JPS603408B2 - Method for manufacturing aromatic polyester - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing aromatic polyester using a quinone compound as a raw material.

It is conventionally known that when producing an aromatic polyester, an aromatic polyester having a high degree of polymerization can be obtained by reacting a bisphenol compound and a dicarboxylic acid dihalide, for example, bisphenol A and phthalic acid dichloride.

However, although quinone compounds are similar in chemical structure to pisphenol compounds, they have not been used as raw materials for aromatic polyesters.

The first reason for this is that quinone compounds are chemically stable and inert, and do not easily react with dicarboxylic acid dihalides and the like. Second, although it is possible to first convert a quinone compound into a bisphenol compound using a strong reducing agent and then react it with a dicarboxylic acid dihalide, even if a polyester could be obtained through such a process, the two-step process would be insufficient. This is because it is industrially disadvantageous because it requires several steps, and there are problems such as undesirable side reactions occurring in the first step and low yield. Therefore, although there are many quinone compounds with diverse structures that are attractive as raw materials for aromatic polyesters, they have not been utilized at all due to the above-mentioned problems.

The present inventors conducted various studies to use quinone compounds as a raw material, which had never been considered as a raw material for aromatic polyesters, and found that a quinone compound and the aforementioned dicarboxylic acid dihalide were combined in a reducing atmosphere. Surprisingly, they found that the reaction occurs extremely easily and in high yields when they coexist, leading to the completion of the present invention.
Therefore, an object of the present invention is to provide a method for producing aromatic polyester with high yield and high degree of polymerization with high purity using a quinone compound, which has conventionally been considered not to be a raw material for aromatic polyester.

Another object of the present invention is to provide a simple and high-yield method for producing a specific aromatic polyester, which has been impossible or extremely difficult to produce by conventionally known methods.

That is, the present invention provides a method for producing an aromatic polyester, which is characterized by reacting a quinone compound and a dicarboxylic acid dihalide in a reducing atmosphere. The quinone compounds referred to in the present invention include, for example, polycyclic aromatic quinone compounds such as anthraquinone, anthanthrone, bianthrone, pyrantrone, violanthrone, isoviolanthrone, dibenzopyrenequinone, dibenzoanthraquinone, benzanthraquinone, naphthoanthraquinone, and the like; nuclear substitution conductors, e.g. halides,
Alkyl derivatives, aryl derivatives, alkoxy derivatives,
There are aryloxy derivatives, etc.

Examples of dicarboxylic acid dihalides include divalent aliphatic carboxylic acids such as adipic acid dichloride, adipic acid dibromide, pimelic acid dichloride, corkic acid dichloride, azelaic acid dichloride, sebacic acid dichloride, and 1,10-decanedicarboxylic acid dichloride. Examples include dihalides, divalent aromatic dicarboxylic acid dihalides such as phthalic acid dichloride, isophthalic acid dichloride, and terephthalic acid dichloride.

In the present invention, the above-mentioned two types of raw materials are reacted in a reducing atmosphere. At this time, the reducing agent used to maintain the reaction system in a reducing atmosphere includes, for example, sodium sulfite, sodium hydrogen sulfite, Examples include sodium dithionate.

To describe in more detail a representative example of the embodiment of the present invention, first, the above-mentioned quinone compound is dispersed in water, then the above-mentioned reducing agent is added in an amount of 1 to 10 N sonic equivalent to the quinone compound, and then the above-mentioned carboxylic acid dihalide is dispersed in water. These mixtures are rapidly dissolved by adding 1 to 1 sonic equivalent of the quinone compound.

At this time, in order to neutralize the hydrochloric acid produced by the reaction and to further enhance the reducing atmosphere in the system by keeping the pH in the system high, an alkali equivalent of 2 to 100 times the amount of the quinone compound is used. It's okay. Examples of such alkalis include caustic soda, caustic potash, and the like. Furthermore, in order to prevent the carboxylic acid dihalide from decomposing on contact with water, an organic solvent with no affinity for water, such as methylene dichloride, chloroform, tetrachloroethane, diisopropylether, dibutyl ether, anisole, etc. Even better results can be obtained if the above-mentioned carboxylic acid dihalide is dissolved before use. Also, since the reaction carried out in the present invention is often heterogeneous, suitable surfactants such as benzyltrimethylammonium halide, coconut oil alkyltrimethylammonium halide, etc. may be used to achieve higher reaction rates. phosphonium salts such as ammonium salts of, n-heptyltrimethylphosphonium halide, methyltriphenylphosphonium halide,
arsonium salts such as triphenylmethylarsonium halide, benzyltriphenylarsonium halide,
Sulfonium salts such as dimethyl-2-hydroxyphenylsulfonium halide and tribenzylsulfonium hydrogen sulfate and sulfonate salts such as sodium laurylbenzenesulfonate are converted into quinone compounds 10
The reaction effect can be enhanced by adding 0.1 to 20 parts by weight per part by weight of .・When carrying out the above reaction, there is no need to particularly control the reaction temperature, but if the carboxylic acid dichloride has extremely high reactivity and is easily decomposed by water, cooling may be necessary, and conversely, if the carboxylic acid dichloride has low reactivity, cooling may be necessary. It is desirable to perform heating.

