JPS6236392A - Organic phosphorus compound - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula (E is -CH2CH2-; Ar is aromatic group; benzene ring may containing substituent group selected from lower alkyl and halogen; m+n are 1-20). USE:A raw material for producing a polyester having improved polyester-forming properties, providing a flamel-retardant polyester having improved heat resistance, also useful as a flame-retardant and a stabilizer. PREPARATION:9,10-Dihydro-9-oxa-10-phosphaphenanthren-10-oxide is reacted with a quinone (e.g., p-benzoquinone, etc.,) corresponding to an aromatic dihydroxy compound in a solvent such as ethyl Cellosolve, etc., under heating and reacted with ethylene carbonate or ethylene oxide under pressure in a solvent such as xylene, etc.

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.
A reaction product of 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (referred to as IIcA) and a vinyl compound having an ester-forming group is known (for example, Japanese Patent Publication No. 55-41610) ).

(Problems to be Solved by the Invention) When the above-mentioned phosphorus compounds are used as raw materials for producing polyester, the aliphatic groups of the phosphorus compounds are incorporated into the main chain of the polyester, resulting in a decrease in the heat resistance of the resulting polyester. There was a problem.

The present invention has good polyester forming properties.

The object of the present invention is to provide a flame-retardant polyester with excellent heat resistance, and also to provide a compound that can be uniformly blended with polyester and is useful as a flame retardant or stabilizer as it is.

(Means for Solving the Problems) The present invention achieves the above objects, and the gist thereof is as follows.

(1) An organic phosphorus compound represented by the following structural formula (1).

o=p-.

HO-(EO)m-A r-(OR)n-OH formula (1
), E represents -CH2CHz-, Ar represents an aromatic group, and the Hensen ring may have a substituent selected from a lower alkyl group or a halogen. Furthermore, m and n represent integers whose sum is 1 to 20.

The phosphorus compound of the present invention is produced by reacting IIcA and a quinone corresponding to an aromatic dihydroxy compound by heating in a solvent such as ethyl cellosolve, and then reacting with ethylene carbonate or ethylene oxide in a solvent such as xylene under pressure. be synthesized.

Specific examples of aromatic dihydroxy compounds include the following.

o-, m-, p-dihydroxyhensen.

1.2-, 1.3-, 1.4-, 1.5-, 1.6-.

1.7 +, 1.8-+ 2.3-+ 2.6-, 2
．． 7-dihydroxynaphthalene.

2.2'-,4,4'-dihydroxydiphenyl.

2.2'-dihydroxy1.1'-binaphthyl.

2-methyl-1,4-dihydroxynaphthalene.

1,4-dihydroxy-3,3',5,5'-tetramethoxybiphenyl/4,4'-dihydroxy-diphenyl ether.

Bis(4-hydroxy-2-methylphenyl)-ether.

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

Bis(4-hydroxyphenyl)-sulfide.

Bis(4-hydroxyphenyl)-sulfone.

Bis(4-hydroxyphenyl)-)y-'f-7°bis(4-hydroxyphenyl)-methane.

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

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

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

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

1.1-bis(4'-hydroxyphenyl)-ethane.

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

2.2-Bis(4'-hydroxy-3'-methylphenyl)-pro, pan.

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

2.2-bis(4'-hydroxy-3',5'-dichlorophenyl) to propane.

2.2-bis(4'-hydroxy-3',5'-dibromophenyl)-propane.

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

Bis(4-hydroxyphenyl)-phenylmethane.

Bis(4-hydroxyphenyl)-diphenylmethane.

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

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

Bis(4-hydroxyphenyl)-(4'-chlorophenyl)-methane 5 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-3,5-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)-sulfide.

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-dihydroxyanthraquinone.

1.8-dihydroxy-3-methylanthraquinone.

1.2-Dihydroxy-3-nitroanthraquinone.

1.8-dihydroxy-2,4,5,7-tetranitroanthraquinone.

5.6-Sihydroxy-2-anthraquinonecarboxylic acid.

3.4-dihydroxyanthraquinone-2-sulfonic acid.

3.7-dihydroxy-10-methylxanthine.

Dihydroxyacridone.

1.3-Dihydroxyxanthone.

2.7-cyhydroxy-9-phenylxanthine.

Methylene-di-β-naphthol.

Quinones corresponding to the above-mentioned aromatic dihydroxy compounds can be used, but typical ones include p
-, o-benzoquinone, 1.2 +, 1.4-.

