JPH0812692A - New nitrogen-containing organic phosphorus compound and its production - Google Patents

Abstract

PURPOSE:To obtain a new compound useful as an additive for resins such as flame-retardant/resin improver, having high contents of phosphoric and nitrogen and excellent hydrophoblc nature. CONSTITUTION:This compound is expressed by formula I [(m) is 1-3; (n) is 0-2; m+n=3; R<1> and R<2> are each a 1-10C alkyl, alkenyl, cycloalkyl or an aryl of formula II (R<3> is a 1-4C alkyl; (L) is 0-3); R is triazine ring] such as a compound of formula III. The compound of formula I is obtained by dehydrohalogenating a halophosphoric diester of formula IV (X is Cl or Br) with melamine.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel nitrogen-containing organic phosphorus compound which is mainly useful as a resin additive such as a flame retardant and a method for producing the same, more specifically, a halophosphoric acid diester and dehalogenation of melamine. TECHNICAL FIELD The present invention relates to a nitrogen-containing organic phosphorus compound having a high phosphorus and nitrogen content and good thermal stability, which is produced by a hydrogenation reaction, and a method for producing the same.

[0002]

2. Description of the Related Art Organic phosphorus compounds, particularly phosphoric acid esters, are widely used as plasticizers and flame retardants for resins, and are known to exhibit excellent flame retardant action especially for resins containing oxygen atoms. . Typical phosphoric acid esters include triphenyl phosphate and tricresyl phosphate. However, these esters have a drawback that they are liable to volatilize, causing problems such as contamination of the working environment during extrusion / molding with resin, mold deposit, and exudation on the surface of the molded product. In response to this, it has been proposed to use a polyphosphate ester having good thermal stability.

On the other hand, it is well known that phosphorus and nitrogen as flame retardants have a synergistic effect, and is described in, for example, "Polymer Flame Retardancy = Its Chemistry and Practical Technology =" (1992, published by Taiseisha). Has been done. In particular, by combining an organic phosphoric acid ester and a triazine compound with a thermoplastic resin, it is possible to impart high flame retardancy without impairing the physical properties of the resin, for example, JP-A-54-38348 and JP-A-5-279513.
No. etc. However, triazine compounds,
In particular, melamine, which is generally used as a flame retardant, has a sublimation property and causes a problem of causing mold deposit during resin molding. On the other hand, for example, JP-A-2-180959
And Japanese Patent Application Laid-Open No. 5-194438 disclose a method of forming a salt of a phosphoric acid and a triazine compound. However, with this method, it is difficult to increase the concentrations of phosphorus and nitrogen, which are the active ingredients, and the hydrophilic property tends to cause deterioration of the electrical characteristics and appearance of the resin composition.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a nitrogen-containing organic phosphorus compound having a high phosphorus and nitrogen content, being hydrophobic and having good thermal stability, and a method for producing the same.

[0005]

Means for Solving the Problems As a result of intensive studies aimed at achieving the above-mentioned object, the present inventors have made halophosphoric acid diester a dehydrohalogenation reaction of melamine,
It was found that an organic compound containing both phosphorus and nitrogen and having good hydrophobicity and thermal stability was obtained, and the present invention was completed.

That is, the present invention has the general formula (2)

[0007]

Embedded image

(Wherein X is chlorine or bromine, R ¹ and R ² are independently C ¹ to C ¹⁰ alkyl group, alkenyl group, cycloalkyl group, or

[0009]

[Chemical 6]

(Wherein R ³ represents a C _{1 to} C ₄ alkyl group, and 1 represents an integer of 0 to 3). And a nitrogen-containing organic phosphorus compound represented by the following general formula (1), which is obtained by a dehydrohalogenation reaction of melamine, which is a single or different mixture of halophosphoric acid diester, and a method for producing the same. is there.

[0011]

[Chemical 7]

(Where m is an integer of 1 to 3, n is an integer of 0 or 1 or 2, the sum of m and n is 3, and R
¹ and R ² are each independently a C1 to C10 alkyl group, alkenyl group, cycloalkyl group, or

[0013]

Embedded image

(Wherein R ³ represents a C _{1 to} C ₄ alkyl group, and 1 represents an integer of 0 to 3), and R represents a triazine ring. ) Examples of the halophosphate diester represented by the general formula (2), which is a raw material of the present invention, include dimethyl chlorophosphate, diethyl chlorophosphate, methylethyl chlorophosphate, dipropyl chlorophosphate, diisopropyl chlorophosphate, and di-n-chlorophosphate.
Butyl, diisobutyl chlorophosphate, di-t-chlorophosphate
Butyl, methylbutyl chlorophosphate, di-n-chlorophosphate
Pentyl, dineopentyl chlorophosphate, di-chlorophosphate
n-hexyl, di-n-octyl chlorophosphate, di-2-ethylhexyl chlorophosphate, di-n-decyl chlorophosphate, diallyl chlorophosphate, dibutenyl chlorophosphate, dicyclohexyl chlorophosphate, diphenyl chlorophosphate, dicresyl chlorophosphate, chlorophosphate Dixylyl, di (trimethylphenyl) chlorophosphate, di (ethylphenyl) chlorophosphate, di (propylphenyl) chlorophosphate, di (isopropylphenyl) chlorophosphate, di (butylphenyl) chlorophosphate, phenylcresyl chlorophosphate, chlorophosphoric acid Phenylxylyl, dimethyl bromophosphate, diethyl bromophosphate, methylethyl bromophosphate, dipropyl bromophosphate, diisopropyl bromophosphate, di-n-butyl bromophosphate, di-2-ethylhexyl bromophosphate, di-n-decyl bromophosphate, Mo phosphate diallyl, bromo phosphate Jibuteniru, bromo acid dicyclohexyl, bromo diphenyl phosphate, bromo phosphate dicresyl, bromo phosphoric dixylyl, but like bromo phosphate di (trimethylphenyl) may be mentioned as particularly preferred ones, chloro diphenyl phosphate,
There are dicresyl chlorophosphate and dixylyl chlorophosphate.
These halophosphoric acid diesters can be synthesized, for example, by adding a 2-fold molar amount of the corresponding alcohols and / or phenols to phosphorus oxyhalide under a Lewis acid catalyst, and performing a dehydrohalogenation reaction. .

The dehydrohalogenation reaction of the halophosphoric acid diester of the general formula (2) with melamine is usually carried out under anhydrous conditions at 10
It is carried out at a temperature of 0 to 200 ° C. and is almost completed in 2 to 10 hours. The desorbed hydrogen halide reacts with melamine and its decomposed product, such as ammonia, to form a salt. Therefore, the charge amount of melamine to the halophosphoric acid diester of the general formula (2) is usually at least twice the equivalent, Equimolar to 2
The range of double mole (3 to 6 equivalents) is desirable. Since the viscosity of the reaction product increases with the progress of the reaction, the reaction temperature is raised as necessary to complete the reaction.

The resulting reaction product contains, in addition to the compound of the general formula (1), the above-mentioned hydrochloride, and a small amount of diarylphosphoric acid ester amide, etc., depending on the conditions. Of these, hydrochlorides can be removed by washing with water or the like. A hydrophilic solvent of about the same weight is added to the product to form a low-viscosity slurry, which is mixed with at least twice the amount of warm water, whereby efficient washing can be performed. Examples of the hydrophilic solvent used here include alcohols such as methanol and ethanol,
Examples thereof include ketones such as acetone and methyl ethyl ketone, ethers such as tetrahydrofuran, and the like.

[0017]

EXAMPLES The present invention will be specifically described below with reference to examples.

[0018]

Example 1 135 g (0.5 mol) of diphenyl chlorophosphate and 63 g (0.5 mol) of melamine were placed in a 500 ml three-necked flask equipped with a stirrer, and under a dry nitrogen stream at 120 ° C. for 2 hours at 150 ° C. The reaction was performed for 2 hours at 180 ° C. for 2 hours to obtain a reaction product as a white lump.

To this reaction product, 100 g of ethanol was added, and the mixture was heated and stirred to form a low-viscosity slurry, which was poured into 1000 ml of stirring pure water, which was then heated and stirred under reflux for another 30 minutes. Then, the white powder was collected by filtration while hot and dried under reduced pressure to obtain 128 g of a compound. The elemental analysis value of the obtained composition is C: 54.7 wt.
%, H: 4.4 wt%, N: 13.7 wt%, O: 1
7.5 wt%, P: 9.5 wt%, Cl: 0.2 wt%
And the theoretical value of the compound of structural formula (A) (C: 54.9 wt
%, H: 4.1 wt%, N: 14.2 wt%, O: 1
(6.3 wt%, P: 10.5 wt%).

[0020]

[Chemical 9]

The 5% weight loss temperature measured by the thermobalance method is 3
It was 20 ° C. This compound was mixed with modified PPE resin, which is a mixture of polyphenylene ether and polystyrene, and subjected to a flame retardancy test and a high temperature and high humidity exposure test. As a result, excellent hydrolysis resistance and high flame retardance performance due to the addition of a small amount showed that.

[0022]

INDUSTRIAL APPLICABILITY According to the present invention, a novel nitrogen-containing material having a high phosphorus and nitrogen content, being hydrophobic and having good thermal stability, which is mainly useful as a resin additive such as a flame retardant and a resin modifier. An organic phosphorus compound can be obtained.

Claims (4)

[Claims] 1. A nitrogen-containing organic phosphorus compound represented by the following general formula (1). Embedded image (In the formula, m is an integer of 1 to 3, n is an integer of 0 or 1 or 2, the sum of m and n is 3, and R ¹ and R ² are independently C ¹ to C ¹⁰ alkyl. Group, alkenyl group, cycloalkyl group, or (Here, R ³ represents a C ₁ -C ₄ alkyl group, and l is 0
Represents an integer of 3), and R represents a triazine ring. ) 2. The compound according to claim ¹ , wherein R ¹ and R ² in the general formula (1) are each independently a phenyl group, a cresyl group or a xylyl group. 3. A compound represented by the general formula (2): (In the formula, X is chlorine or bromine, R ¹ and R ² are independently C 1
To C10 alkyl group, alkenyl group, cycloalkyl group, or (Here, R ³ represents a C ₁ -C ₄ alkyl group, and l is 0
Represents an integer of 3). The method for producing the compound according to claim 1, wherein the halophosphoric acid diester represented by the formula (4) and melamine are subjected to dehydrohalogenation reaction. 4. X in the general formula (2) is chlorine, R ¹ ,
The method for producing a compound according to claim 3, wherein R ² is independently a phenyl group, a cresyl group or a xylyl group.