CH522017A - Preparation of polymers contg phosphory and nitrogen - Google Patents

Abstract

Preparation of polymers contg phosphorys and nitrogen.. M1-. Is effected by reacting 1 mole of a compound of formula:- (where R is org. radical, Hal is Cl, Br or F, m is 3-12, n is O-m, and (2m-n) is 4, where Hal and R are bonded to P atoms and each P atoms is bonded to >=2 halogen atoms). (a) with m/4-m/2 moles of compound (II) R1(XH)4 (where X is O or NH, R1 is:- where A is C or PCl, Y1 is O, S, SO2, CH2 (C(CH3)2 and Y2 is H or in pairs form -S- bridges), or (b) with (2m-n)/8-(2m-n)/2 moles of a compound of formula:- (where R2 is H or alkyl, Z is a hydrocarbon group opt. containing heteroatoms or is a group:- phenylene or alkylene, V is O, S, SO, SO2 or P=O or a C1-6 hydrocarbon bridges, and a, b, c and d are 1-10, C2-18 alkylene or opt. substd. phenylene) and opt. treating the product with NH3 or primary or secondary amines. The polymers are useful as flame-proofing agents for textiles, synthetic resins and plastics.

Description

  

  
 



  Process for the production of polymers containing phosphorus and nitrogen
It has been found that the reaction of cyclic phosphonitrile halides with polyfunctional, alkoxylated amines or diamines gives rise to water-soluble condensation products which do not become water-insoluble even with long reaction times. These products are suitable, especially after prior reaction with ammonia, as highly effective flame retardants for cellulose textiles.



   The invention therefore relates to a process for the preparation of polymers containing phosphorus and nitrogen, which is characterized in that 1 mol of a phosphonitrile halide of the formula
EMI1.1
 where Hal is chlorine, bromine or fluorine,
R is an organic radical, m is an integer from 3 to 8, n is an integer from 2 to 2m, where 2 m-n is at least 2, and Hal and R are bonded to phosphorus atoms, with n to n moles of an alkoxylated amine
4 formula
EMI1.2
 implements,

   where R2 is hydrogen or low molecular weight alkyl,
Z is a hydrocarbon radical optionally containing heteroatoms or a radical of the formula
EMI1.3
  
EMI2.1
 or -alkylene-, X is a direct bond, -O-, w -SO-, -S02-,
EMI2.2
 or a straight-chain or branched, saturated or unsaturated, optionally substituted hydrocarbon bridge, with 1 to 6 carbon atoms between the benzene nuclei, and a, b, c and d are integers from 1 to 10, and
Alkylene contains 2 to 18 carbon atoms, is straight-chain or branched, saturated or unsaturated, substituted or unsubstituted and the benzene nuclei can carry substituents.



   As phosphonitrile halides of the formula (III), for. B. the reaction products of ammonium halides with phosphorus pentahalides, preferably of NH4Cl with PCl5, are in question. In general, you can directly the resulting mixtures or the fractions isolated therefrom, for. Use, for example, (PsNsCl6) (P4N4Cl8) or (PxNxCl-x), where x is 5 to 8 (cf. French Patent No. 1,281,571, page 1). A suitable mixture contains e.g. B.



     60-70% (P: IN: .Clf 10-15 O / o (P4N4Cl8) and the remainder a mixture (P.NxCl2x) with x = 5 to 8.



   The organic radical R is z. B. an optionally substituted hydrocarbon radical of the aliphatic, cycloaliphatic, aromatic or heterocyclic series bonded to the phosphorus atom via a hetero atom such as oxygen, sulfur or nitrogen. The radical R is preferably an aromatic radical such as phenyl. As an example, the compound of the formula
EMI2.3


<tb> <SEP> C1 <SEP> cl
<tb> <SEP> P
<tb> <SEP> N <SEP> N
<tb> ci <SEP> il <SEP> 1 <SEP> Phenyl
<tb> <SEP> P
<tb> C1 <SEP> / <SEP> XNt <SEP> \ Phenyl
<tb> are listed.



