JP2010055945A - Manufacturing method of ionically dissociative functional polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of an ionically dissociative functional polymer which is to be conducted in a milder condition than a conventional one. <P>SOLUTION: The manufacturing method of an ionically dissociative functional polymer has a process (1) in which, in a solvent of a boiling point 160°C or higher containing at lease one kind out of a group composed of halogenated aromatic compound and a perfluoro aliphatic compound, an ionically dissociative functional molecule precursor composed of a bonding of a precursor group of an ionically dissociative group through a spacer group of which at least a part is fluorinated and a combination molecule are made to perform reaction on fullerene to obtain a reaction product composed of a bonding of the ionically dissociative functional molecule precursor through a linking chain of a linking molecule origin. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for producing an ion dissociative functional polymer.

  As a proton conductor used for a solid polymer electrolyte fuel cell or the like, Nafion (Nafion (trade name), manufactured by DuPont, perfluorosulfonic acid resin) is most widely used.

  Nafion's molecular structure consists of two substructures with essentially different properties: (1) a perfluorinated single-stranded main chain that forms a hydrophobic molecular skeleton, and (2) a hydrophilic sulfone. It consists of perfluorinated side chains that contain acid groups and function as proton donating sites. Since this structure is a perfluorinated structure that does not contain unsaturated bonds, it is thermally and chemically stable, but it is necessary for developing proton conductivity in dry and high temperatures. The water stored in the resin is lost, and the proton conductivity tends to decrease.

On the other hand, a material mainly composed of a carbon cluster derivative in which a proton dissociable group such as a hydrogen sulfate ester group (—OSO ₃ H) or a sulfonic acid group (—SO ₃ H) is introduced into a carbon cluster such as fullerene, It is known that proton conduction is possible within a solid structure (see, for example, Patent Document 1). A carbon cluster derivative in which a proton dissociable group is introduced into fullerene via a spacer group is also known (see, for example, Patent Document 2).

  Patent Documents 1 and 2 describe that by introducing a functional group into a carbon cluster such as fullerene, a material that conducts ions such as protons can be obtained. When applied to an electrochemical device such as a fuel cell, the material is required to be chemically and thermally stable under conditions required for the electrochemical device.

As a chemically and thermally stable proton conductive fullerene derivative, Patent Document 2 discloses an ion dissociative functional molecule in which an ion dissociable group is bonded to fullerene via a spacer group at least partially fluorinated. An ion dissociative functional polymer having a structure bonded via a linking molecule-derived linking chain is disclosed. The ion dissociative functional polymer is chemically and thermally stable and has water insolubility, and is useful as a proton conductor used in solid polymer electrolyte fuel cells and the like.
International Publication No. 01/006519 Pamphlet JP 2003-303513 A

  The ion-dissociative functional polymer described in Patent Document 2 is chemically and thermally stable as described above, has water insolubility, and is a proton used in a solid polymer electrolyte fuel cell or the like. Although it is useful as a conductor, its production conditions have not yet been fully examined.

  An object of this invention is to provide the manufacturing method of an ion dissociative functional polymer performed on conditions milder than before.

In order to solve the above problems, the present inventors have conducted intensive studies, and as a result, by using a specific solvent, the precursor of an ion-dissociable group can be introduced into fullerene via a spacer group at least partially fluorinated. An ion dissociable functional molecule precursor formed by bonding body groups is reacted with a linking molecule to obtain a reaction product obtained by binding the ion dissociable functional molecule precursor via a linking molecule-derived linking chain. The present inventors have found that the reaction conditions in step (1) can be performed under milder conditions than in the past, and the present invention has been completed.

That is, the method for producing an ion dissociative functional polymer of the present invention comprises a fullerene in a solvent having a boiling point of 160 ° C. or higher, containing at least one selected from the group consisting of a halogenated aromatic compound and a perfluoroaliphatic compound. In addition, an ion dissociable functional molecule precursor formed by bonding a precursor group of an ion dissociable group through a spacer group at least partially fluorinated,
It comprises a step (1) of reacting a linking molecule to obtain a reaction product obtained by binding the ion dissociative functional molecule precursor through a linking molecule-derived linking chain.

  The halogenated aromatic compound is at least one halogenated aromatic selected from the group consisting of trichlorobenzene, o-dibromobenzene, m-dibromobenzene, o-dichlorobenzene, m-dichlorobenzene, and 1-chloronaphthalene. Preferably, the perfluoroaliphatic compound is at least one perfluoroaliphatic compound selected from the group consisting of perfluorotrialkylamines and C12-30 perfluoroalkanes. The perfluorotrialkylamine is preferably at least one perfluorotrialkylamine selected from the group consisting of perfluorotripentylamine and perfluorotributylamine.

It is preferable that the reaction temperature in the said reaction is 160-300 degreeC.
In the reaction, it is preferable to use 1.0 to 5.0 equivalents of a linking molecule with respect to 1.0 equivalent of an ion dissociative functional molecule precursor.

The precursor group of the ion dissociable group is preferably at least one group selected from the group consisting of —SO ₂ F, —SO ₂ Cl, —COF, and —COCl.
The connecting chain is preferably a chain represented by the following general formula (1).

_{- (CF 2) n- ··· (} 1)
(In the general formula (1), n is an integer of 5 to 10.)
The spacer group preferably has a structure represented by the following general formula (2), and more preferably a group represented by the following general formula (3).

-(CF ₂ ) m- (2)
(In the general formula (2), m is an integer of 1 to 10.)
_{- (CF 2) m-O-} (CF 2) m- ··· (3)
(In the above general formula (3), m is each independently an integer of 1 to 10.)
The step (1) may be performed in the presence of a radical initiator.

  The amount of the radical initiator used is preferably more than 0.1 equivalent and 10 equivalents or less with respect to 1.0 equivalent of the linking molecule.

  In the method for producing an ion-dissociative functional polymer of the present invention, the step (1) can be performed under milder conditions than in the prior art, that is, under normal pressure or slightly increased pressure, and with a reduced amount of linking molecules used. Therefore, an ion dissociative functional polymer can be produced with an advantage in industrial processes.

Next, the present invention will be specifically described.
The method for producing an ionically dissociative functional polymer of the present invention includes a method for producing fullerene in a solvent having a boiling point of 160 ° C. or higher, including at least one selected from the group consisting of a halogenated aromatic compound and a perfluoroaliphatic compound. , Reacting a linking molecule with an ion dissociative functional molecule precursor formed by bonding a precursor group of an ionic dissociable group via a spacer group that is at least partially fluorinated, And having a step (1) of obtaining a reaction product obtained by bonding the ion dissociative functional molecule precursor.

  The method for producing an ion dissociation functional polymer of the present invention includes at least one selected from the group consisting of a halogenated aromatic compound and a perfluoroaliphatic compound in the step (1), and has a boiling point of 160 ° C. or higher. The solvent is used. Since the solvent has a boiling point of 160 ° C. or higher, the reaction can be performed under normal pressure when the ion dissociative functional molecule precursor and the linking molecule are reacted.

That is, when an ion dissociative functional molecule precursor is generally reacted with a linking molecule, the reaction is usually performed at a high temperature of 160 to 300 ° C. In the conventional method, a mixed solvent of C ₆ F ₆ and CS ₂ is used. Among them, an ion dissociative functional molecule precursor was reacted with a linking molecule. However, since CS _{2 has} a boiling point of 46 ° C. and the mixed solvent boils at about 50 ° C., it has been necessary to carry out the reaction under pressure using an autoclave or the like in the conventional method. Further, in the conventional method, it is necessary to use a large amount of linking molecules (for example, 24 equivalents per equivalent of the ion dissociative functional molecule precursor). (For example, 1.0 to 5.0 equivalents per equivalent of ion dissociable functional molecule precursor).

[Solvent having a boiling point of 160 ° C. or higher]
Step (1) of the method for producing an ion dissociative functional polymer of the present invention includes at least one selected from the group consisting of a halogenated aromatic compound and a perfluoroaliphatic compound as described above, and has a boiling point of 160. Perform in a solvent at or above

  In the present invention, a solvent having a boiling point of 160 ° C. or higher and containing at least one selected from the group consisting of a halogenated aromatic compound and a perfluoroaliphatic compound is also simply referred to as a solvent.

  By using the above solvent, an ion dissociation function in which a precursor group of an ion dissociable group is bonded to fullerene through a spacer group at least partially fluorinated under normal pressure or slight pressure. A molecular precursor and a linking molecule can be reacted.

  The halogenated aromatic compound is not particularly limited as long as it has a boiling point of 160 ° C. or higher. Usually, trichlorobenzene, o-dibromobenzene, m-dibromobenzene, o-dichlorobenzene, m-dichlorobenzene, 1- At least one halogenated aromatic compound selected from the group consisting of chloronaphthalene is used.

  As trichlorobenzene, any of 1,3,5-trichlorobenzene, 1,2,3-trichlorobenzene, and 1,2,4-trichlorobenzene may be used, but in terms of price and availability, 1, 2,4-trichlorobenzene is preferred.

  Further, the perfluoroaliphatic compound is not particularly limited as long as the boiling point is 160 ° C. or higher, but is usually at least selected from the group consisting of perfluorotrialkylamines and perfluoroalkanes having 12 to 30 carbon atoms. One perfluoroaliphatic compound is used.

  As the perfluorotrialkylamine, for example, perfluorotripentylamine, perfluorotributylamine and the like are used, and as the perfluoroalkane having 12 to 30 carbon atoms, perfluoropentadecane and the like are used.

As the solvent, perfluorotripentylamine and 1,2,4-trichlorobenzene are preferable.
The solvent may be a mixed solvent containing components other than the halogenated aromatic compound and the perfluoroaliphatic compound, but the boiling point of the solvent is 160 ° C. or higher.

[Ion dissociative functional molecular precursor]
In step (1) of the method for producing an ion dissociative functional polymer of the present invention, ion dissociation in which a precursor group of an ion dissociable group is bonded to fullerene via a spacer group at least partially fluorinated. Sexual functional molecule precursor is used.

  In the present invention, an ion dissociative functional molecule precursor obtained by binding a precursor group of an ion dissociable group to a fullerene via a spacer group at least partially fluorinated is simply an ion dissociable functional molecule. Also referred to as precursor.

The number of carbon atoms of the fullerene is not particularly limited, and a conventionally known fullerene such as C ₃₆ , C ₆₀ , C ₇₀ , C ₇₆ , C ₇₈ , C ₈₂ , C ₈₄ , C ₉₀ , C ₉₆ , C _266, etc. should be used. Can do. In addition,
Fullerenes may be a mixture having different carbon numbers. As the fullerene, it is preferable to use a readily available C ₆₀ or C ₇₀ or mixtures thereof.

  The fullerene may be a fullerene to which a functional group such as a halogen atom, a hydrocarbon group, a fluorinated hydrocarbon group, an ether group, an ester group, an amide group, or a ketone group is added.

The spacer group is not particularly limited, but an organic group having a fluorine atom is usually used from the viewpoint of thermal and chemical stability.
The spacer group is preferably a group having a structure represented by the following formula (2).

-(CF ₂ ) m- (2)
(In the general formula (2), m is an integer of 1 to 10.)
Moreover, as a spacer group, the organic group containing an ether structure is preferable, and specifically, it is preferable that it is group represented by following General formula (3).

_{- (CF 2) m-O-} (CF 2) m- ··· (3)
(In the above general formula (3), m is each independently an integer of 1 to 10.)
The precursor group of the ion dissociable group is not particularly limited as long as it can be converted into an ion dissociable group by a treatment such as hydrolysis. Precursor groups of the ionic dissociative group is usually -SO ₂ F, -S
At least one group selected from the group consisting of O ₂ Cl, —COF, —COCl,
It is preferably at least one group selected from the group consisting of —SO ₂ F and —COF.

  The ion dissociative functional molecule precursor is formed by binding a precursor group of an ion dissociable group to fullerene via a spacer group. When the spacer group is represented by Rf and the precursor group of the ion dissociable group is represented by Y, the ion dissociative functional molecule precursor has a structure in which -Rf-Y is bonded to fullerene. The number of —Rf—Y bonded to the fullerene is not particularly limited, but is usually 3 to 10 on average per molecule of fullerene, and preferably 5 to 8.

  The ion dissociative functional molecule precursor used in the present invention is usually obtained by binding a molecule having the -Rf-Y structure to fullerene. As the molecule having the -Rf-Y structure, a molecule represented by I-Rf-Y having an iodine atom at the end of the molecule is used.

  The method for producing the ion dissociative functional molecule precursor used in the present invention is not particularly limited, and is described in, for example, Japanese Patent Application Laid-Open Nos. 2003-303513, 2006-131517, and 2007-22996. In addition, it can be obtained by a conventionally known production method.

Wherein an example of a method of manufacturing the ion-dissociative functional compound precursor -Rf-Y indicates to the case of _{-CF 2 -CF 2 -O-CF 2} -CF 2 -SO 2 F as an example. First, fullerene and I—CF ₂ —CF ₂ —O—CF ₂ —CF ₂ —SO ₂ F are reacted in 1,2,4-trichlorobenzene under heating at about 200 ° C. In the reaction, an iodine atom and a radical (• CF ₂ —CF ₂ —O—CF ₂ — are formed at the end of the iodine atom side of I—CF ₂ —CF ₂ —O—CF ₂ —CF ₂ —SO ₂ F by heating. It decomposes into CF ₂ —SO ₂ F) and the radical is introduced into fullerene. By purifying the reaction mixture obtained by the above reaction, an ion dissociative functional molecule precursor formed by bonding —CF ₂ —CF ₂ —O—CF ₂ —CF ₂ —SO ₂ F to fullerene can be obtained.

[Linked molecule]
In step (1) of the method for producing an ion dissociative functional polymer of the present invention, a linking molecule is used.
The linking molecule is not particularly limited as long as it can react with the ionic dissociative functional molecule precursor and obtain a reaction product obtained by binding the ionic dissociative functional molecule precursor via a linking molecule-derived linking chain. but usually as the linking chain, alkyl group, aryl group, - (CF ₂₎ n-
(N is an integer of 5 to 10) and has at least one group selected from the group consisting of a fluorinated alkyl group, an ether group, an ester group, an amide group and a ketone group.

Specific examples of the connecting chain include a chain represented by the following general formula (1).
_{- (CF 2) n- ··· (} 1)
(In the general formula (1), n is an integer of 5 to 10.)
The linking molecule used in the present invention is a compound having the above linking chain, for example, a compound represented by X—R—X (X is Cl, Br or I, and R is a linking chain).

  In the present invention, when the compound represented by X—R—X is used as the linking molecule, in the step (1), X is eliminated and the end of R is the ion dissociable functional molecule precursor. Bonds to fullerene derived structures. A high molecular weight reaction product can be obtained by bonding the end of R to a structure derived from different fullerenes. That is, in the reactive organism obtained in the step (1), a plurality of fullerene-derived structures of the ion dissociative functional molecule precursor are bonded via a linking chain.

As the compound represented by X—R—X, a compound represented by X— (CF ₂ ) n—X (
However, n is an integer of 5-10. ) Is preferred.
[Step (1)]
In the step (1) of the method for producing an ion dissociative functional polymer of the present invention, the ion dissociative functional molecule precursor and the linking molecule are reacted in the solvent to form a linking molecule-derived linking chain. In this step, a reaction product obtained by bonding the ion dissociative functional molecule precursor is obtained.

In the present invention, a reaction product obtained by bonding the ion dissociative functional molecule precursor via a linking molecule-derived linking chain is also simply referred to as a reaction product.
Although there is no limitation in particular as reaction conditions of a process (1), Usually, it carries out at the temperature of 160-300 degreeC. By using the solvent as the solvent in step (1), the reaction product can be obtained under milder conditions than before. That is, when an ion dissociative functional molecule precursor and a linking molecule are reacted in a mixed solvent of C ₆ F ₆ and CS ₂ , it is necessary to perform the reaction under pressure using an autoclave or the like as described above. However, in step (1) of the present invention, by using a solvent having a boiling point of 160 or more, for example, the reaction can be carried out under normal pressure or slightly increased pressure of 10 kPa or less.

Moreover, the quantity of the connection molecule | numerator used for a process (1) is 1.0-5.0 equivalent with respect to 1.0 equivalent of an ion dissociative functional molecule precursor normally, Preferably it is 1.1-3.0. Is equivalent.
Moreover, the usage-amount of a solvent does not have limitation in particular, Usually, it is 1-10 times amount of an ion dissociative functional molecule precursor by weight ratio.

Further, step (1) may be performed in the presence of a radical initiator in order to reduce the reaction time.
The radical initiator is preferably an organic peroxide such as benzoyl peroxide, lauroyl peroxide, potassium peroxide, cumene hydroperoxide, t-butyl hydroperoxide, dichromyl peroxide, di-t-butyl peroxide, Di-t-butyl peroxide is more preferred.

Although the usage-amount of the said radical initiator does not have limitation in particular, Usually, it exceeds 0.1 equivalent and is 10 equivalent or less with respect to 1.0 equivalent of connecting molecules, and 1-5 equivalent is preferable.
The reaction time in step (1) is not particularly limited, but is usually 0.5 to 3 days when performed in the presence of a radical initiator, and when performed in the absence of a radical initiator. Usually 3 to 10 days.

[Other processes]
In the method for producing an ion dissociative functional polymer of the present invention, the reaction product obtained by binding the ion dissociative functional molecule precursor via the connecting chain derived from the connecting molecule obtained in the step (1) has. The step of obtaining an ion dissociative functional polymer by converting a precursor group of an ion dissociable group into an ion dissociable group is included.

  That is, in the ion dissociable functional polymer obtained by the production method of the present invention, an ion dissociable group is bonded to fullerene via a spacer group that is at least partially fluorinated, and a plurality of fullerenes are linked. It is connected through a chain.

The ion dissociable group possessed by the ion dissociative functional polymer of the present invention is not particularly limited. For example, a sulfonic acid group (—SO ₂ OH), a carboxyl group (—COOH), a sulfonamide group (—SO ₂ —). NH _2), at least one group selected from the group consisting of carboxamide group (-CO-NH _2).

  The ion dissociable group is a proton dissociable group that releases protons as ions, and the ion dissociable group of the ion dissociable functional polymer of the present invention includes an alkali metal in which the hydrogen atom of the ion dissociable group is an alkali metal. It may be a group substituted with an atom. Examples of the alkali metal atom include a lithium atom, a sodium atom, a potassium atom, a rubidium atom, and a cesium atom.

The method for converting the precursor group of the ion dissociable group into an ion dissociable group is not particularly limited. For example, the precursor group of the ion dissociable group is a —SO ₂ F group, and the ion dissociable group is when a sulfonic acid group (-SO ₂ OH) is the reaction product in C ₆ F ₆ and THF (tetrahydrofuran) was hydrolyzed and reacted with water and sodium hydroxide, -SO ₂ F
The group is converted to -SO ₃ Na groups. Subsequently, the reaction mixture obtained by converting the —SO ₂ F group into —SO ₃ Na group is reacted with a strong acid such as HCl, H ₂ SO ₄ , HClO ₄ , HNO ₃ to convert the —SO ₃ Na group into a sulfonic acid group. It can be converted to (—SO ₂ OH) to obtain an ion dissociative functional polymer.

The ion dissociative functional polymer obtained by the method for producing an ion dissociative functional polymer of the present invention is excellent in thermal and chemical stability, and can suitably release ions. When the ion dissociable group is a proton dissociable group, the ion dissociable functional polymer of the present invention is excellent in proton conductivity. Specifically, the proton conductivity measured in an atmosphere of an ion dissociative functional polymer at a temperature of 19 ° C. and a relative humidity of 70% for 1 day or longer is usually 1.0 × 10 ⁻² S / cm. That's it.

The ion dissociative functional polymer of the present invention can be used for various applications such as proton conductors and ion exchange resins used in fuel cells.
In particular, when the ion dissociable group is a proton dissociable group, it can be used as a proton conductor used in a fuel cell.

EXAMPLES Next, although an Example is shown and this invention is demonstrated further in detail, this invention is not limited by these.
[Production of ion-dissociable functional molecule precursor]
An ion dissociative functional molecule precursor was produced by the following method.

Dropping funnel, a condenser (cooler), glass three-necked flask 500ml equipped with a thermometer and a stirrer, under nitrogen atmosphere, fullerene (manufactured by Frontier Carbon Corporation nanom mix ST (C ₆₀ to about 60%, C ₇₀ about 25%))) 3.0 g was added followed by 300 ml of 1,2,4-trichlorobenzene.

While stirring the three-necked flask to which the fullerene and 1,2,4-trichlorobenzene were added, the temperature was maintained at 200 ° C., and I-CF was used as a molecule having a spacer group and a precursor group of an ion dissociable group. 22.6 g of ₂ -CF ₂ -O-CF ₂ -CF ₂ -SO ₂ F (24 times the amount of the fullerene material; 24 equivalents to 1 equivalent of fullerene) was added from the dropping funnel over about 1 day. It was dripped. After completion of dropping, the mixture was reacted at 200 ° C. for 6 days with stirring.

  After completion of the reaction, the reaction mixture was taken out from the three-necked flask, 1,2,4-trichlorobenzene was distilled off from the reaction mixture under reduced pressure, and the residue was vacuum-dried at 150 ° C. overnight. To the residue after drying, 200 ml of hexane was added and heated to reflux for 30 minutes. After cooling, the hexane layer was removed by decantation, and the residue was vacuum-dried to obtain 9.20 g of an ion dissociable functional molecule precursor that was a dark brown powder.

In the above reaction, the precursor raw material molecule is thermally decomposed into iodine atoms and radicals (.CF ₂ —CF ₂ —O—CF ₂ —CF ₂ —SO ₂ F) at the end on the iodine atom side. As a result, The generated radical is added to the fullerene molecule by an unpaired electron bonded to the iodine atom.

In addition, when ¹⁹ F-NMR of the ion dissociative functional molecule precursor was measured, the ion dissociative functional molecule precursor was detected via a spacer group (—CF ₂ —CF ₂ —O—CF ₂ —CF ₂ —). compound precursor groups (-SO ₂ F) is added to _{(fullerenes) n - (CF 2 -CF 2} -O-CF 2 -C
F ₂ —SO ₂ F) _m (n is mainly 60 and m is an integer of about 6 to 10).

As a result of elemental analysis of the ion dissociative functional molecule precursor, the fluorine content was 42% by mass.
The sulfur content was 8.1% by mass. From this, when the fullerene is C ₆₀ in the ion dissociative functional molecule precursor, a precursor-containing spacer group (—CF ₂ —CF ₂ —O—CF ₂ ) composed of a precursor group and a spacer group is introduced into one molecule. The average introduced number of —CF ₂ —SO ₂ F) was determined to be 7.

The structure of the ion dissociable functional molecule precursor when fullerene is C ₆₀ is represented by the following general formula (4).

（上記式（４）において、ｍは６〜１０の整数であり、ｍの平均は７である。）
〔実施例１〕
（工程（１））
攪拌器を取り付けたガラス製２００ｍｌ四つ口フラスコに、上記イオン解離性機能分子前駆体１０．０ｇ（３．５５ｍｍｏｌ）を加え、連結分子としてＩＣ₈Ｆ₁₆Ｉを３．６７
ｇ（５．６１ｍｍｏｌ）および１,２,４−トリクロロベンゼンを２０ｍｌ（室温で２９ｇ）加え、窒素気流雰囲気下、２００℃のオイルバスで７日間加熱・攪拌しつづけた。このとき、次第にフラスコ内にヨウ素結晶が析出していった。また、時折反応液をサンプリングして¹⁹Ｆ−ＮＭＲを測定し、連結分子由来の−５９ｐｐｍのピークが小さくなっていく様子を確認した。その積分値は、反応開始から３日目には反応開始時に比べておよそ３分の２であり、7日目には１０分の１以下であり、反応が順調に進行していた。

(In the above formula (4), m is an integer of 6 to 10, and the average of m is 7.)
[Example 1]
(Process (1))
10.0 g (3.55 mmol) of the above ion dissociative functional molecule precursor is added to a glass 200 ml four-necked flask equipped with a stirrer, and IC ₈ F ₁₆ I as a connecting molecule is 3.67.
20 g (29 g at room temperature) of g (5.61 mmol) and 1,2,4-trichlorobenzene were added, and the mixture was continuously heated and stirred in a 200 ° C. oil bath for 7 days under a nitrogen stream. At this time, iodine crystals gradually precipitated in the flask. Moreover, the reaction solution was sampled occasionally and ¹⁹ F-NMR was measured, and it was confirmed that the peak at −59 ppm derived from the linking molecule was getting smaller. The integrated value was about two-thirds compared to that at the start of the reaction on the third day from the start of the reaction, and less than one-tenth on the seventh day, and the reaction proceeded smoothly.

  The temperature of the oil bath was set to 150 ° C., and 1,2,4-trichlorobenzene was distilled off in the form of vacuum distillation, and further dried under reduced pressure at 150 ° C. for 1 hour. After returning to room temperature, the residue in the four-necked flask was washed once with 20 ml of chloroform and four times with 10 ml, filtered off with insoluble matter, and the resulting solid was dried under reduced pressure at room temperature overnight to give a black solid. Reaction product was obtained.

(Hydrolysis step)
The reaction product, which was a black solid obtained in step (1), was pulverized in a mortar and transferred to a 200 ml eggplant flask, to which 10 ml of THF and 50 ml of 1N NaOH aqueous solution were added, and mixed at room temperature for 30 minutes. Next, a condenser (cooler) was attached to the flask and refluxed in an oil bath at 80 ° C. for 1 hour. Subsequently, the temperature of the oil bath was set to 100 ° C., and THF was distilled off by atmospheric distillation, and then allowed to cool to room temperature.

  While cooling the flask in an ice-water bath, 20 ml of concentrated hydrochloric acid was added, and this liquid was subjected to a HITACHI cooling centrifuge 05PR-22 (setting 10 ° C., 3000 rpm × 15 min, the same applies hereinafter) to separate the precipitate and the supernatant, and the supernatant The liquid was removed.

After adding 30 ml of 10% hydrochloric acid to the precipitate and mixing well, it was similarly centrifuged to separate the precipitate and the supernatant, and the supernatant was removed.
Add 30 ml of 10% hydrochloric acid to the precipitate, transfer to a flask, heat in an oil bath at 80 ° C. for 1 hour, sufficiently cool in an ice-water bath, and then centrifuge again to separate the precipitate from the supernatant. The supernatant was removed.

After adding 30 ml of 10% hydrochloric acid to the precipitate and mixing well, it was similarly centrifuged to separate the precipitate and the supernatant, and the supernatant was removed.
After adding 30 ml of water to the precipitate and mixing well, it was similarly centrifuged to separate the precipitate and the supernatant, and the supernatant was removed.

After adding water to the precipitate, the step of centrifuging (hereinafter referred to as washing) was repeated a total of 5 times.
The washed precipitate was transferred to a petri dish and dried in a blow dryer at 50 ° C. for 2 days.

After the dried precipitate was pulverized in a mortar, it was further vacuum-dried overnight in a sample oven set at 30 ° C. to obtain 7.30 g of an ion dissociative functional polymer.
Incidentally, the above hydrolysis step, the sulfonyl fluoride groups -SO ₂ F are converted to sulfonic acid groups (-SO ₂ OH).

[Example 2]
The 20 ml of 1,2,4-trichlorobenzene (29 g at room temperature) used in Example 1 was changed to 20 ml of perfluorotripentylamine (trade name Fluorinert FC-70) (38 g at room temperature), and IC ₈ F ₁₆ I The amount used was changed to 4.13 g (6.31 mmol), and heating and stirring for 7 days in Example 1 were performed for 8 days. A polymer was obtained.

Example 3
(Process (1))
To a glass 200 ml four-necked flask equipped with a stirrer, 11.5 g (4.09 mmol) of the ion dissociable functional molecule precursor was added, and 30 ml of 1,2,4-trichlorobenzene (44 g at room temperature) was added. The mixture was heated and stirred in an oil bath at 200 ° C. in a nitrogen stream atmosphere. Thereto, 1.64 g (4.04 mmol) of IC ₈ F ₁₆ I and 0.90 g (6.16 mmol) of di-t-butyl peroxide (hereinafter sometimes referred to as (t-BuO) ₂ ) and 1 , 2,4-trichlorobenzene dissolved in 9.5 g was added in 8 portions every 1 hour and stirred overnight.

On the next day, a solution prepared by dissolving 2.11 g (3.23 mmol) of IC ₈ F ₁₆ I and 0.71 g (4.86 mmol) of (t-BuO) ₂ in 7.6 g of 1,2,4-trichlorobenzene was used. Divided and added every hour and stirred overnight.

On the next day, 1.06 g (7.26 mmol) of (t-BuO) ₂ dissolved in 2.1 g of 1,2,4-trichlorobenzene was divided into 8 portions and added every other hour and stirred overnight.
All stirring was performed at 200 ° C. Occasionally, the reaction solution was sampled and ¹⁹ F-NMR was measured, and it was confirmed that the peak at −59 ppm was reduced.

On the next day (3 days after the start of the reaction), the temperature of the oil bath was set to 150 ° C., and 1,2,4-trichlorobenzene was distilled off in the form of vacuum distillation, followed by vacuum drying at 150 ° C. for 1 hour. After returning to room temperature, the residue in the flask was washed once with 20 ml of chloroform and 4 times with 10 ml, and the insoluble matter was collected by filtration. The obtained solid was dried under reduced pressure at room temperature overnight to be a black solid. A reaction product was obtained.

(Hydrolysis step)
The hydrolysis step was performed in the same manner as in Example 1 to obtain 9.26 g of an ion dissociable functional polymer.
[Comparative Example 1]
The 1,2,4-trichlorobenzene used in Example 1 was changed to a CS ₂ / C ₆ F ₆ mixed solvent (CS ₂ : C ₆ F ₆ (volume ratio = 1: 1)), and the same procedure as in Example 1 was performed. The same procedure as in Example 1 was performed except that heating and stirring at 200 ° C. were changed to 45 ° C. (reflux temperature of the mixed solvent).

At 3 days after heating and stirring initiated, no precipitation of iodine into the flask, since there is no change in by ¹⁹ F-NMR, whereby the determined reaction does not occur, and stopped the reaction.
(Ion conductivity measurement)
The ion dissociative functional polymer synthesized in Examples 1 to 3 was vacuum-dried at room temperature for 12 hours, and then 200 mg of the obtained powder was formed into a circular pellet with a diameter of 1.3 cm with a tablet molding machine at a press pressure of 300 MPa. Press molded. The pellets were sandwiched between gold-plated electrodes in a state where they were in close contact, and placed in an atmosphere at a temperature of 19 ° C. and a relative humidity of 70% for 3 days or more.

The pellet electrode assembly was subjected to impedance measurement using an AC impedance analyzer at a frequency of 1 MHz to 1 Hz and an applied voltage of 10 mV.
After completion of the measurement, the area and thickness of the pellet were measured. The proton conductivity of each ion dissociative functional polymer was calculated from the analyzed measurement data.

Claims (11)

In a solvent having a boiling point of 160 ° C. or higher, including at least one selected from the group consisting of a halogenated aromatic compound and a perfluoroaliphatic compound,
An ion dissociable functional molecule precursor formed by binding a precursor group of an ion dissociable group to fullerene via a spacer group at least partially fluorinated;
React with linking molecules,
A method for producing an ion dissociative functional polymer, comprising a step (1) of obtaining a reaction product obtained by binding the ion dissociable functional molecule precursor through a connecting chain derived from a connecting molecule. The halogenated aromatic compound is at least one halogenated aromatic selected from the group consisting of trichlorobenzene, o-dibromobenzene, m-dibromobenzene, o-dichlorobenzene, m-dichlorobenzene, 1-chloronaphthalene. A compound,
The perfluoroaliphatic compound is at least one perfluoroaliphatic compound selected from the group consisting of perfluorotrialkylamines and perfluoroalkanes having 12 to 30 carbon atoms. The manufacturing method of the ion dissociation functional polymer of description. The ion dissociation function according to claim 2, wherein the perfluorotrialkylamine is at least one perfluorotrialkylamine selected from the group consisting of perfluorotripentylamine and perfluorotributylamine. Polymer production method.   The method for producing an ion dissociative functional polymer according to any one of claims 1 to 3, wherein a reaction temperature in the reaction is 160 to 300 ° C.   5. The ion dissociation property according to claim 1, wherein 1.0 to 5.0 equivalents of a linking molecule are used for 1.0 equivalent of an ion dissociative functional molecule precursor in the reaction. A method for producing functional polymers. 6. The precursor group of the ion dissociable group is at least one group selected from the group consisting of —SO ₂ F, —SO ₂ Cl, —COF, and —COCl. The manufacturing method of the ion dissociation functional polymer in any one of. The method for producing an ion-dissociative functional polymer according to any one of claims 1 to 6, wherein the linking chain is a chain represented by the following general formula (1).
_{- (CF 2) n- ··· (} 1)
(In the general formula (1), n is an integer of 5 to 10.) The said spacer group has a structure represented by following General formula (2), The manufacturing method of the ion dissociative functional polymer in any one of Claims 1-7 characterized by the above-mentioned.
-(CF ₂ ) m- (2)
(In the general formula (2), m is an integer of 1 to 10.) The method for producing an ion-dissociative functional polymer according to any one of claims 1 to 8, wherein the spacer group is a group represented by the following general formula (3).
_{- (CF 2) m-O-} (CF 2) m- ··· (3)
(In the above general formula (3), m is each independently an integer of 1 to 10.) The method for producing an ion dissociative functional polymer according to any one of claims 1 to 9, wherein the step (1) is performed in the presence of a radical initiator.   The method for producing an ion-dissociative functional polymer according to claim 10, wherein the amount of the radical initiator used is more than 0.1 equivalent and 10 equivalents or less with respect to 1.0 equivalent of a linking molecule. .