
phenylphenol, isopropylphenol and mixtures thereof. 
Another preferred class of hydroxyl-containing materials includes 
cyclohexanedimethanol, isopropylidene diphenol, hydroquinone, catechol and 
resorcinol. 
It is essential that the alcohol, i.e. the original hydroxyl-containing 
moiety, contain no free-hydroxyl groups after the reaction with a 
phosphorus oxyhalide or phosphorus thiohalide, since a free-hydroxyl group 
would react with any remaining P-chlorine linkages, thus leaving no 
reactive site for the subsequent amidation. 
Alkyl radicals represented by R.sub.1 and R.sub.2 in formulas (1) and (2) 
include methyl, ethyl, propyl, isopropyl, butyl, amyl, hexyl, heptyl, 
octyl, nonyl, decyl, octadecyl, benzyl, .beta.-phenylethyl. 
Aryl radicals represented by R.sub.1 and R.sub.2 in formulas (1) and (2) 
include phenyl, alkyl-substituted phenyl, e.g., methyl phenyl, diethyl 
phenyl, naphthyl, chlorophenyl. 
Cycloalkyl radicals represented by R.sub.1 and R.sub.2 in formulas (1) and 
(2) include cyclohexyl, cyclopentyl, cyclobutyl. 
Five and six-member rings, containing oxygen, sulfur, nitrogen and 
combinations thereof, represented by R.sub.1 and R.sub.2, together, in 
formulas (1) and (2) include thiazole, pyridine, pyrrole, isoxazole, 
oxazole, pyrazole, imidazole, thiazoline, thiazolidine, thiopyran, 
collidine, hexahydropyridine, piperidine, morpholine, condensed ring 
systems such as benzopyrrole, quinoline and carbazole. 
The phosphorus halides and phosphorus thiohalides which are utilized herein 
include, for example, phosphorus oxytrichloride, phosphorus oxytribromide, 
phosphorus oxytrifluoride, phosphorus oxydichloride bromide, phosphorus 
oxydibromide chloride, phosphorus oxydifluoride chloride and the 
corresponding thiophosphorus analogs. 
The phosphorohalidates, which are reacted with a secondary amine to obtain 
the compounds of this invention, are prepared as described above and by 
methods known in the art, are represented by the formulas 
##STR4## 
wherein hal represents halogen, e.g., chlorine, fluorine, bromine or 
iodine and Z, X and n are as defined in formulas (1) and (2). 
Illustrative phosphorohalidates utilized to prepare the novel compounds of 
this invention include phenyl phosphorodichloridate, chlorophenyl 
phosphorodichloridate, chlorophenyl phosphorodibromidate, nitrophenyl 
phosphorodichloridate, cresyl phosphorodichloridate, methoxyphenyl 
phosphorodibromidate, nonylphenyl phosphorodichloridate, cumylphenyl 
phosphorodichloridate, biphenyl phosphorodichloridate, naphthyl 
phosphorodichloridate, isopropylphenyl phosphorodichloridate, 
tert-butylphenyl phosphorodichloridate, isodecylphenyl 
phosphorodichloridate, isodecyl phosphorodichloridate, isopropylidene 
di-p-phenylene bisphosphorodichloridate, isopropylidene di-p-phenyl 
phosphorodichloridate, cyclohexylenedimethylene bis phosphorodichloridate, 
dicresyl phosphorodichloridate, dixylyl phosphorodichloridate, n-propylene 
bis phosphorodichloridate, n-butylene bis phosphorodichloridate and the 
polyphosphorodichloridates of carbohydrates and other hydroxyl-containing 
polymeric materials. 
The secondary amines utilized in accordance with this invention are 
characterized by the formula 
##STR5## 
wherein R.sub.1 and R.sub.2 individually or together are as defined in 
formulas (1) and (2). Preferably, one of R.sub.1 and R.sub.2 is a methyl 
group. 
Illustrative amines include the alkylamines, e.g., dimethylamine, methyl 
ethyl amine, methyl butyl amine, dibutyl amine, dioctyl amine, 
di-n-hexylamine, didecyl amine, di-n-octadecylamine, dibenzylamine, 
di-.beta.-phenylethylamine; cycloalkyl amines, e.g., butylcyclohexyl 
amine, dicyclopentyl amine; and similar compounds. 
The reaction of a slight excess of a polyfunctional amine with a 
phosphorohalidate affords polymeric compounds of this invention having the 
formula 
##STR6## 
wherein R represents an alkylene group of 1 to 50 carbon atoms or an 
arylene group; 
R.sub.3 and R.sub.4 individually represent an alkyl group of 1 to 10 carbon 
atoms or, together with the nitrogen atom, a 5 or 6 member heterocyclic 
ring; 
X represents oxygen or sulfur; 
Z represents the residue of a hydroxyl-containing moiety; and 
n represents an integer from 1 to 40. 
