DE2338506A1 - FIRE RETARDANT PRODUCTS AND METHOD FOR MANUFACTURING THEREOF - Google Patents

Description

'• Fire retardants and their manufacturing process "

This invention relates to (a) new methods of manufacture of phosphoramidates, (b) new fire-retardant polymer preparations, which contain certain known phosphoramidates, (c) new phosphoramidates and (d) new fire retardant Polymer preparations containing 'new phosphoramidates.

43-4047A 409808/1171 " ² "

(0811) 48 82 72 (98 82 72) 48 70 43 <98 70 43) 48 3310 <98 3310) Telegrams: BERGSTAPFPATENT Munich TELEX 05 24 560 BERG d '- Banki Bayerische Vereinsbank Munich 453100 Post check: Munich 653

ORIGINAL iNSPECTED

(a) Heretofore there has been a process for the preparation of phosphoramidates in that one reacts a corresponding phosphorus halidate with an excess of a suitable amine in an organic diluent. This procedure is disadvantageous because salts are formed during the reaction, which precipitate from the organic solution and are separated off and because the only means of scavenging the hydrogen chloride formed during the reaction is that one uses amine in excess, which is quite expensive.

It was of course also known that aqueous caustics were hydrogen chloride scavengers, but this knowledge was on the preparation of phosphoramidates not applicable because it was considered obvious that aqueous alkaline agents Agent would hydrolyze the phosphorus halidate intermediate into phosphoric acid.

(b) Known phosphoramidates

In the following patents phosphoramidates are described, those of simple aliphatic and aromatic alcohols, phosphorus oxyhalide or thiohalide and one Amine produced:

U.S. Patent 2,385,713 U.S. Patent 2,912,451 U.S. Patent 3,328,494 U.S. Patent 3,531,550 U.S. Patent 3,584,085

409808/1171

ORlGiNAL INSPECTED

2338508

In the Ü.S. Patent 2 385 713 compounds of the formula (Phenyl-0 - ^ p (O) (NXg) _n ^{t) are written} "where X = H or a hydrocarbon and m + η = 3. The compounds are esters of amidophosphoric acids with substituted phenols and have utility as germicides and bactericides. With regard to the present invention, no distinction is made in the specified patent between the use of primary and secondary amines; the patent does not contain any references to the use of phosphorodiamidates as fire retardants.

U.S. Patent 2,912,451 discloses acyclic tetramethylphosphorodiamidates described which have usefulness as weed control agents. With regard to the present Invention is in the patent specification only the Amidier.un.t Only tetramethylphosphoramidates are described with dimethylamine and there are no references to the use of phosphorodiamidates as fire retardants, although certain compounds are described which fall within the scope of formula (I) of this invention.

In U.S. Patent 3,328,494 there are 0- (2-naphthyl) phosphorothionates described, which may be mono- or diamido-substituted, and have utility as herbicides.

409808/1171 ~ ⁴ ~

INSPECTES

In view of the present invention, the patent does not contain the description of a method of use an alkali metal hydroxide and while certain N.N'-di-lower alkylamido compounds, falling within the scope of formula (I) of this invention will be described not between these compounds and the diamido compounds described and the description does not contain any references to the use of phosphorodiamidates as fire retardants.

In U.S. Patent 3,531,550, certain phosphoric ester mono- and diamides which are useful as functional fluids. With regard to the present In accordance with the invention, there is no description of a method which provides for the use of alkali metal hydroxide and during certain compounds are described in the context of the formula (i) of this invention are no indications for the use of phosphorodiamidates found as a fire retardant.

In U.S. Patent 3,584,085 the use is specific Phosphorus monoamidates described as fire retardants for polyurethanes. With regard to the present invention the use of an alkali metal hydroxide is not described and there are hydroxyalkyl, halophenyl, hydrogen and alkyl-substituted amides, which are not described fall within the scope of general formula (I) of this invention.

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ORIGINAL INSPECTED

-> ~ 2338508

(c) New phosphoramidates

In the following patents phosphoramidates are described, which are factually related to the compounds of the formula (II) of this invention:

U.S. Patent 3,254,050 U.S. Patent 3,335,129 DB patent specification 2 104 569

In U.S. Patent 3,254,050 there are certain bisphenol biphosphites described as fire retardants for various resin systems. With regard to the present invention according to the patent no amidates are made from bisphenol compounds, as defined in the formula (II) of the present invention.

In U.S. Patent 3,335,129, certain phosphorus mono- and diamidates which are useful as fire retardants for various resin systems. With regard the present invention, the compounds provided for in the patent must contain free hydroxyl groups, to have a reactive site so that it reacted with the resin systems that are to be made fire retardant can be. In contrast, the compounds of formula (II) of this invention do not contain free hydroxyl groups .

In the DB patent 2 104 569 certain haloalkyl

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INSPECTED

amides described as fire retardants for polyurethanes. The compounds of the formulas (II) and (III) of the patent differ from the compounds of the formula (II) of these Invention, since the compounds of this invention are not haloalkylamide substituted phosphorus compounds.

(d) New polymer preparations

In the following patents are phosphoramidate / resin preparations which contain the compounds as defined in formula (II) for the polymer preparations, are relevant.

U.S. Patent 3,256,249 DB patent specification 2 104 569

In U.S. Patent 3,256,249, a factual one emerges Relation to the polymer preparations of this invention which contain compounds of the formula (ΪΙ). In of the patent are hydroxylated phosphorus mono- and diamides as fire retardants in various resin systems described. In contrast to these compounds, the polymer preparations of the invention do not contain any hydroxylated compounds Phosphoramidate fire retardants.

In DB patent specification 2,104,569 there are haloalkylamide-substituted ones Phosphorus compounds described as fire retardants for polyurethanes. With regard to the present invention are the compounds of formulas (II) and (III) the-

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409808/1171

ORIGINAL INSPECTED

ser patent haloalkylamide-substituted compounds, while the compounds of formula (II) of this invention do not contain any haloalkylamide substituents.

It has now been discovered that certain phosphoramidates are valuable as fire retardant additives and that such compounds can be prepared by a phosphorus halidate with an amine in an organic diluent, which contains an aqueous solution of an alkali metal or ammonium hydroxide, is converted.

The compounds of this invention are prepared by reacting a hydroxy 1 containing moiety with a phosphorus oxyhalide or thiophosphorus halide to form a phosphorus halidate, which is then reacted with a secondary Amine in an organic diluent which contains an aqueous solution of an alkali metal hydroxide, is reacted.

The compounds of this invention have the following Formulas on

(I) ZO-P (NR ₁ R ₂ ) ₂ and (II) Z

• I

O - P

wherein:

X oxygen or sulfur,

Z is the radical of a hydroxyfc-containing moiety, the radicals R ₁ and R ₂ independently of one another are alkyl, cycloalkyl or aryl

are and can be the same or different, the radicals

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ORiGlNAL

INSPECTED

233850g

R ₁ and R ₂ together can form a 5- or 6-membered ring which can contain oxygen, sulfur or nitrogen or their combinations,

η is an integer of 2 or more and the number of hydroxyl groups on the hydroxyl group-containing one Output part is.

It should be noted that the acid, alkali and ammonium salts of the compounds of formulas (I) and (II) fall within the scope of the invention, i.e. the hydrochlorides, sulfates, Toluenesulfonates and the like. If accordingly below reference is made to a group of compounds or to a specific compound within a group so this includes their acid, alkali and ammonium salt.

In general, the reaction can run for the production the compounds of formulas (i) and (II) of the invention are represented as follows:

XX X

(a) ZOH + Phal ₃ -> ZO - Phal ₂ + 2NR ₁ R ₂ - * ZO -

(b) Z (OH) _n + nPhal ₃ - »Z (0Phal ₂ ) _n

It

wherein X, Z, R ₁ , R ₂ and η have the meaning defined above _e

The hydroxyl group-containing compounds with a Phosphorus oxyhalide or thiohalide to form phosphorus

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ORlGlNALiNSPECTED

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phorhalidates or thiophosphorus halides are converted, correspond to the formulas

(III) ZOH and (IV) Z -f- OH) _n

where η is an integer with a fourth of 2 or greater.

The particular hydroxyl group-containing one intended for use The connection is not critical insofar as it relates to the production of the phosphorus halide product, because any hydroxyl group-containing material which reacts with a phosphorus oxyhalide or phosphorothiohalide can, can be used. In addition, the hydroxyl group-containing Compound the reaction product of a hydroxyl group-containing compound with an alkylene oxide be.

Examples of compounds containing hydroxyl groups of the formula ZOH and Z —f OH) include, for example, substituted and unsubstituted hydrocarbon chains, which as such are aliphatic or branched, saturated or unsaturated, aromatic or mixed aliphatic / aromatic or cyclic, for example aliphatic and aromatic Alcohols such as mono- and polyhydroxy-aliphatic or aromatic alcohols and phenols, carbohydrates and hydroxyl group-containing higher polymers of natural or synthetic origin,

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INSPECTED

- -JO -

Examples of aliphatic alcohols that can be used include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, nonanol, isononanol, decanol, "octadecanol, allyl alcohol, phytol, ethylene glycol, fern oil, propylene glycol, trimethylene glycol, glycerine, β-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 ₇ - and C ₁₁ alcohol and C alcohol of Cg, Co, C ₁ Q and C ₁₂ alcohols.

Cyclic alcohols include, cyclopentanol, cyclohexanol, pentahydroxycyclohexane, terpineol, hexahydroxycyclohexane, Cyclopropylcarbinol, borneol, cyclohexanediol, cyclohexanedimethanol.

To aromatic alcohols include Trimellitalkohol, benzyl alcohol, .beta.-phenylethanol _t ß-phenoxyethanol, "-Phenyläthanol, Phenylallylalkohol, diphenylcarbinol, triphenyl, salicyl.

Phenols include phenol, bis- (alkylidene) -phenols such as 4. 4 ^f -isopropylidenediphenol, allylphenol, nitrosophenol, cresol, methylphenol, ethylphenol, thymol, carvacrol, p - «- propenylphenol, resorcinol, aminophenol, catechol, quinol, adrenaline, Hexylresorcinol, hydroquinone, trihydroxybenzene, pyrogallol.

^J -11-

409808/1171

ORIGINAL INSPECTED

To carbohydrates include aldotetroses, aldopentoses, for example xylose, ribose, the aldo as glucose, disaccharides, for example sucrose, lactose, maltose, trisaccharides, for instance raffinose _s sorbitol, rhamnose, fructose, glycosides, cellobiose, polysaccharides , for example starch, cellulose.

Higher polymer materials include the polyalkylene glycols, Polyvinyl alcohol, hydrolyzed vinyl acetate / vinyl alcohol copolymers, Phenolic resins.

Other materials containing hydroxyl groups, such as dihydroxyacetone, Glyceryl monostearate, glyceraldehyde, cellosolve acetate and hydroxyacetophenone can be used »

The primary or secondary alcohols or phenols are the preferred hydroxyl group-containing materials. Tertiary Alcohols are unsuitable because their reaction with a phosphoryl halide is an alkyl halide rather than a phosphorus halide supplies.

A preferred class of hydroxyl group-containing compounds are 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, trifluoromethyl

A09808 / 117 1 ~ ^Λ2 ~

ORIGINAL INSPECTS *

phenol, allylphenols bericylphenol, vanillin, 4-chloro-3,5-dime thy! phenol, 4-chloro-1-naphthol, 2-chloro-4-nitrophenol, Gyanophenol, di-tert-butylphenol, diraethoxyphenol, methyl salicylate, Fluorophenol. Particularly preferred from this group are phenol, ores oil, cumylphenol, nonylphenol and chlorophenols Xylenol, tert-butylphenol, phenylphenol, isopropylphenol and their mixtures »

Another preferred class of hydroxyl group-containing materials include cyclohexanedimethanol, isopropylidenediphenol, Hydroquinone, catechol and resorcinol.

It is essential that the alcohol after the reaction with a phosphorus oxyhalide or thiophosphorus halide be none free hydroxy groups with any of the remaining Would convert phosphorus bonds, so that no reactive site would remain for the subsequent amidation.

The alkyl radicals represented by the radicals R. and Rp in the formulas (I) and (II) include methyl, ethyl, propyl, isopropyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, Deeyl, octadecyl, benzyl, ß-phenylethyl.

On aryl residues represented by the residues R. and Rp in the formulas (I) and (II) represented include phenyl, alkyl-substituted Phenyl, for example methylphenyl, diethylphenyl, naphthyl, chlorophenyl.

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• ^l '-M-'; ORIGINAL INSPECTED

Cycloalkyl radicals represented by the radicals R ₁ and Rp in the formulas (I) and (II) include cyclohexyl, cyclopentyl, cyclobutyl.

5- and 6-membered rings containing oxygen, sulfur, nitrogen and their combinations contain and the radicals R. and Rp linked together in formulas (I) and (II) Represented include furan, thiazole, pyridine, Thiophene, pyrrole, isoxazole, oxazole, pyrazole, imidazole, thiazoline, Thiazolidine, thiopyran, collidine, hexahydropyridine, piperidine, morpholine, condensed ring systems such as benzofuran, Benzopyrrole, quinoline, carbazole and xanthone, the sulfones and similar materials.

Among the phosphorus halides and thiophosphorus halides, the used here include, for example, phosphorus oxytrichloride, phosphorus oxytribromici, phosphorus oxytrifluoride, Phosphorus oxydichloride bromide, phosphorus oxydibromide chloride, phosphorus oxydifluoride chloride and the corresponding thiophosphorus analogs.

The phosphorus halidates associated with a secondary amine to form the compounds of this invention as described above are prepared and implemented by known processes, have the following general formulas

X X

(V) ZO-Phal ₂ and (VI) Z - (- 0P-hal ₂ ) _n ,

409808/1171

INSPECTED

2333506

wherein hai is a halogen, for example chlorine, fluorine, bromine or Is iodine and Z, X and η have the meanings defined in formulas (I) and (II).

About phosphorus halidates, which are used to produce the new compounds May be used in this invention include phenyl phosphorus dichloridate, chlorophenyl phosphorus dichloridate, Chlorophenyl phosphorus dibromidate, nitrophenyl phosphorus dichloridate, Cresyl phosphorus dichloridate, methoxyphenyl phosphorus dibroraidate, Nonylphenyl phosphorus dichloridate, 'curaylphenyl phosphorus dichloridate, Biphenyl phosphorus dichloridate, naphthyl phosphorus dichloridate, Isopropylphenyl phosphorus dichloridate, tert-butylphenyl phosphorus dichloridate, Isodecylphenyl phosphorus dichloridate, isodecyl phosphorus dichloridate, isopropylidene di-pphenylene bis-phosphorus dichloridate, Isopropylidene di-p-phenylphosphorus dichloridate, Cyclohexylenedimethylene bis-phosphorus dichloridate, Dicresyl phosphorus dichloridate, dixylyl phosphorus dichloridate, n-propylene-bis-phosphorus dichloridate, n-butylene-bisphosphorus dichloridate and the polyphosphorus dichloridates of carbohydrates and other hydroxyl group-containing polymers Materials.

