JP2007091788A - Method for producing polyarylene polymer - Google Patents

Abstract

The present invention provides a method capable of accurately controlling the molecular weight of a polymer produced in the production of a polyarylene polymer having a sulfonate group.
One or more compounds selected from aromatic halogen compounds, aromatic trifluoromethylsulfonyloxy compounds, and aromatic methylsulfonyloxy compounds containing a compound having a sulfonate group as a substituent are subjected to a coupling reaction. When the polyarylene polymer is produced, when the polymerization solution reaches a predetermined solution viscosity, the compound having a carboxyl group, an acid anhydride group, a hydroxyl group, an amino group or an amide group, and one kind selected from water A method for producing a polyarylene polymer having a sulfonic acid ester group, wherein the polymerization reaction is stopped by adding the above compound to a polymerization solution to control the molecular weight of the polymer.
[Selection figure] None

Description

  The present invention relates to a method for adjusting the molecular weight of a polymer in the production process of a polyarylene polymer having a sulfonate group.

  It is well known that polyarylene polymers are produced by coupling reactions of aromatic halogen compounds, aromatic trifluorosulfonyloxy compounds, and aromatic trimethylsulfonyloxy compounds using Ni catalysts, etc., and the reaction is completed. Thereafter, the polymerization solution is generally poured into a large amount of a poor solvent such as methanol to solidify and recover the polymer.

  In the coupling reaction, in the latter stage of the reaction, the molecular weight is rapidly increased because the coupling reaction between the high molecular weight products produced by the sequential reaction is mainly performed. For this reason, when it is attempted to stop the polymerization reaction by the method as described above, since it takes time to add the polymerization solution to the poor solvent, the polymerization reaction proceeds continuously while trying to add. Therefore, there is a problem that it is difficult to adjust the molecular weight of the obtained polymer. In addition, in the case of a coupling polymerization reaction using a compound having a sulfonic acid ester group, the sulfonic acid ester group is relatively unstable, so that the sulfonic acid ester group is decomposed by reaction with a terminator or by the action of the terminator. There is a problem that reaction occurs.

  As described above, in the prior art, there is no appropriate molecular weight adjustment method in the polymerization reaction of an aromatic halogen compound having a sulfonic acid ester group, an aromatic trifluorosulfonyloxy compound, or an aromatic trimethylsulfonyloxy compound, particularly on an industrial scale. It has been desired to develop a method for accurately adjusting the molecular weight of the polymer produced during production.

  The present invention has been made against the background of the above-mentioned conventional technical problems, and when the polymer in the polymerization reaction reaches the target molecular weight, the polymerization reaction is stopped and the molecular weight of the polymer to be produced is accurately determined. It aims to provide a way that can be controlled.

According to the present invention, the following method for producing a polyarylene polymer is provided to achieve the above object of the present invention.
(1) One or more compounds selected from an aromatic halogen compound, an aromatic trifluoromethylsulfonyloxy compound and an aromatic methylsulfonyloxy compound containing a compound having a sulfonate group as a substituent are subjected to a coupling reaction. When producing a polyarylene polymer, at least one selected from a compound having a carboxyl group, an acid anhydride group, a hydroxyl group, an amino group or an amide group, and water when the polymerization solution reaches a predetermined solution viscosity. Is added to the polymerization solution in an amount of 0.05 to 30 mol relative to 1 mol of the transition metal catalyst used in the coupling reaction, thereby controlling the molecular weight of the polymer by stopping the polymerization reaction. A process for producing a polyarylene polymer having a sulfonate group.
(2) When a polyarylene polymer is produced by coupling reaction of an aromatic sulfonic acid ester derivative represented by the following general formula (1) and a compound represented by the following general formula (2), When reaching a predetermined solution viscosity, a compound having a carboxyl group, an acid anhydride group, a hydroxyl group, an amino group or an amide group, and one or more compounds selected from water,
The molecular weight of the polymer is adjusted by stopping the polymerization reaction by adding 0.05 to 30 mol amount to 1 mol of the transition metal catalyst used in the coupling reaction to the polymerization solution. 2. A process for producing a polyarylene polymer according to 1.

(In the formula, X represents a halogen atom excluding fluorine, an atom or group selected from —OSO ₂ CH ₃ and —OSO ₂ CF ₃ ; Y represents —CO—, —SO ₂ —, —SO—, —CONH—; , -COO-
, — (CF ₂ ) ₁ — (wherein 1 is an integer of 1 to 10), —C (CF ₃ ) ₂ — represents at least one structure selected from the group consisting of: (CH ₂ ) ₁ — (wherein 1 is an integer of 1 to 10), —C (CH ₃ ) ₂ —, —O—, —S— represents at least one structure selected from the group consisting of Ar Represents an aromatic group having a substituent represented by —SO ₃ R or —O (CH ₂ ) _j SO ₃ R or —O (CF ₂ ) _j SO ₃ R (where R is a carbon number of 4 to 20). And j represents an integer of 1 to 12.) m shows the integer of 0-10, n shows the integer of 0-10, k shows the integer of 1-4.

