JPH0356253B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to 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 Polymers that maintain excellent properties as ether polymers and have high heat resistance are particularly desired from various fields. The present inventors have continued to conduct various studies for the purpose of obtaining an aromatic polyether polymer having particularly excellent heat resistance and meeting the above-mentioned main points. The inventors have found that the invention is compatible with the purpose of the invention, and have completed the present invention. That is, the present invention provides 1) General formula () (In the formula, A is -CH ₂ - or

[Formula] is shown, and n represents 10 to 1000. ) is an aromatic polyether polymer represented by: The aromatic polyether polymer of the present invention has a methyl group in the bisphenol residue in the polymer. It has been revealed that polyether polymers containing such methyl groups in the bisphenol residue have superior physical properties and improved heat resistance compared to terminally substituted corresponding polyether polymers. . 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 It was confirmed that the temperature increased by about 30 to 40°C compared to the polyether-based polymer having residues, and that most of the polymers exhibited a Tg of 200°C or higher. Therefore, the polymer of the present invention has mechanical properties,
Since various physical properties such as electrical properties are maintained up to relatively high temperatures and dimensional stability is good, 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 of the present invention can be melt-processed and can be used to mold parts that require precision. . The polymer of the present invention is represented by the general formula (). The part represented by A in formula (1) is -CH ₂ - or

[Formula]. n indicates the degree of polymerization, and is usually an integer in the range of 10 to 1000. The polymer of the present invention can be obtained by the production method shown below. The bisphenols used in the method of the present invention are represented by the general formula (). Specifically, bis(3,5-dimethyl-4-hydroxyphenyl)methane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, etc. can be mentioned, and these may be used alone. Or it can be used as a mixture of two or more types. As the halogen compound used in the method of the present invention, those represented by the general formula () are used, and specific examples include bis(4-chlorophenyl)ketone, bif(4-fluorophenyl)
Ketone, bis(4-bromophenyl)ketone, bis(4-iodophenyl)ketone, etc. can be mentioned, and these can be used alone or as a mixture of two or more types. Particularly preferred halogen compounds include bis(4-chlorophenyl)ketone and bis(4-fluorophenyl)ketone. 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. 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. Examples of alkali metals 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. A preferable solvent for the polymerization reaction is one in which all of the raw material bisphenols, halogen compounds, and the polyether polymer to be produced have high solubility, and bisphenol alkali salts and alkali metal compounds have high solubility. It is preferable that the 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, the effect as a solvent will not be recognized,
In particular, even if the produced polymer has a low molecular weight, it will precipitate, making it impossible to obtain a practical high molecular weight polymer. On the other hand, if the amount of solvent is greater than the amount of the above reaction, the monomer concentration will decrease, and in order to increase the molecular weight, a higher temperature and longer reaction time will be required, making it impossible to obtain favorable results. 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 alkali salt of bisphenols is produced 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 alkali 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 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 dehydration can be completed without using a large excess of azeotropic solvent.Azeotropic dehydration The time required 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 preferable to conduct the reaction within 10 hours, and it is possible to complete the reaction within 5 hours. More preferred. 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 50 to 450°C, preferably carried out in the range of 100 to 400°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.
Further, the reaction may be carried out at a constant temperature, or the temperature may be gradually changed or the temperature may be changed stepwise. 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 examples of the halides include methyl chloride, ethyl chloride, methyl bromide, 4-chlorodiphenylsulfone, 4-chlorobenzophenone, 4,4'-dichlorodiphenylsulfone, p-
Examples include chlornitrobenzene. 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. . Examples of commonly used non-solvents for polymers include methanol,
Examples include ethanol, isopropanol, acetone, methyl ethyl ketone, water, etc., and these 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 at 25°C 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 85℃,
The mixture was further heated until reflux started. When water in the reaction system is removed azeotropically with chlorobenzene and chlorobenzene is returned to the reaction system while azeotropic dehydration continues, the internal temperature rises from around 120°C to around 140°C, and 145
Distillation of water was no longer observed around ℃. Heating was continued to distill off most of the chlorobenzene, yielding a white slurry. When the temperature of the reaction solution was cooled to around 130℃ and 21.8g of bis(4-chlorophenyl)ketone powder was added, the temperature of the viscous reaction solution rose to 150℃, but the reaction was then continued at 135℃ for 6 hours. Ta. 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 4 g of a pale gray polymer.
(This is referred to as Polymer A.) The analytical values of the polymer are as follows. Viscosity ηred = 0.316 (chloroform) IR (KBr, cm ^-1 ): 760, 845, 920, 1160,
1230, 1280, 1310, 1360, 1380, 1480,
1505, 1600, 1655, 2960, 3020 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 Example 2 Bis(3,5-dimethyl-4-hydroxyphenyl)methane was used instead of 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)methane at 25.6
The reaction and post-treatment were carried out in the same manner as in Example 1, except that 41.3 g of colorless dry powder was obtained (this was referred to as Polymer B). The analytical values of Polymer B are as follows. Viscosity ηred = 0.86 (chloroform) IR (KBr, cm ^-1 ): 760, 850, 920, 1160,
1230, 1280, 1310, 1380, 1420, 1480,
1500, 1600, 1660, 2920, ¹ HNMR (CDCl ₃ ): δ=2.12 (s, nuclear substitution CH ₃ ),
3.87 (S, CH ₂ ), 6.84 (d, H ² ), J _2.3 = 8
Hz, 6.98 (s, H ¹ ), 7.78 (d, H), J _3.2 =
8Hz intensity ratio = 6:1:2:2:2 Examples 3 and 4 Using the powders of Polymer A and Polymer B obtained in Examples 1 and 2, press sheets with a thickness of 0.2 to 0.3 mm were created under the conditions shown in Table 1, respectively.
Table 1 shows the properties of the sheet.

[Table] Examples 5 and 6 The sheets obtained in Examples 3 and 4 were redissolved in chloroform, and both were found to be soluble. Also, a part of the press sheet was dissolved in chloroform,
Table 2 shows the results of measuring ηred. Reactions such as crosslinking and reticulation did not proceed during hot press molding, and there was no change in ηred even after press processing. This shows that both polymers A and B can be press-processed, and it can be seen that melt processing such as extrusion and injection is possible.

[Table] Examples 7 and 8 The glass transition temperature (Tg) of the sheets obtained in Examples 3 and 4 was heat-reacted in an oven maintained at 180°C for 1 hour using the TMA method (Perkin
Using Elmer's thermophysical tester TMS-1 model
Measured in Penetration Mode, load 50g, temperature increase rate
Measurement was performed at 10°C/min (40 to 50 c.c. min) in a measurement atmosphere of He gas flow. As a result, the Tg of Polymer A was 207℃,
The Tg of Polymer B was 217°C. Comparative Example 1 2,2-bis(4-hydroxyphenyl) instead of 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane in Example 1
Example 1 using 0.1 mol (22.8 g) of propane
Polymer C was obtained by carrying out the same reaction and post-treatment. These polymers were confirmed to have the following repeating units by IR, ¹ HNMR, elemental analysis, etc. A pressed sheet was prepared from the obtained polymer C under the same conditions as in Examples 3 and 4, and the glass transition temperature of this sheet was measured under the same processing and measurement conditions as in Examples 7 and 8, respectively. As a result, polymer C
Tg was 155°C.

Claims (1)

[Claims] 1 General formula () An aromatic polyether polymer represented by (wherein A represents -CH ₂ - or [Formula], and n represents 10 to 1000).