The secondary amines used in this invention have the following general formula

(VII) HN

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ORIGINAL INSPECTED

2238506

in which the radicals R ^ and R _2, independently of one another or together, have the meanings defined in formulas (I) and (II). One of the radicals IL and R ₂ is preferably a methyl group

Amines include, for example, the alkylamines, for example methylamine, dimethylamine, methyläthylaiain, methylbutylaniin, dibutylamine, dioctylamine, di-n-hexylamine, didecylamine, di-noctadecylamine, dibenzylamine, di-ß-phenyläthylemin _{, 2- s} the arylamines, for example toluidine, Naphthylamine, bichlorophenylamine, cycloalkylamines, for example butylcyclohexylamine, dicyclopentylamine, heterocyclic amines, for example furfurylamine, pyridine, piperidine, imidazole, polyamines, for example hexamethylenediamine, pentamethylenehexamines, unsaturated amines, for example diallylamine, diallylamine

The implementation of a polyfunctional amine in a slight excess with a phosphorus halidate provides the polymeric compounds of this invention of the formula

? 4

(VIII) H-H 4h4- N -

Il

P-N OZ

? 4

N -

it ι4

P-N-H ι

OZ

wherein R is an alkylene group having 1 to 50 carbon atoms or an arylene group, the radicals R ^ and R independently. each other represent an alkyl group having 1 to 10 carbon atoms

409808/1171 ~ ¹⁶ ""

2333506

or, together with the nitrogen atom, a 5- or 6-membered one form a heterocyclic ring, Z is oxygen or sulfur and Z is the remainder of a hydroxyl group-containing Is partial, and η has a fourth from 1 - 40. Pol; yfunctional parts Amines which are used to prepare the compounds of formula (VIII) have the general formula

R ₅ R

I I

(IX) HN - (r- R -3- NH

in which the radicals R, R, and R ^ are defined in formula (VIII) Meaning '.

Typical amines corresponding to formula (IX) include compounds in which R is preferably an alkylene group with 1 to 10 carbon atoms and one of the radicals R- and R.

j 4

preferably methyl, for example bis (methylamine) methane, bis (methylamino) ethane, ₃ bis (methylamino) propane ,, bis (amino) butane, bis (ethylamino) octane, bis (methylamino ) benzene and the like.

Preferred groups of compounds according to the invention include compounds of the formulas

R ₅ X

B % ^ 0P

T ³ S ^R 5> ^

AO9808 / Π? 1 ^1?

(XI)

(XII) Q -f- O - GH ₉ - GH - ^

(A)

η 1

Λ
I!

Il

OP

in which the remnants

R .. and R _{2 are} independently an alkyl group with 1 to 10 carbon atoms or an aryl or an alkylaryl group,

each of the radicals R ₁ and R ₂ , independently of one another, together with its linked nitrogen atom is a 5- or 6-membered heterocyclic R? ng Mli.et «which can optionally contain oxygen, sulfur or o" jioi: st- ^ ff ₉ Rc hydrogen, a ^ j-kylgruppe with up to 20 carbon atoms

atoms, one aryl, one \ lkyl? .ι ^ 'ΐ £ ->' ΐν: - £ ~. oäer is halogen, *

the radicals R ^ and Ry, independently of one another, are hydrogen » an alkyl group with '· to 10 carbon atoms, an Ar;, "l-

group or an alkyiar, - lgr Ro is a hydrogen, alkyl and aralkyl group, X is oxygen or sulfur, A is methylene or phenyl. ' B hydrogen or

Cycloalkyl, aryl

Λ ti

-OP (NR ₁ R;). ,

Q is an alkyl group with 1 to 'C ■ "·; ·: .lens tof fat omen _{L is} an aryl group, an alkyl aryl group, ΐ: · ...:. ^ ~: &: Λ-οη- or eulfonic acid-

η Q ο ι o /

U 3 w ν Γ /

-18-

ORKaJNAL INSPECTED

group, an aliphatic or aromatic ester group or

-OP ^ NH ₁ R ₂ J ₂

n1 is a whole number "with a value of 0 or 1 to 6 when A = methylene or an integer from 1 to 2 when A = phenylene and
n2 is an integer with a value from 1 to 50

The compounds of formula (X) are for example thereby produced by using isopropylidenedipnenol (for example Bisphenol A) or phenylisopropylphenol with phosphorus oxychloride or thiophosphorus chloride and then the Phosphorus dichloridate intermediate with that described above secondary amine converts.

For compounds of the general formula (X) in which B = hydrogen, listen to g &. example mvei
C ₆ H ₅ C (CH ₃ 1 aC _e H ₄ OP (O) / N (GH ₃ )

CeH ₃ CH ₂ C ₆ H ₄ OP (O / (ifj ^ a
CeH ₅ CH ₂ C ₆ H ₃ (CH ₃ ) OP ( 0} / β { U ₃ H ₇ ) £

( ^
C ₆ H ₅ C (CH ₃ J ₂ CeH ₃ (C ₂ H ₅ ) OPfO) (N

/, ₂₃

CeH ₅ C (CHsCeHs) ₂ CeH ₄ OP (S> ί IT j

\ _v C ₄ HaZ

CeH ₅ C (C ₃ H ₇ ) SCeH ₃ (CeH ₅ JOP (O)

) OP (S) (/ jO)

-19-

Regarding compounds of the formula (X) in which B = -OP (KR ₁ R ₉ ) ,,

belong for example

_x \ / C ₃ H ₇ \

N) (O) PO (HsCe) H ₃ CeC (CgH ₁₈ CeHs) ₂ CeHa (CeHs) OP (O) IN) H ₅ C ₆ ' J ₂ \ ^v C ₆ H ₅ Z ₂

(O ^ N) s (O) PO / CH3C) ₂ HCH ₃ Ce7H3C _e C / _e C H ₃ CH (CH _{3) 2} CeH _Ä 7 ₃ / CeH3CH (CH ₃₎ ^

OP (O) (N ^ ~ 0) ₂

9C ₈ H ₄ C _{8) 2} N7 ₂ (S) POH ₄ C ₆ C (C ₂ H _{3) 2} C _e H ₄ OP (S) / ß {CeH ₄ C ₉ H ₁ 9) _Ä 7a

Nja (O) POH ₄ CeC (C ₅ H ₁ IJ ₂ CeH ₄ OP (O) (N ^ eH ₄ CH (CH ₃ ) ^ 7a

The compounds of the formula (XI) are prepared, for example, by adding benzyl alcohol, cyclohexanemethanol, Phenylphenol, cyclohexanol, hydroxymethylphenol, hydroxycyclohexanemethanol, bis-hydroxydiphenyl, cyclohexanediol, cyclohexanedimethanol, bis- (hydroxymethyl) -benzene or others suitable compounds with a phosphorus oxyhalide or thxophosphorus halide and an amine as above with regard to described on the formula (X), implemented.