2.6-naphthoquinone, 2.2'-,4,4'-diphenoquinone and 3.10-perylenequinone.

1 (When reacting ethylene carbonate or ethylene oxide with the reaction product of C^ and quinone.

It is preferable to prepare the latter at a ratio of 2 to 30 moles 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 sum of m and n 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 producing polyester. Undesirable.

Moreover, in order to obtain a phosphorus compound in good yield, it is desirable to carry out this reaction using a catalyst. Catalysts include lithium, sodium, potassium, magnesium, aluminum, calcium, iron, cobalt, nickel, copper, zinc, germanium, and 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. is used. Solvents include toluene, xylene, ethylbenzene, cumene, and pseudocumene.

Alkyl aromatic hydrocarbons such as cymene and methylnaphthalene are preferably used.

This reaction is usually carried out at 80 to 150°C for 5 to 60 minutes.

Purification of the reaction product can be performed by a recrystallization method,
As the solvent, aromatic hydrocarbons having a boiling point of 100 to 250°C and a melting point of 20°C or less are preferable. Specific examples of recrystallization solvents include, in addition to the alkyl aromatic hydrocarbons listed as reaction solvents, ketones such as acetophenone and anisole, ether compounds, and alcohols such as methanol and ethanol. In terms of quality, 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, if necessary, a diol such as ethylene glycol, the phosphorus compound has good flame retardancy and heat resistance. It gives 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 microscopic melting point measuring device.

In addition, phosphorus compounds can be identified using infrared absorption spectra, N
MR spectrum, melting point measurement, single element analysis, and liquid chromatography were used.

Example 1 1) cA and p-henzoginone were reacted in ethyl cellosolve at 90°C to form phosphinic acid vi F form (IIC
A・PBQ) was obtained.

0.1 mol of this IIcA-r'BQ and 0.6 mol of ethylene carbonate (EC) were placed in a glass flask, and 0.5 x 10-' of potassium carbonate was added as a catalyst.
mol, add 0.8 mol of mixed xylene as a solvent, 10
The reaction was allowed to proceed at 0°C for 10 minutes with stirring. (The initial slurry-like state turned into a cloud-like state.) The reaction solution was cooled to 30°C, the resulting starch syrup was decanted with silane, and the solvent was distilled off using an evaporator.
Dissolved in 500mj2 of methanol at 50°C.

This solution was cooled to 5°C, and the formed crystals were filtered and dried under reduced pressure to obtain white crystals with a melting point of 150-153°C.

When the white crystals were isolated and purified by column treatment, white crystals having a melting point of 152.5 to 152.9'c were obtained in a yield of 95.8%.

The obtained white crystals were analyzed by infrared absorption spectrum, NMR spectrum, and elemental analysis.

The following results were obtained.

In other words, in the infrared absorption spectrum, 2900C
I1)- Absorption based on methylene group at ', 880 cm-
'Absorption based on the asymmetric 3-substituted Henze/ring and approx.
Very weak absorption based on hydroxyl groups was observed from 400 to 3600 cm-'.

In addition, in the NM1) spectrum, the ratio of the absorption of hydrogen atoms based on benzene rings and the absorption of hydrogen atoms based on methylene groups is 1). 1: 8.0 (theoretical value 1): 8)
Met.

In addition, the result of two-element analysis was 64.1% carbon (theoretical value 64%).
．． 1%), hydrogen 5.0% (theoretical value 5.1%).

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

1-10-F, O-Δ r-OF-OH On the other hand, the results of liquid chromatography confirmed that the above white crystals contained the compound of the above formula with a purity of 99.9% or more. .

Examples 2 to 15 In Example 1, phosphinic acid derivative (IICA・P
When the molar ratio of BQ) and ethylene carbonate (EC) (1) and 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 22 In Example 1, the quinones shown in Table 2 were used instead of p-henzoquinone, and the portion 8r in formula 3 (1) corresponded to each quinone. A phosphorus compound shown in Table 2 was obtained.

Table 2 According to the present invention, an organic phosphorus compound is provided which is useful as a raw material for producing a polyester that provides a flame-retardant polyester having excellent heat resistance, or as a flame retardant or stabilizer for the polyester.

Claims (1)

[Claims] (1) An organic phosphorus compound represented by the following structural formula [I]. [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula [I], E is -CH_2CH_2-, Ar
represents 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 sum is 1 to 20.