JPH0613541B2 - Novel organic phosphorus compound and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel organophosphorus compound and a method for producing the same, more specifically, it is used as a raw material for polyester having excellent heat resistance and flame retardancy. The present invention relates to a novel organophosphorus compound that can be used as an additive such as a stabilizer or a flame retardant, and a method for producing the same.

(Prior Art) Conventionally, the following structural formula was used as a raw material of heat-resistant polyester having excellent flame retardancy and as an additive such as a stabilizer and a flame retardant
9,10-dihydro-9-oxa-1 represented by (III)
0-phosphaphenanthrene-10-oxide (HC
Derivatives having an ester-forming functional group of A) are known (Japanese Patent Publication No. 55-41610, etc.).

(Problems to be Solved by the Invention) However, if the compound represented by the structural formula (III) is added in an amount sufficient to impart sufficient flame retardancy to the polyester, the physical properties of the polyester may be impaired or the cost may be high. There was a problem of becoming.

Therefore, a main object of the present invention is to provide a novel and inexpensive organophosphorus compound capable of imparting a high degree of flame retardancy without impairing the good physical properties of polyester.

(Means for Solving Problems) In order to achieve the above-mentioned object, the inventors of the present invention have made earnest studies on organic phosphorus compounds that do not have the above-mentioned problems, and as a result, if they are organic phosphorus compounds having a specific structure, The present invention has been accomplished by finding that it can be used as a very suitable raw material of polyester, a stabilizer, a flame retardant, or the like.

That is, the present invention provides (1) an organophosphorus compound represented by the following general formula (I), (2) an organophosphorus compound represented by the following general formula (II), a cyclic conjugated diketone, an unsaturated dicarboxylic acid, and an unsaturated compound. The gist is a method for producing an organophosphorus compound represented by the following general formula (I), which comprises reacting an unsaturated compound selected from a dialkyl dicarboxylate and an unsaturated diol.

(However, R ₁ is an ethylene group or a 1,2-phenylene group, A is a trivalent benzene ring group, a trivalent naphthalene ring group or a trivalent aliphatic group having 2 to 4 carbon atoms, and R ₂ is-. OH or —COOR ₃ (R ₃ is a hydrogen atom or a lower alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a butyl group and an octyl group), and n is an integer of 1 or 2. Specific examples of-(R ₂ ) ₂ include the following.

The organic phosphorus compound represented by the general formula (I) of the present invention includes an organic phosphorus compound represented by the general formula (II) (referred to as phosphinic acid), a cyclic conjugated diketone (referred to as quinone), an unsaturated dicarboxylic acid, and an unsaturated dicarboxylic acid. It can be produced by reacting a dialkyl acid and an unsaturated compound selected from unsaturated diols in a solvent such as ethyl cellosolve.

Examples of quinones include benzoquinone, 2,6-naphthoquinone, and 1,4-naphthoquinone. Examples of unsaturated dicarboxylic acid and unsaturated dicarboxylic acid dialkyl include maleic acid, fumaric acid, itaconic acid, dimethyl fumarate, dimethyl itaconic acid and the like. Furthermore, examples of the unsaturated diol include 2-butene-1,4-diol. Among these, particularly preferred are benzoquinone, 1,4-naphthoquinone, maleic acid, itaconic acid and 2-butene-1,4-diol.

When producing the organophosphorus compound of the present invention, the molar ratio of the phosphinic acid and the unsaturated compound when charged is usually 0.8 to 1.2,
It is preferably 0.9 to 1.1, and most preferably equimolar.
In order to obtain the organophosphorus compound of the present invention in a short time, it is effective to use a solvent, and examples of the solvent include methanol, ethanol, propanol, chloroform, dimethylformamide, dimethylsulfoxide, dioxane and methylcellosolve. , Ethyl cellosolve, propyl cellosolve, butyl cellosolve, pentyl cellosolve, hexyl cellosolve, heptyl cellosolve, and other ethylene glycol ethers, etc., but usually 1 to 20 moles of ethyl cellosolve per 1 mole of phosphinic acid, optimally 3 ~ 6 mol may be used. The reaction temperature and time may be below the boiling point of the solvent used for 5 to 180 minutes, preferably 80 to 120 minutes. Further, as a recrystallization solvent for increasing the purity of the product, an aromatic hydrocarbon having a boiling point of 100 to 250 ° C and a melting point of 20 ° C or less is preferable. Examples of aromatic hydrocarbons include alkyl aromatic hydrocarbons such as toluene, orthoxylene, metaxylene, paraxylene, mixed xylenes having various compositions, ethylbenzene, cumene, pseudocumene, cymene and methylnaphthalene. Also,
In addition, ketones and ether compounds such as acetophenone and anisole, and alcohols such as methanol and ethanol may be used. Of these, toluene, various xylenes, and mixed xylenes are preferable in terms of purity and quality of the product obtained.

Among the organic phosphorus compounds of the present invention, an organic phosphorus compound in the form of an aromatic diol derivative is used as a diol component, and an aromatic dicarboxylic acid, such as terephthalic acid or isophthalic acid, is used as a dicarboxylic acid component, which has novel heat resistance and flame retardancy. Good polyesters can be produced. Moreover,
The organophosphorus compound of the present invention is used as it is or as an ester-forming derivative, or in the form of a polyester oligomer or polymer as an additive for other general-purpose polyesters such as polyethylene terephthalate, polybutylene terephthalate, a stabilizer and a flame retardant. It is also possible to do so.

(Example) Next, an Example is given and this invention is demonstrated more concretely.
The yield of the organophosphorus compound referred to in the Examples is obtained by dividing the yield by the theoretical yield. The melting point was measured using a microscope melting point measuring device.

On the other hand, the phosphorus compound of the present invention was identified by infrared absorption spectrum, melting point measurement and elemental analysis.

Example 1 Thermometer, gas inlet, stirrer and diameter 3 cm, length 30 cm
In a four-necked flask with an internal volume of 2000 cm ₃ equipped with an Arene cooling tube, the phosphinic acid derivative represented by the following structural formula (IV)
212.2 g, 1,4-naphthoquinone 316.3 g and ethyl cellosolve 901.2 g were charged.

Nitrogen gas was slowly blown from the gas blowing port, and the contents were heated to 90 ° C with stirring. During this process, the content changed from a white slurry to a colorless transparent solution. After stirring at 90 ° C for 30 minutes, the mixture was allowed to cool and returned to room temperature, the resulting crystals were separated and dried under reduced pressure to obtain white crystals. Furthermore,
This crystal was recrystallized from orthoxylene. Yield 92%
Met.

The white crystals were analyzed by infrared absorption spectrum, elemental analysis and liquid chromatography, and the following results were obtained, confirming that they were organic phosphorus compounds having the following structural formula (V).

That is, in the infrared absorption spectrum, an absorption due to P = O of phosphinic acid was observed at 1270 κ, and a broad absorption due to a hydroxyl group was observed at 3400 to 3600 κ. In addition, the raw material P-
Absorption around 2400 κ based on H and absorption around 1663 κ based on C═O of 1,4-naphthoquinone were not observed.

Elemental analysis shows C = 58.8% (theoretical value 59.1%), H =
The result of 5.1% (theoretical value 4.9%) was obtained. On the other hand, the result of liquid chromatography showed that the organophosphorus compound having the structural formula (V) was present in a purity of 99.9% or more.

Examples 2 to 4 The same procedures as in Example 1 were carried out except that the other phosphinic acid derivative shown in Table 1 was used instead of the compound represented by the structural formula (IV), and each of the various organophosphorus compounds of the present invention was used. The compound was obtained.

The organophosphorus compound was analyzed and identified by infrared absorption spectrum, elemental analysis and liquid chromatography.

The results of Examples 1 to 4 are shown in Table 2.

Examples 5 to 8 The same procedure as in Example 1 was carried out except that the unsaturated compounds shown in Table 3 were used instead of 1,4-naphthoquinone to obtain various organophosphorus compounds of the present invention. .

The organophosphorus compound was analyzed and identified by infrared absorption spectrum, elemental analysis and liquid chromatography.