Compounds of the general formula (XI) in which B = hydrogen include, for example

CeH ₁₁ CH ₂ OP (O) N (I ⁰

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INSPECTED

C ₆ H ₅ CH ₂ OP (O) NNH

X To compounds of the formula (XI) in which B = belong for example:

(o "~ N) ₂ (O) POH ₂ CC ₆ H ₄ CH ₂ OP (O) (N H ₃ C _x

(O) POCeHgCeH ₅ OP (O)

N '

HgC ₂

ZTH ₃ C) ₂ n7 ₂ (O) POCeH ₁ o0P (0) Zn (CE

The compounds of formula (XII) are prepared by adding a poly oil (for example the reaction product of a Alkylene oxide and a glycol) with a phosphorus oxyhalide or thiohalide and an amine, as described above, reacted.

Compounds of the formula (XII) include, for example: C ₁ 5H ₃₁ OC ₁ 5H ₃₀ OP (O) ZN (CH ₃ ) £ / _z

C ₁₂ H ₂₅ Oc ₅₅ H ₇₀ OC ₃₅ H ₇₀ OP (O) (hJp;

CeH ₅ OC ₄ oH ₈ oOC ₄ oH ₈ oOP (S) (VJ

I7 / 2

\ ^x C ₃ H ₇

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ORIGINAL INSPECTED

/ ^ ₃ \
HOOCIaH ₂₄ OC ₁₂ H ₂₄ OP (O) N)

H ₅ C ₂ OC (O) OC ₆ HiaOC ₆ H ₁ aOP (O) / N (C ₅ Hi x) £ 7z

The proportion of phosphorus dihalidate and amine that are converted may change depending on the reaction conditions. in the in general, however, sufficient amine is added to convert the phosphorus dihalidate completely into the corresponding phosphorus diamidate to convert, i.e. 2 moles or more of amine per mole of phosphorodihalidate are used.

The reaction of the phosphorus dihalidate and the amine can take place in be carried out in an aqueous medium, but is preferably carried out in an organic diluent which is an aqueous Solution of an alkali metal or ammonium hydroxide contains, carried out, so that the alkali metal hydroxide is released Can catch hydrogen chloride. To organic diluents, which can be used include any conventional organic diluent, such as chlorobenzene, Tetrahydrofuran and the like.

The temperature of the phosphorohalidate / amine reaction may vary from about O to about 10O ⁰ C, although the preferred temperature ranging from about 10 to about 60 ⁰ C "Higher temperatures can be used, but decrease the yield.

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4098G8 / 1 1 ^ f

The following examples illustrate specific embodiments for the preparation of certain compounds of the invention, without limiting the scope of the invention.

example 1

228 g (1.0 mol) of bisphenol A, 460 g (3.0 mol) of phosphorus oxychloride and 3.0 g of pyridine are placed in a 1 liter flask equipped with a mechanical stirrer, condenser and thermometer. The solution is heated to reflux. At about 90 ⁰ C, hydrogen chloride begins to form and is passed to a iVasserwäscher. After 2 1/2 hours, the temperature of the reaction mass stabilizes at 135 ° C. and no further hydrogen chloride is released. The excess phosphorus oxychloride is removed by vacuum distillation of the mass at 100 ° C./40 torr. 144 g of phosphorus oxychloride are obtained in this way. The remainder is 459 g of product ($ 99 <the theoretical yield) and this is isopropylidene di-p-phenylene-bis-phosphorus dichloridate:

0
Il / \ t j / \ 0
Il Cl ₂ PO -H (O) -H Ci / OPCl ₂ CH.

Example 2

In a 2 1 flask with mechanical stirrer, dropping funnel, The cooler and thermometer are given 100 g of 25% dimethylamine solution and 340 g of 50% sodium hydroxide solution. The mixture

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during the addition, it is cooled to 15 ^° C. using an ice-water bath. 461 g (1.0 mol) of isopropylidene-di-p-phenylene-bis-phosphorus dichloridate (prepared as in Example 1) in 200 ml of monochlorobenzene are added dropwise over 2 hours via a dropping funnel. The temperature is maintained at 15 ° + 2 ⁰ C. After complete addition the mixture is stirred for 1/2 hour and heated it to 60 ⁰ C for half an hour. The layers are separated and the organic layer is washed at 7O ⁰ C with 700 ml of water 20 minutes. The organic layer is then stripped off under vacuum at 135 ° C./40 torr and steam is then bubbled through at 135.degree. C./40 torr for 30 minutes. The product is dehydrated and filtered. In this way, 465 g (94% of the theoretical yield) of product which is isopropylidenedi-p-phenylene-bis (tetramethylphosphorodiamidate) are obtained:

(CH ₃ )]

O CH, O r

PO - / O V - C - ■ / O V - OP - ■

CH ^

-J 2

Example 3

Morpholine (400 g) is dissolved in 600 ml of water which has been cooled to 15 ° C. in a 2 l 3-necked flask which is cooled by a water bath. A 50% solution of sodium hydroxide (340 g) and then, using a dropping funnel, isopropylidene-di-p-phenylene-bis-phosphorus dichloridate (461 g) in monochlorobenzene (200 ml) are added over 2 hours, the temperature is held between 15+ 2 ⁰ C. After adding

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The mixture is stirred for half an hour at 15 ° C. and then heated to 60 ° C. for half an hour. The mixture is placed in a 2 l dropping funnel and the salt layer is removed. The organic layer is washed with 700 ml of water at 60 to 65 ^° C. for 2 minutes. The water layer is removed and the organic layer is washed with 10 g of sodium hydroxide in 700 ml of water at 70 to 75 ⁰ C for 20 minutes, it strips off and treated with steam at 135 ° C / 4O Torr half an hour. In this way, a 90% yield of the product is obtained, namely isopropylidene di-p-phenylene-bis- (dimorpholinophosphorodiamidate):

If other amines are used in place of morpholine in the above process, the following compounds are obtained:

Amine compound

HN

^V NJ (O) POH ₄ C ₆ C (CH ₃ ) ₂ C ₆ H ₄ OP (O) IN

(3 ⁽ ^) n) ₂ (o) poh ₄ c ₆ c (ch ₃ ) ₂ c ₆ h ₄ op (o) (hn (c ₂ h ₅ ) ₂ / ΓΗ ₅ σ ₂ ) ₂ ΐί7 ₂ (ο) ΡθΗ ₄ ο ₆ σ (θΗ ₃ ) 2σ ₆₄₅

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409808/1 171

Example 4

Cumylphenol (424 g), phosphorus oxychloride (460 g) and pyridine (3.0 g) are placed in a 1 liter flask equipped with a reflux condenser, thermometer and mechanical stirrer. The mixture was heated to reflux, beginning at 95 ⁰ C under formation of hydrogen chloride. After 3 hours, the temperature rises to 145 ^° C. and is kept there for a further half an hour. The mixture is stripped off in vacuo to give phosphorus oxychloride. The residue is diluted with monochlorobenzene (200 ml) and a previously prepared solution of dimethylamine (800 g - 25% in water) and sodium hydroxide (350 g - 50% in water) is added. and cools the mixture to 15 to 20 ^° C. during the 11/2 hour addition, then heats to 70 ^° C. and separates the layers. The organic layer is washed with water at 70 ^° C., dehydrated, treated with steam and filtered.

