JPS63258923A - Production of aromatic polyether ketone - Google Patents

Abstract

PURPOSE:To produce, in high efficiency, high-crystallinity aromatic polyether ketone having high heat resistance, flame retardancy and solvent resistance by reaction of an aromatic dihalide of specific structure in the presence of an alkali metal (bi)carbonate under heating. CONSTITUTION:In the presence of an alkali metal carbonate or bicarbonate such as potassium carbonate, an aromatic dihalide of formula I (X<1>, X<2> are halogen) are heated at temperature of 250-400 deg.C to effect reaction to give an aromatic polyether ketone of formula II, preferably of over 0.7 intrinsic viscosity. The compound of formula I is novel and obtained by Friedel-Craft reaction of terephthaloyl dichloride and 2 or more times molar amount of diphenyl ether to give 4,4'-diphenoxyterephthalophenone followed by Friedel-Craft condensation reaction between the product and 2 or more molar amount of p-halogenobenzoyl chloride.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a novel method for producing aromatic polyetherketones. More specifically, the present invention has a chemical structure in which phenylene groups are linked via an ether group and a ketone group, and has physical properties such as heat resistance, flame retardance, solvent resistance, mechanical properties, and thermoplastic moldability. The present invention relates to an efficient and industrially advantageous method for producing highly crystalline aromatic polyetherketones with excellent properties.

Conventional technology Conventionally, as polymer compounds having a chemical structure in which phenylene groups are linked via an ether group and a ketone group, for example, those having a structural formula and those having a structural formula are known, and these have excellent properties. It is attracting attention as a molding material because of its heat resistance, flame retardance, and mechanical strength (Japanese Patent Publication No. 57-22938, Japanese Patent Publication No. 56-1982).
33419, Japanese Patent Publication No. 60-32642).

As a method for producing these polymers, an activated aromatic cybaride and a dihydroxy aromatic compound are subjected to dinucleophilic polycondensation in the presence of an alkali (Japanese Patent Publication No. 57-2293B , Special Public Service 1986-32
4542) and a method of electrophilic polycondensation of an aromatic acid halide and an aromatic ether compound by Friedel-Crafts reaction (Japanese Patent Publication No. 56-33419).

By the way, the former method and the latter method not only differ in the reaction format and the molecular structure of the produced polymer, but also in the physical properties of the resulting polymer. ), and as a result, the modulus at high temperatures (200 to 350'C) tends to be low. This is thought to be due to the formation of bonds due to orientation, which causes heterobonds and branching in the polymer chains.

Furthermore, in the Friedel-Crafts reaction, polyetherketones with a higher melting point, such as those with the structural formula 0%, are also known, but this reaction produces unstable xanthohydrol groups at the terminals during polymerization. Another problem is that a special operation called reduction treatment is required for stabilization.

In this way, the aromatic polyetherketone obtained by the Friedelta-lat reaction differs in polymer structure from the equivalent obtained by the nucleophilic polymerization reaction, and is inferior in practical performance. However, it has not yet become industrialized.

On the other hand, regarding nucleophilic polymerization reactions, it is possible to produce polymers of the above structural formulas (1) and (II) (Japanese Patent Publication No. 57-22938, Japanese Patent Publication No. 60-32642), For polymers with higher melting points than those, for example, it is necessary to raise the polymerization temperature, and the conventional polymerization method using aromatic sulfone solvent under such conditions (Japanese Patent Application Laid-Open No. 52-96700) If this is done, branching occurs and gelation occurs, making it impossible to produce the desired polymer.

Therefore, the present inventors discovered that the melting point and glass transition temperature are higher than the conventional aromatic polyetherketones represented by the structural formulas (1) and (II), and the crystallinity is lower than that of the conventional aromatic polyetherketones.
In order to develop aromatic polyether keto/ which has excellent physical properties such as flame retardancy, solvent resistance, mechanical properties, and thermoplastic moldability, we first developed 4,4'-bis(4,4'-bis( p
-halogenobenzoyl)diphenyl ether and 4.4'
- dihydroquine terephthalophenone, or 4,4'-bis(p-hydroquine benzoyl) diphenyl ether and 4,4'-dihaloterephthalophenone, using these specific polymerization solvents. It has been discovered that by polycondensation under specific conditions, a crystalline polymer having the above-mentioned excellent physical properties and having a repeating unit represented by the formula can be obtained.

However, in such a production method, side reactions are likely to occur, two types of raw materials are required, a high molecular weight product cannot be obtained unless the molar ratio of the Ame-gami-summer is matched, and the resulting polymer has terminal Since it has a phenol group that is unstable to heat, there are problems such as the need for terminal stabilization, which has not always been satisfactory.

