JPH01221386A - Organic phosphorous compound - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (E represents -CH2CH2-; Ar represents aromatic group; benzene ring may have a substituent selected from lower alkyl and halogen; m+n is 1-20). EXAMPLE:A compound expressed by formula II. USE:A raw material for producing a flame-retardant polyester, which acts as a flame retarder and a stabilizer on the polyester. PREPARATION:A diphenylphosphine oxide expressed by formula III is reacted with a quinone corresponding to an aromatic dihydroxy compound in a solvent such as ethyl cellosolve, etc., while being heated. Subsequently it is further reacted with ethylene carbonate or ethylene oxide in a solvent such as ethyleneglycol diethyl ether.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an organic phosphorus compound useful as a raw material for producing flame-retardant polyester or as a flame retardant or stabilizer for polyester.

(Prior Art) Conventionally, 9.1 has been used as a phosphorus compound useful as a raw material for producing flame-retardant polyester or as a flame retardant for polyester.
A reaction product of 0-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter abbreviated as HCA) and a vinyl compound having an ester-forming group is known (for example, Japanese Patent Publication No. 55-41610 Publication No.).

In addition, the present inventors previously proposed a reaction product of HCA and quinones (Japanese Patent Application Laid-Open No. 62-36392).

(Problem to be Solved by the Invention) When the above-mentioned phosphorus compound is added to polyester in an amount sufficient to impart sufficient flame retardancy, in the former case, the polyester becomes weak due to the bulky phenanthrene ring. If the phosphorus compound has an aliphatic group as in the latter case, the heat resistance of the phosphorus compound is poor, and since the aliphatic group is incorporated into the main chain of the polyester, the heat resistance of the resulting polyester decreases accordingly. There were some problems.

The present invention has good polyester forming properties.

The object of the present invention is to provide an organic phosphorus compound which can provide flame-retardant polyester with heat resistance, can be uniformly blended with polyester, and is useful as a flame retardant stabilizer as it is.

(Means for Solving the Problems) The above objects are achieved by the two organophosphorus compounds of the present invention.

That is, the gist of the present invention is an organic phosphorus compound represented by the secondary structural formula (1).

0 = P (1) HO-(EO
) m-Ar -(OE)n-OH (E is -CH
2CH2- and Ar represent an aromatic group, and the benzene ring may have a substituent selected from a lower alkyl group or a halogen. Also.

m and n represent integers whose phases are from 1 to 20. ) The phosphorus compound of the present invention is prepared by heating diphenylphosphine oxide (hereinafter abbreviated as PPA) having the following structural formula (■) and a quinone corresponding to an aromatic dihydroxy compound in a solvent such as ethyl cellosolve. It is synthesized by reacting ethylene carbonate or ethylene oxide in a solvent such as , ethylene glycol diethyl ether.

Specific examples of aromatic dihydroxy compounds include the following.

1.2-, 1.3-, 1.4-dihydroxybenzene.

1.2 +, 1.3 +, 1.4 +, 1
．． 5 +, 1.6-t 1゜7 +, 1.8
+, 2.3 +, 2.6 +, 2.7-
Dihydroxynaphthalene.

2.2'-,4,4'-dihydroxydiphenyl.

2.2'-dihydroxy-1,1'-binaphthyl.

2-Methyl-1,4-dihydroxynaphthalene.

゛l, 4-dihydroxy-3.3', 5.5'-tetramethoxybiphenyl.

4,4'-dihydroxy-diphenyl ether.

Bis(4-hydroxy-2-methylphenyl)-tsu-thyl.

Bis(4-hydroxy-3-chlorophenyl)-ether.

Bis(4-hydroxyphenyl)-sulfide.

Bis(4-hydroxyphenyl)-sulfone.

Bis(4-hydroxyphenyl)-ketone.

Bis(4-hydroxyphenyl)-methane.

Bis(4-hydroxy-3-methylphenyl)-methane.

Bis(4-hydroxy-3,5-dichlorophenyl)-
methane.

Bis(4-hydroxy-3,5-difluorophenyl)
-Methane.

Bis(4-hydroxy-3,5-dibromophenyl)-
methane.

1,1-bis(4'-hydroxyphenyl)-ethane.

2.2-bis(4'-hydroxyphenyl)-7'iz
bread.

2.2-bis(4'-hydroxy-3'-methylphenyl)-propane.

2.2-bis(4'-hydroxy-3'-chlorophenyl)-propane.

2.2-bis(4'-hydroxy-315'-dichlorophenyl)-propane.

2.2-bis(4'-hydroxy-3te57-dibromophenyl)-propane.

1.1-bis(4'-hydroxyphenyl)-n-
butane.

