JP2001002685A - Phosphazene composition and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition useful as e.g. a flame retardant intended for plastics and free from concern about emitting dioxins when burnt by including a specific cyclic phosphazene and a specific chain phosphazene so as to be a specific level or lower in the total halogen content of the final composition. SOLUTION: This composition is obtained by including a cyclic phosphazene of formula I (Ar is an aryl; m is 3-10) and a chain phosphazene of formula II (n is 1-7) so as to be <=0.05 wt.% in the total halogen content of the final composition; more precisely, this composition is obtained by reaction of an alkali metal phenolate of the formula ArOM (M is an alkali metal) (e.g. sodium phenolate) with a mixture of a cyclic halogenated phosphazene of formula II (X is a halogen) and a chain halogenated phosphazene of formula IV in a solvent such as toluene containing a nitrogen-contg. chain or cyclic organic compound (e.g. N,N-dimethylformamide) pref. at 60-100 deg.C for 0.5-24 h.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a phosphazene composition and a method for producing the same.

[0002]

2. Description of the Related Art There is a report on a method for producing phosphazenes as follows. Yokoyama [Nippon Kagaku Magazine Vol. 81, No. 3, p481 (1960)] discloses a condensation reaction of phenols with triphosphonitrile chloride catalyzed by pyridine.

[0003] However, according to the above-mentioned Japanese Chemical Magazine, Vol. 81, No. 3, p 481 (1960), the obtained phenyl phosphonitrile is not a solid but a yellow viscous liquid containing many impurities and cannot be purified.

Japanese Patent Application Laid-Open No. 58-219190 discloses a polyhydroxyphenyl ester of phosphonitrilic acid having a phenolic hydroxyl group, which is substantially free of polycondensate and residual chlorine, and a process for producing the same. I have. This is obtained by reacting a phosphonitrile halide and a sodium salt or a K salt of monomethoxyphenol in which one of the hydroxyl groups of the dihydric phenol is protected with a methyl group to obtain phosphonitrilic acid polymethoxyphenyl ester,
A polyhydroxyphenyl ester of phosphonitrile having a phenolic hydroxyl group, characterized by reacting pyridine hydrohalide to convert a methoxy moiety into a hydroxyl group, and a method for producing the same.

However, in Japanese Patent Application Laid-Open No. 58-219190, 1.1 times of Na salt of monomethoxyphenol is used with respect to 1 chlorine of phosphonitrile halide, and the reaction is carried out in a tetrahydrofuran solvent. The reaction time is 14 hours at room temperature and 3 hours at reflux temperature, and the residual chlorine content is 0.175%.

Further, halogen-based flame retardants have been used as a flame retardant to be added to plastics. However, there is a possibility that harmful halogen-based gas is generated at the time of combustion or harmful substances such as dioxin are generated. Therefore, a non-halogen flame retardant is required at present. The phosphazenes represented by the general formulas (4) and (5) do not contain a halogen in the structural formula, but all of X in the general formulas (1) and (2) are necessarily replaced by a conventional production method. It cannot be converted to an aryloxy group, and some compounds of the product are in a state where X remains in the structural formula.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned disadvantages of the prior art and to provide a novel production method capable of obtaining a phosphazene composition having a very low halogen content without purification. Another object of the present invention is to provide a phosphazene composition having a total halogen content of 0.05% by weight or less.

[0008]

The inventors of the present invention have conducted intensive studies on the reaction conditions (catalyst, solvent and reaction temperature) which essentially do not leave halogen in the structural formula of the product in the production of phosphazene. The inventors have found that, when a halogenated phosphazene and an alkali metal phenolate are reacted in a solvent containing a nitrogen-containing organic compound, a phosphazene composition containing virtually no halogen can be obtained, and the present invention has been completed. is there. According to the production method of the present invention, the halogen content in the phosphazene composition is at most 0.05% by weight or less, preferably 0.01% by weight or less.
It can be:

The halogenated phosphazene generally has the following general formula (1)

Embedded image (In the formula, X is a halogen, and m is an integer of 3 to 10.)
And a cyclic halogenated phosphazene represented by the following general formula (2)

Embedded image (Wherein, X is a halogen and n is an integer of 1 to 7), and is obtained in the form of a mixture with a chain halogenated phosphazene represented by the following general formula: Equation (4)

Embedded image (Wherein, Ar is an aryl group, and m is an integer of 3 to 10), and the following general formula (5)

Embedded image (Wherein, Ar is an aryl group, and n is an integer of 1 to 7), which is a mixture with a chain phosphazene represented by the following formula: wherein the total halogen content is 0.05% by weight or less. A major feature of the present invention is that a product is obtained, which can be used as it is as a flame retardant such as plastics.

That is, the first of the present invention is the following general formula (4)

Embedded image (Wherein, Ar is an aryl group and m is an integer of 3 to 10), and the following general formula (5)

Embedded image (Wherein, Ar is an aryl group and n is an integer of 1 to 7), wherein the total halogen content is 0.05% by weight or less. About things.

That is, the second aspect of the present invention is the following general formula (1)

Embedded image (In the formula, X is a halogen, and m is an integer of 3 to 10.)
And a cyclic halogenated phosphazene represented by the following general formula (2)

Embedded image (Wherein X is a halogen and n is an integer of 1 to 7), and a mixture with a chain halogenated phosphazene represented by the following general formula (3):

Embedded image Wherein Ar is an aryl group and M is an alkali metal, wherein an alkali metal phenolate is reacted in a solvent containing a nitrogen-containing chain or cyclic organic compound. Equation (4)

Embedded image (Wherein, Ar is an aryl group and m is an integer of 3 to 10), and the following general formula (5)

Embedded image (Wherein, Ar is an aryl group, and n is an integer of 1 to 7) and a chain phosphazene represented by the following formula:

According to the conventional method, unsubstituted halogen-containing compounds remain in the phosphazene composition. For a solid phosphazene composition, it is possible to remove the unsubstituted halogen-containing compound by recrystallization, but the recrystallization must be repeated many times. Further, since a liquid phosphazene composition cannot be distilled, it is impossible to obtain a phosphazene composition containing no halogen by purification. The present invention solves the above problem, and succeeded for the first time in reducing the halogen content to 0.05% by weight or less, thereby making it possible to obtain an additive free from generation of dioxin.

The halogenated phosphazene used as a raw material in the present invention is not particularly limited, and the cyclic halogenated phosphazene of the general formula (1) may be a single product such as a trimer or a mixture of a trimer and a tetramer. Or an oligomer containing a large amount of trimers and tetramers, and a single product or a mixture of n or more as the chain halogenated phosphazene of the general formula (2), or an oligomer containing many n = 2 All of which can be mentioned, in particular, trimer and 4
Oligomers rich in monomers are preferred. The present invention can also use crude halogenated phosphazene products containing impurities. The halogenated phosphazene in which the condensation reaction between the halogenated phosphazene and the alkali metal phenolate is not completed and the halogen component remains remains usable as a raw material.

A method for synthesizing a halogenated phosphazene is described, for example, in Yokoyama [Nippon Kagaku Magazine Vol. 80, No. 10, p118 (1)
959)], a cyclic and linear chlorophosphazene mixture is obtained by reacting phosphorus pentachloride and ammonium chloride in monochlorobenzene, and this chlorophosphazene mixture is recrystallized from petroleum ether to obtain mp. 1
It is known that it is reported that hexachlorophosphazene [general formula (1) m = 3] of white rhombic crystals at 12 to 113 ° C. is obtained. The relationship between m and n of the cyclic halogenated phosphazene represented by the general formula (1) and the chain phosphazene represented by the general formula (2) obtained by such a method is, for example, that m is 3 to 5. In addition, n is not always the same, such as 3 to 7.

The nitrogen-containing linear or cyclic organic compound includes, for example, amine compounds and amide compounds, and the use of amide compounds gives particularly preferable results. The addition amount is preferably 0.01 to 10 times the weight of the halogenated phosphazene. The nitrogen-containing linear or cyclic organic compound can also be used as a solvent, and is preferably 0.1 to 1.0 times by weight.

Examples of the amine compounds include triethylamine, tri-n-butylamine, pyridine,
2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,3-lutidine, 2,4-lutidine, 2,
5-lutidine, 2,6-lutidine, 3,4-lutidine,
3,5-lutidine, morpholine, piperidine, pyrrolidine, 1-methylpiperidine, 2-methylpiperidine,
-Methylpiperidine, 4-methylpiperidine, 2,6-
Lupetidine, 3,5-lupetidine, hexamethylenetetramine and the like.

The amide compounds include, for example,
N, N-dimethylformamide, N, N-diethylformamide, N-methyl-N-phenylformamide,
N, N-dimethylacetamide, N, N-diethylacetamide, 2-pyrrolidone, 3-pyrrolidone, 4-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone and the like.

The phenolate moiety in the alkali metal phenolates naturally constitutes the OAr group of the general formula (4) or (5) in the phosphazene composition which is the product. And this alkali metal phenolate is 1
Only one kind may be used, or two or more kinds may be used in combination. When two kinds are used in combination, it goes without saying that there are two kinds of aryloxy groups in the product. The alkali metal phenolates are alkali metal salts of phenols. Examples of the alkali metal include sodium and potassium. Examples of the phenols (phenol, naphthol and 4-phenylphenol) include monovalent phenol (substituted). C0 to C8 as substituents,
And divalent phenols (0 to 4 substituents, C1 to C8 straight-chain or branched alkyl groups as substituents) and the like.

Specific examples of the monovalent phenol include phenols such as phenol, 1-naphthol, 2-naphthol and 4-phenylphenol; o-cresol, m-phenol.
-Cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o
-Propylphenol, m-propylphenol, p-
Propylphenol, o-isopropylphenol, m
-Isopropylphenol, p-isopropylphenol, o-butylphenol, m-butylphenol, p
-Butylphenol, o- (2-methylpropyl) phenol, m- (2-methylpropyl) phenol, p-
(2-methylpropyl) phenol, o-tert-butylphenol, m-tert-butylphenol, p-tert-butylphenol, o-pentylphenol, m-pentylphenol, p-pentylphenol, o- (2-methylbutyl) phenol, m-
(2-methylbutyl) phenol, p- (2-methylbutyl) phenol, o- (3-methylbutyl) phenol, m- (3-methylbutyl) phenol, p- (3-
1-hydroxy-2, such as methyl butyl) phenol, o-tertiary amylphenol, m-tertiary amylphenol, and p-tertiary amylphenol.
-Methylnaphthalene, 1-hydroxy-3-methylnaphthalene, 1-hydroxy-4-methylnaphthalene, 1-
Hydroxy-5-methylnaphthalene, 1-hydroxy-
6-methylnaphthalene, 1-hydroxy-7-methylnaphthalene, 1-hydroxy-8-methylnaphthalene, 2
-Ethyl-1-hydroxynaphthalene, 3-ethyl-1
-Hydroxynaphthalene, 4-ethyl-1-hydroxynaphthalene, 5-ethyl-1-hydroxynaphthalene,
6-ethyl-1-hydroxynaphthalene, 7-ethyl-
1-hydroxynaphthalene, 8-ethyl-1-hydroxynaphthalene, 2-hydroxy-1-methylnaphthalene, 2-hydroxy-3-methylnaphthalene, 2-hydroxy-4-methylnaphthalene, 2-hydroxy-5
Methyl naphthalene, 2-hydroxy-6-methylnaphthalene, 2-hydroxy-7-methylnaphthalene, 2-hydroxy-8-methylnaphthalene, 1-ethyl-2-hydroxynaphthalene, 3-ethyl-2-hydroxynaphthalene, 4- Ethyl-2-hydroxynaphthalene, 5-
Ethyl-2-hydroxynaphthalene, 6-ethyl-2-
Monomethylphenols such as 2-methyl-4-phenylphenol and 2-ethyl-4-phenylphenol such as hydroxynaphthalene, 7-ethyl-2-hydroxynaphthalene, and 8-ethyl-2-hydroxynaphthalene; 2,3-xylenol; 2,4-xylenol,
2,5-xylenol, 2,6-xylenol, 3,4
-Xylenol, 3,5-xylenol, 2-ethyl-
