CA2027078A1 - Aminomethane phosphonic acid aryl esters and a process for their preparation - Google Patents

Aminomethane phosphonic acid aryl esters and a process for their preparation

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Publication number
CA2027078A1
CA2027078A1 CA002027078A CA2027078A CA2027078A1 CA 2027078 A1 CA2027078 A1 CA 2027078A1 CA 002027078 A CA002027078 A CA 002027078A CA 2027078 A CA2027078 A CA 2027078A CA 2027078 A1 CA2027078 A1 CA 2027078A1
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Prior art keywords
group
optionally substituted
aromatic
formula
stands
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French (fr)
Inventor
Uwe Arndt
Hans-Dieter Block
Wolfgang-Hans Schulz-Schlitte
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Bayer AG
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Bayer AG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
    • C08K5/5333—Esters of phosphonic acids
    • C08K5/5353—Esters of phosphonic acids containing also nitrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40—Esters thereof
    • C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having three nitrogen atoms as the only ring hetero atoms
    • C07F9/6521—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2/00—Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
    • C08G2/30—Chemical modification by after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
    • C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
    • C08G79/04—Phosphorus linked to oxygen or to oxygen and carbon

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Fireproofing Substances (AREA)

Abstract

ABSTRACT OF THE DISCLOSURE

An aminomethane phosphonic acid aryl ester of the following formula or salts thereof:

where R1 stands for an optionally substituted aromatic group, an optionally substituted arylene alkylene group, an optionally substituted aliphatic group, an H atom, a group of the following formula , an nth part of a group of the formula , a group when n = 2, an optionally substituted amino group or a CH2-OH group, n stands for an integer with a value from 1 to 100, R2 stands for an optionally substituted aromatic group, an optionally substituted heteroaromatic group, an -H-atom, a group corresponding to the following formula , a -?-R7- group or a CH2-OH group, R3, R4, R5, and R6. denot-ing, independently of one another, aromatic groups or substituted aromatic groups, R7 stands for an H-atom, an optionally substituted aliphatic group, an optionally substituted aromatic group, an optionally substituted hetero aromatic group an option-ally substituted amino or imino group or an optionally substituted aromatic, hetero aromatic or aliphatic group attached through oxygen or sulphur.
These esters are useful as flame retardants in foams, thermoplasts and duroplasts, and as cocondensable components in oligo and polycondensates based on monomers containing hydroxyl groups.

Description

- 2027078 ~ ~

, :

, " ~.

Aminomethane phosphonic acid aryl esters and a process for their preaaration -.
: .:

This invention relates to aminomethane phosphonic acid aryl esters of aliphatic and aromatic amines and polyamines, to a process for their preparation and to -~
their use as flame retardants and as cocondensable -5 components in oligo and polycondensates based on monomers -~-containing hydroxyl groups. ~
Compounds containing phosphorus, especially phosphonic ~-~ ~ acid esters, are highly effective flam~ retardants used ; in f~oams, thermoplasts and duroplasts. One phosphorus~
10~ containing compound commonly used for this purpose $s dimethyl methylphosphonate (DMMP), as described in EP~0~108 713, but the use~of DMMP does entail difficulties.
Firstly,~the~substance is a re~atively volatile liquid bp~.181~-C~)~so thatlt may~get~lo6t by volatilization, espec-~ially at~elevated temper~atures; secondly, ~ike mostphosphonic~cid~esters~of lower al-iphatic alcohols, it has~an~al~ylating~aotion in the presence of substances -~
capabIe of being~alkylated, such as amines.
EP 0 149 48~ describes the use of phosphonic acid 20 ~sa?ts of methane phosphonic acid in which the disadvantages ~-m~ntioned above~are less severe but there are m~ny appli-catlons for~which~flame retardants in the form of -alts ; cannot~be~used without;~reservations, e.g. in thermoplasts used in the electrical field.
~ ~ It was an object~of the present invention to pr~ovide a class of compounds which would be less volatile than the known classes of~substances and would at the same -~
Le A 27 222 . .