The product (628 g - 91% yield) is cumylphenyl tetramethyl phosphorodiamidate:

0) C —— <0 V— OP

CH ₃

"N (CHj

3'2

Example 5

In a 1 l flask with reflux cooler, mechanical stirrer and thermometer are added nonylphenol (440 g), phosphorus

409808/1171

" ^2β 2338508

oxychloride (460 g) and pyridine (3.0 g). The procedure of Example 4 is used and the mixture residue is diluted with monochlorobenzene (200 ml) and a morpholine (400 g) / alkaline (350 g) solution is then added. A yield (707 g) of nonylphenyldimorpholinophosphorodiamidate is obtained:

Repeating the above procedure, adding 100 g Diinethylamine in 25% solution instead of 400 g of chloropholine used, a 90 ^ ige yield (633 g) of Nonylphenyltetramethylphosphorodiamidate:

Il

OP

Example 6

Cyclohexanedimethanol 1.4 (3 LIoI), phosphorus oxychloride (3 mol) and pyridine (3 g) are placed in a 1 l flask, as in Example 4. I lan uses the procedure of Example 4 and dilutes the reaction mixture with chlorobenzene and adds 4 moles of dimethylamine in alkali. The product is cyclohexylenedimethylene bis (tetramethylphosphorodiamidate), .C) ₉ Κ7 ₉ (O) POCH ₉ C ^ H _{1 o} CH ₉ 0P ( O) / R (GR, )? _ 7 _P.

-27- 409808/1171

" ²⁷ ~ 233850?

Dimethylamine can be replaced by any other secondary amine replaced to form the desired phosphoramidate analog will·

Example 7

Phosphorus oxychloride and diethylene glycol in a molar ratio of 2: 1 are placed in a steel-jacketed reaction vessel with a capacity of 2040 1 and equipped with a stirrer and heat source. After 2 hours of reaction at 15 ^° C. and 1 hour at 30 ^° C., a 25% solution of dimethylamine in alkali is added in a ratio of 4 moles of dimethylamine per mole of diethylene glycol bis-phosphorus dichloridate intermediate. The temperature is lowered to 15 ^° C. and held for 30 minutes. An oil yield of product, the diethylene glycol bis (tetramethylphosphorodiamidate), / TH ₃ C) ₂ | j7 ₂ (O) POCH ₂ CH ₂ OCH ₂ CH ₂ OP (O) ^ T (CH ₃ ) _{2, is obtained} _7 ₂ is.

The compounds of the present invention are useful as fire retardant for a wide variety of natural and synthetic polymers. The compounds can be used in concentrations from about 0.1% by weight of polymer up to about 50% by weight or more may be added depending on the particular purpose for which the polymer is intended.

Synthetic polymeric materials, i.e., high molecular weight organic materials not found in nature are where the compounds of the invention are beneficial

-23- 4.09808 / 1171

ORlGtNAL INSPECTED

can be used, can either be linear or crosslinked polymers and they can be in the form of films, Sheets, coatings, foams and the like are present. It can be polymers obtained by addition or condensation polymerization can be obtained.

A significant class of polymers which, with the compounds of the invention, have valuable fire-retardant properties may be awarded, include those obtained from a polymerizable monomeric compound with ethylenic saturation receives. There is a particularly preferred class of polymers to which fire retardancy can be imparted from polymerized vinyl and vinylidene compounds, i. those which have the CHp = C ^ radical. Connections with Such a radical are, for example, solid polymeric alkenes such as polyethylene, polypropylene, polyisobutylene or ethylene / propylene copolymers, the polymerized acrylyl and alkacrylic 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 methaerylate, 2- (diethylamino) ethyl or 2-chloroethyl acrylate or methaerylate, acrylic acid anhydride or methacrylic anhydride, methacrylamide or chloracrylamide, Ethyl or butyl chloroacrylate, the olefinic aldehydes such as acrolein, methacrolein and their acetals, the vinyl

-29- 409808/1171

2338501

and vinylidene halides such as vinyl chloride, vinyl fluoride, vinylidene fluoride and 1-chloro-i-fluoroethylene, polyvinyl alcohol, the Vinyl carboxylates such as vinyl acetate, vinyl chloroacetate, vinyl propionate and vinyl 2-ethylhexanoate, the N-vinylimides such as N-vinylphthalimide and N-vinylsuccinamide, the N-vinyllactarns such as N-vinylcaprolactam and N-vinylbutyrolactam, the vinyl aromatics Hydrocarbon compounds such as styrene, alpha-methylstyrene, 2,4-dichlorostyrene, alpha- or beta-vinylnaphthalene, Divinylbenzene and vinyl fluorene, the vinyl ethers such as ethyl vinyl ether or isobutyl vinyl ether, the vinyl-substituted ones heterocyclic compounds such as vinyl pyridine, vinyl pyrrolidine, vinyl furan or vinyl thiophene, the vinyl or Vinylidene ketones such as methyl vinyl ketone or isopropenyl ethyl ketone and vinylidencyanide. Homopolymers of the above-mentioned compounds or copolymers and terpolymers the same are excellent in fire retardancy by the compounds of the present invention. examples for Such copolymers or terpolymers are those obtained by polymerizing the following monomeric mixtures receives. Vinyl chloride / vinyl acetate, ethylene / vinyl chloride / vinyl acetate, acrylonitrile / vinyl pyridine, styrene / methyl methacrylate, Styrene / N-vinylpyrrolidone, cyclohexyl methacrylate / vinyl chloroacetate, Acrylonitrile aynylidenecyanide, methyl methacrylate / Vinyl acetate, ethyl acrylate / iS / ethacrylamide / ethyl chloroacrylate, Vinyl chloride // inylidene chloride / vinyl acetate.

Other polymers of compounds with the ethylenic

-30-409808 / 1171

ORJGiNAL INSPECTED

Group ^ C = C ^ are homopolymers, copolymers and Terpolymers of alpha-, beta-olefinic dicarboxylic acids and their derivatives, such as the anhydrides, esters, amides, nitriles and imides, for example methyl, butyl, 2-ethylhexyl or Dodecyl fumarate or maleate, maleic acid, Cn maleaic acid, Citraconic or itaconic anhydride, pumaronitrile, dichlorofumaronitrile or citraconnitrile, pumaramide, maleamide or N-phenylmaleamide. Examples of particularly useful The copolymers are polymers and terpolymers which are produced from the alpha-, beta-olefinic dicarboxylic acids 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 fire retardants for polymers and copolymers of unsaturated, cyclic esters of carboxylic acid, for example homopolymer Vinylene carbonate or the copolymers of vinylene carbonate with ethylene compounds such as ethylene, vinyl chloride, Vinyl acetate, 1,3-butadiene, acrylonitrile, methacrylonitrile, or the esters of methacrylic or acrylic acid.

One easily obtains one from the compounds of the invention

-31- 409808/117 1

ORIGINAL INSPECTED

^"31 ~ 2338508

Fire retardancy also applies to polyaryl carbonate polymers, such as the linear polyaryl carbonates made from diphenols or dihydroxyaromatic ones Compounds including single or fused ring cores with two hydroxyl groups, as well as from Monohydroxy-substituted aromatic radicals linked in pairs by different links. For examples for these polymers include dihydroxybenzenes, naphthalenes and the like, the dihydroxydiphenyl ethers, sulfones, alkanes, -ketones and the like.

The compounds of the invention also act as fire retardants for polymers, copolymers or terpolymers polymerizable compounds with a large number of double bonds, such as for rubber-like, conjugated diene polymers such as homopolymerized 3-butadiene, 2-chlorobutadiene or isoprene and linear copolymers or terpolymers such as butadiene / acrylonitrile, isobutylene / butadiene, Butadiene / styrene, for esters of saturated di- or polyhydroxy compounds with olefinic carboxylic acids such as ethylene glycol dimethacrylate, Triethylene glycol dicrotonate or glyceryl triacrylate, for 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 divinylbeazole, as well as the crosslinked polymeric materials such as methyl methacrylate / diallyl methacrylate copolymer or butadiene /

■ -32-

409808/1171

ORIGINAL

" ³² " 233850 o

Styrene / divinylbenzene terpolymer.

The cellulose derivatives are made by the compounds of the present invention Invention made fire retardant · 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 and the like are fire retardant be made.

The compounds of the present invention are eminently suitable for liquid resin preparations of polyester type, fire retardant to make, for example, the linear polyester, which is produced by the reaction of one or more polyhydric alcohols with one or more alpha-, beta-unsaturated polycarboxylic acids alone or together with one or more saturated polycarboxylic acid compounds are obtained or for the crosslinked polyester resins obtained by reacting a linear polyester with a compound having a CHp = C group contains, are obtained.

The compounds of the present invention are considered to be fire retardant Agent suitable for epoxy resins. Such resins are condensation products made by reacting a polyhydroxy compound and an epichlorohydrin, wherein the condensation products are subsequently hardened by adding curing agents.

-33-

409808/1171

ORIGINAL INSPECTED

nen for example ethylene glycol, 4.4 ^f -isopropylidenediphenol and similar materials. The crosslinking agent used in the curing step can be a dicarboxylic acid compound such as phthalic anhydride or adipic acid, but more commonly it is generally a polyamine such as ethylene diamine, para-phenylamine diamine or diethylene triamine.

Polyurethanes are a class of polymer materials that can be made fire retardant by the compounds of the present invention. The polyurethanes are similar to the Above-mentioned polyesters, materials that are used in construction, for example as insulation foams, for manufacture of textile fibers, as a resin base in the production of curable coating preparations and as impregnation adhesives in the manufacture of laminates from wood and other fiber materials. Essentially they are the polyurethanes Condensate products of a diisocyanate and a compound having a molecular weight of at least 500 and preferably about 1500 to 5000 and at least two reactive Hydrogen ions. The useful, active hydrogen-containing Compounds can be polyesters made from polycarboxylic acids and polyhydric alcohols, polyhydric polyalkylene ethers with at least two hydroxyl groups, polytnioether glycols, Polyester amides and similar materials are produced.

The polyesters or polyester amides used for making

-34- 4098Q8 / 1171

ORlGiNALlNSPECTED

233850a

of polyurethanes are used, can be branched and / or straight, for example the esters of adipin, sebacin, 6-aminocapron-, phthal-, isophthal-, terephthal-, -oxal-, Malon-, Bernstein-, LIalein-jCyclohexan-1,2-dicarbon-, Cyclohexan-1,4-dicarbon-, Polyacrylic, naphthalene-1.2-dicarbon, Pumaric or itaconic acids with polyalcohols, such as ethylene glycol, Diethylene glycol, pentaglycol, glycerine, sorbitol, triethanolamine and / or amino alcohols, such as ethanolamine, 3-aminopropanol and with mixtures of the above-mentioned polyalcohols and Amines.

The alkylene glycols and polyoxyalkylene or polythioalkylene glycols, which are used for the production of polyurethanes can be ethylene glycol, propylene glycol, butylene glycol, Diethylene glycol, triethylene glycol, polythioethylene glycol, Dipropylene glycol and the like.

In general, any of the polyesters can be polyisocyanate-modified Polyesters, polyester amides, polyisocyanate-modified ones Polyester amides, alkylene glycols, polyisocyanate-modified ones Alkylene glycols, polyoxyalkylene glycols and polyisocyanate-modified ones Polyoxyalkylene glycols with three reactive hydrogen atoms, three reactive carboxylic acid and / or especially hydroxyl groups are used for the production of polyurethanes. In addition, any organic compound containing at least two hydroxyl and / or carboxy groups is used.

-35-

409808/1171

OfUGtNAL JNSPEGTED

Among the organic polyisocyanates used in the production of Polyurethanes are suitable 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 bis-phenyl carbamates of tolylene diisocyanate and the like.

Phenolic resins can be made by the compounds of the present invention can be made fire retardant, the compounds being incorporated into the phenolic resin either by milling or by molding or by adding to film-forming or impregnating or binding solutions before casting, phenolic resins, in which the present compounds are used, for example, the phenol aldehyde resins from Phenols such as phenol, gresol, xylinol, resorcinol, 4-butylphenol, Cumylphenol, 4-phenylphenol, nonylphenol, and aldehydes such as Formaldehyde, acetaldehyde or butyraldehyde, produced in the presence of either acetic or basic catalysts depending on whether the resin is used as a molding or extrusion resin or as a resin base for coating and impregnation tubs ext ungen should be used.

Aminoplasts are another group of aldehyde resins made fire retardant by the compounds of the invention can be. Examples of aminoplasts are the heat-convertible condensation products of an aldehyde with urea,

-36- 409808/1171

ORIGINAL INSPECTED

Thiourea, guanidine, cyanamide, dicyandiamide, alkyl or arylguanamines with the triazines such as melamine, 2-fluoro-4,6-diamino-1,3.5-triazine and the like · If the aminoplasts are used as impregnating agents, bonding adhesives, coatings or for casting films to find, the compounds of the present invention are introduced into solutions or suspensions in which the aminoplast is supported. The resulting mixtures give solid, fire-retardant laminates when paper, glass, fabric or fiber surfaces are impregnated and cured with them.

Another class of compounds rendered fire retardant by the compounds of the present invention are the nylons, for example the superpolyamides, which are generally obtained by ain diamine, for example hexamethylenediamine, condensed with a dicarboxylic acid, for example adipic acid.

Other polyamides that are fire retardant according to the present invention are made are the polypeptides that can be prepared, for example, by taking N-carbobenzyloxyglycine with glycine or a mixture of glycine and lysine or an N-carboxyamino acid anhydride, such as Ni-carboxy-DL-phenylalanine anhydride, Piperidone, 2-oxohexamethyleneimine and other cyclic amides. The compounds of the present Invention can be incorporated into the molding or extrusion formulations for the purpose of fire retardancy.

-37- 409808/1 171

OflQINAL

23385Q8

The compounds of the present invention are also useful as fire retardants for linear polymers, which are obtained by the self-condensation of bifunctional compounds obtained, for example, for polyethers resulting from self-condensation from dihydric alcohols such as ethylene glycol, propylene glycol or hexamethylene glycol, the polyester, which can be achieved by the self-condensation of hydroxy acids, such as lactic acid or 4-hydroxybutyric acid, for polyamides that are produced by the self-condensation of aminocarboxylic acids, such as 4-aminobutyric acid, and for polyanhydrides produced by the self-condensation of dicarboxylic acids, such as sebacin or adipic acid.

The preferred synthetic polymers produced by the compounds According to the present invention, the vinyl halide polymers are in the form of milled ones Products, plastisols and foams, rigid and flexible polyurethane coatings and foams, epoxy resins, ABS and GRS rubbers, aminoplasts and phenolic resins. The vinyl halide polymers can be simple, mixed homopolymers of vinyl chloride or vinylidene chloride, such as polyvinyl chloride or polyvinylidene chloride, or it can be mixed polymers or terpolymers, in which the essential polymeric structure of polyvinyl chloride at intervals Remainders of other ethylenically unsaturated compounds, which are copolymerizable therewith, is interrupted, the essential Properties of the polymeric structure of the polyvinyl

-30-A09808 / 1171

ORiGiNAL INSPECTED

Chloride is retained if not more than 40 % of a comonomer is copolymerized with it. Particularly preferred copolymers include ethylene / vinyl chloride and vinyl chloride / acrylonitrile copolymers. Particularly preferred terpolymers include ethylene / vinyl chloride / acrylonitrile, ethylene / vinyl chloride / acrylic acid and ethylene / vinyl chloride / acrylamide terpolymers.