6-methylphenol, 3-ethyl-6-methylphenol, 4-ethyl-6-methylphenol, 5-ethyl-6-methylphenol, 2-ethyl-3-methylphenol, 2-ethyl-4-methylphenol, 2-ethyl-5-methylphenol, 3-ethyl-4-methylphenol, 3-ethyl-5-methylphenol, 2-methyl-3-propylphenol, 2-methyl-4-propylphenol, 2-methyl-5 -Propylphenol, 2-methyl-6-propylphenol, 3-methyl-2-propylphenol, 4-methyl-2-propylphenol, 5-methyl-2-propylphenol, 3
-Methyl-4-propylphenol, 3-methyl-5
Propylphenol, 2-methyl-3-isopropylphenol, 2-methyl-4-isopropylphenol,
2-methyl-5-isopropylphenol, 2-methyl-6-isopropylphenol, 3-methyl-2-isopropylphenol, 4-methyl-2-isopropylphenol, 5-methyl-2-isopropylphenol,
3-methyl-4-isopropylphenol, 3-methyl-5-isopropylphenol, 2-butyl-6-methylphenol, 3-butyl-6-methylphenol,
-Butyl-6-methylphenol, 5-butyl-6-methylphenol, 2-butyl-3-methylphenol,
2-butyl-4-methylphenol, 2-butyl-5
Methylphenol, 3-butyl-4-methylphenol, 3-butyl-5-methylphenol, 2- (2-methylpropyl) -6-methylphenol, 3- (2-methylpropyl) -6-methylphenol, -(2-methylpropyl) -6-methylphenol, 5- (2-methylpropyl) -6-methylphenol, 2- (2-methylpropyl) -3-methylphenol, 2- (2-methylpropyl)- 4-methylphenol, 2- (2-methylpropyl) -5-methylphenol, 3- (2-methylpropyl) -4-methylphenol, 3- (2-methylpropyl) -5-methylphenol, 2- ( 3-methylpropyl) -6-methylphenol, 3- (3-methylpropyl) -6-methylphenol, 4- (3-methylpropyl) -6 Methylphenol, 5- (3-methylpropyl) -6-methylphenol, 2- (3-methylpropyl) -3-methylphenol, 2- (3-methylpropyl) -4-methylphenol, 2- (3- Methylpropyl) -5-methylphenol, 3- (3-methylpropyl) -4-methylphenol, 3- (3-methylpropyl) -5-methylphenol, 2-tert-butyl-6-methylphenol, 3- Tert-butyl-6-methylphenol, 4-tert-butyl-6-methylphenol, 5-tert-butyl-
6-methylphenol, 2-tert-butyl-3-
Methylphenol, 2-tert-butyl-4-methylphenol, 2-tert-butyl-5-methylphenol, 3-tert-butyl-4-methylphenol, 3-tert-butyl-5-methylphenol, 2,3 -Diethylphenol, 2,4-diethylphenol, 2,5-diethylphenol, 2,6-diethylphenol, 3,4-diethylphenol, 3,5
-Diethylphenol, 2,3-dipropylphenol, 2,4-dipropylphenol, 2,5-dipropylphenol, 2,6-dipropylphenol, 3,4
-Dipropylphenol, 3,5-dipropylphenol, 2,3-di-isopropylphenol, 2,4-di-isopropylphenol, 2,5-di-isopropylphenol, 2,6-di-isopropylphenol,
3,4-di-isopropylphenol, 3,5-di-isopropylphenol, 2,3-di-tert-butylphenol, 2,4-di-tert-butylphenol, 2,5-di-tert-butylphenol,
2,6-di-tert-butylphenol, 3,4-
Di-tert-butylphenol, 3,5-di-tert-butylphenol, 2,3-di-tert-amylphenol, 2,4-di-tert-amylphenol, 2,5-di-tert-amylphenol, 2 , 6-di-tert-amylphenol, 3,
4-di-tert-amylphenol, 3,5-di-
Tertiary amyl phenol, 1-hydroxy-2,
3-dimethylnaphthalene, 1-hydroxy-2,5-dimethylnaphthalene, 1-hydroxy-2,6-dimethylnaphthalene, 1-hydroxy-2,7-dimethylnaphthalene, 2-hydroxy-1,3-dimethylnaphthalene,
2-hydroxy-1,5-dimethylnaphthalene, 2-hydroxy-1,7-dimethylnaphthalene, 2-hydroxy-1,8-dimethylnaphthalene, 2,3-diethyl-
1-hydroxynaphthalene, 2,5-diethyl-1-hydroxynaphthalene, 2,6-diethyl-1-hydroxynaphthalene, 2,7-diethyl-1-hydroxynaphthalene, 1,3-diethyl-2-hydroxynaphthalene, 1 , 5-Diethyl-2-hydroxynaphthalene,
1,7-diethyl-2-hydroxynaphthalene, 1,8
2,6-diethyl-2-hydroxynaphthalene,
Examples thereof include dialkylphenols such as dimethyl-4-phenylphenol and 2,6-diethyl-4-phenylphenol.

Examples of the dihydric phenol include catechol, 1,2-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 3,4-dihydroxynaphthalene, o, o-biphenol and the like. Can be

In the production of the phosphazene of the present invention,
A conventional dispersant or ion exchange resin may be added.

As the dispersant, tetramethylammonium chloride, tetraethylammonium chloride,
Tetrabutylammonium bromide, tetrabutylammonium hydroxide, tetrabutylammonium hydrogensulfate, trilaurylmethylammonium chloride, di-hardened tallow alkyldimethylammonium acetate, trimethylphenylammonium chloride, benzyltrimethylammonium chloride, cetyltrimethylammonium chloride, stearyltrimethylammonium Chloride, distearyldimethylammonium chloride and the like.

As the ion exchange resin, Amberlite IR-116, IR-118 (H), IR-120B,
IR-122, IR-124 (trade name, manufactured by Organo Corporation)
And amber list 15, A-26, A-27, A-
21, 252, 200C, 200CT, IRC-50,
IRC-84, IRC-718, IRA-401, IR
A-402, IRA-400 (trade name, manufactured by Organo Corporation)
And the like.

As a reaction method, for example, after adding the nitrogen-containing chain or cyclic organic compound to a slurry of an alkali metal phenolate, the slurry is added dropwise to a solution of a halogenated phosphazene or a solution of the halogenated phosphazene is added to the slurry. The reaction may be carried out by dropping the solution. The reaction temperature is preferably from 40 to 140 ° C., particularly preferably 60 to 140 ° C.
-100 ° C is preferred. The reaction time is 0.5 to 24
Time is preferred. Any solvent may be used as long as it dissolves or disperses the raw materials and does not react with the reaction substrate.Examples thereof include toluene, xylene, hexane, heptane, cyclohexane, tetrahydrofuran, and 1,4-dioxane. Examples of the nitrogen-containing organic compound include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-
Dimethyl-2-imidazolidinone is preferred.

The nitrogen-containing chain or cyclic organic compound alone can be used as a solvent. In this case, for example, N, N-dimethylformamide,
N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone and the like are preferred.

The number of m and n in the obtained phosphazene composition depends on the number of m and n in the raw material, and the OAr in the general formulas (4) and (5) also depends on the OAr in the raw material. is there. The properties of the composition include liquid, wax, and solid. When OAr is a phenoxy group and m is 3, the melting point is 113 to 114 ° C., and when OAr is a phenoxy group and m = 4, it is 85.9.
８６86.7 ° C., and the weight ratio of m = 3 and m = 4 to 8
The mixture of the general formula (4) containing the mixture at a ratio of 0:20 has a melting point of 90 to 112 ° C., and the range of the melting point is widened. This is thought to be due to the fact that m = 4 acts as an impurity in contrast to m = 3. As described above, the melting point is lowered due to a decrease in the purity of m = 3 due to a decrease in the purity of m = 3. Therefore, in the case of a mixture, as the number of the mixed species increases, the melting point decreases, and the properties of the solid, the wax, and the liquid change. These solid, waxy and liquid phosphazenes have advantages in handling, making use of their properties, and appropriately select phosphazenes of appropriate properties according to the properties of the partner to be added as a flame retardant or the like. Can be used.

The halogen contained in the obtained phosphazene was analyzed by GC-MASS and coulometric titration. In the GC-MASS analysis, a compound containing a halogen was confirmed by mass spectrometry of each component. In the coulometric titration method, the obtained phosphazene was thermally decomposed, captured as hydrogen halide in an absorbing solution, and when an equivalent amount of silver was electrolyzed into silver halide, the amount of halogen was determined from the amount of electricity.

[0028]

The present invention will be described below in more detail with reference to examples, but the present invention is not limited thereto. The percentages below are percentages by weight except for the yield.

Example 1 87.5 g of 48% NaOH in a 1 L flask equipped with a stirrer, a thermometer, a fractionation receiver for measuring moisture, and a reflux condenser.
(1.05 mol), 220 mL of toluene and 98.8 g (1.05 mol) of phenol were charged and heated under stirring to carry out azeotropic dehydration (64 mL of recovered water) to remove the water in the flask, thereby performing Na salification of phenol. . This is 80
C. and cooled to 25.0 g of N, N-dimethylformamide.
(0.342 mol) and stirred at 80 ° C. under stirring at 80 ° C. in toluene solution of chlorophosphazene mixture ｛chlorophosphazene mixture [60.3% of m = 3 in the general formula (1), m
= 4 10.9%, m = 5 or more 19.7%,
9.1% of a chain phosphazene represented by the general formula (2)]
58.0 g (0.5 unit mol), toluene 275
mL｝ was added dropwise over 2 hours, and a stirring reaction was performed at the same temperature for 10 hours. After the reaction was completed, 200 mL of water was added to the flask to dissolve the inorganic salt, and then the organic layer was separated using a separating funnel. The organic layer was neutralized with 5% sulfuric acid, washed with water, toluene was distilled off, and brown wax-like phenoxyphosphazene was analyzed for chlorine by coulometric titration. The chlorine content was 0.00% by weight. Was.

Comparative Example 1 A flask equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel was charged with tetrahydrofuran and 42.0 g of 60% NaH.
(1.05 mol) and then stirred at room temperature. A solution obtained by diluting 98.8 g (1.05 mol) of phenol with 180 mL of tetrahydrofuran was gradually dropped from a dropping funnel. After the completion of the dropwise addition, the mixture was heated and stirred at 40 ° C. for 30 minutes. Next, the temperature is returned to room temperature. The obtained solution of Na salt of phenol in tetrahydrofuran is used directly in the next reaction. In a 1 L flask equipped with a stirrer, a reflux condenser, a thermometer, and a dropping funnel, 600 mL of a mixture of tetrahydrofuran and chlorophosphazene [m is represented by the general formula (1).
= 3, 60.3%, m = 4, 10.9%, m =
5 or more 19.7%, chain phosphazenes 9.1% represented by the general formula (2)] 58.0 g (0.5 unit)
mol) and stirred at room temperature. When the chlorophosphazene mixture was completely dissolved, the above solution of the phenol Na salt in tetrahydrofuran was gradually dropped from the dropping funnel. After completion of the dropwise addition, heating and stirring are continued for 24 hours. After the completion of the reaction, the mixture was cooled, insoluble materials were filtered off, and the filtrate was concentrated to obtain a mixture of 107.9 g of a phenoxyphosphazene mixture (yield).
93.2%). When the obtained phosphazene was analyzed for chlorine by coulometric titration, the chlorine content was 0.68% by weight.

Comparative Example 2 An experiment was conducted under the same conditions as in Example 1 except that the additive N, N-dimethylformamide was not used. As a result, the time required to complete the reaction was as long as 250 hours, and 108.8 g of the obtained phenoxyphosphazene mixture was obtained.
(Yield 94.0%) was a brown wax. When the obtained phosphazene was analyzed for chlorine by coulometric titration, the chlorine content was 0.21% by weight.

Example 2 Under the same conditions as in Example 1, a phenol Na salt slurry was added dropwise to a toluene solution of hexachlorophosphazene over 2 hours. As a result, 113.4 g (yield: 98.1%) of a brown wax-like phenoxyphosphazene mixture was obtained. When the obtained phosphazene was analyzed for chlorine by coulometric titration, the chlorine content was 0.00% by weight.

Example 3 An experiment was conducted under the same conditions as in Example 1 except that N, N-dimethylacetamide was used instead of N, N-dimethylformamide as an additive. As a result, 112.3 g (yield 97.0 g) of a brown wax-like phenoxyphosphazene mixture was obtained.
%). When the obtained phosphazene was analyzed for chlorine by coulometric titration, the chlorine content was 0.00% by weight.

Example 4 An experiment was conducted under the same conditions as in Example 1 except that N-methyl-2-pyrrolidone was used instead of N, N-dimethylformamide as an additive. As a result, 111.0 g (yield 95.9 g) of a brown wax-like phenoxyphosphazene mixture was obtained.
%). When the obtained phosphazene was analyzed for chlorine by coulometric titration, the chlorine content was 0.00% by weight.

Example 5 An experiment was conducted under the same conditions as in Example 1 except that 1,3-dimethyl-2-imidazolidinone was used as an additive instead of N, N-dimethylformamide. As a result, 111.1 g (yield: 96.0%) of a brown wax-like phenoxyphosphazene mixture was obtained. When the obtained phosphazene was analyzed for chlorine by coulometric titration, the chlorine content was 0.00% by weight.

Example 6 An experiment was conducted under the same conditions as in Example 1 except that xylene was used as the solvent instead of toluene. As a result, 112.3 g (yield) of a brown wax-like phenoxyphosphazene mixture was obtained.
97.1%). When the obtained phosphazene was analyzed for chlorine by coulometric titration, the chlorine content was 0.00% by weight.

Example 7 An experiment was conducted under the same conditions as in Example 1 except that dimethylformamide was used as the solvent instead of toluene. As a result, a brown wax-like phenoxyphosphazene mixture 110.
0 g (95.0% yield) was obtained. When the obtained phosphazene was analyzed for chlorine by coulometric titration, the chlorine content was 0.00% by weight.

Example 8 An experiment was conducted under the same conditions as in Example 1 except that the Na salt of phenol was used instead of the Na salt of phenol. As a result, 125.6 g (yield 97.0%) of a brown wax-like p-tolyloxyphosphazene mixture was obtained. When the obtained phosphazene was analyzed for chlorine by coulometric titration, the chlorine content was 0.00% by weight.

Example 9 An experiment was conducted under the same conditions as in Example 1 except that the phenol Na salt was used instead of m-cresol Na salt. As a result, 124.0 g (yield 96.0%) of a m-tolyloxyphosphazene mixture of a brown oil was obtained. When the obtained phosphazene was analyzed for chlorine by coulometric titration, the chlorine content was 0.00% by weight.

[0040]

(1) According to the present invention, a chlorine-containing compound cannot be confirmed by GC-MASS analysis, and 0.0
For the first time, it was possible to provide a phosphazene composition containing no more than 5% by weight, preferably no more than 0.01% by weight, of halogen in its structural formula. (2) The method of the present invention requires only a short reaction time and is economical. (3) Since the composition of the present invention does not contain a halogen as described above, there is no fear of generating dioxins during combustion.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08K 5/5399 C08K 5/5399 C08L 85/02 C08L 85/02 (72) Inventor Masayuki Nishimatsu Kobe, Hyogo Prefecture 1-3-3 Higashikawasaki-cho, Chuo-ku Chemipro Kasei Co., Ltd. (72) Inventor Tomoyuki Yamashita 1-3-3 Higashikawasakicho, Chuo-ku, Kobe-shi, Hyogo Pref. 1-3-3, Higashikawasaki-cho, Chuo-ku, Kobe-shi, Japan

Claims (3)

[Claims] 1. The following general formula (4): (Wherein, Ar is an aryl group and m is an integer of 3 to 10), and the following general formula (5): (Wherein, Ar is an aryl group and n is an integer of 1 to 7), wherein the total halogen content is 0.05% by weight or less. object. 2. The following general formula (1): (In the formula, X is a halogen, and m is an integer of 3 to 10.)
And a cyclic halogenated phosphazene represented by the following general formula (2): (Wherein X is a halogen, and n is an integer of 1 to 7), and a mixture with a chain halogenated phosphazene represented by the following general formula (3): Wherein Ar is an aryl group and M is an alkali metal, wherein an alkali metal phenolate is reacted in a solvent containing a nitrogen-containing chain or cyclic organic compound. Formula (4) (Wherein, Ar is an aryl group and m is an integer of 3 to 10), and the following general formula (5): (Wherein, Ar is an aryl group and n is an integer of 1 to 7.) A method for producing a phosphazene composition comprising a chain phosphazene represented by the following formula: 3. The nitrogen-containing linear or cyclic organic compound is at least one organic compound selected from the group consisting of amine compounds and amide compounds.
A method for producing the phosphazene composition described above.