   The Z substituent when it stands for a hydrocarbon radical. is z. B. an aliphatic, optionally substituted radical with 1 to 22 carbon atoms (methyl, ethyl. IsoDroDyl, n-butyl, n-amyl. N-hexyl, n-oxyl. N-decyl. N-dodecyl. N-tetradecyl cetyl. Stearvl , Arachinvl.

  Behenvl, secondary Octvl. 2-Aethylhexvl, oxo Nonvl. oxo-Decvl Olevl. Benzvl Phenylether). a cycloaliphatic radical (cyclohexyl, 4-methylcyclohexyl, cyclooctyl) or an optionally substituted aromatic radical (phenyl, 2-, 3- or 4-methylphenyl, 3- or 4-chlorophenyl, 4-fluorophenyl, 4-bromophenyl, 2, 4- or 2,5-dichlorophenyl, 2- or 4-methoxy- or -ethoxyphenyl, 4-ethylphenyl, 2,4- or 2,5-dimethylphenyl, naphthyl-1 or naphthyl-2).



   The remainder Y is derived z. B. of the following diamines: 4,4'-diamino-1,1'-diphenyl, 4,4'-diamino-2,2'- or -3,3'-dimethyl-, -dimethoxy- or diethoxy- or -dichloro-l, l'-diphenyl, 4,4'-diamino-1,1'-diphenyl-3,3'-dicarboxylic acid, -3'-sulfonic acid, -2,2'- or -3,3'- disulfonic acid, 4,4'-diamino-2, 2'-dimethyl-1,1'-diphenyl-5-sulfonic acid, 4,4'-diamino-3,3'-dimethyl-1, 1'-diphenyl-6,6 '-disulphonic acid, 4,4'-dilamino-3,3'-dicarboxymethoxy-l, 1'-diphenyl-4,4'-diamino-1,1'-diphenyl ether, 4,4'-diamino-1, '-diphenyl sulfide-2,2'-disulfonic acid, 4,4'-diamino-1,1'-diphenylmethane, 1,1-di- (4'-aminophenyl) -ethane, 2,2-di- (4th '-aminophenyl) propane, cyclohexyl, phenyl,

   2-chlorophenyl- or 4-chlorophenyl-di- (4'-aminophenyl) methane, 4,4'-diamino-dibenzyl-2,2'-disulfonic acid, 4,4'-diamino-2,2'-disulfonic acid, 1,2-di- (4'-aminophenyl) -ethane, 1,4-di- (4'-aminophenyl) -butane, 1,6- (4'-aminophenyl) -hexane, 1,3- or 1 , 4-diaminobenzene, 1,3-diamino-4-methyl- or -4-chlorobenzene, 1,4-diamino-2-chlorobenzene, 1,2-diaminoethane, 1,2- or 1,3-diaminopropane, 1,4-diaminobutane,
1,6-diaminohexane, 1, 1O-diaminodecane, 1, 12-di-aminododecane, 1,1 8-diamino-octodecane.



  Mentionable compounds of the formula (1V) are, for. B. N-methyl-, N-ethyl-, N-isopropyl-, N-cyclohexyl-, N-benzyl-N, N-di- (2'-hydroxyethyl) amine, tris- (2'-hydroxyethyl) - amine, N, N-bis- (2'-hydroxypropyl) -N-2 "-hydroxyethylamine, bis- [4-N, N-di- (2'-hydroxylethyl) - or - (2'-hydroxypropyl) - aminophenylmethane, 1,2-bis- [4-N, N-di- (2'-hydroxyethyl) - or - (2'-hydroxypropyl) -aminophenvll-ethane, 1,2-bis-rdi- (2 ' -hydroxyethyl) - or - (2'-hvdrnxvnropyl) -amino -ethane or -propane, 4,4'-bis-rdi- (2'-hydroxyethyl) -aminol -1,1'-diphenyl, 1,4 -Bis- [di42'-hydroxyethyl) -amino] -benzene and the addition products of ethylene oxide or propylene oxide with the aforementioned compounds.

 

   The reaction of the phosphonitrile halides of the formula (III) with the compounds of the formula (IV) can be carried out in the presence or absence of solution or diluents or of cabalizers and in a wide temperature range.



   Suitable solvents or diluents are only solvents or diluents which are indifferent to the reactants, preferably those which dissolve at least one of the reactants, e.g. B. from the hydrocarbon series, preferably aromatic, optionally chlorinated or nitrated hydrocarbons, e.g.

  B. the benzene series, further ethers such as diethyl ether, diisopropyl ether, methyl butyl ether, D; oxane, furan, tetrahydrofuran, anisole, phenetole, tertiary amines, pyridine, the picolines, Ch: noline, dimethyl or diethylaminobenzene, N-methyl or N Aethylpiperidine, N-methyl- or N-ethyl-morpholine, amides such as dimethylformamide, dimethylacetamide, tetramethylurea, sulfoxides and sulfones such as dimethyl sulfoxide, tetramethylene sulfone and, as an organophosphorus solvent, hexamethylphosphoramide of the formula
EMI3.1

Suitable catalysts are, for. B. the tertiary amines mentioned above, especially triethylamine.



   The temperature can vary within wide limits, e.g. B. between 50C and +200 "C. At low temperatures, the reactivity of the reactants decreases and the solubility is also quite limited, so that in practice a temperature of about -20 ° C. is generally not fallen below - and if possible the reaction at a temperature that can be comfortably maintained, for example -10 "to 0 OC is implemented as the lower limit. On the other hand, at a high temperature the reaction rate is too high to allow good control of the reaction, so that temperatures of 100 cm to 200 ° C. are more likely to be used to complete the reaction in the case of sluggish reactants.

  By keeping the temperature constant, the conversion can be better controlled, so that reproducible and more uniform end products are obtained. In order to keep the temperature constant, a solvent which boils at the reaction temperature can be used. Temperatures from -10 "to 100 ° C. and in particular from 0 to 50" C. are preferred.



   The reaction probably takes place gradually with the formation of P-O-C bonds, e.g. B.
EMI3.2




  or in the presence of a tertiary base:
EMI3.3

Further, similar reaction steps result in oligomeric and polymeric condensation products.



   When the reaction is complete, you can use the reaction product z. B. by diluting with a suitable agent, preferably with an alcohol such as methanol, ethanol, isopropanol, or with another organic solvent such as acetone or chloroform, precipitate, then suction and dry.



   The use of an excess of phosphorus nitrile halide results in products. which can enter into further reactions due to their content of free halogen atoms.



   Residual halogen atoms can be converted by reaction with ammonia, primary or secondary amines. As amines z. B. aliphatic, cycloaliphatic, aromatic or heterocyclic primary or secondary amines such as methylamine, ethylamine, allylamine, dimethylamine, ethyleneimine, aniline, cyclohexylarmine, morpholine, piperidine, in question. The reaction with ammonia can be carried out either by introducing the condensation products into liquid ammonia, by passing gaseous ammonia through a suspension in a suitable medium, e.g.

  B. an alcohol such as methanol or ethanol or by entering the condensation products in an alcoholic ammoniacal solution in a wide temperature range (100 to + 100 "C, preferably 330 to +30 OC).



   In a further, subsequent reaction, ethylene oxide or propylene oxide can be added to the products reacted with ammonia.



   The products obtained serve as flame retardants for textiles, plastics and synthetic resins, as antistatic agents, heat stabilizers and agents for the anti-caking finish of textiles.



   In the following examples, the parts are parts by weight and the percentages are percentages by weight.



   The temperatures are given in degrees Celsius.



   example 1
37 parts of a mixture of cyclic phosphonitrile chlorides of the approximate composition 60-70 O / o (PNCl). 10-15 O / o (PNCl.) 4 and the remainder / 0 (PNCI.), Q are dissolved in 100 parts of dimethylformamide and, with external cooling, at 20 with a solution of 25 parts of 1,2-bis-rdi (2 ' -hydroxyäthyl) aminol-ethane in 100 parts of dimethylformamide.



  When the addition is complete, 27 parts of triethylamine are added, likewise at 20. The reaction mixture is stirred for 24 hours at room temperature, then left to stand for a further 3 days at room temperature and then treated with 200 parts of ethanol. The precipitate obtained is filtered off, washed with alcohol and dried. The slightly yellowish colored product is soluble in water and can be reprecipitated from the aqueous solution with ethanol. It is also soluble in dimethyl sulfoxide, but insoluble in alcohols, aliphatic and aromatic hydrocarbons, chlorinated hydrocarbons, ethers, ring ethers and acetone. The product is very hygroscopic.



   Example 2
10 parts of a mixture of cyclic phosphorodhornitrile chlorides (equivalent to Example 1) in 30 parts of dimethylformamide are mixed with a solution of 16 parts of an Anlaqerunsorodllktes of 7.2 mol of ethylene oxide in 1 Mnl of 1 2-bis-rdi- (2'- hvdroxyäthvl) -aminol -ethane added in 30 parts of nimethvlformamide.

  Then 7.5 parts of Tristhalatin are added and the reaction mixture is stirred at room temperature for 24 hours and then left to stand for 3 days (molasses. 100 parts of acetone are then added to the mixture, the precipitated product is filtered off, washed with acetone and dissolved in a little methanol again, filtered, and precipitated again with acetone. The slightly yellowish colored reaction product is soluble in water, alcohols and chloroform, but insoluble in ether, aromatic and aliphatic hydrocarbons, and in acetone.



   Example 3
34.8 parts of a mixture of cyclic phosphonitrile chlorides (cf. Example 1) in 100 parts of dimethylformamide are mixed under the conditions given in Example 1 with a solution of 15 parts of triethanolamine in 100 parts of dimethylformamide.



  Then 20 parts of triethylamine are added and the reaction mixture is stirred at 200 for 16 hours.



  Then methanol is added, the precipitate is filtered off, washed with methanol and dried. The product obtained is very soluble in water.



   Example 4
50 parts of the reaction product obtained in Example 1 are suspended in 200 parts of methanol.



  At 10 to 200, 10 parts of gaseous ammonia are slowly introduced. The reaction product is then filtered off, washed with methanol and dried. It is a white powder that is very soluble in water and in ethylene glycol, is sparingly soluble in methanol and ethanol and is insoluble in other solvents (optionally halogenated hydrocarbons such as benzene, toluene, xylene, chlorobenzene, in acetone, dimethylformamide, dimethyl sulfoxide) .

 

      PATENT CLAIMS 1. A process for the preparation of polymers containing phosphorus and nitrogen, characterized in that 1 mol of a phosphorus nitrile halide of the formula
EMI4.1
 wherein
R is an organic residue,
Hal is chlorine, bromine or fluorine, m is an integer from 3 to 8, and n is a number from 2 to 2m,
2m-n is at least 2 and
Hal and R are bonded to phosphorus atoms, with 4 to n moles of an alkoxylated amine
4 formula

** WARNING ** End of DESC field could overlap beginning of CLMS **.



   

 

Claims (1)

** WARNING ** Beginning of CLMS field could overlap end of DESC **. Residual halogen atoms can be converted by reaction with ammonia, primary or secondary amines. As amines z. B. aliphatic, cycloaliphatic, aromatic or heterocyclic primary or secondary amines such as methylamine, ethylamine, allylamine, dimethylamine, ethyleneimine, aniline, cyclohexylarmine, morpholine, piperidine, in question. The reaction with ammonia can be carried out either by introducing the condensation products into liquid ammonia, by passing gaseous ammonia through a suspension in a suitable medium, e.g. B. an alcohol such as methanol or ethanol or by entering the condensation products in an alcoholic ammoniacal solution in a wide temperature range (100 to + 100 "C, preferably 330 to +30 OC). In a further, subsequent reaction, ethylene oxide or propylene oxide can be added to the products reacted with ammonia. The products obtained serve as flame retardants for textiles, plastics and synthetic resins, as antistatic agents, heat stabilizers and agents for the anti-caking finish of textiles. In the following examples, the parts are parts by weight and the percentages are percentages by weight. The temperatures are given in degrees Celsius. example 1 37 parts of a mixture of cyclic phosphonitrile chlorides of the approximate composition 60-70 O / o (PNCl). 10-15 O / o (PNCl.) 4 and the remainder / 0 (PNCI.), Q are dissolved in 100 parts of dimethylformamide and, with external cooling, at 20 with a solution of 25 parts of 1,2-bis-rdi (2 ' -hydroxyäthyl) aminol-ethane in 100 parts of dimethylformamide. When the addition is complete, 27 parts of triethylamine are added, likewise at 20. The reaction mixture is stirred for 24 hours at room temperature, then left to stand for a further 3 days at room temperature and then treated with 200 parts of ethanol. The precipitate obtained is filtered off, washed with alcohol and dried. The slightly yellowish colored product is soluble in water and can be reprecipitated from the aqueous solution with ethanol. It is also soluble in dimethyl sulfoxide, but insoluble in alcohols, aliphatic and aromatic hydrocarbons, chlorinated hydrocarbons, ethers, ring ethers and acetone. The product is very hygroscopic. Example 2 10 parts of a mixture of cyclic phosphorodhornitrile chlorides (equivalent to Example 1) in 30 parts of dimethylformamide are mixed with a solution of 16 parts of an Anlaqerunsorodllktes of 7.2 mol of ethylene oxide in 1 Mnl of 1 2-bis-rdi- (2'- hvdroxyäthvl) -aminol -ethane added in 30 parts of nimethvlformamide. Then 7.5 parts of Tristhalatin are added and the reaction mixture is stirred at room temperature for 24 hours and then left to stand for 3 days (molasses. Then 100 parts of acetone are added to the mixture, the precipitated product is filtered off, washed with acetone and dissolved in a little methanol again, filtered, and precipitated again with acetone. The slightly yellowish colored reaction product is soluble in water, alcohols and chloroform, but insoluble in ether, aromatic and aliphatic hydrocarbons, and in acetone. Example 3 34.8 parts of a mixture of cyclic phosphonitrile chlorides (cf. Example 1) in 100 parts of dimethylformamide are mixed under the conditions given in Example 1 with a solution of 15 parts of triethanolamine in 100 parts of dimethylformamide. Then 20 parts of triethylamine are added and the reaction mixture is stirred at 200 for 16 hours. Then methanol is added, the precipitate is filtered off, washed with methanol and dried. The product obtained is very soluble in water. Example 4 50 parts of the reaction product obtained in Example 1 are suspended in 200 parts of methanol. At 10 to 200, 10 parts of gaseous ammonia are slowly introduced. The reaction product is then filtered off, washed with methanol and dried. It is a white powder that is very soluble in water and in ethylene glycol, is sparingly soluble in methanol and ethanol and is insoluble in other solvents (optionally halogenated hydrocarbons such as benzene, toluene, xylene, chlorobenzene, in acetone, dimethylformamide, dimethyl sulfoxide) . PATENT CLAIMS 1. A process for the preparation of polymers containing phosphorus and nitrogen, characterized in that 1 mol of a phosphorus nitrile halide of the formula EMI4.1 wherein R is an organic residue, Hal is chlorine, bromine or fluorine, m is an integer from 3 to 8, and n is a number from 2 to 2m, 2m-n is at least 2 and Hal and R are bonded to phosphorus atoms, with 4 to n moles of an alkoxylated amine 4 formula EMI5.1 implements what R2 hydrogen or low molecular weight alkyl, Z is a hydrocarbon radical optionally containing a hetero atom or a radical of the formula EMI5.2 or alkylene, X is a direct bond, -O-, --S -, - SO--, soo EMI5.3 or a straight-chain or branched, saturated or unsaturated, optionally substituted hydrocarbon bridge, with 1 to 6 carbon atoms between the benzene nuclei, and a, b, c and d are integers from 1 to 10, and Alkylene contains 2 to 18 carbon atoms, is straight-chain or branched, saturated or unsaturated, substituted or unsubstituted and the benzene nuclei can carry substituents. II. The polymers obtained by the process according to claim I.