JP2010077185A - Aromatic polyethersulfone having hydroxyphenyl terminal group, and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aromatic polyethersulfone having a reactive hydroxyphenyl end group, which is suitable as an alloying agent for thermoplastic resins and thermosetting resins, and to remove the aromatic polyethersulfone in an economical and simple manner in a short time. An aromatic polyether sulfone having a hydroxyphenyl end group suitable as an alloying agent is obtained by polymerizing an aromatic polyether sulfone obtained by polymerization in advance. Aromatic polyether sulfone having a hydroxyphenyl end group, and a method for producing the same, comprising heating a monovalent phenol compound and / or water and a basic compound in an aprotic polar solvent.
[Selection figure] None

Description

  The present invention relates to an aromatic polyethersulfone (hereinafter abbreviated as PES), which has been difficult to produce by conventional production methods, and a production method thereof. More specifically, the present invention relates to a PES having a terminal group composition and a number average molecular weight that are difficult to produce by ordinary direct polycondensation and a method for producing the same, and the PES of the present invention is obtained by conventional direct polycondensation. Unlike PES, it is a PES having a high hydroxyphenyl end group content that is excellent in compatibilizing effect for thermoplastic resins and thermosetting resin alloys.

  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 into polycarbonate with a specific composition 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 end 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 believed that the hydroxyphenyl terminus is reduced.

  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 the reactive hydroxyphenyl end group rather than the halogenophenyl end group. Theoretically, when the charge ratio of dihalogenodiphenylsulfone and dihydric phenol compound is 1: 1 and equivalent, the highest molecular weight can be achieved. The terminal group composition at that time is the 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 terminal group balance are lost due to the oxidation reaction at the time of polymerization, making it difficult to increase the molecular weight, the hydroxyphenyl terminal is decomposed at the time of polymerization, and the halogenophenyl terminal group There was a problem that the ideal polycondensation reaction was hindered by the oxidation reaction, such as the problem that the amount was larger than the amount of hydroxyphenyl end groups, and it was difficult to control the molecular weight and the amount of hydroxy end groups. 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 thermoplastic resin or epoxy resin, coloring or hydrolysis due to thermal decomposition or alloying is accelerated, or residence stability is 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) having a structure represented by the general formula (a-1) and / or (a-2), and having a hydroxyphenyl terminal group ratio (%) (determined by ¹ H-NMR in deuterated dimethyl sulfoxide) 6.9 ppm peak area ratio (hydroxyphenyl end group) / (6.9 ppm peak area (derived from hydroxyphenyl end group) +7.7 ppm peak area (derived from chlorophenyl end group))] × 100 Aromatic polyether sulfone (A) having a reduced viscosity of 0.07 or more and 0.45 or less measured in a DMF solvent at 25 ° C. and 1 g / dl using a capillary viscometer. ),

(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 polyethersulfone (A) according to (1), wherein the hydroxyphenyl terminal group ratio (%) is 70% or more,
(3) The aromatic polyethersulfone (A) according to any one of (1) and (2), wherein the hydroxyphenyl terminal group ratio (%) is 80% or more,
(4) Aromatic polyethersulfone (B) having a structure represented by general formula (b-1) and / or (b-2), and general formula (c-1) and / or (c-2) (1) to (1) to (2) obtained by heating the dihydric phenol compound (C) and / or water (D) represented by the formula (1) and the basic compound (E) at 200 ° C. or less in an aprotic polar solvent. 3) The process for producing an aromatic polyethersulfone (A) according to any one of

(5) The addition amount of the dihydric phenol compound (C) is 0.01 to 0.5 times mol with respect to 1 mol of the aromatic polyethersulfone (B). Production method of aromatic polyethersulfone (A),
(6) The method for producing a polyethersulfone (A) according to any one of (4) and (5), wherein the dihydric phenol compound (C) is bisphenol-A or bisphenol S,
(7) The hydroxyphenyl end group described in (4) is characterized in that the amount of water (D) added is 0.1 to 30 times mol for 1 mol of aromatic polyethersulfone (B). A process for producing an aromatic polyethersulfone (A),
(8) The aromatic polyether sulfone according to any one of (4) to (7), wherein the basic compound (E) is at least one selected from sodium carbonate, potassium carbonate, anhydrous sodium carbonate and anhydrous potassium carbonate. (A) production method,
(9) The raw material aromatic polyethersulfone (B) 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 (hydroxy 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) (4) A process for producing the aromatic polyethersulfone (A) according to any one of to (8),
(10) The raw material aromatic polyethersulfone (B) has a hydroxyphenyl end group composition of 10 mol% or less (measured by ¹ H-NMR in deuterated dimethyl sulfoxide, [6.9 ppm peak area (hydroxy 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) (4) A process for producing the aromatic polyethersulfone (A) according to any one of to (9),
Is to provide.

  According to the present invention, a PES having a high hydroxyphenyl end content, which could not be obtained by a conventional direct polycondensation method, was obtained, and the PES of the present invention alloyed PES with a thermoplastic resin or a thermosetting resin. In this case, the PES is suitable for finely dispersing the PES in the matrix resin. Furthermore, according to the method of the present invention, it is possible to provide a method for efficiently producing PES having a high content of reactive hydroxyphenyl end groups in a short time by an economical and simple method.

  Embodiments of the present invention will be described below.

(I) Aromatic polyethersulfone (A) of the present invention
The PES (A) of the present invention has a structure represented by the general formula (a-1) and / or (a-2), and has a hydroxyphenyl terminal group ratio (%) (in deuterated dimethyl sulfoxide). , Measured by ¹ H-NMR, [6.9 ppm peak area ratio (hydroxyphenyl end group) / (6.9 ppm peak area (from hydroxyphenyl end group) +7.7 ppm peak area (from chlorophenyl end group)) )]] Calculated by x100 is 60% or more, and a reduced viscosity measured in a DMF solvent at 25 ° C. and 1 g / dl using a capillary viscometer is 0.07 or more and 0.45 or less. Aromatic polyethersulfone (A).

(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 .

Here, the hydroxyphenyl terminal group ratio (%) in PES (A) was chloro-substituted to 7.7 ppm by, for example, 1000 accumulations using 400 MHz ¹ H-NMR in a deuterated DMSO solvent. The proton adjacent to the aromatic carbon (1H _Cl ), the proton adjacent to the aromatic carbon substituted with a hydroxyl group at 6.9 ppm (1H _OH ), and the proton adjacent to the unsubstituted aromatic carbon (1H) are high. Since it can be observed with resolution, and the area ratio of ¹ H-NMR reflects the number of moles, as well known, the hydroxyphenyl terminal group ratio and chlorophenyl terminal group ratio (mol%) should be calculated by the following formulas. Can do.
[Hydroxyphenyl end group composition (mol%)] =
[Peak area of 1H _OH ] / ([peak area of 1H _OH ] + [peak area of 1H _Cl ]) × 100
[Chlorophenyl end group composition (mol%)] =
[1H _Cl peak area] / ([1H _OH peak area] + [1H _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%.

  The hydroxyphenyl end group composition (%) in the PES (A) of the present invention thus determined is 60 mol% or more, preferably 70 mol%, more preferably 80 mol%.

  There is no limitation on the upper limit, and according to the production method of the present invention described later, it is possible to produce a product having a hydroxyphenyl end group ratio (%) of 100%.

  The PES (A) having hydroxyphenyl end groups of the present invention contains a high content of highly reactive hydroxyphenyl end groups, and further has heat resistance, chemical resistance, flame retardancy, electrical properties and mechanical properties. In particular, compared to PES obtained by the conventional direct polycondensation method or low molecular weight PES in which the amount of hydroxyphenyl end groups is increased by shifting the molar balance, the productivity is further improved, and the amount of hydroxyphenyl end groups is further increased. It is also characterized by a high molecular weight distribution and a very low metal content.

  The reduced viscosity of the PES (A) having a hydroxyphenyl end group of the present invention is compliant with JIS K2283, using a capillary viscometer such as Canon Fiske, Ostwald, Ubbelohde, etc. in DMF as a solvent at 25 ° C., 1 g / The reduced viscosity measured by dl is the hydroxyl group end group amount, molecular weight, glass transition temperature of the final polymer, and end group reactivity when this polymer is alloyed into a thermoplastic resin or thermosetting resin. In addition, it is 0.07 to 0.45, preferably 0.19 to 0.40, and more preferably 0.24 to 0.40 from the viewpoint of the effect of improving the compatibility by the end group reaction.

  When this reduced viscosity is replaced with DMF as a solvent and number average molecular weight (Mn) converted from polystyrene as a standard substance using gel permeation chromatography (GPC), the number average molecular weight is preferably 10,000 to 1,000,000. More preferably, it is 26000-54000, More preferably, it is 32000-54000.

  When the reduced viscosity of the resulting hydroxyl group-containing PES (A) is lower than 0.07, the polymer or oligomer on the low molecular weight side dissolves or swells in a poor solvent, and as a result, the polymer recovery rate and washing efficiency There is a tendency 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.

  Moreover, when the reduced viscosity of PES (A) is higher than 0.45, when used as a thermoplastic resin or thermosetting resin alloy, the viscosity becomes high and kneading becomes difficult, or PES is coarsely dispersed. A sufficient compatibility effect may not be obtained.

(II) Method for producing aromatic polyethersulfone (B) used in the present invention PES (B) used in the present invention is a structure represented by the general formula (b-1) and / or (b-2) R in the formulas may be the same or different and each represents 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 Represents an integer of ~ 3. Y represents one selected from a direct bond, oxygen, sulfur, SO ₂ , CO, C (CH ₃ ) _2, CH (CH ₃ ), and CH ₂ .

  Such PES (B) 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.

(X in the formula represents Cl or F, R 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 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 .

  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.

  In addition, trace amounts of water during polymerization, water entering from the outside during the reaction, and water generated during the polymerization hinder the progress of the polymerization, so in order to separate the water in the reaction system, an aprotic polar solvent is used. A solvent that is compatible and forms an azeotrope with water under 0.101 MPa can be used. Examples of such solvents include, but are not limited to, hydrocarbon solvents such as pentane, hexane, heptane, octane, cyclohexane, dodecane, benzene, toluene, xylene, naphthalene, and ethylbenzene, diisopropyl ether, ethyl butyl ether, dioxane, and the like. Ether solvents, ketone solvents such as acetylacetone and methyl ethyl ketone, alcohol solvents such as ethanol, isopropanol, n-propanol, isobutyl alcohol, hexanol and benzyl alcohol, ethyl acetate, methyl acetate, butyl acetate, butyl butyrate, methyl benzoate Ester solvents such as formic acid, acetic acid, propionic acid, valeric acid, benzoic acid and other carboxylic acid solvents, chloroform, bromoform, 1,2-dichloromethane, 1,2-dichloroe Halogen solvents such as ethylene, carbon tetrachloride, chlorobenzene and hexafluoroisopropanol, and amine solvents such as ethylenediamine, aniline, pyridine and methylpyridine, preferably hydrocarbons, more preferably from benzene, toluene and xylene. At least one selected can be used.

  The amount of water azeotropic solvent used is not particularly limited as long as it can remove water in the system, but is preferably in the range of 0.01 to 10 times the weight of the total monomer, more preferably The amount is 0.02 to 5 times.

  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.

  PES (B) used in the present invention can be produced by the above-described method, but in order to produce PES (A) having a hydroxyphenyl end group finally obtained efficiently and with high purity. The PES (B) is based on JIS K2283, and a reduced viscosity measured at 25 ° C. and 1 g / dl in DMF as a solvent using a capillary viscometer such as Canon Fiske, Ostwald, Ubbelohde, etc. To 1.0, more preferably 0.35 to 0.8, and more preferably 0.4 to 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 PES (B) 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 (A) 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.

  When the reduced viscosity of PES (B) is high (number average molecular weight is high), in order to obtain hydroxyl group-containing PES (A) having a preferred range of molecular weight, dihydric phenol compound (C) and / or water (D ) And basic compound (E) are added in an increased amount, so that the unreacted dihydric phenol compound (C) and basic compound (E) exhibiting acidity remain in the polymer, the polymer is colored, It tends to be difficult to clean, collect and separate.

  In addition, the end group composition of PES (B) used in the production method of the present invention is such that PES (B) and PES (A) having a reactive hydroxyphenyl end group can be efficiently produced. It is preferable to use PES having relatively more chlorophenyl ends than hydroxyphenyl end groups. More specifically, in the method of the present invention in which PES (B) is used as a raw material and a hydroxyphenyl terminal is introduced by reaction with a divalent phenol compound (C) and / or water (D), the hydroxyphenyl terminal is introduced. From the aspect of introduction efficiency and post-treatment efficiency after reaction, the hydroxyphenyl end group composition in PES (B) is preferably 0 to 50 mol%, more preferably 0 to 30 mol%, still more preferably 0 to 0 mol%. 10 mol%.

  Such PES (B) 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 “Sumika Excel” series made by Kagaku Co., Ltd.) can be used. Among these, SUMIKAEXCEL 3600P, 4100P, 4800P, 5003P, and 5200P are preferable, and SUMIKAEXCEL 3600P, 4100P, and 4800P equivalents are more preferable.

(III) Method for Producing PES (A) Having Reactive Hydroxyphenyl End Group PES (A) having a reactive hydroxyphenyl end group of the present invention is generally known in the 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 the polycondensation, high molecular weight PES (B) is used as a raw material, and the dihydric phenol compound (C) and PES (A) having a reactive hydroxyphenyl end group is produced by heating water (D) and basic compound (E) in an aprotic polar solvent. is there.

  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 (B) having a relatively higher molecular weight than PES (A) having a target hydroxyphenyl terminal 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 residual monomers, solvents and alkalis remain in the reaction solution after polymerization, the PES (B) used in the present invention is particularly preferably washed and dried after recovery.

  Heating the dihydric phenol compound (C) (here c-1 is exemplified) and / or water (D) and the basic compound (E) in an aprotic polar solvent using the present polymer (B) as an intermediate raw material By the nucleophilic substitution reaction of the PES (B) to the polymer main chain with the dihydric phenol compound (C) and / or water (D) (position of the arrow α in the formula), the PES having a hydroxyphenyl end group (A) is induced.

  In the reaction of the present invention, in addition to the nucleophilic substitution reaction to the polymer main chain, a nucleophilic substitution reaction of a halogenophenyl end and a dihydric phenol compound (C) and / or water (D) (in the formula, β ), A hydroxyphenyl end group is formed. 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 is stochastically dominant, but the dihydric phenol compound (C) and By adjusting the addition amount of water (D), the addition amount of the basic compound (E), the reaction temperature, and the reaction time, not only the nucleophilic substitution reaction to the polymer main chain (reaction of α), The nucleophilic substitution reaction (β reaction) to the halogenophenyl terminal can also proceed simultaneously, and PES (A) having a high hydroxyphenyl terminal 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, in order to produce an excessive amount of hydroxyphenyl ends in the resulting polymer, when the divalent phenol compound is charged in excess of 10% (r = 1.0 / 1.1), the number average degree of polymerization is 21, Hydroxyphenyl terminal group composition is about 52.4%, and when 50% excess of divalent phenol compound is charged (r = 1.0 / 1.5), the number average degree of polymerization is only 5, The phenyl 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. It was.

  The present inventors have found that the hydroxyphenyl terminal can be efficiently and quantitatively introduced by this reaction, and further, according to this reaction, a PES having the desired hydroxyphenyl terminal group can be obtained in a high yield. 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 dihydric phenol compound (C) used in the present invention is represented by the following general formula (c-1) and / or (c-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.
Examples of such dihydric phenol compound (C) include hydroquinone, catechol, resorcin, 4,4′-biphenol, 2,2-bis (4-hydroxyphenyl) propane, and 2,2-bis (4-hydroxyphenyl). Methane, bis (4-hydroxyphenyl) alkanes such as 2,2-bis (4-hydroxyphenyl) ethane, dihydroxydiphenyl sulfones such as 4,4′-dihydroxydiphenylsulfone, 4,4′-dihydroxydiphenyl ether, etc. Examples include dihydroxyphenyl ethers and structural isomers thereof. Among these, hydroquinone, 4,4′-biphenol, 4,4′-dihydroxydiphenylsulfone (bisphenol) from the viewpoint of availability, practicality, and price. -S), 2,2-bis (4-hydroxyphene) Propane (bisphenol-A), bis (4-hydroxyphenyl) methane (bisphenol-F), 4,4′-ethylidenebisphenol (bisphenol-E), 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl Sulfones are preferred, and structural isomers of these dihydric phenol compounds (C) may be used, but 4,4′-dihydroxydiphenyl sulfone (bisphenol-S), 2,2-bis (4 -Hydroxyphenylpropane) (bisphenol-A), bis (4-hydroxyphenyl) methane (bisphenol-F), 4,4'-ethylidenebisphenol (bisphenol-E), particularly preferably 4,4'-dihydroxy Diphenylsulfone (bisphenol-S) 2,2-bis (4-hydroxyphenylpropane) (bisphenol-A).

  The addition amount of the dihydric phenol compound (C) used in this reaction depends on the target end group amount and target molecular weight of the PES (A) having a hydroxyphenyl end group to be finally obtained, but rather These can be controlled by the addition amount of the dihydric phenol compound (C). In order to allow this reaction to proceed quantitatively, the amount is preferably 0.001 to 2.0 times mol, more preferably 0.01 to 1.5, and still more preferably 0.01 to 1 mol of PES (B). It is -1.0 times mole, Most preferably, it is 0.01-0.5 times mole. Here, the number of moles of PES (B) is calculated based on the molecular weight of one repeating unit represented by the formulas (b-1) and (b-2).

  When the addition amount of the dihydric phenol compound (C) is 2.0 mol or more, the molecular weight of the resulting aromatic polyethersulfone (A) having a hydroxyphenyl end group becomes too small, and it is difficult to recover and wash the polymer. In addition, the unreacted dihydric phenol compound (C), the salt of the dihydric phenol compound, or the basic compound (E) itself that shows acidity tends to remain in the polymer or the polymer tends to be colored. In particular, with an increase in the amount of hydroxyphenyl end groups introduced, the solubility of the polymer and the interaction with the basic compound increase, so that washing, recovery and separation tend to be difficult. On the other hand, at 0.001 or less, it is difficult to quantitatively introduce the hydroxyphenyl end group.

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

  When the amount of water (D) added is 50 times mol or more, the molecular weight of the resulting aromatic polyethersulfone (A) having a hydroxyphenyl end group becomes too small, making it difficult to recover and wash the polymer. Since the solubility of PES (B) in the solvent is reduced and it is likely to be precipitated, the concentration of PES (B) in the aprotic polar solvent to be used may be lowered 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 (D) added or the amount of basic compound (E) is used to control the target end group amount or molecular weight of PES (A). 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 (B) as an intermediate raw material and added water (D) Since the reaction with water existing in the system may proceed, it becomes difficult to control the target end group amount of PES (A) having a hydroxyphenyl end group and the target molecular weight. It is preferable to remove moisture as much as possible.

  In order to allow the reaction of the present invention to proceed quantitatively, an aprotic polar solvent is used as the organic solvent for this reaction. 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 aprotic polar solvent used in this reaction is not particularly limited as long as it dissolves PES (B) and the dihydric phenol compound (C). The range of 5 to 20 times weight is preferable. More preferably, the amount is 2 to 10 times.

  If it is less than 0.5 times, the raw material PES (B) and dihydric phenol compound (C) will not dissolve, and operations such as stirring during the reaction will be difficult, and a uniform reaction will be difficult. If the amount of solvent exceeds 20 times, the polymer concentration and the concentration of the dihydric phenol compound (C) and / or water (D) will decrease, the reaction rate will be slow, and reprecipitation, washing and recovery will be difficult. The increase in the amount of solvent affects the decrease in production amount and the solvent recovery cost.

  In the present invention, it is important to carry out this reaction in an aprotic polar solvent. However, in some cases, an organic solvent other than the aprotic polar solvent can be used in combination. In particular, trace amounts of moisture contained in the raw material, moisture entering from the outside during the reaction, binding water of the basic compound to be used, water in the basic compound aqueous solution, moisture at the time of preparation of the basic compound, etc. In addition to the above reaction, that is, the nucleophilic substitution reaction of PES (B), which is an intermediate raw material, and dihydric phenol compound (C) and / or water (D), hydrolysis by water present in the system may proceed. . Since water in the reaction system may inhibit the reaction of the present invention, it is compatible with an aprotic polar solvent for the purpose of separating the water in the reaction system, and water is used under 0.101 MPa. Solvents that form an azeotrope with can be used. Examples of such solvents include, but are not limited to, hydrocarbon solvents such as pentane, hexane, heptane, octane, cyclohexane, dodecane, benzene, toluene, xylene, naphthalene, and ethylbenzene, diisopropyl ether, ethyl butyl ether, dioxane, and the like. Ether solvents, ketone solvents such as acetylacetone and methyl ethyl ketone, alcohol solvents such as ethanol, isopropanol, n-propanol, isobutyl alcohol, hexanol and benzyl alcohol, ethyl acetate, methyl acetate, butyl acetate, butyl butyrate, methyl benzoate Ester solvents such as formic acid, acetic acid, propionic acid, valeric acid, benzoic acid and other carboxylic acid solvents, chloroform, bromoform, 1,2-dichloromethane, 1,2-dichloroe Halogen solvents such as ethylene, carbon tetrachloride, chlorobenzene and hexafluoroisopropanol, and amine solvents such as ethylenediamine, aniline, pyridine and methylpyridine, preferably hydrocarbons, more preferably from benzene, toluene and xylene. At least one selected can be used.

  The amount of water azeotropic solvent used is not particularly limited as long as it can remove water in the system, but is preferably in the range of 0.01 to 10 times the weight of the total monomer, more preferably The amount is 0.02 to 5 times. In the reaction of the present invention, the reaction rate can be further improved by adding the basic compound (E) to the reaction system. Examples of the basic compound (E) used include sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide, sodium acetate, potassium acetate, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, Alkali metal compounds such as sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, anhydrous potassium carbonate, anhydrous sodium carbonate, alkalis such as calcium hydroxide, magnesium hydroxide, calcium bicarbonate, barium bicarbonate, magnesium bicarbonate, calcium carbonate Earth metal compounds, quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, tertiary amines such as trimethylamine and triethylamine, N, N-dimethylamine, N, N-diethylamine and the like Secondary amine, N- methylamine, N- primary amines ethylamine and ammonia. Among these, for ease of handling, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, anhydrous sodium carbonate, anhydrous potassium carbonate, etc. can be used, and sodium carbonate, potassium carbonate, anhydrous sodium carbonate, anhydrous carbonate One or more selected from potassium can be preferably used.

  The addition amount of the basic compound (E) is preferably in the range of 0.1 to 3 times mol, more preferably 0.5 to 1 times mol per mol of the dihydric phenol compound (C) used.

  When the addition amount of the basic compound (E) is 3 times mol or more with respect to 1 mol of the dihydric phenol compound (C), an acidic dihydric phenol compound or a salt of the dihydric phenol compound, and further the basic compound (E) It tends to remain in the polymer itself or to color the polymer. On the other hand, at 0.5 or less, it becomes difficult to introduce a reactive hydroxyphenyl end group.

  Moreover, the addition amount of the basic compound (E) when water is used is preferably in the range of 0.01 to 2 moles, more preferably 0.01 to 1 time, with respect to 1 mole of water (D) used. Is a mole.

  When the addition amount of the basic compound (E) is 2 mols or more with respect to 1 mol of water (D), the basic compound (E) 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.

  The heating temperature depends on the type of solvent used, the boiling point of the solvent, the concentration of the reaction solution, the addition amount of the dihydric phenol compound (C) and / or water (D), and the addition amount of the basic compound (E). Usually, it is preferable to implement at 100-250 degreeC, More preferably, it is 100-200 degreeC. When the reaction is carried out at a temperature higher than 250 ° C., the thermal decomposition of the dihydric phenol compound salt and the thermal decomposition of the PES (A) itself having a hydroxyphenyl end group generated in the reaction system proceed, so that the molecular weight control and the hydroxyphenyl end Control of the amount of introduced groups becomes difficult, and a tendency such as a decrease in thermal stability and retention stability of the finally obtained PES (A) 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 largely depends on the type / addition amount of the dihydric phenol compound (C) and / or the addition amount of water (D), the type / addition amount of the basic compound (E), the reaction concentration, and the reaction temperature. Although it varies, it is usually in the range of 10 minutes to 10 hours, preferably 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. Basic compounds of dihydric phenol compounds are easily oxidized when heated in the presence of oxygen, preventing the intended reaction. As a result, it is difficult to control the molecular weight and the amount of hydroxyphenyl end groups introduced, and the polymer Also causes coloring.

  The PES having a crude hydroxyphenyl end group obtained by the method of the present invention can be reacted after the basic compound contained in the reaction solution is separated by filtration or centrifugation, or without filtration or centrifugation. The solution can be separated as a precipitated solid by adding a poor solvent to the 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 (A) having a hydroxyphenyl terminal 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 (A) having a hydroxyphenyl end group can be obtained by washing PES after contact with an acid with a poor solvent and then drying.

  For example, the amount of the hydroxyphenyl end group of PES (A) obtained according to a preferred embodiment in DMSO at 150 ° C. for 5 hours is proportional to the amount of dihydric phenol compound (C) and / or water (D) added. Moreover, in order to obtain PES (A) having a reduced viscosity of 0.07 to 0.45 and a hydroxyphenyl end group amount of 60 to 100%, PES (B) having a hydroxyphenyl end group amount of 50% was used. In this case, the preferred reduced viscosity of PES (B) is in the range of about 0.09 to 0.62, and when PES (B) having a hydroxyphenyl end group content of 0% is used, the preferred reduced viscosity of PES (B). Is approximately in the range of 0.13 to 0.85 or more.

  However, if the reduced viscosity of the PES (B) used is low (number average molecular weight is low), the molecular weight of the finally obtained hydroxyl group-containing PES (A) 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, in order to obtain a hydroxyl group-containing PES (A) having a high molecular weight within a preferable range when the reduced viscosity of PES (B) is high (number average molecular weight is high), dihydric phenol compound (C) and / or water Since the amount of addition of (D) or basic compound (E) increases, unreacted dihydric phenol compound (C) showing acidity or basic compound (E) remains in the polymer, or the polymer is colored or Since the cleaning, recovery and separation tend to be difficult, the reduced viscosity of the raw material PES (B) is more preferably more than 0.4 and not more than 0.6.

  The reduced viscosity referred to here is a reduced viscosity measured at 25 ° C. and 1 g / dl in DMF as a solvent using a capillary viscometer such as Canon Fiske, Ostwald, Ubbelohde, etc. according to JIS K2283. .

  Further, the amount of alkali metal remaining in the PES (A) having a hydroxyphenyl terminal 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 (A) 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 a thermosetting resin alloyed with PES (A) having a hydroxyphenyl end group according to the present invention has a PES (A) finely dispersed in a polymer matrix, and further nanosized. Depending on the amount of end groups, molecular weight and blending amount of PES (A) having hydroxyphenyl end groups to be used, it exhibits a completely compatible structure, and has excellent mechanical properties, heat resistance, and electrical properties. 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 (A) 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 according to JIS K2283 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 a nitrogen stream, temperature increase rate 10 ° C./min.
Sample charge weight: about 10mg
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 adjacent to the chloro group at 7.7 ppm (2 × H _Cl ) and two protons adjacent to the hydroxyl group at 6.9 ppm (2 × H _OH ) 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 (B)>
[Reference Example 1] Preparation of PES (B-1) With reference to the text and examples described in Patent Document 14 (Japanese Patent Laid-Open No. 5-86186), a stirrer, thermometer, cooler, distillate separator and nitrogen Into a 1 L four-necked flask equipped with an introduction tube, 4,4′-dihydroxydiphenylsulfone (hereinafter abbreviated as DHDPS) (50.06 g, 0.20 mol), toluene 100 ml, 1,3-dimethyl-2-imidazolide Non (250.8 g), 40% aqueous potassium hydroxide solution (56.00 g, 0.39 mol) was weighed, and the reaction system was completely purged with nitrogen by passing nitrogen gas with 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, 4,4′-dichlorodiphenylsulfone (hereinafter abbreviated as DCDPS) (57.40 g, 0.20 mol) was added to the reaction system together with 40 g of toluene, and the reaction system 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 (B)) / 0.2 × 100) ), Glass transition temperature (Tg) = 234 ° C., 10% weight loss temperature was 510 ° C. Reduced viscosity was 0.58, chlorophenyl end group / hydroxyphenyl end group measured by 400 MHz ¹ H-NMR. = 50/50 (mol%) Table 1 shows a series of results.

[Reference Example 2] Preparation of PES (B-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 (30.40 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 solution 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 (B-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 terminal, a hydroxyphenyl terminal group, and a t-butyl group near 1.2 ppm as a new peak were confirmed. From this proton area ratio, chlorophenyl terminal group / hydroxyphenyl terminal group / p-tert-butylphenyl terminal = 20/10/70 (mol%).

[Reference Example 4] Method for producing PES having chlorophenyl terminal group (B-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 (30.40 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 solution 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 (B-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 (A) having hydroxyphenyl end group using dihydric phenol (C)>
[Example 1]
PES (B-1) synthesized in Reference Example 1 (5.00 g, 10.7 mmol (5 / 464.53 × 1000) was added to a 100 mL three-necked flask equipped with a nitrogen inlet tube, a thermometer, and a Dean-Stark azeotropic distillation apparatus. DHDPS (0.27 g, 1.07 mmol), anhydrous potassium carbonate (0.15 g, 1.10 mmol), N-methyl-2-pyrrolidone (NMP) 50 ml, toluene 5 ml as a water azeotropic solvent Was weighed. Under a nitrogen flow, the reaction temperature was increased to 150 ° C. while stirring the NMP reaction solution with a rotor, and the reaction was completed in 5 hours while removing water as an azeotrope with toluene. The reaction solution is added dropwise to 500 ml of 0.1% dilute hydrochloric acid to obtain a powdery precipitate, which is further washed twice with 500 ml of water and vacuum-dried at 80 ° C. for 6 hours to obtain a white fine powdery polymer. I got a powder. Yield is 5.1 g, yield is 97.4% (yield is calculated by weight of recovered PES / (weight of charged PES (B-1) + charged DHDPS) × 100), glass transition temperature = 204 ° C., 10% weight The weight loss temperature was 470 ° C., and the reduced viscosity (ηsp / c) was 0.41. ^{In 1} H-NMR, no chlorophenyl end group was confirmed, and PES having a hydroxyphenyl end group composition of 100 mol% was obtained. The alkali metal content was 80 ppm. The results are summarized in Tables 2 and 3.

[Examples 2 and 3]
The same procedure as in Example 1 was performed except that sodium hydroxide and calcium hydroxide were used as the basic compound.

[Examples 4 and 5]
As a dihydric phenol compound, it carried out like Example 1 except having used bisphenol-A and hydroquinone (HQ) instead of DHDPS. The results are shown in Tables 2 and 3.

[Examples 6 to 9]
It was carried out in the same manner as in Example 1, except that the amount of DHDPS and anhydrous potassium carbonate added was changed, and DMSO was used as a solvent in place of NMP instead of NSE and dried overnight or longer. The results are summarized in Tables 2 and 3.

[Examples 10 to 15]
PES (B-2 to B-5) synthesized in Reference Examples 2 to 5 was prepared in a 1 L four-necked flask equipped with a stirrer, a nitrogen introduction tube, a thermometer, and a cooling tube, using the charging compositions shown in Tables 2 and 3. ) Or commercially available PES (Sumitomo Chemical Co., Ltd., Sumika Excel 3600P, 4800P), DHDPS, anhydrous potassium carbonate, 400 ml of dimethyl sulfoxide (DMSO), which has been subjected to a drying treatment for overnight or longer with molecular sieves added to the solvent. 20 ml of toluene was added as a water azeotropic solvent. While stirring the DMSO reaction solution under a nitrogen flow, the reaction temperature was increased to 150 ° C., and the reaction was completed in 5 hours while removing water as an azeotrope with toluene. The reaction solution was added dropwise to 4 l of 0.1% dilute hydrochloric acid to obtain a powdery precipitate, which was further washed twice with 4 l of water and vacuum-dried at 80 ° C. for 6 hours. I got a powder. The results are summarized in Tables 2 and 3.

[Comparative Example 1]
The amount of DHDPS and DCDPS was changed, and DHDPS (62.57 g, 0.25 mol) was used in excess of DCDPS (57.43 g, 0.20 mol) and DHDPS in a 1.25-fold molar excess with respect to 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 38.3 g (yield 41.2%: yield = (38.3 / 464.53 (molecular weight of PES) /0.2×100), glass transition temperature) = 152 ° C., 10% weight loss temperature was 299 ° C. Reduced viscosity was 0.024 dl / g According to 400 MHz ¹ H-NMR, chlorophenyl end group / hydroxyphenyl end group = 41/59 (mol%) ), Softening behavior of the polymer was observed during the reprecipitation, and the remaining amount of alkali metal was 1500 ppm.

[Comparative Example 2]
The charge amount of DHDPS and DCDPS was changed, and DHDPS (75.08 g, 0.30 mol), DCDPS (57.40 g, 0.20 mol), and DHDPS were used in a 1.5-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 Tables 2 and 3.

[Comparative Example 3]
The charge amount of DHDPS and DCDPS was changed, and DHDPS (52.56 g, 0.21 mol), DCDPS (57.40 g, 0.20 mol), and DHDPS were used in a 1.05-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 Tables 2 and 3.

[Comparative Example 4]
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 Tables 2 and 3.

  From Examples 1 to 15, PES (B-1) and a dihydric phenol compound (C) such as DHDPS, bisphenol-A, HQ and the like (basic compounds such as anhydrous potassium carbonate, sodium hydroxide, calcium hydroxide ( E) in the presence of NMP, DMSO and other aprotic polar solvents, depending on the amount of dihydric phenol compound added, regardless of the molecular weight and the terminal group structure of the raw material PES. It can be seen that a phenyl end group can be introduced, a recovery rate is high, and a polymer having a low alkali metal content is obtained.

  From the results of Examples 1 to 3, when sodium hydroxide or calcium hydroxide was used instead of anhydrous potassium carbonate, although a tendency such as a slight decrease in yield and an increase in the amount of residual metal was observed, in any case Also, it can be seen that PES having a high hydroxyphenyl end group content was obtained, the thermal stability and residual alkali metal content were low, and a polymer excellent in thermal stability and polymer purity was obtained.

  From the results of Examples 4 and 5, it was confirmed that similar results were obtained even when bisphenol-A or HQ was used as the dihydric phenol compound instead of DHDPS.

  From the results of Examples 6 to 9, it can be seen that almost the same results can be obtained even when DMSO is used as the reaction solvent instead of NMP. Moreover, it turns out that the hydroxyphenyl terminal group composition and reduced viscosity of obtained PES (A) depend on the quantity of the added dihydric phenol.

Further, 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 a raw material, was observed in Example 7 after the reaction. It can be confirmed that the proton (a) adjacent to the hydroxyl group observed near 6.9 ppm is increased. (See Figure 1)
From the results of Examples 10 to 13, a polymer having a high hydroxyphenyl end group amount can be obtained with high yield and high purity regardless of the molecular weight and the end group structure of PES used as a raw material. I understand that.

  Moreover, even if it uses the commercially available PES manufactured by the conventionally well-known polycondensation method from the result of Examples 14-15, it turns out that the same result is obtained.

  On the other hand, in Comparative Examples 1, 2, and 3 in which the charged molar ratio of DCDPS and DHDP was shifted and polycondensed directly, the amount of hydroxyphenyl end groups was increased by shifting the charged molar ratio. The lowering of the molecular weight due to the shift of the molar ratio was markedly lower than that of 1 to 15. Further, the loss in the recovery process was large, and a remarkable reduction 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, it can be seen that in Comparative Example 4 in which DHDPS was added at the end of the polymerization and end-capping was attempted, the reaction was not particularly progressed as compared with Reference Example 3.

<Production of PES (A) having hydroxyphenyl end group using water (D)>
[Example 16]
PES (B-1) synthesized in Reference Example 1 (50 g, 107 mmol (50 / 464.53 × 1000) was calculated on a 1 L four-necked flask equipped with a stirrer, nitrogen inlet tube, thermometer, and cooling tube (Dimroth). )), Anhydrous potassium carbonate (2.8 g, 20.2 mmol), DMSO (400 ml) dehydrated with molecular sieves overnight or more, and water (2.7 g, 150 mmol) were weighed, and DMSO under nitrogen flow While stirring the reaction solution, 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% acid methanol, and the precipitated powder was added with 4 l of water. Washed twice and dried in vacuum at 80 ° C. for 6 hours. The obtained polymer powder is in the form of a white powder, the yield is 51.6 g, the yield is 98% (the yield is calculated by the weight of recovered PES / charged PES (B-1) × 100), glass transition temperature = 207 ° C. The 10% weight loss temperature was 510 ° C., and the reduced viscosity (ηsp / c) was 0.50. By 400 MHz ¹ H-NMR, PES of chlorophenyl end group / hydroxyphenyl end group = 33/67 (mol%) was obtained. The alkali metal content was 20 ppm. The results are shown in Tables 4 and 5.

[Examples 17 and 18]
It implemented like Example 16 except having changed the addition amount of water and anhydrous potassium carbonate. The results are shown in Tables 4 and 5.

[Examples 19 to 22]
The raw material PES (B) was changed to the PES (B-2 to B-5) synthesized in Reference Examples 2 to 5, and the addition amounts of water and anhydrous potassium carbonate were changed, as in Example 16. Carried out. The results are shown in Tables 4 and 5.

[Example 23]
The raw material PES (B) was used in the same manner as in Examples 19 to 22, except that a commercially available PES (manufactured by Sumitomo Chemical Co., Ltd., SUMIKAEXCEL 3600P) was used, and NMP was used instead of DMSO as a reaction solvent. The results are shown in Tables 4 and 5.

[Example 24]
The raw material PES (B) was used in the same manner as in Example 23 except that a commercially available PES (Sumitomo Chemical Co., Sumika Excel 4800P) was used and the reaction temperature was 180 ° C. The results are shown in Tables 4 and 5.

[Example 25]
The raw material PES (B) was changed to DMSO, which was a commercially available PES (Sumitomo Chemical Co., Sumika Excel 4800P), and the amount of water and anhydrous potassium carbonate added and the solvent was dehydrated over a molecular sieve overnight. Were carried out in the same manner as in Example 16. The results are shown in Tables 4 and 5.

[Comparative Example 5]
PES (B-1) synthesized in Reference Example 1 (5.0 g, 10.7 mmol (5 / 464.53) was added to a 100 mL four-necked flask equipped with a stirrer, a nitrogen introducing tube, a thermometer, and a cooling tube (Dimroth). × 1000))) and water (1.35 g, 75.0 mmol), 50 ml of N-methyl-2-pyrrolidone (NMP) are weighed, and the reaction temperature is increased to 150 ° C. while stirring the NMP reaction solution. The reaction was completed in 5 hours, and the reaction solution was added dropwise to 500 ml of 0.1% acid methanol, and the precipitate was washed twice with 500 ml of water and once with 500 ml of methanol. The resultant was vacuum-dried at 6 ° C for 6 hours to obtain a white powdery polymer. The results are shown in Tables 4 and 5.

[Comparative Example 6]
It implemented by the method similar to the comparative example 5 except not adding water and adding anhydrous potassium carbonate (0.70 g, 5.06 mmol). The results are shown in Tables 4 and 5.

  From Examples 16 to 25, by reacting PES (B), water (D), and basic compound (E) in an aprotic polar solvent, a hydroxyphenyl end group was introduced according to the amount of water added. It can be seen that a polymer with a high recovery rate and a low alkali metal content can be obtained.

  From the results of Examples 16 to 18, it is understood that the hydroxyphenyl terminal and the reduced viscosity depend on the amount of added water.

Further, 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 a raw material, was found in Example 17 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 2)
From the results of Examples 19 to 22, 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. I understand that.

  From the results of Example 23, it can be seen that even if NMP is used instead of DMSO as the reaction solvent, almost equivalent results can be obtained.

  From the results of Example 24, it can be seen that the reactivity tends to improve as the reaction temperature increases.

  From the results of Example 25, it can be seen that even when a commercially available PES produced by a generally known polycondensation method is used, a hydroxyphenyl end group can be similarly introduced according to the amount of water added.

  On the other hand, from the results of Comparative Examples 5 and 6, it can be seen that the reaction does not proceed at all when water or a basic compound is not added.

<Alloyation of PES (A) having a hydroxyphenyl end group and a thermoplastic resin>
[Examples 26 to 28, Comparative Examples 7 to 9]
The following three types of polymers were used as thermoplastic resins for alloys.
Polyethylene terephthalate resin (T704T manufactured by Toray) with Tm = 255 ° C., Tmc = 178 ° C., intrinsic viscosity 1.15 (phenol / tetrachloroethane = 5/5 (V / V), 25 ° C.) (hereinafter abbreviated as PET)
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 6, various PES 5 g synthesized in Example 10 and Reference Example 1 and 45 g of the thermoplastic resin 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.

  Although a series of results are shown in Table 6, from the alloying examination results of Examples 26 to 28 and Comparative Examples 7 to 9, PES (A) 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 (A) having a hydroxyphenyl end group and a thermosetting resin>
[Examples 29 and 30, Comparative Example 10] (Alloying with thermosetting resin)
Tetraglycidyldiaminodiphenylmethane (Epikote 604) (manufactured by Japan Epoxy Resin Co., Ltd.) as an epoxy resin, the PES synthesized in Examples 15 and 17, 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 7, and a defoaming kneader (manufactured by Shinky Corporation: 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 26 to 28. The results are shown in Table 7.

  The epoxy resin cured product using the PES having hydroxyphenyl end groups obtained in Examples 29 and 30 was more in the epoxy resin than the PES containing no hydroxyphenyl end groups of Comparative Example 10. It can be seen that it is finely dispersed.

  The results of observing the cross section of the obtained epoxy resin composition with a transmission electron microscope are shown in FIG. 3 (Comparative Example 10 using 0% PES: hydroxyphenyl group in Reference Example 7) and FIG. 4 (Example 15). PES: Example 29 using 82% hydroxyphenyl groups) and FIG. 5 (Example 30 using 92% PES: hydroxyphenyl groups in Example 17).

  In Comparative Example 10 in which PES having no hydroxyphenyl terminal was kneaded, it was not dispersed and phase separation was observed, whereas in Examples 29 and 30, it was found that the dispersion was finely dispersed at 10 nm or less. .

It is a figure which shows the NMR chart of PES obtained by the reference example 1, and PES obtained by Example 7. FIG. It is a figure which shows the NMR chart of PES obtained by the reference example 1, and PES obtained by Example 17. FIG. 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 29. It is a figure which shows the transmission electron micrograph of the cross section of the epoxy resin composition obtained in Example 30.

Claims (10)

It has a structure represented by general formula (a-1) and / or general formula (a-2) and has a hydroxyphenyl terminal group ratio (%) (determined by ¹ H-NMR in deuterated dimethyl sulfoxide. , [6.9 ppm peak area ratio (hydroxyphenyl end group) / (6.9 ppm peak area (derived from hydroxyphenyl end group) +7.7 ppm peak area (derived from chlorophenyl end group))] × 100 Aromatic polyethersulfone (A) having a reduced viscosity of not less than 0.07 and not more than 0.45 measured in a DMF solvent at 25 ° C. and 1 g / dl using a capillary viscometer. .

(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 . The aromatic polyether sulfone (A) according to claim 1, wherein the hydroxyphenyl terminal group ratio (%) is 70% or more. The aromatic polyethersulfone (A) according to any one of claims 1 and 2, wherein the hydroxyphenyl terminal group ratio (%) is 80% or more. Aromatic polyethersulfone (B) having a structure represented by general formula (b-1) and / or (b-2), and represented by general formula (c-1) and / or (c-2) The dihydric phenol compound (C) and / or water (D) and the basic compound (E) obtained by heating at 200 ° C. or less in an aprotic polar solvent. A process for producing the aromatic polyethersulfone (A) according to 1.

5. The aromatic polysulfone according to claim 4, wherein the addition amount of the dihydric phenol compound (C) is 0.01 to 0.5 times mol per mol of the aromatic polyether sulfone (B). A process for producing ethersulfone (A). The method for producing a polyethersulfone (A) according to any one of claims 4 and 5, wherein the dihydric phenol compound (C) is bisphenol-A or bisphenol S. 5. The aromatic having a hydroxyphenyl end group according to claim 4, wherein the addition amount of water (D) is 0.1 to 30 times mol for 1 mol of the aromatic polyethersulfone (B). A process for producing polyethersulfone (A). The basic polyether (E) is at least one selected from sodium carbonate, potassium carbonate, anhydrous sodium carbonate and anhydrous potassium carbonate. Production of aromatic polyethersulfone (A) according to any one of claims 4 to 7. Method. The raw material aromatic polyethersulfone (B) 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 (hydroxyphenyl 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 (A) of any one of Claims. The raw material aromatic polyethersulfone (B) has a hydroxyphenyl end group composition of 10 mol% or less (measured by ¹ H-NMR in deuterated dimethyl sulfoxide, [6.9 ppm peak area (hydroxyphenyl 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 (A) of any one of Claims.

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