7 ~

time provide good flame retardancY-and would be free from alkylating properties.
This problem is solved according to the invention by providing aminomethane phosphonic acid aryl esters corresponding to the following general formula tI) and salts thereof:
r, ¦¦,OR3 ]
R1~N-CH2-P~ 4 ~ I ) wherein R1 ~tands for a monovalent or polyvalent, optionally substituted, mononuclear or multinuclear aromatic group, a monovalent or Polyvalent, optionally substituted aryl~ne alkylene group, an optionally substitued aliphatic group, an H atom, a group corresponding to the followina formula . .
O
¦¦,OR5 I:5 2 ~oR6 an nth part of a group of the formula R7 ~ q ~
n ~:~ a -C- group when n = 2, an optionally substituted amino : group or a CH2-OH group, n stands for an integer with a value from 1 to 100, R stands for an optionally substituted aromatic group, an optionally substituted heteroaromatic group, an -H-atom, a group corresponding to the following formula ¦I,ORS
-CH2-P~ 6 Le A 27 222 2 ~7078 ::

a -C-R7- group or a CH2-OH group, R3, R4, R5-and R6 denot-ing, independently of one another, aromatic groups or substituted aromatic groups, R7 stands for an H-atom, an optionally substituted ~liphatic group, an optionally substituted aromatic group, an optionally substituted hetero aromatic group, an option-~lly substituted amino or imino group or an optionally ~ubstituted aromatic, hetero aromatic or aliphatic group attached through oxygen or sulphur.
Salts of the aminomethane phosphonic acid aryl esters corresponding to the general formula (Ij are obtainable by the quaternization of one or more nitrogen atoms by means of alkyl;abing substances such as alkyl iodides, alkyl bromides or alkyl chlorides or phosphorous acLd esters or phosphoric acid esters or phosphonic acid esters or phosphin~c acid esters of lower aliphatic alcohols or by the partial saponification of one or more ester groups and neutralization with bases such as alkali metal hydroxides or amines.
;~ 20 ~ Examples of su~table aromatic groups include phenyl ;groups and substituted phenyl groups, e.q.~alkyl substituted isomeric methyl and dimethylphenyl groups, the isomeric mo~ ~nd diethylphenyl gn~, ths ~ ric mono-~nd di-isopropylphenyl groups, the isomeric mono- -~ ~nd~di-tcrt.-butylphenyl groups, i-octylphenyl, nonylphenyl, phenylphenyl, isopropylphenylphenyl, dodecylphenyl, methylenephenylphenyl, I~opropylidenephenylphenyl or cyclohexylphenyl, or halogenat~d phenyl groups, e.g.
the isomeric~mono- ~nd dichlorophenyl qroups, the isomeric 30;~mono- ~nd dibromophenyl groups or amino substituted phenyl ~-~roups~such as aminophenyl, or phenyl groups with mixed -~ubstituents.
The optio~ally sabstituted alkyl groups may be unsub-stituted and straight chained alkyl groups such as methyl, ethyl, n-propyl, n-butyl, etc. ~nd isomers thereo, such Le A 22 i22 3 .
:.,,;~:

~ 7 (~ 7 8 as i-propyl, i-butyl, tert;-butyl, etc.. The substituted alkyl groups may be monohydroxyl-substituted or poly-hydroxyl-substituted straight chain or branched groups, e.g. the CH2-OH group, the CH2-CH2-OH group, the CH2-CH2-CH2-O~ group, the CH2-CH(OH))-CH3 group; the CH2-C~(OH)-C2H5 group or the =CH2-CH(OH)-C~2-Cl group;
or mono- or polyamino substituted straiqht chained or branched groups, e.g. the CH2-NH2 group, the CH2-CH2 NH2 ~ro~p, the C~2-CH2-CH2-NH2 qroup or the CH2~CH(NH2)-CH~
group or imino substituted groups, halogen substituted alkyl groups or mixed substituted alkyl groups.
- The invention further relates to a process fo~ the preparation of aminomethanephosphonic acid aryl esters corresponding to the general formula (I) ~5 CH2-~ R~ ~n ~I) wherein R1 stands for a monovalent or polyvalent, optionally substituted, mononuclear or multinuclear aromatic group, ~ . ;
a monovalent or polyvalent, oPtionallv substituted arylene alkylene group, an optionally substituted aliPhatic group, an H atom, a group corresponding to the following formula i ¦¦pRS
-CH2-~ 6 an nth part of a group of the formula R
n Le A 27 222 4 2~ 7~78 .
o a -C- group when n = 2, an optionally substituted amino group or a-CH2-OH group, n stands for an integer with a value from 1 to 100, R2 stands for an optionally substituted aromatic group, 5 an optionally substituted heteroaromatic group, an H :~
atom, a group corresponding to the following formula o ¦¦,OR5 ' O
a group of the formula -C-R7 or a CH2-OH group, R3, R4, R5 and R6 denote, independently of one another, aromat$c or substituted aromatic groups, and : . R7 stands for an H atom, an optionally substituted aliphatic group, an optionally substituted aromatic group, an option-ally substituted hetero aromatic group, an optionally substituted amino or~imino group or an optionally sub-stituted aromatic, heteroaromatic or aliphatic group : a:ttached through bxygen or sulphur by~the reaction of a nitrogen-containing compound correspond-:~
: ing to the general formula (II) ]n (II) 20 wherein~ :
R1, R2 and n have the meanings indicated a~ove with a triarylphosphite corresponding to the general formula.(III) R4 ~III) ~ `OR
:

