JPS62175491A - Novel organic phosphorus compound and production thereof - Google Patents

Abstract

NEW MATERIAL:A compound shown by formula I (R1 is ethylene or 1,2- phenylene; A is di--trifunctional aromatic, aliphatic or alicyclic group; each organic group may be replaced with halogen or 1-20C hydrocarbon which may contain halogen; m and n are 1-2]. EXAMPLE:A compound shown by formula II. USE:A raw material for heat-resistant and flame-resistant polyester, a stabilizer and a flame-retardant. PREPARATION:An organic phosphorus compound (e.g., phosphinic acid derivative shown by formula IV, etc.,) shown by formula III is reacted with an unsaturated compound (e.g., 1,4-naphthoquinone, etc.,) selected from a cyclic conjugated diketone, unsaturated dicarboxylic acid, an unsaturated diol and their derivatives) to give a compound shown by formula I.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a novel organic phosphorus compound and a method for producing the same, and more specifically to its use as a raw material for polyester having excellent heat resistance and flame retardancy. The present invention relates to a novel organic phosphorus compound that can be used as a stabilizer or an additive such as a stabilizer or a flame retardant, and a method for producing the same.

(Prior art) Conventionally, the following structural formula (
9,10-dihydro-9-oxa-10 represented by [)
-phosphaphenanthrene-10-oxide (HCA)
Derivatives having an ester-forming functional group are known (Japanese Patent Publication No. 55-41610, etc.).

(Problems to be Solved by the Invention) However, if the compound represented by the above structural formula (1) is added to polyester in an amount sufficient to impart sufficient flammability, it may impair the physical properties of polyester or become economically expensive. There was a problem with becoming.

Therefore, the main object of the present invention is to provide a novel and inexpensive organic phosphorus compound that can impart a high degree of flame retardancy without impairing the good physical properties of polyester.

(Means for Solving the Problems) In order to achieve the above object, the present inventors have conducted extensive research on organic phosphorus compounds that do not have the above-mentioned problems, and have found that if an organic phosphorus compound has a specific structure, We have arrived at the present invention based on the discovery that it can be used as a very suitable raw material for polyester, or as a stabilizer, a flame retardant, and the like.

That is, the present invention provides (1) an organic phosphorus compound represented by the following general formula (1) and (2) an organic phosphorus compound represented by the following general formula (It), and a cyclic conjugated diketone, an unsaturated dicarboxylic acid, and an unsaturated diol. The gist of the present invention is a method for producing an organic phosphorus compound represented by the following general formula (1), which is characterized by reacting the organic phosphorus compound with an unsaturated compound selected from these derivatives.

A, R2 hem (Tatashi, R1 is an ethylene group or a 1;2-phenylene group.

A represents a divalent or 31iffi aromatic group, aliphatic group, or alicyclic group. Further, any organic group may be substituted with a halogen atom, or may be substituted with a hydrocarbon group having 1 to 20 carbon atoms, which may or may not contain a halogen atom. Further, n and m represent integers of 1 or 2. ) In general formula (1), 82 is * -0
Examples include Ht-COOR3°-0CR2C)I20H. Here, 83 is a hydrogen atom or has 1 to 10 carbon atoms such as a methyl group, ethyl group, butyl group, or octyl group.
is a lower alkyl group. Also, as A, methylene/
group, alkylene group such as ethylene group, impropylidene group, cyclohexylene group, alkylidene group, p-phenylene group, 2m-phenylene group, 1,4-naphthalene group, 2
, arylene group such as 6-naphthalene group, 1°2.3-
In addition to alkanetriyl groups such as propanetriyl groups, there are also cyclic organic residues such as those shown below. It may be substituted with ~20 hydrocarbon groups, etc.

Specific examples of -A(Rz) include the following.

HOOCCH-C)I2COOH -CH2Cf(2-C00H -CH2CH2-C00CH3 -CH2CH2COOC2H5 ] CH-COOC2H5 (Jt2-COOC2H5 CH2-CHCOOCH3 CH2C00CH3 -CH3OK -COOC2H5 ■ CH2C00C2H5 Cf(20H -Ct(2-Cf(oH The organic phosphorus compound represented by general formula (1) of the present invention is.

An organic phosphorus compound represented by the general formula ([1) (hereinafter abbreviated as phosphinic acid), a cyclic conjugated diketone (hereinafter abbreviated as quino/), an unsaturated dicarboxylic acid, an unsaturated diol or a derivative thereof (for example, I.

It can be produced by reacting these acids, rides, acid amides, nitriles, esters, acid anhydrides, etc. with unsaturated compounds in a solvent such as ethyl cellosolve.

Examples of quinone include 2,6-naphthoquinone.

1.4 naphthoquinone, 1.2-naphthoquinone, 4.4'
-diphenoquinone, 2,2'-diphenoquinone, benzoquinone, etc. Examples of unsaturated dicarboxylic acids include itaconic acid and maleic acid.

Examples include fumaric acid, dimethyl itaconate, and dimethyl fumarate. Examples of unsaturated diols include 2-butene-1,4-diol and 2-butene-1,4-diol.
Examples include diacetoxybutane. Among these, benzoquinone, 1°4-naphthoquinone, itaconic acid, maleic acid, and 2-butene-1,4-diol are particularly preferably used.

When producing the organic phosphorus compound of the present invention, the molar ratio of phosphinic acid and unsaturated compound at the time of charging is usually 0.8 to 1.
．． 2. Preferably 0.9 to 1.1. The optimum ratio is equimolar. Furthermore, in order to obtain the organic phosphorus compound of the present invention in a short time, it is effective to use a solvent, and examples of the solvent used at °C include methanol, ethanol, furopanol, and chloroform.

Dimethylformamide, dimethyl sulfoxide.

dioxane and methyl cellosolve, ethyl heptarosolve,
Propyl cellosolve, butyl cellosolve.

Examples include ethylene glycol ethers such as pentyl cellosolve, hexyl cellosolve, and heptyl cellosolve.2 Usually, ethyl cellosolve is used in an amount of 1 to 20 moles of Ai per 1 mole of phosphinic acid.

Optimally, 3 to 6 moles may be used. In addition, the temperature and time of one reaction are below the boiling point of the solvent used for 5 to 180 minutes,
Preferably, the reaction time may be 80 to 120 minutes. Also,
As a recrystallization solvent to increase the purity of the product, boiling point 1
Aromatic hydrocarbons having a melting point of 00 to 250°C and a melting point of 20°C or less are preferred. Examples of aromatic hydrocarbons include toluene/,
Examples include alkyl aromatic hydrocarbons such as orthogylene, meta-xylene, para-xylene, mixed xylene of various compositions, ethylbenzene, cumene, pseudocumene, cymene, methylnaphthalene, and the like. Also.

Other ketones and ether compounds such as acetophenone, anisole, etc., and alcohols such as methanol, ethanol, etc. may also be used. Among these, preferred toluene, various xylenes, and mixed xylenes are preferred from the viewpoint of purity and quality of the products obtained.

Among the organic phosphorus compounds of the present invention, the diol component is an organic phosphorus compound in the form of an aromatic diol derivative, and the dicarboxylic acid component is an aromatic dicarbo/acid such as terephthalic acid or isophthalic acid to achieve novel heat resistance and flame retardancy. It is possible to produce polyester with good quality. Sara (7I
:3 The organic phosphorus compound of the present invention can be used as it is or as an ester-forming derivative, or in the form of a polyester oligomer or polymer, and can be used as an additive for other general-purpose polyesters, such as polyethylene terephthalate, a stabilizer for polyethylene terephthalate, a flame retardant, etc. It is also possible to use it as

(Example) Next, the present invention will be explained in more detail with reference to Examples.

Note that the yield of the organic phosphorus compound referred to in the Examples was determined by dividing the yield by the theoretical yield. Moreover, the melting point was measured using a microscope melting point measuring device.

On the other hand, the two phosphorus compounds of the present invention were identified by infrared absorption spectroscopy, melting point measurement, and elemental analysis.

Example 1 Thermometer, gas blower, stirrer and diameter 3crn.

Internal volume 200 with 30crn long Aline cooling pipe
A phosphinic acid derivative 212.2.9, 1.4- represented by the following structural formula ([V)] was placed in a 0ci Yotsuro flask.
naphthoquino/316.3.9 and ethyl cellosolve 90
1.2g was charged.

The contents were heated with stirring until the temperature reached 90°C.

During this process, the contents changed from a white slurry to a colorless and transparent solution. After stirring at 90°C for 30 minutes.

The mixture was allowed to cool to room temperature, and the resulting crystals were separated and dried under reduced pressure to obtain white crystals. Furthermore, this crystal was recrystallized from ortho-xylene. The yield was 92%.

Furthermore, when this white crystal was analyzed by infrared absorption/absorption spectroscopy, elemental analysis, and liquid chromatography, the following results were obtained, confirming that it is an organic phosphorus compound having the following structural formula (9). did.

That is, the absorption power based on P=O of phosphinic acid is 3400 to 36 at 1270 in the infrared absorption spectrum.
Broad absorption based on hydroxyl groups was observed in 00. Also, based on the P-H of the raw material, absorption near < 2400, 1
．． No absorption was observed near 1663 based on C=0 of 4-naphthoquinone.

As a result of elemental analysis, C = 58.8% (theoretical value 59.1
qb).

A result of H=5.1% (theoretical value 4.9%) was obtained.

on the other hand.

From the results of liquid chromatography, it was found that the organic phosphorus compound having the above-mentioned structural formula has a sequence degree of 99.9% or more.

