JP2010270013A - Manufacturing method for ionically dissociable functional polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing an ionically dissociable functional polymer useful as a proton conductor in a higher yield than before. <P>SOLUTION: The manufacturing method for the ionically dissociable functional polymer comprises a step (1) of allowing a precursor (A) of an ionically dissociable functional molecule comprising fullerene and a precursor group of an ionically dissociable group bonded thereto via an at least partially fluorinated spacer group, at least one compound (B) selected from a precursor of an ionically dissociable functional molecule comprising fullerene, different in the molar number of precursor groups of the ionically dissociable group per gram from the precursor (A) of an ionically dissociable functional molecule, and a precursor of an ionically dissociable group bonded thereto via an at least partially fluorinated spacer group, and fullerene, and a linking molecule (C) to react thereby to obtain a reaction product comprising the precursor (A) of an ionically dissociable functional molecule and the compound (B) bonded via a linking chain derived from the linking molecule (C). <P>COPYRIGHT: (C)2011,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 a material that conducts ions such as protons can be obtained by introducing a functional group into a carbon cluster such as fullerene. When applied to an electrochemical device such as a battery, 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 method of manufacturing the ion dissociative functional polymer useful as a proton conductor with a sufficient yield rather than before.

  In order to solve the above problems, the present inventors have conducted intensive studies, and as a result, the number of moles of the ion dissociable functional molecule precursor (A) and the precursor group of the ion dissociable group per gram is ion dissociative. By using at least one compound (B) selected from an ion dissociative functional molecule precursor and fullerene, which is different from the functional molecule precursor (A), as a raw material, an ion dissociative functional polymer can be obtained with higher yield than before. The present invention has been completed by finding that it can be produced.

  That is, the method for producing an ion dissociative functional polymer of the present invention comprises an ion dissociative functional molecule precursor in which a precursor group of an ion dissociable group is bonded to fullerene via a spacer group that is at least partially fluorinated. The number of moles of the precursor group of the ion dissociable group per gram of the body (A) is different from that of the ion dissociable functional molecule precursor (A), and through a spacer group at least partially fluorinated with the fullerene. Derived from a linking molecule (C) by reacting at least one compound (B) selected from an ion dissociable functional molecule precursor and a fullerene obtained by bonding a precursor group of an ionic dissociable group with a linking molecule (C). A step (1) of obtaining a reaction product obtained by bonding the ion dissociative functional molecule precursor (A) and the compound (B) through the connecting chain.

  The reaction preferably includes a step of bringing the mixture containing the ion dissociative functional molecule precursor (A) and at least a part of the compound (B) into contact with at least a part of the linking molecule (C).

  In the reaction, the ion-dissociative functional molecule precursor (A) is contacted with at least a part of the linking molecule (C), and then the blend obtained by the contact and at least a part of the compound (B) It is preferable to have a process of contacting with. It is preferable that the contact between the blend and at least a part of the compound (B) is performed by adding the compound (B) to the blend in multiple portions.

  Per 1 g of the compound (B) when the number of moles of precursor group of the ion dissociable group per gram of the ion dissociative functional molecule precursor (A) is a [mmol / g] The number of moles of the precursor group of the ion dissociable group is preferably 0a to 0.9a [mmol / g].

It is preferable to use 100 to 500 mol% of the linking molecule (C) with respect to 100 mol% in total of the ion dissociative functional molecule precursor (A) and the compound (B).
In the ion dissociative functional molecule precursor (A) and the compound (B), the precursor group of the ion dissociable group is selected from the group consisting of —SO ₂ F, —SO ₂ Cl, —COF, and —COCl. It is preferably at least one group.

In the linking molecule (C), the linking 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.)

In the ion dissociative functional molecule precursor (A) and the compound (B), the spacer group preferably has a structure represented by the following general formula (2).
-(CF ₂ ) m- (2)
(In the general formula (2), m is an integer of 1 to 10.)

In the ion dissociative functional molecule precursor (A) and the compound (B), the spacer group is preferably 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 of the present invention is chemically and thermally stable and water-insoluble, and is useful as a proton conductor used in a solid polymer electrolyte fuel cell or the like. An ion dissociative functional polymer can be produced with a higher yield than conventional ones.

  The ion dissociative functional polymer obtained by the method for producing an ion dissociative functional polymer of the present invention has physical properties equivalent to those of conventional ion dissociative functional polymers, and is also useful as a proton conductor. is there.