Problems to be Solved by the Invention The present invention solves these problems and improves heat resistance, flame retardancy,
A method for efficiently and industrially advantageously producing an aromatic polyetherketone having a repeating unit represented by the formula (V), which has excellent physical properties such as solvent resistance, mechanical properties, and thermoplastic moldability. It was made for the purpose of providing.

Means for Solving the Problems The present inventors have conducted intensive research to achieve the above object, and as a result, in the presence of an alkali metal carbonate or bicarbonate,
It was discovered that the object could be achieved by subjecting an aromatic cybaride having a specific structure to a heating reaction at a predetermined temperature, and based on this knowledge, the present invention was completed.

That is, in the present invention, in the presence of an alkali metal carbonate or bicarbonate, the general formula % formula % (in the formula, Xl and are respectively) is a rogen atom, which may be the same, which may be different from each other) is subjected to a heating reaction at a temperature in the range of 250 to 400°C,
The present invention provides a method for producing an aromatic polyetherketone having a repeating unit represented by the formula %.

The present invention will be explained in detail below.

In the method of the present invention, an aromatic dinolide represented by the above general formula is used as a raw material monomer. As X in formula (to), a fluorine atom and a chlorine atom are preferable, and specific examples of such aromatic cybarides include the following. Among these compounds the formula (
Aromatic difluoride represented by formula (Vl-1) is highly reactive and gives a high molecular weight polymer in a short time polymerization, but is expensive, while aromatic dichloride represented by formula (Vl-2) has a slow reaction rate. Since it is inexpensive, it is industrially advantageous. In addition, these aromatic sybarides are 1
A species may be used, or two or more species may be used in combination.

These aromatic cybarides are new compounds, but for example, 4,4'-diphenoxyterephthalophenone is produced by first reacting terephthalic acid dichloride with diphenyl ether in an amount twice as much in mole or more by Friedel-Crafts reaction. Then, this substance and more than twice the molar amount of p
- an alkali metal carbonate used in the method of the present invention, which can be produced by condensing O with halogenobenzoyl chloride by a Friedel-Crafts reaction;
As the bicarbonate, for example, potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate, and mixtures thereof are preferably used. When comparing potassium salts and sodium salts, potassium salts generally react faster, but
Sodium salts have characteristics such that the reaction rate is accelerated by a catalyst and there are few side reactions.

In the present invention, these alkali gold 1iJ': salt 1
One oxygen atom is released from the molecule, and two halogen atoms in the aromatic cybaride are eliminated to form an ether bond, yielding a polymer having a repeating unit represented by the above formula (g). Therefore, the alkali metal salt is
It is essential to use 1 equivalent or more.

However, if too much of the alkali metal salt is used, it will be disadvantageous in terms of production cost and may also cause undesirable side reactions. Therefore, the preferred amount of the alkali metal salt to be used is selected within the range of 1 to 10 moles per mole of aromatic cybaride. Further, when these alkali metal salts are used after being finely pulverized, the reaction rate becomes faster.

In the method of the present invention, the speed of the polymerization reaction can be increased by using a silica compound as a catalyst.

Examples of this silica-based compound include various silicas called silicon dioxide, silicic anhydride, silica, etc.
Silica alumina (aluminum silicate), zeolite,
Examples include various mineral compounds containing silica such as activated clay, seviolite, montmorillonite, and giso earth.

It is preferable to use these silica-based compounds in finely ground form because the reaction proceeds more quickly, and their addition: 1 [Although there are no particular restrictions on the weight of aromatic cibaride used as a raw material] Based on the past, it is selected in the range of 0.1 to 100 weight) -11%. If this amount is less than 0.1% by weight, the effect as a catalyst will not be sufficiently exhibited, and if it exceeds 100% by weight, the polymerization rate will not be high enough for the amount, which may be undesirable in some cases. Side reactions may occur.

When the silica-based compound is used as a catalyst, the polymerization rate is further accelerated by using copper or a copper compound as a co-catalyst. When using sodium salt as the alkali metal salt or when using sodium salt as the alkali metal salt, the use of such a co-catalyst is particularly effective.As the co-catalyst copper or copper compound, for example, metallic copper, -valent, A divalent copper compound can be used. Examples of the divalent copper compound include cuprous chloride, cuprous bromide, cuprous iodide, cuprous chloride, Cupric chloride, cupric bromide, etc. cupric chloride, cuprous oxide, cupric oxide, copper hydroxide, copper sulfate, basic steel carbonate, copper acetylacetonate,
Preferred examples include copper acetate and copper sulfide. these are,
It may be used in a form containing crystal water, or two or more types may be used in combination.

