JPH03227320A - Aromatic polyether ketone, production thereof and molded article thereof - Google Patents

Abstract

PURPOSE:To obtain the title polymer having excellent heat stability, heat resistance, chemical resistance, etc., and suitable for fiber, film, etc., by polymerizing an aromatic ether with a dicarboxylic acid dihalide in the presence of a Lewis acid catalyst and then adding a phosphorus compound thereto. CONSTITUTION:(C) Lewis acid such as aluminum chloride is added to (A) an aromatic ether such as diphenyl ether and (B) an aromatic dicarboxylic acid dihalide such as terephthaloyl dichloride at a molar ratio of 0.01-100 based on the component A and the component A is reacted with the component B e.g. in an inert gas atmosphere at -20 to 100 deg.C to afford a polymer having recurring units expressed by the formula (R<1> to R<20> are H, halogen, etc.,; X is O, etc.; l is 0-2; m is 0-3; n is 0 or 1). (D) A phosphorus compound such as phosphorous acid is added to the above-mentioned polymer to provide the aimed polymer being <=2wt.% in ratio of weight reduction which occurs when heated in air at 400 deg.C for 1hr.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a crystalline thermoplastic aromatic polyetherketone having a high glass transition point and particularly excellent heat resistance and chemical resistance, and a product made using the crystalline thermoplastic aromatic polyetherketone. The present invention relates to a molded article and a method for producing the aromatic polyetherketone.

[Prior art] Formula (r) (wherein RI and R10 each represent a hydrogen atom, a halogen atom, a hydrocarbon group, or an alkoxy group, X represents a direct bond or an oxygen atom, and l represents 0 to 2 Indicates an integer, m
represents an integer of θ to 3, and n is 0 or 1). Etherketone is already commercially available and is touted to have excellent heat resistance and chemical resistance. Furthermore, aromatic polyetherketones having the structure of formula (IV) have been proposed,
It is also said to have excellent heat resistance.

However, these aromatic polyether ketones have the problem that if they are simply purified after polymerizing the raw material compounds, when they are melted and heat treated, they become infusible due to gas generation and gelation, and are thermally unstable. have.

Conventionally, stabilizers such as various thermal antioxidants have been used to improve the thermal stability of polymers. However, due to the stability and volatility of these stabilizers themselves, they are used under conditions of 300° C. or lower for boat fishing. When trying to use such a stabilizer for the purpose of stabilizing polyetherketone, considering that the temperature during molding and processing of polyetherketone is around 400°C, the thermal stability of the stabilizer itself may be affected. It is expected that it will be practically unusable due to the problems of stability and volatility. In other words, the formula (1
) It must be said that it is extremely difficult to stabilize the polymer in the molding/processing temperature range of aromatic polyetherketones having repeating units.

Under such circumstances, it has been proposed to add a phosphorus compound to polyetherketone having the structure of formula (IV) for the purpose of preventing gelation during heating and melting (Japanese Unexamined Patent Publication No. 159430/1989). Publication No. 63-1594
Publication No. 31).

Although this partially solves the problem of gelation during heating and melting, the problem of gas generation remains unsolved.

Therefore, an aromatic polyetherketone having a thermally sufficiently stabilized repeating unit of formula (J) (hereinafter simply referred to as "r formula (1)"), a method for producing the same, and the aromatic polyetherketone The reality is that molded products with excellent heat resistance and chemical resistance have not yet been provided.

[Problem to be solved by the invention]

The object of the present invention is to provide an aromatic polyetherketone of formula (1) which has significantly improved thermal stability compared to the hitherto known aromatic polyetherketones of formula (1).

Another object of the invention is that the formula (
The object of the present invention is to provide a method for producing an aromatic polyetherketone (1).

Still another object of the present invention is to provide a molded article made of the aromatic polyetherketone of formula (1) with significantly improved thermal stability and excellent in heat resistance and chemical resistance.