Next, the present invention will be specifically described.
The method for producing an ionically dissociative functional polymer of the present invention includes an ion dissociative functional molecule precursor obtained by bonding a precursor group of an ion dissociable group to fullerene via a spacer group that is at least partially fluorinated. (A) and the number of moles of the precursor group of the ion dissociable group per gram are different from those of the ion dissociable functional molecule precursor (A), and ions are introduced through a spacer group at least partially fluorinated with fullerene. At least one compound (B) selected from an ion dissociable functional molecule precursor and a fullerene formed by bonding a precursor group of a dissociable group is reacted with a linking molecule (C) to derive from the linking molecule (C). It has the process (1) which obtains the reaction product which the said ion dissociative functional molecule precursor (A) and a compound (B) couple | bond together through a connection chain.

  In the present specification, an ion dissociative functional molecule precursor (A) obtained by bonding a precursor group of an ion dissociable group to fullerene via a spacer group at least partially fluorinated is referred to as an ion. Also described as a dissociative functional molecule precursor (A), the number of moles of precursor groups of ion dissociable groups per gram is different from that of the ion dissociable functional molecule precursor (A), and at least a part of the fullerene is fluorinated. At least one compound (B) selected from an ion dissociable functional molecule precursor and a fullerene formed by bonding a precursor group of an ion dissociable group via a spacer group is also referred to as a compound (B). In addition, the number of moles of precursor group of the ion dissociable group per gram is different from that of the ion dissociable functional molecule precursor (A), and the ion dissociable group is formed via a spacer group that is at least partially fluorinated with the fullerene. The ion dissociative functional molecule precursor formed by bonding the precursor groups is also referred to as an ion dissociative functional molecule precursor (B ′).

[Ion dissociative functional molecule precursor (A), compound (B)]
The manufacturing method of the ion dissociation functional polymer of this invention has the above-mentioned process (1). In the step (1), an ion dissociative functional molecule precursor (A) and a compound (B) are used.

  As described above, the ion dissociative functional molecule precursor (A) is an ion dissociative function in which a precursor group of an ion dissociable group is bonded to fullerene via a spacer group that is at least partially fluorinated. It is a molecular precursor. That is, fullerene is used as a kind of raw material for the ion dissociative functional molecule precursor (A).

  As described above, the compound (B) is a fullerene spacer in which the number of moles of the precursor group of the ion dissociable group per gram is different from that of the ion dissociable functional molecule precursor (A). It is at least one compound selected from an ion dissociable functional molecule precursor and a fullerene formed by bonding a precursor group of an ion dissociable group through a group. That is, fullerene is used as a kind of raw material of the ion dissociative functional molecule precursor (B ′) or as the compound (B) itself.

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. The fullerene may be a mixture of fullerenes 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 in the ion dissociative functional molecule precursor (A) and the fullerene in the compound (B) may be the same type of fullerene or different types of fullerenes.

  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 of the ion dissociative functional molecule precursor (A) and the ion dissociative functional molecule precursor (B ′) is not particularly limited, but is usually fluorine from the viewpoint of thermal and chemical stability. Organic groups having atoms are used.

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.)

The spacer group is preferably an organic group having an ether structure, and specifically, an organic group having a plurality of structures represented by the formula (2) and having an ether structure is preferable. And more preferably a group represented by
_{- (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 spacer group possessed by the ion dissociative functional molecule precursor (A) and the spacer group possessed by the ion dissociative functional molecule precursor (B ′) may be the same or different.

The precursor group of the ion dissociable functional molecule precursor (A) and the ion dissociative functional molecule precursor (B ′), which is a precursor group of the ion dissociable group, is converted into an ion dissociable group by a treatment such as hydrolysis. If it is group which can be done, there will be no limitation in particular. The precursor group of the ion dissociable group is usually at least one group selected from the group consisting of —SO ₂ F, —SO ₂ Cl, —COF, and —COCl, and includes —SO ₂ F and —COF. It is preferably at least one group selected from the group consisting of

  The precursor group of the ion dissociable group possessed by the ion dissociative functional molecule precursor (A) and the precursor group of the ion dissociable group possessed by the ion dissociable functional molecule precursor (B ′) may be the same. May be different.

  The ion dissociative functional molecule precursor (A) and the ion dissociative functional molecule precursor (B ′) are formed by binding a precursor group of an ion dissociable group to a 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 amount of -Rf-Y bonded to the fullerene is not particularly limited. In the case of the ion dissociative functional molecule precursor (A), it is usually 1.0 per gram of the ion dissociative functional molecule precursor (A). It is preferably ˜5.0 mmol, and more preferably 1.5 to 3.0 mmol. That is, the number of moles of the precursor group of the ion dissociable group per gram which the ion dissociative functional molecule precursor (A) has is preferably 1.0 to 5.0 mmol, and 1.5 to 3. More preferably, it is 0 mmol.

