JPH0739488B2 - Amorphous polymer and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel amorphous polymer and a method for producing the same. More specifically, the present invention provides a heat-resistant amorphous polymer having a high glass transition temperature and excellent thermal stability and having a smaller polarity than conventional ones, and a method for efficiently producing the same. It is about.

Conventional technology Conventionally, as a representative of heat-resistant amorphous resin, fragrance
Group polyether sulfones (eg, ICI, Victrex P
ES ) Or polyether imide (eg GE, Ultem
) Is known. These resins are expensive glass
It has a transition point and has excellent heat resistance that can withstand use at high temperatures.
Although it is a engineering resin, it has a sulfone group in the molecule.
Since it has a highly polar group such as an imide group,
Large change in performance due to humidity and high dielectric constant, etc.
From the drawback that it is inevitable to be restricted to applications in the electrical field
Have Further, the sulfone group and the imide group are heat stable.
Since the property is not always sufficient, the
There is also a problem with the stability of coalescence.

On the other hand, as a resin having more excellent thermal stability,
Aromatic polyether ketones are known. For example Vict
rex PEEK (Manufactured by ICI) or general formulaIn x, various values of x, or
Known to have introduced the ethylene structure or naphthalene structure.
However, all of these resins are crystalline polymers.
By the way, until now the amorphous wholly aromatic polyether ketone has
unknown.

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention Under the circumstances, the present invention is resistant to use at high temperature and excellent in stability during molding, and has a small polarity,
The purpose of the invention is to provide a heat-resistant amorphous polymer having low hygroscopicity.

Means for Solving the Problems As a result of intensive studies to develop a heat-resistant amorphous polymer having the above-mentioned preferable properties, the present inventors have found that a part of the ether bond of an aromatic polyether ketone. Furthermore, it was found that the aromatic polyether ketone can be made amorphous by introducing a dibenzofuran structure, and the present invention was completed based on this finding.

That is, the present invention has the formula And an amorphous polymer having a molecular weight corresponding to a reduced viscosity of 0.2 dl / g or more measured at a temperature of 25 ° C. as a 0.5% (weight / volume) solution in N-methylpyrrolidone. It is a thing.

According to the present invention, the amorphous polymer is 2,8-bis (4-halogenobenzoyl) in the presence of a silica-based compound catalyst.
-Dibenzofuran can be produced by reacting an alkali metal carbonate or hydrogen carbonate with 2,8-bis (4-halogenobenzoyl) -dibenzofuran and 2,8-bis (4-halogenobenzoyl) -dibenzofuran in the presence of an alkali. It can also be produced by polycondensation with -bis (4-hydroxybenzoyl) -dibenzofuran.

Hereinafter, the present invention will be described in detail.

The amorphous polymer of the present invention is an aromatic polyether ketone whose repeating unit has a dibenzofuran structure as shown by the above formula (II).

This amorphous polymer is, in the first method of the present invention,
It can be produced by subjecting 2,8-bis (4-halogenobenzoyl) -dibenzofuran to self-etherification polycondensation with an alkali metal carbonate or hydrogen carbonate in the presence of a silica-based compound catalyst. it can. This reaction can be represented by, for example, the following reaction formula.

(However, X is a halogen atom and M is an alkali metal.) Examples of the alkali metal carbon salt or hydrogen carbonate used in the above reaction include potassium carbonate, sodium carbonate, cesium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, Preference is given to sodium potassium carbonate and the like, and these may be used alone or in combination of two or more. Further, when the potassium salt and the sodium salt are compared, generally, the potassium salt tends to advance the reaction faster.

These alkali metal salts have a faster reaction rate when pulverized and used, and the amount used is high in order to obtain a polymer.
At least 1 g atom (0.5 mol for carbonate and 1 mol for hydrogen carbonate) of alkali metal is required for 1 g of halogen in the monomer. The reaction rate can be increased by using an excess amount of the alkali metal salt, but using an excessively large amount of the alkali metal salt is disadvantageous in terms of production cost, and in some cases, an undesirable side reaction may occur. May occur. Therefore, the preferable amount of the alkali metal salt used is 1 mol of the raw material monomer.
It is selected in the range of 1 to 4 mol in the case of carbonate and 2 to 8 mol in the case of hydrogen carbonate.

In the reaction, a silica-based catalyst is used, and as the silica-based catalyst, for example, silica-based such as dry silica, wet silica, silica gel, or silica-alumina-based catalyst can be used. Examples of the silica-alumina-based catalyst include, in addition to silica-alumina having various compositions, mineral-based compounds such as zeolite, activated clay, sepiolite, montmorillonite, and diatomaceous earth.

These catalysts are preferably used by finely pulverizing because the reaction proceeds rapidly, and the amount used is not particularly limited, but is usually 0.1 to 100% by weight, preferably 1 to 30% based on the raw material monomer. It is selected in the range of weight%. If the amount used is less than 0.1% by weight, the effect of adding the catalyst will not be sufficiently exerted, and if it exceeds 100% by weight, the reaction rate will not be so fast relative to the amount added, and in some cases it may not be desirable. Reaction may occur.

The reaction can be carried out without a solvent, but may be carried out in a suitable solvent. Generally, in the production of an aromatic polyether ketone by polycondensation, the aromatic polyether ketone produced is crystalline and hardly soluble in a solvent.
It is necessary to carry out the reaction at a high temperature of 0 ° C. or higher, and thus it is necessary to use a special solvent such as aromatic sulfone or aromatic ketone that is stable at a high temperature. On the other hand, since the polymer of the present invention is amorphous, it is soluble in common solvents, and polymerization should be carried out at a low temperature of 300 ° C. or lower using a more common solvent such as sulfolane. Is also possible.

The solvent that can be used in the reaction is not particularly limited, and any solvent that is stable at the reaction temperature can be used. Examples of such a medium include acetophenone, benzophenone, xanthone, ketones such as phenoxyzenzophenone, sulfolane, sulfones such as diphenylsulfone, dimethyl sulfoxide, sulfoxides such as diphenyl sulfoxide,
Ethers such as diphenyl ether, amides such as N-methylpyrrolidone and hexamethylphosphoric triamide, hydrocarbons such as biphenyl, terphenyl, naphthalene and decalin, halogenated hydrocarbons such as chlorinated biphenyl and dichlorobenzene. Is mentioned. These solvents have a high boiling point and can be used for the reaction at atmospheric pressure, but when the reaction is performed under pressure, a solvent having a lower boiling point can also be used. Further, the polymerization reaction tends to proceed more easily in a solvent having a higher polarity.

The reaction temperature varies depending on the type of halide and the type of alkali metal salt used, but it is usually selected in the range of 150 to 400 ° C. If this temperature is lower than 150 ° C, the reaction rate is too slow to be practical, and if it exceeds 400 ° C, undesired side reactions are likely to occur.

Raw material monomer 2,8-bis (4-halogenobenzoyl)
-As a halogen atom of dibenzofuran, a fluorine atom proceeds faster than a chlorine atom, but since a fluorine compound is generally more expensive than a chlorine compound, 2,8-bis (4-chlorobenzoyl) -dibenzofuran is used. Using a small amount of copper salt as a co-catalyst to accelerate the reaction,
It is also advantageous to carry out the reaction.

In the second method of the present invention, in the presence of alkali, 2,
By subjecting 8-bis (4-halogenobenzoyl) -dibenzofuran and 2,8-bis (4-hydroxybenzoyl) -dibenzofuran to polycondensation by a nucleophilic substitution reaction, an objective amorphous polymer is obtained. It can be manufactured.
This reaction can be represented by the following reaction formula.

As the alkali in this reaction, an alkali metal carbonate or hydrogen carbonate can be used. As these alkali metal salts, various alkali metal salts described in the first method can be used. Further, these alkali metal salts are usually used in a ratio such that the amount of alkali metal is 0.5 to 4 g atom per 1 mol of the raw material 2,8-bis (4-hydroxybenzoyl) -dibenzofuran. Furthermore, in this method, one of the raw materials, 2,8
-Bis (4-hydroxybenzoyl) -dibenzofuran may be used in the form of an alkali metal salt in advance.

Starting materials 2,8-bis (4-halogenobenzoyl) -dibenzofuran and 2,8-bis (4-hydroxybenzoyl)-
Dibenzofuran is used in a substantially equimolar ratio, and the reaction may be carried out without solvent or in a suitable solvent. As the solvent, various solvents mentioned in the first method can be used. Reaction temperature is usually 150
It is selected in the range of ~ 400 ° C.

2,8-bis (4-halogenobenzoyl) -dibenzofuran and 2,8-bis (4-hydroxybenzoyl) -dibenzofuran used in the method of the present invention are novel compounds.
8-Bis (4-halogenobenzoyl) -dibenzofuran can be easily produced by subjecting dibenzofuran and 4-halogenobenzoyl chloride to a Friedel-Crafts reaction. Examples of this 2,8-bis (4-halogenobenzoyl) -dibenzofuran include 2,8
-Bis (4-chlorobenzoyl) -dibenzofuran, 2,
8-bis (4-fluorobenzoyl) -dibenzofuran, 2- (4-chlorobenzoyl) -8- (4-fluorobenzoyl) -dibenzofuran and the like can be mentioned. In addition, 2,8-bis (4-hydroxybenzoyl)
-Dibenzofuran can be easily produced by hydrolyzing the aforementioned 2,8-bis (4-halogenobenzoyl) -dibenzofuran.

The amorphous polymer of the present invention can be produced by the Friedel-Crafts reaction in addition to the method of the present invention. For example, the desired amorphous polymer is obtained by reacting 4,4'-diphenyl ether dicarboxylic acid chloride with dibenzofuran in the presence of an anhydrous aluminum chloride catalyst in a solvent such as dichloromethane.
Even in this Friedel-Crafts reaction, since the obtained amorphous polymer is soluble in the solvent, a high molecular weight compound is easily obtained as compared with the conventional crystalline polyether ketone.
Since it is necessary to use expensive anhydrous aluminum chloride and there is a problem in treating aluminum chloride after use, it cannot be said to be an industrial method.

The amorphous polymer of the present invention is 0.5% in N-methylpyrrolidone.
% (Weight / volume) solution must have a molecular weight corresponding to a reduced viscosity of 0.2 dl / g or higher measured at a temperature of 25 ° C. If the reduced viscosity is less than 0.2 dl / g, the mechanical properties are inferior and the molded product cannot be put to practical use.

Effect of the Invention The amorphous polymer of the present invention has a high glass transition temperature,
It is suitable for various molded products and films that are used at high temperatures, and has high thermal stability, so that the molding temperature can be increased and the moldability is excellent. Furthermore, since it has lower polarity and hygroscopicity than conventional heat-resistant amorphous new resins, it has the property that there is little change in properties due to moisture absorption, and it is suitable for applications where such properties are required. To be

EXAMPLES Next, the present invention will be described in more detail with reference to Examples.
The invention is in no way limited by these examples.

Production Example 1 Production of 2,8-bis (4-fluorobenzoyl) -dibenzofuran 2 A four-necked flask was charged with 177 g (1.05 mol) of dibenzofuran and 700 ml of nitrobenzene 434 g (3.25 mol) of nitrobenzene, while stirring under a nitrogen atmosphere. p
-Approximately 30 parts of 349 g (2.2 mol) of fluorobenzoyl chloride
It dripped over minutes. Subsequently, the reaction temperature was raised to 100 ° C. and kept at that temperature for 1 hour. After cooling, the reaction product was poured into a large amount of methanol (95%), the precipitate formed was washed with water and methanol, and then recrystallized from toluene to obtain the desired product (310 g).
(Yield 72%) was obtained.

Corresponding chloro compound [2,8-bis (4-chlorobenzoyl) -dibenzofuran] was produced by the same procedure.

Production Example 2 2,8-bis (4-hydroxybenzoyl)-
Production of dibenzofuran 1-Autoclave 36 g (87 m) of 2,8-bis (4-fluorobenzoyl) -dibenzofuran produced in Production Example 1
mol), 8 g (450 mmol) of sodium hydroxide, 360 ml of dimethylsulfoxide and 180 ml of water were charged, and after nitrogen substitution, the temperature was raised to 130 ° C. in 1 hour while stirring, and the reaction was carried out at this temperature for 9 hours. After cooling the reaction product, the white precipitate obtained by neutralizing with hydrochloric acid was washed with water, dried and recrystallized with ethanol to obtain 20 g of 2,8-bis (4-hydroxybenzoyl) -dibenzofuran.

Example 1 In a 200 ml flask, 2,8-bis (4-
Fluorobenzoyl) -dibenzofuran 20.6 g (0.05 mol), potassium carbonate 11 g (0.08 mol), silica (Nippon Aerosil Co., Ltd., Aerosil 300) 2.0 g and diphenyl sulfone 30 g were charged, and after nitrogen substitution, it took 30 minutes. The temperature was raised from room temperature to 300 ° C., and the reaction was continued for 3 hours.
After cooling, the reaction product was crushed and washed repeatedly with water and acetone to obtain 19.3 g of pale yellowish purple powder. This product was dissolved in chloroform, N-methylpyrrolidone and concentrated sulfuric acid to give N-
0.5% (weight / volume) in methylpyrrolidone, the reduced viscosity at 25 ° C. was 0.74 dl / g.

It was confirmed by wide-angle X-ray diffraction that the polymer was amorphous, and the glass transition point was 230 ° C. The infrared absorption spectrum of this polymer is shown in the figure.

Example 2 Instead of 2,8-bis (4-fluorobenzoyl) -dibenzofuran in Example 1, 2, obtained in Preparation Example 1 was used.
8-bis (4-chlorobenzoyl) -dibenzofuran 22.
When 3 g (0.05 mol) was used, 30 mg of cupric chloride was newly added, and the reaction was carried out in the same manner as in Example 1 except that the reaction time was 6 hours, a pale yellow-purple powder was obtained. . This polymer was amorphous and had a reduced viscosity at 25 ° C. and a glass transition point which were almost the same as those of the product of Example 1.

Example 3 In a 200 ml flask, 2,8-bis (4-
20.6 g (0.05 mol) of fluorobenzoyl) -dibenzofuran, 20.4 g (0.05 mol) of 2,8-bis (4-hydroxybenzoyl) -dibenzofuran obtained in Production Example 2, 6.9 g (0.05 mol) of potassium carbonate and diphenyl Sulfone 40
After charging g, the same operation as in Example 1 was performed to obtain a pale yellow-purple powder.

The polymer was amorphous and had a reduced viscosity at 25 ° C. and a glass transition temperature of about the same as the product of Example 1.

[Brief description of drawings]

The figure is an infrared absorption spectrum chart of an example of the amorphous polymer of the present invention.

Claims (3)

[Claims] 1. A formula And an amorphous polymer having a molecular weight corresponding to a reduced viscosity of 0.2 dl / g or more measured at a temperature of 25 ° C. as a 0.5% (weight / volume) solution in N-methylpyrrolidone. 2. A formula characterized by reacting 2,8-bis (4-halogenobenzoyl) -dibenzofuran with an alkali metal carbonate or hydrogen carbonate in the presence of a silica-based compound catalyst. And a method for producing an amorphous polymer having a molecular weight corresponding to a reduced viscosity of 0.2 dl / g or more measured at a temperature of 25 ° C. as a 0.5% (weight / volume) solution in N-methylpyrrolidone. . 3. In the presence of alkali, 2,8-bis (4-halogenobenzoyl) -dibenzofuran and 2,8-bis (4-)
Hydroxybenzoyl) -dibenzofuran with polycondensation And a method for producing an amorphous polymer having a molecular weight corresponding to a reduced viscosity of 0.2 dl / g or more measured at a temperature of 25 ° C. as a 0.5% (weight / volume) solution in N-methylpyrrolidone. .