[Means to solve the problem]

As a result of intensive research to achieve the above object, the present inventors have discovered that phosphorus can be By treating with a phosphorus compound or its salt in which at least one of the bonding groups is an acidic group, gas generation and gelation during heating and melting are significantly suppressed, and the aromatic polyester has significantly improved thermal stability. The present inventors discovered that ether ketones can be obtained and completed the present invention.

That is, the gist of the present invention is as follows.

(1) Formula (1) (In the formula, R1 to Rzo each represent a hydrogen atom, a halogen atom, a hydrocarbon group, or an alkoxy group, X represents a direct bond or an oxygen atom, and l is an integer of 0 to 2. and m
represents an integer of 0 to 3, and n is 0 or 1), which has a weight loss rate of 2 when heated in air at 400°C for 1 hour.
% or less [hereinafter also referred to as heat-resistant aromatic polyetherketone (I)].

(2) Molded product made of heat-resistant aromatic polyetherketone N).

(3) In any step after producing the aromatic polyether ketone, the aromatic polyether ketone is A method for producing a heat-resistant aromatic polyetherketone (1), comprising the steps of:

In this specification, chloro and bromine are exemplified as suitable halogen atoms. Examples of the hydrocarbon group include alkyl (for example, lower alkyl having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl), cycloalkyl (for example, cyclopropyl,
Examples include cycloalkyl having 3 to 6 carbon atoms such as cyclobutyl and cyclohexyl), aryl (phenyl, naphthyl, etc.), and aralkyl (benzyl, etc.). Examples of the alkoxy group include lower alkoxy having 1 to 4 carbon atoms such as methoxy, ethoxy, n-propoxy, isopropoxy, and n-butoxy.

The heat-resistant aromatic polyether ketone (1) of the present invention has a weight loss rate of 1 when heat-treated in air at 400°C for 1 hour.
% or less, but the weight loss rate is preferably 1.5%
The content is preferably 0.8% or less.

Furthermore, the heat-resistant aromatic polyether ketone (+
) has a viscosity increase rate of 5% or less when heat-treated at 400°C for 30 minutes in nitrogen, preferably 3% or less, and more preferably 2% or less.
% or less.

In this specification, weight loss rate refers to a thermogravimetric analyzer (
Using Shimadzu DT-30), under air atmosphere for 40 minutes.
The amount of weight loss that occurs when heat treated at 0'C for 1 hour is shown as a percentage of the weight before heat treatment.

In this specification, the viscosity increase rate is the ratio of the polymer viscosity after heat-treating about 1 g of polymer at 400° C. for 30 minutes in a nitrogen atmosphere to the polymer viscosity before the heat treatment. In addition, the polymer viscosity is 98% concentrated sulfuric acid 10
It is expressed as the logarithmic viscosity measured at 30°C at a concentration of 5 g of polymer IO relative to 0-.

The aromatic polyetherketone of formula (1) is produced, for example, by the following method.

1 Method 2 (V) (In the formula, R1 to RI2, X and l have the same meanings as above)
f-R20, X and m have the same meanings as above, and Y represents a halogen atom.
2-dichloroethane, methylene chloride, nitrobenzene,
A method of polymerizing using a Lewis acid as a catalyst in the presence of chloroborum, orthodichlorobenzene, etc.).

The conditions for the polymerization reaction are as follows. That is, the polymerization is
Under an inert gas atmosphere such as nitrogen, -20'C or higher 100°C
Hereinafter, the reaction is preferably carried out at a reaction temperature of -5 to 30'C.

Examples of the aromatic ether of formula (V) include diphenyl ether, 1,4-diphenoxybenzene, biphenyl,
Bis(4-phenoxyphenyl)ether, 4,4゛-
bis(4-phenoxyphenyl)diphenyl ether,
3,3''-dimethylphenylenzene, 3,3''-dimethoxy phenyl ether, 1,4-bis(3-methoxyphenoxy)benzene, 1,4-bis(2-chlorophenoxy)benzene, terphenyl, 4- Examples include phenoxybiphenyl, 4,4°-diphenoxybiphenyl, and these aromatic ethers may be used alone or in combination.

Further, as the aromatic dicarboxylic acid di/'%ride of formula (IV), terephthalic acid dichloride, isophthalic acid dichloride, diphenyl ether-4°4°-dicarboxylic acid dichloride, 1,4-bis(4-chloroformylphenyl ) Benzene, 2.5-dimethyltecyphthalic acid dichloride 4.4゛~diphenic acid dichloride, 2
．． Examples include 6-naphthalene dicarboxylic acid dichloride, and these aromatic dicarboxylic acid cybarides may be used alone or in combination.

Lewis acids include anhydrous aluminum trichloride, anhydrous aluminum tribromide, anhydrous gallium trichloride, boron trifluoride ethyl ether complex, stannic chloride, stannous chloride, ferric chloride, titanium tetrachloride, Boron trichloride, antimony pentachloride, phosphorus trichloride, phosphorus pentachloride, tellurium pentachloride,
Examples include niobium pentachloride and tungsten hexachloride, and particularly preferred are halides of Group I of the periodic table, especially aluminum chloride. The amount of Lewis acid used is 0.01 to 100, preferably 0.1 to 1 in molar ratio to aromatic ether.
It is 0.0.

1. I A compound represented by the formula (■) (wherein R5, and R1 are the same as above) or a salt thereof; A method of polymerizing a compound represented by the following formula in the presence of an organic solvent (for example, diphenylsulfone, sulfolane, dimethylsulfoxide, N-methylpyrrolidone, etc.).

The conditions for the polymerization reaction are as follows. That is, the polymerization reaction is carried out at a high temperature of 150 to 400°C, preferably 280 to 350°C, in an atmosphere of an inert gas such as nitrogen.

Examples of the salt of the compound of formula (■) include alkali metal salts such as sodium salt and potassium salt.

Examples of the compound of formula (■) and its salt include hydroquinone, 4.4'-dihydroxydiphenyl ether, 4.4°-dihydroxybenzophenone, and 4.4'-dihydroxybenzophenone.
-dihydroxybiphenyl, 1,4-bis-(4-nidroxybenzoyl)benzene, etc., and these compounds may be used alone or in combination.

Examples of the compound of formula (■) include 4.4° difluorobenzophenone, 1,4-bis-(4-fluorobenzoyl)benzene, 4,4°-bis-(4-fluorobenzoyl)biphenyl, 414°-bis -(4°-fluorobenzoyl)diphenyl ether and the like, and these aromatic ethers may be used alone or in combination.

The aromatic polyetherketone of the formula (I) thus obtained is treated with the phosphorus compound as a post-treatment to form a heat-resistant aromatic polyetherketone (1).
It is said that

The treatment with a phosphorus compound may be carried out at any time after the completion of the reaction, for example, during washing of the produced polymer, during filtration (it may be added to the filtrate), during drying, during molding/processing after completion of drying, etc. Particularly preferred is the time of drying and the time of molding/processing.

The treatment with the phosphorus compound is usually carried out by adding the phosphorus compound to the aromatic polyetherketone of formula (I).

The addition of the phosphorus compound is usually 0.0% based on the atomic weight of phosphorus relative to the aromatic polyetherketone of formula (1). OO1%~1.
0%, preferably 0.003% to 0.05%.

The phosphorus compound is usually used after being diluted with a solvent such as acetone, benzene, toluene, hexane, tetrahydrofuran, or methyl ethyl ketone.

The phosphorus compound used is a phosphorus compound or a salt thereof in which at least one of the binding groups that binds to phosphorus is an acidic group, in other words, at least one of the binding groups that binds to phosphorus is an organic group, a metal, or an amino group. It is a phosphorus compound that has an acidic group that does not directly bond with other substances. Examples of salts of phosphorus compounds include alkali metal salts (sodium salts, potassium salts, etc.).

As the phosphorus compound, either a trivalent phosphorus compound or a pentavalent phosphorus compound can be used.

Specific examples of trivalent phosphorous compounds include phosphorous acid, methylphosphinic acid, ethylphosphinic acid, phenylphosphinic acid, ethyl phenylphosphinic acid, sodium phosphite, potassium phosphite, and methylphosphinic acid.
Sodium, sodium phenylphosphinic acid, potassium phenylphosphinic acid, dimethylphosphinic acid,
Examples include diethylphosphinic acid and diphenylphosphinic acid, but are not particularly limited to these.

Further, specific examples of pentavalent phosphorus compounds include phosphoric acid, metaphosphoric acid, polyphosphoric acid, sodium dihydrogen phosphate,
Potassium dihydrogen phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, methylphosphonic acid, ethylphosphonic acid, phenylphosphonic acid, dimethylphosphonic acid, diethylphosphonic acid, diphenylphosphonic acid, methylphenylphosphonic acid, ethylphenylphosphonic acid , methyl phosphoric acid, ethyl phosphoric acid, phenyl phosphoric acid, dimethyl phosphoric acid, diethyl phosphoric acid, diphenyl phosphoric acid, ethyl phenyl phosphoric acid, sodium methyl phosphonate, potassium methyl phosphonate, sodium phenyl phosphonate, potassium phenyl phosphonate, etc. These include, but are not particularly limited to.

The heat-resistant aromatic polyetherketone (I) of the present invention can be made into a molded article by itself or by blending with other components by means known per se. Examples of loose molded products include fibers, films, molded products, etc., but are not limited thereto.

The method for manufacturing the above-mentioned molded article may be a method known per se.

〔effect〕

Heat-resistant aromatic polyetherketone (1
) has significantly improved thermal stability.

In addition, it has excellent moldability and processability due to its excellent thermal stability, and this heat-resistant aromatic polyether ketone (1)
It is expected that molded products such as fibers, films, and molded products with good heat resistance and chemical resistance will be obtained.

〔Example〕

The content of the present invention will be explained in detail with reference to Examples, but the present invention is not limited thereto.

Examples 1 to 5 56.68 g of diphenyl ether (0,33
30 moles), 43.94 g of terephthalic acid dichloride (
0,2165 mol), isophthalic acid dichloride 23.6
6 g (0,1166 mol) of aluminum chloride dissolved in 1,2-dichloroethane IN was ice-cooled, and anhydrous aluminum chloride 111.
1 g (0,8325-rr) was slowly added over 50 minutes. After the addition was completed, the reaction system was maintained at about 15° C., and the reaction was continued with stirring for 5 hours.

The reaction was stopped by adding 600 m of methanol, and the precipitated polymer was collected by filtration. The obtained polymer was washed in methanol 12 at room temperature and subsequently in methanol 11 under reflux. Subsequently, the polymer was washed under reflux in 1 liter of acetic acid and then in methanol, and then the polymer was collected by filtration and heated at 130"C.
It was dried under reduced pressure overnight. Add 100m of formic acid to the dried polymer.
After purification under reflux in 900 d of acetic acid, washing under reflux was performed in 12 methanol, and the polymer was collected by filtration.

The filtered polymer was dried under reduced pressure at I 30 'C overnight.

The logarithmic viscosity of the obtained polymer was o, 95, and the yield was approximately 1
It was 00%.

The phosphorus compounds shown in Table 1 were diluted with a solvent such as acetone and benzene and blended with 5 g of the polymer thus obtained, and then dried under reduced pressure at 80'C overnight. The weight reduction rate and viscosity increase rate of the polymer to which the phosphorus compound was added were evaluated. The results are shown in Table 1, and all were extremely good.

Comparative Examples 1 to 4 Thermal stability was evaluated in exactly the same manner as in Examples 1 to 5 for the case where no phosphorus compound was added to the control polymer and for the phosphorus compounds shown in the Comparative Examples section of Table 1. The results are shown in Table 1, and a large amount of gas was generated, and the polymer after treatment was not uniformly melted.

Examples 6 to 9 12.50 g of hydroquinone (0,1
134 mol), 4,4'-difluorobenzophenone 2
5.0 g (0,1146 mol) and 150 g of diphenylsulfone were added, and vacuum nitrogen replacement was repeated three times. The reaction system was heated to 200°C, and 16% of potassium carbonate was added while stirring.
40 g (0,1191 mol) was added and the same temperature was maintained for 1 hour. Subsequently, the temperature of the reaction system was raised to 250°C and held at the same temperature for 1 hour, and then the reaction temperature was raised to 330°C and the reaction was continued for 3 hours.After cooling the reaction mixture, 200ml of methanol was added and the mixture was heated under reflux. Washed. The washed product was filtered, and 500 Jd of methanol was added to the filter cake to wash it under reflux, and then the polymer was collected by filtration.

Subsequently, the polymer was washed twice with 500 m of distilled water under continuous flow, and then washed twice with 500 m of methanol under continuous flow, and then the polymer was collected by filtration and dried under reduced pressure at 130 ''C overnight.The obtained polymer had a logarithmic viscosity. is 0.8 and the yield is approximately 10
It was 0%.

The phosphorus compounds shown in Table 2 were diluted with a solvent such as acetone and benzene and blended with 10 g of the polymer thus obtained, and then dried under reduced pressure at 80'C overnight. The blended polymers were melt-kneaded for 30 minutes at 400''C under a nitrogen atmosphere, and then the polymers were scraped out and pulverized. The thermal stability of the polymers was evaluated according to Examples 1 to 5.

The results are shown in Table 1, and all were extremely good.

Comparative Examples 5 to 7 Thermal stability was evaluated in accordance with Examples 6 to 9, except that no phosphorus compound was added as a control and the phosphorus compounds shown in the comparative examples in Table 2 were used. The results are shown in Table 1, and a large amount of gas was generated, and the polymer after treatment was not uniformly melted.

Examples 10-12 43.94 g of terephthalic acid dichloride, 23.66 g of isophthalic acid dichloride and 56 g of diphenyl ether
．． A polymer having a logarithmic viscosity of 0.95 was obtained by a conventional method in the presence of anhydrous aluminum chloride in a solvent of 1,2-dichloroethane. After adding 0.046% phenylphosphinic acid to this polymer, it was melt extruded to a thickness of 13
An unstretched film of 4 μm was obtained. Furthermore, the unstretched film was subjected to simultaneous biaxial stretching at 170° C. to obtain a stretched film with a thickness of 22 μm. Film production by melt extrusion of the polymer was carried out smoothly without any trouble. Table 3 shows the physical property values of the obtained film.

Comparative Example Day A film was prepared by melt extruding a polymer polymerized according to Example 10 without adding a phosphorus compound. The obtained film contained numerous bubbles caused by gas generation, and many foreign substances thought to be caused by gelation were observed.

[Margin below]

Claims (4)

[Claims] (1) Formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R^1 to R^2^0 each represent a hydrogen atom, a halogen atom, a hydrocarbon group, or an alkoxy group. , X represents a direct bond or an oxygen atom, l represents an integer of 0 to 2, m represents an integer of 0 to 3, and n is 0 or 1). An aromatic polyether ketone having a weight loss rate of 2% or less when heat treated in air at 400°C for 1 hour. (2) The aromatic polyetherketone according to claim (1), which has a viscosity increase rate of 5% or less when heated in nitrogen at 400° C. for 30 minutes. (3) A molded article made of the aromatic polyetherketone according to claim (1) or (2). (4) In any step after producing the aromatic polyetherketone, the aromatic polyetherketone is treated with a phosphorus compound or a salt thereof in which at least one of the bonding groups bonded to phosphorus is an acidic group. The claim (
1) The method for producing an aromatic polyetherketone as described above.