Polyfunctional amines which are used to prepare the compounds of formula 
(8) are represented by the formula 
##STR7## 
wherein R, R.sub.3 and R.sub.4 are defined in formula (8). 
Illustrative amines corresponding to formula (9) include those compounds 
where R preferably represents an alkylene group of 1 to 10 carbon atoms 
and one of R.sub.3 and R.sub.4 is preferably methyl, e.g., 
bis(methylamino)methane, bis(methylamino)ethane, bis(methylamino)propane, 
bis(methylamino)butane, bis(ethylamino) octane, bis(methylamino)benzene 
and the like. 
Preferred groups of compounds in accordance with this invention include 
compounds of the formulas 
##STR8## 
wherein R.sub.1 and R.sub.2 individually represent an alkyl group of 1 to 
10 carbon atoms or an aryl group or an alkyl-aryl group; 
R.sub.1 and R.sub.2, each together with its attached nitrogen atom, 
represent a 5 or 6 member heterocyclic ring which may additionally contain 
oxygen, sulfur or nitrogen; 
R.sub.5 represents hydrogen, an alkyl group of 1 to 20 carbon atoms, an 
aryl group, an alkylaryl group or halogen; 
R.sub.6 and R.sub.7 individually represent hydrogen, an alkyl group of 1 to 
10 carbon atoms, an aryl group or an alkylaryl group; 
R.sub.8 represents hydrogen or an alkyl, cycloalkyl, alkaryl, aryl or 
aralkyl group; 
X represents oxygen or sulfur; 
A represents a methylene or phenylene group; 
B represents hydrogen or 
##STR9## 
Q represents an alkyl group of 1 to 20 carbon atoms, an aryl group, an 
alkylaryl group, a carbonyl or sulfonyl group, an aliphatic or aromatic 
ester group or 
##STR10## 
n.sub.1 represents an integer having a value of 0, or 1 to 6 when 
A .dbd. methylene or 1 to 2 when A .dbd. phenylene; and 
n.sub.2 represents an integer having a value of 1 to 50. 
Compounds of formula (10) are prepared, for example, by reaction of 
isopropylidene diphenol (e.g., bisphenol A) or phenylisopropylphenol with 
phosphorus oxychloride or phosphorus thiochloride and subsequent reaction 
of the phosphorodichloridate intermediate with a secondary amine described 
above. 
Exemplary compounds represented by formula (10), where B .dbd. hydrogen, 
include: 
C.sub.6 H.sub.5 C(CH.sub.3).sub.2 C.sub.6 H.sub.4 OP(O)[N(CH.sub.3).sub.2 
].sub.2 
C.sub.6 H.sub.5 CH.sub.2 C.sub.6 H.sub.4 OP(S)[N(CH.sub.3).sub.2 ].sub.2 
##STR11## 
C.sub.6 H.sub.5 CH.sub.2 C.sub.6 H.sub.3 (CH.sub.3)OP(O)[N(C.sub.3 
H.sub.7).sub.2 ].sub.2 
##STR12## 
##STR13## 
C.sub.6 H.sub.5 C(C.sub.3 H.sub.7).sub.2 C.sub.6 H.sub.3 (C.sub.6 
H.sub.5)OP(O)[N(C.sub.6 H.sub.5).sub.2 ].sub.2 
C.sub.6 H.sub.5 C(C.sub.12 H.sub.25).sub.2 C.sub.6 H.sub.3 (C.sub.5 
H.sub. 11)OP(O)[N(C.sub.10 H.sub.21).sub.2 ].sub.2 
##STR14## 
##STR15## 
Exemplary compounds of formula (10), where B = 
##STR16## 
##STR17## 
##STR18## 
##STR19## 
##STR20## 
Compounds of formula ( 11) are prepared, for example, by reaction of 
benzyl alcohol, cyclohexanemethanol, phenylphenol, cyclohexanol, 
hydroxymethylphenol, hydroxycyclohexanemethanol, bis-hydroxy diphenyl, 
cyclohexanediol, cyclohexanedimethanol, bis(hydroxymethyl)benzene or 
other appropriate compounds with a phosphorus oxyhalide or phosphorus 
Exemplary compounds represented by formula (11), where B .dbd. hydrogen, 
include: 
##STR21## 
Exemplary compounds of formula (11), where 
##STR22## 
include: [(H.sub.3 C).sub.2 N].sub.2 (O)POH.sub.2 CC.sub.6 H.sub.10 
CH.sub.2 OP(O)[N(CH.sub.3).sub.2 ].sub.2 
##STR23## 
[(H.sub.3 C).sub.2 N].sub.2 (O(POC.sub.6 H.sub.10 OP(O)[N(CH.sub.3).sub.2 
].sub.2 
Compounds of formula (12) are prepared by reaction of a polyol (e.g., the 
reaction product of an alkylene oxide and a glycol) with a phosphorus 
oxyhalide or thiohalide and an amine ad described above. 
Exemplary compounds represented by formula (12) include: 
##STR24## 
The proportion of phosphorodihalidate and amine which are reacted will 
vary, depending upon reaction conditions. Generally, however, sufficient 
amine is added to completely convert the phosphorodihalidate to the 
corresponding phosphorodiamidate, e.g., two moles or more of amine per 
mole of phosphorodihalidate. 
The reaction of the phosphorodihalidate and amine may be conducted in an 
aqueous medium but is preferably conducted in an organic diluent 
containing an aqueous solution of an alkali metal or ammonium hydroxide so 
that the alkali metal hydroxide will scavenge liberated hydrogen chloride. 
Organic diluents which may be used include any of the conventional organic 
diluents such as chlorobenzene, tetrahydrofuran and the like. 
The temperature of the phosphorohalidate/amine reaction may vary from about 
0.degree. to about 100.degree. C., although the preferred temperature 
range is from about 10.degree. to about 60.degree. C. Higher temperatures 
may be used but reduce yield. 
The following examples illustrate specific embodiments of the preparation 
of certain compounds of the invention and are not to be construed as 
limiting the scope thereof.

EXAMPLE 1 
In a one-liter flask, fitted with mechanical stirrer, condenser and 
thermometer, are placed 228 g. (1.0 mole) of bisphenol A, 460 g. (3.0 
moles) of phosphorus oxychloride, and 3.0 g. of pyridine. The solution is 
heated to reflux. At about 90.degree. C., hydrogen chloride starts to 
evolve and is passed to a water scrubber. After 21/2 hours, the 
temperature of the reaction mass stabilizes at 135.degree. C. and no 
further hydrogen chloride is liberated. The excess phosphorus oxychloride 
is removed by vacuum distillating the mass at 100.degree. C. to 40 mm of 
Hg. There is recovered 144 g. of phosphorus oxychloride. The residue is 
459 g. of product (99% of theory) and is isopropylidene di-p-phenylene 
bis-phosphorodichloridate: 
##STR25## 
EXAMPLE 2 
In a two liter flask, fitted with mechanical stirrer, dropping funnel, 
condenser and thermometer, are placed 800 g. of 25 percent dimethyl amine 
solution and 340 g. of 50 percent sodium hydroxide solution. The mixture 
is cooled during the addition to 15.degree. C. by means of an ice water 
bath. By means of a dropping funnel, 461 g. (1.0 mole) of isopropylidene 
di-p-phenylene bis-phosphorodichloridate (prepared as described in Example 
1) in 200 ml. of monochlorobenzene is added dropwise over a two hour 
period. The temperature is maintained at 15.degree..+-.2.degree. C. After 
the addition is complete, the mixture is stirred for one-half hour and 
then heated to 60.degree. C. over a half hour period. Layers are separated 
and the organic layer is washed at 70.degree. C. with 700 ml. of water for 
20 minutes. The organic layer is then vacuum stripped to 135.degree. C./40 
mm. Hg and then steam sparged at 135.degree. C./40 mm. Hg. for 30 minutes. 
The product is dehydrated and filtered. There is obtained 465 g. (94% of 
theory) of the product, which is isopropylidene di-p-phenylene 
bis(tetramethylphosphorodiamidate): 
##STR26## 
EXAMPLE 3 
Morpholine (400 gms.) is dissolved in 600 ml. water, cooled to 15.degree. 
C. in a 2 liter, 3-necked flask cooled by a water bath. A fifty percent 
solution of sodium hydroxide (340 gms.) is added and then, using a 
dropping funnel, isopropylidene di-p-phenylene bis phosphorodichloridate 
(461 gms.) in monochlorobenzene (200 ml.) is added over a two-hour period 
maintaining the temperature at 15.degree..+-.2.degree. C. After addition, 
the mixture is stirred at 15.degree. C. for one-half hour and then heated 
to 60.degree. C. over one-half hour. The mixture is placed in a two liter 
separatory funnel and the salt layer is discarded. The organic layer is 
washed with 700 ml. water at 60.degree.-65.degree. C. for 2 minutes. The 
water layer is discarded and the organic layer is washed with 10 gms. 
sodium hydroxide in 700 ml. water at 70.degree.-75.degree. C. for 20 
minutes, stripped and steamed at 135.degree. C./40 mm. Hg. for one-half 
hour. There is obtained a 90 percent yield of product, isopropylidene 
di-p-phenylene bis(dimorpholinophosphorodiamidate): 
##STR27## 
Substituting other amines in place of morpholine in the above procedure 
affords the following compounds: 
__________________________________________________________________________ 
Amine Compound 
__________________________________________________________________________ 
##STR28## 
##STR29## 
##STR30## 
##STR31## 
##STR32## 
##STR33## 
In a one liter flask, fitted with reflux condenser thermometer and 
mechanical stirrer, are placed cumylphenol (424 gms.), phosphorus 
oxychloride (460 gms.) and pyridine (3.0 gms.). The mixture is heated to 
reflux which starts at 95.degree. C. with evolution of hydrogen chloride. 
