JPS63313795A - Organic phosphorus compound - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (R1 and R2 are monofunctional aromatic group; R<3> and R<4> are H or monofunctional organic group having ester-forming functional group; Ar is trifunctional aromatic group having >=2 aromatic rings, provided that the aromatic ring may have a substituent group). EXAMPLE:A compound expressed by formula II. USE:A raw material for polyesters, stabilizer and flame retardant for polymers. PREPARATION:Water in an amount of preferably 1-8 times based on a phosphinic halide expressed by formula III (X is halogen) is added thereto and the reaction mixture is heated and hydrolyzed in a solvent, such as benzene or xylene, preferably at 50-100 deg.C for 1-30hr to provide a phosphine oxide expressed by formula IV, which is then reacted with the corresponding cyclic conjugated diketone in a solvent, such as ethyl cellosolve, at 0.8/1.2-1.2/0.8 molar ratio, preferably at 60-130 deg.C for 30-180min and, as necessary, further reacted with an acid anhydride of a lower fatty acid, etc.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a novel organic phosphorus compound, and more specifically, it is used as a raw material for polyester having excellent heat resistance and flame retardancy, or for stabilization. The present invention relates to novel organophosphorus compounds that can be used as additives such as additives and flame retardants.

(Prior art) Conventionally, the following structural formula (
The compound represented by a) (Japanese Patent Publication No. 59-36933) and the compound represented by the following structural formula (b) or (C) (Japanese Patent Publication No. 60-126293 and 61-23)
No. 6787) is known.

(Problems to be Solved by the Invention) However, when polyester is produced using the structural formula (a) or its derivative, or when it is added as an additive, the physical properties of the resulting polyester may be impaired or the heat resistance may be poor. do. on the other hand.

There is a problem in that it is economically expensive to produce polyester using the structural formulas (b) and (c) or derivatives thereof, or to add them as additives.

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, flame retardant, etc.

That is, the gist of the present invention is an organic phosphorus compound represented by the following general formula (J).

R30-Ar -0R4 (However, R1 and R2 are the same or different monovalent aromatic groups, R3' and R4 are the same or different groups, and are monovalent groups having a hydrogen atom or an ester-forming functional group. The organic group Ar represents a trivalent aromatic group having two or more aromatic rings.Also, the aromatic ring may have a substituent.) In general formula (1), R1 and R2 are: Examples include phenyl group, biphenyl group, and naphthyl group.

On the other hand, R3 and R4 are hydrogen atoms, carbon atoms 2-
! -10 lower acyl group, -CH2CH20H, and the like. On the other hand, Ar represents an aromatic ring such as a naphthalene ring, a biphenyl ring, a phenanthrene ring, or an anthracene ring.

Therefore, specific examples of the organic phosphorus compound represented by the formula (■) include compounds represented by the following structural formulas (d) to (n).

O −6+ C1 8 - The organic phosphorus compound of the present invention has 9 For example, the structural formula (U
1 to 20 times, preferably 1 to 8 times the amount of water, is added to the subphosphine halide represented by ), and benzene is added.

CJ, Org. Chern, 242013. (1
959)], and then the corresponding cyclic conjugated diketone (hereinafter abbreviated as quinone) in a suitable solvent such as ethyl cellosolve, benzene, xylene, etc.
The reaction is carried out at a molar ratio of 1.210.8 at 50 to 200°C, preferably 60 to 130°C, for 30 to 180 minutes, and if necessary, lower fatty acid anhydride or ethylene carbonate,
It can be produced by reacting with ethylene oxide or the like.

In addition, the organic phosphorus compound of the present invention can be prepared by adding quinone and 1 to 10 times as much water as quinone to a solvent such as benzene or xylene, keeping the temperature at 20 to 100°C, and adding the following structural formula (II) to the organic phosphorus compound of the present invention. 1 to 1 of the phosphinite no-ride shown by
．． It can be produced by adding twice the equivalent [
Zh, 0bshch, Khim, 1972.42
(1),).

2415-18 (Russ):).

Phosphinite halides, such as diphenylphosphinite chloride, can be used to combine cheap phosphorus trichloride and benzene into 35
C J, Org, who can synthesize phenyldichlorophosphine by heating at 0 to 80°C (Japanese Patent Publication No. 44-3354), and obtain diphenylphosphine chlorite by heating this with aluminum chloride.
Chem, 25, 2001 (1960)] O=P
(1) ■ (However, IRI and R2 represent the same or different types of monovalent aromatic groups. The aromatic ring may be substituted with a halogen atom, and the number of carbon atoms that may or may not contain a halogen atom. Optionally substituted with 1 to 2o hydrocarbon groups.X
represents a halogen atom. ) In recrystallization, the solvent used is 2, for example, benzene, toluene, ortho-xylene, meta-xylene.

