CN1318475C - Polyarylidene and its preparation method, and polymer solid electrolyte and proton conductive film - Google Patents

Abstract

Aromatic sulfonate derivatives shown in general formula (1) are disclosed; in the formula, X is an atom or group selected from halogen atoms other than fluorine, -OSO ₃ CH ₃ and -OSO ₃ CF ₃ , A is a divalent electron-withdrawing group, B is a divalent electron-donating group or directly connected, R ^a is a hydrocarbon group with 1-20 carbon atoms, and Ar is an aryl group having a substituent represented by -SO ₃ R ^b (wherein , R ^b is a hydrocarbon group of 1-20 carbon atoms), m is an integer between 0-10, n is an integer between 0-10, and k is an integer between 1-4. Also disclosed is a method for preparing a polyarylene having a sulfonic acid group, the method comprising the steps of: coupling and polymerizing the aromatic compound comprising a derivative represented by the general formula (1) to prepare a polyarylene, And the polyarylene group is hydrolyzed, and the method has high safety, and it is easy to control the amount of sulfonic acid groups introduced into the polymer and the introduced positions thereof.

Description

Polyarylene and its preparation method, as well as polymer solid electrolyte and proton conductive membrane

The application date of this invention is August 22, 2003, the application number is 03155160.2, and the title of the invention is "aromatic sulfonate derivatives, polyarylenes and their preparation methods, and polymer solid electrolytes and proton-conducting membranes." "A divisional application of the invention patent application.

technical field

The present invention relates to novel aromatic sulfonate derivatives, polyarylenes comprising repeating structural units derived from said derivatives, polyarylenes having sulfonic acid groups prepared by hydrolysis of said polyarylenes and methods for their preparation , the present invention also relates to a polymer solid electrolyte and a proton conductive membrane, the electrolyte comprising a polyarylene group containing sulfonic acid groups, the conductive membrane comprising the polymer solid electrolyte.

Background technique

The electrolyte is usually used in the state of (aqueous) solution. Recently, however, the aqueous solution state has been replaced by a solid state because the solid state has properties of easy processing when it is applied to electric and electronic materials. And recently there is a trend of being light, thin, short and small, and saving electric power.

In general, both inorganic compounds and organic compounds are known as proton-conducting materials. An example of said inorganic compound is uranyl phosphate, which is a hydrate. These inorganic compounds are not sufficiently contacted at their interfaces, and there are many problems in forming a conductive film on a substrate or an electrode.

On the other hand, examples of the organic compound are polymers belonging to cation exchange resins, for example, sulfonated vinyl polymers such as sulfonic acid polystyrene, perfluoroalkylsulfonic acid polymers (represented by Nafion (trade name, Do Pont Co., Ltd.)), perfluoroalkyl carboxylic acid polymers, and polymers prepared by introducing sulfonic acid groups or phosphoric acid groups into heat-resistant polymers (such as polybenzimidazole or polyether ether ketone) Polymer (polymerpreprints, Japan, Vol.42, No.7, PP.2490-2492 (1993), polymer preprints, Japan, Vol.43 No.3, PP.735-736 (1994), polymer preprints, Japan, Vol.42No.3, PP.730(1993)).

However, sulfonated vinyl polymers such as sulfonated polystyrene have a problem of poor chemical stability (durability). PFSA electrolytic membranes are difficult and expensive to prepare. For this reason, it is difficult to use in general applications, such as vehicles, domestic fuel units, etc., and is only suitable for specially limited applications. After its use, the perfluorosulfonic acid electrolytic membrane also has a great environmental problem in waste disposal because of a large amount of fluorine atoms in its molecule. Polymers prepared by introducing sulfonic acid groups or phosphoric acid into heat-resistant polymers such as polybenzimidazole, polyether ether ketone, etc. also have problems of poor resistance to hot water and durability.

On the other hand, sulfonated aromatic polymers are known as proton conductive materials, are industrially produced at low cost, and have excellent hot water resistance and durability. The sulfonated aromatic polymer is usually prepared by polymerizing an aromatic compound to prepare a polymer, and then reacting the polymer with a sulfonating agent to introduce sulfonic acid groups into the polymer.

However, the conventional method has many problems, such as high production risk due to the use of a large amount of sulfonating agent such as concentrated sulfuric acid, oleum, chlorosulfonic acid, etc. in the introduction of sulfonic acid, and the limitation of industrial raw materials. The liquid handling load is high. Also, the conventional method has a problem that it is inconvenient to control the amount and the position where the sulfonic acid group is introduced into the polymer.

Contents of the invention

The present invention intends to solve the above-mentioned problems associated with the prior art, and an object of the present invention is to provide a proton conductive material having excellent hot water resistance and durability, which can be industrially produced at low cost.

Another object of the present invention is to provide a method for preparing a polyarylene having a sulfonic acid group, which can prepare a polyarylene having a sulfonic acid group without using a large amount of a sulfonating agent, and The processing load is low in recycled polymers, which facilitates the control of the amount and location of sulfonic acid groups introduced into the polymer.

Another object of the present invention is to provide polyarylenes having sulfonic acid groups obtained by said method.

Another object of the present invention is to provide novel aromatic sulfonate derivatives suitable for preparing the polyarylene having sulfonic acid groups, and to provide polyarylene.

Still another object of the present invention is to provide a polymer solid electrolyte comprising a polyarylene having a sulfonic acid group, and a proton conducting membrane comprising the polymer solid electrolyte.

The invention provides the following novel aromatic sulfonate derivatives, polyarylenes, polyarylenes with sulfonic acid groups and preparation methods thereof. The invention also provides polymer solid electrolytes, proton conductive membranes and preparation methods thereof. Therefore, the above objects of the present invention can be achieved.

In the present invention, the polyarylene is obtained by using a dihalide having an aromatic ring or an aromatic compound having two groups represented by -OSO ₃ R (R is CH ₃ , CF _{3 ,} etc.) as a raw material, and A polymer obtained by performing a polymerization reaction directly linked to an aromatic ring.

(1) Aromatic sulfonate derivatives represented by general formula (1);

In the formula, X is an atom or group selected from a halogen atom other than fluorine, -OSO ₃ CH ₃ and -OSO ₃ CF ₃ , A is a divalent electron-attracting (electron attRactive) group, and B is a divalent electron-donating group Group or direct connection, R ^a is a hydrocarbon group of 1-20 carbon atoms, Ar is an aryl group having a substituent represented by -SO ₃ R ^b , wherein, R ^b is a hydrocarbon group of 1-20 carbon atoms, m is an integer between 0-10, n is an integer between 0-10, and k is an integer between 1-4.

(2) A polyarylene group comprising a repeating structural unit derived from an aromatic compound, which at least comprises a repeating structural unit represented by the general formula (1');

In the formula, A is a divalent electron-withdrawing group, B is a divalent electron-donating group or directly connected, R ^a is a hydrocarbon group with 1-20 carbon atoms, and Ar has a substituent represented by -SO ₃ R ^b Aryl, wherein, R ^b is a hydrocarbon group of 1-20 carbon atoms, m is an integer between 0-10, n is an integer between 0-10, and k is an integer between 1-4.

(3) polyarylenes comprising 0.5-100 mol% of repeating structural units represented by general formula (1') and 0-99.5 mol% of repeating structural units represented by general formula (A') below;

In the formula, R ¹ -R ⁸ are identically or differently selected from at least one atom or group in hydrogen, fluorine atom, alkyl, fluorine-substituted alkyl, allyl and aryl, and W is a divalent electron-withdrawing group group, T is a divalent electron-donating group, and P is 0 or a positive integer.

(4) A method for preparing a polyarylene having a sulfonic acid group, the method comprising the following steps: coupling and polymerizing the aromatic compound comprising an aromatic sulfonate derivative shown in general formula (1), and preparing a polyarylene Aryl, and hydrolyzed polyarylene.

(5) A polymer solid electrolyte comprising a polyarylene having a sulfonic acid group produced by the method (4).

(6) A proton-conducting membrane comprising a polymer solid electrolyte.

In one aspect, the present invention provides a polyarylene comprising a repeating structural unit derived from an aromatic compound, and at least comprising a repeating structural unit represented by the general formula (1'):

In the formula, A is a divalent electron-withdrawing group, B is a divalent electron-donating group or directly connected, R ^a is a hydrocarbon group with 1-20 carbon atoms, and Ar has a substituent represented by -SO ₃ R ^b In the aryl group, -SO ₃ R ^b , R ^b is a hydrocarbon group with 1-20 carbon atoms, m is an integer between 0-10, n is an integer between 0-10, and k is an integer between 1-4.

In a preferred embodiment, the polyarylene group comprises 0.5-100 mol% of the repeating structural unit represented by the general formula (1'), and 0-99.5 mol% of the repeating structural unit represented by the general formula (A');

In the formula, R ¹ -R ⁸ are the same or different, and are at least one atom or group selected from hydrogen, fluorine atom, alkyl, fluorine-substituted alkyl, allyl and aryl, and W is a divalent electron-withdrawing group group, T is a divalent organic group, and P is 0 or a positive integer.

In another aspect, the present invention provides a method for preparing a polyarylene having a sulfonic acid group, the method comprising the steps of: coupling and polymerizing an aromatic sulfonic acid ester derivative represented by general formula (1); family of compounds, preparing a polyarylene, and hydrolyzing the polyarylene:

In the formula, X is an atom or group selected from a halogen atom other than fluorine, -OSO ₃ CH ₃ and -OSO ₃ CF ₃ , A is a divalent electron-withdrawing group, B is a divalent electron-donating group or a direct Connected, R ^a is a hydrocarbon group of 1-20 carbon atoms, Ar is an aryl group having a substituent represented by -SO ₃ R ^b , in -SO ₃ R ^b , R ^b is a hydrocarbon group of 1-20 carbon atoms, m is an integer between 0-10, n is an integer between 0-10, and k is an integer between 1-4.

In yet another aspect, the present invention provides a polymer solid electrolyte comprising the polyarylene having sulfonic acid groups prepared by the above method.

In yet another aspect, the present invention provides a proton-conducting membrane for a fuel cell, the membrane comprising the above-mentioned polymer solid electrolyte.

Description of drawings

Fig. 1 is the IR spectrum of the white powder prepared in Example 1(1).

Fig. 2 is the NMR spectrum of the white powder prepared in Example 1(1).

Fig. 3 is the NMR spectrum of the white powder prepared in Example 1(1).

Fig. 4 is the IR spectrum of the white crystals prepared in Example 1(2).

Fig. 5 is the NMR spectrum of the white crystals prepared in Example 1(2).

Fig. 6 is the NMR spectrum of the white crystals prepared in Example 1(2).

Fig. 7 is the IR spectrum of the white crystals prepared in Example 1(3).

Fig. 8 is an NMR spectrum of white crystals prepared in Example 1(3).

Fig. 9 is an NMR spectrum of white crystals prepared in Example 1(3).

FIG. 10 is the IR spectrum of the white crystals prepared in Example 2.

FIG. 11 is the NMR spectrum of the white crystals prepared in Example 2.

FIG. 12 is the NMR spectrum of the white crystals prepared in Example 2.

FIG. 13 is the IR spectrum of the polyarylene prepared in Example 3. FIG.

FIG. 14 is an NMR spectrum of the polyarylene prepared in Example 3. FIG.

FIG. 15 is an IR spectrum of the polyarylene prepared in Example 4. FIG.

FIG. 16 is an NMR spectrum of the polyarylene prepared in Example 4. FIG.

FIG. 17 is an NMR spectrum of the polyarylene prepared in Example 4. FIG.

FIG. 18 is an NMR spectrum of the polyarylene prepared in Example 5. FIG.

FIG. 19 is an IR spectrum of the polyarylene having sulfonic acid groups prepared in Example 6. FIG.

FIG. 20 is an NMR spectrum of the polyarylene having sulfonic acid groups prepared in Example 6. FIG.

FIG. 21 is an IR spectrum of the polyarylene having sulfonic acid groups prepared in Example 7. FIG.

FIG. 22 is an NMR spectrum of the polyarylene having sulfonic acid groups prepared in Example 7. FIG.

FIG. 23 is an IR spectrum of the polyarylene having sulfonic acid groups prepared in Example 8. FIG.

FIG. 24 is an IR spectrum of the copolymer prepared in Example 9. FIG.

FIG. 25 is an NMR spectrum of the copolymer prepared in Example 9. FIG.

FIG. 26 is an IR spectrum of the polyarylene having sulfonic acid groups prepared in Example 9. FIG.

FIG. 27 is an NMR spectrum of the polyarylene having sulfonic acid groups prepared in Example 9. FIG.

FIG. 28 is an NMR spectrum of the phenoxyphenol disulfonic acid compound prepared in Example 10. FIG.

Fig. 29 is an NMR spectrum of 2,5-dichloro-4'-(4-phenoxyphenol)benzophenone disulfonic acid compound prepared in Example 10.

FIG. 30 is an NMR spectrum of the S-2,5-DCPPB chloro-sulfonated compound prepared in Example 10. FIG.

31 is the IR spectrum of S-2,5-DCPPB neopentyl ester prepared in Example 10.

FIG. 32 is an NMR spectrum of S-2,5-DCPPB neopentyl ester prepared in Example 10. FIG.

Detailed ways

Aromatic sulfonate derivatives, polyarylenes, polyarylenes having sulfonic acid groups and preparation methods thereof, as well as polymer solid electrolytes and proton conductive membranes will be described in detail below.

(Aromatic Sulfonate Derivatives)

The aromatic sulfonate derivative of the present invention is represented by the general formula (1).

In the formula, X is an atom or group selected from halogen atoms (chlorine, bromine and iodine) other than fluorine, -OSO ₃ CH ₃ and -OSO ₃ CF ₃ .

A is a divalent electron-withdrawing group, examples of which are -CO-, -CONH-, -(CF ₂ ) _P - (wherein, P is an integer between 1-10), -C(CF ₃ ) ₂ -, - COO-, -SO-, and _-SO2- .

B is a divalent electron-donating group or a direct connection, examples of which are -O-, -S-, -CH=CH-, -C≡C-,

and

The electron-withdrawing group refers to a group whose Hammett substitution constant is not lower than 0.06 when the phenyl group is in the meta position; refers to a group whose Hammett substitution constant is not lower than 0.01 when the phenyl group is in the para position.

^R is a hydrocarbon group of 1-20 carbon atoms, preferably a hydrocarbon group of 4-20 carbon atoms, examples of which are straight chain hydrocarbon groups, branched chain hydrocarbon groups, alicyclic hydrocarbon groups and hydrocarbon groups with five-membered heterocyclic rings, such as methyl , ethyl, n-propyl, isopropyl, tert-butyl, isobutyl, n-butyl, sec-butyl, neopentyl, cyclopentyl, hexyl, cyclohexyl, cyclopentylmethyl, cyclohexylmethyl base, adamantyl (adamantyl), adamantylmethyl, 2-ethylhexyl, bicyclo[2,2,1]heptyl, bicyclo[2,2,1]heptylmethyl, tetrahydrofurfuryl base, 2-methylbutyl, 3,3-dimethyl-2,4-dioxoRane (dioxoRane) methyl, cyclohexylmethyl, adamantylmethyl and bicyclo[2,2,1]heptyl base methyl. Among them, n-butyl, neopentyl, tetrahydrofurfuryl, cyclopentyl, cyclohexyl, cyclohexylmethyl, adamantylmethyl and bicyclo[2,2,1]heptylmethyl are preferred, and, Neopentyl is even more preferred.

Ar is an aryl group having a substituent represented by -SO ₃ R ^b , and exemplary aryl groups include phenyl, naphthyl, anthracenyl, and phenathyl. Among them, phenyl and naphthyl are preferable.

As for the substituent -SO ₃ R ^b , the phenanthrenyl group has one or two or more substituents, and when it has two or more substituents -SO ₃ R ^b , these substituents are mutually can be the same or different.

R ^b is a hydrocarbon group of 1 to 20 carbon atoms, preferably a hydrocarbon group of 4 to 20 carbon atoms, examples of which are the aforementioned hydrocarbon groups of 1 to 20 carbon atoms. Among them, n-butyl, neopentyl, tetrahydrofurfuryl, cyclopentyl, cyclohexyl, cyclohexylmethyl, adamantylmethyl and bicyclo[2,2,1]heptylmethyl are preferred, and, Neopentyl is even more preferred.

m is an integer between 0-10, preferably 0-2, n is an integer between 0-10, preferably 0-2, and k is an integer between 1-4.

More specific examples of the aromatic sulfonate derivatives represented by the general formula (1) of the present invention include compounds represented by the following types (a) to (c).

Compounds of type (a)

The compound represented by the type (a) is a compound represented by the following general formula (1-a).

In formula (1-a), X, A and R ^b have the same meanings as in general formula (1).

In the aromatic sulfonate derivative represented by the general formula (1-a), A is preferably -CO- or -SO ₂ -. R ^b is preferably neopentyl, tetrahydrofurfuryl, cyclopentylmethyl, cyclohexylmethyl, adamantylmethyl or bicyclo[2,2,1]heptylmethyl, more preferably neopentyl .

Examples of aromatic sulfonate derivatives represented by the general formula (1-a) are as follows:

Other examples of aromatic sulfonate derivatives represented by the general formula (1-a) include replacing the chlorine atom in the above compound with a bromine atom or iodine atom to obtain a compound, and substituting -SO ₂ - for -CO- in the above compound to obtain compound and a compound obtained by substituting a bromine atom or an iodine atom for the chlorine atom in the above compound, and substituting -SO ₂ - for -CO- in the above compound.

The R ^b group in the general formula (1-a) is derived from a primary alcohol. The β carbon is preferably a tertiary carbon or a quaternary carbon because it has excellent stability in the polymerization step and does not inhibit the polymerization reaction or cause crosslinking due to the formation of sulfonic acid by the deesterification reaction. Also, it is preferred that these ester groups are derived from primary alcohols and that the beta position is a quaternary carbon.

The method for compound shown in synthetic type (a)

Step (1) sulfonation reaction of compound (I) (for example, the method using acetylsulfuric acid and sodium hydroxide):

For example, at 60°C, react 3- 5 hours. After the reaction, the reaction was terminated with 1-propanol, and a 3 mole times NaOH aqueous solution was poured. The resulting solution was concentrated to obtain a fine powder of sodium 2,5-dichlorobenzophenone-3'-sulfate.

Step (2) Chlorination of compound (II) (for example, using phosphoryl chloride):

For example, 2,5-dichlorobenzophenone-3'-sodium sulfate as compound (II) is dissolved in about 3-4 times (weight/volume) solvent (mixed solvent, sulfolane/acetonitrile/=H/b (volume ratio)), heated to 70°C, and reacted with phosphorus oxychloride at 10°C for about 5 hours. After the reaction, the reactants were diluted with copious amounts of cold water to deposit the product. After filtration, the product was recrystallized from toluene to obtain purified crystalline 2,5-dichlorobenzophenone-3'-sulfate chloride.

When using 5-10 molar times of chlorosulfonic acid to replace the acetylsulfuric acid used in step (1), then the conversion of sulfonated chlorides is carried out immediately.

Step (3) Esterification of compound (III) (eg, method using isobutanol):

For example, 2,5-dichlorobenzophenone-3'-sulfuric acid chloride as compound (III) is added dropwise to 2,5-dichlorobenzophenone-3'-sulfuric acid chloride Or more (usually 1-3 mole times) cooled mixed solution of isobutanol and pyridine to carry out the reaction. The reaction is carried out at a maximum of 20°C. Depending on the scale of the reaction, the reaction time is about 10 minutes to 5 hours. The reaction mixture solution was treated with dilute hydrochloric acid and washed with water, and then the target product was extracted with ethyl acetate. The extract was concentrated and separated, followed by recrystallization from methanol to obtain an aromatic sulfonate derivative (compound IV).

Compounds of type (b)

The compound represented by the type (b) is a compound represented by the following general formula (1-b).

In the general formula (1-b), X, A, B, Ar and m have the same meanings as in the general formula (1).

In the aromatic sulfonate derivatives represented by general formula (1-b), B is preferably a divalent electron-donating group, and the Araryl group with -SO ₃ R ^b substituent is preferably two-nuclear or more A polynuclear aryl group, and R ^b is preferably a hydrocarbon group with 3-20 carbon atoms.

Preferred examples of the polynuclear aryl group include naphthyl, anthracenyl and phenanthrenyl, most preferably naphthyl.

Either one or two or more substituents -SO ₃ R ^b are present in the polynuclear aryl group. When there are two or more substituents, the substituents may be the same or different. In the present invention, the compound preferably has a structure in which two substituents -SO ₃ R ^b exist in the polynuclear ring.

R ^b is preferably isopropyl, n-butyl, neopentyl, tetrahydrofurfuryl, cyclopentyl, cyclohexyl, cyclohexylmethyl, adamantylmethyl or bicyclo[2,2,1]heptyl methyl, and preferably neopentyl.

m is preferably an integer between 0-3.

Examples of aromatic sulfonate derivatives described in general formula (1-b) are as follows:

Other examples of aromatic sulfonate derivatives described in general formula (1-b) include compounds obtained by substituting bromine atoms or iodine atoms for chlorine atoms in the above compounds, substituting -SO ₂ - for -CO- in the above compounds, The obtained compound and the compound obtained by substituting bromine atom or iodine atom for chlorine atom in the above compound, and substituting -SO ₂ - for -CO- in the above compound.

The R ^b group in the general formula (1-b) is derived from a primary alcohol. The β carbon is preferably a tertiary carbon or a quaternary carbon because it has excellent stability in the polymerization step and does not inhibit the polymerization reaction or cause crosslinking due to the formation of sulfonic acid by the deesterification reaction. Also, it is preferred that these ester groups are derived from primary alcohols and that the beta position is a quaternary carbon.

The method for compound shown in synthetic type (b)

For example, the compound shown in the type (b) can be synthesized by the following method, such as the compound shown in the general formula (1-b), in the formula, Ar is a naphthyl group with a substituent -SO ₃ R ^b , and m is 1, namely A compound represented by the following general formula (1-b-1).

In the formula, A, B and X have the same meaning as the general formula (1-b), r and s are each an integer between 0-4, and satisfy r÷s≥1.

Step (1) etherification reaction:

For illustration, in the presence of potassium carbonate, sodium carbonate, etc., in aprotic polar solvents such as dimethyl sulfoxide, N,N'-dimethylacetamide, N-methylpyrrolidone, etc. The nucleophilic substitution reaction of 2,5-dichloro-4'-fluorobenzophenone and naphthol sulfuric acid to prepare naphthalenesulfonic acid derivatives. Examples of naphthalenesulfonic acids include 2-naphthol-3,6-disulfonic acid, 2-naphthol-6,8-disulfonic acid, 1-naphthol-3,6-disulfonic acid, 2-naphthol- 6-sulfonic acid, 1-naphthol-4-sulfonic acid and 2-naphthol-7-sulfonic acid. Among them, 2-naphthol-6,8-disulfonic acid is preferable.

Step (2) conversion of sulfonyl chloride

The naphthalenesulfonic acid derivative as compound (II) is reacted with phosphorus oxychloride or thionyl chloride in an organic solvent such as acetonitrile to convert it into sulfonyl chloride.

Step (3) esterification reaction

An aromatic sulfonate derivative (compound IV) is produced by reacting sulfonyl chloride as compound (III) with an alcohol in an organic solvent such as pyridine or the like.

Compounds of type (c)

The compound type (c) is a compound represented by the following general formula (1-c).

In formula (1-c), assuming that m+n≥1, X, A, B, Ar, ^Ra , m, n and k have the same meanings as in general formula (1). When n=0, Ar is phenyl.

Examples of the aromatic sulfonate derivative represented by the general formula (1-c) of the present invention include the following compounds.

Other examples of aromatic sulfonate derivatives represented by general formula (1-c) include compounds obtained by substituting bromine atoms or iodine atoms for chlorine atoms in the above compounds, substituting -SO ₂ - for -CO- in the above compounds, The obtained compound and the compound obtained by substituting bromine atom or iodine atom for chlorine atom in the above compound, and substituting -SO ₂ - for -CO- in the above compound.

The R ^b group represented by the general formula (1-c) is derived from a primary alcohol. The β carbon is preferably a tertiary carbon or a quaternary carbon because it has excellent stability in the polymerization step and does not inhibit the polymerization reaction or cause crosslinking due to the formation of sulfonic acid by the deesterification reaction. Also, it is preferred that these ester groups are derived from primary alcohols and that the beta position is a quaternary carbon.

The method of compound shown in synthetic type (c)

Compounds represented by type (c) can be synthesized by the following method.

Step (1) sulfonation

To illustrate, 4-phenoxyphenol as compound (I) was reacted in concentrated sulfuric acid at room temperature for 2 hours to prepare its sulfonated product. Using 4-phenylphenol or 4-(4-phenoxy)phenoxyphenol, the corresponding sulfonated product can be prepared by the same method as above.

Also, instead of concentrated sulfuric acid, a sulfonating agent such as anhydrous sulfonic acid, oleum, chlorosulfonic acid, etc., or a complex of these acids and dioxane, acetic acid, etc. may be used for the sulfonation reaction. The position or amount of introduction of the sulfonic acid can be controlled by the sulfonating agent used or the reaction temperature. When the sulfonated product is isolated, it can be in a sulfonic acid-free form, or it can be neutralized with an aqueous base to form a sulfonate such as potassium salt, sodium salt, and the like.

Step (2) etherification

To illustrate, the affinity of 2,5-dichloro-4'-fluorobenzophenone as compound (III) and the disulfate salt of 4-phenoxyphenol as compound (II) was carried out in the presence of potassium carbonate. nuclear substitution reaction. Aprotic polar solvents such as N,N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, sulfolane and the like can be used as the solvent. Also, the reaction can be smoothly performed by removing water generated from the reaction starting from a system using a solvent capable of causing azeotropy with water (such as toluene, etc.). The reaction temperature is preferably from 100°C to the boiling point of the solvent. When 2,5-dichloro-4'-fluorobenzophenone is used, etherification is carried out by selecting a fluorine group whose reactivity is higher than that of a chlorine group.

Chlorination of step (3) sulfonic acid:

For illustration, in an inert solvent such as acetonitrile, etc., 2,5-dichloro-4'-(4-phenoxy)phenoxybenzophenone disulfone as compound (IV) prepared by the above reaction Potassium acid salt reacts with phosphorus oxychloride or thionyl chloride to convert sulfonate (potassium salt) into disulfonyl chloride.

Step (4) esterification:

For illustration, 2,5-dichloro-4'-(4-phenoxy)phenoxybenzophenone disulfonyl chloride and various compounds having 4 Alcohols with one or more carbon atoms react to prepare aromatic sulfonate derivatives (compound VI).

(polyarylene having sulfonic acid groups)

Only by polymerizing at least one monomer selected from the aromatic sulfonate derivatives represented by the general formula (1), or copolymerizing at least one monomer selected from the aromatic sulfonate derivatives described in the general formula (1) A monomer and other aromatic monomers are preferably at least one monomer selected from the compounds represented by the following general formula (A) to prepare polyarylene, and then prepare the present invention by hydrolysis of polyarylene Polyarylene with sulfonic acid groups.

In general formula (A), R' and R'' are identical or different halogen atoms other than fluorine or compounds represented by -OSO ₂ Z, wherein Z is an alkyl group, a fluorine-substituted alkyl group or an aryl group. Exemplary alkyl groups represented by Z are methyl and ethyl, examples of fluorine-substituted alkyl groups are trifluoromethyl, and exemplary aryl groups are phenyl and p-tolyl.

R ¹ -R ⁸ may be the same or different, and each is at least one atom or group selected from hydrogen, fluorine atom, alkyl, fluorine-substituted alkyl, allyl and aryl.

Exemplary alkyl groups are methyl, ethyl, propyl, butyl, pentyl and hexyl, preferably methyl and ethyl.

Exemplary fluorine-substituted alkyl groups are trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluorobutyl, perfluoropentyl and perfluorohexyl, preferably trifluoromethyl and pentafluoroethyl.

An exemplary allyl group is propenyl.

Exemplary aryl groups are phenyl and pentafluorophenyl.

W represents a divalent electron-withdrawing group, and examples of the electron-withdrawing group include the same groups described above.

T is a divalent organic group, and may be an electron-withdrawing group or an electron-donating group. Examples of the electron-withdrawing group and the electron-donating group are the same as above.

P is 0 or a positive integer, and the maximum value is usually 100, preferably 80.

When P=0, examples of compounds represented by general formula (A) include 4,4'-dichlorobenzophenone, 4,4'-dichlorobenzanilide, bis(chlorophenyl)difluoro Methane, 2,2-bis(4-chlorophenyl)hexafluoropropane, 4-chlorobenzoic acid-4-chlorophenyl, bis(4-chlorophenyl)sulfoxide, bis(4-chloro substituted phenyl) sulfones, compounds obtained by substituting a bromine atom or an iodine atom for chlorine atoms in these compounds, and compounds obtained by substituting at least one halogen atom substituted at the 4-position to the 3-position.

When P=1, examples of compounds represented by general formula (A) include 4,4'-bis(4-chlorobenzoyl)diphenyl ether, 4,4'-bis(4-chlorobenzoyl) Amino) diphenyl ether, 4,4'-bis(4-chlorophenylsulfonyl)diphenyl ether, 4,4'-bis(4-chlorophenyl)diphenyl ether dicarboxylate , 4,4'-bis[(4-chlorophenyl)-1,1,1,3,3,3-hexafluoropropyl]diphenyl ether, 4,4'-bis[(4-chloro substituted phenyl)-1,1,1,3,3,3-hexafluoropropyl] diphenyl ether, 4,4'-bis[(4-chlorophenyl)-tetrafluoroethyl]diphenyl base ether, a compound obtained by substituting a chlorine atom in the above compound with a bromine atom or an iodine atom, a compound obtained by substituting at least one halogen atom substituted at the 4-position to the 3-position, and a compound obtained by substituting the 4-position to the 3-position of diphenyl ether A compound obtained by substituting at least one halogen atom at the - position.

Other examples of compounds represented by general formula (A) include 2,2-bis[4-(4-(4-chlorobenzoyl)phenoxy)phenyl], 1,1,1,3,3, 3-hexafluoropropane, bis[4-(4-(4-chlorobenzoyl)phenoxy)phenyl]sulfone, and compounds represented by the following general formula.

The compound represented by the general formula (A) can be synthesized, for example, by the following method.

First, in order to change the bisphenol with the electron-withdrawing group into the corresponding bisphenol alkali metal salt, a polar solvent with a high dielectric constant such as N-methyl-2-pyrrolidone, N,N-dimethyl Add alkali metals such as lithium, sodium, potassium, etc. to acetamide, sulfolane, diphenyl sulfone, dimethyl sulfoxide, etc., to hydrogenate alkali metals, alkali metal hydrates, alkali metal carbonates, etc.

Usually, the alkali metal reacts with a slight excess to the phenolic hydroxyl group, and is usually used in 1.1-2 equivalent multiples, preferably in 1.2-1.5 equivalent multiples. In this step, in the presence of water azeotropic solvents such as benzene, toluene, xylene, hexane, cyclohexane, octane, chlorobenzene, dioxane, tetrahydrofuran, anisole, phenetole, etc., The reaction is an aromatic dihalogen compound substituted with a halogen atom such as fluorine, chlorine, etc., which is activated by an electron-withdrawing group. Examples of said aromatic dihalogen compounds are 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-chlorofluorobenzophenone, bis(4- Chlorophenyl)sulfone, bis(4-fluorophenyl)sulfone, 4-fluorophenyl-4'-chlorophenylsulfone, bis(3-nitro-4-chlorophenyl)sulfone, 2,6-dichlorobenzonitrile, 2,6-difluorobenzonitrile, hexafluorobenzene, decafluorobiphenyl, 2,5-difluorobenzophenone, 1,3-bis(4-chloro Benzoyl) benzene, etc. In terms of reactivity, fluorine compounds are preferably used. However, for the following aromatic coupling reaction, it is necessary to arrange the aromatic nucleophilic substitution reaction so that the terminal is a chlorine atom. The active aromatic dihalide is used in an amount of 2-4 mole times per mole of bisphenol, preferably 2.2-2.8 mole times. The bisphenol may preform an alkali metal salt of the bisphenol prior to the aromatic nucleophilic substitution reaction. The reaction temperature is 60-300°C, preferably 80-250°C. The reaction time is 15 minutes-100 hours, preferably 1-24 hours.

The most preferred method involves the use of chlorofluoro compounds as active aromatic dihalides, the terminals of which each have halogen atoms of different reactivity, since the fluorine atoms preferentially lead to nucleophilic substitution reactions with phenoxides, It is adapted to obtain said compounds with directionally activated chlorine end groups.

In the general formula, W is the same as described in the general formula (A).

Also, as described in JP-A-2(1990)-159, there is a method for synthesizing plastic compounds containing directional electron-withdrawing groups and electron-donating groups by integrating nucleophilic substitution reactions and electrophilic substitution reactions to proceed.

In particular, diphenoxy substituents were prepared by nucleophilic substitution reactions of aromatic dihalides activated with electron-withdrawing groups, such as (4-chlorophenyl)sulfone, and phenol. Afterwards, this substituent was subjected to a Friedel-CRafts reaction with 4-chlorobenzoic acid chloride to obtain the target compound. The compounds described above are applicable to the electron-withdrawing group-activated aromatic dihalides used herein. Although, the phenol compound may be substituted, the unsubstituted phenol compound is preferable from the standpoint of heat resistance and flexural properties. The alkali metal salts are preferred for the phenol substitution reaction, and suitable examples of alkali metal compounds for use herein include the compounds described above. The alkali metal compound is used in an amount of 1.2-2 mole multiples per 1 mole of phenol. In the reaction, the above-mentioned polar solvent or a solvent azeotropic with water can be used. The diphenoxy compound reacts with the chlorinated chlorobenzoic acid as an acylating agent in the presence of a Friedel-CRafts reaction activator, such as a Lewis acid such as aluminum chloride, boron tribromide, zinc chloride, etc. The chlorinated chlorobenzoic acid is used in an amount of 2-4 mole times per mole of diphenoxy compound, preferably 2.2-3 mole times. The Friedel-CRafts reaction activator is used in multiples of 1.1-2 equivalents per 1 mole of activated chloride such as chlorobenzoic acid used as an acylating reagent. The reaction time is 15 minutes to 10 hours, and the reaction time is -20-80°C. Solvents used herein include chlorobenzene, nitrobenzene, etc., which are inactive for Friedel-CRafts reactions.

Moreover, the compound represented by the general formula (A) includes a compound prepared by combining bisphenol and at least one electron-withdrawing group W selected from >C═O, -SO ₂ - and >C(CF ₃ ) ₂ , the bisphenol is an ether oxygen that provides an electron-donating group T, and in the general formula (A), P is 2 or greater. In particular, alkali metal salts of bisphenols such as 2,2-bis(4-hydroxybenzene base)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(4-hydroxyphenyl)acetone, 2,2-bis(4-hydroxyphenyl)sulfone, etc. and excess Active aromatic halides such as 4,4-dichlorobenzophenone and bis(4-chlorophenyl)sulfone undergo substitution reactions, and then polymerize using the monomer synthesis method described above to prepare the compound.

Examples of these compounds include compounds represented by the following general formula.

In the above formula, q is an integer of 2 or more, preferably 2-100.

The polyarylene group of the present invention includes repeating structural units derived from aromatic monomers, and it contains at least repeating structural units represented by the following general formula (1').

In the general formula (1'), A, B, ^Ra and Ar are the same groups as those in the general formula (1), and m, n and k are also the same as those described in the general formula (1) .

In addition to the general formula (1'), the repeating structural unit constituting the polyarylene of the present invention is, for example, represented by the general formula (A'). The repeating structural unit constituting the polyarylene group of the present invention other than the general formula (1') is represented by the general formula (A').

In the general formula (A'), R ¹ -R ⁸ , W and T are the same atoms or groups as those in the general formula (A), and P is also the same number as in the general formula (A).

The content ratio of the repeating structural unit represented by the general formula (1') contained in the polyarylene of the present invention is not particularly limited, preferably 0.5-100 mol%, more preferably 10-99.999 mol%. Moreover, the content ratio of the repeating structural unit represented by the general formula (A') contained in the polyarylene of the present invention is preferably 0-99.5 mol%, more preferably 0.001-90 mol%.

(Synthesis of polyarylene)

By reacting at least one monomer selected from the aromatic sulfonate derivatives represented by general formula (1) in the presence of a catalyst, or making 0.5-100 mole %, more preferably 10-99.999 mole %, in the presence of a catalyst At least one monomer selected from aromatic sulfonate derivatives represented by general formula (1) and 0-99.5 mole %, preferably 0.001-90 mole % of other aromatic monomers, preferably at least one The polyarylene of the present invention is prepared from compounds represented by general formula (A). The catalyst used in the reaction is a catalyst system comprising a transition metal compound. The catalyst system comprises (1) a transition metal salt and a compound for a ligand (hereinafter referred to as "ligand component") or a transition metal complex (comprising a copper salt) having a coordinating ligand, and (2) a reducing agent and optionally a salt to increase the rate of polymerization.

Examples of the transition metal salt include 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 compounds such as ferric chloride, Iron bromide and iron iodide, and cobalt compounds such as cobalt chloride, cobalt bromide and cobalt iodide. Among them, nickel chloride and nickel bromide are preferable.

Examples of the ligand component include triphenylphosphine, 2,2'-dipyridine, 1,5-cyclooctadiene, 1,3-bis(diphenylphosphino)propane and the like. Among them, triphenylphosphine and 2,2'-bipyridine are preferable. The above compounds for the ligand component may be used alone or in combination of two or more.

Moreover, the transition metal complexes of the coordinating ligands include nickel chloride bis(triphenylphosphine), nickel bromide bis(triphenylphosphine), nickel iodide bis(triphenylphosphine), nickel iodide bis(triphenylphosphine), Nickel nitride combined with two (triphenylsulfone), nickel chloride combined with 2,2'-bipyridine, nickel bromide combined with 2,2'-bipyridine, nickel iodide combined with 2,2'-bipyridine, nitriding Nickel combined with 2,2'-dipyridine, bis(1,5-cyclooctadiene) nickel, tetrakis(triphenylphosphine)nickel, tetrakis(triphenylphosphine)nickel, tetrakis(triphenylphosphine)palladium wait. Among them, nickel chloride with bis(triphenylphosphine) and nickel chloride with 2,2'-bipyridine are preferable.

Reducing agents used in the above catalyst systems include, for example, iron, zinc, manganese, aluminum, magnesium, sodium, calcium, and the like. Among them, zinc, magnesium and manganese are preferable. These reducing agents are further activated by exposing the reducing agent to an acid such as an organic acid or the like.

Salts used in the above catalyst systems include sodium compounds such as sodium fluoride, sodium chloride, sodium bromide, sodium iodide and sodium sulfate, potassium compounds such as potassium fluoride, potassium chloride, potassium bromide, potassium iodide and potassium sulfate, and ammonium compounds such as tetraethylammonium fluoride, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, and tetraethylammonium sulfate. Among them, sodium bromide, sodium iodide, potassium bromide, tetraethylammonium bromide, and tetraethylammonium iodide are preferable.

As for the ratio of each component used, based on 1 mole of the total amount of the monomer, the transition metal salt or transition metal complex is used in an amount of 0.0001-10 moles, preferably 0.01-0.5 moles. When the amount thereof is less than 0.0001 mol, the polymerization reaction sometimes does not proceed sufficiently, and on the other hand, when the amount exceeds 10 mol, the molecular weight thereof sometimes decreases.

In the catalyst system, when using the transition metal salt and the ligand component, based on 1 mole of the transition metal salt, the amount of the ligand component is usually 0.1-100 moles, preferably 1-10 moles . When the amount thereof is less than 0.1 mol, the catalyst activity may not be sufficient, and on the other hand, when the amount thereof is less than 100 mol, the molecular weight thereof may decrease.

The amount of the reducing agent used is generally 0.1-100 moles, preferably 1-10 moles, based on 1 mole of the total amount of the monomers. When the amount thereof is less than 0.1 mol, the polymerization reaction sometimes does not sufficiently react, and on the other hand, when it exceeds 100 mol, purification of the resulting polymer is sometimes too difficult.

Furthermore, when a salt is used, the amount thereof is usually 0.001-100 mol, preferably 0.01-1 mol, based on 1 mol of the total amount of the monomers. When the amount thereof is less than 0.001 mol, the effect of increasing the polymerization reaction rate is sometimes insufficient. On the other hand, when the amount thereof exceeds 100 mol, purification of the resulting polymer is sometimes too difficult.

Polymerization solvents used herein include tetrahydrofuran, cyclohexane, dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, v- Butyllactone, sulfolane, v-butyl lactam, dimethylimidazolone, tetramethylurea, etc. Among them, tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone are preferable. These polymerization solvents are preferably sufficiently dried before use.

The concentration of all monomers contained in the polymerization solvent is usually 1-90% by weight, preferably 5-40% by weight.

Also, the polymerization temperature in the polymerization reaction is usually 0-200°C, preferably 50-120°C. The polymerization time is usually 0.5-100 hours, preferably 1-40 hours.

In this way, at least one monomer selected from aromatic sulfonic acid ester derivatives represented by the general formula (1) is (copolymerized) polymerized, or at least one monomer selected from the aromatic sulfonic acid represented by the general formula (1) is copolymerized. An ester derivative monomer and at least one monomer selected from compounds represented by the general formula (A) are used to prepare a polyarylene-containing polymerization solution.

The molecular weight of the thus obtained polyarylene, that is, the weight average molecular weight in terms of polystyrene, is 10,000-1,000,000, preferably 20,000-800,000 as measured by gel permeation chromatography (GPC).

(polyarylene having sulfonic acid groups)

Through the hydrolysis reaction of the above-mentioned polyarylene group, the sulfonate group (-SO ₃ R ^a , -SO ₃ R ^b ) in the repeating structural unit represented by the general formula (1') is converted into a sulfonic acid group (-SO ₃ H), to prepare the polyarylene with sulfonic acid groups of the present invention.

Exemplary hydrolysis reactions include:

(1) A method of introducing the above polyarylene group into an excess of water or alcohol each containing a small amount of hydrochloric acid, followed by stirring for 5 minutes or more.

(2) At a temperature of about 80-120° C., reacting the above-mentioned polyarylene in trifluoroacetic acid for 5-10 hours,

(3) At a temperature of about 80-150°C, react the above-mentioned polyarylene group in a solution for 3-10 hours, and then add hydrochloric acid, and use 1 mole of the sulfonic acid group contained in the polyarylene group In terms of (-SO ₃ R ^a , -SO ₃ R ^b ), the solution contains 1-3 molar ratios of lithium bromide, and the solution is, for example, an N-methylpyrrolidone solution.

The thus obtained polyarylene having sulfonic acid groups has 0.5-3 meq/g, preferably 0.8-2.8 meq/g of sulfonic acid. When its amount is less than 0.5meq/g, its proton conductivity cannot be increased. On the other hand, when its amount exceeds 3meq/g, its hydrophilicity is improved, and the resulting polyarylene is soluble in water, or even insoluble In water, it can be dissolved in hot water, and even if it is insoluble in water, its durability will be reduced.

The amount of the sulfonic acid group can be easily controlled by changing the ratio of the aromatic sulfonate derivative (1) to the compound (A), and further changing the type of the monomer and the mixture thereof.

From the COC absorption value at 1230-1250cm ^-1 or the C=O absorption value at 1640-1660cm ^-1 through infrared absorption spectroscopy, the structure of the polyarylene group with sulfonic acid can be confirmed, and it can also be obtained from nuclear magnetic resonance The spectrum ( ¹ H-NMR) was determined by the peak of the aromatic proton at 6.8-8.0 ppm.

In the present invention, it is preferable that 90% or more of the sulfonic acid groups (-SO ₃ R ^a , -SO ₃ R ^b ) contained in the polyarylene group are converted into sulfonic acid groups (-SO ₃ H).

(polymer solid electrolyte)

The polymer solid electrolyte of the present invention contains a polyarylene group having the above-mentioned sulfonic acid group.

The polymer solid electrolyte of the present invention is suitable for use in, for example, electrolytes for primary batteries, electrolytes for secondary batteries, proton conductive membranes for fuel cells, display elements, various sensors, signal transmission media, solid capacitors, ion exchange membranes, and the like.

(Proton Conducting Membrane)

The proton conducting membrane of the present invention contains a polyarylene group having a sulfonic acid group. In the preparation of the proton conducting membrane from polyarylene with sulfonic acid groups, in addition to the polyarylene with sulfonic acid groups, inorganic acids such as sulfuric acid and phosphoric acid can also be used simultaneously, including carboxylic acid and an appropriate amount of water of organic acids.

In the present invention, the polyarylene having a sulfonic acid group is dissolved in a solvent, a solution is prepared, the resulting solution is poured onto a substrate by casting, and molded into a film by a casting method for forming a film, and thus The proton conducting membrane is prepared. In this case, the substrate is not particularly limited as long as it can be used in an ordinary solution casting method. For example, where a plastic or metal substrate is used, it is preferable to use a substrate made of a thermoplastic resin, such as a polyethylene terephthalate (PET) film.

The solvents capable of dissolving polyarylenes with sulfonic acid groups include aprotic polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, ν-butyl lactone, N, N-dimethylacetamide, dimethyl sulfoxide, dimethyl urea, dimethyl imidazolone, etc., in terms of solubility and solution viscosity, N-methyl-2-pyrrolidone (hereinafter referred to as "NMP "). The aprotic polar solvents can be used alone or in combination of two or more of them.

As for the solvent capable of dissolving the polyarylene having a sulfonic acid group, a mixture of the above-mentioned aprotic polar solvent and alcohol can be used. Examples of the alcohol include methanol, ethanol, propanol, isopropanol, sec-butyl alcohol, tert-butyl alcohol, etc., and methanol is particularly preferred because of its ability to reduce the viscosity of the solution over a wide range of compositions. Effect. The alcohols may be used alone or in combination of two or more.

Although the solution viscosity depends on the molecular weight or polymer concentration of the polyarylene having sulfonic acid groups, the solution viscosity is usually 2000-100000 mPa·s, preferably 3000-50000 mPa·s. When the solution viscosity is lower than 2000 mPa·s, the solution has poor retention during film formation and sometimes runs off the substrate. On the other hand, when it exceeds 100000 mPa·s, the viscosity is too high, so that it cannot be extruded from the die orifice of a mold, and it is sometimes difficult to form a film by casting.

When using a high-boiling-point solvent as a casting solvent, the film produced in the above manner sometimes has a large amount of residual solvent, but when the resulting green film is immersed in water, the solvent contained in the green film can be replaced by water, which can Reduce residual solvent in the resulting film.

Application examples of the method of immersing the green film in water may be a batch method of immersing a sheet in water and a laminated film to be formed in the form of a film on a commonly obtained base film (for example, PET), or from a base A continuous process in which the separated membranes are immersed in water and then air-dried.

The batch method is preferably used because it can suppress wrinkles formed on the surface of the film due to the process of mounting the treated film in a frame.

The green film is preferably soaked in water at a contact ratio of not less than 10 parts by weight, preferably 30 parts by weight, per 1 part by weight of the green film. It is preferable to keep its contact ratio as large as possible in order to reduce the amount of solvent remaining in the resulting proton-conducting membrane. Also, in order to effectively reduce the amount of solvent remaining in the resulting proton conductive membrane, the water used in the impregnation can be replaced, or the concentration of the organic solvent in the water can be kept at a fixed concentration or reduced by overflow. In order to effectively suppress the planar distribution of the organic solvent remaining in the proton conductive membrane, the concentration of the organic solvent in water may be made uniform by stirring or the like.

The dry thickness of the proton conductive membrane prepared by this method is usually 10-100 microns, preferably 20-80 microns.

Furthermore, in the present invention, polyarylene is molded into a film by the above-mentioned method without hydrolysis, and then hydrolyzed in the same method as above, and thus the polyarylene containing sulfonic acid group can also be prepared. Proton-conducting membranes of polyarylenes.

The aromatic sulfonate derivative and polyarylene of the present invention can be used for the above-mentioned polyarylene having sulfonic acid and its preparation method.

Example

The invention is illustrated in detail below with reference to the following non-limiting examples.

In Examples, measurement of the amount of sulfonic acid groups, proton conductivity, and thermal decomposition initiation temperature, and evaluation of tensile strength properties, hot water resistance, and resistance to Fenton's reagent were performed in the following manner.

Measuring the amount of sulfonic acid groups

The resulting polyarylene having sulfonic acid groups is fully washed with water until the washing water is neutral to remove residual free acid, and then dried. A specified amount of the resulting product was weighed and dissolved in a THF/water mixed solvent, and titrated using phenolphthalein as an indicator and NaOH standard solution to determine the amount of sulfonic acid from the neutralization point.

Measuring proton conductivity

By fixing a platinum wire (φ = 0.5 mm) on the surface of a strip cut film with a width of 5 mm, and keeping the sample in a device with constant temperature and constant humidity, and measuring the alternating current between the platinum wires Impedance to determine resistance to alternating current. That is, the impedance was measured at an alternating current of 10 KHz under the conditions described below. A chemical impedance measurement system (manufactured by NF circuit design block Co., Ltd.) was used as a device for measuring resistance, and JW241 manufactured by Yamato Scientific Co. Ltd. was used as a device for constant temperature and constant humidity. Five platinum wires were fixed at intervals of 5 mm, the distance between the lead wires became 5-20 mm, and the resistance of the alternating current was measured. The specific resistance of the thin film is calculated from the distance of the leads and the gradient of resistance, the impedance of the alternating current is calculated from the reciprocal of the specific resistance, and the proton conductivity is calculated from this impedance.

Specific resistance R (Ω/cm) = 0.5 (cm) × film thickness (cm) × gradient between resistance wires (Ω/cm)

Tensile Strength Properties

A 3 mm x 65 mm strip cut film sample was prepared, and the modulus of elasticity, breaking strength and elongation were measured using a tensile testing machine.

Hot water tolerance test

The film was cut into a 2.0 cm×3.0 cm rectangle and weighed to prepare a test piece for the test. This film was placed in a 250 ml polycarbonate bottle, about 100 ml of distilled water was added thereto, and heated at 120°C for 24 hours using a pressure cooker tester (PC-242HS manufactured by HIR ^A YAMA MFS CORP). After completion of the test, each film was taken out from the hot water, and the water present on the surface was lightly wiped with KIMWIPE (trade name). The water content is determined by weighing the film with water. Also, the dimensions of the film are measured to determine the degree of expansion. Further, this film was dried using a vacuum dryer for 5 hours, whereby water was evaporated to dryness, and then, the film prepared after the hot water test was weighed to determine the residual weight.

Tolerance Test of Fenton's Reagent

The film was cut into a 3.0 cm×4.0 cm rectangle and weighed to prepare a test piece for the test. This film was immersed in 200 ml of distilled water for 48 hours, whereby the residual solvent contained in the film was eluted. During this step, the distilled water was changed twice. After immersion in water, the film was laminated with a filter, thereby extracting the water present on the surface, and then air dried overnight and weighed.

Prepare a 3% hydrogen peroxide solution by diluting a commercially available 30% hydrogen peroxide solution with distilled water. Ferrous sulfate heptahydrate was added to the solution and dissolved so that Fe(II) ions were 20 ppm, thereby preparing Fenton's reagent. 200ml of this solution was poured into a 250ml polyester bottle, heated using a water bath and kept at 45°C. After confirming that the temperature of the solution was at 45°C, each film was added to the bottle and heated for 26 hours. After 26 hours, the solid was removed from solution and air dried overnight. The solids were weighed to determine the gravimetric residue.

thermal decomposition temperature

The decomposition temperature of the polyarylene having a sulfonic acid group measured by TGA (thermogravimetric analysis) (under a nitrogen atmosphere, a temperature increase rate of 20° C./min.) was taken as the thermal decomposition temperature.

Example 1

(1) Preparation of the sodium salt of 4-[4-(2,5-dichlorobenzoyl)phenoxy]benzenesulfonic acid (A-SO ₃ Na)

Add 2,5-dichloro-4'-phenoxybenzophenone (A, 137.3g, 400mmol) to a three-necked flask equipped with a stirrer and a condenser, followed by 500ml of 1,2-dichloroethane (1,2-DCE) and dissolved. Further, 2M acetylsulfuric acid freshly prepared from 56ml of concentrated sulfuric acid, 152ml of acetic anhydride and 400ml of 1,2-DCE was added to the solution with stirring, and reacted in an oil bath at 60°C for 3 hours. After the indicated time, the reaction was stopped by adding 30 ml 1-propanol. Thereafter, the reaction solution was concentrated until the volume was 400 ml, and then an aqueous NaOH solution (120 g (3 mol)/water 400 ml) was added. The 1,2-DCE in the solution was distilled off by azeotropy, and then the resulting transparent pale yellow solution was cooled to obtain a sediment, and the deposited sediment was filtered. The deposit was vacuum-dried at 70°C, thereby preparing the sodium salt (A-SO ₃ Na) of 4-[4-(2,5-dichlorobenzoyl)phenoxy]benzenesulfonic acid as a white fine powder. The crude crystals were used in the following step without purification. As for the obtained white powder, the IR spectrum is shown in FIG. 1 , and the NMR spectrum is shown in FIG. 2 and 3 .

(2) Preparation of 4-[4-(2,5-dichlorobenzoyl)phenoxy]benzenesulfonic acid chloride (A-SO ₂ Cl)

300ml of acetonitrile and 200ml of sulfolane were added to 215g (about 400ml) of crude crystals of A-SO ₃ Na as solvents, and phosphorus oxytrichloride (245.3g, 1.6 moles) was added, and then reacted at 70°C to obtain a reaction mixture. Furthermore, 5 ml of N,N-dimethylacetamide was added thereto, and the resulting yellow suspension was stirred at 71-73°C for 40 minutes and then cooled to 3°C. 1 L of cooling water was added to the suspension at such a rate that the temperature of the reaction system did not exceed 10°C. The resulting sediment was collected, washed with cold water, and recrystallized with 350 ml of toluene to obtain 153 g of the target white crystal A-SO ₂ Cl with a melting point of 130.5-131.5° C. (87% yield based on A). Figure 4 shows the IR spectrum and Figures 5 and 6 show the NMR spectrum.

(3) Preparation of isobutyl 4-[4-(2,5-dichlorobenzoyl)phenoxy]benzenesulfonate (A-SO ₃ iso-Bu)

Under mechanical stirring, 22.09 g (50 mmol) of A-SO ₂ Cl was added dropwise to 2-methyl-1-propanol (4.0 g, 55 mmol) and 30 ml of pyridine under cooling within 40 minutes. As a result, a thick suspension was obtained and stirring was continued for a further 1 hour at 12-15°C. Add 30ml of concentrated hydrochloric acid and 100g of ice water to the suspension at one time. The suspension is stirred until it gradually becomes homogeneous. Afterwards, the homogeneous suspension was quickly filtered through a Buchner funnel. A white sticky sediment was recovered. The sediment was redissolved in 300 ml of ethyl acetate and washed with water through a separatory funnel. The obtained organic layer was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. After concentration, the light yellow oily liquid was dissolved in 30 ml of hot hexane, and stood in a refrigerator for several days to obtain 16.67 g of the target white crystal A-SO ₃ iso-Bu, whose melting point was 73-74 ° C, The yield was 70%. Figure 7 shows the IR spectrum and Figures 8 and 9 show the NMR spectrum.

Example 2

Preparation of neopentyl 4-[4-(2,5-dichlorobenzoyl)phenoxy]benzenesulfonate (A-SO ₃ neo-Pe)

Under mechanical stirring, the same A-SO ₂ Cl (22.09g, 50mmol ). As a result, a thick suspension was obtained and stirring was continued for a further 1 hour at 12-15°C.

The suspension was reacted with 30 ml of concentrated hydrochloric acid and 100 g of ice water to produce a sediment. The deposit was collected by filtration, washed with cold water and dried, then brought into contact with 150 ml of boiling toluene. Insoluble components (most of which were the pyridinium salt of A- _SO3H ) were removed by filtration, and the filtrate was concentrated to prepare 40 ml of a concentrate. The concentrate was left to stand in a refrigerator, and white crystals of A-SO ₃ neo-Pe (melting point: 112.0-112.5° C.) were deposited. The amount thereof was 16.92 g, and the yield was 69%. Figure 10 shows the IR spectrum and Figures 11 and 12 show the NMR spectrum.

Synthesis Example 1

Preparation of oligomers (referred to as "BCPAF oligomers")

Add 67.3 g (0.20 mol) of 2,2-bis(4-hydroxyphenyl)-1 , 1,1,3,3,3-hexafluoropropane (bisphenol AF), 60.3g (0.24 mole) 4,4'-dichlorobenzophenone (4,4'-DCBP), 71.9g (0.52 mol) of potassium carbonate, 300ml of N, N-dimethylacetamide (DMAc) and 150ml of toluene were reacted under heating at 130°C in a nitrogen atmosphere while stirring in an oil bath. The reaction was carried out until the water produced by the reaction azeotroped with toluene and was removed from the system through a Dean-Stark tube. After about 3 hours of reaction, little water production was seen. Thereafter, when the reaction temperature was gradually increased to 150°C, most of the toluene was removed, and then the reaction was continued at 150°C for 10 hours. After reacting for 10 hours, 10.0 g (0.040 mol) of 4,4'-DCBP was added, and the reaction was continued for another 5 hours. The resulting reaction solution was left to cool, and then the deposited inorganic compound generated as a by-product was filtered off, and the filtrate was introduced into 4 L of methanol. The deposited product was collected by filtration, dried and dissolved in 300 ml of tetrahydrofuran. The solution was redeposited in 4 L of methanol to yield 95 g of the target polymer (85% yield).

The weight-average molecular weight of the obtained polymer was 12,500 as measured by GPC (THF solvent) in terms of polystyrene. Also, the polymer is soluble in THF, NMP, DMAc and sulfolane, has a Tg of 110°C, and a thermal decomposition temperature of 498°C.

The resulting polymer is an oligomer represented by the following general formula (I) (hereinafter referred to as "BCPAF" oligomer).

Synthesis Example 2

Preparation of oligomers (referred to as "BCPFL oligomers")

Except that 67.3 g (0.20 mol) of 2,2-bis(4-hydroxyphenyl)-1,1,1 was replaced by 80.6 g (0.23 mol) of 9,9-bis(4-hydroxyphenyl)fluoro (FLBP), 3,3,3-hexafluoropropane (bisphenol AF), and using NMP instead of DMAc as a solvent, repeat the steps described in Synthesis Example 1 for reaction and post-treatment. As a result, 103 g of the target polymer was obtained. (Yield: 83%).

The weight average molecular weight of the obtained polymer was 12300 as measured by GPC (THF solvent) in terms of polystyrene. Also, the polymer was soluble in THF, NMP and DMI, had a Tg of 175°C, and a thermal decomposition temperature of 524°C.

The obtained polymer is an oligomer represented by the following general formula (II) (hereinafter referred to as "BCPFL" oligomer).

Polymerization reaction of polyarylene

Example 3

Preparation of polyarylene (polyAB-SO ₃ i-Bu) with isobutyl group as protecting group

Under a nitrogen atmosphere, 15.34g (32mmol) of ASO ₃ -isobutyl prepared in Example 1, 10.52g (1.33mmol) of BCPAF oligomers prepared in Synthesis Example 1, 0.65g (1mmol) of Ni(PPH ₃ ) ₂ Cl ₂ , 33.50 g (13.33 mmol) PPh ₃ , 0.65 g (4.83 mmol) NaI and 5.45 g (83.33 mmol) zinc dust were added 60 ml of dry N-methylpyrrolidone (NMP).

The reaction mixture was heated (finally to 74° C.) with stirring and reacted for 3 hours. During the reaction, a viscosity increase in the reaction solution was observed. The polymerization solution was diluted with 250 ml THF, stirred for 30 minutes, and filtered using Celite (TM John-Manville as a filter aid). The filtrate was poured into an excess of 1500 ml of methanol, thereby coagulating. The resulting coagulum was collected by filtration, air dried, and redissolved in THF/NMP (200ml/30ml), coagulated and deposited by an excess of 1500ml methanol. The condensate thus treated was air-dried and then dried by heating to obtain 20.54 g of the target yellow flaky polymer (polyAB-SO ₃ i-Bu) of a sulfonic acid derivative protected with isobutyl (yield: 78%) .

As for polystyrene, the number average molecular weight of the polymer measured by GPC (THF solvent) was 13200, and the weight average molecular weight was 33300. Figure 13 shows the IR spectrum and Figure 14 shows the NMR spectrum.

Example 4

Preparation of polyarylenes with neopentyl groups as protecting groups (polyAB-SO ₃ neo-Pe)

Using 39.46g (98.33mmol) of ASO ₃ -neopentyl prepared in Example 2, 18.70g (0.167mmol) of BCPAF oligomer prepared in Synthesis Example 1, and 1.96g (0.30mmol) of Ni(PPH ₃ ) ₂ Cl _2. 10.49g (4.00mmol) of PPH ₃ , 0.45g (0.30mmol) of NaI, 15.69g (24.00mmol) of zinc powder and 129ml of dry NMP, and carry out the polymerization reaction according to the same steps as described in Example 3. After 60 minutes from the start of the polymerization reaction, a rise in viscosity in the reaction solution was observed. The polymerization was continued for 3 hours. Thereafter, the polymerization reaction solution was diluted with THF, followed by post-treatment. As a result, 47.0 g of an objective yellow fibrous copolymer of a neopentyl-protected sulfonic acid derivative was obtained. (polyAB-SO ₃ neo-Pe) (yield: 92%).

In the case of polystyrene, the polymer had a number average molecular weight of 53,700 and a weight average molecular weight of 187,000 as measured by GPC (THF solvent). Figure 15 shows the IR spectrum and Figures 16 and 17 show the NMR spectrum.

Example 5

Preparation of polyarylenes with neopentyl groups as protecting groups (polyAB-SO ₃ neo-Pe)

Use 7.62g (0.62mmol) of the BCPFL oligomer prepared in Synthesis Example 2 to replace the BCPAF oligomer used in 4.88g (0.62mmol) of Example 4, and use 17.81g (44.38mmol) of A-SO prepared in Example 2 ₃ neo-Pe, 0.88g (1.35mmol) Ni(PPH ₃ ) ₂ Cl ₂ , 4.72g (18.00mmol) PPH ₃ , 0.20g (1.35mmol) NaI, 7.06g (108.00mmol) zinc powder and 60ml dry NMP , Carry out the polymerization and post-treatment in the same steps as described in Example 4.

As a result, 21.0 g of an objective yellow fibrous copolymer of a neopentyl-protected sulfonic acid derivative was obtained. (polyAB-SO ₃ neo-Pe) (yield: 77%).

In the case of polystyrene, the polymer has a number average molecular weight of 22,100 and a weight average molecular weight of 90,800 as measured by GPC (THF solvent). Figure 18 shows the IR spectrum.

Conversion to polyarylenes with sulfonic acid groups by hydrolysis

Example 6

Conversion of polyarylenes with isobutyl groups as protecting groups (polyAB-SO ₃ i-Bu) into polyarylenes with sulfonic acid groups (polyAB-SO ₃ H)

5.08 g (2.7 mmol as SO ₃ i-Bu) of the polyAB-SO ₃ i-Bu prepared in Example 3 was dissolved in 60 ml of NMP and heated to 90°C. A mixture of 50 ml of methanol and 8 ml of concentrated hydrochloric acid was added at one time to the reaction solution. The reaction was carried out in suspension under slight reflux for 10 hours. The distillation apparatus was set, and excess methanol was distilled off, whereby a pale green transparent solution was obtained. The solution was cast on a glass plate to form a thin film. After the film was formed, the film was immersed in water for 3 days, air-dried and vacuum-dried to obtain a film with a dry thickness of 50 micrometers. According to IR spectrum and quantitative analysis of ion exchange column, the sulfonate group (-SO ₃ R) was quantitatively converted into sulfonic acid group (-SO ₃ H).

Figure 19 shows the IR spectrum and Figure 20 shows the NMR spectrum. The polyarylene containing sulfonic acid groups had a sulfonic acid group content of 1.46 meq/g (the content of sulfonic acid groups prepared in the polymerization reaction was 1.47 meq/g).

Example 7

Conversion of polyarylenes with neopentyl groups as protecting groups (polyAB- _SO3neo -Pe) for sulfonic acids into polyarylenes with sulfonic acid groups (polyAB- _SO3H )

4.50 g (8 mmol as SO ₃ neo-Pe) of polyAB-SO ₃ neo-Pe was gradually added to 35 ml of trifluoroacetic acid. The resulting viscous solution was heated to gentle reflux. During the reaction, a further 5 ml of trifluoroacetic acid were added. After 2 hours, the polymer had settled and stirring was continued for a total of 4 hours. After the reaction, the reaction mixture was left standing until the temperature dropped to room temperature. The sediment was collected by filtration as aggregates. Under stirring conditions, the aggregate was suspended in 400 ml THF and washed, after which the aggregate was collected by filtration and air-dried to obtain a crude product. The crude product was washed twice with water to finally obtain a light brown powder polymer.

An 8% by weight NMP solution of the obtained polymer was cast on a glass plate to form a thin film. After film formation, the film was air-dried and vacuum-dried to obtain a film with a dry thickness of 40 microns. According to IR spectrum and quantitative analysis of ion exchange column, the sulfonate group (-SO ₃ R) was quantitatively converted into sulfonic acid group (-SO ₃ H).

Figure 21 shows the IR spectrum and Figure 22 shows the NMR spectrum. The polyarylene containing sulfonic acid groups had a sulfonic acid group content of 2.0 meq/g (the content of sulfonic acid groups prepared in the polymerization reaction was 2.0 meq/g).

The properties of the obtained polyarylene film having sulfonic acid groups are as follows.

(1) Proton conductivity

85℃ 95%RH: 0.268S/cm

85℃ 70%RH: 0.100S/cm

85℃ 30%RH: 0.018S/cm

(2) Tensile properties

Room temperature: elastic modulus 4.4Gpa, tensile strength 153Mpa, yield strength 98Mpa, elongation 52%

120°C: elastic modulus 4.4Gpa, tensile strength 131Mpa, elongation 38%

(3) Moisture content

95°C for 48 hours: 65%

After immersion at 95°C for 500 hours, the film was stable without changing the equivalent weight of sulfonic acid.

(4) thermal stability

120°C for 500 hours: After heat treatment at 120°C for 500 hours, no insoluble components were generated, and the film was stable without changing the equivalent weight of sulfonic acid.

Thermal decomposition temperature: 162°C

Example 8

Conversion of polyarylenes with neopentyl groups as protecting groups (polyAB- _SO3neo -Pe) for sulfonic acids into polyarylenes with sulfonic acid groups (polyAB- _SO3H )

Except that 4.90g of poly AB-SO ₃ neo-Pe prepared in Example 5 and 40ml of trifluoroacetic acid were used instead of the poly AB-SO ₃ neo-Pe used in Example 4, the steps of Example 7 were repeated to finally produce shallow Brown powder polymer.

An 8% by weight NMP solution of the obtained polymer was cast on a glass plate to form a thin film. After film formation, the film was air-dried and vacuum-dried to obtain a film with a dry thickness of 40 microns. According to IR spectrum and quantitative analysis of ion exchange column, the sulfonate group (-SO ₃ R) was quantitatively converted into sulfonic acid group (-SO ₃ H).

Figure 23 shows the IR spectrum. The polyarylene containing sulfonic acid groups had a monomeric sulfonic acid group content of 1.8 meq/g (the content of sulfonic acid groups prepared in the polymerization reaction was 2.2 meq/g).

The properties of the obtained polyarylene film having sulfonic acid groups are as follows.

(1) Proton conductivity

85℃ 95%RH: 0.250S/cm

85℃ 70%RH: 0.095S/cm

85℃ 30%RH: 0.018S/cm

(2) Tensile properties

Room temperature: elastic modulus 4.6Gpa, tensile strength 136Mpa, elongation 44%

120°C: elastic modulus 4.6Gpa, tensile strength 117Mpa, elongation 30%

(3) Moisture content

95°C for 48 hours: 70%

After immersion at 95°C for 500 hours, the film was stable without changing the equivalent weight of sulfonic acid.

(4) thermal stability

After heat treatment at 120°C for 500 hours, no insoluble components were generated and the film was stable without changing the equivalent weight of sulfonic acid.

Thermal decomposition temperature: 170°C

Example 9

Polymerization reaction of polyarylene

In a nitrogen atmosphere, 100ml of dry N,N-dimethylacetamide (DMAc) was added to 26.66g (41.7mmol) of the compound represented by the following general formula (3), 17.47g (1.56mmol) of the compound produced in Synthesis Example 1 In the mixture of the obtained BCPAF oligomer, 0.79g (1.2mmol) Ni(PPH ₃ ) ₂ Cl ₂ , 4.20g (16.01mmol) PPH ₃ , 0.18g (1.20mmol) NaI, 6.28g (96.07mmol) zinc powder .

Under stirring conditions, the reaction solution was heated (finally heated to 79° C.) and reacted for 3 hours. During the course of the reaction, a rise in viscosity in the reaction solution was observed. Thereafter, the polymerization reaction solution was diluted with 425 ml of DMAc, and after stirring for 30 minutes, was filtered using Celite as a filter aid. A portion of the filtrate was poured into methanol and coagulated. The resulting copolymer of sulfonate derivatives having neopentyl groups, in terms of polystyrene, had a number average molecular weight of 59400 and a weight average molecular weight of 178300 as measured by GPC (THF solvent). Figure 24 shows the IR spectrum and Figure 25 shows the NMR spectrum.

The filtrate was concentrated by an evaporator to 344 g, and 10.00 g (0.12 mol) of LiBr was added thereto, and the reaction was carried out at an internal bath temperature of 110° C. (bath temperature 120° C.) for 7 hours under a nitrogen atmosphere. After the reaction, the reaction solution was cooled to room temperature, and poured into 4 L of acetone, and condensed. The resulting condensate was collected by filtration and air dried. Afterwards, the coagulum was pulverized by a mixer and washed with 1500 ml of 1N hydrochloric acid under stirring. After filtration, the resulting product was washed with ion-exchanged water so that the pH was 5 or more, and a powdery polymer was finally obtained.

An 8% by weight NMP solution of the obtained polymer was cast on a glass plate to form a thin film. After film formation, the film was air-dried and vacuum-dried to obtain a film with a dry thickness of 40 microns. According to IR spectrum and quantitative analysis by ion exchange column, the sulfonate group was quantitatively converted into sulfonic acid group.

The polyarylene containing sulfonic acid groups had a sulfonic acid group content of 2.0 meq/g (the theoretical value of the sulfonic acid group content determined from the molar ratio of monomers prepared in the polymerization reaction was 2.0 meq/g). Figure 26 shows the IR spectrum and Figure 27 shows the NMR spectrum of the resulting polyarylene containing sulfonic acid groups.

The properties of the obtained polyarylene film having sulfonic acid groups are as follows.

(1) Proton conductivity

85℃ 95%RH: 0.275S/cm

85℃ 70%RH: 0.106S/cm

85℃ 30%RH: 0.022S/cm

(4) thermal stability

After heat treatment at 120°C for 500 hours, no insoluble components were generated and the film was stable without changing the equivalent weight of sulfonic acid.

Example 10

S-2,5-DCPPB Chlorosulfonated Compound Sulfonate

            (S-2,5-DCPPB Neopentyl Ester)

In the above general formula, Np is neopentyl.

(1) Synthetic disulfonated compounds of phenoxyphenol

370 g (0.69 mol) of 4-phenoxyphenol was added to a 1 L three-necked flask equipped with a stirrer, a thermometer and a catheter for introducing nitrogen, and 740 ml of concentrated sulfuric acid was added dropwise in about 1 hour. After the dropwise addition was complete, the solution was stirred at 50° C. for 3 hours. After the reaction was completed, the reaction solution was diluted with 200ml of water, and neutralized with KOH solution (KOH 1.5Kg/water, 750ml). The solid thus deposited was filtered and washed with acetone to obtain 1709 g of a white powder. The powder comprises potassium salt of phenoxyphenol disulfonated compound (SPPO) and potassium hydroxide. Figure 28 shows the NMR spectrum of the powder.

(2) Synthesis of 2,5-dichloro-4'-(4-phenoxyphenoxy)benzophenone disulfonated compound (S-2,5-DCPPB)

Add 43.7g (0.31 moles) of SPPO, 43.14g (0.10 moles) of 2,5-dichloro-4'-fluorobenzophenone, 2.6 g (8 mmol) of tetra-n-butylammonium bromide (TBAB) and 200 ml of dimethyl sulfoxide were stirred at 160° C. in a nitrogen atmosphere. Also, 30 g (65 mmol) of SPPO and 1.0 g (3 mmol) of TBAB were appropriately added, and the reaction was continued. After 30 hours, the resulting salt was filtered and the filtrate was poured into 4.5 L of acetone. The solid thus deposited was filtered and washed 4-5 times with 1-1.5 L of acetone. The solid was dried in vacuo to yield 81 g of S-2,5-DCPPB (70% yield). Figure 29 shows the NMR spectrum of the compound.

(3) Synthesis of S-2,5-DCPPB chlorosulfonated compound

146.5 g (0.22 mol) of S-2,5-DCPPB and 650 ml of acetonitrile were added to a 1 L three-necked flask equipped with a stirrer, a thermometer, and a catheter for introducing nitrogen, and stirred at 70°C. To the solution was added dropwise 220 g of phosphorus oxychloride over 15 minutes, followed by stirring for 5 hours. After the reaction was completed, 1.3 Kg of ice water was added dropwise to the reaction solution, and diluted with 2.5 L of toluene. The organic phase was dried with anhydrous magnesium sulfate. After removing the remaining inorganic phase by silica gel chromatography (developing solvent: toluene), the residue was recrystallized from toluene/hexane to obtain 71 g of the target compound (yield 52%). Figure 30 shows the NMR spectrum of the compound.

(4) Synthesis of S-2,5-DCPPB neopentyl ester

59.5 g (94 mmol) of S-2,5-DCPPB chlorosulfonated compound and 400 ml of pyridinium salt were added to a 1 L three-necked flask equipped with a stirrer, a thermometer and a catheter for introducing nitrogen, and cooled in ice water. 20.5 g (233 mmol) of neopentyl alcohol were added to the solution and stirred, after which the ice-water bath was removed, and the solution was stirred at room temperature for 5 hours. Pyridine thus deposited was removed by filtration, and the residue was extracted with toluene/ethyl acetate (600ml/600ml). The extracted solution was washed several times with aqueous hydrochloric acid (concentrated hydrochloric acid 300 ml/water 300 ml), and then washed several times with 5% aqueous sodium bicarbonate and saturated aqueous sodium chloride. The solvent was distilled off and separated by silica gel chromatography (developing solvent: toluene) to obtain 36 g of S-2,5-DCPPB neopentyl ester. Figure 31 shows the IR spectrum and Figure 32 shows the NMR spectrum of the ester.

Example 11

synthetic polyarylene

Add 21.4g (29mmol) of S-2,5-DCPPB neopentyl ester, 9.90g (0.9mmol) of S-2,5-DCPPB neopentyl ester, 9.90g (0.9mmol) of synthetic implementation to the 500mL three-necked flask equipped with a stirrer, a thermometer and a conduit introducing nitrogen. The BCPAF oligomer that example 1 makes, 0.59g (0.9mmol) dichloride two (triphenylphosphine) nickels, 0.13g (0.9mmol) sodium iodide, 3.15g (12mmol) triphenylphosphine and 4.71g (72mmol) zinc and dried under vacuum for 2 hours. After that, the flask was flushed with dry nitrogen, and 73 ml of dehydrated dimethylacetamide was added to the flask, and then polymerization was started.

While controlling the reaction temperature to not higher than 90°C, the polymerization reaction was continued for 3 hours. Thereafter, the polymerization reaction solution was diluted by adding 80 ml of tetrahydrofuran, and then poured into a methanol/concentrated hydrochloric acid solution (methanol 2.7 L/concentrated hydrochloric acid 0.3 L).

The product thus deposited was filtered, washed with methanol, and then air-dried. The dried polymer was dissolved in tetrahydrofuran, and insoluble components were removed by filtration, after which the residue was redeposited in 3.5 L of methanol. The polymer was filtered and vacuum dried to yield 23.5 g of polyarylene (80% yield). In the case of polystyrene, the polymer had a number average molecular weight of 61,000 and a weight average molecular weight of 278,000 as measured by GPC (THF solvent).

In the general formula, NP is neopentyl.

Example 12

Synthesis of polyarylenes with sulfonic acid groups

23.5 g of the polyarylene prepared in Example 11 and 6.34 g (73 mmol) of lithium bromide were added to a 300 mL three-necked flask equipped with a stirrer, a thermometer, and a catheter for introducing nitrogen, and stirred at 120° C. for 7 hours. The resulting reaction solution was poured into acetone to coagulate the polymer. The resulting solid polymer was treated twice with distilled water/concentrated hydrochloric acid solution (3.0 L/0.37 L), then washed with distilled water until the pH was neutral. The solid polymer was dried at 70° C. for 12 hours to obtain 19.9 g of a polyarylene having a sulfonic acid group represented by the following general formula.

In the case of polystyrene, the polymer has a number average molecular weight of 78,000 and a weight average molecular weight of 230,000 as measured by GPC (THF solvent). The polyarylene having a sulfonic acid group had an ion exchange capacity of 2.19 meq/g. Using N-methylpyrrolidone, a film with a thickness of 40 μm was prepared by the casting method.

performance evaluation

The properties of the obtained film were evaluated. The results are listed in Table 1.

Table 1

evaluation item unit Proton conductivity (85℃, 90%RH) S/cm 0.25 Elastic Modulus Gpa 3.5 Breaking strength Mpa 84 Extensibility % 46 Resistance to hot water (120°C, 100 hours) Weight retention, % 100 Resistance to Fenton's reagent (3% H2O ₂ , 20ppm Fe2+, 45°C, 20 hours) Weight retention, % 100 thermal decomposition start temperature ℃ 240

Effect of the present invention

The polyarylene having sulfonic acid group and the preparation method thereof of the present invention have high safety and low load in polymer recovery, because in converting polyarylene into polyarylene having sulfonic acid group, No sulfonating agents were used. Moreover, the amount of sulfonic acid groups introduced into the polymer and the positions of their introduction are easy to control.

The aromatic sulfonate derivative and polyarylene of the present invention are used for the above-mentioned polyarylene with sulfonic acid and its preparation method.

The proton conductive membrane of the present invention has excellent conductivity.

Claims (5)

1. A polyarylene group comprising a repeating structural unit derived from an aromatic compound, and comprising at least a repeating structural unit represented by the general formula (1'): In the formula, A is -CO-, -C(CF ₃ ) ₂ - or -SO ₂ -, B is -O-, R ^a is a hydrocarbon group with 1-20 carbon atoms, and Ar is a hydrocarbon group consisting of -SO ₃ R ^b The aryl group represented by the substituent, in -SO ₃ R ^b , R ^b is a hydrocarbon group with 1-20 carbon atoms, m is an integer between 0-10, n is an integer between 0-10, and k is 1 An integer of -4. 2. The polyarylene according to claim 1, characterized in that, the polyarylene comprises 0.5-100 mol% of the repeating structural unit represented by the general formula (1'), and 0-99.5 mol% of the general formula A repeating structural unit shown in formula (A'); In the formula, R ¹ -R ⁸ are the same or different, and are at least one atom or group selected from hydrogen, fluorine atom, alkyl, fluorine-substituted alkyl, allyl and aryl, and W is a divalent electron-withdrawing group group, T is a divalent organic group, and P is 0 or a positive integer. 3. A method for preparing a polyarylene having a sulfonic acid group, said method comprising the steps of: coupling and polymerizing an aromatic compound comprising an aromatic sulfonate derivative shown in general formula (1), preparing the polyarylene , and hydrolyzes the polyarylene:

In the formula, X is a halogen atom selected from fluorine, A is -CO-, -C(CF ₃ ) ₂ - or -SO ₂ -, B is -0-, R ^a is 1-20 carbon atoms Hydrocarbyl, Ar is an aryl group having a substituent represented by -SO ₃ R ^b , in -SO ₃ R ^b , R ^b is a hydrocarbon group with 1-20 carbon atoms, m is an integer between 0-10, and n is An integer between 0-10, k is an integer between 1-4. 4. A polymer solid electrolyte comprising polyarylene having sulfonic acid groups prepared by the method of claim 3. 5. A proton-conducting membrane for a fuel cell, said membrane comprising the polymer solid electrolyte according to claim 4.

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