In any case, the reaction temperature is preferably within the range of -10°C to 100°C. The reaction time also depends on the reactivity of the quinone compound and carboxylic acid dichloride, so the optimal reaction time varies greatly depending on the individual combination, but generally the optimal reaction time exists within the range of 1 minute to 1 m hour. do. After the reaction is complete, the reaction mixture is poured into methanol, acetone, or water, and the resulting aromatic polyester precipitate is filtered, or immediately passed through a furnace to separate the aromatic polyester, and then washed with an appropriate solvent. All you have to do is purify it.

The present invention will be more specifically explained with reference to the following examples, but the present invention is not limited to these examples.
Example 1 After dispersing 83 anthraquinone in water, 2
00 ml of sodium dithionite and 250 ml of caustic soda were added, and stirring was continued until they were dissolved.

Next, a tetrachloroethane solution containing 96 days of azelaic acid dichloride and 12 days of coconut oil alkyltrimethylammonium chloride was added, and the liquid temperature was brought to 15 degrees.
The container was cooled with water to keep it at a constant temperature, and the container was rapidly evaporated. 1
After 0 minutes of continuous heating, the reaction solution was allowed to stand still, and the reaction solution was separated into two layers.

When only the lower organic layer was extracted and poured into acetone for 20 minutes, a white fine particle precipitate was precipitated. This precipitate was separated in a furnace, washed repeatedly with water and acetone, and then vacuum-dried to obtain a pure white polymer powder of 142 mm. (Yield 98%) This polymer has an infrared absorption spectrum of 1758 skin-1, 1620 skin-1, 1360 skin-1,
It has absorptions at 110-1, 750-1, 350-39-1 in the ultraviolet absorption spectrum, and 172-1, 140-12, and 126-12 in the 1°C-NMR spectrum. It turned out to be a polyester with a structure.

Furthermore, when the solution viscosity of this polymer was measured, it was found that
It was found that the polymer had an extremely high degree of polymerization, h=0.88 (in 3000 tetrachloroethane). Shoto in
h is expressed as follows: inh=(lnt/t.

)/C (where, to is the capillary fall time (seconds) of only tetrachloroethane, t is the capillary fall time (seconds) of the tetrachloroethane solution of the polymer, and C is the concentration of the polymer in the tetrachloroethane solution. The unit is evening/100'.

) is the value calculated by Comparative Example Example 1 was repeated except that 1200 ml of sodium dithionite was not added.

No polymer was produced even if tozusa was continued for more than one field hour, and only sodium azelate, which is a hydrolyzate of the raw materials anthraquinone and azelaic acid dichloride, was recovered.

Comparative Example 2 208 grams of anthraquinone was dispersed in 100 grams of diethylene glycol dimethyl ether, and 100 grams of sodium borohydride, a strong reducing agent, was added to reduce the solution.

The reaction solution was added to IN hydrochloric acid for 20 minutes, and the resulting precipitate of anthrahydroquinone was separated in a furnace and dried. Next, the above anthrahydroquinone was dissolved in water containing 100 ml of caustic soda, and a tetrachloroethane solution containing 220 ml of azelate dichloride and 7 ml of coconut oil alkyltrimethylammonium chloride was added, and the solution temperature is 15
While cooling the container with water to maintain the temperature of 0, the container was rapidly lit.
After boiling for 3 minutes, a polymer powder was obtained in the same manner as in Example 1, but the amount was only 180 mm (yield 50%), and the solution viscosity of this polymer was 0.2 mm (yield: 50%). 30
°C in tetrachloroethane) and had a low degree of polymerization.

Example 3 Example 1 was repeated by replacing the azelaic acid chloride 96 of Example 1 with various dicarboxylic acid dihalides shown in Table 1.

The results are shown in Table 1. Table 1 Example 4 After dispersing 83 anthraquinone in water, 2
After adding 0.00 ml of sodium dithionite and 250 ml of caustic soda and continuing stirring until dissolved, 11 ml of triphenylmethylarzonium chloride was added and stirring was continued for another 10 minutes.

This solution contains 849 isophthalic acid dichloride 2
Add the dichloroethane solution and bring the temperature of the solution to 100-30
Rapid loss of water was continued for 35 minutes while cooling the vessel to a temperature within the range of 0. After completing Nada Azusa, the above reaction solution was poured into hexane for 10 minutes, and the resulting polymer precipitate was separated in a furnace, washed repeatedly with water and methanol, and vacuum dried.
Two pure white polymers were obtained (95% yield).

Claims (1)

[Claims] 1. A method for producing an aromatic polyester, which comprises reacting a quinone compound and a dicarboxylic acid dihalide in a reducing atmosphere.