JP5023426B2 - Method for producing polyarylene polymer - Google Patents

Description

  The present invention relates to a method for producing a polyarylene polymer such as a polyarylene ether or polyarylene sulfide. More specifically, the present invention relates to a method for producing a polymer by using an aromatic dihalogen compound and a dihydric phenol compound or a divalent thiophenol compound as monomers and performing polycondensation in an organic solvent.

  Polymers such as polyethersulfone, polyetherketone and polysulfidesulfone are obtained by polycondensation of an aromatic dihalogen compound and a dihydric phenol compound or divalent thiophenol compound in an organic polar solvent in the presence of an alkali metal compound. The method of manufacturing is well known. The water produced as a by-product in this polycondensation reaction is required to be removed from the reaction system in order to hydrolyze the polymer. For this reason, water is removed by azeotropic distillation with toluene or chlorobenzene, or water is removed using a dehydrating material such as molecular sieve (see, for example, Patent Document 1).

  Furthermore, polyethersulfone having an ionic group such as a sulfonic acid group has been produced by a method using azeotropic dehydration as a polymer for a proton exchange membrane of a fuel cell that has been attracting attention in recent years (for example, patent literature) 2 or 3). However, when using a monomer having an ionic group such as a sulfonic acid group, the removal of water is inhibited by the polar ionic group, the polymerization rate is slow, it is difficult to obtain a high molecular weight polymer, and the production efficiency is good. Had no problem.

  Also known is a method of producing a high molecular weight polyethersulfone by reacting at a high temperature of 240 ° C. or higher using diphenylsulfone as a solvent (see, for example, Patent Document 4). However, since diphenyl sulfone is solid at room temperature, since the composition containing the produced polymer is solid, there is a problem that grinding is necessary for post-treatment and handling becomes complicated. Further, the monomer having an ionic group has the same problem as the above method.

JP-A-5-255505 JP-A-5-1149 US Patent Application Publication No. 2002/0091225 JP 2004-107606 A

  The present invention has been made against the background of the problems of the prior art, and an aromatic dihalogen compound and a dihydric phenol compound or a divalent thiophenol compound are polycondensed in an organic solvent in the presence of an alkali metal compound. In the method for producing a polymer, a high molecular weight polymer can be obtained safely and easily, and even when a monomer having an ionic group and having bound water is used, a high-volume polyarylene polymer can be easily obtained. It provides a method of obtaining

  As a result of intensive studies to solve the above problems, the present inventors have finally completed the present invention. That is, the present invention employs the following configuration.

(1) In a method for producing a polymer by polycondensing an aromatic dihalogen compound and a dihydric phenol compound or a divalent thiophenol compound in an organic polar solvent in the presence of an alkali metal compound, A method for producing a polyarylene-based polymer, characterized in that dehydration is performed under reduced pressure.
(2) The method for producing a polyarylene polymer according to (1), wherein the organic polar solvent is N-methyl-2-pyrrolidone.
(3) The aromatic dihalogen compound and at least one of a dihydric phenol compound or a divalent thiophenol compound have an ionic group, as described in (1) or (2) above A method for producing a polyarylene polymer.
(4) The ionic group is one or more groups selected from the group consisting of sulfonic acid groups, sulfonic acid group salts, phosphonic acid groups, phosphonic acid group salts, phosphoric acid groups, and phosphoric acid group salts. The method for producing a polyarylene-based polymer as described in (3) above, wherein
(5) The method for producing a polyarylene polymer according to (4), wherein the aromatic dihalide has an ionic group.
(6) The method for producing a polyarylene polymer according to (5), wherein the aromatic dihalide includes a compound having a structure represented by the following chemical formula 1.

（化学式１）
（化学式１において、ＸはＦ、Ｃｌ、Ｂｒ、Ｉのハロゲン元素のいずれかを、Ｙは、スルホニル基又はカルボニル基のいずれかを、Ｚは、スルホン酸基及びその塩、ホスホン酸基その塩、リン酸基及びその塩、アルキルスルホン酸基及びその塩からなる群より選ばれる基を表す。）
（７）前記イオン性基を含む芳香族ジハロゲン化物又は二価フェノール化合物又は二価チオフェノール化合物が、結合水を含む状態で重合に用いることを特徴とする前記の（３）〜（６）のいずれかに記載のポリアリーレン系ポリマーの製造方法。
（８）脱水時の減圧度が−１〜−３６０ｍｍＨｇの範囲にあることを特徴とする請求項１〜７のいずれかに記載のポリアリーレン系ポリマーの製造方法。

(Chemical formula 1)
(In Chemical Formula 1, X is any one of halogen elements of F, Cl, Br and I, Y is either a sulfonyl group or a carbonyl group, Z is a sulfonic acid group and a salt thereof, or a phosphonic acid group or a salt thereof. And a group selected from the group consisting of a phosphoric acid group and a salt thereof, an alkylsulfonic acid group and a salt thereof.
(7) The above-mentioned (3) to (6), wherein the aromatic dihalide, dihydric phenol compound or divalent thiophenol compound containing the ionic group is used for polymerization in a state containing bound water. The manufacturing method of the polyarylene-type polymer in any one.
(8) The method for producing a polyarylene polymer according to any one of claims 1 to 7, wherein the degree of vacuum during dehydration is in the range of -1 to -360 mmHg.

  According to the method of the present invention, an aromatic dihalogen compound and a dihydric phenol compound or a divalent thiophenol compound are polycondensed in an organic polar solvent in the presence of an alkali metal compound, thereby producing a polypolymer having a high degree of polymerization. Arylene-based polymers can be easily obtained in a short time. In particular, even when a monomer having an ionic group and bound water is used, a polymer having a high degree of polymerization can be easily obtained in a short time. Furthermore, since it is obtained as a polymer solution after the completion of the reaction, there is an advantage that it is easy to handle without pulverization for post-treatment, and can be easily purified.

  The polyarylene polymer in the present invention is an aromatic dihalogen compound, a dihydric phenol compound or a divalent thiophenol compound as a monomer, and a polyarylene ether polymer which is polycondensed in an organic polar solvent in the presence of an alkali metal compound or Hereinafter, the method for producing the polyarylene polymer of the present invention will be described in detail.

  As the aromatic dihalogen compound in the present invention, 4,4′-dichlorodiphenylsulfone, 4,4′-dichlorobenzophenone, 4,4′-dichlorodiphenylphosphine oxide, 4,4′-bis (4-chlorophenylsulfonyl) biphenyl 2,6-dichlorobenzonitrile, 2,4-dichlorobenzonitrile, 2,6-dichloro-1-trifluoromethylbenzene, 2,4-dichloro-1-trifluoromethylbenzene, 4,4′-difluorodiphenyl Sulfone, 4,4′-difluorobenzophenone, 4,4′-difluorodiphenylphosphine oxide, 4,4′-bis (4-fluorophenylsulfonyl) biphenyl, 2,6-difluorobenzonitrile, 2,4-difluorobenzonitrile 2,6-difluoro-1- Trifluoromethyl benzene, there may be mentioned 2,4-difluoro 1-trifluoromethylbenzene are not limited thereto. Among them, 4,4′-dichlorodiphenyl sulfone, 4,4′-difluorodiphenyl sulfone, 2,6-dichlorobenzonitrile, 2,6-difluorobenzonitrile, 4,4′-dichlorobenzophenone, 4,4′-difluoro Benzophenone is preferred.

  As the dihydric phenol compound and divalent thiophenol compound in the present invention, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene, 9,9- Bis (4-mercaptophenyl) fluorene, 9,9-bis (3-methyl-4-mercaptosiphenyl) fluorene, 4,4′-biphenol, 4,4′-dimercaptobiphenyl, bis (4-hydroxyphenyl) Sulfone, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) butane, 3,3-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxy-3,5-dimethyl) Enyl) propane, bis (4-hydroxy-3,5-dimethylphenyl) methane, bis (4-hydroxy-2,5-dimethylphenyl) methane, bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl) ) Diphenylmethane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, hydroquinone, resorcin, 1,4-dimercaptobenzene, 1,3-dimercaptobenzene, bis (4-hydroxyphenyl) ketone, 4,4 '-Thiobisbenzenethiol, 4,4'-thiodiphenol, 3-methyl-4,4'-dihydroxy-p-terphenyl, 4,4'-dihydroxy-p-terphenyl, 1,3-bis ( 4-hydroxy) adamantane, 2,2-bis (4-hydroxy) adamantane, naphth Can be exemplified alkylene bisphenols are not limited thereto. Of these, 4,4'-biphenol and 9,9-bis (4-hydroxyphenyl) fluorene are preferred.

  These aromatic dihalogen compounds and dihydric phenol compounds or divalent thiophenol compounds may be used not only as one kind but also as a mixture of several kinds. Moreover, you may have an ionic group. The ionic group means a group having a moiety bonded by an ionic bond, for example, a sulfonic acid group, a sulfonic acid group salt, a phosphonic acid group, a phosphonic acid group salt, a phosphoric acid group, a phosphoric acid group salt. An acidic group can be exemplified, but other known groups may be used.

  The ionic group may be bonded directly to the benzene ring of the monomer, or may be bonded via an alkyl group, an alkoxy group, a phenyl group, a benzyl group, or the like. The ionic group may be introduced into either an aromatic dihalogen compound and a dihydric phenol compound or a divalent thiophenol compound. However, when introduced into an aromatic dihalogen compound, there is little decrease in reactivity. This is preferable because it is completed. An ionic group may be introduced into the dihydric phenol compound or the divalent thiophenol compound, but if the ionic group is an acidic group as described above, the divalent phenol compound can be obtained by the electron withdrawing property of the ionic group. Alternatively, it is not preferable because the reactivity of the divalent thiophenol compound is lowered. When an ionic group is introduced into a dihydric phenol compound or a divalent thiophenol compound, it is preferably introduced at a meta position relative to a hydroxyl group or a mercapto group.

  Use of an aromatic dihalogen compound containing an ionic group is suitable for producing a polymer for a proton exchange membrane of a fuel cell. Examples of the aromatic dihalogen compound containing an ionic group include the following compounds.

  For example, 3,3′-disulfo-4,4′-dichlorodiphenyl sulfone, 3,3′-disulfo-4,4′-difluorodiphenyl sulfone, 3,3′-disulfo-4,4′-dichlorobenzophenone, 3, , 3′-disulfo-4,4′-difluorobenzophenone, and those obtained by converting the sulfonic acid group into a salt with a monovalent cation species. Examples of monovalent cation species include sodium, potassium, lithium, other metal species, various amines, and the like. Sodium, potassium, and the like are preferable, but are not limited thereto. Preferred examples include sodium 3,3′-disulfonate-4,4′-dichlorodiphenylsulfone, sodium 3,3′-disulfonate-4,4′-difluorodiphenylsulfone, sodium 3,3′-disulfonate-4. , 4′-dichlorobenzophenone, sodium 3,3′-disulfonate-4,4′-difluorobenzophenone.

  Examples of the aromatic dihalogen compound not containing an ionic group suitable for use in combination with an aromatic dihalogen compound containing an ionic group include 4,4′-dichlorodiphenylsulfone, 4,4′-difluorodiphenylsulfone, 2,6 -Dichlorobenzonitrile, 2,6-difluorobenzonitrile, 4,4'-dichlorobenzophenone and 4,4'-difluorobenzophenone are preferred.

  As the dihydric phenol compound or divalent thiophenol compound in which the aromatic dihalogen compound containing an ionic group is as described above, 4,4′-biphenol and 9,9-bis (4-hydroxyphenyl) fluorene are preferable.

  Examples of the dihydric phenol compound and divalent thiophenol compound containing an ionic group include sulfonated products, alkylsulfonated products, phosphonated products, phosphoric oxides, and salts of the above divalent phenol compounds and divalent thiophenol compounds. Can be used. For example, hydroquinonesulfonic acid monopotassium salt, 3,7-disulfonic acid sodium-2,6-dihydroxynaphthalene and the like can be mentioned, but not limited to these compounds, any known compound can be used. .

  In general, a compound containing an ionic group is less reactive than a compound containing no ionic group. This may be due to steric hindrance of the ionic group, water bound to the ionic group, inhibition of dehydration due to the polarity of the ionic group, etc., and the compound containing the ionic group is a divalent phenol compound or divalent thiophenol. In some cases, the reactivity is also lowered due to the electron withdrawing property of the ionic group. Therefore, the ionic group is preferably introduced into the aromatic dihalogen compound.

  The amount of ionic groups in the polymer is the molar ratio of aromatic dihalogen compounds containing ionic groups to aromatic dihalogen compounds containing no ionic groups, divalent phenolic compounds containing ionic groups and divalent thiophenol compounds and ions. It can be adjusted by the molar ratio of the dihydric phenol compound and divalent thiophenol compound that do not contain a sex group. When the ratio of the aromatic dihalogen compound containing an ionic group is between 10 and 80 mol%, a polymer suitable for a proton exchange membrane for a fuel cell can be obtained.

  Examples of the alkali metal compound used in the present invention include lithium, sodium and potassium compounds, and hydroxides and carbonates. Among these, carbonates are preferable from the viewpoint of easy polycondensation reaction, and potassium carbonate and sodium carbonate are preferable examples. These alkali metal compounds are preferably present in an excess from an equimolar amount to the alkali metal atom and the hydroxyl group or mercapto group with respect to the dihydric phenol compound or divalent thiophenol compound. A preferred molar ratio to the hydroxyl group or mercapto group is 1.0 to 1.2. In addition, any basic compound capable of forming a dihydric phenol compound or a dihydric phenol compound into an active phenoxide structure can be used without being limited thereto.

The organic polar solvent that is a polycondensation reaction solvent in the present invention is a solvent that is liquid at room temperature and has a boiling point of 150 ° C. or higher.
Examples of such solvents include, but are not limited to, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone. Is not to be done. Among them, N-methyl-2-pyrrolidone is preferable because it can be obtained at a low price with high purity and is easy to handle with little toxicity and danger. The purity of the solvent is preferably 98% or more, more preferably 99% or more, and further preferably 99.9% or more. Moreover, it is preferable that a moisture content is 0.1% or less.

Dehydration in the reaction system must be performed under reduced pressure. For example, Also in a method of removing moisture by heating the organic polar solvent and water to the temperature near the boiling point of the organic polar solvent under an inert gas stream and removing the organic polar solvent and water from the reaction system at the same time, it is preferably performed under reduced pressure. . By reducing the pressure of the reaction system, the boiling point of water or the solvent is lowered, and it becomes easier to remove.

  The amount of the organic polar solvent used is preferably in the range of 1.5 to 10 times, more preferably in the range of 1.8 to 4 times that of the polymer to be produced. If the amount of the organic polar solvent is too large, the reaction rate may decrease, or it may be difficult to recover the polymer after completion of the reaction. If the amount of the organic polar solvent is too small, the viscosity of the reaction system becomes abnormally large and handling may be difficult.

  The polymerization is preferably performed under an inert gas stream. As the inert gas, a known gas can be used as long as it does not affect the reaction, but nitrogen and argon are preferable. The inert gas used preferably has a low water content. Moreover, since reactive gases, such as oxygen and nitrogen dioxide, cause a decrease in polymerizability, it is preferable that they are not mixed in an inert gas. Moreover, when depressurizing at the time of dehydration, it can also be carried out in an inert gas atmosphere.

  The reaction solution can be depressurized by any known method such as a vacuum pump, an aspirator, or a forced exhaust device. The degree of decompression can be adjusted with a needle valve or the like, and can be measured with a manometer or a differential pressure gauge. The decompression is preferably performed from the outlet of the reaction vessel, and when a condenser is used, it is preferably attached after the condenser. It is preferable that the reaction container is properly sealed so that outside air is not mixed.

  The degree of vacuum is preferably in the range of −1 to −360 mmHg, and more preferably −1 to −50 mmHg.

  The reaction temperature is preferably in the range of −15 to ± 0 ° C. with respect to the boiling point of the solvent used at normal pressure.

  The method for heating the reaction vessel is not particularly limited, but can be heated by any known method such as a heat medium or a heater. The heating temperature is not less than the boiling point of the organic polar solvent to be used, more preferably in the range of +5 to + 50 ° C., and further preferably in the range of +10 to + 30 ° C. with respect to the boiling point. If the heating temperature becomes too high, side reactions such as polymer fixation to the vessel wall of the reaction vessel and cross-linking, branching, and decomposition of the polymer are liable to occur.

  The polymerization time varies depending on the monomer used, but generally, when the proportion of the monomer containing an ionic group increases, it tends to take a longer time to obtain a polymer with a high degree of polymerization. When polymerizing for a long time, it is preferable to carry out the polymerization continuously. However, the reaction can be continued by heating again after the temperature is once lowered to stop the reaction. It is preferable to keep an inert gas atmosphere in the reaction vessel by flowing an inert gas while the temperature is lowered.

  In the production method of the present invention, a polymer having a high molecular weight can be obtained even if a compound containing an ionic group having low reactivity is used as a monomer. In addition, when the monomer having an ionic group has bound water, it is preferable to remove the bound water by drying before polymerization. However, according to the method of the present invention, it is highly effective even in a state having bound water. A polymer having a degree of polymerization can be obtained. The monomer can be dried by a known method and is not particularly limited, but is preferably performed by heating or drying under reduced pressure. The drying temperature is preferably between 100 and 200 ° C. When an ionic group-containing monomer containing bound water is used, it is necessary to measure the amount of water in the monomer in advance and calculate the amount to be charged based on that.

  The degree of polymerization of the polymer can be measured using any known method. For example, since the degree of polymerization of a polymer generally increases with time, a polymer having a desired degree of polymerization can be obtained by stopping the polymerization when a predetermined degree of polymerization is reached. The degree of polymerization can be determined by the viscosity of the polymerization solution or GPC (size exclusion chromatography). The viscosity may be determined by measuring the sampled solution off-line, measuring it with an in-line viscometer, or detecting the torque applied to the stirring blade as the current value of the motor and converting it to the viscosity. The degree of polymerization can also be controlled by the molar ratio of the aromatic dihalogen compound and the dihydric phenol compound and / or divalent thiophenol compound, the addition of a terminal terminator, or the like. As the terminal terminator, an aromatic monohalogen compound, a monohydric phenol compound and / or a monovalent thiophenol compound can be used. The end terminator may be added from the beginning of the polymerization or may be added during the reaction.

  One method for measuring the degree of polymerization of a polymer is to measure the logarithmic viscosity of a dilute solution. The purified polymer was dissolved in N-methylpyrrolidone at a concentration of 0.5 g / dl, and the viscosity was measured using a Ubbelohde viscometer in a constant temperature bath at 30 ° C., and expressed as ln [ta / tb] / c. When the logarithmic viscosity (ta is the drop time of the sample solution, tb is the drop time of the solvent only, and c is the polymer concentration) is 0.8 dL / g or less, the mechanical properties of the polymer molded product deteriorate. It is not preferable. It is preferably 0.8 dL / g, more preferably 1.5 dL / g or more, and by using the method of the present invention, the logarithmic viscosity of the polymer can be 2.0 dL / g or more. Polymers having mechanical properties can also be obtained.

  The obtained polymer can be purified by any known method. In general, the polymer solution is dropped, dispersed and reprecipitated in a solvent that does not dissolve the polymer and is miscible with the organic polar solvent. As a solvent used for reprecipitation, it is preferable to use water or a mixture of water with another organic solvent and water since inorganic salts formed as a by-product can be removed at the same time. Further, after removing the inorganic salt from the polymer solution by filtration, it can be reprecipitated with a solvent other than water. As the reprecipitation solvent in this case, acetone, methyl ethyl ketone, ethyl acetate, methyl acetate, or the like can be used. When the viscosity of the polymer solution is high, it can be diluted with a solvent capable of dissolving the polymer. As a solvent that can be used for dilution, in addition to N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, hexamethylene phosphoric triamide, 1,3-dimethyl- 2-imidazolidinone and the like can be used.

When producing a proton exchange membrane, it can be formed by a casting method or the like using a solution obtained by dissolving a reprecipitated polymer in an appropriate solvent, a solution obtained by filtering a polymerization solution, or the like.
That is, a method of casting a solution on a substrate such as a glass plate, removing a solvent by heating or dipping in a non-solvent to obtain a film, and then removing impurities such as residual solvent and residual salt by washing with water, etc. These known methods can be employed. In addition, when a film is formed using a salt type polymer having an ionic group, in addition to the above-described treatment method, an ionic group is converted from a salt type to an acid type by performing treatment with an acid as necessary. A method of removing residual solvent and residual free acid by washing with water can be employed.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely using an Example, this invention is not limited to these Examples. Various measurements were performed as follows.

・ Solution viscosity:
The polymer powder was dissolved in N-methylpyrrolidone at a concentration of 0.5 g / dl, and the viscosity was measured using a Ubbelohde viscometer in a constant temperature bath at 30 ° C., and the logarithmic viscosity ln [ta / tb] / c) Evaluation was made (ta is the number of seconds for dropping the sample solution, tb is the number of seconds for dropping only the solvent, and c is the polymer concentration).

・ Measurement of moisture content:
About 10 μL of an organic polar solvent containing water was taken in a microsyringe, and the moisture content was measured using a moisture content measuring apparatus AQ-7 manufactured by Hiranuma Seisakusho.

Example 2
Nitrogen inlet tube, stirring blade, the temperature detection end, condenser, electric heater jacket, titanium fitted with a back pressure valve closed vessel (inner volume 12L), to remove the bound water by 15 hours drying under reduced pressure at 120 ° C. 3,3 Sodium disulfonate-4,4'-dichlorodiphenylsulfone (abbreviation: S-DCDPS) 750.0 g (1.527 mol), 2,6-dichlorobenzonitrile (abbreviation: DCBN) 528.4 g (3.072 mol) , 4,4′-biphenol (abbreviation: BP) 856.3 g (4.599 mol), potassium carbonate 730.9 g (5.288 mol), N-methyl-2-pyrrolidone (abbreviation: NMP) 5398.1 g Nitrogen was allowed to flow at a flow rate of 8 L / min, and the heating was started by setting the heater temperature to 220 ° C. while stirring. A vacuum pump via a needle valve was connected to the exhaust outlet of the reactor, and the degree of vacuum was adjusted to -15 mmHg. The condenser was cooled by passing water at about 25 ° C. The pipe of about 1 m from the reaction vessel to the condenser was kept warm with glass wool. 30 minutes after the start of heating, the temperature of the solution reached 150 ° C., and foamed vigorously to raise the liquid level. One hour after the start of heating, when the temperature of the reaction solution reached around 190 ° C., NMP and water began to be distilled from the condenser. At this time, the temperature at the inlet of the condenser was about 150 ° C. Two hours and 00 minutes after the start of heating, the temperature of the reaction solution reached 203 ° C., so removal of NMP and water from the condenser from the reaction system was stopped, and the reaction solution was refluxed into the reaction vessel. And the vacuum pump was removed and the inside of reaction container was returned to the normal pressure. After reacting for 4 hours, the heater was stopped, and the reaction was stopped by cooling the container. The reaction solution was allowed to cool with stirring, and when the temperature reached 30 ° C., the solution was taken out. The polymerization solution was thinly spread on a glass plate, immersed in water and allowed to stand for 1 day to solidify the polymer. The obtained polymer film was immersed in fresh water several times, then washed in boiling water for 1 hour to remove residual NMP, and then dried at 120 ° C. It was 1.91 dL / g when logarithmic viscosity was measured about the obtained polymer.

Example 3
Polymerization was carried out in the same manner as in Example 2 except that 774.0 g of S-DCDPS having 3.2% bound water (750.0 g as dried S-DCDPS) was used as it was for S-DCDPS. The logarithmic viscosity of the obtained polymer was 1.81 dL / g.

Comparative Example 2
In the same manner as in Example 2, the raw material was placed in a reaction vessel and dehydrated without reducing pressure. After 2 hours and 30 minutes from the start of the reaction, the temperature of the reaction solution reached 203 ° C., so removal of NMP and water from the condenser from the reaction system was stopped, and the reaction solution was refluxed into the reaction vessel. The reaction was allowed for 5 hours. Thereafter, the heater was stopped, the reaction was stopped by cooling the container, and the logarithmic viscosity of the polymer obtained in the same manner as in Example 1 was measured. As a result, it was 1.32 dL / g.

  As described above, according to the method of the present invention, a polymer having a high degree of polymerization can be polymerized in a short time, and even when the monomer has an ionic group, the polymerization can be performed satisfactorily. And a polymer having a high degree of polymerization can be obtained. Surprisingly, even when the monomer has an ionic group and has bound water, it can be polymerized as it is without drying.

According to the present invention, a polyarylene ether-based polymer or a polyarylene sulfide-based polymer can be obtained with simple equipment, which is industrially useful.
In addition, a polymer having an ionic group such as a sulfonic acid group, which was not easy to achieve a high degree of polymerization by the conventional method, can be easily produced at a high degree of polymerization. It can be suitably used as a material for proton exchange membranes for fuel cells, and contributes industrially.

It is a schematic diagram which shows the outline | summary of an example of the polymer polymerization apparatus in this invention. It is a < ¹ > H-NMR spectrum which measured the polymer synthesize | combined in Example 1 in this invention at room temperature in deuterated dimethylsulfoxide.

Explanation of symbols

1: Stirring motor 2: Stirring blade 3: Jacket heater 4: Reaction vessel 5: Nitrogen inlet tube 6: Distilled solvent reservoir 7: Condenser 8: Exhaust port 9: Polymer solution extraction valve 10: Reflux-distillation switching valve 11 : Flow meter 12: Depressurization degree adjusting valve 13: Outside air inlet (for depressurization degree adjustment)
14: Exhaust port from vacuum pump 15: Vacuum pump

Claims (8)

Aromatic dihalogen compounds and dihydric phenol compounds In an organic polar solvent in the presence of an alkali metal compound , dehydration in the reaction system is heated near the boiling point of the organic polar solvent under an inert gas stream, and the organic polar solvent and water react simultaneously. A method for producing a polyarylene polymer, characterized in that in the method for producing a polymer by removing it outside the system and subjecting it to polycondensation, dehydration in the reaction system is carried out under reduced pressure. The method for producing a polyarylene-based polymer according to claim 1, wherein the organic polar solvent is N-methyl-2-pyrrolidone. Aromatic dihalogen compounds and dihydric phenol compounds The method for producing a polyarylene polymer according to claim 1, wherein at least one of the compounds has an ionic group. The ionic group is at least one group selected from the group consisting of a sulfonic acid group, a sulfonic acid group salt, a phosphonic acid group, a phosphonic acid group salt, a phosphoric acid group, and a phosphoric acid group salt. 4. The method for producing a polyarylene polymer according to claim 3, The method for producing a polyarylene polymer according to claim 4, wherein the aromatic dihalide has an ionic group. The method for producing a polyarylene polymer according to claim 5, wherein the aromatic dihalide contains a compound having a structure represented by the following chemical formula 1.

(Chemical formula 1)
(In Chemical Formula 1, X is any one of halogen elements of F, Cl, Br and I, Y is either a sulfonyl group or a carbonyl group, Z is a sulfonic acid group and a salt thereof, or a phosphonic acid group or a salt thereof. , Phosphate groups and their salts Represents a group selected from the group consisting of ) Aromatic dihalide or dihydric phenol compound containing the ionic group Is used for polymerization in a state containing bound water, The method for producing a polyarylene polymer according to any one of claims 3 to 6. The method for producing a polyarylene polymer according to any one of claims 1 to 7, wherein the degree of vacuum during dehydration is in the range of -1 to -360 mmHg.

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