JP2010001447A - Manufacturing method for aromatic polyether sulfone having hydroxyphenyl terminal end group - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aromatic polyether sulfone having a reactive hydroxyphenyl end group preferable as an alloying agent of a thermoplastic resin and a thermosetting resin, and a method for efficiently manufacturing the aromatic polyether sulfone by an economical and simple method in a short time. <P>SOLUTION: The manufacturing method for the aromatic polyether sulfone having the hydroxyphenyl end group is characterized in that the aromatic polyether sulfone having the hydroxyphenyl end group preferable as the alloying agent is obtained by heating the aromatic polyether sulfone previously obtained by polymerization, water and a basic compound in an aprotic polar solvent. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an aromatic polyethersulfone (hereinafter abbreviated as PES) containing a large amount of hydroxyphenyl end groups, which has been difficult to produce by conventional production methods, and a production method thereof. More specifically, the present invention relates to a method for efficiently producing a high-purity PES having a high hydroxyphenyl end group content and excellent in compatibilizing effect for thermoplastic resins and thermosetting resin alloys by an economical and simple method.

  PES has excellent heat resistance, mechanical properties, electrical properties, flame retardancy, chemical resistance, hydrolysis resistance, radiation resistance, low dielectric properties, and molding processability. Widely used in electrical and electronic parts, automotive parts, aircraft parts and medical equipment parts such as magnetic disk and other disk support plates, electrical insulating protective films, interlayer insulating films for integrated circuits, integrated circuit substrate materials, etc. Yes.

  In addition, taking advantage of the above-described excellent properties, it is widely used as a modifier for improving the performance of thermoplastic resins and thermosetting resins by blending PES into thermoplastic resins and thermosetting resins.

  Examples of methods for alloying PES include (1) a method of melt-kneading a thermoplastic resin and PES, (2) a method of alloying a thermoplastic resin and PES in a solvent, and (3) thermosetting. A method is known in which PES is dissolved in a prepolymer of a resin in a solvent or in the absence of a solvent and then cured to be alloyed.

  (1) As a thermoplastic resin alloy, a method for improving the chemical resistance of polycarbonate and improving the moldability of PES by alloying PES with a specific composition in polycarbonate and controlling the morphology is disclosed. (Patent Document 1).

  (2) As an example of alloying a thermoplastic resin and PES in a solvent, a method is disclosed in which the polyamideimide resin is alloyed with PES in an NMP solution to improve the flexibility and impact resistance of the polyamideimide resin. (Patent Document 2).

  (3) As an example of alloying by dissolving PES in a prepolymer of a thermosetting resin and curing it, toughness is improved by alloying PES into a thermosetting resin such as an epoxy resin or a maleimide resin. PES is alloyed with a thermosetting resin such as epoxy resin or acrylic resin that is used as a method or a thermosensitive resin or wiring board material to maintain the original characteristics of the matrix thermosetting resin. Methods for improving physical properties are disclosed (Patent Documents 3 and 4).

  In order to improve the quality of the resin composition by alloying, it is necessary to refine the phase separation structure of each polymer component. However, in the techniques (1) to (3), PES is contained in the matrix resin. At present, the particles are coarsely dispersed, and further fine dispersion technology is required to improve quality by alloying.

  As a method for improving the dispersibility of the polymer, generally, a method of using a compatibilizer or a combination of alloy components at the molecular level by a chemical reaction may improve the dispersibility or further compatibilize. These findings are reviewed in reviews such as “Polymer Alloy Fundamentals and Applications” edited by the Society of Polymer Science, Tokyo Chemistry Doujin Publishing.

  In Patent Document 5, a polyfunctional epoxy resin is used as a raw material for a thermosetting resin matrix in order to further finely disperse PES in the thermosetting resin matrix by the method described in (3) above. Disclosed is a method in which a functional group capable of reacting with an epoxy group, for example, a hydroxyphenyl end group, is introduced into a polymer terminal to promote a reaction between polymers and finely disperse PES in a thermosetting resin matrix. Yes. In addition, the fiber reinforced composite material composed of the epoxy resin composition using this technology has PES finely dispersed in a matrix resin, and further the rigidity (for example, compressive strength) and toughness (for example, compression after impact). It is disclosed that it is excellent in strength.

  Similarly, Patent Documents 6 and 7 disclose that an aminophenyl terminal is introduced as a functional group capable of reacting with epoxy at the polymer terminal of PES, and the same effect is exhibited.

  In general, PES is prepared by pre-synthesising a polycondensation reaction between a dihalogenodiphenylsulfone compound and a dihydric phenol compound in an organic polar solvent in the presence of an alkali metal compound or an alkali metal disalt of a dihydric phenol compound. And obtained by a polycondensation reaction with a dihalogenodiphenyl compound (Patent Documents 8, 9, and 10).

  Usually, in order to increase the molecular weight of the polycondensation reaction, the dihalogenodiphenyl compound is usually used in an equimolar amount with respect to the dihydric phenol compound. At this time, one of the polymer ends is theoretically a hydroxyphenyl end group and the other end. Becomes a halogenophenyl end group. However, PES polymerized by the prior art has a high melt viscosity, and has a problem in workability as compared with engineering plastics that can be extruded and injection molded. That is, since it is a material having a high glass transition temperature, it has been known that melt processing under high temperature conditions is required, and therefore, melt viscosity increases at the stage of melt processing. This is because the terminal of PES polymerized by the conventional technique contains a highly active hydroxyphenyl end group, which reacts with the halogenophenyl end by heating, or due to thermal degradation or oxidative degradation of the hydroxyphenyl end group. It is considered a thing.

  Therefore, as a method for reducing the hydroxyphenyl end group of PES and improving the melt stability, for example, in Patent Documents 11 and 12, after polymerization of PES from a dihydric phenol compound, an alkali metal salt, and dihalogenodiphenyl sulfone, A method of blocking reactive hydroxyphenyl end groups by reacting with methane, or Patent Document 13 discloses that a dihalogenodiphenylsulfone is used in excess of a dihydric phenol compound, followed by polymerization, and then an excess of halogenophenyl. A method for improving meltability by introducing a reaction-inactive phenyl group by adding an equivalent or more monohydric phenol compound to the terminal and blocking the terminal is disclosed.

  Patent Document 14 also discloses a method of using 1,3-dimethyl-2-imidazolidinone as a polymerization solvent, conceived to suppress side reactions during polymerization and improve the melt stability of the polymer. .

  As described above, various attempts have been made to improve the melt processability of PES. Among them, the hydroxyphenyl end groups that cause a decrease in melt processability are reduced or blocked, and the reaction is inactive. A halogenophenyl terminal is preferred. However, when PES is used as a modifier for alloying thermoplastic resins or thermosetting resins, PES having reactive hydroxyphenyl end groups reacts with thermoplastic resins or thermosetting resins. Although it is considered preferable because it can be promoted, there is a problem that not only the problem of the production of the polymer itself but also the melt processability at the time of alloying is poor. When a reaction-inactive halogenophenyl-terminated PES is used as an alloying agent, which is excellent in polymer production and melt processability, as described in Patent Documents 1 to 3, PES is a thermoplastic resin or a thermosetting resin. There was a problem of coarse dispersion instead of dispersion.

  On the other hand, in Patent Document 5, although there is no detailed description about the method for producing PES having a hydroxyphenyl end group, it is usually produced by a known method, that is, polycondensation of a dihydric phenol compound using dihalogenodiphenylsulfone as a raw material. Has been. Normally known polycondensation is carried out by polymerizing dihydric phenol compound in excess of dihalogenodiphenylsulfone from the polycondensation theory, or by adding more than an equivalent amount of dihydric phenol compound to the halogenophenyl terminal at the end of polymerization. By adding, it becomes possible to introduce an equivalent amount or more of reactive hydroxyphenyl end groups rather than halogenophenyl end groups (theoretically, the charging ratio of dihalogenodiphenyl sulfone and dihydric phenol compound is 1: 1. In the case of equivalent, the highest molecular weight can be obtained, and the terminal group composition at that time is halogenophenyl terminal group: hydroxyphenyl terminal group = 50: 50 (mol%)). However, even when the charging ratio is 1: 1, depending on the polymerization conditions, the alkali metal phenoxide or the alkali metal salt of the dihydric phenol compound that becomes the growth terminal during the polymerization is easily oxidized during the polymerization. The problem of coloring at the time of polymerization, the problem that the charged molar balance and the growth end group balance are lost due to the oxidation reaction at the time of polymerization, making it difficult to increase the molecular weight, the amount of halogenophenyl end groups is more than the amount of hydroxyphenyl end groups There was a problem that the ideal polycondensation reaction was hindered by the oxidation reaction, such as an increase in the number of problems, and it was difficult to control the molecular weight and the hydroxy end group amount. In order to further increase the amount of reactive hydroxyphenyl end groups, when an excess of dihydric phenol compound is positively used, as is known in the polycondensation theory, the molar balance of the two-component monomers is shifted. However, although the amount of terminal groups can be slightly increased, there is a problem that the molecular weight of the polymer is remarkably reduced at the same time. That is, there is an essential problem of the polycondensation method in which an increase in the amount of hydroxyphenyl end groups and a decrease in the molecular weight of the polymer proceed simultaneously.

  Further, with reference to the method disclosed in Patent Document 13 (particularly, page 4, line 18 and after), the present inventors have described a method of adding a dihydric phenol compound at the end of polymerization and blocking the end with the dihydric phenol compound. However, in this case, the polymerization of the chlorophenyl terminal and the dihydric phenol compound in the polymer proceeds, and the intended high hydroxyphenyl terminalization does not proceed. And there was a problem that the coloring progressed.

  Furthermore, as described above, when an excessive divalent phenol compound is used positively before the start of polymerization and at the end of the polymerization, an acidic dihydric phenol compound or dihydric phenol compound added excessively in the obtained PES. Alkali metal salts and alkali metal salts themselves remain in the polymer, causing problems such as lowering the thermal stability and residence stability of the polymer, and more difficult to purify and remove due to interaction with hydroxyphenyl end groups There was a problem of becoming. Usually, after PES, the polymerization reaction solution is dropped into a poor solvent for precipitating PES, thereby precipitating a white solid, and performing cleaning such as washing and filtration, or performing filtration or the like. Without recovering the polymer powder, if the molecular weight of the polymer is reduced at the same time by increasing the amount of hydroxyphenyl end groups, it becomes difficult to recover the powder as in the case of high molecular weight PES. Depending on the case, there is a problem that the polymer is softened in a poor solvent and the polymer is recovered in a lump state. In this way, it is difficult to recover the polymer as a powder in the stage of precipitating the polymer in a poor solvent. Therefore, an excessively added acidic dihydric phenol compound or dihydric phenol compound is added to increase the hydroxyphenyl end group. In addition to the problem of significant reduction in productivity in the reprecipitation purification / removal of unreacted monomers of the alkali metal salt or the alkali metal salt itself, the alkali metal salt remains in the PES having hydroxyphenyl end groups. There was a problem. When such PES is alloyed with a thermoplastic resin or a thermosetting resin, depending on the type of the thermoplastic resin or epoxy resin, coloring due to thermal decomposition, alloying, hydrolysis may be accelerated, or the retention stability may be reduced. In addition, there is a problem that the electrical characteristics are remarkably deteriorated, and in order to use it as a modifier for alloys, further improvement in purity is required.

On the other hand, Patent Documents 6 (page 12, upper right line 15) and 7 (page 10, upper right line 10) both use the above-mentioned patents by PES into which an amino terminal group having a higher reactivity with epoxy than a hydroxyphenyl terminal group is introduced. It is disclosed that the same effect as in Document 5 can be obtained. The PES introduced with an amino group used in Patent Document 6 can be obtained by a polycondensation of dihalogenodiphenylsulfone with a potassium metal salt of a dihydric phenol compound and then a reaction with a potassium salt of an aminophenol compound. It is disclosed. However, both methods of Patent Documents 6 and 7 have the same problems as the known examples of the hydroxyphenyl end group PES, and the aminophenol compound and its metal salt are more than the divalent phenol compound and its metal salt. In addition, it has a chemical property that it is more susceptible to thermal decomposition and oxidative decomposition. Further, in the case of end-capping with an aminophenol compound, both the amino group and the hydroxyphenyl group react with the polymer growth end. For this reason, there are problems that it is difficult to control the end group and the molecular weight, and the purification and post-treatment efficiency is also lowered. In addition to the problems that the obtained PES is further inferior in thermal stability, residence stability and hydrolysis resistance, both the aminophenyl terminal and the hydroxyphenyl terminal having different reactivity exist, so that the thermoplastic resin and thermosetting When alloying with a resin, it is difficult to promote a uniform reaction, and as a result, there is a problem that it is difficult to make the dispersibility uniform.
<Patent Documents 1 to 7: Known Examples of PES Thermoplastic Resin and Thermosetting Resin Alloy>
<Patent Documents 8 to 14: Known examples relating to PES production>
JP-A-7-11134 (Claim 1) JP-A-6-228438 (Claim 1) JP-A-6-157906 (Claim 1) JP 2001-106921 A (Claim 8) Japanese Patent Laying-Open No. 2005-105151 (Claim 1) JP-A 1-1118565 (Claims 1 and 5) JP-A-2-58569 (Claim 12) Japanese Patent Publication No.42-7799 (Claim 1) Japanese Examined Patent Publication No. 45-21318 (Claim 1) JP-A-48-19700 (Claim 1) JP-A-53-12991 (Claim 1) JP-A-53-16098 (Claim 1) JP-A-5-163352 (Claim 1) JP-A-5-86186 (Claim 1)

  The present invention solves the above-mentioned problems of the prior art, and is suitable for finely dispersing PES in a matrix resin and further dispersing it in nano-size when a thermoplastic resin or thermosetting resin and PES are alloyed. Another object of the present invention is to provide a method for efficiently producing a high-purity PES having a reactive hydroxyphenyl end group in a short time by an economical and simple method.

In response to the above problems, the present invention
(1) An aromatic polyethersulfone (A) having a structure represented by general formula (a-1) and / or general formula (a-2), water (B), and basic compound (C) A process for producing an aromatic polyethersulfone (D) having a hydroxyphenyl end group, characterized by heating in an aprotic polar solvent;

(In the formula, each R may be the same or different and represents any one selected from an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 8 carbon atoms, and m is 0 to 3). Y represents an integer selected from a direct bond, oxygen, sulfur, SO ₂ , CO, C (CH ₃ ) _2, CH (CH ₃ ), and CH _2.
(2) The amount of water (B) added is from 0.1 to 30 times mol of 1 mol of aromatic polyethersulfone (A). A process for producing aromatic polyethersulfone (D),
(3) Hydroxyphenyl according to any one of (1) and (2), wherein the basic compound (C) is one or more selected from sodium carbonate, potassium carbonate, anhydrous sodium carbonate, and anhydrous potassium carbonate. A process for producing an aromatic polyethersulfone (D) having a terminal group,
(4) The aprotic polar solvent is at least one selected from N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, and sulfolane. A method for producing an aromatic polyethersulfone (D) having a hydroxyphenyl end group according to any one of (1) to (3), which is a seed,
(5) The method for producing an aromatic polyethersulfone (D) having a hydroxyphenyl end group according to any one of (1) to (4), wherein the heating temperature is 100 to 200 ° C.,
(6) The raw material aromatic polyethersulfone (A) has a hydroxyphenyl end group composition of 50 mol% or less (measured by ¹ H-NMR in deuterated dimethyl sulfoxide, [6.9 ppm peak area (hydroxyl Phenyl end group)] / (peak area of 6.9 ppm (derived from hydroxyphenyl end group) + peak area of 7.7 ppm (derived from chlorophenyl end group)) × 100) (1) A process for producing an aromatic polyethersulfone (D) having a hydroxyphenyl end group according to any one of to (5),
(7) The aromatic polyethersulfone (D) having a hydroxyphenyl end group to be obtained has a hydroxyphenyl end group composition of 60 mol% or more (measured by ¹ H-NMR in deuterated dimethyl sulfoxide, [6. 9 ppm peak area (hydroxyl end group)] / (6.9 ppm peak area (derived from hydroxyphenyl end group) +7.7 ppm peak area (derived from chlorophenyl end group)] × 100) A method for producing an aromatic polyethersulfone (D) having a hydroxyphenyl end group according to any one of (1) to (6),
(8) The resulting reduced viscosity of the aromatic polyethersulfone (D) having a hydroxyphenyl end group, measured in DMF at 25 ° C. and 1 g / dl is 0.2 to 0.4. The method for producing an aromatic polyethersulfone (D) having a hydroxyphenyl end group according to any one of (1) to (7),
(9) The aromatic polyethersulfone (D) having a hydroxyphenyl end group to be obtained has a hydroxyphenyl end group composition of 80 mol% or more, and the aromatic having a hydroxyphenyl end group according to (7) The manufacturing method of a group polyethersulfone (D) is provided.

  According to the present invention, a PES having a reactive hydroxyphenyl end group, which is suitable for finely dispersing PES in a matrix resin when a thermoplastic resin or a thermosetting resin and PES are alloyed, It is possible to provide a method for producing efficiently in a short time by an economical and simple method.

Embodiments of the present invention will be described below.

(1) Aromatic polyethersulfone (A) (hereinafter abbreviated as PES (A))
The PES (A) used in the present invention has a structure represented by the general formula (a-1) and / or the general formula (a-2).

(In the formula, each R may be the same or different and represents any one selected from an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 8 carbon atoms, and m is 0 to 3). Y represents an integer selected from a direct bond, oxygen, sulfur, SO ₂ , CO, C (CH ₃ ) _2, CH (CH ₃ ), and CH _2.

  Such PES (A) can be produced by a generally known method, and can be produced, for example, by the methods described in Patent Documents 8 to 14.

  For example, a dihalogenodiphenyl compound represented by general formula (I) and a dihydric phenol compound represented by general formula (II-1) and / or (II-2) in an organic solvent in the presence of an alkali metal compound Or a polyhalogenodiphenyl compound, a dihydric phenol compound represented by general formula (II-1) and / or (II-2) and an alkali metal compound prepared in advance. Can be manufactured.

(In the formula, X represents Cl or F, and each R may be the same or different and is selected from an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 8 carbon atoms. M represents an integer of 0 to _3. Y represents any one selected from a direct bond, oxygen, sulfur, SO ₂ , CO, C (CH ₃ ) _2, CH (CH ₃ ), and CH _2. )

  The dihalogenodiphenyl compound is usually used in an equimolar amount with respect to the dihydric phenol compound. In order to finely adjust the molecular weight and the end group composition, the dihydric phenol compound can be used in an equimolar to slightly excess amount or a small amount. In order to adjust the molecular weight and the terminal group composition, a small amount of monohalogenodiphenyl compound or monohydric phenol compound can be added to the polymerization solution.

  The reaction temperature for polycondensation depends on the characteristics of the solvent used, but it is usually preferable to carry out the reaction at 140 to 340 ° C. When polycondensation is performed at a temperature higher than 340 ° C. or higher, the decomposition reaction of the produced polymer proceeds, so that there is a tendency that a high-molecular-weight body or high-purity PES cannot be obtained. It tends not to be obtained.

  The reaction time varies greatly depending on the type of reaction raw material components, the type of polymerization reaction, and the reaction temperature, but is usually in the range of 10 minutes to 100 hours, preferably in the range of 30 minutes to 24 hours. As a reaction atmosphere, it is preferable that oxygen does not exist, and it is preferable to carry out in nitrogen or other inert gas. Alkali metal salts of dihydric phenol compounds are easily oxidized when heated in the presence of oxygen, hindering the intended polymerization reaction, making it difficult to increase the molecular weight, and also causing coloration of the polymer.

  In the polycondensation reaction, an appropriate terminal stopper, for example, a monofunctional chloride such as methyl chloride, t-butyl chloride, or 4,4′-dichlorodiphenylsulfone, or a polyfunctional chloride is added to the reaction solution at the end of the polymerization. It is added as a terminal terminator for coalescence and can be blocked by reacting at 90 to 150 ° C., for example.

  Here, examples of the organic solvent used include sulfoxide solvents such as dimethyl sulfoxide and hexamethylene sulfoxide, amide solvents such as N, N-dimethylformamide and N, N-dimethylacetamide, and N-methyl-2-pyrrolidone. , Piperidone solvents such as N-methyl-2-piperidone, 2-imidazolinone solvents such as 1,3-dimethyl-2-imidazolidinone, diphenyl compounds such as diphenyl ether and diphenyl sulfone, methylene chloride, chloroform, dichloroethane, Examples thereof include halogen solvents such as tetrachloroethane and trichloroethylene, lactone solvents such as γ-butyrolactone, sulfolane solvents such as sulfolane, and mixtures of two or more of these.

  Further, for the purpose of separating water generated during polymerization, a hydrocarbon solvent such as benzene, toluene, xylene or the like can be used as a water azeotropic solvent.

  Examples of the alkali metal compound include alkali metal carbonates, alkali metal hydroxides, alkali metal hydrides, alkali metal alkoxides, and the like. Of these, alkali metal carbonates such as potassium carbonate and sodium carbonate are preferable, and anhydrous alkali metal salts such as anhydrous potassium carbonate and anhydrous sodium carbonate are particularly preferable.

  Crude PES obtained by polycondensation is obtained by adding a poor solvent of PES to the reaction solution after separation of the alkali metal compound contained in the reaction solution by filtration or centrifugation, or without filtration or centrifugation. Alternatively, the reaction solution can be added to a poor solvent and separated as a precipitated solid. Examples of the poor solvent for PES include alcohols such as methanol, ethanol, isopropanol and butanol, nitriles such as acetonitrile, and water. Two or more of these poor solvents can be mixed and used. The poor solvent may contain a good solvent for the polymer such as the polymerization reaction solvent as long as the polymer can be precipitated.

  The precipitated solid can be washed with a poor solvent and then dried to obtain a PES powder.

  The PES (A) used in the present invention can be produced by the above-described method, but in order to produce the PES (D) having a hydroxyphenyl end group finally obtained efficiently and with high purity. In the DES of PES (A), the reduced viscosity measured at 25 ° C. and 1 g / dl is preferably 0.25 to 1.0, more preferably 0.35 to 0.8, more preferably 0.4. And less than 0.6.

  When this reduced viscosity is replaced with a number average molecular weight (Mn) converted from DMF as a solvent and polystyrene as a standard substance using gel permeation chromatography (GPC), the number average molecular weight is preferably 33,000 to 140000. More preferably, it is 47000-110000, More preferably, it is 54000-80000.

  When the reduced viscosity of the PES (A) used in the production method of the present invention is low (number average molecular weight is low), the molecular weight of the finally obtained hydroxyl group-containing PES (D) becomes extremely small, and the polymer on the low molecular weight side Or the oligomer is dissolved or swollen in a poor solvent, and as a result, the polymer recovery rate and the cleaning efficiency tend to decrease. Furthermore, the tendency for the amount of impurities, such as an alkali metal compound, to increase in a polymer by the fall of washing | cleaning efficiency is recognized. In addition, the glass transition temperature is lowered with the reduction in molecular weight, and the heat resistance, which is the original characteristic of PES, may be lowered.

  In addition, when the reduced viscosity of PES (A) is high (number average molecular weight is high), in order to obtain hydroxyl group-containing PES (D) having a preferred range of molecular weight, water (B) or basic compound (C) As the amount of added increases, the solubility of PES (A) decreases, the basic compound (C) remains in the polymer, the polymer tends to be colored, and washing, recovery and separation are difficult. .

  In addition, the terminal group composition of PES (A) used in the production method of the present invention is to produce PES (A) and PES (D) having a reactive hydroxyphenyl terminal group efficiently. It is preferable to use PES having relatively more chlorophenyl end groups than hydroxyphenyl end groups. More specifically, in the method of the present invention in which PES (A) is used as a raw material and a hydroxyphenyl end group is introduced by reaction with water in the presence of a basic compound, the hydroxyphenyl end group introduction efficiency, reaction From the standpoint of post-treatment efficiency, the hydroxyphenyl end group composition in PES (A) is preferably 0 to 50 mol%, more preferably 0 to 30 mol%, and still more preferably 0 to 10 mol%.

  Such PES (A) can be produced by a known method as described above, but a commercially available PES produced by the above method (for example, “ULTRASON E” series manufactured by BASF, Sumitomo Chemical ("Sumika Excel" series) can be used. Among these, SUMIKAEXCEL 3600P, 4100P, 4800P, 5003P, and 5200P are preferable, and SUMIKAEXCEL 3600P, 4100P, and 4800P equivalents are more preferable.

(2) Production method of PES (D) having a reactive hydroxyphenyl end group The PES (D) having a reactive hydroxyphenyl end group of the present invention is a generally known method, that is, with respect to a dihydric phenol compound. Rather than being produced directly by polycondensation of dihalogenodiphenyl compounds or by adding an end-capping agent in the latter half of polycondensation, high molecular weight PES (A) is used as a raw material in the presence of basic compound (C). The PES (D) having a reactive hydroxyphenyl end group is produced by heating in water (B) and an aprotic polar solvent.

  In the conventional production method, a dihydric phenol compound and a dihalogenodiphenyl compound are used as raw material monomers, whereas in the method of the present invention, the dihalogenodiphenyl compound is greatly different in that it is not used in the reaction.

(In the formula, X represents Cl or F, and each R may be the same or different and is selected from an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 8 carbon atoms. M represents an integer of 0 to _3. Y represents a direct bond, oxygen, sulfur, SO ₂ , CO, C (CH ₃ ) _2, CH (CH ₃ ), or CH ₂ , N represents an integer of 1 or more.)

  In order to further clarify the present invention, the reaction scheme is shown in the above formula. First, PES (A) having a relatively higher molecular weight than PES (D) having a target hydroxyphenyl end group is polymerized in advance. Here, it is polymerized by a conventionally known method from a dihalogenodiphenyl compound (I) and a dihydric phenol compound (II) (here, II-1 is exemplified), and then recovered, and then washed and dried as necessary. Can be used. Since the residual monomer, solvent and alkalis remain in the reaction solution after polymerization, the PES (A) used in the present invention is particularly preferably washed and dried after recovery.

  By using this polymer (A) as an intermediate raw material and heating in water (B) and an aprotic polar solvent in the presence of the basic compound (C), the polymer main chain of PES (A) by water (B) is obtained. The PES (D) having a hydroxyphenyl end group is derived by the nucleophilic substitution reaction (position of arrow α in the formula).

  Further, in the reaction of the present invention, in addition to the nucleophilic substitution reaction to the polymer main chain, the hydroxyphenyl end group is also converted by a nucleophilic substitution reaction of a halogenophenyl end group and water (B) (position β in the formula). Generate. Since the halogenophenyl terminal is slightly present only at the polymer terminal with respect to the number of moles of the polymer main chain, the nucleophilic substitution reaction to the polymer main chain becomes probabilistic, but the addition amount of water (B) By adjusting the addition amount of basic compound, reaction temperature, and reaction time, not only nucleophilic substitution reaction to the polymer main chain (α reaction) but also nucleophilic substitution reaction to halogenophenyl terminal (β reaction) ) Can also proceed at the same time, and PES (D) having a high hydroxyphenyl end group amount can be induced.

On the other hand, in the case of the known polycondensation, the charged molar ratio (r) of the divalent phenol compound and dihalogenodiphenylsulfone, the polymer molecular weight obtained at that time, and the polymer end group composition are as follows. As described in Doujinshi, p206), etc.
r = number of moles of dihalogenodiphenylsulfone charged (a) / number of moles of charged divalent phenol compound (b) (where excess component is the denominator, a / b = r), and reaction rate is p And the number average degree of polymerization (Pn) of the polymer obtained at that time is
Pn = (1 + r) / [2r (1-p) + (1-r)]
Assuming a reaction rate of 100% (p = 1),
Pn = (1 + r) / (1-r)

  From this formula, when the divalent phenol compound is present in an excess of 1%, the number average degree of polymerization is 201. The terminal group ratio is [halogenophenyl terminal] / [hydroxyphenyl terminal] = r = 1.0 / 1.01 according to the charged molar ratio of each monomer component, and the hydroxyphenyl terminal group composition is about 50.2%. (In addition, when the reaction rate is 100% or less, it becomes a lower value).

  On the other hand, when the divalent phenol compound is charged in excess of 10% (r = 1.0 / 1.1) in order to generate excessive hydroxyphenyl end groups in the polymer obtained, the number average degree of polymerization is 21. When the hydroxyphenyl end group composition is about 52.4% and a divalent phenol compound is added in an excess of 50% (r = 1.0 / 1.5), the number average degree of polymerization is only 5 The hydroxyphenyl end group composition is about 60 mol%, and the theoretical molecular weight at that time is very low molecular weight, and it is theoretically impossible to obtain a polymer having a high molecular weight and a high hydroxyphenyl end group composition. there were.

  The present inventors have found that the hydroxyphenyl end group can be efficiently and quantitatively introduced by this reaction. Further, according to this reaction, PES having the desired hydroxyphenyl end group can be obtained in a high yield, More preferably, it has been found that this reaction has a high hydroxyphenyl end group, has a higher molecular weight than the conventional method, can further simplify the post-treatment process, and has a high purity.

  The water (B) used in the present invention is not particularly limited, but it is preferable to use water with as few impurities as possible in view of the content of impurities in the resulting polymer.

  The amount of water (B) used in this reaction depends on the target end group amount and target molecular weight of PES (D) having a hydroxyphenyl end group to be finally obtained. It can be controlled by the amount of water (B) added. In order to allow this reaction to proceed quantitatively, the molar amount is preferably 0.01 to 50 times, more preferably 0.1 to 40 times, particularly preferably 0.1 to 30 times the amount of 1 mol of PES (A). Is a mole. Here, the number of moles of PES (A) is calculated based on the molecular weight of one repeating unit represented by the formulas (a-1) and (a-2).

  When the amount of water (B) added is 50 times mol or more, not only the molecular weight of the resulting aromatic polyethersulfone (D) having a hydroxyphenyl end group becomes too small, but it becomes difficult to recover and wash the polymer. Since the solubility of PES (A) in the solvent is reduced and it is likely to be precipitated, the concentration of PES (A) in the aprotic polar solvent to be used may be reduced in order to proceed the reaction uniformly. Necessary. However, since the reactivity decreases as the concentration decreases, the reaction progresses for a long time, and further, the amount of solvent increases, making it difficult to recover and wash the polymer. Not realistic. On the other hand, if it is 0.01 times or less, it is difficult to quantitatively introduce the hydroxyphenyl end group.

  In the present invention, the amount of water (B) to be added and the amount of basic compound (C) are used to control the target end group amount and molecular weight of PES (D). Moisture that enters from the outside during the reaction, moisture at the time of preparation of the basic compound, etc., other than the target reaction of the present invention, that is, the nucleophilic substitution reaction of PES (A) as an intermediate raw material and added water (B) Since the reaction with water present in the system may proceed, it becomes difficult to control the target end group amount and the target molecular weight of the PES (D) having a hydroxyphenyl end group to be obtained. Therefore, it is preferable to remove these moisture as much as possible.

  Examples of the basic compound (C) used in the reaction of the present invention include sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide, sodium acetate, potassium acetate, sodium bicarbonate, hydrogen carbonate. Alkali metal compounds such as potassium, lithium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, anhydrous potassium carbonate, anhydrous sodium carbonate, calcium hydroxide, magnesium hydroxide, calcium hydrogen carbonate, barium hydrogen carbonate, magnesium hydrogen carbonate , Alkaline earth metal compounds such as calcium carbonate, quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, tertiary amines such as trimethylamine and triethylamine, N, N-dimethylamine, N, N Secondary amine diethylamine, N- methylamine, N- primary amines ethylamine and ammonia. Among these, from the ease of handling, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, anhydrous sodium carbonate, anhydrous potassium carbonate, etc. can be used, among them, sodium carbonate, potassium carbonate, anhydrous sodium carbonate, One or more kinds selected from anhydrous potassium carbonate can be preferably used.

  The amount of the basic compound (C) to be added is not particularly limited because it is affected by the solubility in the solvent to be used, but it is in the range of 0.01 to 2 moles per mole of water (B) used. Is more preferable, and it is 0.01-1 times mole more preferably.

  When the addition amount of the basic compound (C) is 2 moles or more with respect to 1 mole of water (B), the basic compound (C) tends to exist non-uniformly without dissolving in the solvent. Excess basic compound tends to remain in the polymer or the polymer will be colored. On the other hand, at 0.01 mol or less, it becomes difficult to introduce a reactive hydroxyphenyl end group.

  In the present invention, an aprotic polar solvent is used as the organic solvent for the reaction in order to allow the reaction to proceed quantitatively. Specifically, dimethyl sulfoxide, N, N-dimethylformamide (DMF), N, N-dimethylacetamide, N-methyl-2-pyrrolidone (NMP), N-methyl-2-piperidone, 1,3-dimethyl- 2-Imidazolidinone and a mixture of two or more of these may be mentioned, with dimethyl sulfoxide, DMF and NMP being particularly preferred.

  The amount of the solvent used in this reaction is not particularly limited as long as it dissolves PES (A) in the presence of water (B) and basic compound (C). The range of 1 to 20 times the weight is preferable. More preferably, the amount is 2 to 10 times.

  If it is less than 1 time, the raw material PES (A) will not dissolve, and operations such as stirring during the reaction will be difficult, and a uniform reaction will be difficult. When the amount of the solvent exceeds 20 times, the concentration of the polymer or water (B) decreases, the reaction rate becomes slow, and reprecipitation formation, washing, and recovery tend to be difficult. The increase in production affects the production volume and solvent recovery costs.

  The temperature during the reaction of the present invention depends on the type of solvent used, the boiling point of the solvent, the concentration of the reaction solution, the amount of water (B) added, and the amount of basic compound (C) added, but usually 100 to 250 ° C. It is preferable to carry out at 100, more preferably 100 to 200 ° C. When the reaction is performed at a temperature higher than 250 ° C., the thermal decomposition of the basic compound and the thermal decomposition of the PES (D) itself having a hydroxyphenyl end group generated in the reaction system proceed, so that the molecular weight is controlled and the hydroxyphenyl end group is introduced. It becomes difficult to control the amount, and a tendency such as a decrease in thermal stability and retention stability of the finally obtained PES (D) and coloring are observed. On the other hand, when this reaction is performed at a temperature lower than 100 ° C., there is a problem that the reaction becomes very slow.

  The time required for the reaction varies greatly depending on the amount of water (B) added, the type and amount of basic compound (C), the reaction concentration, and the reaction temperature, but is usually in the range of 10 minutes to 10 hours. Preferably, it is carried out in the range of 30 minutes to 5 hours. As the reaction atmosphere, it is preferable that oxygen does not exist, and good results can be obtained when the reaction is performed in nitrogen or other inert gas. Phenol-terminated basic compounds of PES (D) produced are easily oxidized when heated in the presence of oxygen, hindering the intended reaction, and as a result, it is difficult to control the molecular weight and the amount of hydroxyphenyl end group introduction. In addition, it also causes the coloring of the polymer.

  The PES having a crude hydroxyphenyl end group obtained by the method of the present invention is obtained by separating the basic compound contained in the reaction solution by filtration or centrifugation, or without filtration or centrifugation. It can be separated as a precipitated solid by adding a poor solvent to the reaction solution or adding a reaction solution to the poor solvent. Examples of the poor solvent for PES having a hydroxyphenyl end group include alcohols such as methanol, ethanol, isopropanol and butanol, nitriles such as acetonitrile, and water. Two or more of these poor solvents can be mixed and used. The poor solvent may contain a good solvent for the polymer such as the polymerization reaction solvent as long as the polymer can be precipitated.

  In order to obtain PES (D) having a hydroxyphenyl end group of the present invention, it is preferable to contact an acid in any step of the present invention. The step of contacting is not particularly limited, but preferably, the alkali metal salt contained in PES is brought into contact with PES by contacting the acid with PES at any step after precipitation after the reaction or with a poor solvent or after recovery. It can be removed efficiently.

  Acids used include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, perchloric acid, sulfurous acid, chromic acid, hypochlorous acid, perchloric acid, hydrogen cyanide, bromic acid, boric acid, acetic acid, formic acid One or two or more mixed acids selected from organic acids such as oxalic acid, tartaric acid, stearic acid, naphthenic acid, picric acid, and malic acid can be used, and the type of acid is not limited thereto.

  The amount of the acid used is not particularly limited because it is affected by the solubility in the solvent used, but is preferably in the range of 0.001 to 2 moles per mole of PES, more preferably 0.01. ˜1 mole. When the amount of the acid is less than the above range, the alkali metal salt cannot be sufficiently removed, which is not preferable.

  PES (D) having a hydroxyphenyl end group can be obtained by washing PES after acid contact with a poor solvent and then drying.

(3) Characteristics of PES (D) having hydroxyphenyl end group The end group composition of PES (D) having a hydroxyphenyl end group obtained by the present invention is, for example, 400 MHz ¹ H-NMR in a deuterated DMSO solvent. , And the number of times of accumulation is 100, two protons (H 2 _{Cl 2} ) adjacent to the aromatic carbon chlorinated to 7.7 ppm and two adjacent to the aromatic carbon substituted with a hydroxyl group at 6.9 ppm Since proton (H _OH ) can be observed with high resolution, and the area ratio of ¹ H-NMR reflects the number of moles as well known, the composition of hydroxyphenyl end groups and chlorophenyl end groups (mol%) is It can be calculated by the following formula.
[Hydroxyphenyl end group composition (mol%)] =
[ _HOH peak area] / ([ _HOH peak area] + [ _HCl peak area] × 100
[Chlorophenyl end group composition (mol%)] =
[H _Cl peak area] / ([H _OH peak area] + [H _Cl peak area] × 100

  That is, when the hydroxyphenyl end group and the chlorophenyl end group are present in a ratio of 1: 1, the hydroxyphenyl end group / chlorophenyl end group composition can be expressed as 50/50 mol%.

  According to the production method of the present invention, by selecting the reaction conditions such as the end group composition of PES (A) as a starting material and the amount of water (B) used during the reaction within the scope of the present invention, Although it is possible to adjust the amount of hydroxyphenyl end groups and the molecular weight as appropriate, the preferred hydroxyphenyl end group composition (mol%) of the finally obtained PES (D) is preferably 60 mol% or more, more preferably It is 70 mol% or more, more preferably 80 mol% or more.

  In particular, according to the production method of the present invention, it is possible to produce those having a hydroxyphenyl end group of 60 mol% or more, and more preferably 80 mol% or more, which has been difficult to produce by a conventionally known production method.

  The PES (D) having a hydroxyphenyl end group obtained by a preferred embodiment of the present invention contains a high content of highly reactive hydroxyphenyl end groups, and further has heat resistance, chemical resistance, flame retardancy, electrical Excellent in properties and mechanical properties, especially PES (A) obtained by a conventional method, or superior in productivity compared with low molecular weight PES in which the amount of hydroxyphenyl end groups is increased by shifting the molar balance, It is also characterized by high phenyl end group content, narrow molecular weight distribution, and extremely low metal content.

  The preferred molecular weight of the PES (D) having a hydroxyphenyl end group obtained by a preferred embodiment of the present invention is the hydroxyphenyl end group amount, molecular weight, glass transition temperature of the polymer finally obtained, The reduced viscosity measured at 25 ° C. in DMF of the polymer is 0.2 to 0 from the viewpoint of the effect of improving the compatibility due to the end group reaction in addition to the end group reactivity when alloying into the thermosetting resin. .4 is preferred, more preferably 0.25 to 0.4. When this reduced viscosity is replaced with a number average molecular weight (Mn) converted from polystyrene as a standard substance in DMF as a solvent using gel permeation chromatography (GPC), the number average molecular weight is 2600-54000. More preferably, it is 33000-54000.

  The PES (D) having a hydroxyphenyl end group of the present invention is not particularly limited because of influences such as reaction temperature, reaction time, water content, and the type of raw material used, but the hydroxyphenyl end group obtained by a preferred embodiment PES (D) having a tendency to depend on the molecular weight obtained and the amount of hydroxyphenyl end groups depends on the molecular weight of the starting material PES (A) and the amount of water (B) added.

  For example, the amount of hydroxyphenyl end groups of PES (D) obtained by a preferred embodiment in DMSO at 150 ° C. for 5 hours is proportional to the amount of water (B) added. Further, in order to obtain 0.2 to 0.4 which is a preferable reduced viscosity of PES (D) and a hydroxyphenyl end group amount of 60 to 100%, PES (A) having a hydroxyphenyl end group amount of 50% is obtained. When used, the reduced viscosity of the preferred PES (A) is in the range of about 0.25 to 0.55 or more, and when PES (A) having a hydroxyphenyl end group content of 0% is used, the preferred PES (A) has a reduced viscosity. The reduced viscosity is in the range of about 0.35 to 0.75 or more.

  However, if the reduced viscosity of the PES (A) used is low (number average molecular weight is low), the molecular weight of the finally obtained hydroxyl group-containing PES (D) becomes small, and the low molecular weight polymer or oligomer is a poor solvent. As a result, the polymer recovery rate and the cleaning efficiency tend to decrease. Furthermore, the tendency for the amount of impurities, such as an alkali metal compound, to increase in a polymer by the fall of washing | cleaning efficiency is recognized. In addition, the glass transition temperature is lowered with the reduction in molecular weight, and the heat resistance, which is the original characteristic of PES, may be lowered. In addition, when the reduced viscosity of PES (A) is high (number average molecular weight is high), in order to obtain hydroxyl group-containing PES (D) having a preferred range of molecular weight, water (B) or basic compound (C) As the amount of added increases, the solubility of PES (A) decreases, the basic compound (C) remains in the polymer, the polymer tends to be colored, and washing, recovery and separation are difficult. Therefore, the reduced viscosity of PES (A) is most preferably more than 0.4 and not more than 0.6.

  In addition, the reduced viscosity said here is the reduced viscosity measured at 25 degreeC and 1 g / dl in DMF. Further, the amount of alkali metal remaining in the PES (D) having a hydroxyphenyl end group is small because of the influence on thermal stability, residence stability, and coloring when alloying with a thermoplastic resin or a thermosetting resin. The more preferable. The use purpose for alloying with a thermoplastic resin or a thermosetting resin, and the amount of residual alkali metal obtained by a preferred embodiment of the present invention is preferably 1000 ppm or less, more preferably 500 ppm, and still more preferably 100 ppm or less.

  Further, PES (D) having a hydroxyphenyl end group obtained by a preferred embodiment is excellent in thermal stability, retention stability, non-coloring property, etc. as an alloy polymer with various thermoplastic resins and thermosetting resins. The composition comprising a thermoplastic resin or thermosetting resin alloyed with PES (D) having a hydroxyphenyl end group according to the present invention has a finely dispersed PES (D) in the polymer matrix, and further has a nano size. Depending on the amount of PES (D) having a hydroxyphenyl end group used, the molecular weight, and the blending amount, a completely compatible structure is exhibited, and mechanical properties, heat resistance, and electrical properties are extremely excellent. It is possible to provide a thermoplastic resin alloy and a thermosetting resin alloy.

  In particular, according to the production method of the present invention, PES (D) having a reactive hydroxyphenyl end group suitable for these alloys can be obtained in a very simple manner, efficiently and with the desired hydroxyphenyl end group. This makes it possible to quantitatively produce a polymer having a desired molecular weight.

  The present invention will be described more specifically with reference to the following examples. These examples are illustrative and not limiting.

(1) Reduced viscosity (η _sp / c)
The reduced viscosity was measured using an Ostwald capillary viscometer in DMF at 25 ° C. and 1 g / dl.

The reduced viscosity (η _sp / c) was calculated based on the following description, and a value obtained by averaging five measured values was used.
ηsp / c = (t−t ₀ ) / t ₀ / c
t; passage time (in seconds) between marked lines in the polymer solution viscometer
t ₀ ; transit time (in seconds) between marked lines of viscometer of pure solvent
c: Concentration of polymer solution (g / dl)

(2) Quantification of alkali metal content The alkali metal content in PES was quantified by the following method. The sample was weighed into a quartz crucible, incinerated using an electric furnace, the incinerated product was dissolved in concentrated nitric acid, and then the volume was made up with dilute nitric acid. The obtained constant volume solution was subjected to ICP gravimetric analysis (apparatus; 4500 manufactured by Agilent) and ICP emission spectroscopic analysis (apparatus; Optima 4300 DV manufactured by PerkinElmer).

(3) Measurement of weight loss rate during heating of PES The weight loss rate during heating of PES was measured using a thermogravimetric analyzer under the following conditions. In addition, the sample used the fine granule of 2 mm or less.
Apparatus: Perkin Elmer TGA7
Measurement atmosphere: 100 ° C. to 600 ° C. under nitrogen flow, temperature rising rate 10 ° C./min Sample charge weight: about 10 mg

  The thermal stability was evaluated by measuring the temperature under the above conditions and setting the temperature indicating 10% weight loss as “10% weight loss temperature”.

(4) Number average molecular weight measurement The number average molecular weight of the polymer was determined by gel permeation chromatography (GPC) as the number average molecular weight in terms of standard polystyrene. For GPC measurement, a differential refractometer RID-10A manufactured by Shimadzu Corporation is used for the detector, LC-10ADvp is used for the pump, and two columns for Showa Denko Co., Ltd. GPC and Shodex KD-806M are connected. went. The measurement conditions were a flow rate of 0.5 mL / min, dimethylformamide (DMF) was used as an eluent, and 0.1 mL of a solution having a sample concentration of 1 mg / mL was injected.

(5) PES terminal group composition Using a 400 MHz ¹ H-NMR (Nuclear Magnetic Resonance) apparatus (AL-400 manufactured by JEOL Ltd.), measured in a deuterated DMSO solution with a sample concentration of 1 mg / mL at 100 integrations. did.

Two protons (H _Cl ) adjacent to the chloro group at 7.7 ppm and two protons (H _OH ) adjacent to the hydroxyl group at 6.9 ppm are observed. Using these peak area ratios, the terminal group composition was calculated from the following relational expression.
[Hydroxyphenyl end group composition (mol%)] =
[H _OH peak area] / ([H _OH peak area] + [H _Cl peak area]) × 100
[Chlorophenyl end group composition (mol%)] =
[H _Cl peak area] / ([H _OH peak area] + [H _Cl peak area]) × 100

(6) Alloying with thermoplastic resin Using a small Brabender manufactured by Toyo Seiki, blended at a predetermined temperature for 15 minutes, melted and mixed, and the resulting composition was pelletized and dried.

(7) Morphological observation of thermoplastic resin and thermosetting resin alloy Using a transmission electron microscope (HITACHI, ELECTRON MICROSCOPE H-700), the morphology of the obtained resin composition was observed and photographed on the photograph. The 30 longest particle systems of the dispersed individual spherical dispersed phases were measured, and the value obtained by averaging these values was taken as the average particle diameter.

(8) Measurement of thermal characteristics Using a robot DSC manufactured by Seiko Electronics Industry Co., Ltd., the sample was heated at a rate of 20 ° C./min from 30 ° C. to 280 ° C. in a nitrogen atmosphere at a temperature of 30 ° C. to 280 ° C., and retained at 5 ° C. The temperature was lowered at 20 ° C./min for 5 minutes, the temperature was raised to 300 ° C. at 20 ° C./min, and the glass transition temperature (Tg) obtained at the second temperature rise was measured.

<Preparation of PES (A)>
[Reference Example 1] Preparation of PES (A-1) 1 L of 1 L equipped with a stirrer, a thermometer, a cooler, and a nitrogen introduction pipe was referred to the text and examples described in Patent Document 14 (Japanese Patent Laid-Open No. 5-86186). In a four-necked flask, 4,4′-dihydroxydiphenylsulfone (hereinafter abbreviated as DHDPS) (50.06 g, 0.20 mol), toluene 100 ml, 1,3-dimethyl-2-imidazolidinone (250.8 g), A 40% aqueous potassium hydroxide solution (56.0 g, 0.39 mol) was weighed, and the reaction system was completely purged with nitrogen by passing nitrogen gas while stirring. The mixture was heated to 130 ° C. while passing nitrogen gas. As the temperature of the reaction system increased, the reflux of toluene was started, water in the reaction system was removed by azeotropy with toluene, and azeotropic dehydration was performed at 130 ° C. for 4 hours while returning the toluene to the reaction system. Thereafter, the cooler is replaced with a distillate separator, and 4,4′-dichlorodiphenylsulfone (hereinafter abbreviated as DCDPS) (57.40 g, 0.20 mol) is added to the reaction system together with 40 g of toluene. Was heated to 150 ° C. The mixture was reacted for 4 hours while distilling toluene to obtain a dark brown solution with high viscosity. The temperature of the reaction solution was cooled to room temperature, and the reaction solution was dropped into 1 kg of methanol to precipitate polymer powder. The polymer powder was recovered by filtration, 1 kg of water was added thereto, 1N hydrochloric acid was further added, and the slurry solution was added until the pH became 3-4 to make it acidic. After collecting the polymer powder by filtration, the polymer powder was washed twice with 1 kg of water. Furthermore, it wash | cleaned with 1 kg of methanol, and vacuum-dried at 150 degreeC for 12 hours. The obtained polymer powder was white powder and the yield was 88.3 g (yield 95.0%: yield = (88.3 / 464.53 (molecular weight of PES (A)) / 0.2 × 100) ), Glass transition temperature (Tg) = 234 ° C., 10% weight loss temperature was 510 ° C. Reduced viscosity was 0.58, as measured by 400 MHz ¹ H-NMR, chlorophenyl end group / hydroxyphenyl The end group was 50/50 (mol%), and a series of results are shown in Table 1.

[Reference Example 2] Preparation of PES (A-2) PES was prepared by the method described in Patent Document 13 (JP-A-5-163352). To a 1 L four-necked flask equipped with a stirrer, a nitrogen inlet tube, a thermometer, and a condenser tube, diphenyl sulfone (611.6 g), DCDPS (57.43 g, 0.20 mol), DHDPS (47.55 g, 0.19) Mol) and anhydrous potassium carbonate (30.4 g, 0.2200 mol) were weighed and gradually heated to 130 ° C. in a nitrogen atmosphere. After the diphenylsulfone was dissolved, the reaction temperature was raised to 300 ° C. while stirring the reaction solution, and polymerization was started. The reaction was completed in 2 hours, the reaction solution was dropped into 1 kg of acetone / methanol 1: 1 mixed solvent, the precipitated solid was pulverized, washed twice with 1 kg of water, and vacuum-dried at 130 ° C. for 12 hours. . The reduced viscosity was 0.35 (g / dl). It was chlorophenyl terminal group / hydroxyphenyl terminal group measured by 400 MHz ¹ H-NMR = 52/48 (mol%). The results are shown in Table 1.

[Reference Example 3] Production of p-tert-butylphenyl terminal-containing PES (A-3)
An end-capped PES was prepared by the method of Reference 13 (Japanese Patent Laid-Open No. 5-163352). To a 1 L four-necked flask equipped with a stirrer, a nitrogen inlet tube, a thermometer, and a condenser tube, diphenyl sulfone (611.6 g), DCDPS (57.44 g, 0.20 mol), DHDPS (48.04 g, 0.19) Mol), anhydrous potassium carbonate (30.40 g, 0.22 mol), and p-tert-butylphenol (2.44 g, 0.016 mol) as an end-capping agent, and gradually heated to 130 ° C. in a nitrogen atmosphere. did. After the diphenylsulfone was dissolved, the reaction temperature was raised to 300 ° C. while stirring the reaction solution, and polymerization was started. The reaction was completed in 2 hours, the reaction solution was dropped into 1 kg of acetone / methanol 1: 1 mixed solvent, the precipitated solid was pulverized, washed twice with 1 kg of water, and vacuum dried at 130 ° C. The results are shown in Table 1.

  In NMR, a phenylchloro end group, a hydroxyphenyl end group, and a t-butyl group as a new peak near 1.2 ppm were confirmed. From this proton area ratio, chlorophenyl end group / hydroxyphenyl end group / p-tert-butylphenyl The terminal group was 20/10/70 (mol%).

[Reference Example 4] Method for producing PES having chlorophenyl terminal group (A-4)
End-capped PES was prepared by the method of Patent Document 13 (Japanese Patent Laid-Open No. 5-163352). To a 1 L four-necked flask equipped with a stirrer, a nitrogen inlet tube, a thermometer, and a condenser tube, diphenyl sulfone (611.6 g), DCDPS (57.44 g, 0.20 mol), DHDPS (48.04 g, 0.19) Mol) and anhydrous potassium carbonate (30.4 g, 0.22 mol) were weighed and gradually heated to 130 ° C. in a nitrogen atmosphere. After the diphenylsulfone was dissolved, the reaction temperature was raised to 300 ° C. while stirring the reaction solution, and polymerization was started. After 2 hours of reaction time, 0.096 L (0.04 mol) of chloromethane was blown and end-capped, then the reaction solution was dropped into 1 kg of acetone / methanol 1: 1 mixed solvent, and the precipitated solid was pulverized and 1 kg of water And then dried in vacuo at 130 ° C. The reduced viscosity was 0.35. The results are shown in Table 1.

  Since no hydroxyphenyl end group was confirmed by NMR, it is presumed that all ends were converted to chlorophenyl end groups.

[Reference Example 5] Production of bisphenol A type PES (A-5)
2,2-bis (4-hydroxyphenyl) propane (hereinafter abbreviated as bisphenol-A (bisA)) (45.66 g, 0.20 mol) instead of DHDPS (50.06 g, 0.20 mol) in Reference Example 1 ) Was performed in the same manner as Reference Example 1 except that.

The obtained polymer powder was white powder, and the yield was 85.0 g (yield 96.0%: yield = (85.0 / 442.55 (molecular weight of PES) /0.2×100). Reference Example 1 Since the main chain skeleton was different from ˜4, the glass transition temperature = 191 ° C., the 10% weight loss temperature was 488 ° C. The reduced viscosity was 0.56 (g / dl), 400 MHz ¹ H-NMR. Chlorophenyl end group / hydroxyphenyl end group = 50/50 (mol%) measured by the following formula.

[Reference Example 6]
"Sumika Excel 3600P" manufactured by Sumitomo Chemical Co., Ltd.
The reduced viscosity was 0.36, glass transition temperature 224 ° C., 10% weight raw material temperature 510 ° C., and 400 MHz ¹ H-NMR, only chlorophenyl end groups were observed.

[Reference Example 7]
"Sumika Excel 4800P" manufactured by Sumitomo Chemical Co., Ltd.
From a reduced viscosity of 0.48, a glass transition temperature of 230 ° C., a 10% weight loss temperature of 510 ° C., and 400 MHz ¹ H-NMR, only chlorophenyl end groups were observed.

<Production of PES (D) having hydroxyphenyl terminal group>
[Example 1]
PES (A-1) synthesized in Reference Example 1 (5 g, 10.7 mmol (5 / 464.53 × 1000) was added to a 100 mL four-necked flask equipped with a stirrer, nitrogen introducing tube, thermometer, and cooling tube (Dimroth). )), Water (1.35 g, 75.0 mmol), N-methyl-2-pyrrolidone (NMP) 50 ml, anhydrous potassium carbonate (0.7 g, 5.06 mmol) were weighed, and the NMP reaction solution was measured. While stirring, the reaction temperature was raised to 150 ° C., the reaction was completed in 5 hours, and the reaction solution was dropped into 500 ml of 0.1% acid methanol, and the precipitated powder, twice with 500 ml of water, It was washed once with 500 ml of methanol and vacuum-dried at 130 ° C. The obtained polymer powder was in the form of a white powder, the yield was 4.85 g, the yield was 97.1% (the yield was calculated by the weight of recovered PES / the charged PES (A-1) × 100), the glass transition temperature = The 207 ° C., 10% weight loss temperature was 508 ° C., and the reduced viscosity (ηsp / c) was 0.36. By 400 MHz ¹ H-NMR, PES of chlorophenyl end group / hydroxyphenyl end group = 20/80 (mol%) was obtained. The alkali metal content was 80 ppm. The results are shown in Table 2.

[Example 2]
The same procedure as in Example 1 was performed except that dimethyl sulfoxide (DMSO) was used instead of NMP. The obtained polymer powder was white powder, the yield was 4.89 g, the yield was 97.7%, the glass transition temperature = 208 ° C., the 5% weight loss temperature was 509 ° C., and the reduced viscosity (ηsp / c) was 0.37. Met. By 400 MHz ¹ H-NMR, PES of chlorophenyl end group / hydroxyphenyl end group = 14/86 (mol%) was obtained. The alkali metal content was 80 ppm. The results are shown in Table 2.

[Example 3]
It implemented by the method similar to Example 2 except having changed the addition amount of water and the addition amount of anhydrous potassium carbonate by the preparation composition shown in Table 2. The results are shown in Table 2.

[Examples 4 to 6]
It implemented by the method similar to Example 1 except having changed the addition amount of water, the addition amount of anhydrous potassium carbonate, and reaction temperature by the preparation composition shown in Table 2. A series of results are shown in Table 2.

[Examples 7 and 8]
It implemented by the method similar to Example 1 except having used sodium hydroxide and lithium hydroxide as an alkali metal salt. A series of results are shown in Table 2.

[Comparative Example 1]
It implemented by the method similar to Example 1 except not adding an alkali metal. The results are shown in Table 2.

[Comparative Example 2]
The same procedure as in Example 1 was performed except that water was not added. The results are shown in Table 2.

[Comparative Example 3]
The charge amount of DHDPS and DCDPS was changed, and DHDPS (55.96 g, 0.22 mol) was used in a 1.1-fold molar excess with respect to DCDPS (57.43 g, 0.20 mol) and DHDPS over DCDPS. Except for this, the same procedure as in Reference Example 1 was performed. The obtained polymer powder was white powder and the yield was 68.8 g (yield 74.1%: yield = (68.8 / 464.53 (molecular weight of PES) /0.2×100), glass transition temperature) = 167 ° C., 10% weight loss temperature was 405 ° C. Reduced viscosity was 0.23 dl / g According to 400 MHz ¹ H-NMR, chlorophenyl end group / hydroxyphenyl end group = 60/40 (mol%) ), Softening behavior of the polymer was observed during reprecipitation, and the remaining amount of alkali metal was 1100 ppm.

[Comparative Example 4]
The amount of DHDPS and DCDPS was changed, and DHDPS (60.06 g, 0.24 mol), DCDPS (57.40 g, 0.20 mol), and DHDPS were used in a 1.2-fold molar excess with respect to DCDPS. Except for this, the same procedure as in Reference Example 1 was performed. The results are shown in Table 2.

[Comparative Example 5]
At the end of the polymerization, the same procedure as in Reference Example 3 was carried out except that DHDPS (4.00 g, 0.016 mol) was added instead of p-tert-butylphenol (2.44 g, 0.016 mol) as a terminal blocking agent. did. The results are shown in Table 2.

  From Examples 1 to 8, PES (A-1), water (B), and basic compound (C) are reacted in an aprotic polar solvent, thereby depending on the amount of water added. It can be seen that a polymer having a high recovery rate and a low alkali metal content can be obtained.

  From the results of Examples 1 to 4, it was found that the amount of hydroxyphenyl end groups can be increased in the addition range of 1.4 times mole to 14.0 times mole ratio of water relative to PES. It can also be seen that even if DMSO is used as the reaction solvent instead of NMP, almost the same result can be obtained.

  From the results of Examples 4 to 6, it was found that the yield decreased at a reaction temperature of 200 ° C. However, when the reaction temperature was increased, a tendency to improve the reactivity could be confirmed, and water and basicity were higher than those at 150 ° C. It can be seen that PES having a high hydroxyphenyl end group content can be obtained even with a small amount of the compound added.

  From the results of Examples 7 and 8, when sodium hydroxide or lithium hydroxide is used instead of anhydrous potassium carbonate, a tendency such as a decrease in reactivity and an increase in the amount of residual metal is observed, but in either case It can be seen that PES having a hydroxyphenyl end group of 60% or more was obtained, and the polymer had low thermal stability and residual alkali metal content, and was excellent in thermal stability and polymer purity.

  On the other hand, from the results of Comparative Examples 1 and 2, it can be seen that when no water or basic compound was added, the reaction did not proceed at all.

  Further, in Comparative Examples 3 and 4 in which the charged molar ratios of DCDPS and DHDP were shifted and polycondensed directly, the hydroxyphenyl end groups increased by shifting the charged molar ratio, but when the content was increased, The decrease in the molecular weight of the polymer due to the shift in the ratio became significant, and there was a lot of loss in the recovery process, and a significant decrease in the polymer yield was observed. Furthermore, it turns out that thermal stability falls and the residual amount of the alkali metal which is an impurity in a polymer is increasing. Further, in Comparative Example 5 in which DHDPS was added at the end of the polymerization and end-capping was attempted, even when compared with Reference Example 3, the hydroxyphenyl end groups were not increased, and it was found that the reaction did not proceed in particular. .

[Examples 9 to 13]
The reaction was carried out under the conditions shown in Table 3. PES (A-1 to A-5) (50 g) synthesized in Reference Examples 1 to 5 (50 g) and water (13.) were added to a 1 L four-necked flask equipped with a stirrer, a nitrogen introducing tube, a thermometer, and a cooling tube (Dimroth). 5 g) (7.0 moles per mole of PES), DMSO 500 ml, anhydrous potassium carbonate (7.0 g) (0.07 moles per mole of water), and the synthesis procedure was the same as in Example 1. Carried out. The solution after the reaction was dropped into 5 liters of 0.1% strength acid methanol, and the precipitated solid was pulverized, washed twice with 5 liters of water, and dried in vacuum at 130 ° C. A series of results are shown in Table 3.

[Example 14]
This was carried out in the same manner as in Example 9, except that a commercially available PES (Sumitomo Chemical Co., Ltd., SUMIKAEXCEL 3600P) was used and NMP was used as the reaction solvent instead of DMSO. The results are shown in Table 3.

[Example 15]
It implemented by the method with Example 14 except having made reaction temperature 180 degreeC using commercially available PES (the Sumitomo Chemical Co., Ltd. make, Sumika Excel 4800P). The results are shown in Table 3.

  From the results of Examples 9-13, PES (A-1 to 4) having different molecular weights and terminal group structures and PES (A-5) consisting of bisphenol-A units were used. It can be seen that by reacting in a polar solvent, a hydroxyphenyl end group can be introduced under mild conditions of 150, and a polymer having a high yield and a low alkali metal content can be obtained. That is, it can be seen that a polymer having a high hydroxyphenyl end group amount can be obtained in a high yield and a high purity regardless of the molecular weight and the end group structure of PES used as a raw material.

  From the results of Examples 14 and 15, it can be seen that the same results can be obtained even when a commercially available PES produced by a generally known polycondensation method is used.

<Alloyation of PES (D) having a hydroxyphenyl end group and a thermoplastic resin>
[Examples 16 to 18, Comparative Examples 6 to 8]
The following three types of polymers were used as thermoplastic resins for alloys.
-Tm = 255 ° C., Tmc = 178 ° C., polyethylene terephthalate resin (Toray T704T) (hereinafter abbreviated as PET) having an intrinsic viscosity of 1.15 (phenol / tetrachloroethane = 5/5 (Vol / Vol), 25 ° C.)
Polybutylene terephthalate resin with Tm = 226 ° C. and intrinsic viscosity 0.85 (Toray 1100S) (hereinafter abbreviated as PBT)
Nylon 6 resin with a relative viscosity of 2.80 at Tm = 225 ° C. and 98% sulfuric acid 1 g / dl (CM1010 manufactured by Toray) (hereinafter abbreviated as N6)

  Under the conditions shown in Table 4, various PES 5 g synthesized in Example 9 and Comparative Examples 1 to 3 and the thermoplastic resin 45 g were blended at a predetermined temperature for 15 minutes using a small Brabender manufactured by Toyo Seiki, and melt mixed. The resulting composition was pelletized.

  Morphological observation of PES in the thermoplastic resin matrix was performed on a photograph by observing the morphology of the obtained resin composition pellets using a transmission electron microscope (HITACHI, ELECTRON MICROSCOPE H-700). The longest particle diameter of each dispersed spherical dispersed phase was measured, and the number averaged value was taken as the average particle diameter.

  A series of results are shown in Table 4. From the results of alloying studies in Examples 16 to 18 and Comparative Examples 6 to 8, PES (D) having a hydroxyphenyl end group obtained by the method of the present invention is PET, It turned out that it is suitable for alloying with polyesters, such as PBT, and thermoplastic resins, such as nylon.

<Alloyation of PES (D) having a hydroxyphenyl end group and a thermosetting resin>
[Examples 19 and 20, Comparative Example 9] (Alloying with thermosetting resin)
Tetraglycidyldiaminodiphenylmethane (Epikote 604) (manufactured by Japan Epoxy Resin Co., Ltd.) as an epoxy resin and PES (D) synthesized in Example 9, Example 12 and Comparative Example 3 in the blending ratio shown in Table 5 in a kneader Heat to 130 ° C. and mix. Subsequently, the obtained mixture was cooled to 80 ° C., and 4,4′-diaminodiphenylsulfone (hereinafter abbreviated as DDS) as a curing agent was added at a ratio shown in Table 5 and mixed well to obtain an epoxy resin composition. . The obtained epoxy resin composition was reacted and cured at 180 ° C. for 2 hours in a heating furnace to obtain a cured epoxy resin. The average particle size of PES finely dispersed in the epoxy resin was measured by the same method as in Example 16. The results are shown in Table 5.

  The epoxy resin cured product (Examples 19 and 20) using the PES having hydroxyphenyl end groups obtained in Examples 9 and 12 was the same as that using the PES obtained in Comparative Example 3 (Comparative Example 9). In comparison, it is more finely dispersed in the epoxy resin, and the use of PES having a higher hydroxyphenyl end group content and a lower molecular weight obtained in Example 9 is more finely dispersed. Recognize.

[Examples 21 to 28]
PES, water and anhydrous potassium carbonate are weighed into a 1 L four-necked flask equipped with a stirrer, nitrogen inlet tube, thermometer, and cooling tube (Dimroth) according to the charge composition shown in Table 6, and molecular sieve is added to the solvent. 400 ml of dimethyl sulfoxide (DMSO), which had been put in and dried overnight, was added. While stirring the DMSO reaction solution under a nitrogen flow, the reaction temperature was raised to 150 ° C., the reaction was completed in 5 hours, and the reaction solution was dropped into 4 l of 0.1% dilute hydrochloric acid to form a powder. Was further washed twice with 4 l of water and vacuum-dried at 80 ° C. for 6 hours to obtain white fine powdery polymer powder. The results are summarized in Table 6.

  From the results of Examples 21 to 28 and Examples 4 to 6, regardless of the difference in molecular weight and terminal group structure of the PES used as a raw material, the polymer having a high hydroxyphenyl end group amount was obtained in high yield and high purity. It turns out that it became possible to obtain.

^From the result of ¹ H-NMR, the proton (b) adjacent to the chloro group observed in the vicinity of 7.7 ppm, which was confirmed in the PES of Reference Example 1 used as the raw material, was slightly in Example 22 after the reaction. It can be confirmed that the proton (a) adjacent to the hydroxyl group observed in the vicinity of 6.9 ppm is increased. (See Figure 1)
The difference between the results of Examples 1 to 8 and Examples 21 to 23 seems to be the effect of using DMSO dehydrated with molecular sieves for more than one night as the solvent used in Examples 21 to 23.

[Examples 29 to 31]
It implemented by the method similar to Examples 16-18 except having used PES synthesize | combined in Example 23 by the conditions shown in Table 7.

  A series of results are shown in Table 7. PES (D) having a hydroxyphenyl end group obtained by the method of the present invention is suitable for alloying with a thermoplastic resin such as polyester such as PET and PBT, and nylon. I found out. The reason why the dispersibility is improved as compared with Examples 16 to 18 is considered to be improved by the fine powder recovery performed in Example 23.

[Examples 32-33, Comparative Example 10]
Tetraglycidyl diaminodiphenylmethane (Epikote 604) (manufactured by Japan Epoxy Resin Co., Ltd.) as an epoxy resin, the PES synthesized in Examples 22 and 26, and the PES in Reference Example 7 were heated to 130 ° C. in a test tube and took 3 hours or more. To make it uniform. Subsequently, the obtained mixture was cooled to 80 ° C., and 4,4′-diaminodiphenylsulfone (hereinafter abbreviated as DDS) as a curing agent was added at a ratio shown in Table 8, and a defoaming kneader (manufactured by Shinky Co., Ltd .: Awa After kneading at 2000 rpm for 3 minutes using Tori Netaro ARV-310), the mixture was uniformly mixed well under reduced pressure and degassing at 0.6 rpm for 5 minutes at 2000 rpm to obtain an epoxy resin composition. The obtained epoxy resin composition was reacted and cured at 180 ° C. for 2 hours in a heating furnace to obtain a cured epoxy resin. The average particle size of PES finely dispersed in the epoxy resin was measured by the same method as in Examples 19 and 20. The results are shown in Table 8.

  The epoxy resin cured product using PES having hydroxyphenyl end groups obtained in Examples 22 and 26 was more in the epoxy resin than the case where PES not containing hydroxyphenyl end groups of Comparative Example 10 was used. It can be seen that it is finely dispersed. It can also be seen that the more the hydroxyphenyl end groups are, the lower the molecular weight, the finer the dispersion. Compared with Examples 19 and 20, the fine dispersibility of Examples 32 and 33 is greatly improved after the reprecipitation and fine powder recovery carried out in Examples 21 to 28 and the addition of the curing agent. It is thought that it improved by the defoaming kneading conditions.

  The result of observing the cross section of the obtained epoxy resin composition using a transmission electron microscope is shown in FIG. 2 (Comparative Example 10 using PES: hydroxyphenyl group of Reference Example 7) and FIG. 3 (Example 26). PES: Example 33 using 57% hydroxyphenyl groups) and FIG. 4 (Example 32 using 92% PES: hydroxyphenyl groups in Example 22).

  In Comparative Example 10 in which PES having no hydroxyphenyl end group was kneaded, it was observed that a phase separation was observed without being dispersed, whereas in Example 33, PES was slightly dispersed with an average particle size of 30 to 40 nm. In Example 32, it can be seen that fine dispersion is obtained at 10 nm or less.

It is a figure which shows the NMR chart of PES obtained in Reference Example 1, and PES obtained in Example 22. It is a figure which shows the transmission electron micrograph of the cross section of the epoxy resin composition obtained by the comparative example 10. FIG. It is a figure which shows the transmission electron micrograph of the cross section of the epoxy resin composition obtained in Example 33. It is a figure which shows the transmission electron micrograph of the cross section of the epoxy resin composition obtained in Example 32.

Claims (9)

Aromatic polyethersulfone (A) having a structure represented by general formula (a-1) and / or general formula (a-2), water (B), and basic compound (C) are aprotic. A method for producing an aromatic polyethersulfone (D) having a hydroxyphenyl end group, characterized by heating in a polar solvent.

(In the formula, each R may be the same or different and represents any one selected from an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 8 carbon atoms, and m is 0 to 3). Y represents an integer selected from a direct bond, oxygen, sulfur, SO ₂ , CO, C (CH ₃ ) _2, CH (CH ₃ ), and CH _2. 2. The aromatic having a hydroxyphenyl end group according to claim 1, wherein the addition amount of water (B) is 0.1 to 30 times mol for 1 mol of the aromatic polyethersulfone (A). A process for producing polyethersulfone (D). The aromatic compound having a hydroxyphenyl end group according to any one of claims 1 and 2, wherein the basic compound (C) is one or more selected from sodium carbonate, potassium carbonate, anhydrous sodium carbonate, and anhydrous potassium carbonate. For producing a group A polyethersulfone (D). The aprotic polar solvent is at least one selected from N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, and sulfolane. The manufacturing method of aromatic polyether sulfone (D) which has a hydroxyphenyl terminal group of any one of Claims 1-3. Heating temperature is 100-200 degreeC, The manufacturing method of aromatic polyether sulfone (D) which has the hydroxyphenyl terminal group of any one of Claims 1-4 characterized by the above-mentioned. The raw material aromatic polyethersulfone (A) has a hydroxyphenyl end group composition of 50 mol% or less (determined by ¹ H-NMR in deuterated dimethyl sulfoxide, [6.9 ppm peak area (hydroxyl phenyl end group )] / (Peak area of 6.9 ppm (derived from hydroxyphenyl end group) + peak area of 7.7 ppm (derived from chlorophenyl end group)] × 100)) The manufacturing method of aromatic polyether sulfone (D) which has a hydroxyphenyl terminal group of any one of Claims. The aromatic polyethersulfone (D) having a hydroxyphenyl end group thus obtained has a hydroxyphenyl end group composition of 60 mol% or more (measured by ¹ H-NMR in deuterated dimethyl sulfoxide, [6.9 ppm peak Area (hydroxyl end group)] / (peak area of 6.9 ppm (derived from hydroxyphenyl end group) + peak area of 7.7 ppm (derived from chlorophenyl end group)) × 100) The manufacturing method of aromatic polyether sulfone (D) which has a hydroxyphenyl terminal group of any one of Claims 1-6. The aromatic polyethersulfone (D) having a hydroxyphenyl end group obtained has a reduced viscosity of 0.2 to 0.4 as measured in DMF at 25 ° C. and 1 g / dl. Item 8. A process for producing an aromatic polyethersulfone (D) having a hydroxyphenyl end group according to any one of Items 1 to 7. 8. The aromatic polyether having a hydroxyphenyl end group according to claim 7, wherein the aromatic polyethersulfone having a hydroxyphenyl end group (D) has a hydroxyphenyl end group composition of 80 mol% or more. A method for producing sulfone (D).

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