Le A 27 222 5 a~7g wherein ~3, R4 and R8 stand for identical or different aromatic groups in a molar ratio of from 0.01 to 100 mol-~, based on S the NH functions present, and with paraformaldehyde in a ratio of from 100 to 600 mol-~ of paraformaldehyde, based on the triarylph~sphite, at temperatures from 20 to 300C.
The paraformaldehyde may be supplied in the form of gaseous formaldehyde.
Compounds which are exceptionally rich in phosphorus may be prepared by using, as nitrogen-containing compound, a compound containing more than one NH function.
- The reactions proceed particularly smoothly if the ~5 triarylphosphite is used in less than the stoichiometric quantity, based on all the NH functions present.
The reactions are preferably carried out at temperatures from 90 to 160C.
~; Processes in which the triarylphosphite used is tri-phenylphosphite and the nitrogen-containing compound is urea, ethylene diamine, o-phenylenediamine, m-phenylene diamine, p-phenylenediamine, isopropylene-bis-p-phenylene d~amine or derivatives thereof, acrylic acid amide, meth-acrylic acid amide or derivatives thereof or oligomeric 25 ~to polymeric adducts thereof are particularly preferred.
The optionally substituted nitrogen-containing compound, the triarylphosphite and paraformaldehyde may be reacted ,together by a single stage reaction.
It has been found particularly advantageous to employ ~-~ 30 a variation of the process in which the optionally substi-tuted, nitrogen-containing compound and the triarylphosphite ~are first introduced into the reaction vessel and the paraformaldehyde is 6ubsequently~added thereto.
It has also been found very advantageous to employ a process variation in which the optionally substituted, nitrogen.containing compound, the triarylphosphite and the paraformaldehyde are continuously reacted together.
Le A 27 222 ` 6 ~ 7 07 ~

The invention further relates in particular to amino-methane phosphonic acid aryl esters corresponding to the general formula (IV) O ¦¦,OR3 ~O~N~~C~~N~ I OR4 (IV) S wherein - -R1, R3 and R4 have the.meanings indicated above and R9 and R10, independently of one another and of R1 and R2, have the same meaningS as R1, and salts of these com- ~:;
- pounds as well as aminomethane phosphonic acid aryl e.sters 10 corresponding to the general--formula (V) .
..
~ 1lP R~ :
:;: R9~ ,CH2 P~ (V) O,N --~R--)---N~ 1 OR4 ;~:., ~ . ..
wherein R1, R3 and R4 have the meanings indicated above and :R9~and R10, which are independent of one another and lS~ of R~ nd R2, have the ame aean~ s R1 while R rtands or an organic group~ such as~an~optionally substituted .
. ~lkylene or optlonally substituted arylene, and salts of these compounds.
The:~minomethane: p osphonic acid ~ryl esters according .~ `:
~.: , to the invention are eminently suitable for use as flame retardants in foams uch as polyurethane foams, polyiso~
~: 20 cyanurate foams or polycarbodi~mide foams based on iso-cyanates or carbodiimides, thermoplasts such as polyethylene terephthalate, polybutylene terephthalate, polyamide 6, `~ polyamide 6,6, polycarbonate, polyvinyl chloride, poly- -acrylonitrile, polyacrylate, polymethacrylate, polybuta-diene, polystyrene and copolymers and cocondensates of various monomers and blends of different thermoplasts, Le A 27 222 7 ~0~7~

e.g. a polycarbonate/acrylonitrile/butadiene/styrene blend, and ~uroplasts such as phenol formaldehyde resins based on unsubstituted phenol, cresol, xylenol and higher homologous phenols, or formaldehyde resins based on aliphatic or aromatic amines such as urea, thiourea, dicyandiamide, melamine and the isomeric phenylene diamines; or resins based, for example, on maleic acid, phthalic acid, diols or styrene, optionally in combination with other flame retardants, e.g. triarylphosphates such as triphenylphosphate, diphenylcresylphosphate or tri-cresylphosphate, the isomeric isopropyl-phenyl phenyl-phosphates, the isomeric tert.-butylphenylphenyl-phosphates and isomeric ~-methylbenzylphenylphenyl-phosphates;or trialkylphosphates, e.g. triethylphosphate, 15 trichloroethylphosphate, trichloropropylphosphate, tris- ~-dichloropropylphosphate, ethylene glycol-bis-di-2-chloro-ethylphosphate, ethylene glycol-bis-di-2-chloropropyl-phosphate, diethylene glycol-di-2-chloroethylphosphate --or bis-chloromethyl-propanediol-bis-di-2-chloroethyl- - -20 phosphate; or phosphonic acid esters, e.g. methane phosphon-ic acid-dimethylester, methane phosphonic acid diphenyl-ester or benzene phosphonic acid diphenylester; or phos-phinic~acid;esters, e.g.;1-methoxy-1-oxophospholene, 1-phenoxy-1~-oxophospholer,~ or triphenylphosphane oxide;
25~ ~or~aliphatic or aromatio phosphanes, e.g. tributylphos-phane or tr~phenylphosphane; and salts of these compounds as well as combinations of these compounds. The aminomethane ~i~ `phosphonic acid aryl esters according to the invention are also eminently suitable as cocondensable components 30 in oligo and polycondensates based on monomers containing h hydroxyl qroups.
The following ic a general method of preparation of the compounds according to-the invention:
The nitrogen-containing compound which is to be substituted 35 is brought into contact with a triarylphosphite in a molar ratio of from 0.01 to 100 mol-~ per NH function present and with paraformaldehyde in a molar ratio of Le A 27 222 8 7 0 7 8 - ~

from 100 to 600 mol-~, based on the triarylphosphite present, at temperatures from 20 to 300C. When the vola-tile constituents have been distilled off after termina-tion of the re~ction, the compounds according to the S invention may be used for the purpose of the invention, optionally after purification by washing.
In a preferred embodiment, the compounds according to the invention are prepared as follows: -The quantities of nitrogen-containing compound and triarylphosphite corresponding to the required composi:
tion of the product are introduced into a reaction vessel equipped with stirrer and heated to 140 - 150C. The quantity of paraformaldehyde required for the desired composition of the product is slowly added gradua1ly ~-at this temperature without further heating, at such a rate that the reaction temperature does not fall below ~-140C or rise above 150C. When all the paraformaldehyde has been added and the reaction has been completed, the volatile constituents are distilled off in a vacuum.
The invention will now be illustrated in more detail .
with the aid of the following Examples (data for purity .
denote percentages of phosphorus unless otherwise indicated). ~ .

. ~ -;.