Examples 2 to 4 The same procedure as Example 1 was carried out except that other phosphinic acid derivatives shown in Table 1 were used instead of the compound represented by the structural formula ([V)], and various organic compounds of the present invention were used. A phosphorus compound was obtained.

Such organic phosphorus compounds have an infrared absorption spectrum.

Analyzed by elemental analysis and liquid chromatography.

Identified.

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

Examples 5 to 8 Various organic phosphorus compounds of the present invention were obtained in the same manner as in Example 1 except that other unsaturated compounds shown in Table 3 were used instead of 1.4-naphthoquinone. .

Such organic phosphorus compounds have an infrared absorption spectrum.

Analyzed by elemental analysis and liquid chromatography.

Identified.

Table 1 Table 2 Table 3 Reference Example 1 The organic phosphorus compound obtained in Example 5 was reacted with a large excess of ethylene carbonate in an ethylceronlube solvent using potassium carbonate as a catalyst to obtain a diethylene oxide adduct. . Bis(β-hydroxyethyl) obtained from 10 parts by weight of this phosphorus compound, terephthalic acid and ethylene glycol
Terephthalate and 1 part of its low polymer 90ii were polycondensed at 280° C. at 0.2 μl by adding 2×10 5 mol of dimethyl tin maleate per 1 mol of the total acid components as a catalyst. The resulting polyester had a melting point of 247C, an intrinsic viscosity of 0.67, and a phosphorus atom content of 87.
It was 80 ppm.

The obtained polyester was spun and stretched according to a conventional method, and the number of times of flame contact was measured as a tubular knitted fabric, which was 5.0 times.
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.

Using 10 parts by weight of this phosphorus compound and 90 parts by weight of bis(β-hydroxyethyl) terephthalate and its low polymer, Reference 1! In the same way as AJ I, the intrinsic viscosity is 0.69.
．． A polyester having a phosphorus atom content of 10,094 ppm was obtained.

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

Reference Example 3 A phosphinic acid derivative was synthesized in the same manner as Reference Example 1 except that a phosphorus compound represented by structural formula M was used instead of the phosphorus compound used in Reference Example 1, and this phosphinic acid derivative was used to synthesize Reference Example Polycondensation was performed in the same manner as in 1 to obtain an intrinsic viscosity of 0.64.
A polyester with a 177 atom content of 6,800 ppm was obtained.

This polyester was made into a cylindrical knitted fabric in the same manner as in Reference Example 1, and the number of times it was exposed to flame was measured to be 3.6 times, indicating that the flame resistance was slightly insufficient.

In addition, in the reference example, the intrinsic viscosity [η] of the polyester is a value measured at a temperature of 20.0° C. using a mixture of equal amounts of phenol and tetrachloroethane as a solvent.

The content of phosphorus atoms in the polyester was determined by fluorescent X-ray method. Moreover, "phosphorus content" indicates the weight percent as phosphorus atoms relative to the structural units of polyester.

In addition, the flame resistance was determined by spinning and drawing the yarn according to the conventional method, making it into a tubular knitted fabric, and rolling the 1.9 to a length of 10.0 crn.
Insert it into a wire coil with a diameter of 0.0 mm, hold it at a 45 degree angle, and insert it into a micro burner (diameter (1.64 m)) from the bottom end.
ignite it, move away from the fire source, and extinguish it if it is 1-, then repeat the ignition.t7. Calculate the number of ignitions required until all samples are completely combusted, and calculate the number of ignitions (number of flame contacts) for the five samples.
This is Table 12.

(Effects of the Invention) The phosphorus compound of the present invention is a novel compound that can be used not only as a raw material for polyester with excellent heat resistance and flame retardancy, but also as a stabilizer and flame retardant for polymers.

Claims (2)

[Claims] (1) An organic phosphorus compound represented by the following general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (However, R_1 represents an ethylene group or 1,2-phenylene group, and A represents a divalent or trivalent aromatic group, aliphatic group, or alicyclic group. In addition, any organic group may be substituted with a halogen atom, or may be substituted with a hydrocarbon group having 1 to 20 carbon atoms, which may or may not contain a halogen atom. n represents an integer from 1 to 2.) (2) an organic phosphorus compound represented by the following general formula (II);
A method for producing an organic phosphorus compound represented by the following general formula (I), which comprises reacting with an unsaturated compound selected from a cyclic conjugated diketone, an unsaturated dicarboxylic acid, an unsaturated diol, or a derivative thereof. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (However, R_1 is an ethylene group or 1,2-phenylene group, and A is a divalent or trivalent aromatic Represents a group group, an aliphatic group, or an alicyclic group.Also, any organic group may be substituted with a halogen atom, or a hydrocarbon having 1 to 20 carbon atoms containing or not containing a halogen atom. It may be substituted with a group. Also, n and m represent integers of 1 to 2.)