Paraxylene, mixed xylenes of various compositions, alkyl aromatic hydrocarbons such as ethylbenzene, cumene, etc., alcohols such as acetophenone, anisole, etc., chloroform, dichloromethane, acetone, ethyl cellosolve, etc. can be used. Among these, ethyl cellosolve is preferred in terms of purity and quality of the product obtained.

In the organic phosphorus compound of the present invention, this compound is used as a diol component.9 For example, an aromatic dicarboxylic acid such as terephthalic acid or isophthalic acid is used as a dicarboxylic acid component, and if necessary, 4-
New heat resistance achieved by combining aromatic oxycarboxylic acids such as hydroxybenzoic acid.

A polyester with good flame retardancy, preferably a thermotropic liquid crystal polyester, can be produced. Furthermore, the organic phosphorus compound of the present invention can be used as it is, or in the form of an ester-forming derivative, or in the form of a polyester oligomer polymer, and can also be used as a stabilizer or flame retardant for general-purpose polyesters, such as polyethylene terethalate and polybutylene terephthalate. It is also possible to use it as an additive.

(Example) Next, the organic phosphorus compound of 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, nine phosphorus compounds of the present invention were identified by infrared absorption spectra and elemental analysis IC.

Reference example 1 Thermometer, gas blower, stirrer and diameter 3 cm.

Internal volume 300 with 30 crn length Aline cooling pipe
17.1 ml of diphenylphosphinite chloride in a four-eye flask! 9 (0,078 mol) and benzene 80 cIl, and after purging with nitrogen, water 6.0
g (0.33 mol) was added thereto, and the mixture was further replaced with nitrogen. Nitrogen gas was slowly blown into the mixture and the contents were heated with stirring until the temperature reached 80°C. After reacting for 16 hours, the mixture was allowed to cool.

Benzene was removed by vacuum distillation. 50% ether to the residue
crft was added and extracted, and the ether layer was concentrated to obtain a colorless and transparent oily substance 15.0.1i'.

When this oily substance was analyzed by infrared absorption spectrum and elemental analysis, the following results were obtained.

It was confirmed that it was an organic phosphorus compound having the following structural formula (IV). The yield was 95.0%.

The results of the infrared absorption spectrum are shown in Figure 2.

In elemental analysis, C = 71.0wt% (theoretical value 71.3w
Section t).

H = 5.58wt% (theoretical value 5.48wt%)
, P = 15.5 wt% (theoretical value 15', 3 wt%
) results were obtained.

Reference Example 2 Bis(hentamethylphenyl)phosphinite chloride instead of diphenylphosphinite chloride 28.
White crystals were obtained in the same manner as in Reference Example 1 except that 2 g (0,078 mol) was used. This was recrystallized from benzene to obtain white crystals with a melting point (decomposition point) of 240°C. As a result of elemental analysis and infrared absorption spectrum, the following structural formula (v
) was confirmed to be an organic phosphorus compound. The yield was 52%.

The infrared absorption spectrum is 1590 crn and 148
The benzene ring peak is at 3m, 2360crnK
Absorption based on P-H, absorption based on -CH3 at 1370 crn, and absorption based on 1) 30tMKP=0 were observed.

The result of elemental analysis is C = 77.57wt% (theoretical value 7
7.16 wt%), H = 9.08 wt% (theoretical value 9.12 wt%), P = 9.57 wt% (
The theoretical value was 9.04 wt%).

Reference Example 3 Bis(2) instead of diphenylphosphinite chloride
,3,5,6-titramethylphenyl)phosphinite chloride 25.9a? (0,078 mol) was carried out in the same manner as in Reference Example 1 to obtain white crystals. This was recrystallized from benzene to obtain white crystals with a melting point (decomposition point) of 203°C. As a result of elemental analysis and infrared absorption spectrum, it was confirmed that it was an organic phosphorus compound having the following structural formula (VI). The yield was 65%.

and 1487> The peak of wise benzene ring is 2365
Absorption based on PH in Sen-1, absorption based on -CH3 in 1372crn, 1) 35crnKP=0
Absorption based on.

Absorption of penta-substituted benzene was observed at 860 crn.