(In the formula, X represents a halogen atom excluding fluorine, an atom or group selected from —OSO ₂ CH ₃ and —OSO ₂ CF ₃ , and A and D are independently a direct bond, —CO—, —SO ₂ — , -SO-
, —CONH—, —COO—, — (CF ₂ ) ₁ — (1 is an integer of 1 to 10), — (CH ₂ ) ₁ — (1 is an integer of 1 to 10), —CR ′ _2- (R ′ represents an aliphatic hydrocarbon group, an aromatic hydrocarbon group or a halogenated hydrocarbon group), at least selected from the group consisting of a cyclohexylidene group, a fluorenylidene group, —O—, and —S—. 1 represents a structure, B is independently an oxygen atom or a sulfur atom, R ^{1 to} R ¹⁶ may be the same as or different from each other, hydrogen atom, fluorine atom, alkyl group, part or all of which are halogen Represents at least one atom or group selected from the group consisting of a halogenated alkyl group, an allyl group, an aryl group, a nitro group, and a nitrile group. s and t represent an integer of 0 to 4, and r represents 0 or an integer of 1 or more. )

  According to the present invention, in the production of a polyarylene polymer having a sulfonate group, the molecular weight of the polyarylene polymer to be produced can be accurately adjusted, which is particularly effective at the time of production on an industrial scale. .

Hereinafter, the method for producing a polyarylene polymer having a sulfonate group according to the present invention will be specifically described.
In producing a polyarylene polymer having a sulfonic acid ester group in the present invention, an aromatic halogen compound, an aromatic trifluoromethylsulfonyloxy compound, and an aromatic compound containing a compound having a sulfonic acid ester group as a monomer One or more compounds selected from methylsulfonyloxy compounds, that is, aromatic halogen compounds, aromatic trifluoromethylsulfonyloxy compounds or aromatic methylsulfonyloxy compounds (hereinafter, these are also collectively referred to as “aromatic compounds”) And at least one compound selected from compounds having a sulfonic acid ester group and one or more compounds selected from an aromatic compound not having a sulfonic acid group. When a polyarylene polymer is produced by coupling reaction of these compounds, when the polymerization solution reaches a predetermined viscosity, the polymerization reaction is stopped by adding a polymerization reaction terminator to the polymerization solution. Adjust the molecular weight of the polymer.

  In the method for producing a polyarylene polymer having a sulfonate group of the present invention, the aromatic compound containing a sulfonate group that is particularly preferably used includes a compound represented by the following general formula (1). .

Wherein, X is a halogen atom other than fluorine (chlorine, bromine, iodine), - OSO ₂ CH _3, shows an atom or group selected from -OSO ₂ CF _3.
Y represents —CO—, —SO ₂ —, —SO—, —CONH—, —COO—, — (CF ₂ ) ₁ — (
l is an integer of 1 to 10), and represents at least one structure selected from the group consisting of —C (CF ₃ ) ₂ —.

Z is a direct bond or at least one selected from the group consisting of — (CH ₂ ) ₁ — (wherein 1 is an integer of 1 to 10), —C (CH ₃ ) ₂ —, —O—, and —S—. The structure of the species is shown. R represents a hydrocarbon group having 1 to 20 carbon atoms, preferably 4 to 20 carbon atoms, specifically, methyl group, ethyl group, n-propyl group, iso-propyl group, tert-butyl group, iso-butyl group. Group, n-butyl group, sec-butyl group, neopentyl group, cyclopentyl group, hexyl group, cyclohexyl group, cyclopentylmethyl group, cyclohexylmethyl group, adamantyl group, adamantanemethyl group, 2-ethylhexyl group, bicyclo [2.2. 1] heptyl group, bicyclo [2.2.1] heptylmethyl group, tetrahydrofurfuryl group, 2-methylbutyl group, 3,3-dimethyl-2,4-dioxolanemethyl group, cyclohexylmethyl group, adamantylmethyl group, Linear hydrocarbon group such as bicyclo [2.2.1] heptylmethyl group, branched hydrocarbon group, alicyclic hydrocarbon group, 5-membered Such as a hydrocarbon group having a heterocyclic ring. Of these, n-butyl group, neopentyl group, tetrahydrofurfuryl group, cyclopentyl group, cyclohexyl group, cyclohexylmethyl group, adamantylmethyl group, and bicyclo [2.2.1] heptylmethyl group are preferable, and neopentyl group is more preferable. .

Ar represents an aromatic group having a substituent represented by —SO ₃ R, and specific examples of the aromatic group include a phenyl group, a naphthyl group, an anthracenyl group, and a phenanthyl group. Of these groups, a phenyl group and a naphthyl group are preferable.

The substituent —SO ₃ R is substituted with one or more aromatic groups. When two or more substituents —SO ₃ R are substituted, these substituents may be the same or different from each other. It may be. Here, R represents a hydrocarbon group having 1 to 20 carbon atoms, preferably 4 to 20 carbon atoms, and specific examples thereof include the above hydrocarbon groups having 1 to 20 carbon atoms. Of these, n-butyl group, neopentyl group, tetrahydrofurfuryl group, cyclopentyl group, cyclohexyl group, cyclohexylmethyl group, adamantylmethyl group, and bicyclo [2.2.1] heptylmethyl group are preferable, and neopentyl group is more preferable. .

Ar may be an aromatic group having a substituent represented by —O (CH ₂ ) _j SO ₃ R or —O (CF ₂ ) _j SO ₃ R (where R is a carbon number of 4 to 20). Represents a hydrocarbon group, and j represents an integer of 1 to 12.) Specific examples of the aromatic group include those similar to the above.

Substituent —O (CH ₂ ) _j SO ₃ R, Substituent —O (CF ₂ ) _j SO ₃ R is substituted with one or more aromatic groups, and substituent —SO ₃ R, substituted When two or more groups —O (CF ₂ ) _j SO ₃ R are substituted, these substituents may be the same as or different from each other. Here, R represents a hydrocarbon group having 4 to 20 carbon atoms, and specific examples thereof include the above hydrocarbon groups having 4 to 20 carbon atoms. Of these, n-butyl group, neopentyl group, tetrahydrofurfuryl group, cyclopentyl group, cyclohexyl group, cyclohexylmethyl group, adamantylmethyl group, and bicyclo [2.2.1] heptylmethyl group are preferable, and neopentyl group is more preferable. .

m shows the integer of 0-10, n shows the integer of 0-10, k shows the integer of 1-4.
Specific examples of the compound represented by the general formula (1) include the following compounds.

A compound in which the —Cl group of the above compound is replaced by —Br or —I;
A compound in which the —Cl group of the above compound is replaced by —OSO ₂ CH ₃ ;
A compound in which the —Cl group of the above compound is replaced by —OSO ₂ CF ₃ .

The above aromatic compounds having a sulfonic acid ester group may be used alone or in combination.
In the method for producing a polyarylene polymer having a sulfonic acid ester group of the present invention, the aromatic compound not containing a sulfonic acid ester group which is particularly preferably used includes a compound represented by the following general formula (2). .

In the formula, X represents the same atom or group as X in the formula (1).
A and D are independently a direct bond, or —CO—, —SO ₂ —, —SO—, —CONH—, —
COO—, — (CF ₂ ) ₁ — (l is an integer of 1 to 10), — (CH ₂ ) ₁ — (l is an integer of 1 to 10), —CR ′ ₂ — (R ′ is An aliphatic hydrocarbon group, an aromatic hydrocarbon group, and a halogenated hydrocarbon group), a cyclohexylidene group, a fluorenylidene group, -O-, and -S-. .

B is independently an oxygen atom or a sulfur atom.
R ^{1 to} R ¹⁶ may be the same as or different from each other, and are a hydrogen atom, a fluorine atom, an alkyl group, a halogenated alkyl group in which a part or all of them are halogenated, an allyl group, an aryl group, a nitro group, a nitrile group. At least one atom or group selected from the group consisting of Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, a hexyl group, a cyclohexyl group, and an octyl group. Examples of the halogenated alkyl group include a trifluoromethyl group, a pentafluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, and a perfluorohexyl group. Examples of the allyl group include a propenyl group, and examples of the aryl group include a phenyl group and a pentafluorophenyl group.

s and t represent an integer of 0 to 4, and r represents 0 or an integer of 1 or more.
Specific examples of the compound represented by the general formula (2) include the following compounds.

A compound in which the —Cl group of the above compound is replaced with —Br or —I, a compound in which the —Cl group of the above compound is replaced with —OSO ₂ CH ₃ , a compound in which the —Cl group of the above compound is replaced with —OSO ₂ CF ₃ Such.

In the above, p is 2 or more, preferably 2 to 100.
Although the said compound can be used independently, it is also possible to use multiple simultaneously.

<Polymer structure>
In the present invention, the compound represented by the general formula (1) and the compound represented by the general formula (2) are usually subjected to coupling polymerization to obtain a copolymer represented by the following general formula (3). It is done.

In the above general formula (3), A, B, D, Y, Z, Ar, R, m, n, r, s, t, k, and R ^{1 to} R ¹⁶ are respectively represented by the above general formula (1) and ( 2) A, B, D, Y, Z,
Ar, the same meaning R, m, n, r, s, t, and k and R ¹ to R ^16. x and y are x + y = 1
The molar ratio in the case of 00 mol% is shown.

  The polymer obtained by hydrolyzing the sulfonate group of the polymer of the general formula (3) is a polymer electrolyte used in fuel cells, hydrohalic acid electrolysis, salt electrolysis, oxygen concentrators, humidity sensors, gas sensors and the like. Used for.

  In order to produce a polyarylene polymer, the above monomer is reacted in the presence of a catalyst. The catalyst used is a catalyst system containing a transition metal compound. This catalyst system includes (1) a transition metal salt. And a compound serving as a ligand (hereinafter referred to as “ligand component”), or a transition metal complex coordinated with a ligand (including a copper salt), and (2) a reducing agent as an essential component, Further, a “salt” may be added to increase the polymerization rate.

  Here, as the transition metal salt, nickel compounds such as nickel chloride, nickel bromide, nickel iodide and nickel acetylacetonate; palladium compounds such as palladium chloride, palladium bromide and palladium iodide; iron chloride and iron bromide And iron compounds such as iron iodide; cobalt compounds such as cobalt chloride, cobalt bromide, and cobalt iodide. Of these, nickel chloride, nickel bromide and the like are particularly preferable.

As the ligand component, triphenylphosphine, 2,2′-bipyridine, 1,5-
Examples include cyclooctadiene and 1,3-bis (diphenylphosphino) propane. Of these, triphenylphosphine and 2,2′-bipyridine are preferred. The compound which is the said ligand component can be used individually by 1 type or in combination of 2 or more types.

Furthermore, as the transition metal complex in which the ligand is coordinated, for example, nickel chloride bis (triphenylphosphine), nickel bromide bis (triphenylphosphine), nickel iodide bis (triphenylphosphine), nickel nitrate bis (Triphenylphosphine), nickel chloride (2,2'-bipyridine), nickel bromide (2,2'-bipyridine), nickel iodide (2,2'-bipyridine), nickel nitrate (2,2'-bipyridine) ), Bis (1,5-cyclooctadiene) nickel, tetrakis (triphenylphosphine) nickel, tetrakis (triphenylphosphite) nickel, tetrakis (triphenylphosphine) palladium and the like. Of these, nickel chloride bis (triphenylphosphine) and nickel chloride (2,2′-bipyridine) are preferred.

  Examples of the reducing agent that can be used in the catalyst system include iron, zinc, manganese, aluminum, magnesium, sodium, calcium, and the like. Of these, zinc, magnesium and manganese are preferred. These reducing agents can be used after being more activated by bringing them into contact with an acid such as an organic acid.

  Examples of the “salt” that can be used in the above catalyst system include sodium compounds such as sodium fluoride, sodium chloride, sodium bromide, sodium iodide, sodium sulfate, potassium fluoride, potassium chloride, potassium bromide, Examples include potassium compounds such as potassium iodide and potassium sulfate; ammonium compounds such as tetraethylammonium fluoride, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, and tetraethylammonium sulfate. Of these, sodium bromide, sodium iodide, potassium bromide, tetraethylammonium bromide, and tetraethylammonium iodide are preferred.

  The proportion of each component used is usually 0.0001 to 10 mol, preferably 0.01 to 0.5 mol, per 1 mol of the total amount of the above monomers of the transition metal salt or transition metal complex. When the amount is less than 0.0001 mol, the polymerization reaction may not proceed sufficiently. On the other hand, when the amount exceeds 10 mol, the molecular weight may decrease.

  When a transition metal salt and a ligand component are used in the catalyst system, the ratio of the ligand component used is usually 0.1 to 100 mol, preferably 1 to 10 mol, per 1 mol of the transition metal salt. is there. When the amount is less than 0.1 mol, the catalytic activity may be insufficient. On the other hand, when the amount exceeds 100 mol, the molecular weight may decrease.

  Moreover, the usage-amount of a reducing agent is 0.1-100 mol normally with respect to the total of 1 mol of the said monomer, Preferably it is 1-10 mol. If the amount is less than 0.1 mol, polymerization may not proceed sufficiently. If the amount exceeds 100 mol, purification of the resulting polymer may be difficult.

  Furthermore, when using "salt", the usage-ratio is 0.001-100 mol normally with respect to the total of 1 mol of the said monomer, Preferably it is 0.01-1 mol. If it is less than 0.001 mol, the effect of increasing the polymerization rate may be insufficient, and if it exceeds 100 mol, purification of the resulting polymer may be difficult.

  Examples of the polymerization solvent that can be used include tetrahydrofuran, cyclohexanone, dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, and the like. It is done. Of these, tetrahydrofuran, N, N-dimethylformamide, N, N-dimethylacetamide, and N-methyl-2-pyrrolidone (hereinafter also referred to as “NMP”) are preferable. These polymerization solvents are preferably used after sufficiently dried.

The total concentration of the monomers in the polymerization solvent is usually 1 to 90% by weight, preferably 5 to 40% by weight.
Moreover, the superposition | polymerization temperature at the time of superposing | polymerizing is 0-200 degreeC normally, Preferably it is 50-120 degreeC. The polymerization time is usually 0.5 to 100 hours, preferably 1 to 40 hours.

  Thus, the polymerization solution containing the polyarylene polymer having a sulfonic acid group is obtained by polymerizing the compound represented by the general formula (1) and the compound represented by the general formula (2). It is done. In order to obtain a polymer having a target molecular weight, a relationship between the concentration of the polymer in the polymerization solvent used during polymerization and the solution viscosity with respect to the molecular weight is obtained in advance, and a solution corresponding to the molecular weight of the target polymer is obtained. When the viscosity is reached, a polymerization reaction terminator is added to the polymerization solution. When the polymerization reaction terminator is added, the polymerization reaction is quickly stopped, and a polymer having a target molecular weight can be obtained accurately.

  In the present invention, one or more compounds selected from a compound having a carboxyl group, an acid anhydride group, a hydroxyl group, an amino group or an amide group, and water are used as a polymerization reaction terminator. The polymerization reaction terminator that can be used in the present invention is not particularly limited as long as it is a compound having the above functional group, but examples of preferred compounds include the following compounds.

Formic acid, acetic acid, propionic acid, butyric acid, valeric acid, acrylic acid, methacrylic acid, isobutyric acid, itaconic acid, octylic acid, oleic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid A compound having a carboxyl group such as carboxylic acid such as maleic acid, fumaric acid, citraconic acid, 1,2,3-propanetricarboxylic acid, fluoroacetic acid, trifluoroacetic acid, chloroacetic acid, dichloroacetic acid, and trichloroacetic acid;
Compounds having an acid anhydride group such as acetic anhydride, itaconic anhydride, citraconic anhydride, propionic anhydride, maleic anhydride, butyric anhydride and the like;
Compounds having a hydroxyl group such as alcohol compounds such as methanol, ethanol, 2-propanol, 1-butanol, cyclohexanol, allyl alcohol, ethylene glycol, propylene glycol and glycerin;
Compounds having a carboxyl group and a hydroxyl group such as hydroxycarboxylic acids such as glycolic acid, lactic acid, 2-hydroxybutyric acid, ethyl lactate, glyceric acid, hydroxymalonic acid, malic acid, tartaric acid and citric acid;
Compounds having a carboxyl group such as ketocarboxylic acid such as pyruvic acid and acetoacetic acid;
Compounds having an amino group and a carboxyl group such as amino acids such as glycine, alanine, leucine, valine and serine;
Amino such as amine compounds such as methylamine, allylamine, ethylamine, isopropylamine, diethylamine, diisopropylamine, triethylamine, 2-ethylhexylamine, t-butylamine, 3-methoxypropylamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, diethylenetriamine A compound having a group;
Compounds having an amide group such as amide compounds such as propionamide, butyramide, isobutyramide, acrylamide and oxalic acid diamide;
Amino groups such as amino alcohols such as 2-aminoethanol, 2-amino-1-butanol, diethanolamine, and triethanolamine, and hydroxylamines such as N-methylhydroxylamine, N-ethylhydroxylamine, and N, N-dimethylhydroxylamine And a compound having a hydroxyl group;
Water or the like can be suitably used.

Of these compounds, acetic acid, oxalic acid, lactic acid, water, and ethylene glycol are particularly preferable.
The amount of these polymerization terminators used is 0.05 to 30 mol, preferably 0.1 to 20 mol, more preferably 1 to 10 mol, per 1 mol of the transition metal complex or transition metal salt used as the polymerization catalyst. It is. A polymerization reaction terminator can be used individually by 1 type or in combination of 2 or more types. When two or more types are used in combination, the total amount is used in an amount within the above range. In addition, the polymerization reaction terminator can be dissolved and diluted in a polymerization solvent and charged into the polymerization solution. If the amount of the polymerization reaction terminator used is less than the lower limit, the polymerization reaction may not be stopped properly, and the molecular weight may not be adjusted accurately. On the other hand, when the amount of the polymerization reaction terminator used is larger than the upper limit, side reactions such as decomposition reaction of the sulfonic acid ester group may occur, which is not preferable.
[Example]
EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.
[Synthesis Example 1] Synthesis of Oligomer (I) 29.8 g (104 mmol) of 4,4′-dichlorodiphenylsulfone was added to a 1 L three-necked flask equipped with a stirrer, thermometer, Dean-stark tube, nitrogen introduction tube, and cooling tube. 2,7.4 g of 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane
(111 mmol) and 20.0 g (145 mmol) of potassium carbonate were weighed. After nitrogen substitution, 168 mL of sulfolane and 84 mL of toluene were added and stirred. The reaction solution was heated to reflux at 150 ° C. in an oil bath. Water produced by the reaction was trapped in a Dean-stark tube. After 3 hours, when almost no water was observed, toluene was removed from the Dean-stark tube out of the system. The reaction temperature was gradually raised to 200 ° C. and stirring was continued for 5 hours. Then, 7.5 g (30 mmol) of 4,4′-dichlorobenzophenone was added, and the reaction was further continued for 8 hours.

The reaction solution was allowed to cool, and diluted with 100 mL of toluene. Inorganic salts insoluble in the reaction solution were filtered, and the filtrate was poured into 2 L of methanol to precipitate the product. The precipitated product was filtered and dried, then dissolved in 250 mL of tetrahydrofuran, and poured into 2 L of methanol for reprecipitation. The precipitated white powder was filtered and dried to obtain 56 g of a hydrophobic unit. The number average molecular weight (Mn) measured by GPC was 10,500. The obtained compound was confirmed to be an oligomer represented by the formula (I).

Synthesis of sulfonate group-containing polyarylene (III) 3- (2,5-dichlorobenzoyl) benzenesulfone having the structure of the following formula (II) in a 1 L three-necked flask equipped with a stirrer, thermometer, and nitrogen inlet tube Neopentyl acid 135.5
g (338 mmol), oligomer 44 of Mn 10,500 obtained in Synthesis Example (1) above
. 5 g (4.2 mmol), bis (triphenylphosphine) nickel dichloride 6.71 g (10.3 mmol), sodium iodide 1.54 g (10.3 mmol), triphenylphosphine 35.9 g (136 mmol), zinc 53.7 g (820 mmol) was weighed and purged with dry nitrogen. To this was added 580 mL of N, N-dimethylacetamide (DMAc), stirring was continued while maintaining the reaction temperature at 80 ° C., the polymerization solution was sampled, and the viscosity of the polymerization solution measured at 40 ° C. using a B-type viscometer. Was 6,000 mPa · s, 0.9 g of water (5-fold mol amount relative to the Ni catalyst) was added to stop the reaction. The number average molecular weight in terms of polystyrene determined by GPC (THF) measurement of the polymer immediately before the addition of water was 46,000, and the weight average molecular weight was 173,000.

After adding water and holding at 80 ° C. for 2 hours, the molecular weight of the polymer was determined by GPC (THF) measurement. The number average molecular weight in terms of polystyrene was 46,000, and the weight average molecular weight was 17
No change in molecular weight was observed immediately before the addition of water, confirming that the reaction was completely stopped. In addition, by ¹ H-NMR, it was confirmed that the sulfonate group remained without being decomposed by the integral ratio of the hydrogen of the neopentyl group of the sulfonate group and the hydrogen of the aromatic ring in the polymer. confirmed.

(Synthesis Example 2)
Synthesis of oligomer (IV) 2,2-bis (4-hydroxyphenyl) -1 was added to a 1 L three-necked flask equipped with a stirrer, thermometer, cooling tube, Dean-Stark tube, and three-way cock for introducing nitrogen. , 1,1,3,3,3-hexafluoropropane (bisphenol AF) 67.3 g (0.20 mol), 4,4′-dichlorobenzophenone (4,4′-DCBP) 60.3 g (0.24) Mol), 71.9 g (0.52 mol) of potassium carbonate, 300 mL of N, N-dimethylacetamide (DMAc) and 150 mL of toluene were heated in a nitrogen atmosphere in an oil bath and reacted at 130 ° C. with stirring. When water produced by the reaction was azeotroped with toluene and reacted while being removed from the system with a Dean-Stark tube, almost no water was produced in about 3 hours. The reaction temperature was gradually increased from 130 ° C to 150 ° C. Thereafter, most of the toluene was removed while gradually raising the reaction temperature to 150 ° C., and the reaction was continued at 150 ° C. for 10 hours. Then, 10.0 g (0.040 mol) of 4,4′-DCBP was added, and another 5 Reacted for hours. The resulting reaction solution was allowed to cool, and then the by-product inorganic compound precipitate was removed by filtration, and the filtrate was put into 4 L of methanol. The precipitated product was separated by filtration, collected, dried, and dissolved in 300 mL of tetrahydrofuran. This was reprecipitated in 4 L of methanol to obtain 95 g (yield 85%) of the target compound.

The number average molecular weight in terms of polystyrene determined by GPC (THF solvent) of the obtained polymer was 11,200.
The obtained compound was an oligomer represented by the formula (IV) (hereinafter referred to as “BCPAF oligomer”).

Synthesis of sulfonic acid ester group-containing polyarylene (V) 26.66 g (42 mmol) of a compound having a neopentyl sulfonate group having the structure of the following formula (VI) in a 1 L three-necked flask equipped with a stirrer, thermometer and nitrogen inlet tube ), 17.5 g (1.6 mmol) of oligomer (IV) obtained in Synthesis Example (1), 0.79 g (1.2 mmol) of bis (triphenylphosphine) nickel dichloride, 0.18 g (1) of sodium iodide. 0.2 mmol), 4.2 g (16 mmol) of triphenylphosphine, and 6.3 g (96 mmol) of zinc were weighed and substituted with dry nitrogen. To this was added 140 mL of N, N-dimethylacetamide (DMAc), stirring was continued while maintaining the reaction temperature at 80 ° C., the polymerization solution was sampled, and the viscosity of the polymerization solution measured at 40 ° C. using a B-type viscometer. Was 7,000 mPa · s, 0.76 g of oxalic acid (7-fold mol amount relative to the Ni catalyst) was added as a reaction terminator to stop the reaction. The number average molecular weight in terms of polystyrene determined by GPC (THF) measurement of the polymer immediately before the addition of oxalic acid was 57,000, and the weight average molecular weight was 189,000.

After adding oxalic acid and holding at 80 ° C. for 2 hours, the molecular weight of the polymer was determined by GPC (THF) measurement. The number average molecular weight in terms of polystyrene was 56,000, and the weight average molecular weight was 188,000. No change in molecular weight was observed just before oxalic acid was added to stop the reaction, confirming that the reaction was completely stopped. In addition, by ¹ H-NMR, it was confirmed that the sulfonate group remained without being decomposed by the integral ratio of the hydrogen of the neopentyl group of the sulfonate group and the hydrogen of the aromatic ring in the polymer. confirmed.

In Example 1, polymerization and reaction termination were performed in the same manner except that 3.2 g of ethylene glycol (5 times mol with respect to Ni catalyst) was used as a reaction terminator. The molecular weight (THF, polystyrene equivalent) of the polymer immediately before the addition of ethylene glycol is a number average molecular weight of 45,000,
The weight average molecular weight was 173,000. In addition, after addition of ethylene glycol, 2
The molecular weight (THF, polystyrene equivalent) of the polymer after holding for a time is 45,
000 and a weight average molecular weight of 172,000. It was confirmed that the reaction was completely stopped by addition of ethylene glycol. In addition, by ¹ H-NMR, it was confirmed that the sulfonate group remained without being decomposed by the integral ratio of the hydrogen of the neopentyl group of the sulfonate group and the hydrogen of the aromatic ring in the polymer. confirmed.
[Comparative Example 1]
In Example 1, the polymerization reaction was carried out for 5 hours without adding water as a reaction terminator. The polymer solution was sampled at 3 hours from the start of the reaction, and the molecular weight of the polymer was measured (GPC; THF). The number average molecular weight in terms of polystyrene was 46,000, and the weight average molecular weight was 168,000. The molecular weight (THF, polystyrene equivalent) of the polymer after completion of the reaction for 4 hours was 53,000 for the number average molecular weight and 215,000 for the weight average molecular weight.

From this, it was confirmed that the polymerization reaction was not completed at the reaction time of 3 hours, and if the reaction terminator was not added, the polymerization reaction further proceeded and the molecular weight was increased.
[Comparative Example 2]
In Example 1, polymerization and reaction termination were performed in the same manner except that 0.002 g of water (0.01 times mol with respect to the Ni catalyst) was used as a reaction terminator. The molecular weight (THF, polystyrene equivalent) of the polymer immediately before the addition of water was a number average molecular weight of 44,000 and a weight average molecular weight of 167,000. After the addition of water, the reaction was continued at 80 ° C. for 2 hours. The molecular weight (THF, converted to polystyrene) was a number average molecular weight of 52,000 and a weight average molecular weight of 206,000, and it was confirmed that the reaction was not stopped sufficiently.
[Comparative Example 3]
In Example 2, polymerization and reaction termination were performed in the same manner except that 10.8 g of oxalic acid (100 times mol with respect to Ni catalyst) was used as a reaction terminator. After addition of oxalic acid, the polymerization solution was found to be viscous, suggesting decomposition of the sulfonic acid ester group. When ¹ H-NMR of the polymer after addition of oxalic acid was measured, the integral ratio of the hydrogen of the neopentyl group of the sulfonate group and the hydrogen of the aromatic ring in the polymer showed that a part of the sulfonate group was It was confirmed that it was decomposed.

Claims (2)

  A polyarylene system comprising a coupling reaction of one or more compounds selected from an aromatic halogen compound, an aromatic trifluoromethylsulfonyloxy compound and an aromatic methylsulfonyloxy compound, including a compound having a sulfonate group as a substituent When producing a polymer, when the polymerization solution reaches a predetermined solution viscosity, a compound having a carboxyl group, an acid anhydride group, a hydroxyl group, an amino group or an amide group, and one or more compounds selected from water are added. The sulfone is characterized in that the molecular weight of the polymer is adjusted by stopping the polymerization reaction by adding 0.05 to 30 mol amount to the polymerization solution with respect to 1 mol of the transition metal catalyst used in the coupling reaction. A method for producing a polyarylene polymer having an acid ester group. When a polyarylene polymer is produced by coupling reaction of an aromatic sulfonic acid ester derivative represented by the following general formula (1) and a compound represented by the following general formula (2), the polymerization solution is a predetermined solution. When the viscosity is reached, 1 mol of a transition metal catalyst used in the coupling reaction is added to at least one compound selected from a compound having a carboxyl group, an acid anhydride group, a hydroxyl group, an amino group or an amide group, and water. 2. The polyarylene having a sulfonate group according to claim 1, wherein the molecular weight of the polymer is adjusted by stopping the polymerization reaction by adding 0.05 to 30 mol amount to the polymerization solution. Method for producing a polymer;

(In the formula, X represents a halogen atom excluding fluorine, an atom or group selected from —OSO ₂ CH ₃ and —OSO ₂ CF ₃ ; Y represents —CO—, —SO ₂ —, —SO—, —CONH—; , -COO-
, — (CF ₂ ) ₁ — (wherein 1 is an integer of 1 to 10), —C (CF ₃ ) ₂ — represents at least one structure selected from the group consisting of: (CH ₂ ) ₁ — (wherein 1 is an integer of 1 to 10), —C (CH ₃ ) ₂ —, —O—, —S— represents at least one structure selected from the group consisting of Ar Represents an aromatic group having a substituent represented by —SO ₃ R or —O (CH ₂ ) _j SO ₃ R or —O (CF ₂ ) _j SO ₃ R (where R ^b represents a carbon number of 4 to 20 represents a hydrocarbon group, and j represents an integer of 1 to 12.) m shows the integer of 0-10, n shows the integer of 0-10, k shows the integer of 1-4. )

(In the formula, X represents a halogen atom excluding fluorine, an atom or group selected from —OSO ₂ CH ₃ and —OSO ₂ CF ₃ , and A and D are independently a direct bond, —CO—, —SO ₂ — , -SO-
, —CONH—, —COO—, — (CF ₂ ) ₁ — (1 is an integer of 1 to 10), — (CH ₂ ) ₁ — (1 is an integer of 1 to 10), —CR ′ _2- (R ′ represents an aliphatic hydrocarbon group, an aromatic hydrocarbon group or a halogenated hydrocarbon group), at least selected from the group consisting of a cyclohexylidene group, a fluorenylidene group, —O—, and —S—. 1 represents a structure, B is independently an oxygen atom or a sulfur atom, R ^{1 to} R ¹⁶ may be the same as or different from each other, hydrogen atom, fluorine atom, alkyl group, part or all of which are halogen Represents at least one atom or group selected from the group consisting of a halogenated alkyl group, an allyl group, an aryl group, a nitro group, and a nitrile group. s and t represent an integer of 0 to 4, and r represents 0 or an integer of 1 or more. ).