Bis(4-hydroxyphenyl)-phenylmethane.

Bis(4-hydroxyphenyl)-diphenylmethane.

Bis(4-hydroxyphenyl)-4'-methylphenylmethane.

1.1-bis(4'-hydroxyphenyl)-2,2
゜2-Trichloroethane.

Bis(4-hydroxyphenyl)-(4'-ly-orophenyl)-methane.

1,1-bis(4'-hydroxyphenyl)-cyclohexane.

Bis(4-hydroxyphenyl)-cyclohexylmethane.

2.2-bis(4'-hydroxynaphthyl)-propane.

Bis(4-hydroxy-3,5-dimethylphenyl)-
methane.

Bis(4-hydroxy-3,s-dimethylphenyl)-
Ketones.

Bis(4-hydroxy-3,5-dichlorophenyl)-
Ketones.

Bis(4-hydroxy-3-chlorophenyl)-sulfide.

Bis(4-hydroxy-3,5-dichlorophenyl)-
sulfide.

Bis(4-hydroxy-3,5-dichlorophenyl)-
ether.

Bis(3-hydroxyphenyl)-sulfite.

Bis(3-hydroxyphenyl)-sulfone.

Bis(3-hydroxyphenyl)-ether.

3-hydroxyphenyl-4'-hydroxyphenyl-
ether.

3.4-bis(4'-hydroxyphenyl)hexane.

1.5-dihydroxyanthracene.

1.2 +, 1.4 +, 1.6 +, 1
．． 7 +, 2.3 +, 2゜5 +, 2.
6 +, 2.7-, 3.4 +, 3.6 +
, 3.10-.

9.10-Dihydroxyphenanthrene.

3.8-dihydroxyretin.

3.4-dihydroxyanthrone.

1,8-dihydroxy-3-methylanthrone.

1,2-dihydroquine anthraquinone.

1.8-dihydroxy-3-methylanthraquinone.

to 1,2-dihydroxy-3-nitroanthraquino, ], 1,8-dihydroxy-2,4,5,7-titranitroanthraquinone.

5.6-Sihydroxy-2-andraquinone carboxylic acid.

3.4-dihydroxyanthraquinone-2-sulfonic acid.

3.7-Sihydroxy-10-methylxanthine.

Dihydroxyacridone.

1.3-Dihydroxyxanthone.

2,7-dihydroxy-9-phenylxanthine.

Methylene-di-β-naphthol.

In order to produce the organic phosphorus compound of the present invention, quinones corresponding to the above-mentioned aromatic dihydroxy compounds can be used, including *P-so-benzoquinone, 1.2
+, 1.4 +, 2.6-nafdoquinone.

2.2'-,4,4'-diphenoquinone is particularly preferred.

When ethylene carbonate or ethylene oxide is reacted with the reaction product of PPA and chino/, it is preferable to use 2 to 30 moles of the latter per 1 mole of the former. If this molar ratio is too small, the former will remain as an unreacted product, and if it is too large, the m and n dregs will become too large, which will lower the melting point and glass transition point of the resulting polyester when used as a raw material for polyester production. I don't like it.

In addition, in order to obtain a high yield of phosphorus compounds, it is desirable to carry out this reaction using a catalyst.As a catalyst, lithium, sodium, potassium, magnesium, aluminum, calcium, iron, cobalt, nickel, m, Zinc, germanium, silver.

Metal compounds such as tin, titanium, manganese and lead are used.

In addition, this reaction is preferably carried out in the presence of a solvent because it can be carried out in a short time, and the ratio is usually 0.3 to 10 mol, preferably 0.5 to 2 mol, per 1 mol of ethylene carbonate or ethylene oxide. A solvent is used in Solvents include toluene, xylene, ethylbenzene, cumene, and huitocumene.

Alkyl aromatic hydrocarbons such as cymene and methylnaphthalene, ethylene glycol dimethyl ether, and ethylene glycol diethyl ether are preferably used.

It is usually sufficient to carry out this reaction at 80 to 150°C for 30 minutes to several hours.

The reaction product can be purified by a combination of extraction and recrystallization. For example, after extracting and removing unreacted ethylene carbonate f using water or the like as an extraction solvent, the resulting oil can be purified by recrystallization. As a recrystallization solvent, boiling point 100-250
℃, aromatic hydrocarbons having a melting point of 20℃ or less are preferred. Specific examples of recrystallization solvents include the alkyl aromatic hydrocarbons listed as reaction solvents in 9, as well as ketones such as acetophenone and anisole, ether compounds, and alcohols such as methanol and ethanol. From this point of view, toluene and xylene (including mixed xylenes) are particularly preferred.