Over a period of three hours the temperature slowly rises to 145.degree. 
C. and is maintained at that temperature for an additional one-half hour. 
The mixture is vacuum stripped to recover phosphorus oxychloride. The 
residue is diluted with monochlorobenzene (200 ml.) and added to a 
previously prepared solution of dimethylamine (800 gms. -- 25 percent in 
water) and sodium hydroxide (350 gms. -- 50 percent in water). The mixture 
is cooled to 15.degree.-20.degree. C. during the addition over one and 
one-half hours. The mixture is then heated to 70.degree. C. and the layers 
are separated. The organic layer is washed with water at 70.degree. C., 
dehydrated, steamed and filtered. 
The product (628 gms. -- 91 percent yield) is cumylphenyl 
tetramethylphosphorodiamidate: 
##STR34## 
EXAMPLE 5 
In a one liter flask, fitted with reflux condenser, mechanical stirrer and 
thermometer, are placed nonylphenol (440 gms.), phosphorus oxychloride 
(460 gms.) and pyridine (3.0 gms.). The procedure of Example 4 is then 
followed and the mixture residue is diluted with monochlorobenzene (200 
ml.) and added to a morpholine (400 gms.)/caustic (350 gms.) solution. A 
ninety percent yield (787 gms.) of nonylphenyl 
dimorpholinophosphorodiamidate is obtained: 
##STR35## 
Repeating the above procedure with substitution of 800 gms. dimethylamine 
of 25 percent solution for 400 gms. morpholine affords a ninety percent 
yield (633 gms.) of nonylphenyl tetramethylphosphorodiamidate: 
##STR36## 
EXAMPLE 6 
In a one liter flask, equipped as in Example 4, are placed 
cyclohexanedimethanol 1,4 (3 moles), phosphorus oxychloride (3 moles) and 
pyridine (3 grams). The procedure of Example 4 is then followed and the 
reaction mixture is diluted with chlorobenzene and added to 4 moles of 
dimethylamine in caustic. The product is cyclohexylenedimethylene 
bis(tetramethylphosphorodiamidate), [(H.sub.3 C).sub.2 N].sub.2 
(O)POCHl.sub.2 C.sub.6 H.sub.10 CH.sub.2 OP(O)[N(CH.sub.3).sub.2 ].sub.2. 
Dimethylamine may be replaced by other secondary amines to afford desired 
analogous phosphoroamidates. 
EXAMPLE 7 
To a 50 gal. steel-jacketed vessel, equipped with agitator and thermowell, 
there is charged phosphorus oxychloride and diethylene glycol in a 2:1 
molar ratio. After reaction at 15.degree. C. for two hours and 30.degree. 
C. for one hour, there is added a 25 percent solution of dimethylamine in 
caustic in a ratio of four moles of dimethylamine to each mole of 
diethylene glycol bis phosphorodichloridate intermediate. The temperature 
is lowered to 15.degree. C. and held for 30 minutes. An 88 percent yield 
of product is afforded, which is diethylene glycol 
bis(tetramethylphosphorodiamidate), [(H.sub.3 C).sub.2 N].sub.2 
(O)POCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OP(O)[N(CH.sub.3).sub.2 ].sub.2. 
The compounds of the present invention are useful as flame retardants for a 
wide variety of natural and synthetic polymer materials. The compounds may 
be used in concentrations of from about 0.1 percent by weight of polymer 
up to about 50 weight percent or more depending on the particular use for 
which the polymer material is intended. 
Synthetic polymer materials, i.e., those high molecular weight organic 
materials which are not found in nature, with which the compounds of the 
invention are advantageously employed may be either linear or crosslinked 
polymers and may be in the form of sheets, coatings, foams and the like. 
They may be either those which are produced by addition or condensation 
polymerization. 
An important class of polymers which are beneficially flame retarded with 
the compounds of the invention are those obtained from a polymerizable 
monomer compound having ethylenic unsaturation. A particularly preferred 
class of polymers which are flame retarded consist of the polymerized 
vinyl and vinylidene compounds, i.e., those having the CH.sub.2 .dbd. C &lt; 
radical. Compounds having such a radical are, for example, the solid 
polymeric alkenes, such as polyethylene, polypropylene, polyisobutylene or 
ethylene/propylene copolymers; polymerized acrylyl and alkacrylyl 
compounds such as acrylic, fluoroacrylic and methacrylic acids, 
anhydrides, esters, nitriles and amides, for example, acrylonitrile, ethyl 
or butyl acrylate, methyl or ethyl methacrylate, methoxymethyl or 
2-(2-butoxyethoxy)ethyl methacrylate, 2-(cyanoethoxy)ethyl 
3-(3-cyanopropoxy)propyl acrylate or methacrylate, 2(diethylamino)ethyl or 
2-chloroethyl acrylate or methacrylate, acrylic anhydride or methacrylic 
anhydride; methacrylamide or chloroacrylamide; ethyl or butyl 
chloroacrylate; the olefinic aldehydes such as acrolein, methacrolein and 
their acetals; the vinyl and vinylidene halides such as vinyl chloride, 
vinyl fluoride, vinylidene fluoride and 1-chloro-1-fluoroethylene; 
polyvinyl alcohol; the vinyl carboxylates such as vinyl acetate, vinyl 
chloroacetate, vinyl propionate, and vinyl 2-ethyl-hexanoate; the N-vinyl 
imides such as N-vinyl phthalimide and N-vinylsuccinamide; the N-vinyl 
lactams such as N-vinyl caprolactam and N-vinyl butyrolactam; vinyl 
aromatic hydrocarbon compounds such as styrene, alpha-methylstyrene, 
2,4-dichlorostyrene, alpha- or beta-vinylnaphthalene, divinyl benzene and 
vinyl fluorene; the vinyl ethers such as ethyl vinyl ether or isobutyl 
vinyl ether; vinyl-substituted heterocyclic compounds such as vinyl 
pyridine, vinyl pyrrolidone, vinylfuran or vinylthiophene; the vinyl or 
vinylidene ketones such as methyl vinyl ketone or isopropenyl ethyl 
ketone; vinylidene cyanide. Homopolymers of the above compounds or 
copolymers and terpolymers thereof are beneficially flame retarded by the 
compounds of the present invention. Examples of such copolymers or 
terpolymers are those obtained by polymerization of the following monomer 
mixtures; vinyl chloride/vinyl acetate, ethylene/vinyl chloride/vinyl 
acetate, acrylonitrile/vinyl pyridine, styrenemethyl/methacrylate, 
styrene/N-vinyl pyrrolidone, cyclohexyl methacrylate/vinyl chloroacetate, 
acrylonitrile/vinylidene cyanide, methyl methacrylate/vinyl acetate, ethyl 
acrylate/methacrylamide/ethyl chloroacrylate, vinyl chloride/vinylidene 
chloride/vinyl acetate. 
Other polymers of compounds having the ethylenic group, &gt;C .dbd. C&lt;, are 
homopolymers, copolymers and terpolymers of the alpha-, beta-olefinic 
dicarboxylic acids and derivatives thereof such as the anhydrides, esters, 
amides, nitriles and imides, for example, methyl, butyl, 2-ethylhexyl or 
dodecyl fumarate or maleate; maleic, chloromaleic, citraconic or itaconic 
anhydride; fumaronitrile, dichlorofumaronitrile or citracononitrile; 
fumaramide, maleamide or N-phenyl maleamide. Examples of particularly 
useful polymers and terpolymers prepared from the alpha-, beta-olefinic 
dicarboxylic compounds are the copolymers of maleic anhydride and a vinyl 
compound such as ethylene, propylene, isobutylene, styrene, alpha 
methylstyrene, vinyl acetate, vinyl propionate, methyl isopropenyl ketone, 
isobutyl vinyl ether, the copolymers of dialkyl fumarate such as ethyl or 
butyl fumarate and vinyl compounds such as styrene, vinyl acetate, 
vinylidene chloride, ethyl methacrylate, acrylonitrile and the like. 
The compounds of the invention act as flame retardants for the polymers and 
copolymers of unsaturated, cyclic esters of carbonic acid, for example, 
homopolymeric vinylene carbonate or the copolymers of vinylene carbonate 
with ethylenic compounds such as ethylene, vinyl chloride, vinyl acetate, 
1,3-butadiene, acrylonitrile, methacrylonitrile, or the esters of 
methacrylic or acrylic acid. 
Readily flame retarded by the compounds of the invention are also the 
polyarylcarbonate polymers such as the linear polyarylcarbonates formed 
from diphenols or dihydroxy aromatic compounds including single and 
fused-ring nucleii with two hydroxy groups as well as 
monohydroxy-substituted aromatic residues joined in pairs by various 
connecting linkages. Examples of the foregoing include dihydroxy benzenes, 
naphthalenes and the like, the dihydroxydiphenyl ethers, sulfones, 
alkanes, ketones and the like. 
The compounds of the invention also act as flame retardants for polymers, 
copolymers or terpolymers of polymerizable compounds having a plurality of 
double bonds, for example, rubbery, conjugated diene polymerizates such as 
homopolymerized 3-butadiene, 2-chlorobutadiene or isoprene and linear 
copolymers or terpolymers such as butadiene/acrylonitrile, 
isobutylene/butadiene, butadiene/styrene; esters of saturated di- or 
poly-hydroxy compounds with olefinic carboxylic acids such as ethylene 
glycol dimethacrylate, triethylene glycol dicrotonate or glyceryl 
triacrylate; esters of olefinic alcohols with dicarboxylic acids or with 
olefinic monocarboxylic acids such as diallyl adipate, divinyl succinate, 
diallyl fumarate, allyl methacrylate or crotyl acrylate and other 
diethylenically unsaturated compounds such as diallyl carbonate, divinyl 
ether or divinylbenzene, as well as the crosslinked polymeric materials 
such as methyl methacrylate/diallyl methacrylate copolymer or 
butadiene/styrene/divinyl benzene terpolymer. 
The cellulose derivatives are flame retarded by the compounds of the 
present invention. For example, cellulose esters such as cellulose 
acetate, cellulose triacetate or cellulose butyrate, the cellulose ethers 
such as methyl or ethyl cellulose, cellulose nitrate, carboxymethyl 
cellulose, cellophane, rayon, regenerated rayon the the like may be flame 
retarded. 
The compounds of the present invention are well suited for flame retarding 
liquid resin compositions of the polyester type, for example, the linear 
polyesters which are obtained by the reaction of one or more polyhydric 
alcohols with one or more alpha, beta-unsaturated polycarboxylic acids 
alone or in combination with one or more saturated polycarboxylic acid 
compounds, or the crosslinked polyester resins which are obtained by 
reacting a linear polyester with a compound containing a CH.sub.2 = C 
group. 
The compounds of the present invention are compatible flame retardants for 
epoxy resins. Such resins are condensation products formed by the reaction 
of a polyhydroxy compound and epichlorohydrin, which condensation products 
are subsequently cured by the addition of crosslinking agents. The hydroxy 
compounds may be, for example, ethylene glycol, 
4,4'-isopropylidenediphenol and similar materials. The crosslinking agent 
employed in the curing step may be a dicarboxylic compound such as 
phthalic anhydride or adipic acid, but is more generally a polyamine such 
as ethylene diamine, paraphenylamine diamine or diethylene triamine. 
Polyurethanes are a class of polymer materials which are flame retarded by 
the compounds of the present invention. The polyurethanes, like the 
above-mentioned polyesters, are materials which are employed in structural 
applications, for example, as insulating foams, in the manufacture of 
textile fibers, as resin bases in the manufacture of curable coating 
compositions and as impregnating adhesives in the fabrication of laminates 
of wood and other fibrous materials. Essentially, the polyurethanes are 
condensation products of a diisocyanate and a compound having a molecular 
weight of at least 500 and preferably about 1500-5000 and at least two 
reactive hydrogen ions. The useful active-hydrogen containing compounds 
may be polyesters prepared from polycarboxylic acids and polyhydric 
alcohols, polyhydric polyalkylene ethers having at least two hydroxy 
groups, polythioether glycols, polyesteramides and similar materials. 
The polyesters or polyester amides used for the production of the 
polyurethane may be branched and/or linear, for example, the esters of 
adipic, sebasic, 6-aminocaproic, phthalic, isophthalic, terephthalic, 
oxalic, malonic, succinic, maleic, cyclohexane-1,2-dicarboxylic, 
cyclohexane-1,4-dicarboxylic, polyacrylic, naphthalene-1,2-dicarboxylic, 
fumaric or itaconic acids with polyalcohols such as ethylene glycol, 
diethylene glycol, pentaglycol, glycerol, sorbitol, triethanolamine and/or 
amino alcohols such as ethanolamine, 3-aminopropanol, and with mixtures of 
the above polyalcohols and amines. 
The alkylene glycols and polyoxyalkylene or polythioalkylene glycols used 
in the production of polyurethanes may be ethylene glycol, propylene 
glycol, butylene glycol, diethylene glycol, triethylene glycol, 
polythioethylene glycol, dipropylene glycol and the like. 
Generally, any of the polyesters, polyisocyanate-modified polyesters, 
polyester amides, polyisocyanate-modified polyester-amides, alkylene 
glycols, polyisocyanate-modified alkylene glycols, polyoxyalkylene glycols 
and polyisocyanate-modified polyoxyalkylene glycols having three reactive 
hydrogen atoms, three reactive carboxylic and/or especially hydroxyl 
groups may be employed in the production of polyurethanes. Moreover, any 
organic compound containing at least two radicals selected from the group 
consisting of hydroxy and carboxy groups may be employed. 
The organic polyisocyanates useful for the production of polyurethanes 
include ethylene diisocyanate, ethylidene diisocyanate, 
propylene-1,2-diisocyanate, m-phenylene diisocyanate, 2,4-tolylene 
diisocyanate, triphenylmethane triisocyanate, or polyisocyanates in 
blocked or inactive form such as the bisphenyl carbamates of tolylene 
diisocyanate and the like. 
Phenolic resins are flame retarded by the compounds of the present 
invention, which compounds may be incorporated into the phenolic resin 
either by milling and molding applications or by addition to film-forming 
or impregnating and bonding solutions prior to casting. Phenolic resins 
with which the present compounds are employed are, for example, the 
phenol-aldehyde resins prepared from phenols such as phenol, cresol, 
xylinol, resorcinol, 4-butylphenol, cumylphenol, 4-phenylphenol, 
nonylphenol, and aldehydes such as formaldehyde, acetaldehyde or 
butyraldehyde in the presence of either acetic or basic catalysts, 
depending upon whether the resin is intended for use as a molding or 
extruding resin or as the resin base in coating and impregnating 
compositions. 
Aminoplasts are another group of aldehyde resins which are flame retarded 
by the compounds of the invention. Examples of aminoplasts are the 
heat-convertible condensation products of an aldehyde with urea, thiourea, 
guanidine, cyanamide, dicyandiamide, alkyl or aryl guanamines and the 
triazines such as melamine, 2-fluoro-4,6-diamino-1,3,5-triazine and the 
like. When the aminoplasts are to be used as impregnating agents, bonding 
adhesives, coatings and in casting the films, the compounds of the present 
invention are incorporated into solutions or suspensions in which the 
aminoplast is carried. The resulting mixtures give strong, fire-retardant 
laminates when sheets of paper, glass, cloth or fabric are impregnated 
therewith and cured. 
Another class of compounds which are flame retarded by the compounds of the 
present invention are the nylons, for example, the superpolyamides which 
are generally obtained by the condensation of a diamine, for example, 
hexamethylene diamine with a dicarboxylic acid, for example, adipic acid. 
Other polyamides which are flame retarded in accordance with the present 
invention are the polypeptides which may be prepared, for example, by 
reaction of N-carbobenzyl oxyglycine with glycine or mixture of glycine 
and lysine or an N-carboxy amino acid anhydride such as 
N-carboxy-DL-phenylalanine anhydride, piperidone, 2-oxyhexamethyleneimine 
and other cyclic amides. The compounds of the present invention can be 
incorporated into molding or extruding compositions for a flame retardant 
effect. 
The compounds of the present invention are also useful as flame retardants 
for linear polymers obtained by the self-condensation of bifunctional 
compounds, for example, the polyethers which are derived by the 
self-condensation of dihydric alcohols such as ethylene glycol, propylene 
glycol or hexamethylene glycol; the polyesters which are obtained by the 
self-condensation of hydroxy acids such as lactic acid or 4-hydroxybutyric 
acid; the polyamides which are prepared by the self-condensation of 
aminocarboxylic acids such as 4-aminobutyric acid; the polyanhydrides 
which are formed by the self-condensation of dicarboxylic acids such as 
sebasic or adipic acid. 
The preferred synthetic polymer materials which are flame retarded by the 
compounds of the present invention are the vinyl halide polymers in the 
form of milled products, plastisols and foams, rigid and flexible 
polyurethane coating and foams, epoxy resins, ABS and GRS rubbers, 
aminoplasts and phenolics. The vinyl halide polymers can be simple, mixed 
homopolymers of vinyl chloride or vinylidene chloride, such as polyvinyl 
chloride or polyvinylidene chloride, or copolymers or terpolymers in which 
the essential polymeric structure of polyvinyl chloride is interspersed at 
intervals with residues of other ethylenically unsaturated compounds 
copolymerizable therewith. The essential properties of the polymeric 
structure of polyvinyl chloride is retained if not more than about 40 
percent of a comonomer is copolymerized therewith. Especially preferred 
copolymers include ethylene/vinyl chloride and vinyl 
chloride/acrylonitrile copolymers. Especially preferred terpolymers 
include ethylene/vinyl chloride/acrylonitrile, ethylene/vinyl 
chloride/acrylic acid and ethylene/vinyl chloride/acrylamide terpolymers. 
Natural polymeric materials which may be flame retarded by the compounds of 
the present invention include natural rubber, cellulose esters, for 
example, cellulose acetate and cellulose nitrate, ethyl cellulose, cork 
and wood flour products and similar cellulosic materials. 
The polymer formulations which are flame retarded in accordance with the 
present invention, whether in sheet or film form or of foam or molded 
structure, may contain various conventional additives such as fillers, 
extenders crosslinking agents and colorants. Minor amounts of stabilizers, 
for example, are usually incorporated to reduce the effects of heat and 
light. 
When foamable compositions are used, the composition may be a self-blowing 
polymer or the polymer may be blown by chemical or mechanical means or by 
the use of compressed gas. Fillers which are frequently employed to lower 
the cost of the finished material and to modify its properies include 
calcium carbonate and magnesium silicate. When fillers are employed, they 
are generally present in an amount of up to about 150 parts by weight of 
filler per 100 parts by weight of polymer formulation. 
Where a colored or tinted composition is desired, colorants or 
color-pigments are incorporated in amounts of from about one to about five 
parts by weight to 100 parts by weight of polymer. 
Surfactants such as silicones are normally added to foam formulations which 
are mechanically frothed. The surfactants reduced the surface tension of 
the foam and thereby increase the air or gas entrapment characteristics of 
the foam. 
Additionally, glass-forming inorganic materials such as zinc borate, zinc 
oxide, lead oxide, lead silicate and silicon dioxide may be added to 
decrease the flame and smoke generating characteristics of the polymer. 
The flame retardant compounds of the present invention are extremely 
advantageous because of the following combination of properties: (1) The 
compounds are stable at temperatures somewhat in excess of 350.degree. C. 
and can therefore be processed on standard machinery, such as milling 
machines, without degradation or color loss. (2) The compounds contain 
little or no chlorine and therefore contribute little or no hydrogen 
chloride gas during exposure to flames. (3) The compounds are amenable to 
formulation with a less stable acid generator and therefore can be made 
todegrade at lower temperatures if necessary. (4) The compounds are 
excellent acid scavengers, thereby decreasing the amount of acid radicals 
evolved by burning materials. (5) The compounds have high solubility and 
compatibility with a wide variety of synthetic and natural polymer 
materials. 
The following examples will serve to illustrate the utility of the flame 
retardant compounds of the present invention in various polymer 
substances. The "oxygen index" referred to is that data obtained in 
accordance with ASTM D2863-70 and is defined as the minimum concentration 
of oxygen, expressed as volume percent, in a mixture of oxygen and 
nitrogen that will just support combustion of the material under the 
conditions of the test procedure. 
EXAMPLE 8 
In this example, the compound of Example 2 is compared with a commercially 
available flame retardant (ethylene glycol polyphosphate) in a commercial 
epoxy resin ("EPI-REZ", a trade mark of Celanese Chemical Company for 
their epoxy resin). The comparative properties of the resin containing 5 
and 10 phr (parts per hundred resin) of the flame retardants are shown in 
the table below. 
TABLE I 
______________________________________ 
Flame Volatility 
Tensile 
Oxygen Index 
Retardant phr % Loss psi % Oxygen 
______________________________________ 
ethylene 5 +0.59 2650 21.2 
glycol 
polyphos- 10 +0.03 1920 21.2 
phate 
Example 2 5 +0.01 3200 22.0 
Compound 
Example 2 10 +0.02 2880 24.0 
Compound 
______________________________________ 
EXAMPLE 9 
In this example, the compound of Example 2 is formulated with a polymethyl 
methacrylate resin and compared with a control sample containing no flame 
retardant material. The control sample of polymethyl methacrylate had an 
oxygen index of 16.8 whereas the sample of polymethyl methacrylate 
containing 10 phr of the compound of Example 2 of the present invention 
had an oxygen index of 18.4 and a polymethyl methacrylate sample 
containing 30 phr of the compound of Example 2 had an oxygen index of 
21.9. 
EXAMPLE 10 
The compound of Example 2 is compared with ethylene glycol polyphosphate in 
a melamine/formaldehyde resin at a level of 5 phr. The resin 
characteristics are shown in the table below: 
TABLE II 
______________________________________ 
Volatility Oxygen Index - 
Flame Retardant 
phr %Loss %Oxygen 
______________________________________ 
Ethylene glycol 
5 12.0 48.2 
polyphosphate 
Compound of 5 10 49.3 
Example 2 
______________________________________ 
EXAMPLE 11 
The compound of Example 2 was formulated at 10 and 30 phr with a 
thermoplastic polyurethane resin. The material was rolled-milled for five 
minutes at 330.degree. F., and molded at 320.degree. F. for five minutes 
at 1000 psi. The characteristics of the resin are set forth in the 
following table. 
TABLE III 
______________________________________ 
Oxygen Index 
Flame Retardant phr % Oxygen 
______________________________________ 
Control -- 20.6 
Compound of 
Example 2 10 22.4 
Compound of 
Example 2 30 27.6 
______________________________________ 
Comparable flame retardancy is attained by substituting the compounds of 
Examples 3, 4, 5, 6 and 7 for the compound of Example 2 in the 
formulations of Examples 7 through 11. 
While the invention has been described hereinabove with regard to certain 
illustrative, specific embodiments, it is not so limited since many 
modifications and variations are possible in the light of the above 
teachings. It is understood, therefore, that the invention may be 
practiced otherwise than as specifically described without departing from 
the spirit and scope of the invention.