JPH03149223A - Production of aromatic polyetherketone - Google Patents

Abstract

PURPOSE:To produce an arom. polyetherketone excellent in the heat resistance, strengths, etc., with a good processability by reacting diphenyl ether with an arom. dicarboxylic acid dihalide in the presence of a Lewis acid and a complex prepd. in advance from the Lewis acid and a Lewis base. CONSTITUTION:In the presence of a catalyst comprising a Lewis acid (e.g. aluminum trichloride) and a complex of the Lewis acid with a Lewis base (e.g. triethylamine hydrochloride), diphenyl ether is reacted with an arom. dicarboxylic acid dihalide (e.g. terephthalic acid dihalide) in a solvent (e.g. methylene chloride) to give an arom. polyetherketone. Thus, all the steps of polymn. are carried out in a state of a homogeneous soln., and the catalyst is very effectively eliminated in the catalyst elimination step after polymn.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a new method for producing aromatic polyetherketone, which is a polymer, by a homogeneous solution polymerization method.

[Conventional technology]

Aromatic polyetherketones have excellent heat resistance, mechanical strength, chemical resistance, etc., and have a wide range of uses as molded products, fillers, and fibers.

Conventionally, many methods have been proposed for producing the present polymer, including, for example, a method in which diphenyl ether and aromatic dicarboxylic acid civalide are reacted in a solvent using a Lewis acid as a catalyst.

[Problem to be solved by the invention]

However, aromatic polyetherketones are insoluble in most solvents, so in the production methods proposed so far, the polymer precipitates in the reaction medium as the polymerization reaction progresses, resulting in a suspended or slurry state. A reaction must take place. Therefore, it is difficult to obtain an aromatic polyetherketone having a high molecular weight and stable properties, and there are also problems in that the catalyst cannot be efficiently removed from the produced polymer.

[Failure to solve the problem]

The present inventors have solved these problems, and have been working diligently on a method for producing aromatic polyetherketones that can produce aromatic polyetherketones with high molecular weight and stable properties, and that can also efficiently remove the catalyst. As a result of study, we have arrived at the present invention.

That is, the present invention involves reacting diphenyl ether and an aromatic dicarboxylic acid civalide in a solvent in the presence of a previously prepared complex of a Lewis acid and a Lewis base (hereinafter referred to as a Lewis base-Lewis acid complex) and a Lewis acid. This is a method for producing an aromatic polyetherketone, which comprises:

Aromatic polyetherketones produced by the process of the invention are particularly suitable for use with the general formula % [where Ar is a substituted or unsubstituted phenylene group, or a substituted or unsubstituted polycyclic aromatic group (such as naphthyl)] ] According to the present invention, it is possible to produce a high molecular weight aromatic polyetherketone.

Examples of the substituent of the substituted phenylene group include those conventionally known as substituents in this type of polymer.

Examples of the aromatic dicarboxylic acid cybalide used in the present invention include those represented by the general formula: % formula % [In each formula, Ar has the same meaning as above, and X is a halogen] Terephthalic acid Dichloride and isophthalic acid dichloride are preferred.

The Lewis acid used in the present invention is not particularly limited as long as it can form a complex with the carbonyl group of the aromatic polyether ketone produced, and is usually aluminum trichloride, boron trichloride, aluminum tribromide, or aluminum chloride. Examples include ferric iron, stannic chloride, titanium tetrachloride, and antimony pentachloride. In the Friedel-Crafts polymerization reaction of the present invention, the Lewis acid forms a complex with the carbonyl groups of the raw material compound and the produced aromatic polyether ketone and loses its activity as a catalyst. It is preferable to use an equivalent or more Lewis acid, and in the present invention, by using a Lewis acid in an amount of 2 times or more, preferably 2.5 to 4 times the equivalent of the acid halide,
Particularly suitable polymerization rates are obtained.

The Lewis base-Lewis acid complex used in the present invention has the effect of dissolving the polymer produced during the main polymerization reaction, that is, the aromatic polyether ketone, in the reaction medium. , any of them can be used in the present invention. A suitable Lewis base-Lewis acid complex is
It may be selected as appropriate depending on the molecular structure of the aromatic polyetherketone, that is, the type of aromatic dicarboxylic acid cybaride. In particular, the Lewis bases forming the complex used in the present invention include trimethylamine hydrochloride, triethylamine hydrochloride, pyridine, and dimethylformamide. In addition, Lewis acids include aluminum tribromide,
Examples include boron trichloride, aluminum tribromide, ferric chloride, tin chloride, titanium tetrachloride, and antimony pentachloride, with aluminum trichloride being particularly preferred. In addition, when the Lewis acid in the complex is aluminum tribromide, triethylamine hydrochloride is preferable as the Lewis base from the viewpoint of polymerization rate and solubility of the polymer in the reaction medium.