By reacting the phosphorus compound of the present invention with an aromatic dicarboxylic acid such as terephthalic acid or isophthalic acid, and optionally a diol such as ethylene glycol, a polyester with good flame retardancy and excellent heat resistance can be obtained. It is something. Also.

The phosphorus compound of the present invention can also be used as a flame retardant or stabilizer for general-purpose polymers such as polyethylene terephthalate and polybutylene terephthalate, either as it is or in the form of polyester (including oligomers).

(Example) Next, the present invention will be described with reference to examples.

In addition, in the examples, the melting point was measured using a microscope melting point measuring device.

In addition, phosphorus compounds can be identified using infrared absorption spectra, NM
R spectrum, thermogravimetric analysis, nine elemental analysis, and liquid chromatography were used.

Example I PPA and p-benzoquinone in ethyl cellosolve at 1
The reaction was carried out at 25° C. for 2 hours to obtain a phosphinic acid derivative (hereinafter abbreviated as PPQ).

(7) 1 mole of PPQO and 0.3 mole of ethylene carbonate (hereinafter abbreviated as EC) were charged into a glass flask, and 0.01 mole of potassium carbonate was added as a catalyst and ethylene glycol diethyl ether (hereinafter referred to as EG- D
It is abbreviated as E. ) was added at Q, 5 moA/, and 6 at 100°C.
- The reaction was carried out with stirring for a period of time (the initial slurry was separated into two layers).

The reaction solution was cooled to 30°C, the upper EG-DE layer was removed, and the EG-DE contained in the residue was distilled off using an evaporator, followed by extraction with 100°C of water at 50°C. The lower layer was taken out, water was distilled off using an evaporator, and then recrystallized from methanol to obtain white crystals.

The obtained white crystals were subjected to infrared absorption spectrum and thermogravimetric analysis (
TG), NMR spectrum and elemental analysis, the following results were obtained.

That is, the infrared absorption spectrum was as shown in FIG.

In addition, in the NMR spectrum, the ratio of the absorption of hydrogen atoms based on benzene rings and the absorption of hydrogen atoms based on methylene groups is
The ratio was 13:8 (theoretical value 13:8).

In addition, the result of single element analysis is carbon 66.11 (theoretical value 66
．． 3%), hydrogen 6.0% (theoretical (direct 5.8 inches), Su/7
゜3chi (theoretical value 7.8 ratio).

From these results, it was confirmed that the obtained white crystals were a compound of the following formula.

On the other hand, when the decomposition point of this white crystal was measured by thermogravimetric analysis, it was found to be 3'', 45°C. Also, from the results of liquid chromatography, the above white crystal was found to be the compound 97 of the above formula.
It was confirmed that the content was of purity higher than 1.

Examples 2-15 In Example 1, the molar ratio of PPQ and EC.

When the reaction temperature and reaction time were changed as shown in Table 1, the phosphorus compounds shown in Table 1 were obtained.

Table 1 Examples 16 to 21 In Example 1, the quinones shown in Table 2 were used instead of p-benzoquinone, and the Ar part in Formula 9 (1) corresponded to each quinone. The phosphorus compounds shown in Table 2 were obtained.

Reference Example 1 10 parts by weight of the phosphorus compound obtained in Example 1, and 100 parts by weight of bis(β-hydroxyethyl) terephthalate and its low polymer obtained from terephthalic acid and ethylene glycol
2xxo parts by weight per mole of total acid components as a catalyst
Add 1 mol of dimethyltin maleny and heat at 280°C.
4) Polycondensation was carried out using The resulting polyester has a melting point of 24
The content of phosphorus atoms in the polymer was 7610 ppm at 8° C. and an intrinsic viscosity of 0.68.

This polyester was spun and stretched according to a conventional method, and the number of times of flame contact was measured as a tube-knitted fabric, which was 5.0 times, indicating that it had sufficient flame resistance.

(Effects of the Invention) The phosphorus compound of the present invention has features such as (1) high heat resistance, and (2) not impairing the physical properties of polyester even when added to polyester in an amount that provides sufficient flame retardance. However, it is useful as a raw material for producing polyester that provides flame-retardant polyester with excellent heat resistance, or as a flame retardant or stabilizer for polyester.

[Brief explanation of the drawing]

FIG. 1 is an infrared absorption spectrum of the copolyester obtained in Example 1. Patent applicant Nippon Ester Co., Ltd.

Claims (1)

[Claims] (1) An organic phosphorus compound represented by the following structural formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (However, E represents -CH_2CH_2-, Ar represents an aromatic group, and even if the benzene ring has a substituent selected from a lower alkyl group or a halogen, (Also, m and n represent integers whose sum is 1 to 20.)