JPH0356252B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a novel aromatic polyether polymer. The method of obtaining linear aromatic polyether polymers by the reaction of dialkali metal salts of dihydric phenols with activated aromatic dihalides is well known (for example, RN Johnson et al., J. Polym.
Sci.A-1 5 2375 (1967)). These aromatic polyether polymers have excellent mechanical properties at relatively high temperatures, as well as good chemical resistance and electrical properties, so they have already been put to practical use in many fields. As described above, aromatic ether polymers have the advantage of having excellent performance and being easy to process. However, in recent years, there have been many application fields that require even higher heat resistance, and aromatic ether polymers have It maintains the excellent properties of an ether polymer, and has a glass transition temperature of several tens of tens of degrees.
Polymers with high heat resistance at high temperatures are particularly desired from various fields. The present inventors have continued various studies for the purpose of obtaining an aromatic polyether polymer with particularly excellent heat resistance that meets the above-mentioned main points. However, we have found that it is compatible with the purpose of the present invention, and as a result of pursuing a good manufacturing method, we have completed the present invention. That is, the present invention is based on the general formula () (In the formula, A represents a divalent hydrocarbon group having 1 to 10 carbon atoms, _-SO2- , -SO-, -S-, -O-, -CO-, m is 0 or 1, A when m is 0
This indicates that aromatic rings are bonded to each other. ) Bisphenols or their alkali salts represented by the general formula () (In the formula, B represents -SO ₂ -, -CO-.) General formula () characterized by reacting a halogen compound represented by (In the formula, A and m are the same as in the formula (), B is the same as in the formula (), and n is 10
Represents ~1000. ) is a method for producing a polyether polymer represented by: The polyether polymer obtained by the method of the present invention has a substituent on the bisphenol residue in the polymer, and the substituent is a methyl group. It has become clear that polyether polymers containing such substituents in the bisphenol residue have superior physical properties compared to corresponding unsubstituted polyether polymers, and in particular have improved heat resistance. Ta. As the polymer of the present invention, for example, the glass transition temperature (Tg) of a polyether polymer in which methyl groups are substituted at the 3, 3', 5, and 5' positions of bisphenol residues is Compared to polyether-based polymers having residues, the temperature increased by about 30 to 40°C, and it was confirmed that most of the polymers exhibited Tg of 200°C or higher. Therefore, the polymer obtained by the method of the present invention has various physical properties such as mechanical properties and electrical properties.
Since it can be maintained at relatively high temperatures and has good dimensional stability, it has become possible to use it in many applications that were difficult to use conventionally. Moreover, resins with such excellent heat resistance are generally difficult to process, but the polyether polymer obtained by the method of the present invention can be melt-processed and is suitable for molding parts that require precision. can also be used. The polymer obtained by the method of the present invention is represented by the general formula (). The part indicated by A in the formula () is a divalent hydrocarbon group having 1 to 10 atoms, -SO ₂
-, -SO-, -S-, -O-, -CO-, and specific representative examples of hydrocarbon groups having 1 to 10 carbon atoms include -CH ₂ -, -CH(CH ₃ ) −,

【formula】

【formula】

[Formula] CH (CH ₃ ) ₂ ,

【formula】

[Formula] (-φ is Hue ),

【formula】

[Formula] Examples include a cycloxylene group and a cyclopentylene group. B is −SO ₂
-, -CO-, and n indicates the degree of polymerization, which is usually 10 to
An integer in the range 1000. The bisphenols used in the method of the present invention are represented by the formula (). Specifically, bis(3,5-dimethyl-4-hydroxyphenyl)methane, 1,1-bis(3,5-dimethyl-
4-hydroxyphenyl)ethane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)
Propane, 1,1-bis(3,5-dimethyl-4
-hydroxyphenyl)cyclohexane, bis(3,5-dimethyl-4-hydroxyphenyl)
Sulfone, bis(3,5-dimethyl-4-hydroxyphenyl) sulfoxide, bis(3,5-dimethyl-4-hydroxyphenyl) sulfide,
Bis(3,5-dimethyl-4-hydroxyphenyl)ether, bis(3,5-dimethyl-4-hydroxyphenyl)ketone, 3,3',5,5'-tetramethyl-4,4'- Typical examples include dihydroxybiphenyl, which can be used alone or as a mixture of two or more. Among the bisphenols used in the method of the present invention, bis(3,5-dimethyl-4-hydroxyphenyl)methane, bis(3,5-dimethyl-4-hydroxyphenyl)methane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, bis(3,5-dimethyl-4-hydroxyphenyl)
Sulfone, bis(3,5-dimethyl-4-hydroxyphenyl) sulfoxide, bis(3,5-dimethyl-4-hydroxyphenyl) sulfoxide, bis(3,5-dimethyl-4-hydroxyphenyl) ether, Bis(3,5-dimethyl-4
-hydroxyphenyl)ketone, 3,3',5,
Examples include 5'-tetramethyl-4,4'-dihydroxybiphenyl and 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)cyclohexane. Furthermore, since the bisphenols used in the method of the present invention react as alkali salts during polymerization, the process can also be carried out using an alkali salt of bisphenols from the beginning. As the alkali constituting the salt, sodium, potassium, etc. are preferable. As the halogen compound used in the method of the present invention, those shown by the formula () are used,
Specific representative examples include bis(4-chlorophenyl)sulfone, bis(2-chlorophenyl)sulfone, bis(4-fluorophenyl)sulfone, bis(4-bromophenyl)sulfone, bis(4-iodophenyl)sulfone, Bis(4-chlorophenyl)ketone, bis(4-fluorophenyl)ketone, bis(4-bromophenyl)ketone, bis(4-iodophenyl)ketone, bis(2-chlorophenyl)ketone, bis(2-fluorophenyl) Examples include ketones,
These can be used alone or as a mixture of two or more. Particularly preferred halogen compounds in terms of reactivity and availability include bis(4-chlorophenyl)sulfone, bis(4-fluorophenyl)sulfone, bis(4-chlorophenyl)ketone, and bis(4-fluorophenyl). Ketones can be mentioned. The molar ratio of the bisphenol compound to the halogen compound used in the method of the present invention is preferably in the range of 0.7 to 1.3. More preferably
The molar ratio is in the range of 0.85 to 1.15, and the above molar ratio is preferably around 1, especially for the purpose of obtaining a high molecular weight polymer. As already mentioned, the bisphenols used in the method of the present invention act as dialkali metal salts in the actual reaction. Therefore, the dialkali metal salt of bisphenols can be prepared separately and used, or the reaction can proceed while forming the salt before or at the same time as the polymerization reaction. Types of alkali metal salts include lithium, sodium, potassium, and rubidium, but sodium and potassium are particularly preferred because they have high reactivity and are available at relatively low prices. The metal compound used to form the alkali salt includes hydroxide, carbonate, and hydrogen carbonate, and hydroxide and carbonate are particularly preferred from the viewpoint of reactivity. Therefore, in order to prepare dialkali metal salts of bisphenols, sodium hydroxide, potassium hydroxide, sodium carbonate,
It is particularly preferred to use at least one such as potassium carbonate. In the method of the present invention, a solvent is used as necessary. Preferred solvents for the polymerization reaction are those that exhibit high solubility for all of the raw material bisphenols, halogen compounds, and polyether polymers produced, and also have high solubility for bisphenol alkali salts, alkali metal compounds, etc. Preferably. As solvents suitable for such purposes, compounds commonly referred to as polar solvents are often used, but the solvent is not limited thereto. The method of the invention includes:
Specific representative examples of solvents used as necessary include dimethyl sulfoxide, sulfolane (tetramethylene sulfone), diphenyl sulfone,
N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolitone,
Examples include dimethyl sulfone, diethyl sulfone, diethyl sulfoxide, and the like. Furthermore, in addition to polar solvents, diphenyl ether, biphenyl, terphenyl, phenanthrene, naphthalene, diphenylmethane, triphenylmethane, etc. can be advantageously used. The amount of the solvent used if necessary in the method of the present invention is usually in the range of 0.05 to 20 times the weight of the bisphenols used. More preferably, it is in the range of 0.1 to 10 times, and the amount used varies depending on the type of solvent, the bisphenols used, the type of halogen compound, and other reaction conditions. If the amount of solvent used is less than the above range,
It is not effective as a solvent, and in particular, even if the produced polymer has a low molecular weight, it precipitates, making it impossible to obtain a high molecular weight polymer with practical use. On the other hand, if the amount of solvent is increased compared to the above reaction,
Since the monomer concentration decreases, higher temperature and longer reaction times are required to increase the molecular weight, and favorable results cannot be obtained. The actual polymerization reaction in the method of the present invention can be concretely carried out, for example, in the various formats shown below. For example, (1) a method in which anhydrous alkali salts of bisphenols prepared separately in advance and a halogen compound are sufficiently uniformly mixed and heated while stirring to react without using a solvent; An azeotropic solvent is added to the aqueous solution obtained by reacting phenols with an alkali metal compound to perform azeotropic distillation, and after the alkali salt of bisphenols becomes substantially anhydrous, a halogen compound is added and the reaction solvent is removed. (3) A method in which an aqueous solution obtained by reacting bisphenols with an alkali metal compound or its concentrate and a halogen compound are heated in the presence of an azeotropic solvent to perform azeotropic dehydration. (4) In the presence of a solvent, a separately prepared alkali salt anhydride of bisphenols is reacted with a halogen compound. (5) An azeotropic solvent is added to the aqueous solution or its concentrate obtained by reacting bisphenols with an alkali metal compound in the presence of a solvent, and dehydration is performed by azeotropic distillation, so that the alkali salts of bisphenols are substantially removed. After becoming anhydrous, a halogen compound is added and a heating reaction is carried out in the presence of a solvent (in this case, a solvent with a higher boiling point than the azeotropic solvent is used); (6) In the presence of a solvent. , a hydrated alkali salt of bisphenols or an aqueous solution, a halogen compound, and an azeotropic solvent are added, and the polymerization reaction is started while heating to perform azeotropic dehydration, and the dehydration is completed and the azeotropic solvent is distilled off. After that, (reaction) a method of conducting a heating reaction in the presence of a solvent, (7) a method of carrying out a heating reaction in the presence of a solvent, and (7) a method of carrying out a heating reaction in the presence of a solvent and an azeotropic solvent. Examples include a method in which an alkal salt of bisphenols is generated by heating, and the polymerization reaction is proceeded while or after the azeotropic distillation of the water produced at the same time. The most suitable one can be selected depending on the reactivity properties of the halogen compound. As is clear from the above example of the polymerization method, in order to react the alkal salt of bisphenols in an anhydrous state, an azeotropic solvent that is azeotropic with water is used as necessary. Representative examples of specific azeotropic solvents include aromatic hydrocarbons such as benzene, toluene, and xylenes, and halogen compounds such as chlorobenzene and o-dichlorobenzene.
Other compounds are also used. Further, the amount of the azeotropic solvent 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, water is distilled out together with the azeotropic solvent, the distillate is cooled and concentrated, and the water and azeotropic solvent are separated into two layers. If the separated azeotropic solvent layer is allowed to reflux into the reaction system, the azeotropic solvent will be used effectively, so that 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 amount of azeotropic solvent used, etc., but from a practical standpoint it is preferably carried out within 10 hours, and more preferably within 5 hours. More preferably, it is completed. The actual temperature of the polymerization reaction in the method of the present invention varies depending on the type of reaction raw material components, the type of polymerization reaction, etc., but is usually in the range of 80 to 400 ° C.
Preferably, the temperature is 100 to 350°C. If the reaction temperature is lower than the above-mentioned temperature range, the desired polymerization reaction will hardly proceed at a rate that can be used practically, and it will be difficult to obtain a polymer with the required molecular weight. On the other hand, when the reaction temperature is higher than the above range, side reactions other than the desired polymerization reaction cannot be ignored, and the resulting polymer becomes significantly colored. The reaction may also be carried out at a constant temperature,
The temperature may be changed gradually or the temperature may be changed in steps. In the method of the present invention, the time required for the reaction varies greatly depending on the types of reaction raw materials, the type of polymerization reaction, the type of reaction temperature, etc., but is usually 10 minutes to
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 in the method of the present invention is preferably free of oxygen, and good results are obtained when the reaction is carried out in nitrogen or other inert gas. Alkaline salts of bisphenols are easily oxidized when heated in the presence of oxygen, hindering the desired polymerization reaction, making it difficult to achieve a high molecular weight, and also causing coloration of the polymer. In the method of the present invention, in order to stop the polymerization reaction, it is usually sufficient to cool the reactants. However, in order to stabilize phenoxide groups that may be present at the ends of the polymer, an aliphatic halide, aromatic halide, etc. may be added and reacted as necessary. Specific representative examples of the halides include methyl chloride, ethyl chloride, methyl bromide, 4-
chlordiphenyl sulfone, 4-chlorobenzophenone, 4,4'-dichlordiphenyl sulfone,
Examples include p-chloronitrobenzene. 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 solventless reaction or the type of reaction solvent used, the reactants may solidify. Alternatively, diluting with an inert solvent during cooling may be effective in some cases. For the above purpose, it is desirable that the alkali halide produced is insoluble, and such is also advantageous for the separation of the polymer described below. In the case of a solvent reaction, if a suitable diluting solvent is not available, further dilution may be performed with the solvent used in the reaction. Separation and purification of the polymer after the polymerization reaction is completed.
Known methods for aromatic polyether polymers can be applied. For example, a solvent in which the desired polymer is soluble and the alkali halide produced is insoluble is added to the reaction mixture, and the precipitated salt (alkali halide) is filtered off. Examples of solvents for this purpose include chlorobenzene, sym-tetrachloroethane, and the like. The desired polymer can be precipitated by dropping the solution after separating the salt into the polymer non-solvent, or conversely by adding the polymer non-solvent to the polymer solution. . Typical examples of nonsolvents commonly used for polymers include methanol, ethanol, isopropanol, acetone,
Examples include methyl ethyl ketone and water, which may be used alone or as a mixture of two or more. The precipitated polymer is heated and dried under normal pressure or reduced pressure, and the polymer used in various processing methods can be obtained in various forms such as powder, flake, and thin film depending on the precipitation method. A polymer with high purity can be obtained by the above operation, but if a polymer with even higher purity is required, for example, the obtained polymer is redissolved in a solvent and precipitated using the above non-solvent. can be repeated for further purification. Further, purification can also be carried out by thoroughly mixing a polymer solution using a water-insoluble solvent with water in a proportion that does not cause the polymer to precipitate, washing and separating the solution, and then precipitating the polymer. The polymer obtained by the method of 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. Typical molding processing conditions for polymers are shown as examples for extrusion and injection molding.
The temperature ranges from 400°C, preferably from 250 to 380°C.
Furthermore, by adding compounds that lower the melt viscosity, stabilizers, etc., it is possible to further lower the molding temperature than the above range. Further, there are no restrictions on the size, shape, etc. of the molded product, and in addition to ordinary molded products, films, sheet-like products, parts with precision microstructures, etc. can be easily molded by general molding methods. When molding the polymer obtained by the method 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, stearic acid, magnesium stearate, calcium stearate, molybdenum oxide, talc, alumina,
Examples include silica and asbestos, which can be used alone or as a mixture of two or more types. The amount of these fillers used ranges from 0.5 to 15%, preferably from 3 to 120%, based on the weight of the polymer of the invention. In addition, antistatic agents, colorants, flame retardants, lubricants, processing improvers, stabilizers, etc. that are usually added during resin processing may be added to the polymer of the present invention either alone or as a mixture of two or more. I can do it.
The amount added is based on the weight of the polymer of the present invention.
It is in the range of 10 ^-4 to 60%, preferably in the range of 10 ^-3 to 40%. It is also possible to produce a film by a casting method from an organic solvent solution of the polymer obtained by the method of the present invention, and a film that is transparent, tough, and highly heat resistant can be obtained like an extruded film. The polymer of the present invention molded as described above can be used for various electrical and electronic parts, housings, automobile parts, aircraft interior materials, sliding parts, gears, insulating materials, dental materials, steam sterilization containers, etc. It can be used in a wide range of fields. The present invention will be explained in detail in the following examples and comparative examples. The viscosity ηred shown in the examples is a value calculated using the following formula, measured with a viscometer using a solution of 0.2 g of polymer dissolved in 100 ml of solvent at 25°C. ηred=t _s −t ₀ /c・t ₀ where t ₀ = outflow time of pure solvent t _s = outflow time of polymer solution c=polymer concentration in polymer solution (g/dl) Example 1 Stirring containers, thermometers, coolers and distillate separators,
In a 300 ml flask equipped with a dropping funnel and nitrogen inlet tube, 25.6 g (0.1 mol) of bis(3,5-dimethyl-4-hydroxyphenyl)methane, 100 ml of chlorobenzene and 45 ml of dimethyl sulfoxide.
The reaction system was completely replaced with nitrogen by passing nitrogen gas into the solution while stirring. Gradually warm up to 60℃ while passing nitrogen gas, and drop to 44.8℃ from the dropping funnel.
% potassium hydroxide aqueous solution was added dropwise over 10 minutes, and the inside of the dropping funnel was further washed with 5 ml of pure water and added to the reaction solution. The reaction temperature rose to 38°C and was further heated to reflux. If water in the reaction system is removed azeotropically with chlorobenzene and chlorobenzene is returned to the reaction system while continuing azeotropic dehydration, the internal temperature will decrease.
The temperature rose from around 120°C to around 140°C, and water distillation was no longer observed at around 145°C. Continue heating to distill off most of the chlorobenzene.
A pale purple slurry was obtained. When the temperature of the reaction solution was cooled to around 130℃ and 28.7g of bis(4-chlorophenyl)sulfone powder was added, the temperature of the slurry-like reaction solution rose to 188℃, but the reaction was then continued at 160℃ for 6 hours. Ta.
During this time, the reaction solution gradually became viscous. Then, after passing methyl chloride for 10 minutes, the reaction mixture was cooled to 80°C, 250 ml of chlorobenzene was added, and the mixture was cooled to room temperature to precipitate the salt. After filtering out the salt precipitated by pressure filtration, pour it into a homomixer containing a large amount of mixed solvent of acetone/water = 4/1 (volume ratio),
The polymer was precipitated in powder form. The obtained powder was dried at 150° C. for 6 hours to obtain 42 g of white powder. The analytical values of the obtained polymer are as follows. Viscosity ηred = 0.72 (chloroform) IR (KBr, cm ^-1 ): 835, 1105, 1150, 1195,
1230, 1295, 1320, 1475, 1585, 2860 ¹ HNMR (CDCl ₃ ): δ = 2.08 (s, CH ₃ ), 3.87
(s, CH ₂ ), 6.82 (d, H ² ), J _2.3 =8Hz,
6.94 (s, H ¹ ), 7.82 (d, H ³ ), J _3.2 = 8Hz Intensity ratio = 6:1:2:2:2 Example 2 Instead of bis(3,5-dimethyl-4-hydroxyphenyl)methane, 30.6 g of bis(3,5-dimethyl-4-hydroxyphenyl)sulfone,
The reaction was carried out in the same manner as in Example 1, except that 50 ml of sulfolane was used instead of dimethyl sulfoxide. After adding bis(4-chlorophenyl)sulfone, the reaction was carried out at 235°C for 6 hours, and the subsequent treatments were carried out in the same manner as in Example 1. After drying, 48 g of pale pink polymer powder was obtained. The analytical values of the obtained polymer are as follows. Viscosity ηred = 0.30 (chloroform) IR (KBr, cm ^-1 ): 680, 740, 830, 1105,
1150, 1170, 1240, 1290, 1310, 1480,
1590, 2880, 3440 ¹ HNMR (CDCl ₃ ): δ = 2.15 (s, CH ₃ ), 6.83
(d, H ² ), J _2.3 = 8.5Hz, 7.74 (s, H ¹ ),
7.85 (d, H ³ ), J _3.2 = 8.5Hz Intensity ratio = 3:1:1:1:1 Example 3 Instead of bis(3,5-dimethyl-4-hydroxyphenyl)methane, 2,2-bis(3,5-
dimethyl-4-hydroxyphenyl)propane
The reaction and post-treatment were carried out in the same manner as in Example 1, except that 28.4 g was used, and 47 g of colorless dry powder was obtained. The analytical values of the obtained polymer are as follows. Viscosity ηred = 0.30 (chloroform) IR (KBr, cm ^-1 ): 680, 740, 830, 1105,
1150, 1170, 1240, 1290, 1310, 1480,
1590, 2880, 3440 ¹ HNMR (CDCl ₃ ): δ = 1.68

[Formula] 2.08 (s, nuclear substitution CH ₃ ), 6.84 (d, H ² ), J _2.3 = 8Hz, 6.96
(s, H ¹ ), 7.92 (d, H ³ ), J _3.2 = 8Hz Intensity ratio = 3:6:2:2:2 Examples 4 to 6 Press sheets having a thickness of 0.2 to 0.3 mm were prepared using the polymer powders obtained in Examples 1 to 3 under the conditions shown in Table 1, and the properties of the sheets are shown in Table 1.

[Table] Example 7 Bis(3,5-dimethyl-4
-hydroxyphenyl)methane instead of 2,2
- Using 28.4 g of bis(3,5-dimethyl-4-hydroxyphenyl)propane, using 21.8 g of bis(4-fluorophenyl) ketone instead of bis(4-chlorophenyl) sulfone, 6 at 135℃ after adding fluorophenyl)ketone.
The reaction and drying operation was carried out in the same manner as in Example 1 except for the reaction time. After the reaction was completed, the reaction solution was poured into a stirred homomixer containing methanol to precipitate a polymer, which was further washed with water and dried to obtain 44 g of a pale gray polymer. The analytical values of this product are as follows; Viscosity ηred = 0.316 (chloroform) ¹ HNMR (CDCl ₃ ): δ = 1.69

[Formula] 2.11 (s, nuclear substitution CH ₃ ), 6.82 (d, H ² ), J _2.3 =9Hz, 6.98
(s, H ¹ ), 7.75 (d, H ³ ), J _3.2 = 9Hz Intensity ratio = 3:6:2:2:2 Examples 8 to 10 As a result of redissolving the sheets obtained in Examples 4 to 6 in chloroform, it was revealed that all were soluble and reactions such as crosslinking and reticulation did not proceed during hot press molding. Ta. Further, a part of the sheet obtained in Example 4 was dissolved in chloroform, and ηred was measured to obtain the results shown in Table 2.

[Table] There was no change in ηred even after press working, and it became clear that all polymers A, B, and C could be stably processed. Therefore, it can be seen that melt processing such as extrusion and injection is possible. Examples 11 to 13 The glass transition temperature (Tg) of the sheet obtained in Example 4 was heat-treated in an oven at 200° C. for 1 hour and measured by the TMA method, and the results shown in Table 3 were obtained. (Measured in Penetration Mode using Perkin Elmer thermophysical tester TMS-1, load 50g,
Temperature increase rate: 10℃/min, measurement atmosphere: 40 to 50℃ in He flow
cc) Comparative Examples 1 to 3 Bis(3,5-dimethyl-4 in Example 1)
-hydroxyphenyl)methane, bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)methane,
Using 0.1 mol each of either hydroxyphenyl) sulfone or 2,2-bis(4-hydroxyphenyl)propane, the same reaction and post-treatment as in Example 1 were carried out to obtain Polymer A, Polymer B, and Polymer C. were obtained respectively. These polymers were found to have the following repeating units by IR, ¹ HNMR, and elemental analysis. (However, -φ- indicates a paraphenylene group.) For polymers A', B', and C', press sheets were prepared under the same conditions as in Example 4, and this sheet was subjected to the same treatment and treatment as in Examples 10 to 12. The glass transition temperature was determined under the measurement conditions and the results shown in Table 3 were obtained.

[Table] Comparative Example 4 Bis(3,5-dimethyl-4
-hydroxyphenyl)methane instead of bis(3
-Methyl-4-hydroxyphenyl)methane 0.1
Polymer D was obtained by carrying out the same reaction and post-treatment as in Example 1, except that mol was used. The polymer had an ηred of 0.51, and IR, ¹ H-NMR, and elemental analysis revealed that it had the following repeating units. Comparative Example 5 Bis(3,5-dimethyl-4
-hydroxyphenyl)methane instead of bis(3
-chloro-4-hydroxyphenyl)methane 0.1
Polymer E was obtained by carrying out the same reaction and post-treatment as in Example 1, except that mol was used. This polymer had an ηred of 0.31, and IR, ¹ NMR, and elemental analysis revealed that it had the following repeating units. A press sheet was prepared for Polymers D and E under the same conditions as in Example 4, and this sheet was used in Example 10.
The glass transition point was determined under the same processing and measurement conditions as in ~12, and the results shown in Table 4 were obtained.

【table】

Claims (1)

[Claims] 1 General formula () (In the formula, A represents a divalent hydrocarbon group having 1 to 10 carbon atoms, _-SO2- , -SO-, -S-, -O-, -CO-, m is 0 or 1, A when m is 0
This indicates that aromatic rings are bonded to each other. ) Bisphenols or their alkali salts represented by the general formula () (In the formula, B represents -SO ₂ -, -CO-.) General formula () characterized by reacting a halogen compound represented by (In the formula, A and m are the same as in the formula (), B is the same as in the formula (), and n is 10
Represents ~1000. ) A method for producing a polyether polymer represented by: