JPH0551013B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to an injection moldable aromatic polyether polymer that has excellent heat resistance, moisture absorption, moldability, etc. [Prior Art] A method for obtaining a linear aromatic polyether polymer by reacting a dialkali metal salt of a dihydric phenol with an activated aromatic dihalide is well known (for example, RN Johnson et al. , J. Polym.
Sci., A-1 5 2375 (1967)). In particular, dialkali metal salts of 2,2-bis(4-hydroxyphenyl)propane and bis(4-
Polyether polymers obtained from (chlorophenyl) sulfone have excellent mechanical properties at relatively high temperatures and are already in practical use in many fields.
In addition, as a resin with even better heat resistance, there is a polyether polymer obtained from a dialkali metal salt of bis(4-hydroxyphenyl) sulfone and bis(4-halophenyl) sulfone, which requires a high degree of heat resistance. It is used in the electrical and electronic industry, precision industry, and automobile and aviation fields. [Problems to be Solved by the Invention] However, the above polyether sulfone polymer contains a highly polar sulfone bond in the polymer skeleton, so although it has excellent heat resistance, it is highly hygroscopic and is difficult to process. The disadvantage is that the fluidity of time is not sufficient. An object of the present invention is to provide an aromatic polyether polymer having excellent heat resistance without the above drawbacks. [Means for Solving the Problems] In order to achieve the above object, the present inventors continued various studies, found that a product having a specific structure is good, and completed the present invention. That is, the present invention provides the general formula [However, R ¹ to ^{R 4} in the formula each represent a hydrocarbon group having 1 to 8 carbon atoms or a halogen atom,
a to d each independently represent an integer of 0 to 4. Also, when a to d are 2 or more, there are 2 or more
R ¹ to R ⁴ may be the same or different. ] Consists of repeating units shown as , and has a logarithmic viscosity of 0.2
It is an aromatic polyether-based polymer characterized by being in the range of ~2.0 dl/g. The bisphenol residue containing an indane ring contained in the polymer of the present invention is more effective in improving the glass transition temperature of the polymer than the 2,2-bis(4-hydroxyphenyl)propane residue. Unlike bis(4-hydroxyphenyl) sulfone residues, it does not contain sulfone bonds, so sulfone bonds are not introduced into the polymer, and there is no negative effect on hygroscopicity or solvent resistance, making it practical. forms highly aromatic polyethers. The polymer of the present invention is composed of repeating units represented by the general formula, and is further composed of structural units represented by the general formulas A and B. [R ¹ to R ⁴ and a to d in formulas (A) and (B) are the same as in the general formula. ] As described later, the polymer of the present invention is usually a combination of an aromatic halogen compound, which is a raw material compound constituting the structural unit of general formula A, and a bisphenol having an indane ring, constituting the structural unit of general formula B. Manufactured by polycondensation. Specific examples of aromatic halogen compounds that are raw material compounds constituting the structural unit of general formula A include:
Bis(4-chlorophenyl)ketone, bis(2-
chlorphenyl) ketone, bis(3,4-dichlorophenyl) ketone, bis(3-methyl-4-chlorophenyl) ketone, bis(3,5-dimethyl-4-chlorophenyl) ketone, bis(4-fluorophenyl) ketone, Bis(2-fluorophenyl)ketone, bis(3-methyl-4-fluorophenyl)ketone, bis(3-chloro-4-fluorophenyl)ketone, bis(3,5-di-t-
Butyl-4-fluorophenyl)ketone, bis(3,5-diphenyl-4-fluorophenyl)
Ketone, 3-methyl-4,4'-difluorobenzophenone, bis(4-bromophenyl)ketone,
Examples include bis(4-iodophenyl)ketone, which can be used alone or as a mixture of two or more. Particularly preferred are bis(4-fluorophenyl)ketone and bis(4-chlorophenyl)ketone. The raw material bisphenols constituting the structural unit represented by general formula B include hydroxyphenyl indanol derivatives, and specific examples include 1,1,3-trimethyl-3-(4-hydroxyphenyl )-5-indanol, 1,1,3,4,
6-pentamethyl-3-(3,5-dimethyl-4
-hydroxyphenyl)-5-indanol, 1,
1,3,4-tetramethyl-3-(3-methyl-
4-hydroxyphenyl)-5-indanol,
1,1,3-trimethyl-4,6-di-t-butyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)-5-indanol, 1,1,3
-trimethyl-4,6-dibromo-3-(3,5
-dibromo-4-hydroxyphenyl)-5-indanol, 1,1,3-trimethyl-4,6-
Dichloro-3-(3,5-dichloro-4-hydroxyphenyl)-5-indanol, 1,1,3
-trimethyl-3-(3-hydroxyphenyl)-
4-indanol, 1,1,3-trimethyl-3
-(3-hydroxyphenyl)-6-indanol, 1,1,3,5-tetramethyl-3-(3-
Hydroxy-4-methylphenyl)-6-indanol, 1,1,3,6-tetramethyl-3-
(3-methyl-4-hydroxyphenyl)-5-indanol, 1,1,3,5-tetramethyl-3
-(3-methyl-4-hydroxyphenyl)-5-
Examples include indanol, and these can be used alone or in combination of two or more. The above-mentioned hydroxyindanol derivatives are prepared by heating isobropenylphenols or their dimers in the presence of an acid catalyst [for example,
76564, Special Publication Showa 55-11651, USP4334106
USP3288864], directly heating bisphenols in the presence of an acid catalyst [USP2979534], or sulfonating indane compounds obtained by dimerization of α-alkylstyrene derivatives and melting them with alkali [USP2819249, USP2754285]. Obtainable. The molar ratio of bisphenols to halogen compounds used in the production of the polymer of the present invention is from 0.7 to
It is preferable to fall within the range of 1.3. More preferably, it is in the range of 0.85 to 1.15, and especially for the purpose of obtaining a high molecular weight polymer, the above molar ratio is 1.
It is best to have it nearby. As already mentioned, the bisphenols used in the production of the polymer 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, with sodium and potassium being particularly preferred. The metal compounds used to form the alkali salts include hydroxides, carbonates, and bicarbonates, with hydroxides and carbonates being particularly preferred. That is, in order to prepare dialkali metal salts of bisphenols, it is particularly preferable to use at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and the like. A solvent is used as necessary in the production of the polymer of the present invention. A preferred solvent for the polymerization reaction is one that exhibits high solubility for all of the raw material bisphenols, halogen compounds, and the polyether polymer to be produced, and is also soluble in alkali salts of bisphenols, alkali metal compounds, etc. It is preferable that it has the following. As solvents suitable for such purposes, compounds commonly referred to as polar solvents are often used, but the solvent is not limited thereto. Specific representative examples of solvents used as necessary include dimethyl sulfoxide, sulfolane (tetramethylene sulfone), diphenyl sulfone, 1,3-dimethyl-2-imidazolidinone, N,N-dimethylformamide, N,N-dimethylacetamide, N-
Examples include methyl-2-pyrrolidone, dimethyl sulfone, diethyl sulfone, diethyl sulfoxide and the like. Furthermore, in addition to polar solvents, diphenyl ether,
Biphenyl, terphenyl, phenanthrene, naphthalene, diphenylmethane, triphenylmethane and the like can also be used advantageously. The amount of the solvent used as necessary when producing the polymer 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 reaction conditions. From the above range, if the amount of solvent used is small, the effect as a solvent will not be recognized, and even if the produced polymer has a low molecular weight, it will precipitate. will not be obtained. On the other hand, if the amount of solvent is increased beyond the above range,
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 producing the polymer of the present invention can be concretely carried out in 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) A method in which a separately prepared alkali salt anhydride of bisphenols and a halogen compound are reacted in the presence of a solvent. 5) Add an azeotropic solvent to the aqueous solution or its concentrate obtained by reacting bisphenols with an alkali metal compound in the presence of a solvent, and perform dehydration by azeotropic distillation to make the alkali salt of bisphenols substantially anhydrous. After that, a halogen compound is added and a heating reaction is carried out in the presence of a solvent. A hydrated alkali salt of suphenols or an aqueous solution, a halogen compound, and an azeotropic solvent were added, and the polymerization reaction was initiated while heating to perform azeotropic dehydration, and the dehydration was completed and the azeotropic solvent was distilled off. After that, (reaction) a method of carrying out a heating reaction in the presence of a solvent, and (7) heating a mixture of bisphenols, a halogen compound, and an alkali metal carbonate or hydrogen carbonate in the presence of a solvent and an azeotropic solvent. Examples include a method in which an alkali salt of bisphenols is produced, 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 and physical properties of the 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. Specific examples of azeotropic solvents include aromatic hydrocarbons such as benzene, toluene, and xylenes, and halogen compounds such as chlorobenzene and o-dichlorobenzene, but other compounds may also be 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 condensed, 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 is 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 temperature of the polymerization reaction when producing the polymer 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 production of the polymer 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 in the range of 10 minutes to 100 hours, and is preferably is carried out for a period of 30 minutes to 24 hours. The reaction atmosphere 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 increase the molecular weight, and also causing coloration of the polymer. In the production of the polymer 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, an aromatic halide, or the like may be added and reacted as necessary. Specific examples of the halides include methyl chloride, ethyl chloride, methyl bromide, 4-
Chlordiphenyl sulfone, 4-chlorobenzophenone, bis(4-chlorphenyl)ketone, p
- Chlornitrobenzene, etc. can be obtained. 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 alkalilide produced is insoluble is added to the reaction mixture to separate out the precipitated salt (alkali halide). Examples of solvents for this purpose include chlorobenzene, dichloromethane,
Examples include sym-tetrachloroethane. 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. Further purification can be carried out by repeating the above steps. 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 of the present invention must have a degree of polymerization such that the logarithmic viscosity measured by the logarithmic viscosity measurement method described later is 0.2 to 2.0 dl/g, and if it is less than 0.2 dl/g, the molecular weight is too small and the impact resistance is insufficient. If the amount exceeds 2.0 dl/g, processing fluidity becomes extremely poor, making it difficult to use. The polymer 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 each fully possible within the capabilities of general molding machines, and the desired product can be obtained in a desired state. Examples of polymer molding conditions for extrusion and injection molding include molding temperatures ranging from 200 to 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. In addition, there are no restrictions on the size or shape of molded products, and in addition to regular molded products, films,
Sheets, parts with precise microstructures, etc.
It can be easily molded using common molding methods. When molding the polymer of the present invention, a filler component may be added 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,
Examples include molybdenum sulfide, talc, alumina, silica, asbestos, etc., used singly or in combination.
It can be used as a mixture of more than one species. The amount of these fillers used is 0.5 to 150%, preferably 3 to 150%, based on the weight of the polymer of the present invention.
The range is 120%. Furthermore, antistatic agents, colorants, flame retardants, lubricants, processing improvers, stabilizers, etc., which are usually added during resin processing, can also be added to the polymer of the present invention, either singly or as a mixture of two or more. can. The amount added is 10 ^-4 based on the weight of the polymer of the present invention.
~60%, preferably 10 ^-2 ~40%. It is also possible to produce a film using a casting method from a solution of the polymer of the present invention in an organic solvent, and as with an extruded film, a film that is transparent, tough, and highly heat resistant can be obtained. 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. [Example] The present invention will be explained in detail in the following Examples and Comparative Examples. The logarithmic viscosity ηinh in the following examples was measured at 35°C as a solution with a polymer concentration of 0.5 g/dl using a mixed solvent of phenol/tetrachloroethane (weight ratio 6/4), and was calculated according to the following formula: This is what is required. ηinh=1/Clnt ₁ /t ₂ (where t ₁ is the flow time of the polymer solution, t ₂ is the flow time of the solvent only, and C is the polymer solution concentration (g/dl)). In the following, parts, percentages, and ratios are based on weight unless otherwise specified. Example 1 In a 500 ml flask equipped with a stirrer, thermometer, condenser, distillate separator and nitrogen inlet tube,
3-trimethyl-3-(4'-hydroxyphenyl)
26.83 g (0.1 mol) of -5-indanol, 50 ml of toluene, 100 ml of dimethyl sulfoxide, and 23.4 g of a 48.0% aqueous potassium hydroxide solution were taken and heated to 130° C. while nitrogen gas was passed through the mixture while stirring. As the temperature of the reaction solution rose, reflux of toluene started. Azeotropic dehydration is performed while returning toluene into the reaction system.
The test was carried out at 130°C for 4 hours. Thereafter, 21.82 g (0.1 mol) of bis(4-fluorophenyl)ketone and 20 ml of toluene were added to the reaction system, and the temperature of the reaction solution was heated to 140°C. Polymerization was carried out for 1.5 hours while toluene was distilled off to obtain a highly viscous, yellowish solution. The temperature of the reaction solution was cooled to room temperature, and 500 ml of dichloromethane was added to the reaction solution. After dissolving the polymer, this dichloromethane solution was transferred to a tall beaker, 200 ml of a mixed solvent of methanol/water = 1/1 (volume ratio) was added under strong stirring, and the mixture was stirred for 20 minutes. After standing still, remove the upper aqueous phase and add a mixed solvent of methanol/water = 1/1 (volume ratio) 200% again.
ml, and then add 1N hydrochloric acid aqueous solution to make the mixture.
The solution was made acidic to pH 3-4 and stirred for 20 minutes to wash the dichloromethane solution. The washed dichloromethane solution was poured into a homomixer containing 1000 ml of methanol to precipitate the polymer into powder. The resulting powder is colorless and after air drying at room temperature, it is dried at 150℃.
It was dried under reduced pressure for 12 hours. A sheet was prepared by preheating the powdered polymer at 330°C for 1 minute and then applying a pressure of 100 Kg/cm ² at 300°C for 1 minute. The analytical values and physical property values of the obtained polymer were as follows. (1) Logarithmic viscosity ηinh 0.89 (powder) 1.12 (sheet) (2) IR (film cm ^2-1 ); 2990, 1670, 1600, 1510 1490, 1250, 1170, 930

[Table] 10% heating weight loss temperature of the obtained polymer
Td ₁₀ and glass transition temperature Tg were measured by thermogravimetric analysis (TG) method and TMA method, respectively. the result,
The respective measured values were 560°C and 175°C, confirming that the polymer had excellent heat resistance. Comparative example 1 1,1,3-trimethyl-3 in Example 1
-(4'-hydroxyphenyl)-5-indanol and bis(4-fluorophenyl)ketone were replaced by 2,2-bis(4-hydroxyphenyl)propane (0.1 mol) and bis(4- Polymerization was carried out in the same manner as in Example 1 except that chlorphenyl) sulfone (0.1 mol) was used to obtain a colorless polymer powder and a press sheet. The ηinh of both the powder and the press sheet was 0.55. Comparative Example 2 1,1,3-trimethyl-3 in Example 1
-(4'-hydroxyphenyl)-5-indanol, toluene, dimethyl sulfoxide, bis(4
-fluorophenyl)ketone, respectively;
Bis(4-hydroxyphenyl)sulfone (0.1
Polymerization was carried out in the same manner as in Example 1, except that xylene (50 ml + 20 ml), sulfolane (100 ml), and bis(4-chlorophenyl)sulfone (0.1 mol) were used, and the polymerization temperature was 180°C. Polymer powder and pressed sheet were obtained. The ηinh of the powder and press sheet were 0.47 and 0.46, respectively. The press sheets of the polymers obtained in Example 1 and Comparative Examples 1 and 2 were coarsely pulverized using a pulverizer, and the obtained chips (3 to 5 meshes) were heated at 23°C and at a humidity of 50%.
The water content was measured after being left in a room adjusted to 150 hours. The results are shown in Table-1.

[Table] From the results in Table 1, the polymer of the present invention shown in Example 1 clearly has lower hygroscopicity than the well-known polymers of Comparative Examples 1 and 2. Example 2 Bis(4-chlorophenyl) instead of bis(4-fluorophenyl)ketone in Example 1
Using 25.11 g (0.1 mol) of ketone, the solvent was
- instead of dimethyl-2-imidazolidinone, 210
Polymerization was carried out at .degree. C. for 5 hours. Other operations (dehydration, washing, precipitation, drying, etc.) were performed in the same manner as in Example 1. As the polymerization progressed, the color of the reaction system changed from white-purple, bluish-purple, black-purple, dark gray, and finally took on a brown-black color. After washing and precipitation, the polymer was obtained almost quantitatively in the form of a pale yellow powder. In this example, 1,3-dimethyl-2 was used as the solvent.
-Similar results are obtained using sulfolane, dimethylsulfoxide, dimethylformamide, and dimethylacetamide in addition to imidazolidinone. The polymer sheet was prepared in the same manner as in Example 1. The analytical values of the obtained polymer were as follows. (1) Logarithmic viscosity ηinh 0.24 (powder), 0.26 (sheet) (2) IR (film cm ^2-1 ): 2990, 1670, 1600, 1510 1490, 1250, 1170, 930

[Table] Example 3 The polymerization time in Example 1 was changed from 1.5 hours to 0.5 hours.
Polymerization was carried out in the same manner as in Example 1, except that the time was changed to obtain a colorless polymer powder. ηinh of powder is
0.50, and the ηinh of the press sheet was also 0.50. The press sheets obtained in Example 3 and Comparative Examples 1 and 2 were crushed using a crusher, and the melt viscosity of the sample was dried at 150°C for 8 hours using a Koka type flow tester (CFT-500 manufactured by Shimadzu Corporation). It was measured. The measured temperature is
Preheating time is 5 minutes at 380℃, load is 100Kg, die size (10
mmL, 1 mmD) and a plunger of 1 cm ² , and the results shown in Table 2 were obtained.

〔Effect of the invention〕

The polymer of the present invention has lower hygroscopicity than conventionally known sulfone-containing aromatic polyethers and has excellent flow processability, so it can be used in place of conventionally known sulfone-containing aromatic polyethers for various purposes. It is.

Claims (1)

[Claims] 1. General formula [However, R ¹ to ^{R 4} in the formula have 1 to 8 carbon atoms.
represents a hydrocarbon group or halogen atom, a to
d each independently represents an integer of 0 to 4. Also, when a to d are 2 or more, there are 2 or more
R ¹ to R ⁴ may be the same or different. ] Consists of repeating units shown as , and has a logarithmic viscosity of 0.2
1. An aromatic polyether polymer characterized in that it has a molecular weight in the range of ~2.0 dl/g.