Natural polymeric materials made fire retardant by the compounds of the present invention can include natural rubbers, cellulose esters, for example cellulose acetate and cellulose nitrate, ethyl cellulose, Cork and wood products and similar cellulosic materials.

The polymeric formulations made fire retardant according to the present invention, whether they are in Plate or pilm shape or as a foam or as a molded article contain various conventional additives such as fillers, extenders, crosslinking agents and Dyes. Furthermore, small amounts of stabilizers, for example, are usually incorporated in order to reduce the effects of Decrease heat and light.

If foamable preparations are used, the Preparation be a self-expanding polymer or a polymer that is made by means of chemical or mechanical means or

-39-

£ 09808/1171

ORiGfNAL INSPECTED

can be inflated using a compressed gas. To fillers that are often used to reduce the cost Lowering the final material and modifying its properties include calcium carbonate and magnesium silicate. if When fillers are used, they are generally in an amount up to about 150 parts by weight of filler per 100 parts by weight Polymer formulation available.

If you want a colored preparation, dyes can be used or colored pigments are incorporated in amounts of about 1 to about 5 parts by weight per 100 parts by weight of polymer.

Surfactants such as silicones are normally added to foam formulations that are mechanically foamed will. The surfactants decrease the surface tension of the foam and thereby increase the air or air volume Gas entrapment properties of the foam.

Furthermore, glass-forming inorganic materials such as zinc borate, zinc oxide, lead oxide, lead silicate and silicon dioxide can be added to reduce the fire and smoke-forming properties of the polymer. The fire retardant compositions of the present invention are extremely advantageous because of the following combination of properties. (1) The compounds are stable at temperatures ⁰ C to about 35O, and can therefore by standard means, such as mills, can be processed without degradation or loss of color. (2) The

-40-

409808/1171

~ ⁴⁰ "" 233850Θ

bonds do not contain chlorine and therefore form during the Do not expose to gaseous hydrogen chloride to flames. (3) The connections can be with a little stable Acid generators are formulated and they can therefore be prepared so that they, if necessary, at low temperatures be dismantled. (4) The compounds are excellent ■ acid scavengers, reducing the amount of fuel caused by the fuel acid residues formed is reduced. (5) The compounds have high solubility and compatibility with a wide variety of synthetic and natural polymeric materials.

The following examples serve to illustrate the usefulness of the fire-retardant preparations of the present invention in various polymer substances. As used herein, the term "acid off index ¹¹ " indicates that the numbers obtained were obtained according to ASTM method D2863-7O and is defined as the minimum concentration of oxygen, expressed in percent by volume, in a mixture of oxygen and nitrogen, which are just necessary to sustain the combustion of the material under the conditions of the test procedure.

Example 8

In this example the compound of Example 2 is combined with a commercially available fire retardant ("Fyrol 99") Trademark of the Stauffer Chemical Company for their ethylene

-41-

409808/1171

INSPECTED

⁴¹ "$ 233850

glycol polyphosphate fire retardant) in one market available epoxy resin ("EPI-REZ", trademark of Celanese Chemical Company for its epoxy resin). The comparative properties of the resins, the 5 and 10 parts per 100 parts of resin of fire retardants are given in the table below.

Table I.

fire retardant parts volatile- strength oxygen-

keit io _{ver k} “/ _cm 2 index £ lust Kg / cm oxygen

"Fyrol 99" 5 + 0.59 186 21.2 "Fyrol 99" 10 + 0.03 135 21.2 connection of
Example 2 5 + 0.01 225 22.0 connection of
Example 2 10 + 0.02 203 24.0

Example 9

In this example the compound of Example 2 is combined with a. Polymethyl methacrylate resin formulated and with a control sample that does not contain a fire retardant. The polymethyl methacrylate control sample had an acidic acid off index of 16.8, while the polymethyl methacrylate sample, the 10 parts per 100 compound of Example 2 of the present Invention contained, an oxygen index of 18.4 and a polymethyl methacrylate sample containing 30 parts per 100 of the compounds of Example 2 had an oxygen index of 21.9 exhibited

-42- A09808 / 1171

ORIGINAL JNSPECTED

Example 10

The compound of Example 2 is compared with "Fyrol 99" in a melamine / formaldehyde resin at a content of 5 parts per 100. The resin properties are in the table below refer to.

Tabel II Oxygen index -
"A oxygen fire retardant s
middle Parts
per 100 volatility
^c / a loss 48.2 "Fyrol 99" 5 12.0 49.3 connection of
Example 2 5 10 Example 11

The compound of Example 2 was formulated at 10 and 30 parts per hundred, respectively, with a thermoplastic polyurethane resin. The material was subjected to roll milling treatment subjected to 5 minutes at 166 ⁰ C (33O ⁰ F) and 16O ⁰ C (32O ⁰ P) for 5 minutes at 70.3 kg / cm deformed. The properties of the resin / are given in the table below.

Table III

fire retardant parts per 100 oxygen index 2L oxygen

Control -

Compound of Example 2 10 Compound of Example 2 30

A comparable fire resistance is obtained if one uses the ^{J -43-}

409808/1171

ORIGINAL INSPECTED

20th , 6 22nd , 4 27 , 6

bonds of Examples 3, 4, 5, 6 and 7 instead of the connection Preparation of Example 2 in the formulations of Examples 7 to 11 used.

The invention includes all deviations and changes from the examples, which are for the purpose of illustration only were given, insofar as the deviations make use of the general inventive concept.

-Patent claims-

409808/1171

Claims (1)