The amount of this promoter used is usually 0.01 to 500 parts by weight, preferably 0.01 to 500 parts by weight, per 100 parts by weight of the silica compound.
It is selected in a range of 1 to 100 parts by weight.

In the method of the present invention, the polymerization reaction may be carried out in the absence of a solvent or in a suitable solvent. There are no particular limitations on the solvent used, as long as it is inert and stable at the reaction temperature. Examples of such solvents include ketones such as acetophenone, benzophenone, xanthone, and fenoquine benzophenone; sulfones such as sulfolane and diphenyl sulfone; ethers such as diphenyl ether; and N-methylpyrrolidone and hexamethylphosphoric triamide. Examples include amides, hydrocarbons such as piphenyl, terphenyl, naphthalene, and decalin, and logenated hydrocarbons such as chlorinated biphenyls. The example given here has a high boiling point;
Although it can be used for the reaction at normal pressure, it is also possible to polymerize under pressurized conditions if the solvent has a boiling point lower than the polymerization temperature.

Since the reaction proceeds more easily when the polarity of the solvent is high, particularly preferred solvents include diphenylsulfone-benzophenone, xanthone, etc., which have high polarity and are stable at high temperatures.

The polymerization reaction is preferably carried out under an inert gas atmosphere such as nitrogen or argon, and the reaction temperature is 250 to 400 ℃.
Selected in the range of °C. If this temperature is less than 250°C, the reaction rate is too slow to be practical, while if it exceeds 400°C, undesirable side reactions are likely to occur. The preferred reaction temperature varies depending on the type of alkali metal salt and catalyst used, and is therefore appropriately selected within the above range.

In this way, a high molecular weight polymer having repeating units represented by the formula is obtained.

This high molecular weight polymer desirably has an intrinsic viscosity of 0°7 or more. If the intrinsic viscosity is less than 0.7, the mechanical strength of the molding material or film will be poor, which is not preferable.

In addition, the polymer obtained by the method of the present invention has high crystallinity and D
The heat of crystal fusion measured by SC (differential scanning calorimeter) is 8Ca
I/9 or more, usually in the range of 10-20 cal/g.

Since it has such a high heat of crystal fusion, the modulus is high even at high temperatures, and the effect of improving the heat distortion temperature by glass fiber is large.

Effects of the Invention In the method for producing aromatic polyetherketone of the present invention, there are fewer side reactions because unstable phenols are not used, and since only one type of raw material is required, it is easy to secure raw materials. It also has the advantage that the polymerization reaction is simple. Furthermore, the resulting polymer has halogen groups at both ends and is characterized by containing no unstable phenol groups.

The aromatic polyetherketone obtained by the method of the present invention has a high melting point, high molecular weight, high crystallinity, does not contain gels or branches,
It is a thermoplastic polymer, has excellent heat resistance and excellent mechanical properties, and is hardly soluble in solvents other than concentrated sulfuric acid at room temperature, exhibiting extremely excellent solvent resistance.

Therefore, the crystalline aromatic polyetherketone obtained by the method of the present invention is suitable as a molding material used under severe conditions at high temperatures. This polymer can be formed into any desired shape,
For example, it can be used in the form of molded products, coatings, films, fibers, etc. It can also be mixed with various engineering plastics, heat-resistant resins, glass fibers, carbon fibers, inorganic materials, etc. to form alloys and composites. .

EXAMPLES Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way.

The polymer of the present invention is only slightly soluble in concentrated sulfuric acid and is insoluble in general organic solvents, so it is difficult to determine its average molecular weight. Therefore, the intrinsic viscosity is used as a measure of molecular weight.

Further, the physical properties of the polymer were measured as follows.

The measurement sample was prepared by thoroughly pulverizing a solid or powder obtained by polymerization.

(1) Using concentrated sulfuric acid with an intrinsic viscosity density of 1.64 g/d, a solution of 100
Solution containing 0.1 g of cI113 polymer and solution 100
Prepare a solution containing 0.57 ct”5゛si polymer,
The viscosity was measured at 25°C, and the formula % formula % [where ηrθ1 is the relative viscosity, C is the concentration (97100
m1), and C→0 means extrapolating the value of (ηrelt)7c to the point where the concentration C is 0.

(2) Crystal melting point (Tm), glass transition temperature (Tg), crystal heat of fusion (△H) The temperature of the polymer powder was once raised to 400°C, and the rapidly cooled sample was subjected to DSC (Differential Scanning Calorimetry 111).
The temperature was measured at a heating rate of 10/min.

Synthetic terephthalic acid dichloride 20.3 y (0.1 mol)
, 51.1 g (0.3 mol) of diphenyl ether and 26.69 (0.2 mol) aluminum chloride are dissolved in 350 g/0-dichlorobenzene cooled to OC,
The reaction was continued for 4.5 hours while stirring. The reaction mixture was then diluted with a large [? The precipitated solid was filtered out and washed several times with water and methanol.

This product had a melting point of 218C, which was consistent with the standard product of 4,4'-diphenoxyterephthalophenone.

(2) Synthesis of aromatic difluoride (IV-1) 4,4'-diphenoquine terephthalophenone obtained above 4.
7 g (0.01 mol) and 6.00 s (0.0715 mol) of aluminum chloride were added to 60 m of O-dichlorobenzene.
4.0 g of 4-fluorobe/solyl chloride (0.02
5 mol) was added dropwise. After the dropwise addition was completed, the temperature was gradually raised and the reaction was carried out at 60° C. for 3 hours to complete the reaction. Then,
The reaction mixture was added to a mixture of methanol and hydrochloric acid, and the precipitated solid was filtered off and purified by washing with water, aceto/N-methylpyrrolidone, and acetone in this order.

This compound had a melting point of 308° C., and elemental analysis (2) confirmed that it was a compound represented by the formula. The IR spectrum of this compound is shown in FIG.

Reference Example 2 Production of aromatic dichloride (Vl-2) 4,4'-diphenogine terephthalophenone synthesized in Reference Example 1 26.8'! (0,057 mol) and 34.3 g (0,257 mol) of aluminum chloride were dissolved in 350 ml of 〇-dichlorobenzene in chamber 1, and 25.0 mol of 4-chlorobenzoyl chloride was added to the solution while stirring. (
0°146 mol) was added dropwise. Thereafter, the temperature was gradually raised and the reaction was carried out at 60'C for 3 hours to complete the reaction.

Next, the reaction mixture was added to a large amount of methanol/hydrochloric acid mixture, the precipitated solid was filtered out, and water, acetone,
It was purified by washing with N-methylpyrrolid/and acetone in that order.

This substance has a melting point of 623°C, and elemental analysis shows that
It was confirmed that it was an aromatic dichloride represented by the formula %. The IR spectrum of this compound is shown in FIG.

Example 1 In a 200*l flask, 21.4 g (0.03 mol) of the aromatic difluoride (Vl-1) obtained in Reference Example 1, 6.21 g (0.045 mol) of potassium carbonate, and silica [
Aerosil 300 (manufactured by Nippon Aerosil Co., Ltd.) 2°Og and diphenylsulfone 459 were charged, and after purging with nitrogen, the temperature was raised from room temperature to 310°C over 1 hour (2 degrees) and reacted at that temperature for 0.5 hour. .

Next, the reaction mixture was taken out, pulverized, and washed three times with 1B water and dry acetone to obtain 21.5 g of pale yellow solid. This product completely dissolved in concentrated sulfuric acid, resulting in a yellow solution. Further, the intrinsic viscosity at 25° C. at 0°1% by weight in concentrated sulfuric acid was 1.15. Further, by pressing this product at 400°C, a pale yellow strong film was obtained.

Examples 2 to 5 The procedure was repeated in the same manner as in Example 1, except that the aromatic cibaride as the raw material monomer, the silica-based compound as the catalyst, the alkali metal salt, the type and amount of the copper compound as the co-catalyst, and the reaction time were changed as shown in the attached table. A polymer was obtained. The intrinsic viscosities of these polymers are shown in the table.

Note 1) Fluoride: V co60 (anti-C) co% o-@)-co(X
F chloride: C1 + cosha No. 0 COΦ and 0sha 0% CCOCl2 silica Nippon Aerosil (extraction, Aerosil 600) Aluminum silicate: manufactured by Wako Pure Chemical Industries, Ltd., A1□0.・
3S10□ Theolite: manufactured by Toyo Soda Co., Ltd., TSZ-410-KO
A activated white clay 2 Japanese activated white clay (interior, K-5003) Room 1
After rising to 310℃ for 1 hour from the first temperature, the temperature reached 310℃.
Reaction time at °C

[Brief explanation of drawings]

FIG. 1 and FIG. 2 are IR spectra of aromatic cybaride obtained in Reference Examples 1 and 2, respectively, and used as a raw material of the present invention.

Claims (1)

[Claims] 1. In the presence of an alkali metal carbonate or bicarbonate, the general formula ▲ includes a mathematical formula, a chemical formula, a table, etc. ▼ (X^1 and X^2 in the formula are each a halogen atom, (They may be the same or different from each other) are heated to react at a temperature in the range of 250 to 400°C
A method for producing an aromatic polyetherketone having a repeating unit represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼.