JP2008037827A - Method for producing ketal bisphenols - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an industrially advantageous and inexpensive method for producing a ketal bisphenol which has an enhanced purity, excellent long-term stability and polymerization activity. <P>SOLUTION: The method for producing a ketal bisphenol by using a dihydroxybenzophenone and a glycol or an alkylene dithiol as raw materials comprises a process for treating a mixture containing at least the ketal bisphenol and the dihydroxybenzophenone with an alkali aqueous solution having a pH of 9-13. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for producing ketal bisphenols, and more particularly to a method for producing ketal bisphenols with high purity.

  Aromatic polyketones such as aromatic polyetherketone and aromatic polyetheretherketone have the highest level of heat resistance (continuous use temperature) and heat distortion resistance among thermoplastic resins, and are excellent in flame retardancy and at the time of combustion. It is a crystalline resin with an unprecedented characteristic that it generates very little smoke and corrosive gas. In addition, it has excellent mechanical properties, hot water resistance, radiation resistance, and chemical resistance. These properties are mainly due to the high melting point and high crystallinity.

  However, the high crystallinity of the aromatic polyketone hinders the polymerization and processing of the polymer and is insoluble in typical organic solvents at temperatures preferred for producing the aromatic polyketone, such as temperatures below 250 ° C. It was difficult to increase the molecular weight of the group polyketone. Moreover, even if a high molecular weight aromatic polyketone was obtained, the processing method was limited due to its high melting point and solvent insolubility, and it could not be used in a wide range of applications.

  In order to solve such drawbacks, a method of first synthesizing a polyketal ketone as a high molecular weight amorphous polymer and then producing a high molecular weight crystalline aromatic polyether ketone by deprotection of the ketal group Has been reported (for example, see Patent Document 1, Patent Document 2, and Non-Patent Document 3).

  Patent Document 1, Patent Document 2 and Non-Patent Document 3 describe a method for producing a ketal bisphenol as a raw material for a polyketal ketone, in which 4,4'-dihydroxybenzophenone and glycols are alkyl orthoesters and montmorillonite clays. A method of reacting in the presence of such a solid catalyst or a method of reacting in the presence of hydrogen bromide as an acid catalyst is proposed.

  However, unreacted 4,4'-dihydroxybenzophenone remains as impurities in the ketal bisphenols produced by these methods, so that it is stable for a long time when used as a raw material for aromatic polyketals. And the polymerization activity was insufficient. The decrease in long-term stability is because 4,4'-dihydroxybenzophenone has a higher acidity due to the electron-withdrawing effect of the ketone group than ketal bisphenols, and promotes the deprotection reaction of the ketal. The decrease in the activity is because the nucleophilicity is lowered when the aromatic polyketal is polymerized as an alkali metal salt.

Furthermore, since the crystallinity of 4,4'-dihydroxybenzophenone is higher, it is difficult to purify ketal bisphenols by recrystallization, and purification by column chromatography or the like takes a lot of time and is industrial. It is not an advantageous method.
Japanese Patent Publication No. 02-14334 Japanese Patent Publication No. 02-1844 Macromolecules, 20, 1204 (1987)

  An object of the present invention is to provide a method for producing ketal bisphenols which is industrially advantageous and inexpensive, while increasing the purity of ketal bisphenols and improving long-term stability and polymerization activity.

  The method for producing the ketal bisphenols of the present invention for achieving the above object is obtained by using a dihydroxybenzophenone represented by the following general formula (1) and a glycol or alkylenedithiol represented by the following general formula (2) as raw materials. The method for producing a ketal bisphenol as described above comprises a step of treating a mixture containing at least a ketal bisphenol represented by the following general formula (3) and the dihydroxybenzophenone with an alkaline aqueous solution having a pH of 9 to 13. To do.

(In the formula, X ₁ , X ₂ , X ₃ and X ₄ each independently represent a hydrogen atom, a linear or branched hydrocarbon group having 1 to 4 carbon atoms, or an alkoxy group.)

(In the formula, R ₁ , R ₂ , R ₃ and R ₄ each independently represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 4 carbon atoms, and A represents an oxygen atom or a sulfur atom. E represents a single bond or a methylene or ethylene chain which is unsubstituted or substituted with a linear or branched hydrocarbon group having 1 to 4 carbon atoms.

(In the formula, X ₁ , X ₂ , X ₃ , X ₄ , R ₁ , R ₂ , R ₃ , R ₄ , A and E are the same as above.)

  According to the production method of the present invention, a mixture containing the produced ketal bisphenols and unreacted dihydroxybenzophenones is treated with an alkaline aqueous solution having a pH of 9 to 13, thereby utilizing the difference in acidity of the phenolic hydroxyl groups. Only dihydroxybenzophenones are converted to alkali metal salts to make them water-soluble and removed. As a result, the purity of the ketal bisphenols was increased, long-term stability was imparted, and the polymerization activity was greatly improved, making it possible to develop a wide range of applications industrially advantageous and inexpensively.

Hereinafter, the present invention will be described in detail.
The dihydroxybenzophenones used in the present invention are represented by the following general formula (1).

(In the formula, X ₁ , X ₂ , X ₃ and X ₄ each independently represent a hydrogen atom, a linear or branched hydrocarbon group having 1 to 4 carbon atoms, or an alkoxy group.)

  Examples of the dihydroxybenzophenones include 4,4′-dihydroxybenzophenone, 2,4′-dihydroxybenzophenone, 2,2′-dihydroxy-3,3′-dimethyl-benzophenone, and 2,2′-dihydroxy-4,4. Examples include '-dimethyl-benzophenone, 4,4'-dihydroxy-3,3'-dimethyl-benzophenone, 2,2'-dihydroxy-5,5'-dimethyl-benzophenone.

  The glycols or dithiols used in the present invention are represented by the general formula (2).

(In the formula, R ₁ , R ₂ , R ₃ and R ₄ each independently represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 4 carbon atoms, and A represents an oxygen atom or a sulfur atom. E represents a single bond or a methylene or ethylene chain which is unsubstituted or substituted with a linear or branched hydrocarbon group having 1 to 4 carbon atoms.

  In the general formula (2), specific examples of the linear or branched hydrocarbon group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a t-butyl group. Etc. Examples of glycols or dithiols include ethylene glycol, 1,2-propanediol, 2,3-butanediol, 2-methyl-1,2-propanediol, 2-methyl-2,3-butanediol, 2 , 3-Dimethyl-2,3-butanediol, 1,2-pentanediol, 2,3-pentanediol, 1,2-hexanediol, 2,3-hexanediol, 3,4-hexanediol, 1,3 -Propanediol, 2,2-dimethyl-1,3-propanediol, 2-methyl-1,3-propanediol, 2-methyl-1,3-butanediol, 2,3-dimethyl-1,3-butane Diol, ethylenedithiol, 1,3-propanedithiol and the like. From the viewpoint of reactivity and stability, ethylene glycol, 1, - propanediol, ethylene dithiol, 1,3-propanedithiol more preferable.

  The ketal bisphenol obtained by the production method of the present invention is represented by the general formula (3).

(In the formula, X ₁ , X ₂ , X ₃ and X ₄ each independently represent a hydrogen atom, a linear or branched hydrocarbon group having 1 to 4 carbon atoms or an alkoxy group, and R ₁ , R ₂ R ₃ and R ₄ each independently represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 4 carbon atoms, A represents an oxygen atom or a sulfur atom, and E represents a single bond or an unsubstituted group. Or a methylene or ethylene chain substituted with a linear or branched hydrocarbon group having 1 to 4 carbon atoms.

  Examples of ketal bisphenols include 2,2-bis (4-hydroxyphenyl) -1,3-dioxolane, 2,2-bis (4-hydroxyphenyl) -1,3-dioxane, 2,2-bis ( 4-Hydroxyphenyl) -1,3-dithiolane and 2,2-bis (4-hydroxyphenyl) -1,3-dithiane are preferred from the viewpoints of reactivity and stability.

  The method for producing ketal bisphenols of the present invention comprises a step of treating a mixture containing at least the produced ketal bisphenols and unreacted dihydroxybenzophenones with an alkaline aqueous solution having a pH of 9 to 13. Mixtures containing ketal bisphenols and dihydroxybenzophenones are in a state of coexisting with an organic solvent, and treating this with an alkaline aqueous solution having a pH of 9 to 13 makes only the dihydroxybenzophenones water-soluble and removes them from the organic solvent phase. Can do.

  That is, by treating the mixture with an aqueous alkaline solution having a pH of 9 to 13, by utilizing the difference in acidity of the phenolic hydroxyl group, only the dihydroxybenzophenones are converted into an alkali metal salt to be water-soluble and removed. . As a result, it is difficult to remove by conventional methods, and the purity can be significantly increased and long-term stability can be imparted compared to ketal bisphenols used in the form of a mixture containing dihydroxybenzophenones. At the same time, by removing dihydroxybenzophenones, it is possible to greatly improve the polymerization activity and develop a wide variety of polymer types.

  Examples of the alkaline aqueous solution having a pH of 9 to 13 used in the present invention include aqueous solutions of alkali metal carbonates such as sodium carbonate and potassium carbonate, and ammonia. This aqueous alkaline solution can efficiently remove not only glycols or alkylenedithiols but also dihydroxybenzophenones into the aqueous layer. However, when the aqueous alkaline solution is less than pH 9, removal of dihydroxybenzophenones may be insufficient. When the pH is higher than 13, not only glycols, alkylenedithiols and dihydroxybenzophenones but also ketal bisphenols are extracted into the aqueous layer, which may reduce the yield.

  By further concentrating and / or crystallizing the organic solvent containing the ketal bisphenol obtained by the production method of the present invention, the purity of the ketal bisphenol can be further increased. Examples of the crystallization operation method include a method of solid-liquid separation after cooling the concentrated liquid as it is to crystallize ketal bisphenols, or a method of solid-liquid separation after adding a poor solvent to the concentrated liquid and performing cooling crystallization. Etc.

  In the present invention, a method for obtaining a mixture containing at least a ketal bisphenol and a dihydroxybenzophenone is not particularly limited. For example, a dihydroxybenzophenone and a glycol or an alkylenedithiol are combined with an organic sulfonic acid or an organic carboxyl. A method of adding water to a reaction solution obtained by reacting in the presence of acids and extracting with an organic solvent can be mentioned.

  Examples of the organic solvent used for extracting the reaction solution containing ketal bisphenols include toluene, benzene, ethylbenzene, amylbenzene, isopropylbenzene, xylene, heptane, hexane, chlorobenzene, dichlorobenzene, dichloroethane, trichloroethane, chloroform, and chlorotoluene. , Dichlorotoluene, methyl chloride, methylene chloride, amyl alcohol, octanol, t-butanol, benzyl alcohol, methyl tertiary butyl ether, diisobutyl ketone, diisopropyl ketone, methyl ethyl ketone, methyl isopropyl ketone, methyl benzoate, ethyl acetate, propyl acetate, acetic acid Examples include isobutyl, amyl acetate, benzyl acetate, and methyl propionate. The organic solvent can be used alone or in combination of two or more. Of these, ethyl acetate, isobutyl acetate, and methyl isobutyl ketone are preferred.

  The amount of such an organic solvent used may be any amount as long as it is an amount capable of dissolving ketal bisphenols, but is usually 1 to 30 times, preferably 3 to 10 times the amount of ketal bisphenols. It is. If the amount is less than 1 time, the extraction efficiency may decrease because ketal bisphenols are not completely dissolved. If it is 30 times or more, the volumetric efficiency is lowered and the economic efficiency may be deteriorated.

  The amount of glycols or alkylenedithiols used is usually 1 to 30 mol times, preferably 5 to 15 mol times, relative to dihydroxybenzophenones.

  In the formation reaction of ketal bisphenols, the use of organic sulfonic acids or organic carboxylic acids as an acid catalyst provides a short conversion time and a high conversion rate. The amount of the organic sulfonic acids or organic carboxylic acids used is 0.1 mol% to 50 mol%, preferably 0.5 mol% to 5 mol%, based on the dihydroxybenzophenone. When the amount is less than 0.1 mol%, the reaction time becomes long and a high conversion rate may not be obtained. When it exceeds 50 mol%, a high conversion rate may not be obtained.

  In the present invention, organic sulfonic acids or organic carboxylic acids are used alone as an acid catalyst. When used in combination with other acid catalysts, for example, when used in combination with hydrogen bromide, the conversion is significantly reduced. Examples of the organic sulfonic acids or organic carboxylic acids used in this reaction include p-toluenesulfonic acid, benzenesulfonic acid, xylenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, trifluoroacetic acid, formic acid and the like. Preferably, p-toluenesulfonic acid and benzenesulfonic acid are used. Moreover, the acid to be used may contain crystal water.

  In the present invention, the reaction for producing ketal bisphenols is preferably carried out in the presence of alkyl orthoesters because the reaction tends to be fast and the conversion rate tends to be high. Alkyl orthoesters include trimethyl orthoformate, triethyl orthoformate, trimethyl orthoacetate, triethyl orthoacetate, tetramethyl orthosilicate, tetraethyl orthosilicate, 2,2-dimethoxypropane and 2,2-dimethyl-1,3. -Dioxolane and the like. The amount of alkyl orthoester used is usually 1 to 10 moles, preferably 2 to 5 moles, relative to dihydroxybenzophenones.

  The formation reaction of ketal bisphenols is performed in a solvent as necessary. Examples of the solvent include hydrocarbons such as toluene and xylene, and each is used alone or in combination of two or more.

  To mix dihydroxybenzophenones with glycols or alkylenedithiols, for example, in an inert gas atmosphere such as nitrogen gas, in a solvent or in the absence of a solvent, dihydroxybenzophenones and glycols or alkylenedithiols, organic Sulfonic acids or organic carboxylic acids, and alkyl orthoesters used as necessary may be added in any order.

  The reaction temperature is usually in the range of 20 to 150 ° C. Preferably, the reaction is carried out at a temperature from 25 ° C. to near the boiling point of the alkyl orthoester used, and more preferably at a temperature at which the alcohol by-produced from the alkyl orthoester is distilled off.

  The reaction time is usually from 0.1 hour to 10 hours, and the reaction is completed in 0.5 to 8 hours. After the reaction, the reaction mixture may be mixed with an organic solvent, neutralized, and then washed with water.

  The method for purifying a ketal bisphenol according to the present invention comprises treating a mixture containing at least a ketal bisphenol represented by the general formula (3) and a dihydroxybenzophenone represented by the general formula (1) with an alkaline aqueous solution having a pH of 9 to 13. To do. The purification method of the present invention does not limit the mixture containing ketal bisphenols and dihydroxybenzophenones to a mixture obtained by production of ketal bisphenols using dihydroxybenzophenones and glycols or alkylenedithiols as raw materials. It is possible to use. As a specific example thereof, for example, it is suitable as a purification method for removing dihydroxybenzophenones contained as impurities from ketal bisphenols whose purity has been reduced by long-term storage or the like.

  The ketal bisphenols of the present invention are represented by the general formula (3), and the content of dihydroxybenzophenones is 1% by weight or less. If the amount of dihydroxybenzophenone exceeds 1% by weight, the purity becomes insufficient, and the long-term stability and the effect of improving the polymerization activity cannot be sufficiently obtained. Further, the lower limit of the content of dihydroxybenzophenones is preferably 0.001% by weight, and in order to reduce the content further, the purification cost may become enormous. Such ketal bisphenols can be obtained by the production method or purification method of the present invention.

  Applications of the high-purity ketal bisphenols obtained by the present invention can include, for example, various monomers, additives such as antioxidants and antioxidants, precursors thereof, and pharmaceutical raw materials, but are not limited thereto. It is not something. Among these, a monomer use is preferable, and a use as a monomer for producing an aromatic polyketal polymer is more preferable.

  Such an aromatic polyketal polymer refers to a polymer mainly composed of an aromatic ring and containing a ketal moiety. In addition to the ketal moiety, there may be a bonding mode generally used for forming an aromatic polymer such as a direct bond, ether, ketone, sulfone, sulfide, various alkylenes, imides, amides, esters, and urethanes. . The aromatic ring may include not only a hydrocarbon aromatic ring but also a hetero ring. Further, a part of the aliphatic units may constitute a polymer together with the aromatic ring unit. Aromatic units include hydrocarbon groups such as alkyl groups, alkoxy groups, aromatic groups, aryloxy groups, halogen groups, nitro groups, cyano groups, amino groups, halogenated alkyl groups, carboxyl groups, phosphonic acid groups, hydroxyl groups, etc. And may have an arbitrary substituent.

  As a method for synthesizing an aromatic polyketal polymer, for example, it can be synthesized by utilizing an aromatic nucleophilic substitution reaction of a ketal bisphenol and an aromatic dihalide. In addition, you may use together bisphenol other than ketal bisphenol as needed.

  In addition, the aromatic dihalide is not particularly limited as long as the molecular weight can be increased by an aromatic nucleophilic substitution reaction with a ketal bisphenol, and two or more aromatic dihalides may be used in combination. Is also possible. Moreover, what introduce | transduced the ionic group into these aromatic dihydroxy compounds can also be used as a monomer.

  In the polymerization by the aromatic nucleophilic substitution reaction, a polymer can be obtained by reacting the monomer mixture in the presence of a basic compound. The polymerization reaction can be carried out in the temperature range of 0 to 350 ° C, but is preferably 50 to 250 ° C. When the temperature is lower than 0 ° C., the reaction does not proceed sufficiently, and when the temperature is higher than 350 ° C., the polymer tends to be decomposed.

  Such a polymerization reaction can be carried out in the absence of a solvent, but is preferably carried out in a solvent. Use N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, diphenylsulfone, sulfolane, 1,3-dimethyl-2-imidazolidinone as the solvent. However, it is not limited to these, and any solvent that can be used as a stable solvent in the aromatic nucleophilic substitution reaction may be used. These organic solvents may be used alone or as a mixture of two or more.

  Examples of the basic compound used for the polymerization by the aromatic nucleophilic substitution reaction include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate and the like. Any material can be used as long as it can have a phenoxide structure. In the aromatic nucleophilic substitution reaction to be reacted in the presence of such a basic compound, water may be generated as a by-product. In this case, toluene or the like can coexist in the reaction system, and water can be removed from the system as an azeotrope. As a method for removing water out of the system, a water-absorbing agent such as molecular sieve can also be used.

  When this aromatic nucleophilic substitution reaction is carried out in a solvent, it is preferable to charge the monomer so that the resulting polymer concentration is 5 to 50% by weight. When the polymer concentration is less than 5% by weight, the degree of polymerization tends to be difficult to increase. On the other hand, when the polymer concentration is more than 50% by weight, the reaction system becomes too viscous and the reaction product is post-treated. Tend to be difficult. After completion of the polymerization reaction, the solvent is removed from the reaction solution by evaporation, and the residue is washed as necessary to obtain the desired polymer. In addition, the polymer can be obtained by precipitating the polymer as a solid by adding the reaction solution in a solvent having low polymer solubility, and collecting the precipitate by filtration.

  The weight average molecular weight of the aromatic polyketal polymer by GPC method is preferably 10,000 to 1,000,000, more preferably 100,000 to 600,000. If the weight average molecular weight is less than 10,000, the mechanical properties may be insufficient. On the other hand, if it exceeds 1,000,000, the processability may be inferior.

  The purity of the raw material monomers such as ketal bisphenols obtained in accordance with the present invention and bisphenols and aromatic dihalides used in combination is not a problem as long as the purity is high enough not to impair the purpose of the present invention, but may be 98% or more. Preferably, it is 99% or more. The method for analyzing the purity of ketal bisphenols is not particularly limited, and examples thereof include gas chromatography (GC), liquid chromatography (LC), infrared absorption spectrum (IR), and nuclear magnetic resonance spectrum (NMR).

  In addition, the aromatic polyketal polymer obtained by using the ketal bisphenols obtained by the present invention is particularly preferably used as a soluble precursor in producing various molded products because of its excellent solubility and processability. can do. Specifically, as an aromatic polyketal polymer, after processing into various forms such as plate-like, fiber-like, hollow-fiber-like, particle-like, and massive-like in addition to a film shape, it is highly crystalline as required. And converted into an aromatic polyketone polymer having a high melting point.

  In addition, it is also preferable to use an aromatic polyketal polymer and an aromatic polyketone polymer containing an ionic group, which can be applied to various applications. For example, it can be applied to medical applications such as extracorporeal circulation columns and artificial skin, applications for filtration, ion exchange resin applications, various structural materials, and electrochemical applications. Among them, it can be preferably used for various electrochemical applications. Examples of the electrochemical application include a fuel cell, a redox flow battery, a water electrolysis device, a chloroalkali electrolysis device, etc. Among them, the fuel cell is the most preferable use. Furthermore, among fuel cells, it is suitable for a polymer electrolyte material for a polymer electrolyte fuel cell, and there are those using hydrogen as a fuel and those using an organic compound such as methanol as the fuel. It is particularly preferably used for a direct fuel cell using at least one selected from organic compounds of -6 and a mixture of these with water as fuel. As this C1-C6 organic compound, C1-C3 alcohols, such as methanol, ethanol, and isopropyl alcohol, and dimethyl ether are preferable, and methanol is used most preferably.

  When the aromatic polyketal polymer and aromatic polyketone polymer obtained by using the ketal bisphenol obtained by the present invention are used for a fuel cell, they are usually used in a membrane state.

  In addition, aromatic polyketal polymers and aromatic polyketone polymers obtained using the ketal bisphenols obtained by the present invention include plasticizers, stabilizers or mold release agents used in ordinary polymer compounds. These additives can be added within a range not departing from the object of the present invention. In addition, various polymers, elastomers, fillers, fine particles, various additives, etc. may be included for the purpose of improving mechanical strength, thermal stability, processability, etc. within the range that does not adversely affect various properties. Good.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by these Examples. The pH of the alkaline aqueous solution and the purity and stability of the ketal bisphenols were measured by the following methods.

<Measurement method of pH>
Using a glass electrode type hydrogen ion concentration meter [manufactured by Toa Denpa Kogyo Co., Ltd.], the pH of the sample immediately after adjustment was measured at 25 ° C.

<Measurement method of purity>
The reaction mixture was analyzed by gas chromatography (GC) under the following conditions, and the area value of each component was divided by the sum of the area values of gas chromatography such as ketal bisphenols, 4,4'-dihydroxybenzophenone and decomposition compounds. Converted to percentage.

GC device: GC-17A manufactured by Shimadzu Corporation
Column: DB-5 (manufactured by J & W) L = 30 m, Φ = 0.53 mm, D = 1.50 μm
Carrier: helium (linear velocity = 35.0 cm / sec)
Analysis conditions:
Inlet temperature: 300 ° C
Detector temperature: 320 ° C
Temperature program: Oven 50 ° C. × 1 min,
Rate 10 ° C / min,
Final 300 ℃ × 15min
SP ratio 50: 1

<Stability evaluation method>
After placing the sample in a sealed sample can and storing at −22 ° C. and 25 ° C. for 10 days and 50 days, these four samples are quantitatively analyzed by gas chromatography (GC) by the above method to reduce the purity. The presence or absence of was evaluated.

Example 1
In a 500 ml flask equipped with a stirrer, thermometer and distillation tube, 49.5 g of 4,4'-dihydroxybenzophenone, 134 g of ethylene glycol, 96.9 g of trimethyl orthoformate and p-toluenesulfonic acid monohydrate 0 Charge 50g and dissolve. Thereafter, the mixture was stirred at 78 to 82 ° C. for 2 hours. Further, the internal temperature was gradually raised to 120 ° C. and heated until the distillation of methyl formate, methanol and trimethyl orthoformate completely stopped, and then cooled to room temperature to obtain reaction solution 1.

  The reaction solution 1 was diluted with ethyl acetate, the organic layer was washed with 100 ml of 5% aqueous potassium carbonate solution (pH 11.6) and separated, and then the solvent was distilled off. Crystals were precipitated by adding 80 ml of dichloromethane to the residue, filtered and dried to obtain 52.0 g of 2,2-bis (4-hydroxyphenyl) -1,3-dioxolane. GC analysis of the crystals revealed 99.8% 2,2-bis (4-hydroxyphenyl) -1,3-dioxolane and 0.2% 4,4'-dihydroxybenzophenone. In addition, as a result of the stability evaluation, no decrease in purity was observed in any of the evaluation methods.

Example 2
The reaction solution 1 obtained in the same manner as in Example 1 was diluted with ethyl acetate, the organic layer was washed with 100 ml of 5% aqueous sodium carbonate solution (pH 11.0) and separated, and then the solvent was distilled off. The residue was treated in the same manner as in Example 1 to obtain 52.6 g of 2,2-bis (4-hydroxyphenyl) -1,3-dioxolane. GC analysis of the crystals revealed 99.7% 2,2-bis (4-hydroxyphenyl) -1,3-dioxolane and 0.3% 4,4'-dihydroxybenzophenone. In addition, as a result of the stability evaluation, no decrease in purity was observed in any of the evaluation methods.

Example 3
The reaction solution 1 obtained in the same manner as in Example 1 was diluted with ethyl acetate, the organic layer was washed with 100 ml of 2.8% aqueous ammonia (pH 11.4) and separated, and then the solvent was distilled off. The residue was treated in the same manner as in Example 1 to obtain 51.6 g of 2,2-bis (4-hydroxyphenyl) -1,3-dioxolane. GC analysis of the crystals revealed 99.8% 2,2-bis (4-hydroxyphenyl) -1,3-dioxolane and 0.2% 4,4'-dihydroxybenzophenone. In addition, as a result of the stability evaluation, no decrease in purity was observed in any of the evaluation methods.

Example 4
The reaction solution 1 obtained in the same manner as in Example 1 was diluted with isobutyl acetate, the organic layer was washed with 100 ml of 5% potassium carbonate solution (pH 11.6) and separated, and then the solvent was distilled off. The residue was treated in the same manner as in Example 1 to obtain 52.7 g of 2,2-bis (4-hydroxyphenyl) -1,3-dioxolane. GC analysis of the crystals revealed 99.8% 2,2-bis (4-hydroxyphenyl) -1,3-dioxolane and 0.2% 4,4'-dihydroxybenzophenone. In addition, as a result of the stability evaluation, no decrease in purity was observed in any of the evaluation methods.

Example 5
In a 500 ml flask equipped with a stirrer, thermometer and distillation tube, 49.5 g of 4,4′-dihydroxybenzophenone, 164 g of 1,2-propanediol, 96.9 g of trimethyl orthoformate and p-toluenesulfonic acid 1 Charge 0.50 g of hydrate and dissolve. Thereafter, the mixture was stirred at 78 to 82 ° C. for 2 hours. Further, the internal temperature was gradually raised to 120 ° C. and heated until the distillation of methyl formate, methanol, and trimethyl orthoformate completely stopped, and then cooled to room temperature to obtain reaction solution 2.

  The reaction solution 2 was diluted with isobutyl acetate, the organic layer was washed with 100 ml of 5% potassium carbonate solution (pH 11.6) and separated, and then the solvent was distilled off. The residue was treated in the same manner as in Example 1 to obtain 55.0 g of 2,2-bis (4-hydroxyphenyl) -4-methyl-1,3-dioxolane. This crystal was analyzed by GC and found to be 99.6% 2,2-bis (4-hydroxyphenyl) -4-methyl-1,3-dioxolane and 0.4% 4,4'-dihydroxybenzophenone. It was. In addition, as a result of the stability evaluation, no decrease in purity was observed in any of the evaluation methods.

Comparative Example 1
Reaction solution 1 obtained in the same manner as in Example 1 was diluted with ethyl acetate, and the organic layer was washed with 100 ml of 5% aqueous sodium hydrogen carbonate solution (pH 8.4) and separated, and then the solvent was distilled off. Crystals were precipitated by adding 80 ml of dichloromethane to the residue, filtered and dried to obtain 53.5 g of 2,2-bis (4-hydroxyphenyl) -1,3-dioxolane. GC analysis of the crystals revealed 96.8% 2,2-bis (4-hydroxyphenyl) -1,3-dioxolane and 3.1% 4,4'-dihydroxybenzophenone. In addition, as a result of the stability evaluation, the following decrease in purity was observed.

  The purity after storage at 25 ° C. for 10 days was 54.6%, and the purity after storage at 25 ° C. for 50 days was 2.7%. The purity after storage at -22 ° C for 10 days was 94.6%, and the purity after storage at -22 ° C for 50 days was 88.7%. In addition, 4,4'-dihydroxybenzophenone and ethylene glycol were confirmed as decomposition products.

Comparative Example 2
The reaction solution 1 obtained in the same manner as in Example 1 was diluted with ethyl acetate, the organic layer was washed with 100 ml of 5% aqueous sodium hydroxide solution (pH 13.5) and separated, and then the solvent was distilled off. There was almost nothing.

  Ketal bisphenols obtained by the purification method of the present invention are useful as monomers for aromatic polyketals. In addition, aromatic polyketals are useful as soluble precursors of aromatic polyketones.

Claims (5)

In the method for producing a ketal bisphenol using a dihydroxybenzophenone represented by the following general formula (1) and a glycol or alkylenedithiol represented by the following general formula (2) as raw materials, at least the following general formula (3) The manufacturing method of ketal bisphenol including the process of processing the mixture containing the ketal bisphenol shown and the said dihydroxy benzophenone with alkaline aqueous solution of pH 9-13.

(In the formula, X ₁ , X ₂ , X ₃ and X ₄ each independently represent a hydrogen atom, a linear or branched hydrocarbon group having 1 to 4 carbon atoms, or an alkoxy group.)

(In the formula, R ₁ , R ₂ , R ₃ and R ₄ each independently represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 4 carbon atoms, and A represents an oxygen atom or a sulfur atom. E represents a single bond or a methylene or ethylene chain which is unsubstituted or substituted with a linear or branched hydrocarbon group having 1 to 4 carbon atoms.

(In the formula, X ₁ , X ₂ , X ₃ , X ₄ , R ₁ , R ₂ , R ₃ , R ₄ , A and E are the same as above.)   And a step of reacting the dihydroxybenzophenone with glycol or alkylenedithiol in the presence of 0.1 to 50 mol% of organic sulfonic acid or organic carboxylic acid with respect to the dihydroxybenzophenone. The manufacturing method of ketal bisphenol of Claim 1 containing.   The ketal bisphenols are 2,2-bis (4-hydroxyphenyl) -1,3-dioxolane, 2,2-bis (4-hydroxyphenyl) -1,3-dioxane, 2,2-bis (4- The method for producing a ketal bisphenol according to claim 1 or 2, which is any one selected from hydroxyphenyl) -1,3-dithiolane and 2,2-bis (4-hydroxyphenyl) -1,3-dithiane. A method for purifying a ketal bisphenol comprising treating a mixture containing at least a dihydroxybenzophenone represented by the general formula (1) and a ketal bisphenol represented by the general formula (3) with an alkaline aqueous solution having a pH of 9 to 13.

(In the formula, X ₁ , X ₂ , X ₃ and X ₄ each independently represent a hydrogen atom, a linear or branched hydrocarbon group having 1 to 4 carbon atoms, or an alkoxy group.)

(Wherein X ₁ , X ₂ , X ₃ and X ₄ are the same as defined above, and R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom or a straight chain having 1 to 4 carbon atoms. Or a branched hydrocarbon group, A represents an oxygen atom or a sulfur atom, E represents a single bond or an unsubstituted or methylene or ethylene substituted with a linear or branched hydrocarbon group having 1 to 4 carbon atoms. Indicates a chain.) Ketal bisphenols represented by the following general formula (3), wherein the content of dihydroxybenzophenones is 1% by weight or less.

(In the formula, X ₁ , X ₂ , X ₃ and X ₄ each independently represent a hydrogen atom, a linear or branched hydrocarbon group having 1 to 4 carbon atoms or an alkoxy group, and R ₁ , R ₂ R ₃ and R ₄ each independently represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 4 carbon atoms, A represents an oxygen atom or a sulfur atom, and E represents a single bond or an unsubstituted group. Or a methylene or ethylene chain substituted with a linear or branched hydrocarbon group having 1 to 4 carbon atoms.