JP2003192785A - Manufacturing method of arylene ether polymer having sulfoalkoxy group - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of a new arylene ether polymer having a useful sulfoalkoxy group as a polymer material having both thermal resistance and an electric characteristic. <P>SOLUTION: The manufacturing method of a new arylene ether polymer comprises: reacting an arylene ether polymer having a hydroxy group containing a structural unit represented by general formula (1) (wherein R<SP>1</SP>is a 1-6C alkyl group or 6-10C aryl group; a is an integer of 1-4; b is an integer of 0-3; and a+b≤4) with an alkali metal compound and/or an amine compound to generate an alkali metal salt and/or an amine salt before reacting the salt with a sulfonating agent and further an acid. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a novel arylene ether polymer. The arylene ether polymer of the present invention is useful as a polymer material having both heat resistance and electrical characteristics.

[0002]

2. Description of the Related Art Conventionally, arylene ether polymers have been used in various fields as engineering plastics having high heat resistance and high chemical resistance. However, although the arylene ether polymer is excellent in heat resistance and chemical resistance, it is an electrically insulating substance and cannot conduct electricity.
In recent years, highly functional polymer materials having high heat resistance, high chemical resistance, and electrical conductivity have been demanded. As a method of imparting conductivity, introduction of a functional group capable of ion exchange has been attempted. Polymer. Sc
i. , Polym. Chem. Ed. , Vol. 22,
721 (1984) discloses a polyarylene ether sulfone having a sulfo group in which a sulfo group is directly bonded to an aromatic ring.

[0003]

However, since the sulfo group is directly bonded to the aromatic ring in this method, there is a concern that the sulfo group may be eliminated under a specific high temperature condition. The present invention has been made in view of the above problems, and an object thereof is to provide a method for producing a novel arylene ether polymer having a sulfoalkoxy group useful as a polymer material having both heat resistance and electrical properties. is there.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have reacted an arylene ether polymer having a hydroxy group with an alkali metal compound and / or an amine compound, It was found that when an alkali metal salt and / or an amine salt is formed, then reacted with a sulfonating agent and further reacted with an acid, a hydroxy group is converted into a sulfoalkoxy group with high efficiency, and the present invention was completed. It was

That is, the present invention provides the following general formula (1)

[0006]

[Chemical 3] (In the formula, R ¹ is an alkyl group having 1 to 6 carbon atoms or 6 carbon atoms.
-10 is an aryl group, a is an integer of 1-4,
b is an integer of 0 to 3, and a + b ≦ 4. ) An arylene ether polymer having a hydroxy group containing a structural unit represented by the formula (1) is reacted with an alkali metal compound and / or an amine compound to form an alkali metal salt and / or an amine salt, and then reacted with a sulfonating agent. And an arylene ether polymer having a sulfoalkoxy group, which further reacts with an acid.

In the general formula (1), R ¹ has 1 to ¹ carbon atoms.
6 represents an alkyl group having 6 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms. The alkyl group having 1 to 6 carbon atoms is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. The aryl group having 6 to 10 carbon atoms is not particularly limited, and examples thereof include phenyl group, naphthyl group, methylphenyl group, ethylphenyl group, propylphenyl group, butylphenyl group, dimethylphenyl group, diethylphenyl group. Groups and the like. Of these, an alkyl group having 1 to 6 carbon atoms is preferably used, and a methyl group is more preferably used because it is easy to handle.

Among the structural units represented by the general formula (1) of the present invention, the following general formula (3)

[0009]

[Chemical 4] An arylene ether polymer having a hydroxy group having a structural unit represented by is particularly preferably used because it is easily available and easy to handle.

The arylene ether polymer having a hydroxy group used in the present invention may be a homopolymer or a copolymer as long as it contains the structural unit represented by the above general formula (1).

The copolymer is not particularly limited as long as it contains the structural unit represented by the general formula (1). For example, the structural unit represented by the general formula (1) and the following: General formula (2)

[0012]

[Chemical 5] (In the formula, A represents one or more selected from the group consisting of an arylene group, an alkylene group and a silylene group, B represents O,
It represents one or more selected from the group consisting of S and C = O. A copolymer having a structural unit represented by the formula (1) and the like are preferable because the water resistance and mechanical strength can be improved in the arylene ether polymer having a sulfoalkoxy group produced by the method of the present invention.

In the general formula (2), A represents at least one selected from the group consisting of an arylene group, an alkylene group and a silylene group. The arylene group is not particularly limited, and includes, for example, the following general formula (4)

[0014]

[Chemical 6] (In the formula, R ² represents one or more selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group and a phenyl group, and C is an integer of 1 to 4.) And an arylene group having a structural unit represented by the following general formulas (5) to (10)

[0015]

[Chemical 7]

[Chemical 8]

[Chemical 9]

[Chemical 10]

[Chemical 11]

[Chemical 12] And an arylene group having a structural unit represented by. The alkylene group is not particularly limited, and examples thereof include a methylene group, an ethylene group, a propylene group, a methylpropylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group and a nonene group. Moreover, the silylene group is not particularly limited, and examples thereof include a dimethylsilylene group and a diphenylsilylene group. Of these, an arylene group is preferably used, and more preferably 2,6-dimethyl-1, since the raw materials are easily available and easy to handle.
A 4-phenylene group is used.

The method for producing the arylene ether polymer having a hydroxy group used in the present invention is not particularly limited, and for example, commercially available 3-methylcatechol can be used as the 50th (2001) polymer. Debate: Proceedings of the Society of Polymer Science, IIPf008, and Journal
of Photopolymer and Techn
ology: 1999, Volume12, Number
By the method reported in r2,353-358,
After protecting one of the hydroxy groups with a protecting group, the protected 3-methylcatechol is oxidatively polymerized to prepare an arylene ether polymer with one of the hydroxy groups protected by the protecting group. It is possible to prepare an arylene ether polymer having a hydroxy group by reacting with an acid.

The alkali metal compound used in the method of the present invention is not particularly limited as long as it can convert a hydroxy group into an alkali metal salt, and examples thereof include sodium methoxide, sodium ethoxide and potassium. Methoxide, potassium ethoxide, lithium-te
Alkali metal alkoxides such as rt-butoxide, sodium-tert-butoxide, potassium-tert-butoxide; lithium hydride, sodium hydride,
Alkali metal hydrides such as potassium hydride; Alkali metals such as sodium and potassium; Organic alkali metals such as methyllithium and butyllithium; Alkali metal amides such as lithium amide and sodium amide; Sodium hydroxide and hydroxide Examples thereof include alkali metal hydroxides such as potassium; alkali metal carbonates such as sodium carbonate and potassium carbonate. The amine compound is not particularly limited as long as it can convert a hydroxy group into an amine salt, and examples thereof include trimethylamine, triethylamine, pyridine, lutidine and toluidine. These alkali metal compounds and amine compounds can be used not only alone but also as a mixture of two or more kinds.

Of these, the conversion to the alkali metal salt can be carried out efficiently and, in addition, the handleability is excellent,
Alkali metal alkoxides are preferably used, and more preferably sodium methoxide is used.

The amount of the alkali metal compound or amine compound used is not particularly limited, and the conversion to the alkali metal salt or amine salt can be carried out efficiently, so that the hydroxy group contained in the arylene ether polymer having a hydroxy group as a raw material can be efficiently used. The amount is 0.1 to 100 equivalents, preferably 0.5 to 20 equivalents, and more preferably 1 to 10 equivalents, relative to 1 mol of the group.

The sulfonating agent is not particularly limited as long as it can efficiently perform sulfonation, and for example, 1,3-propanesartone, 1,4
-Butane sultone, 1,5-pentane sultone, 1-methyl-1,3-propane sultone, 1-ethyl-1,3
-Propane sultone, 1-propyl-1,3-propane sultone, 1-butyl-1,3-propane sultone, 1
-Methyl-1,4-butanesultone, 1-ethyl-1,
Alkyl sultones having a cyclic ester structure of sulfonic acid such as 4-butane sultone and 1-octyl-1,4-butane sultone; sodium chloromethane sulfonate, sodium bromomethane sulfonate, sodium chloroethane sulfonate, sodium bromoethane sulfonate ,
Sodium chloropropanesulfonate, sodium bromopropanesulfonate, methyl chloromethanesulfonate, methyl bromomethanesulfonate, methyl chloroethanesulfonate, methyl bromoethanesulfonate, ethyl chloromethanesulfonate, ethyl bromomethanesulfonate, ethyl chloroethanesulfonate And sulfoalkyl halides such as ethyl bromoethanesulfonate, trimethylammonium bromomethanesulfonate, trimethylammonium chloroethanesulfonate, and trimethylammonium bromoethanesulfonate. These sulfonating agents can be used not only alone but also as a mixture of two or more kinds.

Of these, alkyl sultone is preferably used because it is easily available and easy to handle.
More preferably, 1,3-propane sultone or 1,4-butane sultone is used.

The amount of sulfonating agent used is not particularly limited,
Since sulfonation can be carried out efficiently, it is 0.1 to 1,000 equivalents, preferably 0.5 to 100 equivalents, relative to 1 mol of hydroxy groups contained in the arylene ether polymer having a hydroxy group as a raw material. It is equivalent, more preferably 1 to 50 equivalent.

The acid is not particularly limited as long as a sulfo group can be efficiently produced. For example, mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid; trichloroacetic acid, trifluoroacetic acid. Acetic acids such as acetic acid; methanesulfonic acids such as trifluoromethanesulfonic acid and methanesulfonic acid; solid acids such as zeolite, silica-alumina, alumina, and heteropolyacid; strongly acidic ion-exchange resins. These acids can be used not only alone but also as a mixture of two or more kinds. Of these, mineral acids are preferably used, and hydrochloric acid is more preferably used because they are easy to handle.

The amount of the acid used is not particularly limited, and is 0.1 to 1,000 equivalents, preferably 0.5 to 1 mol, relative to 1 mol of the sulfonating agent since the sulfo group is efficiently formed.
It is 100 equivalents, more preferably 1 to 20 equivalents.

Here, the reaction of the arylene ether polymer having a hydroxy group with an alkali metal compound and / or an amine compound to form an alkali metal salt and / or an amine salt, followed by a reaction with a sulfonating agent, Each reaction of the reaction with an acid is usually preferably performed in a solvent. The solvent is not particularly limited as long as it does not significantly inhibit the respective reactions, and is not particularly limited. For example, aromatic hydrocarbons such as benzene, toluene, xylene; methanol, ethanol, n
Alcohols such as -propanol, iso-propanol, n-butanol, tert-butanol, n-pentanol, n-hexanol, cyclohexanol, octanol; ethers such as ether, tetrahydrofuran, dioxane, diglyme, triglyme; N, N
-Nitrogen-containing hydrocarbons such as dimethylformamide, hexamethylphosphoryltriamide; dimethylsulfoxide,
Sulfur-containing hydrocarbons such as sulfolane; water and the like. These solvents may be used alone or in combination of two or more.

Then, a reaction of reacting with an alkali metal compound and / or an amine compound to form an alkali metal salt and / or an amine salt, followed by a reaction with a sulfonating agent,
The solvent in the subsequent reaction with the acid does not necessarily have to be the same.

In the reaction of reacting with an alkali metal compound and / or an amine compound to form an alkali metal salt and / or an amine salt and the subsequent reaction with a sulfonating agent, a high reaction efficiency can be obtained, and therefore an ether can be obtained. Mixtures of compounds and alcohols are preferably used, more preferably mixtures of tetrahydrofuran and methanol.

In the reaction with an acid, ethers or water are preferably used, more preferably tetrahydrofuran or water, since high reaction efficiency is obtained.

The concentration of the arylene ether polymer having a hydroxy group used in the present invention depends on the respective reaction, that is, the reaction of reacting with an alkali metal compound and / or an amine compound to form an alkali metal salt and / or an amine salt. Since it becomes possible to efficiently perform the subsequent reaction with the sulfonating agent or the acid, it is preferable that each solvent be 0.1 to 1,0.
00 mmol / l, more preferably 1 to 100
It is mmol / l.

The temperature in the reaction for reacting the polyarylene ether sulfone having a hydroxy group with the alkali metal compound and / or amine compound to form the alkali metal salt and / or amine salt is not particularly limited, and for example, -1
The temperature is from 00 to 150 ° C, preferably from -20 to 80 ° C. The reaction pressure is not particularly limited and is usually 0.001 in absolute pressure.
~ 3 MPa, preferably 0.01-0.3 MPa
Is. The reaction time depends on the temperature and the polymer concentration, and is not generally determined, but is usually 5 minutes to 500 hours. The atmosphere during the reaction is not particularly limited, and for example, nitrogen, argon, helium and the like are preferably used. This reaction can be carried out in a batch system, a semi-batch system, or a continuous system.

The temperature in the subsequent reaction with the sulfonating agent is not particularly limited and is, for example, -20 to 100 ° C, preferably 0 to 80 ° C. The reaction pressure is not particularly limited and is usually 0.001 to 3 MPa in absolute pressure, preferably 0.01 to 0.3 MPa. The reaction time depends on the temperature and the polymer concentration and cannot be determined unconditionally, and is usually 5 minutes to 500 hours. The atmosphere during the reaction is not particularly limited, and for example, nitrogen, argon, helium, etc. are preferably used. This reaction can be carried out in a batch system, a semi-batch system, or a continuous system.

The temperature in the subsequent reaction with acid is not particularly limited and is, for example, −80 to 150 ° C., preferably −
It is 20-80 degreeC. The reaction pressure is not particularly limited and is usually 0.001 to 3 MPa in absolute pressure, preferably 0.01 to 0.3 MPa. Further, the reaction time depends on the temperature and the polymer concentration and cannot be determined unconditionally, and is usually 1 minute to 500 hours. The atmosphere during the reaction is not particularly limited, and for example, nitrogen, argon, helium, etc. are preferably used. This reaction can be carried out in a batch system, a semi-batch system, or a continuous system.

The arylene ether polymer having a sulfoalkoxy group obtained in the present invention can be separated from the reaction solution by a known reprecipitation method.

The arylene ether polymer having a sulfoalkoxy group produced by the method of the present invention is characterized in that the sulfoalkoxy group is bonded to the aromatic ring of the main chain contained in the arylene ether polymer. , The following general formula (11)

[0035]

[Chemical 13] (In the formula, R ³ is an alkyl group having 1 to 6 carbon atoms or 6 carbon atoms.
10 represents an aryl group, R ⁴ represents an alkylene group having 1 to 10 carbon atoms, d is an integer of 1 to 4, and e is 0 to
It is an integer of 3 and d + e ≦ 4. And an arylene ether polymer having a sulfoalkoxy group containing a structural unit represented by the formula (1) in the main chain.

The polyarylene ether sulfone having a sulfoalkoxy group produced by the method of the present invention has excellent heat resistance, high solubility in a solvent and excellent handleability, and therefore has a number average molecular weight in terms of pullulan of 500 to 50.
It is preferably 50,000, particularly 2,000 to 1
It is preferably 0,000. The number average molecular weight as used herein can be measured, for example, by dissolving the arylene ether polymer having a sulfoalkoxy group of the present invention in dimethyl sulfoxide, and injecting this solution into gel permeation chromatography at room temperature.

The arylene ether polymer having a sulfoalkoxy group obtained in the present invention can be used alone as a polymer material, but fillers such as glass fiber, carbon fiber, talc, calcium carbonate and mica; various pigments; oxidation. It can be used by mixing with various stabilizers such as an inhibitor and a light stabilizer. Also, general-purpose resins such as polyethylene, polyvinyl chloride and polystyrene; engineering plastics such as polypropylene and modified polyphenylene ether; alloy blending with super engineering plastics such as polyphenylene sulfide, polyphenylene sulfide ketone, polyimide, polyether imide and liquid crystal polymer It can also be used.

[0038]

EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited to these examples.

The measuring methods used in the examples are shown below. < ¹ H-NMR measurement> The measurement was performed using a nuclear magnetic resonance apparatus (manufactured by JEOL Ltd., trade name JNMGX400). <Molecular weight measurement> For gel permeation chromatography (hereinafter, referred to as GPC) measurement, a high-speed GPC device (manufactured by Tosoh Corp., trade name HLC8220GPC) was used under the following conditions. That is, the polymer was dissolved in a lithium chloride / dimethylsulfoxide solution, the concentration of the polymer solution was adjusted to 1 g / l, 20 μl of the polymer solution was injected into the GPC device, and pullulan was used as a standard sample to calculate the weight average molecular weight in terms of pullulan. (Mw) and number average molecular weight (Mn) were measured.

The molecular weight distribution (Mw / Mn) is represented by a value obtained by dividing the weight average molecular weight (Mw) by the number average molecular weight (Mn). However, when it was not suitable to use pullulan as a standard sample, polystyrene was used as a standard sample and the weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured as polystyrene conversion values. Synthesis Example 1 (Synthesis of 2-triisopropylsilyloxy-6-methylphenol) 500 ml of 3-methylcatechol (manufactured by Tokyo Kasei)
Was placed in a three-necked flask, and this was dissolved in 120 ml of methylene chloride. Then, 5.5 ml of triethylamine (manufactured by Tokyo Kasei) was added. After adding 12.7 ml of triisopropylsilyl chloride (manufactured by Tokyo Kasei) to this solution, the mixture was stirred at room temperature for 12 hours. Ether was added to the reaction solution, and the mixture was washed with a 0.2% aqueous hydrochloric acid solution, and after separating into two phases, the ether layer was separated. The ether solution was dried over anhydrous magnesium sulfate, the solvent was distilled off with an evaporator, and then purified by distillation to obtain 2.3 g of 2-triisopropylsilyloxy-6-methylphenol (yield 21%).

As a result of ¹ H-NMR measurement (chloroform-d solvent), a triplet peak based on a triisopropylsilyloxy group was observed at δ1.0 to 1.5 ppm, and a singlet peak based on a methyl group was obtained at δ2.5 ppm. , Δ6.5, a peak of a singlet based on a hydroxy group and a peak of a multiplet based on an aromatic ring at δ6.6 to 7.0 ppm were observed.

Synthesis Example 2 (Synthesis of (2-hydroxy-6-methyl-1,4-phenylene ether) Polymer) 0.1 g of cuprous chloride was placed in a 100 ml three-necked flask, and 50 ml of toluene and 50 ml of toluene were added thereto. It was dissolved in 19 ml of pyridine. This solution is vigorously stirred under oxygen flow,
The catalyst solution was prepared. In a separate flask, 1.4 g of 2-triisopropylsilyloxy-6-methylphenol obtained in Synthesis Example 1 was dissolved in 30 ml of toluene. This solution was added dropwise to the catalyst solution and stirred at room temperature for 48 hours. After completion of the reaction, the reaction solution was poured into a 1% hydrochloric acid aqueous solution,
The polymer was precipitated. Wash the polymer thoroughly with water,
The mixture was left under a nitrogen stream overnight and further dried under vacuum for 5 hours to give 0.49 g of (2-hydroxy-6-methyl-1,4-phenylene ether) polymer (yield 35%).
Obtained.

As a result of ¹ H-NMR (dimethyl sulfoxide (hereinafter abbreviated as DMSO) -d6 solvent) measurement, δ
A singlet peak based on a methyl group was observed at 2.0 ppm, a multiplet peak based on an aromatic ring was observed at δ 6.0 to 6.7 ppm, and a multiplet peak based on a hydroxy group was observed at δ 9.5 ppm. ¹ H-NMR
The number of hydroxy groups determined from the measurement results was 8.2 per polymer weight (kg). Further, the number average molecular weight determined from GPC measurement (chloroform) was 5,700 (in terms of polystyrene), and the molecular weight distribution was 1.3.

Synthesis Example 3 (2- (tetrahydropyran-2
-Yl) Synthesis of oxy-6-methylphenol) 500 g of 3-methylcatechol (manufactured by Tokyo Kasei)
It was put into a 3-neck flask of 1 l and this was dissolved in 120 ml of toluene. 18 ml of 3,4-dihydro-2H-pyran (manufactured by Tokyo Kasei) was added, and the mixture was cooled to 0 ° C. After adding 0.25 g of p-toluenesulfonic acid pyridine salt to this solution, the mixture was stirred. After 30 minutes, 3,4-dihydro-2H
-36 ml of pyran, then 0.25 g of p-toluenesulfonic acid pyridine salt, and 50 ml of toluene,
Stirring was continued for 2 hours to complete the reaction. Ether was added to the reaction solution, washed with a 0.2% sodium hydroxide aqueous solution, and then separated into two phases to separate an ether layer. After the ether solution was dried over anhydrous magnesium sulfate, the solution was injected into column chromatography (filler; trade name Wakogel, eluent: toluene) to give 2- (tetrahydropyran-2-yl) oxy-6-methylphenol. The toluene solution containing was separated. 2- (Tetrahydropyran-2-yl) oxy-6 was obtained by distilling toluene off using an evaporator and further drying under reduced pressure.
-17.5 g (yield 21%) of methylphenol was obtained.

As a result of ¹ H-NMR measurement (chloroform-d solvent), a multiplet peak based on a pyran ring was observed at δ1.6 to 2.0 ppm, a singlet peak based on a methyl group was obtained at δ2.5 ppm, and δ3. 6-3.
7 ppm, δ3.9-4.1 ppm, and δ5.1-
A peak of a pyran ring-based multiplet was observed at 5.2 ppm, a peak of a hydroxy group-based singlet at δ 6.5 ppm, and a peak of an aromatic ring-based multiplet at δ 6.6 to 7.0 ppm.

Synthesis Example 4 (Synthesis of (2-hydroxy-6-methyl-1,4-phenylene ether)-(2,6-dimethyl-1,4-phenylene ether) copolymer) 200 ml three-necked flask 0.3 g of cuprous chloride was put in and dissolved in 50 ml of toluene and 10 ml of pyridine. This solution is vigorously stirred under oxygen flow,
The catalyst solution was prepared. 2- (tetrahydropyran-2-yl) oxy-6 obtained in Synthesis Example 3 was placed in a separate flask.
6 g of -methylphenol and 3.7 g of 2,6-dimethylphenol were dissolved in 50 ml of toluene. This solution was added to the catalyst solution, then 8 g of anhydrous sodium sulfate was added, and the mixture was stirred at room temperature for 2 hours. After completion of the reaction, this reaction solution was poured into methanol to precipitate a solid. After this polymer was separated by filtration, it was dried under reduced pressure. This solid was dissolved in tetrahydrofuran and poured into a 1% aqueous hydrochloric acid solution to precipitate a polymer. The polymer was washed thoroughly with water, placed under a stream of nitrogen overnight, and dried under vacuum for 6 hours to give (2-hydroxy-6-methyl-1,4-phenylene ether)-(2,6 6.1 g (yield 63%) of a (dimethyl-1,4-phenylene ether) copolymer was obtained.

As a result of ¹ H-NMR (DMSO-d6 solvent) measurement, a peak of a singlet based on a methyl group at δ 2.0 ppm, a peak of a multiplet based on an aromatic ring at δ 6.0 to 6.6 ppm, and δ 9.5 ppm. A multiplet peak based on the hydroxy group was observed at. ¹
The number of hydroxy groups determined from the 1 H-NMR measurement result was 4.1 per polymer weight (kg). The ratio of the 2-hydroxy-6-methyl-1,4-phenylene ether group to the 2,6-dimethyl-1,4-phenylene ether group was 1.0. The number average molecular weight determined from GPC measurement (THF) was 10,000 (in terms of polystyrene), and the molecular weight distribution was 2.8.

Example 1 (2-hydroxy-6-methyl-obtained in Synthesis Example 2)
1,4-phenylene ether) polymer 0.30 g 20
It was put in a 0 ml three-necked flask and dissolved in 50 ml of tetrahydrofuran. Then 2.2 mol / l
After adding 5.7 ml of a methanol solution of sodium methoxide of 1., the mixture was stirred at room temperature for 1 hour. 1,3 in this suspension
-Propane sartone 0.92g was added, and it was made to stir at room temperature for 12 hours. Further, 15 ml of a 0.6 mol / l hydrochloric acid aqueous solution was added to this suspension to obtain a uniform solution. After completion of the reaction, this homogeneous solution was added to hexane (50 ml) to generate a precipitate. The precipitate was filtered off and then vacuum dried at 100 ° C. for 3 hours to obtain 0.21 g of (2-sulfopropoxy-6-methyl-1,4-phenylene ether) polymer (yield 35%). .

As a result of ¹ H-NMR (DMSO-d6 solvent) measurement, at δ 1.8 ppm, a broad peak due to the central methylene group of the propylene group, at δ 2.0 ppm at a singlet peak due to a methyl group, and at δ 2.4 ppm. Broad peak due to the methylene group next to the sulfo group,
A broad peak due to the methylene group adjacent to the ether group was observed at δ 4.0 ppm, and a multiplet peak due to the aromatic ring was observed at δ 6.0 to 6.6 ppm. Note that ¹
The number of sulfopropoxy groups determined from 1 H-NMR measurement was 4.1 per polymer weight (kg). Also, GP
The number average molecular weight determined from C measurement (DMSO) is 8,50.
The molecular weight distribution was 0 (pullulan conversion) and 2.7.

Example 2 (2-hydroxy-6-methyl-obtained in Synthesis Example 4)
1,4-phenylene ether)-(2,6-dimethyl-
0.50 g of 1,4-phenylene ether) copolymer was added to 2
It was put in a 00 ml three-necked flask and dissolved in 100 ml of tetrahydrofuran. Then 2.2 mol
/ L sodium methoxide methanol solution 4.8m
After adding l, the mixture was stirred at room temperature for 1 hour. 1.3 g of 1,3-propanesultone was added to this suspension, and the mixture was stirred at room temperature for 12 hours.
Allowed to stir for hours. Furthermore, in this suspension, 0.6 mol / l
15 ml of a hydrochloric acid aqueous solution was added to obtain a uniform solution. After completion of the reaction, this homogeneous solution was added to hexane (50 ml) to generate a precipitate. After separating this precipitate by filtration,
After vacuum drying for 0.3 hours, 0.33 g of (2-sulfopropoxy-6-methyl-1,4-phenylene ether)-(2,6-dimethyl-1,4-phenylene ether) copolymer was obtained (yield). Rate 43%).

As a result of ¹ H-NMR (DMSO-d6 solvent) measurement, at δ 1.8 ppm, a broad peak due to the central methylene group of the propylene group, at δ 2.0 ppm at a singlet peak due to a methyl group, and at δ 2.4 ppm. Broad peak due to the methylene group next to the sulfo group,
A broad peak due to the methylene group adjacent to the ether group was observed at δ 4.0 ppm, and a multiplet peak due to the aromatic ring was observed at δ 6.0 to 6.6 ppm. Note that ¹
The number of sulfopropoxy groups determined by 1 H-NMR measurement was 2.7 per polymer weight (kg). Also, GP
The number average molecular weight obtained from C measurement (DMSO) is 13,0.
00, the molecular weight distribution was 1.9.

[0052]

INDUSTRIAL APPLICABILITY The present invention provides an efficient method for producing a novel arylene ether polymer which is useful as a polymer material having both heat resistance and electric characteristics, and is industrially very significant. .

Claims (7)

[Claims] 1. The following general formula (1): (In the formula, R ¹ is an alkyl group having 1 to 6 carbon atoms or 6 carbon atoms.
-10 is an aryl group, a is an integer of 1-4,
b is an integer of 0 to 3, and a + b ≦ 4. ) An arylene ether polymer having a hydroxy group containing a structural unit represented by the formula (1) is reacted with an alkali metal compound and / or an amine compound to form an alkali metal salt and / or an amine salt, and then reacted with a sulfonating agent. And further reacting with an acid, a method for producing an arylene ether polymer having a sulfoalkoxy group. 2. The production of an arylene ether polymer having a sulfoalkoxy group according to claim 1, wherein the arylene ether polymer having a hydroxy group consists only of the structural unit represented by the general formula (1). Method. 3. In the general formula (1), a is 1 and b is 1.
Wherein R ¹ is a methyl group, and the method for producing an arylene ether polymer having a sulfoalkoxy group according to claim 1 or 2. 4. An arylene ether polymer having a hydroxy group is a structural unit represented by the general formula (1) and the following general formula (2): (In the formula, A represents one or more selected from the group consisting of an arylene group, an alkylene group and a silylene group, B represents O,
It represents one or more selected from the group consisting of S and C = O. The method for producing an arylene ether polymer having a sulfoalkoxy group according to claim 1, wherein the copolymer has a structural unit represented by the formula (1). 5. The arylene ether polymer having a sulfoalkoxy group according to claim 1, wherein A is a 2,6-dimethyl-1,4-phenylene group. Manufacturing method. 6. An arylene ether polymer having a hydroxy group is a (2-hydroxy-6-methyl-1,4-phenylene ether)-(2,6-dimethyl-1,4-phenylene ether) copolymer. The method for producing an arylene ether polymer having a sulfoalkoxy group according to any one of claims 1, 4 and 5. 7. The method for producing a polyarylene ether sulfone having a sulfoalkoxy group according to any one of claims 1 to 6, wherein alkyl sultone is used as the sulfonating agent.