In the ion dissociative functional molecule precursor (A), the number of -Rf-Y bonded to fullerene is 3 to 10 on average per fullerene molecule, and preferably 5 to 8 on average.
Further, the amount of -Rf-Y bonded to fullerene in the ion dissociative functional molecule precursor (B ') may be different from that of the ion dissociative functional molecule precursor (A), and is not particularly limited. It is preferable that the amount is smaller than that of the ion dissociative functional molecule precursor (A). That is, the ion dissociative functional molecule precursor (B ′) preferably has a smaller number of moles of precursor groups of ion dissociable groups per gram than the ion dissociable functional molecule precursor (A).

  As described above, the compound (B) is at least one compound selected from an ion dissociative functional molecule precursor (B ′) and fullerene, and the compound (B) is an ion dissociative functional molecule precursor (B ′). ), Fullerene, or an ion dissociative functional molecule precursor (B ′) and fullerene may be used.

  Compound (B) is an ion dissociation per gram when the number of moles of the precursor group of the ion dissociable group per gram of the ion dissociative functional molecular precursor (A) is a [mmol / g]. The number of moles of the precursor group of the functional group is preferably 0a to 0.9a [mmol / g]. When the compound (B) is fullerene, the number of moles of the precursor group of the ion dissociable group per gram which the compound (B) has is 0 a [mmol / g], that is, 0 [mmol / g]. .

The number of moles of the precursor group of the ion dissociable group per gram of the ion dissociative functional molecule precursor (A) and the ion dissociative functional molecule precursor (B ′) is usually the precursor group of the ion dissociable group. Is the same as the acid density determined by converting to a proton dissociable group. This is because there is little change in molecular weight before and after converting the precursor group of an ion dissociable group into a proton dissociable group, and the precursor group of the ion dissociable group can be easily converted into a proton dissociable group. And the conversion efficiency is almost 100 mol%. When the precursor group of the ion dissociable group is a —SO ₂ F group, the proton dissociable group is preferably a sulfonic acid group (—SO ₂ OH).

  The average number of precursor groups of ion dissociable groups per molecule of the ion dissociative functional molecule precursor (A) and ion dissociative functional molecule precursor (B ′) is usually determined by ion From the molecular weight when the average of the acid density and the number of precursor groups of the ion dissociable group per molecule obtained by converting the precursor group of the dissociable group into a proton dissociable group is used in the examples. It can be determined by the method described.

  The ion dissociative functional molecule precursor (A) and the ion dissociative functional molecule precursor (B ′) are usually obtained by bonding 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 (A) and the ion dissociative functional molecule precursor (B ′) is not particularly limited, and for example, Japanese Patent Application Laid-Open Nos. 2003-303513 and 2006-131517. , And can be obtained by a conventionally known production method described in JP-A-2007-22996.

An example of the production method of the ion dissociative functional molecule precursor (A) and the ion dissociative functional molecule precursor (B ′) is that —Rf—Y is —CF ₂ —CF ₂ —O—CF ₂ —CF _2. An example of -SO ₂ F is shown. 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.

  The ion dissociative functional molecule precursor (A) and the ion dissociative functional molecule precursor (B ′) have an amount of —Rf—Y per molecule, that is, a precursor group of ion dissociable groups per gram. The number of moles can be adjusted, for example, by changing production conditions such as increasing or decreasing the equivalent of the molecule represented by I-Rf-Y used as a reagent with respect to fullerene or increasing or decreasing the reaction time. .

[Linking molecule (C)]
The manufacturing method of the ion dissociation functional polymer of this invention has the above-mentioned process (1). In the step (1), a linking molecule (C) is used.

The linking molecule (C) is a molecule capable of reacting with the ion dissociative functional molecule precursor (A) and the compound (B), and the ions are connected via a linking chain derived from the linking molecule (C). If the reaction product which a dissociative functional molecule precursor (A) and a compound (B) couple | bond together can be obtained, there will be no limitation in particular. Examples of the linking chain include alkyl groups, aryl groups, fluorinated alkyl groups represented by — (CF ₂ ) n — (n is an integer of 5 to 10), ether groups, ester groups, amide groups, and ketones. It is preferred to have at least one group selected from the group consisting of groups.

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 connecting molecule (C) used in the present invention is a compound having the above connecting chain, for example, a compound represented by X—R—X (X is Cl, Br or I, and R is a connecting chain). Used.

In the present invention, when the compound represented by X—R—X is used as the linking molecule (C), X is eliminated in step (1), and the end of R is the ion dissociative function. The structure derived from fullerene of the molecular precursor (A) and, when the ion dissociative functional molecular precursor (B ′) is used as the compound (B), derived from the fullerene of the ion dissociative functional molecular precursor (B ′) When fullerene is used as the structure of the compound (B), it binds to fullerene. By binding the ends of R to different fullerene-derived structures and fullerenes, a high molecular weight reaction product in which the ion dissociative functional molecule precursor (A) and the compound (B) are bonded can be obtained. That is, in the reactive organism obtained in the step (1), a plurality of fullerene-derived structures of the ion dissociative functional molecule precursor (A) and a structure derived from the compound (B) are bonded via a linking chain. Yes.
The compound represented by X—R—X is preferably a compound represented by X— (CF ₂ ) n—X (where n is an integer of 5 to 10).

[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 (A), the compound (B), and the connecting molecule (C) are reacted to form a connecting molecule. (C) is a step of obtaining a reaction product obtained by bonding the ion dissociative functional molecule precursor (A) and the compound (B) via a linking chain derived from (C).

  In the present invention, a reaction product obtained by bonding the ion dissociative functional molecule precursor (A) and the compound (B) through a linking molecule (C) -derived linking chain is also referred to as a reaction product. .

Step (1) is usually performed in a solvent. The solvent is not particularly limited, and for example, a mixed solvent of C ₆ F ₆ and CS ₂ described in JP-A No. 2003-303513, a halogenated aromatic compound and perfluoro described in Japanese Patent Application No. 2008-219636. A solvent having a boiling point of 160 ° C. or higher, which includes at least one selected from the group consisting of aliphatic compounds, can be used.

When 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 used as the solvent, a mixed solvent of C ₆ F ₆ and CS ₂ is used. Compared with the case where it was, since a process (1) can be performed on mild conditions, it is preferable.

  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 referred to as a solvent having a boiling point of 160 ° C. or higher.

Step (1) is usually performed at a high temperature of 160 to 300 ° C. In the step (1), when a solvent having a boiling point of 160 ° C. or higher is used, the solvent has a boiling point of 160 ° C. or higher. Therefore, when the ion dissociative functional molecule precursor and the linking molecule are reacted, the reaction is performed under normal pressure. Can be done. On the other hand, when the step (1) is performed in a mixed solvent of C ₆ F ₆ and CS ₂ , the boiling point of CS ₂ is 46 ° C., and the mixed solvent boils at about 50 ° C. (1) cannot be performed at 160 to 300 ° C., and it is necessary to perform the reaction under pressure using an autoclave or the like. Further, when the mixed solvent is used, it is necessary to use a large amount of the linking molecule (C). However, by using a solvent having a boiling point of 160 ° C. or higher, the amount of the linking molecule (C) used can be reduced. Can do.

In step (1), a solvent having a boiling point of 160 ° C. or higher is preferably used as the solvent, and the reaction is preferably performed at a normal pressure of 160 to 300 ° C. or a slight pressure of 10 kPa or lower.
In the step (1), the order of bringing the raw materials into contact when the ion dissociative functional molecule precursor (A), the compound (B), and the linking molecule (C) are reacted is not particularly limited. Absent.

  In the reaction, a step of bringing the mixture containing the ion dissociative functional molecule precursor (A) and at least a part of the compound (B) into contact with at least a part of the linking molecule (C) (hereinafter, the process (X) It is also preferable to have In the reaction, the ion dissociative functional molecule precursor (A) and at least a part of the linking molecule (C) are brought into contact with each other, and then the formulation obtained by the contact and at least a part of the compound ( It is also preferable to have the process (henceforth a process (Y)) contacted with B).

  In the step (Y), it is preferable that the contact between the blend and at least a part of the compound (B) is performed by adding the compound (B) to the blend in multiple portions. . The said division | segmentation should just be 2 times or more, and is normally divided | segmented and added to 2-10 times.

  That is, in the reaction, the contact between the ion dissociative functional molecule precursor (A) and at least a part of the linking molecule (C) results in at least a part of the compound (B) and at least a part of the linking molecule (C It is preferable that the contact is earlier or simultaneous with the contact with.

When the reaction includes the step (X), the reaction is preferably any one of the following embodiments (X-1) to (X-4).
Aspect (X-1) is an aspect in which the reaction is carried out by bringing the mixture containing the ion dissociative functional molecule precursor (A) and the compound (B) into contact with the linking molecule (C). That is, it is an aspect in which the mixture containing the total amount of the ion dissociative functional molecule precursor (A) used in the reaction and the total amount of the compound (B) is brought into contact with the total amount of the linking molecule (C). When the mixture and the linking molecule (C) are contacted, the linking molecule (C) may be divided into a plurality of times and contacted with the mixture.

  In the embodiment (X-2), the reaction is performed by bringing the mixture containing the ion dissociative functional molecule precursor (A) and a part of the compound (B) into contact with the linking molecule (C). Is obtained by contacting the compound (i) with the remaining compound (B). That is, the total amount of the linking molecule (C) is brought into contact with a mixture containing the total amount of the ion dissociative functional molecule precursor (A) used in the reaction and a part of the compound (B), and the resulting mixture (i ) And the remaining compound (B). When the mixture and the linking molecule (C) are contacted, the linking molecule (C) may be divided into a plurality of times and contacted with the mixture. Moreover, when contacting the compound (i) with the remaining compound (B), the compound (B) may be divided into a plurality of times and brought into contact with the compound (i).

  In the aspect (X-3), the reaction is performed by bringing a mixture containing the ion dissociative functional molecule precursor (A) and a part of the compound (B) into contact with a part of the linking molecule (C). After obtaining (i), the compound (i) and the remaining compound (B) are contacted to obtain a compound (ii), and then the compound (ii) and the remaining linking molecule (C ) Are brought into contact with each other. That is, a part of the linking molecule (C) is brought into contact with a mixture containing the total amount of the ion dissociative functional molecule precursor (A) used for the reaction and a part of the compound (B), and the resulting mixture ( In this embodiment, i) and the remaining compound (B) are brought into contact with each other, and the obtained compound (ii) is brought into contact with the remaining linking molecule (C). When contacting the mixture with the linking molecule (C), and when the mixture (ii) is contacted with the linking molecule (C), the linking molecule (C) is divided into a plurality of times. You may make it contact with a thing (ii). Moreover, when contacting the compound (i) with the remaining compound (B), the compound (B) may be divided into a plurality of times and brought into contact with the compound (i).

  In the aspect (X-4), the reaction is performed by bringing the mixture containing the ion dissociative functional molecule precursor (A) and a part of the compound (B) into contact with a part of the linking molecule (C). After obtaining (i), the remaining compound (B) and linking molecule (C) are alternately divided into a plurality of times and brought into contact with the compound (i). Specifically, the compound (i) is brought into contact with a part of the compound (B), the remainder of the linking molecule (C) and the remainder of the compound (B) in this order, and the composition (i). , A part of the compound (B), a part of the linking molecule (C), the rest of the compound (B), the rest of the linking molecule (C) in this order, the compound (i) Examples include a mode in which a part of B), a part of the linking molecule (C), a part of the compound (B), the remainder of the linking molecule (C), and the remainder of the compound (B) are contacted in this order.

When the reaction includes a step (Y), the reaction is preferably any one of the following embodiments (Y-1) to (Y-4).
In the aspect (Y-1), the compound (i) obtained by the above-mentioned contact is obtained by bringing the ionic dissociative functional molecule precursor (A) and the linking molecule (C) into contact with each other, and the compound It is an aspect performed by making (B) contact. That is, the total amount of the ion dissociative functional molecule precursor (A) used for the reaction and the total amount of the linking molecule (C) are brought into contact, and the obtained formulation (i) is brought into contact with the total amount of the compound (B). It is an aspect performed by making it. When contacting the ion dissociative functional molecule precursor (A) with the linking molecule (C), the linking molecule (C) is divided into a plurality of times, and the ion dissociating functional molecule precursor (A) and You may make it contact. Moreover, when contacting the compound (i) with the compound (B), the compound (B) may be divided into a plurality of times and brought into contact with the compound (i).

  In the embodiment (Y-2), the compound (i) obtained by the reaction is obtained by bringing the ion-dissociative functional molecule precursor (A) into contact with a part of the linking molecule (C), and then the contact. And the compound (B), and then the compound (ii) obtained by the contact is brought into contact with the remaining linking molecule (C). That is, the total amount of the ion dissociable functional molecule precursor (A) used for the reaction and a part of the linking molecule (C) are brought into contact with each other, and the obtained formulation (i) and the total amount of the compound (B) It is an aspect performed by making it contact and making the obtained compound (ii) and the remainder of a connection molecule | numerator (C) contact. When contacting the ion dissociative functional molecule precursor (A) with the linking molecule (C) and bringing the compound (ii) into contact with the linking molecule (C), the linking molecule (C) You may make it contact with an ion dissociative functional molecule precursor (A) and a compound (ii) in several steps. Moreover, when contacting the compound (i) with the compound (B), the compound (B) may be divided into a plurality of times and brought into contact with the compound (i).

  In the aspect (Y-3), the compound (i) obtained by the reaction is obtained by bringing the ion dissociative functional molecule precursor (A) into contact with a part of the linking molecule (C), and then contacting the ionic dissociative functional molecule precursor (A). And a part of the compound (B) are contacted, and then the formulation (ii) obtained by the contact is brought into contact with the remaining linking molecule (C), and then the formulation obtained by the contact ( In this embodiment, iii) is brought into contact with the remaining compound (B). That is, the total amount of the ion dissociable functional molecule precursor (A) used for the reaction and a part of the linking molecule (C) are brought into contact with each other, and the obtained compound (i) and a part of the compound (B) Is carried out by contacting the resulting formulation (ii) with the remainder of the linking molecule (C), and contacting the resulting formulation (iii) with the remainder of the compound (B). It is an aspect. When contacting the ion dissociative functional molecule precursor (A) with the linking molecule (C) and bringing the compound (ii) into contact with the linking molecule (C), the linking molecule (C) You may make it contact with an ion dissociative functional molecule precursor (A) and a compound (ii) in several steps. In addition, when the compound (B) is contacted with the compound (B) and the compound (iii) is contacted with the compound (B), the compound (B) is divided into a plurality of times. You may make it contact with a thing (i) and a compound (iii).

  In the embodiment (Y-4), the compound (i) obtained by the reaction is obtained by bringing the ion-dissociative functional molecule precursor (A) into contact with a part of the linking molecule (C), and then the contact. And a part of the compound (B) are contacted, and then the mixture (ii) obtained by the contact is obtained, and then the remaining linking molecule (C) and compound (B) are alternately divided into a plurality of times. The embodiment is carried out by contacting with the formulation (ii). Specifically, a mode in which a part of the linking molecule (C), a remaining part of the compound (B), and a remaining part of the linking molecule (C) are brought into contact with the compound (ii) in this order, the compound (ii) A part of the linking molecule (C), a part of the compound (B), the remaining part of the linking molecule (C), the remaining part of the compound (B) in this order, and the compound (ii) Examples include a mode in which a part of the molecule (C), a part of the compound (B), a part of the linking molecule (C), the remainder of the compound (B), and the remainder of the linking molecule (C) are contacted in this order. .

  The amount of the linking molecule (C) used in the step (1) is usually 100 to 500 mol% with respect to 100 mol% in total of the ion dissociable functional molecule precursor (A) and the compound (B), Preferably it is 100-300 mol%.

  The amount ratio of the ion dissociative functional molecule precursor (A) and the compound (B) used in the step (1) is not particularly limited, but the ion dissociative functional molecule precursor (A) and the compound (B) are not limited. Usually, the ion dissociable functional molecule precursor (A) is 15 to 99 mol% and the compound (B) is 85 to 1 mol% per 100 mol% in total, and preferably the ion dissociable functional molecule precursor ( A) is 50 to 99 mol%, and compound (B) is 50 to 1 mol%.

Moreover, the usage-amount of a solvent does not have limitation in particular, Usually, it is 100-1000 mass parts with respect to a total of 100 mass parts of an ion dissociative functional molecule precursor (A) and a compound (B).
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 is more than 0.1 equivalent and 10 equivalent or less with respect to 1.0 equivalent of connection molecule | numerator (C), 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.

[Solvent having a boiling point of 160 ° C. or higher]
The solvent having a boiling point of 160 ° C. or higher will be described. As described above, the solvent having a boiling point of 160 ° C. or higher is 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. The boiling point is a boiling point at 1 atmosphere.

By using a solvent having a boiling point of 160 ° C. or higher, step (1) can be performed under normal pressure or slight pressure.
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 having a boiling point of 160 ° C. or higher, perfluorotripentylamine and 1,2,4-trichlorobenzene are preferable.
The solvent having a boiling point of 160 ° C. or higher may be a mixed solvent containing components other than the halogenated aromatic compound and the perfluoroaliphatic compound.

[Other processes]
In the method for producing an ion dissociable functional polymer of the present invention, an ion dissociable group precursor group contained in the reaction product obtained in the above step (1) is converted into an ion dissociable group, thereby producing ions. A step of obtaining a dissociative functional polymer.

  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 In the case of a sulfonic acid group (—SO ₂ OH), the reaction product is hydrolyzed by reacting with water and sodium hydroxide in C ₆ F ₆ or THF (tetrahydrofuran) to obtain a —SO ₂ F group. and 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. The method for producing an ion dissociative functional polymer of the present invention can obtain an ion dissociative functional polymer with a higher yield than conventional methods.

When the ion dissociable group of the ion dissociative functional polymer 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 (I)]
The ion dissociative functional molecule precursor (I) was produced by the following method.
In a 500 ml glass three-necked flask equipped with a dropping funnel, condenser (cooler), thermometer and stirrer, in a nitrogen stream atmosphere, fullerene (frontier carbon nanometer (registered trademark) mix ST (C ₆₀ approx. 60%, _C70 approx. 25%)) 3.0 g was added, followed by 300 ml of 1,2,4-trichlorobenzene.

While stirring the fullerene and 1,2,4-trichlorobenzene, the temperature is maintained at 200 ° C., and a molecule having a spacer group and a precursor group of an ion dissociable group is used as I—CF ₂ —CF ₂ —O—. 42.6 g of CF ₂ —CF ₂ —SO ₂ F (24 equivalents to 1 equivalent of fullerene) was dropped from the dropping funnel over about 1 day. 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 9.2 g of ion-dissociative functional molecule precursor (I) as a dark brown powder.

In the above reaction, the I—CF ₂ —CF ₂ —O—CF ₂ —CF ₂ —SO ₂ F has an iodine atom and a radical (• CF ₂ —CF ₂ —O—CF ₂₎ at the end on the iodine atom side. Thermally decomposed to -CF ₂ -SO ₂ F), and the resulting radical is added to the fullerene molecule by unpaired electrons bonded to the iodine atom.

In addition, when ¹⁹ F-NMR of the ion dissociative functional molecule precursor (I) was measured, the ion dissociative functional molecule precursor (I) was converted into a spacer group (—CF ₂ —CF ₂ —O—CF ₂ —CF ₂ -) precursor group via the (-SO ₂ F) was shown to be a compound added to the fullerene.

[Production of ion-dissociative functional molecule precursor (II)]
The ion dissociative functional molecule precursor (II) was produced by the following method.
In a 2 l glass three-necked flask equipped with a condenser (cooler), thermometer and stirrer, fullerene (frontier carbon Co., Ltd. nanom (registered trademark) mix ST (C ₆₀ about 60%, _C70 about 25%)) 16 g, and then 72 g (fullerene) of I—CF ₂ —CF ₂ —O—CF ₂ —CF ₂ —SO ₂ F as a molecule having a spacer group and a precursor group of an ion dissociable group 7.1 equivalents to 1 equivalent), and 1.5 liters of 1,2,4-trichlorobenzene.

While stirring the reaction solution, the temperature was kept at 200 ° C. and reacted for 7 days.
After completion of the reaction, the reaction mixture is taken out from the three-necked flask, 1,2,4-trichlorobenzene is distilled off from the reaction mixture under reduced pressure, and the residue is vacuum-dried at 150 ° C. for 3 days to obtain an ion which is a dark brown powder. 47 g of dissociative functional molecule precursor (II) was obtained.

In addition, when ¹⁹ F-NMR of the ion dissociative functional molecule precursor (II) was measured, the ion dissociative functional molecule precursor (II) was converted into a spacer group (—CF ₂ —CF ₂ —O—CF ₂ —CF). ₂ -) precursor group via the (-SO ₂ F) was shown to be a compound added to the fullerene.

[Production of ion dissociable functional molecule precursor (III)]
The ion dissociative functional molecule precursor (III) was produced by the following method.
In a 500 ml glass three-necked flask equipped with a dropping funnel, condenser (cooler), thermometer and stirrer, fullerene (nanom (registered trademark) purple ST (C ₆₀ approx. 99%)) 3.0 g was added, followed by 300 ml of 1,2,4-trichlorobenzene.

While stirring the fullerene and 1,2,4-trichlorobenzene, the temperature is maintained at 200 ° C., and a molecule having a spacer group and a precursor group of an ion dissociable group is used as I—CF ₂ —CF ₂ —O—. 42.6 g of CF ₂ —CF ₂ —SO ₂ F (24 equivalents to 1 equivalent of fullerene) was dropped from the dropping funnel over about 1 day. After completion of dropping, the mixture was reacted at 200 ° C. for 6 days with stirring.

  After completion of the reaction, the reaction mixture is taken out from the three-necked flask, 1,2,4-trichlorobenzene is distilled off from the reaction mixture under reduced pressure, and the residue is vacuum-dried at 150 ° C. for 3 days to obtain an ion which is a dark brown powder. 11.2 g of dissociative functional molecule precursor (III) was obtained.

In addition, when ¹⁹ F-NMR of the ion dissociative functional molecule precursor (III) was measured, the ion dissociative functional molecule precursor (III) was converted into a spacer group (—CF ₂ —CF ₂ —O—CF ₂ —CF). ₂ -) precursor group via the (-SO ₂ F) was shown to be a compound added to the fullerene.

[Calculation of the number of moles of precursor groups of ion dissociable groups per gram of ion dissociable functional molecule precursor and the average number of precursor groups of ion dissociable groups per molecule of ion dissociable functional molecule precursor]
The average number of moles of precursor groups of ion dissociable groups per gram and the number of precursor groups of ion dissociable groups per molecule of ion dissociable functional molecule precursor that the ion dissociative functional molecule precursor has is: It calculated | required with the following method.