Therefore, in order to carry out the polymerization reaction in a homogeneous solution state, which is a feature of the present invention, it is necessary that the Lewis acid-Lewis base complex be present in an amount necessary to dissolve the produced aromatic polyether ketone in the reaction medium. is necessary. The amount of the Lewis acid-Lewis base complex used is usually 2 to 10 times the equivalent, preferably 4 to 7 times the equivalent of the acid halide. In this amount, the aromatic polyetherketone can be suitably dissolved in the reaction medium.

As the solvent of the present invention, known aprotic organic solvents such as methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, 1.1.2.2-tetrachloroethane, nitrobenzene, etc. are used, and Lewis acid-Lewis base Ethylene chloride is particularly preferred from the viewpoint of solubility and polymerization rate of the aromatic polyether ketone due to interaction with the complex. The amount of the solvent used is 1 to 20 times (weight ratio), preferably 2 to 10 times (weight ratio) to the weight of the monomer charged.

The reaction method in the present invention includes a method of adding a slurry solution of a Lewis acid-Lewis base complex containing an excess of Lewis acid to a solution containing diphenyl ether and an aromatic dicarboxylic acid civalide, a method of adding a slurry solution of a Lewis acid-Lewis base complex containing an excess of Lewis acid, and a method of adding a slurry solution of a Lewis acid-Lewis base complex and a Lewis Any method of adding the acid separately may be used.

A polyether ketone having a sufficiently high molecular weight cannot be obtained by the reverse method of the present invention, that is, by adding a monomer or a monomer solution to a system in which a Lewis acid or Lewis base-Lewis # complex is present.

The reason for this is not clear, but it is speculated that side reactions are more likely to occur due to the rapid reaction caused by adding Monomer 1 to a system in which a high concentration of catalyst is present, and the polymerization reaction is inhibited.

In addition, the method of adding a Lewis acid and Lewis base to monomer type 1 or monomer solution has a slower polymerization rate than the method of adding a Lewis acid-Lewis base prepared in advance as in the present invention, and the solubility of the complex in the polymer is also less desirable.

When adding a Lewis acid or a Lewis acid-Lewis base complex in the present invention, it is necessary to cool the reaction system to 0°C to 10°C and suppress heat generation in the reaction system to obtain an aromatic polyether ketone with excellent thermal stability. By carrying out the subsequent reaction at a temperature of 0° C. to 50° C., preferably 10° C. to 40° C., an aromatic polyetherketone, particularly an aromatic polyetherketone with a high degree of polymerization, can be obtained.

〔Example〕

The present invention will be explained below with reference to Examples, but the present invention is not limited to the Examples.

Example 1 15.91 g of trimethylamine hydrochloride and 20 d of dichloroethane were charged into a 200 d glass reactor equipped with a stirrer, a thermometer, a nitrogen gas inlet, and a gas outlet, and the mixture was cooled to 5° C. in a water bath, and aluminum trichloride was heated to 39 d. 96 g was slowly added while suppressing heat generation so that the reaction temperature was 20° C. or less to obtain a complex slurry. 20 with similar equipment
A 0d glass reactor was charged with 5.67 g of diphenyl ether, 4.06 g of terephthalic acid dichloride, and 170 g of isophthalic acid dichloride, and 20 g of dichloroethane was charged.
d was added and dissolved, and the mixture was cooled to 5°C, and the above Lewis acid-Lewis base complex slurry was added dropwise. Since intense heat generation was involved, the addition was carried out slowly to keep the reaction temperature below 15°C. Thereafter, the reaction was carried out at 20° C. for 5 hours to obtain a smooth and uniform polymer solution. The solution was added to Iffi methanol which was being rotated at high speed with a homomixer to precipitate the polymer, which was then filtered to obtain a white polymer. The polymer was treated at room temperature with 500 d of methanol for 1 hour, then with 50 d of acetic acid (1
After washing with 500 ml of methanol for 1 hour and 500 ml of methanol for 1 hour, the mixture was filtered and dried under vacuum at 130° C. overnight. The logarithmic viscosity (ηinh) measured at 30° C. at a concentration of 15 g/100 d using concentrated sulfuric acid as a solvent was 1.25.

Example 2 Using the same apparatus as in Example 1, first 9.16 g of triethylamine hydrochloride and 30 d of dichloroethane were charged, and 5
The mixture was cooled to ℃ and 17.74 g of aluminum trichloride was slowly added to obtain a complex slurry. In another similar apparatus, 2.83 g of diphenyl ether and 2.8 g of terephthalic acid dichloride.
Take 53 g of isophthalic acid dichloride and 0.84 g of isophthalic acid dichloride, add 20 d of dichloroethane, dissolve, and heat in a water bath at 5°C.
It was cooled to The above Lewis acid-Lewis base complex slurry was added to this Chizummer solution. Since there was a large amount of heat generated, the addition was carried out slowly to keep the reaction temperature below 15°C.Then, the reaction temperature was raised to 20°C and polymerization was carried out for 5 hours to obtain a very smooth and uniform polymer solution. A white polymer was obtained by performing the same post-treatment and drying as in Example 1. ηi
nh was 1.44.

Comparative Example 1 The weight of each raw material was the same as in Example 2, and the order of feeding was changed as follows. Triethylamine hydrochloride was placed in a reaction vessel, and 30 ml of dichloroethane was added thereto. After cooling the reaction vessel to 5° C. in a water bath, aluminum trichloride was added. Since it generates heat, it was added slowly to keep the reaction temperature below 20°C.

Then diphenyl ether, terephthalic acid dichloride and isophthalic acid dichloride were added to dichloroethane 2
0jl! A monomer solution dissolved in was added dropwise. Since heat was generated, the mixture was slowly added dropwise to keep the reaction temperature below 20°C. After reacting at 20° C. for 5 hours in the same manner as in Example 2, post-treatment and drying were performed to obtain a white polymer. ηinh is 0.
It was 37.

Comparative Example 2 Using the apparatus of Example 1, 2.83 g of diphenyl ether, 2.53 g of terephthalic acid dichloride, and 0.84 g of isophthalic acid dichloride were placed in a reaction vessel, and 50 d of dichloroethane was added and dissolved. Then, after adding 9.16 g of triethylamine hydrochloride, the mixture was cooled to 5° C. in a water bath, and 17.74 g of aluminum trichloride was added. Since a large amount of heat was generated, the addition was carried out slowly to keep the reaction temperature below 15°C. After the addition of aluminum trichloride was completed, the water bath was removed, the reaction temperature was raised to 20° C., and polymerization was carried out for 5 hours to obtain a uniform and smooth liquid. The same post-treatment and drying as in Example 1 were performed to obtain a pale yellow polymer.

The ηinb of this polymer was 0.86, and the degree of polymerization of the polymer was lower than that in Example 2, in which a Lewis acid-Lewis base complex slurry was added.

Comparative Example 3 Using the same apparatus as in Example 1, the addition of triethylamine hydrochloride was stopped and the amount of aluminum trichloride added was 8.8
The same reaction as in Comparative Example 2 was carried out except that the reaction was changed to Fg. Polymer precipitated in the reaction system 15 minutes after the addition of aluminum trichloride was completed, and this state continued until the end of the polymerization reaction. The same post-treatment as in Example 1 was performed to obtain a pale yellow polymer. ηinh was 0.72.

Experimental example 1 (Quantification of /l in polymer) High frequency plasma emission spectrometer W (Shimadzu ICPQ-1
000), the content of All in the polymers obtained in the Examples and Comparative Examples shown in the table was measured.

-11inh of each polymer and the AN content in the polymer are shown in Table-1.

[Margin below]

Table-1 ηinh A2 content in polymer (ppm) Example 1 1.25 210〃2 1.44
190 Comparative Example 10.37 310 〃2 G, 86 350 〃3 0.72 720 As is clear from Table 1, the polymer obtained by the homogeneous solution polymerization method of the present invention has a high degree of polymerization, and Affi in the polymer The content is low, and the All removal efficiency in the post-treatment process is excellent.

〔effect〕

According to the production method of the present invention, all stages of the polymerization reaction can be carried out in a homogeneous solution state, and the removal efficiency of the catalyst is also excellent in the decatalyst treatment after the polymerization reaction.

Therefore, the present invention is easy to operate and is industrially effective.

In particular, by carrying out the present invention, aromatic polyetherketones with high molecular weight can be produced, and the aromatic polyetherketones thus produced have excellent heat resistance, mechanical strength, chemical resistance, etc. It is.

Claims (1)

[Claims] A method for producing an aromatic polyether ketone, which comprises reacting diphenyl ether and an aromatic dicarboxylic acid dihalide in a solvent in the presence of a previously prepared complex of a Lewis acid and a Lewis base and a Lewis acid.