Reference Example 1 The organic phosphorus compound obtained in Example 5 was reacted with a large excess of ethylene carbonate in an ethyl cellosolve solvent using potassium carbonate as a catalyst to obtain a diethylene oxide adduct. 10 parts by weight of this phosphorus compound, and 90 parts by weight of bis (β-hydroxyethyl) terephthalate obtained from terephthalic acid and ethylene glycol, and 90 parts by weight of its low polymer were used as a catalyst in an amount of 2 × 10 ^-4 mol per 1 mol of all acid components. Dimethyltin malate was added and polycondensed at 280 ° C and 0.2 mmHg. The obtained polyester had a melting point of 247 ° C., an intrinsic viscosity of 0.67, and the content of phosphorus atoms in the polymer was 8780 ppm.

The obtained polyester was spun and stretched according to a conventional method, and the number of flame contact was measured as a cylindrical knitted fabric. As a result, it was 5.0 times, and it had sufficient flame resistance.

Reference Example 2 The organic phosphorus compound obtained in Example 5 was reacted with a slight excess of acetic anhydride to obtain a diacetate body. This phosphorus compound
Using 10 parts by weight and 90 parts by weight of bis (β-hydroxyethyl) terephthalate and its low polymer, a polyester having an intrinsic viscosity of 0.69 and a phosphorus atom content of 10,094 ppm was obtained in the same manner as in Reference Example 1.

This polyester was made into a tubular knitted fabric in the same manner as in Reference Example 1,
The number of times of flame contact was measured and it was 5.0, indicating that it had sufficient flame resistance.

Reference Example 3 Instead of the organic phosphorus compound (IV) used in Example 5, HC
In the same manner as in Example 5 except that A was used, the following structural formula (I
A phosphorus compound having X) was obtained.

Then, this phosphorus compound was converted into a diethylene oxide derivative in the same manner as in Reference Example 1, and then polycondensation was performed in the same manner as in Reference Example 1 to obtain an intrinsic viscosity of 0.64 and a phosphorus atom content of 6,800 p.
Got pm polyester.

When this polyester was used as a cylindrical knitted fabric in the same manner as in Reference Example 1 and the number of times of flame contact was measured, it was 3.6 times, and the flame resistance was slightly insufficient.

In addition, the intrinsic viscosity [η] of polyester in Reference Example is a value measured at a temperature of 20.0 ° C. using an equal mixture of phenol and ethane tetrachloride as a solvent.

The content of phosphorus atoms in the polyester was quantified by the fluorescent X-ray method. Further, the “phosphorus content” indicates the weight% as a phosphorus atom with respect to the constitutional unit of polyester.

For flame resistance, the yarn obtained by spinning and drawing according to the usual method is made into a tubular knitted fabric, which is rolled into a length of 1 g of 10.0 cm and inserted into a wire coil of 10.0 mm diameter, and held at an angle of 45 degrees. Then, ignite with a micro burner (caliber 0.64 mm) from the lower end, repeat ignition again when the fire source is distant and extinguish, find the number of ignitions required until all samples burn out, and ignite 5 samples It was expressed by the number of times (number of times of flame contact).

(Effects of the Invention) The phosphorus compound of the present invention is a novel compound that can be used as a raw material for polyester having excellent heat resistance and flame retardancy, and also as a stabilizer and flame retardant for polymers.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location C09K 21/14 8318-4H

Claims (2)

[Claims] 1. An organic phosphorus compound represented by the following general formula (I). (However, R ₁ is an ethylene group or a 1,2-phenylene group, A is a trivalent benzene ring group, a trivalent naphthalene ring group or a trivalent aliphatic group having 2 to 4 carbon atoms, and R ₂ is-. OH or —COOR ₃ (R ₃ is a hydrogen atom or a carbon atom number of 1 to 10)
Is a lower alkyl group), and n represents an integer of 1 or 2. ) 2. An organic phosphorus compound represented by the following general formula (II) is reacted with an unsaturated compound selected from cyclic conjugated diketone, unsaturated dicarboxylic acid, dialkyl unsaturated dicarboxylic acid and unsaturated diol. A method for producing an organophosphorus compound represented by the following general formula (I): (However, R ₁ is an ethylene group or a 1,2-phenylene group, A is a trivalent benzene ring group, a trivalent naphthalene ring group or a trivalent aliphatic group having 2 to 4 carbon atoms, and R ₂ is-. OH or —COOR ₃ (R ₃ is a hydrogen atom or a carbon atom number of 1 to 10)
Is a lower alkyl group), and n represents an integer of 1 or 2. )