JPH0812688A - New nitrogen-containing organic phosphorus compound and its production - Google Patents

Abstract

PURPOSE:To obtain a new compound useful as a flame-retardant for resins, having high contents of phosphorus and nitrogen and excellent thermal stability. CONSTITUTION:This compound is expressed by formula I [(n) is 1-15; R<1> to R<4> are each a 1-10C alkyl, cycloalkyl, etc.; R<5> and R<6> are H or 1-3C alkyl; R<7> is a 1-6C alkyl, alkenyl, phenyl-C(0), etc.)] such as a compound of formula II. The compound of formula I is obtained by dehydrohalogenating a dihalophosphoric ester of formula III and/or formula IV (X is Cl or Br) as a single substance or a mixture of different substances of a halophosphoric diester with a compound of formula V (R<3> is a 1-4C alkyl; (l) is 0-3) containing two amino groups in the molecule.

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 / or a dihalophosphoric acid ester. And a nitrogen-containing organic phosphorus compound having a high phosphorus and nitrogen content and good thermal stability, which is produced by a dehydrohalogenation reaction of a compound having two amino groups in the molecule, and a method for producing the same.

[0002]

2. Description of the Related Art Organophosphorus compounds, especially 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, low-volatile polyphosphate esters have been developed. For example, Japanese Patent Publication No. Sho 51-1985.
No. 8 and Japanese Examined Patent Publication No. 2-18336 show compounds of the general formula (5).

[0003]

[Chemical 6]

[Wherein n is 0 or an integer of 1 to 20, and R ¹ , R ² , R ³ and R ⁴ are independently a phenyl group, a hydroxyphenyl group or an aryl group having 1 to 3 alkyl groups substituted. represents a group, R ⁵ is a polyhydric phenol residue. 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 Actual Technology =” (1992, published by Taiseisha). There is. In particular, nitrogen-containing organic phosphorus compounds, which have good compatibility with resins and do not impair the physical properties of the composition, are expected as resin additives.

As an organic compound containing both phosphorus and nitrogen, for example, JP-A-2-180959 and JP-A-5-19443.
No. 8 is a salt of phosphoric acid and a triazine compound.
-55153 and JP-A-63-75088 describe 9,
1- of 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and its benzene nucleus substitution product
Compounds in which amines are bound to the 0-position through a methylene group, monophosphoric acid ester amides are disclosed in JP-A-63-235363, JP-A-54-119544 and JP-A-4-194544.
No. 145090 discloses organophosphazene compounds. However, these compounds have many problems such that it is difficult to increase the concentrations of phosphorus and nitrogen which are effective elements, there is a problem in thermal stability, or synthesis is difficult and the product is expensive.

[0006]

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

[0007]

DISCLOSURE OF THE INVENTION As a result of intensive studies to achieve the above-mentioned object, the inventors of the present invention dehalogenated halophosphoric acid diester and / or dihalophosphoric acid ester and a compound having two amino groups. It was found that a compound containing both phosphorus and nitrogen and having good thermal stability was obtained by the reaction, and the present invention was completed.

That is, the present invention relates to a halophosphoric acid diester and / or a dihalophosphoric acid ester represented by the general formulas (2) and / or (3), which are single or heterogeneous mixtures.
The present invention relates to a compound represented by the general formula (1), which is obtained by a dehydrohalogenation reaction of a compound having two amino groups in the molecule, and a method for producing the same.

[0009]

[Chemical 7]

[0010]

Embedded image

(X is Cl or Br, R ¹ and R ² are independently C _{1 to} C ₁₀ alkyl group, alkenyl group, cycloalkyl group, or

[0012]

[Chemical 9]

(Wherein R ³ represents a C _{1 to} C ₄ alkyl group, and l represents an integer of 0 to 3). )

[0014]

[Chemical 10]

[0015]

[Chemical 11]

Examples of the halophosphoric acid diester of the above-mentioned 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-butyl chlorophosphate, methylbutyl chlorophosphate, di-n-pentyl chlorophosphate, dineopentyl chlorophosphate,
Di-n-hexyl chlorophosphate, di-n-octyl chlorophosphate, di-2-ethylhexyl chlorophosphate, di-n-decyl chlorophosphate, diallyl chlorophosphate, dibutenyl chlorophosphate, dicyclohexyl chlorophosphate, diphenyl chlorophosphate, chlorophosphate Dicresyl, dixylyl chlorophosphate, di (trimethylphenyl) chlorophosphate, di (ethylphenyl) chlorophosphate, di (propylphenyl) chlorophosphate, di (isopropylphenyl) chlorophosphate, di (butylphenyl) chlorophosphate, phenyl chlorophosphate Zil, phenyl xylyl chlorophosphate, dimethyl bromophosphate, diethyl bromophosphate, methylethyl bromophosphate, dipropyl bromophosphate, diisopropyl bromophosphate, di-n-butyl bromophosphate, di-2-ethylhexyl bromophosphate, di-bromophosphate - decyl, bromo acid diallyl, bromo phosphate Jibuteniru, bromo acid dicyclohexyl, bromo diphenyl phosphate, bromo phosphate dicresyl, bromo phosphoric dixylyl, etc. bromo phosphate di (trimethylphenyl) and the like. Examples of the dihalophosphate ester represented by the general formula (3) include methyl dichlorophosphate, ethyl dichlorophosphate, propyl dichlorophosphate, isopropyl dichlorophosphate, n-butyl dichlorophosphate, isobutyl dichlorophosphate, t-butyl dichlorophosphate, dichlorophosphate. n
-Pentyl, neopentyl dichlorophosphate, n-hexyl dichlorophosphate, n-octyl dichlorophosphate, 2-ethylhexyl dichlorophosphate, n-decyl dichlorophosphate, allyl dichlorophosphate, butenyl dichlorophosphate, cyclohexyl dichlorophosphate, phenyl dichlorophosphate, cresyl dichlorophosphate. , Xylyl dichlorophosphate, trimethylphenyl dichlorophosphate, ethylphenyl dichlorophosphate, propylphenyl dichlorophosphate, isopropylphenyl dichlorophosphate, butylphenyl dichlorophosphate, methyl dibromophosphate, ethyl dibromophosphate, propyl dibromophosphate, isopropyl dibromophosphate, n-dibromophosphate Butyl, 2-ethylhexyl dibromophosphate, n-decyl dibromophosphate, allyl dibromophosphate, butenyl dibromophosphate, cyclohexyl dibromophosphate Le, dibromo acid phenyl, dibromo acid cresyl, dibromo acid xylyl include dibromo phosphate trimethylphenyl like. Particularly preferred are diphenyl chlorophosphate, dicresyl chlorophosphate, and dixylyl chlorophosphate. These halophosphoric acid diesters and / or dihalophosphoric acid esters can be used, for example, in the presence of a Lewis acid catalyst to give 1 to 1 to phosphorus oxyhalide.
It can be synthesized by adding twice the molar amount of the corresponding alcohols and / or phenols and conducting a dehydrohalogenation reaction.

The compound having two amino groups of the above-mentioned general formula (4) which is the other raw material of the present invention includes, for example, ethylenediamine, butylenediamine, hexamethylenediamine, phenylenediamine, urea, methylurea,
N, N ′ dimethylurea, N, N ′ diethylurea, oxalic acid diamide, guanidine, aminoguanidine, biuret, guanylurea, guanylthiourea, guanamine, methylguanamine, phenylguanamine, and the like are preferable. There are urea, N, N ′ dimethylurea and guanidine.

The dehydrohalogenation reaction of the compound of the general formula (2) and / or (3) with the compound of the general formula (4) is
Usually, the reaction is performed under anhydrous conditions at a temperature of 0 to 150 ° C., and is completed in about 2 to 10 hours. The eliminated hydrogen halide reacts with the compound of the general formula (4) and / or a decomposition product thereof to form a salt, so that the compound of the general formula (4) is used for the compound of the general formula (2) and / or (3). The amount of the compound (1) is usually equimolar (2 times equivalent) or more, and equimolar to 2
A double molar range 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.

In the reaction product obtained, in addition to the compound of the general formula (1) and the above-mentioned salts, the modified or decomposed product of the general formula (4) and the general formula (2) and / or A small amount of low molecular weight phosphoric acid ester amide and the like produced by the dehydrohalogenation reaction of the compound (3) is contained. Of these, salts can be removed by washing with water or the like. Efficient washing can be performed by dissolving the product in a hydrophilic solvent of about the same weight and mixing with water in an amount not less than twice the amount. Examples of the hydrophilic solvent used here include alcohols such as methanol and ethanol, ketones such as acetone and methyl ethyl ketone, and ethers such as tetrahydrofuran.

Each of the nitrogen-containing organic phosphorus compounds synthesized in this manner has a high phosphorus and nitrogen content and excellent thermal stability. Especially when used as a flame retardant for resins, a small amount is highly effective. Is obtained.

[0021]

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

[0022]

Example 1 135 g of diphenylphosphoric chloride
(0.5 mol) and 45 g (0.75 mol) of urea were charged into a 300 ml three-necked flask equipped with a stirrer and reacted under a dry nitrogen stream at 80 ° C. for 4 hours to give a slightly cloudy and extremely viscous reaction product. Obtained. 100 g of methanol is added to this reaction product.
Was added and heated and stirred to form a colorless transparent homogeneous solution, which was poured into 500 ml of stirred pure water. The white waxy component was recovered and dried under reduced pressure to obtain 123 g of the compound.

The elemental analysis value of the obtained composition was C: 5.
4.3 wt%, H: 4.6 wt%, N: 6.0 wt%,
O: 23.1 wt%, P: 12.0 wt%, Cl: 0.
The theoretical value of the compound of the structural formula (A) (C: 5) at 02 wt%.
7.3 wt%, H: 4.2 wt%, N: 5.3 wt%,
O: 21.4 wt%, P: 11.8 wt%).

[0024]

[Chemical 12]

[0025]

Example 2 162 g (0.5 mol) of di (2,6-dimethylphenyl) phosphoric chloride and 45 g of guanidine
(0.75 mol) was charged into a 300 ml three-necked flask equipped with a stirrer, and dried at 80 ° C for 2 hours under a dry nitrogen stream.
The reaction was carried out at 00 ° C. for 4 hours to obtain a viscous reaction product in which a white precipitate was dispersed.

100 g of methanol was added to this reaction product, and the mixture was heated and stirred to form a colorless transparent uniform solution, which was poured into 500 ml of stirring pure water. A white waxy component was recovered and dried under reduced pressure to give compound 145
g was obtained. The elemental analysis value of the obtained composition is C: 61.
0 wt%, H: 6.7 wt%, N: 7.2 wt%, O:
15.5 wt%, P: 9.5 wt%, Cl: 0.04w
The theoretical value of the compound of the structural formula (B) at t% (C: 62.3).
wt%, H: 6.3 wt%, N: 6.6 wt%, O: 1
(5.1 wt%, P: 9.7 wt%).

[0027]

[Chemical 13]

[0028]

Example 3 The weight loss behavior of the nitrogen-containing organic phosphorus compounds obtained in Examples 1 and 2 was measured by TGA (FIG. 1). High thermal stability was observed for triphenyl phosphate and tricresyl phosphate. Measurement conditions Sample amount: Approximately 20 mg Measurement atmosphere: He 100 ml / min Heating rate: 20 ° C / min

[0029]

Example 4 The nitrogen-containing organic phosphorus compound obtained in Examples 1 and 2 was added to polyphenylene ether 50%, polystyrene 5
When mixed with 0% modified PPE resin and subjected to a flame retardancy test, high flame retardancy was exhibited by adding a small amount.

[0030]

As is apparent from the examples, according to the present invention, the phosphorus and nitrogen contents are high and the thermal stability is good.
In particular, a novel nitrogen-containing organic phosphorus compound useful as a flame retardant for resins can be obtained.

[Brief description of drawings]

FIG. 1 is a graph showing the TGA heating loss of the nitrogen-containing organic phosphorus compound of the present invention.

[Explanation of symbols]

1: Curve showing heating loss for the nitrogen-containing organic phosphorus compound obtained in Example 2: Curve showing heating loss for the nitrogen-containing organic phosphorus compound obtained in Example 2: 3: Heating loss of triphenyl phosphate Showing the curve 4: Curve showing the heat loss of tricresyl phosphate

Claims (2)

[Claims] 1. A nitrogen-containing organic phosphorus compound represented by the following general formula (1). Embedded image 2. A halophosphoric acid diester and / or a dihalophosphoric acid ester represented by the general formula (2) and / or (3), which is a single or a heterogeneous mixture, and an intramolecular compound represented by the general formula (4). A compound having two amino groups,
The method for producing a compound according to claim 1, wherein a dehydrohalogenation reaction is carried out. Embedded image Embedded image (X is Cl or Br, R ¹ and R ² are independently C _{1 to} C ₁₀
An alkyl group, an alkenyl group, a cycloalkyl group, or (Here, R ³ represents a C ₁ -C ₄ alkyl group, and l is 0
Represents an integer of 3). ) [Chemical 5]