Patent claims: 1. Compound of formula ί 1 0 - P - (- NH ₁ R ₂ ). , - η X oxygen or sulfur, Z is the radical of a part containing hydroxyl groups, the radicals R ₁ and Rp, independently of one another, are alkyl · ^ cycloalkyl or aryl groups and can be identical or different, the radicals R ₁ and R ₂ together form a 5- or 6-membered ring , which may contain oxygen, sulfur or nitrogen atoms or combinations thereof and η is an integer of 2 or more, as well as their acid, alkali and ammonium salts. 2. A compound according to claim 1, characterized in that X is oxygen, Z is the radical of a part containing dihydroxyl groups, the radicals R ₁ and R _{2 are} independently alkyl, cycloalkyl or aryl groups and η = 2. 3. A compound according to claim.1, characterized in that X is sulfur, Z is the radical of a part containing dihydroxyl groups, the radicals R ₁ and R ^ independently -45- Λ09808 / 1171 ORfGfNAL INSPECTED from each other are alkyl, cycloalkyl or aryl groups and n = 2. 4. Compound of Formula X is oxygen or sulfur,
B is hydrogen or -TOP (X) (NR ₁ Rg) ₂ , the radicals R ₁ and R ₂ independently of one another are an alkyl group of 1 to 10 carbon atoms, an aryl or alkylaryl group, the radicals R ₁ and R ₂ together with their connected nitrogen atom form a 5- or 6-membered heterocyclic ring which can also contain oxygen, sulfur or nitrogen atoms, Rc is hydrogen, an alkyl group of 1 to 20 carbon atoms, an aryl group, an alkylaryl group or halogen; and R ^ and R _{7 are} hydrogen, an alkyl group of 1 to 10 carbon atoms, an aryl group or an alkylaryl group, and their acid, alkali and Ammonium salts. 5 * connection according to claim 4, characterized geke η η -46- 409808/1171 ORIGINAL INSPECTS) draws that B = hydrogen. 6. A compound according to claim 4, characterized in that B = -OP (X) (NR ₁ R ₂ ) ₂ is. 7 «compound according to claim 5," characterized that the radicals R., Rp and R, - methyl groups are, the radicals Rg and R ~ are hydrogen and X is oxygen is. 8 _t compound according to claim 5, characterized in that the radicals R ₁ and Rp together form a morpholinyl ring, R _{1 is} methyl, Rg and R ~ are hydrogen and X is oxygen. 9. A compound according to claim 6, characterized in that the radicals R., R ₂ and R _{5 are} methyl groups, the radicals Rg and R _{7 are} hydrogen and X is oxygen. 10. A compound according to claim 6, characterized in that the radicals R ₁ and Rp together form a morpholinyl ring, R ₁ - is methyl, Rg and R _{7 are} hydrogen and X is oxygen. 11. Compound of Formula -47- 40.980 8/1 171 ORiGtNAL INSPECTED H X ^B. '~ ^ ^A) ^ YZ ^ r ^{(A) n1} where X Oxygen or sulfur,
B hydrogen or -OP (X) (NR ₁ R ₂ J ₂ , the radicals R ₁ and R _{2 are} independently an alkyl group of 1 to 10 carbon atoms, an aryl or alkylaryl group, the radicals R ₁ and R ₂ together with their usual, ie linked nitrogen atom form a 5- or 6-membered heterocyclic v / pus see ring form, which / optionally oxygen, sulfur or May contain nitrogen atoms, R ₁ . Is hydrogen, an alkyl group of 1 to 20 carbon atoms, an ary group, an alkylaryl group or halogen, A is a methylene or phenylene group, nl is an integer from 0, 1 to 6 when A =!.! ethylene and is from 1 to 2 when A = phenylene,
as well as their acid, alkali and ammonium salts. 12. A compound according to claim 11, characterized that B is hydrogen. 13. A compound according to claim 11, characterized in that B -OP (X) (NR ₁ R ₂ ) ₂ is. -4ö- A09808 / 1 171 ORIGINAL INSPECTED 14. A compound according to claim 12, characterized in that X is oxygen, the radicals R ₁ and Rp are methyl, R ₁ - is nonyl and n1 = 0. 15. A compound according to claim 12, characterized in that X is oxygen, the radicals R ₁ and Rg together form a morpholinyl _{ring, R 1} - is nonyl and n1 = 0. 16. A compound according to claim 13, characterized in that X is oxygen, the radicals R ₁ and Rp are methyl, R ^ - is hydrogen and n1 = O. 17. A compound according to claim 13, characterized in that X is oxygen, the radicals R ₁ and Rp together form a morpholinyl ring, Rc is hydrogen and n1 = 0. 18. A compound according to claim 13, characterized in that X is oxygen, R ₁ and Rp are methyl, R _1-7 / on Hydrogen, A is methylene and n1 = 1. 19. A compound according to claim 1Ö, characterized that the ring is saturated. 20. A compound according to claim 13, characterized in that X is oxygen, the radicals R ₁ 409808/1171 ~ ⁴⁹ ~ ORIGINAL INSPECTED lind R ₂ together form a morpholinyl ring ", R ^ is hydrogen, A is methylene and n1 = 1. 21. Compound of Formula Il Q 4- O - GH ₂ - GH - * - _n oil -f- X is oxygen or sulfur, Q is an alkyl group of 1 to 20 carbon atoms, an aryl group, an alkylaryl group, a carbonic or sulfonic acid group, an ester group or -OP (X) (NR ₁ R ₂ ) O, the radicals R. and R ₂ are independently an alkyl group of 1 to 10 carbon atoms, an aryl group or an alkylaryl group, Ro is an ethylene group and n2 = 1 to 50, and their acid and ammonium salts. 22. A compound according to claim 21, characterized in that Q is an aryl or alkylaryl group is. 23. A compound according to claim 21, characterized in that Q is a carboxylic acid or sulfonic acid group is. -50- 409808/1171 ORiGtNAL INSPECTED 2J38506 24. Compound according to claims 21, characterized therein that Q is an ester group. 25. A compound according to claim 21, characterized in that Q is an alkyl group. 26. Compound according to claim 25, characterized by that the alkyl group is an ethyl group, η 2 = 2 and R ^ is an ethylene group. 27. Compound according to claim 21, characterized in that Q is -OP (O) (NR ₁ R ₂ ) 2. 2Ö. Compound according to claim 27, characterized in that n2 = 2, R> ethylene, X is oxygen and the radicals R .. and R _{2 are} methyl groups. 29. A compound according to claim 27, characterized in that n ₂ = 2, R ^ is ethylene, X is oxygen and the radicals R ₁ and R ₂ together form a morpholinyl ring. 30. Compound of Formula X η h-b4h -) - n-- p-n 4-R -) - ν - - ρ - ν - OZ X η OZ -51- / ►09808 / 1171 ORiGiNAL INSPECTED R is an alkylene group of 1 to 50 carbon atoms or is an arylene group, the radicals R, and R, independently of one another are an alkyl group of 1 to 10 carbon atoms or, together with the nitrogen atom, a 5- or 6-membered heterocyclic structure Form a ring, X oxygen or sulfur and Z is the remainder of a part containing hydroxyl groups. 31. A compound according to claim 30, characterized in that R is an alkylene group of 1 to 10 carbon atoms, the radicals R, and R. are methyl groups and X is oxygen. 32. Process for the preparation of phosphoramidates, characterized in that a phosphorodihalidate is used with a secondary amine in an organic diluent which is an aqueous solution of an alkali metal or Contains ammonium hydroxide. 33 «The method according to claim 32, characterized that monochlorobenzene is used as the diluent. 34. The method according to Ansprucn 32, characterized in that the diluent is Tetra -52-409808 / 1171 hydrofuran is used. 35. The method according to claim 32, characterized in that the hydroxide is sodium hydroxide used· 36. The method according to claim 32, characterized in that the hydroxide is potassium hydroxide used. 37. The method according to claim 32, characterized that one as. Hydroxide used ammonium hydroxide. 38. Fire-retardant preparation, characterized in that it is a natural or synthetic Material and a compound according to claim 1 contains. 39. Preparation according to claim 38, characterized in that the material is a natural one Material is. 40. Preparation according to claim 39, characterized that the material is natural rubber, cellulose ester, cork and wood products and ethyl cellulose is. -53- 409808/1171 " ⁵³ k33850B 41. Preparation according to claim 38, characterized in that the material is a synthetic material. 42. Preparation according to claim 41, characterized in that the material is a synthetic Polymer is. 43 · Fire-retardant ^ preparation, thereby marked draws that it is a natural or synthetic material and a compound of the formula ti ZO - contains where
X oxygen or sulfur, Z is the radical of a hydroxyl group-containing part, the radicals R. and R ₂ independently of one another are an alkyl group, a cycloalkyl group or an aryl group and the radicals R ₁ and R ₂ together with their usual nitrogen atom are a 5- or 6-membered heterocyclic group Form a ring, Further
the optionally / oxygen, sulfur or nitrogen atoms may contain. 44. Fire-retardant preparation, characterized in that it is a natural or synthetic Contains material and a compound according to claim 4. -54- 409808/1171 ORK3WAL INSPECTSl 45. Fire retardant ^ preparation, thereby. marked that it contains a natural or synthetic material and a compound according to claim 11. 46. Peuerhenmende preparation, characterized that they are natural or synthetic Contains material and a compound according to claim 21. 409808/1171 ORfQiNAL INSPECTED