The result of elemental analysis is C = 76.48Wt (theoretical value 76
．． 40wt ratio), H = 8.79Wt ratio (theoretical value 8
．． 66 Wt), P = 9.66 Example 1 Thermometer, gas blowing funnel, stirrer 9 dropping funnel and diameter 3
6.2F (0,031 mol) of the oily substance obtained in Reference Example 1 was charged into a Goturo flask with an internal volume of 300 d and equipped with an Allene condensing tube with a length of 30 cn1, and nitrogen gas was slowly blown in from the gas inlet and stirred. While heating the contents until the temperature reached 80°C. Next, a solution of 1°4-naphthoquinone 4.1 (0,031 mol) in 80 cIl of ethyl cellosolve was added dropwise from the dropping funnel over a period of 1 hour, and then the temperature was raised to 120°C, and the temperature was raised to 120°C for 2 hours. I reacted. After cooling, the resulting crystals were separated in a furnace, dried under reduced pressure, and then recrystallized from Ri 1: Rojo, Lum.

8.4F of white crystals were obtained.

When this white crystal was analyzed by infrared absorption spectrum, elemental analysis, and liquid chromatography, the following results were obtained, and it was confirmed that it was an organic phosphorus compound having the above structural formula (d).

The yield was 75%.

The infrared absorption spectrum is shown in Figure 1. According to the results of elemental analysis, C = 73.1wt (theoretical value 73.3wt)
Section).

H= 4.83wt factor (theoretical value 4.75Wt factor), P=
A result of 8.55 Wt (theoretical value 8.60 wt%) was obtained. On the other hand, according to the results of liquid chromatography, the organic phosphorus compound having the structural formula (d) has a purity of 99.9.
The result was that it was present at % or more.

Examples 2 and 3 The same procedure as in Example 1 was carried out except that other quinones shown in Table 1 were used instead of 1.4-naphthoquinone.

Various types of organic phosphorus compounds of the present invention were obtained.

Such organic phosphorus compounds were analyzed by infrared absorption spectroscopy, elemental analysis, and liquid chromatography.

Identified.

The results of Examples 1 to 3 are listed in Table 1.

Table 1 Example 4.5 The procedure was repeated in the same manner as in Example 1 except that other phosphine oxides shown in Table 2 were used in place of the compound represented by the structural formula ((V). An organic phosphorus compound was obtained.The organic phosphorus compound was analyzed and identified by infrared absorption spectroscopy, elemental analysis, and liquid chromatography.

The results of Example 4.5 are listed in Table 2.

Table 2 Reference example 4 The organic phosphorus compound obtained in Example 1 was placed in a reactor.

4-Hydroxybenzoic acid, terephthalic acid, and acetic anhydride were charged in a molar ratio of 35:65:35:160, and as a catalyst, 4 x 10-
Add 4 mol and heat at 150°C for 2 hours at 200°C under nitrogen atmosphere.
The reaction was continued at 280°C for 2 hours and then at 280°C for 2 hours. After that, the reaction was carried out by gradually raising the temperature under reduced pressure, and the final temperature was 320"C, 1
The reaction was carried out for 2 hours under reduced pressure of torr or less.

The obtained polyester had an intrinsic viscosity of 1.58. It was a thermotropic liquid crystalline polyester with a glass transition point of 185°C and excellent heat resistance and flame retardancy.

Reference Example 5 The organic phosphorus compound obtained in Example 1 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. Bis(β-hydroxyethyl) obtained from 10 parts by weight of this phosphorus compound, terephthalic acid and ethylene glycol
Using 90 parts by weight of terephthalate and its low polymer as a catalyst, 2 x 10 mol of dimethyl tin maleate was added to 1 mol of the total acid components, and polycondensation was carried out at 280°C and 0.2 mmHg.

The obtained polyester has a melting point of 249°C and an intrinsic viscosity of 0.
．． It was 69. This polyester was spun and stretched under normal pressure, and the number of times of flame contact was measured as a tubular knitted fabric.
0 times, and had sufficient flame resistance.

(Effects of the Invention) The phosphorus compound of the present invention uses phosphorus trichloride and benzene as raw materials, so it can be produced at low cost.

It is a new compound that can be used as a polyester raw material with excellent heat resistance and flame retardancy, and can also be used as a polymer stabilizer and flame retardant.

[Brief explanation of drawings]

FIG. 1 is an infrared absorption spectrum of the white crystal obtained in Example 1, and FIG. 2 is an infrared absorption spectrum of the oily substance obtained in Reference Example 1.

Claims (1)

[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 and R_2 are the same or different monovalent aromatic groups, R_3 and R_4 are the same or different groups, and are hydrogen atoms or ester-forming groups. A monovalent organic group having a functional group, Ar represents a trivalent aromatic group having two or more aromatic rings.Also, the aromatic ring may have a substituent.)