JPH0475251B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel aromatic polyetherketone copolymer. Most aromatic polyetherketone polymers are crystalline polymers with high melting points (for example, TEAttwood et al. Am.chem.Soc.Polym.
Preprints, 20 [1], 191 (1979)). These crystalline polymers have excellent mechanical properties and heat resistance, as well as good chemical resistance and electrical properties, so they are used as insulation coatings for electric wires and cables.
Used for heat-resistant, insulating parts, etc. of electrical parts. However, these aromatic polyetherketone-based polymers have a high melting point and therefore have problems in processability, particularly in injection molding, extrusion, and U-molding. Therefore, as an aromatic polyetherketone copolymer with a somewhat lower melting point, a terpolymer that already has an aromatic sulfone group (for example, R.Viswanathan,
et al. Am.Chem.Soc.Polym.Preprints, 20 [2]
365 (1979)) has been proposed. However, it cannot be said that it is sufficient, and the range in which the polymer exhibits crystallinity is extremely narrow, and the body part is amorphous. (the bending strength does not change up to around the melting point of the polymer) cannot be used. Therefore, there is a strong desire to develop a practical aromatic polyetherketone polymer that maintains crystallinity and has good processability. With such a demand as a background, the present inventors conducted various studies on aromatic polyetherketone copolymers, and as a result, they discovered a copolymer of the present invention that exhibits crystallinity in a wide temperature range. That is, the present invention provides formulas (), () and () (In the formula, R represents a hydrogen atom or a lower alkyl group.)
and () are not adjacent to each other and are arbitrarily combined via structural units (), and the reduced viscosity is 0.2~
2.0 and structural unit() and structural unit()
It is an aromatic polyetherketone copolymer characterized by having more than 50 moles and not more than 80 moles of structural units () per 100 moles of the total amount. The copolymer of the present invention has the general formula () (In the formula, R represents a hydrogen atom or a methyl group)
Aromatic dihydroxy compound represented by and general formula () It can be obtained by copolymerizing an aromatic dihydroxy compound represented by the formula (wherein n is an integer of 1 to 3) with 4,4'-dihalogeno or dinitrobenzophenone. As the aromatic dihydroxy compound represented by the general formula () used in this method, for example,
Bis(4-hydroxyphenyl)methane, 2,2
-bis(4-hydroxyphenyl)propane, and the like. These can be used alone or in combination
A mixture of more than one species can be used. Examples of the aromatic dihydroxy compound represented by the general formula () include compounds such as hydroquinone and 4,4'-diphenol. Hydroquinone is particularly preferred. Furthermore, the 4,4'-dihalogeno or dinitrobenzophenone includes 4,4'-dichlorobenzophenone, 4,4'-difluorobenzophenone,
4-chloro-4'-fluorobenzophenone, 4,
4'-Dinitrobenzophenone, 4-chloro-4'-
Examples include nitrobenzophenone and 4-fluoro-4'-nitrobenzophenone. These can be used alone or as a mixture of two or more. Particularly preferred halogen compounds or nitro compounds include 4,4'-dichlorobenzophenone, 4,4'-difluorobenzophenone, and 4,4'-dinitrobenzophenone. The amount of the above raw materials to be used is in the range of 0.7 to 1.3 molar ratio, preferably 0.85 to 1.15 molar ratio of 4,4'-dihalogeno or dinitrobenzophenone to 1 mole of aromatic dihydroxy compound in total, and particularly For the purpose of obtaining a copolymer with a high molecular weight, a molar ratio of around 1 is preferred. The ratio of the aromatic dihydroxy compound represented by the general formula () to the aromatic dihydroxy compound represented by the general formula () is not particularly limited, but from the viewpoint of taking advantage of the crystalline polymer, the ratio of the aromatic dihydroxy compound represented by the general formula () to the aromatic dihydroxy compound represented by the general formula () is determined from the viewpoint of taking advantage of the crystalline polymer. A molar ratio of () from 8:2 to 1:99, preferably from 8:2 to 51:49 is desirable. In addition, in order to take advantage of the advantage of good processability, for a total of 100 moles of general formula () and general formula (),
It is desirable that the proportion of general formula () exceeds 50 and is 80 mol or less. By containing the compound of general formula () in the aromatic dihydroxy compound, the copolymer of the present invention exhibiting characteristic performance can be obtained. The above-mentioned aromatic dihydroxy compound acts as a dialkali metal salt in the actual reaction. Therefore, the dialkali metal salt of the aromatic dihydroxy compound may be prepared separately and used, or the salt may be formed before or simultaneously with the polymerization reaction to proceed with the reaction. Examples of the alkali metal include lithium, sodium, potassium, and cesium, with sodium or potassium being particularly preferred. Examples of the metal compound used to form the alkali salt include hydroxide, carbonate, and carbon hydrogen, with hydroxide and carbonate being particularly preferred. A solvent is used in the copolymerization reaction as necessary.
A preferable solvent is one that dissolves the raw material aromatic dihydroxy compound, 4,4'-dihalogeno or dinitrobenzophenone, and the resulting polymer at high concentrations, and further dissolves an alkali salt of the aromatic dihydroxy compound or an alkali metal It is preferable to use one that can also dissolve compounds. Therefore, as a suitable solvent, a polar solvent can usually be used. For example, preferred solvents include dimethylsulfoxide, sulfolane (tetramethylsulfone), diphenylsulfone, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfone, diethylsulfone, diethylsulfoxide, etc. It is mentioned as. Furthermore, in addition to polar solvents, diphenyl ether, biphenyl, terphenyl, phenanthrene, naphthalene, diphenylmethane, triphenylmethane, benzophenone, etc. can also be used. The amount of these solvents used depends on the type of solvent,
Although it varies depending on the type of aromatic dihydroxy compound, halogen compound or nitro compound used, other reaction conditions, etc., it is usually in the range of 0.05 to 20 times the weight of the aromatic dihydroxy compound, more preferably 0.1 to 10 times the weight of the aromatic dihydroxy compound. This is twice the range. In general, if the amount of solvent used is less than the above range, it will not be effective as a solvent, and in particular, the generated polymer will precipitate even if it has a low molecular weight, making it difficult for the reaction to proceed further, making it impractical. It is no longer possible to obtain a polymer with a certain high molecular weight. On the other hand, if the amount of solvent is increased beyond the above range, the monomer concentration will decrease, which may be undesirable, such as requiring a reaction at a higher temperature and for a longer time in order to increase the molecular weight. Polymerization reactions can be carried out in various formats. For example, (1) a method using a separately prepared alkali metal salt of an anhydrous aromatic dihydroxy compound;
The mixture is thoroughly and uniformly mixed with 4,4'-dihalogeno or 4,4'-dinitrobenzophenone, and the mixture is heated and reacted with stirring. At this time, the reaction is carried out without a solvent or in an appropriate solvent. (2) Next, the aromatic dihydroxy compound is reacted with an alkali metal compound, followed by a reaction with 4,4'-dihalogeno or 4,4'-dinitrobenzophenone. That is, an aqueous solution or a concentrated aqueous solution obtained by reacting an aromatic dihydroxy compound with an alkali metal compound is obtained, and then an azeotropic solvent is added to this aqueous solution to perform azeotropic distillation to remove the alkali of the aromatic dihydroxy compound produced. After the metal salt becomes substantially anhydrous, the temperature is raised to distill off the azeotropic solvent, and then the 4,4'-dihalogeno or 4,4'-
This is a method in which dinitrobenzophenone is added and reacted. In this method as well, a reaction medium may not be added or a solvent may be used as a reaction medium in any reaction step. (3) Furthermore, in the method (2) above, 4,4'-dihalogeno or 4,4'-dinitrobenzophenone is added together with the azeotropic solvent, and while dehydration is performed by azeotropic distillation, further distillation is performed after the completion of dehydration. This is a method for carrying out a tsutsugi polymerization reaction. In this method as well, it is possible to add no reaction medium or to use a solvent as a reaction medium in any reaction step. (4) Furthermore, as another method, a mixture of an aromatic dihydroxy compound, 4,4'-dihalogeno or 4,4'-dinitrobenzophenone and an alkali metal carbonate or hydrogen carbonate is prepared in the presence of a solvent. The polymerization reaction is carried out while heating and expelling produced water and carbon dioxide gas with an inert gas. (5) Furthermore, in the method of (4), heating is performed while adding an azeotropic solvent, and the polymerization reaction proceeds simultaneously with the production of an alkali metal salt of an aromatic dihydroxy compound and the removal of the produced water by azeotropic distillation. Among these various methods, aromatic dihydroxy compounds and 4,4'-dihalogeno or 4,
The most suitable method is selected depending on the reactivity, physical properties, etc. of 4'-dinitrobenzophenone. In the above method, the azeotropic solvent used to remove water from the reaction system by azeotropic distillation includes, for example, aromatic hydrocarbons such as benzene, toluene, and xylene, chlorobenzene, O-dichlorobenzene, etc. Examples include halogenated aromatic hydrocarbons, but any other solvent that is inert to the reaction and forms an azeotrope with water can be used. The amount of these azeotropic solvents to be used can be determined based on the amount of water present in the reaction system, the azeotropic composition, etc. In dehydration using an azeotropic solvent, for example, water is distilled out together with the azeotropic solvent, the distillate is cooled and condensed, water and the azeotropic solvent are separated into two layers, and this separated azeotropic solvent layer If the azeotropic solvent is allowed to reflux into the reaction system, the azeotropic solvent will be used effectively, and the dehydration can be completed without using a large excess of the azeotropic solvent. The time required for azeotropic dehydration also varies depending on the amount of water present in the reaction system, the type and amount of azeotropic solvent used, but from a practical standpoint it is preferably carried out within 10 hours, and It is more preferable that the process be completed within hours. The temperature of the polymerization reaction varies depending on the type of reaction raw material components, the ratio of reaction raw material components, the type of solvent, the type of polymerization reaction, etc., but is usually in the range of 40 to 450°C, preferably 60 to 400°C. Implemented within a range. If the reaction temperature is less than 40°C, it will take a long time to obtain a polymer with the desired molecular weight, which is not practical. On the other hand, if the temperature exceeds 450°C, side reactions other than the desired polymerization reaction cannot be ignored, and the resulting polymer becomes significantly colored. Further, the reaction temperature may be constant during the reaction period, or may be changed gradually or stepwise as the reaction progresses. Such a change in reaction temperature can sometimes be made lower as the proportion of aromatic dihydroxy compound used changes, ie as the proportion of aromatic dihydroxy compound of general formula () increases. The time required for the reaction varies widely depending on the type of reaction raw material components, the ratio of raw material components, the type of polymerization reaction, the type of reaction temperature, etc., but it is usually 10 minutes or more.
It is carried out for a period of 100 hours, preferably from 30 minutes to 24 hours. The reaction atmosphere in which the reaction is carried out is preferably free of oxygen, and good results are obtained when the reaction is carried out in nitrogen or other inert gas. Aromatic dihydroxy compounds of the general formula (), especially alkali salts of hydroquinone, are easily oxidized by oxygen, and heating further promotes oxidation, hindering the desired polymerization reaction and making it difficult to increase the molecular weight. others,
Since this may cause coloring of the polymer, it is desirable to perform the reaction in an inert gas atmosphere. The polymerization reaction can usually be stopped by cooling the reactants. However, in order to stabilize phenoxide groups that may be present at the ends of the polymer, an aliphatic halide, an aromatic halide, or the like may be added and reacted as necessary. Examples of such halides include methyl chloride, ethyl chloride, 4-chlorobenzophenone, 4
-Fluorobenzophenone, P-chlornitolbenzene, 4,4'-dichlorodiphenylsulfone,
Bis(4-fluorophenyl)ketone and the like can be mentioned. In addition, when the polymerization reaction is stopped and the reactants are cooled to room temperature, the viscosity of the reactants increases significantly, and depending on the solvent-free reaction, the type of reaction solvent used, the type of raw reactants, and their proportions, the reaction may occur. Since the material may solidify, it is effective to dilute it with an inert solvent before or during cooling in such cases. The solvent for such dilution is preferably one in which the alkali halide produced is insoluble.
Such solvents are also advantageous in the separation of polymers. When a solvent is used in the polymerization reaction, if a suitable diluting solvent is not available, it may be further diluted with the same solvent used in the reaction, or it may be cooled and solidified, and then finely ground using a grinder such as a Waring blender. It may be shaped. Separation and purification of the polymer after the polymerization reaction is completed.
Known methods for aromatic polyether polymers can be employed. For example, a salt (alkali halide) is precipitated by adding a solvent such as chlorobenzene or Sym-tetrachloroethane to the reaction mixture in which the desired polymer is soluble and the alkali halide produced is insoluble. The solution or reaction mixture after separation or salt separation is usually added to the nonsolvent of the polymer, or conversely, by adding the nonsolvent of the polymerization partner into the polymer solution. , the desired polymer can be precipitated. As a non-solvent for the polymer, for example, methanol,
Ethanol, isopropanol, acetone, methyl ethyl ketone, water, etc. are often used. These may be used alone or as a mixture of two or more. The precipitated polymer is washed using the above-mentioned non-solvent, and the obtained polymer is heated and dried under normal pressure or reduced pressure to form the polymer used in various processing methods into powder, flake, thin film, etc. can be obtained in various forms depending on the precipitation method. In the aromatic polyetherketone copolymer of the present invention obtained by polymerizing as described above, the structural units represented by the formula () and the structural units represented by the formula () are not adjacent to each other, and the structural units represented by the formula ( ) are bonded via the structural unit represented by The arrangement of the structural units of the formulas () and (), which are bonded via the structural unit of the formula (), is not necessarily such that the structural units of the formula () and () are bonded alternately and regularly, and the arrangement is arbitrary. That is, they can be bonded alternately, randomly or in a block form via the structural units of formula (). The copolymer of the present invention has a structural unit of the formula (), and a structural unit of the formula (), and has a reduced viscosity of 0.2 to 2, measured at 25°C in sulfuric acid, chloroform or other suitable solvent. It is 2.0. These characteristics give the copolymer of the present invention unique performance and make it possible to lower the melting point over a wide temperature range while maintaining the crystallinity of the polymer (for example,
The compound of the general formula () is 2,2-bis(4-
Hydroxyphenyl)propane, melting point range when the compound of the above general formula () is hydroquinone
It has a temperature of 240℃~337℃. ) This has resulted in a significant improvement in processability and has made it possible to provide composite materials containing a wide range of polymer groups and glass fibers and/or carbon fibers that are suitable for many applications. The copolymer obtained by the present invention can be molded into a desired product using conventional molding methods and conditions. That is, compression molding, extrusion molding, and injection molding are all possible within the capabilities of general molding machines, and the desired product can be obtained in a desired state. The molding temperature for extrusion or injection molding of the copolymer of the present invention is in the range of 200 to 400°C, preferably 250 to 380°C. This is bis(4-fluorophenyl)
The injection molding temperature of poly(aryletherketone) synthesized only from ketone and hydroquinone is 350℃.
This makes it possible to process at a lower temperature than that of ~380℃. Furthermore, there are no restrictions on the size, shape, etc. of the molded product, and in addition to normal molded products, films, sheet-like products, parts with precise microstructures, etc. can be easily molded using general molding methods. When molding the copolymer of the present invention, a filler component may be included depending on the intended use. Typical examples of filler components include glass fiber, carbon fiber, aromatic polyamide fiber, carbon, magnesium oxide, calcium oxide, calcium stearate, molybdenum sulfide, talc, alumina, silica, and asbestos. , can be used alone or as a mixture of two or more types. Among these fillers, fibrous fillers are particularly preferred in order to maintain mechanical properties during heating. The amount of these fillers used is 0.5 to 150%, preferably 3 to 120%, based on the weight of the copolymer of the present invention.
% range. Furthermore, antistatic agents, colorants, flame retardants, lubricants, processing improvers, stabilizers, etc. that are usually added during resin processing can also be added singly or as a mixture of two or more. The amount added is in the range of 10 ^-4 to 60%, preferably 10 ^-3 to 40%, based on the weight of the copolymer of the invention. The copolymer of the present invention can also be produced into a film by a casting method from an organic solvent solution, and like an extruded film, a transparent or opaque, tough, and highly heat-resistant film can be obtained. The copolymer of the present invention can be used for various electrical and electronic parts, housings, automobile parts, aircraft interior materials, sliding parts, gears, insulating materials, medical materials,
It can be used in a wide range of fields such as steam sterilization containers. Examples and comparative examples are shown below. Note that the converted viscosity ηred in the examples is calculated using a solution of 0.2 g of polymer dissolved in 100 ml of chloroform at 25°C when the solvent is chloroform, and a solution of 0.2 g of polymer dissolved in 100 ml of sulfuric acid when the solvent is sulfuric acid. The values were calculated using the following formula, measured using a viscometer using 0.1 g dissolved. ηred (dl/g) = t _s − t _p /C・t _p where t _p = outflow time of pure solvent t _s = outflow time of polymer solution c = polymer concentration in polymer solution (g/
dl) The appropriate solvent, chloroform or sulfuric acid, was used depending on the composition of the polymer. Example 1 Stirrer, thermometer, cooler and distillate separator,
Into a 300 ml flask equipped with a dropping funnel and nitrogen inlet tube, 13.68 g (0.06 mol) of 2,2-bis(4-hydroxyphenyl)propane, 1.65 g (0.015 mol) of hydroquinone, and nitrogen were blown into the flask to remove oxygen. 75 ml of chlorobenzene and 60 ml of dimethyl sulfoxide treated in the same manner were taken, and nitrogen gas was passed into the liquid while stirring to completely replace the reaction system with nitrogen. 19.6 g of a 44.8% potassium hydroxide aqueous solution was added dropwise from the dropping funnel over 10 minutes, and the inside of the funnel was washed with 5 ml of pure water, which was then added to the reaction solution. The solution was heated until the temperature rose to 60°C and reflux started. When the water in the reaction system is removed azeotropically with chlorobenzene and the chlorobenzene layer is returned to the reaction system while continuing azeotropic dehydration, the internal temperature increases from around 120℃.
The temperature rose to around 140°C, and water distillation was no longer observed at around 145°C. Heating was continued to distill off most of the chlorobenzene, yielding a white slurry. Cool the temperature of the reaction solution to around 100°, 4.
When 16.35 g (0.075 mol) of 4'-difluorobenzophenone was added, the temperature of the reaction solution rose to 135°C.
The reaction was allowed to proceed at that temperature for 6 hours. After the reaction was completed, the reaction solution was poured into methanol being stirred with a homomixer to precipitate a copolymer, which was further washed with water and dried to obtain 36.6 g of a white copolymer. Elemental analysis of the obtained copolymer and ^1H-
NMR measurements were performed. The measurement results were as follows. Elemental analysis C H Calculated value (%) 81.06 5.32 Analytical value (%) 81.01 5.27 ¹ H-NMR The copolymer was dissolved using deuterated chloroform and measured with ^{a 1} H-NMR device at 100 MHz. δ = 1.70 (s, H ³ ), 7.01 (d, H ¹ ); J _1,2 = 9Hz, 7.04 (d, H ⁴ ); J _4,5 = 9Hz, 7.28 (s, H ⁶ ), 7.29 ( d, H ² ); J _2,1 =9Hz, 7.80(d,
H ⁵ ); J _5,4 = 9Hz Proton intensity ratio H ¹ :H ² :H ³ :H ⁴ :H ⁵ :H ⁶ =4:4:6:
5:5:1 From these results, the obtained copolymer has the following structural units (), () and (). (The number attached to the hydrogen atom in the formula means that it is the same as the number of the proton mentioned above.) It is contained in the composition ratio of ():():()=4:1:5, and It was confirmed that the usage rate was the same. In addition, the copolymer in chloroform (0.2 g/100
ml) The reduced viscosity measured at 25°C was 1.94 dl/g. Example 2 Except that the molar ratio of 2,2-bis(4-hydroxyphenyl)propane and hydroquinone was 6:4, diphenyl sulfone was used instead of dimethyl sulfoxide as the solvent, and the reaction temperature was 320°C. The reaction was carried out in the same manner as in Example 1. The calculated viscosity of the obtained copolymer was sulfuric acid (0.1 g/
It was 0.21 when measured at 25°C in 100ml). Example 3 (comparative example) 2,2-
Bis(4-hydroxyphenyl)propane 10.62
g (0.045 mol), hydroquinone 11.55 g (0.105
mole), 4,4'-difluorobenzophenone 32.73
After replacing the reaction system with nitrogen, the reaction system was heated to 180°C while passing nitrogen gas. 7.07 g of 99.5% potassium carbonate was added, heated to 200°C and kept for 30 minutes, then heated to 250°C and kept for 30 minutes, further heated to 320°C and reacted for 2 hours.
The reaction solution was transferred to a beaker and cooled to solidify. This material was pulverized using a pulverizer, washed four times with acetone and water, and dried. The converted viscosity of the obtained light gray polymer is sulfuric acid (0.1g/100ml)
It was measured at 25° C. and found to be 0.25 dl/g. Example 4 (comparative example) In a 300 ml flask equipped with a stirrer, thermometer, water separator, condenser, dropping funnel and nitrogen inlet tube,
2-bis(4-hydroxyphenyl)propane
17.10g (0.075 mol), Hydroquinone 8.26 (0.075
mole), 4,4'-difluorobenzophenone 32.73
After replacing the reaction system with nitrogen, add 7.07 g of 99.5% potassium carbonate and add 10 ml of chlorobenzene from which oxygen has been removed by blowing in nitrogen.
The mixture was heated while passing nitrogen gas through it. Chlorobenzene begins to reflux around 140℃, and the resulting water gradually accumulates in the separator. This aqueous layer was separated and the chlorobenzene layer was returned to the reaction system. Then the reaction temperature is 200
The distilled chlorobenzene layer was blown out so that the temperature reached ℃, and the chlorobenzene from which oxygen had been removed was added dropwise from the dropping funnel, and the reaction was carried out at 200℃ for 1 hour.Then, the temperature was raised to 250℃ and the reaction was carried out for 30 minutes, and the temperature was further increased. The mixture was heated to 320°C and reacted for 1 hour. The subsequent operations were the same as in Example 3. The resulting copolymer had a reduced viscosity of 0.25 when measured in sulfuric acid (0.1 g/100 ml) at 25°C. Example 5 (comparative example) 18.83 g of 4,4'-dichlorobenzophenone was used instead of 4,4'-difluorobenzophenone, sulfolane was used instead of dimethyl sulfoxide, and the reaction temperature was changed. The reaction was carried out in the same manner as in Example 1, except that the temperature was changed to 200°C instead of 135°C. The resulting copolymer had a reduced viscosity of 0.40 dl/g as measured in chloroform (0.2 g/100 ml) at 25°C. Examples 6 to 7 (Comparative Example) Polymerization was carried out by changing the molar ratio of the reactants of 2,2-bis(4-hydroxyphenyl)propane and hydroquinone as shown in Table 1. The reduced viscosity of the obtained copolymer is shown in Table 1.

[Table] Example 8 In the method of Example 4, 17.10 g (0.075 mol) of 2,2-bis(4-hydroxyphenyl)propane was replaced with bis(4-hydroxyphenyl).
The reaction was carried out in the same manner as in Example 4, except that 15.00 g (0.075 mol) of methane was used. The calculated viscosity of the obtained copolymer was sulfuric acid (0.1 g/
The copolymer was measured at 25° C. in 100 ml, and was 0.25 dl/g, and the X-ray spectrum of this copolymer confirmed that it had crystallinity. Comparative Example 1 Polymerization was carried out in the same manner as in Example 3, using hydroquinone instead of 2,2-bis(4-hydroxyphenyl)propane in Example 3 (that is, using only hydroquinone as the aromatic dihydroxy compound). The obtained light gray polymer was mixed with sulfuric acid (0.1g/
It had a reduced viscosity of 1.88 dl/g, measured at 25°C in 100 ml). This polymer powder was made into a sheet by the method of Test Example 1 described below, and the glass transition temperature (Tg) and melting point (Tm) were determined by the method of Test Example 2.
were measured, and Tg was 140°C and Tm was 340°C. This polymer naturally had only one melting point (Tm). Comparative Example 2 Instead of 2,2-bis(4-hydroxyphenyl)propane and hydroquinone in Example 3,
Polymerization was carried out in the same manner as in Example 3, except that approximately equimolar amounts of 4,4'-dihydroxybenzophenone and hydroquinone were used. The obtained grayish-white polymer was measured at 25℃ in sulfuric acid (0.1g/100ml).
It had a reduced viscosity of 1.70 dl/g. The glass transition temperature (Tg) of this polymer was measured in the same manner as in Comparative Example 1, and a good copolymer was obtained, with a glass transition temperature (Tg) of 153°C.
The melting point (Tm) was as high as 341°C, and the processability was poor. Test Example 1 Each of the copolymer powders obtained in Examples 1 to 7 was
Pressed for 5 minutes at 380℃ and 100Kg/ ^cm2 ,
A pressed sheet with a thickness of 0.25 mm was created. In each case, strong sheets were obtained. When the reduced viscosity of each of these sheets was measured by the method shown in the above examples, no difference was observed between the sheets and the powder. This revealed that reactions such as crosslinking and stringing did not proceed during hot press molding, and that the polymer could be stably processed. Therefore, it can be seen that melt processing such as extrusion and injection is possible. Test Example 2 As a result of measuring the sheet obtained in Test Example 1 with a DSC (differential calorimeter), the glass transition temperature (T
g) and melting point (Tm) were as shown in Table 2. Furthermore, the Tg and Tg of the polymer obtained in Comparative Example 1
Tm is also listed in Table 2. As is clear from the results in Table 2, both the polymer of the present invention and the polymer obtained in the comparative example have good glass transition temperatures (Tg), but
It can be seen that the polymer of the present invention has a melting point (Tm) significantly lower than that of the polymer of the comparative example, and its processability is extremely good.

【table】

Claims (1)

[Claims] 1 Formulas (), () and () (In the formula, R represents a hydrogen atom or a lower alkyl group.)
and () are not adjacent to each other and are arbitrarily combined via structural units (), and the reduced viscosity is 0.2~
2.0 and structural unit() and structural unit()
An aromatic polyetherketone copolymer having more than 50 moles and less than 80 moles of structural units () per 100 moles of the total amount. 2 The structural unit of formula () is The copolymer according to claim 1, which is