Le A 27 222 9 2707~

Examples Example 1 N-Diphenoxyphnsphonomethyl urea 72 g of product corresponding to a 94~ yield are prepared with a degree of purity of 91% by the reaction S of 15 g (0.25 mol) of urea, 77.5 g ~0.25 mol) of triphenyl-phosphite and 9 g ~0.30 mol) of paraformaldehyde by the instructions given and removal of 29.5 g of volatile products by distillation at a temperature of lSO-C ~nd a pressure of 2 mbar.
Example 2 N,N'-Bis(diphenoxyphosphonomethyl)-urea 127 g of product corresponding to a 92% yield are prepared with a degree of purity of 91% by the reaction of 15 g (0.25 mol) of urea, 155 g (0.5 mol) of triphenyl-phosphite and 18 g (0.6 mol) of paraformaldehyde by the instructions given and removal of 61 g of volatile products by distillation at a temperature of 150C and a pressure of 2 mbar.
ExamPle 3 N,N'-Bis(diphenoxyphosphonomethyl)-1,4-phenylenediamine 69 g of product corresponding to a 92% yield are prepared with a degree of purity of 88~ by the reaction of 13.5 g (0.125 mol) of 1,4-phenylenediamine, 77.5 g (0.25 mol) of triphenylphosphite and 9 g (0.3 mol) of -paraformaldehyde by the instructions given and removal 25~ ~of 31 g of volatile products by distillation at a tempera-ure of 150C and a pressure of 2 mbar.
ExamDle 4 N,N'-Bis(diphenoxyphosphonomethyl)-1,3-phenylene diamine 68 g of product corresponding to a 91% yield are prepared with a degree of purity of 87% by the reaction of 13.5 g (0.125 mol) of 1,3-phenylenediamine, 77.S g (0.25 mol) of triphenylphosphite and 9 g (0.3 mol) of paraformaldehyde~by the instructions given and removal of 32 g of volatile ~roducts by distillation at a temper-ature of 150C and a pressure of 2 mbar.
.

Le A 27 222 10 ,;,.~ " ~.
,~,, ., - , . . ..

Example 5 N,N',N~-Tris(diph~noxyphosphonomethyl)-melamine 203 g of product corresponding t~-a 94~ yield are prepared with a degree of purity of 90~ ~determined by 31P-NMR, sum of all tbe isomers) by the reaction of 31.5 g s (0.25 mol) of mel~mine, 232.5 g ~0.75 mol) of triphenyl-phosphite and 30.0 g (1.00 mol) of paraformaldehyde by the instructions given and removal of 78 g of volatile products by distillation at a temperature of 1S0C and a pressure of 2 mbar.
10 Example 6 N,N'-8is(diphenoxyphosphonomethyl)1,2-diamino- ~- -ethane 126 g of product corresponding to a 91% yield are prepared with a degree of purity of 90~ by the reaction of 15 g (0.25 mol) of ethylenediamine, 155 g (0.5 mol) Of triphenylphosphite and 20 g (0.66 mol) of paraformal-dehyde by the instructions given and removal of 64 g of volatile products by distillation at a temperature of 150C and a pressure of 2 mbar.
Exam~le 7 N-Diphenoxyphosphonomethylacrylamide 149 g of product corresponding to a 94~ yield are prepared with a de~ree of purity of 72% by the reaction -of 35.5 g (0.5 mol) of acrylamide, 155 g (0.5 mol) of triphenylphosphite, 18 g ~0.6 mol) of paraformaldehyde and 2 g (0.02 mol) of p-methoxyphenol as stabilizer by 25 the instructions given and removal of 61.5 g of volatile ~ -~
products by distillation at a temperature of 130C and a pressure of 2 mbar.

It will be appreciated that the instant specification ` 30 and claims are set forth by way of illustration and not limitation, and that various modifications and changes may be made without departing from the spirit and scope of the present invention.

.

Le A 27 222 11 :::

Claims (15)

1. A process for the preparation of an aminomethanephos-phonic acid aryl ester of the formula wherein R1 stands for a monovalent or polyvalent, optionally substituted, mononuclear or multinuclear aromatic group, a monovalent or polyvalent, optionally substituted arylene alkylene group, an optionally substituted aliphatic group, an H atom, a group of the formula , an nth part of a group of the formula , for a -?- group when n = 2, for an optionally substituted amino group or for a CH2-OH group, n stands for an integer with a value from 1 to 100, R2 stands for an optionally substituted aromatic group, an optionally substituted heteroaromatic group, an H atom, a group of the formula , a group of the formula -?-R7 or a CH2-OH group, R3, R4, R5 and R6 denote, independently of one another, unsubstituted aromatic or substituted aromatic groups, R7 stands for an H atom, an optionally substituted aliphatic group, An optionally substituted aromatic group, an optionally substituted heteroaromatic group, an option-ally substituted amino or imino group or for an optionally substituted aromatic, heteroaromatic or aliphatic group attached through oxygen or sulphur, comprising react-ing a nitrogen-containing compound of the formula at temperatures from 20 to 300°C with a triarylphosphite of the formula wherein R3, R4 and R8 stand for identical or different aromatic groups in a molar ratio of from 0.01 to 100 mol-%, based on the NH functions present, and with paraformaldehyde in a ratio of from 100 to 600 mol-% of paraformaldehyde, based on the triarylphosphite.
2. A process according to claim 1, wherein the nitrogen-containing compound is a compound containing more than one N-H function.
3. A process according to claim 1, wherein the tri-arylphosphite is used in less than the stoichiometric quantity, based on all the N-H functions present.
4. A process according to claim 1, wherein the reaction is carried out at temperatures from 90 to 160°C.
5. A process according to claim 1, wherein the tri-arylphosphite is triphenylphosphite.
6. A process according to claim 1, wherein the nitrogen-containing compound is urea, ethylenediamine, o-phenylene-diamine, m-phenylenediamine, p-phenylenediamine and isopropylene-bis-p-phenyldiamine, and derivatives thereof, acrylic acid amide and methacrylic acid amide and derivatives thereof and their oligomeric to polymeric adducts.
7. A process according to claim 1, wherein the optionally substituted, nitrogen-containing compound, the triaryl-phosphite and paraformaldehyde are reacted together in a single stage reaction.
8. A process according to claim 1, wherein the optionally substituted, nitrogen-containing compound and the triarylphosphite are introduced into the reaction vessel and the paraformaldehyde is subsequently added.
9. A process according to claim 1, wherein the optionally substituted, nitrogen-containing compound, the triaryl-phosphite and the paraformaldehyde are reacted together continuously.
10. An aminomethane phosphonic acid aryl ester of the formula wherein R1 stands for a monovalent or polyvalent, optionally substituted, mononuclear or multinuclear aromatic group, a monovalent or polyvalent, optionally substituted arylene alkylene group, an optionally substituted aliphatic group, an H atom, a group of the formula , an nth part of a group of the formula , for a -?- group when n = 2, for an optionally substituted amino group or for a CH2-OH group, n stands for an integer with a value from 1 to 100, R2 stands for an optionally substituted aromatic group, an optionally substituted heteroaromatic group, an H atom, a group corresponding to the following formula , a -?-R7- group or a CH2-OH group, R3, R4, R5 and R6 denot-ing, independently of one another, aromatic groups or substituted aromatic groups, R7 stands for an H-atom, an optionally substituted aliphatic group, an optionally substituted aromatic group, an optionally substituted hetero aromatic group, an option-ally substituted amino or imino group or an optionally substituted aromatic, hetero aromatic or aliphatic group attached through oxygen or sulphur or salts thereof.
11. An aminomethane phosphonic acid aryl ester according to claim 10, of the formula wherein R9 and R10, independently of one another and of R1 and R2, have the same meanings as R1, or salts thereof.
12. An aminomethane phosphonic acid aryl ester according to claim 10, of the formula wherein R9 and R10, independently of one another and of R1 and R2, have the same meanings as R1 while R stands for an alkylene or arylene group,or salts thereof.
13. A flameproof composition comprising a foam, thermoplastic or thermoset and an effective amount of an aminomethanephosphonic acid aryl ester according to claim 10, optionally in combination with other flameproofing agents.
14. A method of crosslinking oligo- or polycondensates of monomers containing hydroxy groups comprising reacting said oligo- or polycondensates with an aminomethane-phosphonic acid aryl ester according to claim 10.
15. A crosslinked oligo- or polycondensate of monomers containing hydroxy groups obtained according to the method according to claim 14.
CA002027078A 1989-10-07 1990-10-05 Aminomethane phosphonic acid aryl esters and a process for their preparation Abandoned CA2027078A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3933549A DE3933549A1 (en) 1989-10-07 1989-10-07 NEW AMINOMETHANPHOSPHONIC ACID ALTERES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE
DEP3933549.6 1989-10-07

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CA2027078A1 true CA2027078A1 (en) 1991-04-08

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EP (1) EP0422439A3 (en)
JP (1) JPH03167195A (en)
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WO2021028496A1 (en) 2018-08-15 2021-02-18 Chemische Fabrik Budenheim Kg Polymer composition comprising phosphonate flame retardant
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