  0.5 g of the ion dissociative functional molecule precursor obtained in the above production example was put in a test tube, and 3 ml of tetrahydrofuran (THF) and 3 ml of 1.0 M NaOH aqueous solution were added thereto. After heating at 50 ° C. for 1 hour, it was left overnight at room temperature. In order to remove excess sodium hydroxide, 3 g of Wako Gel (registered trademark) C300 manufactured by Wako Pure Chemical Industries, Ltd. was used as the column filler, and water: THF (weight ratio) = 1: 1 was used).

Next, vacuum concentration was performed using an evaporator. An aqueous solution obtained by adding an appropriate amount of distilled water to the obtained solid was passed through a column of a cation exchange resin (Amberlite (registered trademark) IR124Na manufactured by Rohm and Haas Co., Ltd.), and the obtained aqueous solution was dried under reduced pressure. After that, it was pulverized in a mortar and further vacuum-dried overnight at 30 ° C., and the precursor group of the ion dissociable group contained in the ion dissociable functional molecule precursor was converted into an ion dissociable group (—SO ₃ H). As a result, 0.5 g of an ion dissociative functional molecule was obtained.

  The acid density (a ′) [mmol / g] of the ion dissociative functional molecule was determined by neutralization titration. The acid density (a ′) [mmol / g] is the same as the molar number (a) [mmol / g] of the precursor group of the ion dissociable group per gram which the ion dissociative functional molecule precursor has. Considered.

The structure of the ion dissociative functional molecule precursor is represented by (fullerene)-(— CF ₂ —CF ₂ —O—CF ₂ —CF ₂ —SO ₂ F) m, and the value of m is the ion dissociation. This corresponds to the average of the number of precursor groups of ion dissociable groups per molecule that the sexually functional molecule precursor has.

Assuming that the fullerene is C ₆₀ , the molecular weight of the ion dissociative functional molecule is represented by 720 + 297 m.
The relationship between the acid density (a ′) and the average (m) number of ion dissociable groups per molecule of the ion dissociative functional molecule precursor is represented by the following formula (α).
a ′ [mmol / g] = 1000 m / (720 + 297 m) (α)
By transforming the formula (α), the following formula (α ′) is obtained.
m = 720a ′ / (1000-297a ′) (α ′)

  From the acid density (a ′) [mmol / g] determined by the above method and the formula (α ′), ions per molecule that the ion dissociative functional molecule precursor of the ion dissociative functional molecule precursor has The average (m) of the number of precursor groups of the dissociable group is obtained.

Moreover, the average molecular weight of the ion dissociative functional molecule precursor was determined from the m, with two significant digits.
Acid density (a ′) of ion dissociative functional molecule converted from the ion dissociative functional molecule precursors (I) to (III), one molecule of the ion dissociative functional molecule precursors (I) to (III) Table 1 shows the average number (m) of the precursor groups of the ion-dissociable groups and the molecular weight.

[Elemental analysis of ion-dissociative functional molecular precursors]
Elemental analysis of the ion dissociative functional molecule precursors (I) to (III) was performed by combustion-ion chromatography, and the fluorine content and the sulfur content were determined.

From the fluorine content and the sulfur content, the number of moles (a) of precursor groups of ion dissociable groups per gram which the ion dissociable functional molecule precursor has in accordance with the following formulas (β) and (γ) was calculated.
a [mmol / g] (fluorine content conversion)
= 10 × fluorine content (wt%) / (19 × 9) (β)
a [mmol / g] (in terms of sulfur content)
= 10 × sulfur content (wt%) / (32) (γ)

  Table 1 shows a obtained from the fluorine content, sulfur content, and fluorine content of the ion dissociative functional molecule precursors (I) to (III) and a obtained from the sulfur content.

フラーレンをＣ₆₀とした際のイオン解離性機能分子前駆体の構造を、下記一般式（４）で表す。

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は表１中のｍと同様である。）

(In the above formula (4), m is the same as m in Table 1.)

[Example 1]
(Process (1))
In a glass 2 L four-necked flask equipped with a stirrer, 50 g (equivalent to 19 mmol) of the ion dissociative functional molecular precursor (I) and fullerene (frontier carbon Co., Ltd. nanom (registered trademark) mix ST (C ₆₀ approx. 60%, C ₇₀ approx. 25%)) 0.7 g (corresponding to 1 mmol), 130 ml of 1,2,4, -trichlorobenzene was added, and the mixture was heated and stirred in a 200 ° C. oil bath in a nitrogen stream. . Thereto, 11.5 g (17.6 mmol) of IC ₈ F ₁₆ I and 3.9 g (27 mmol) of di-t-butyl peroxide (hereinafter sometimes referred to as (t-BuO) ₂ ) were added to 25 ml of trichlorobenzene. The dissolved product was divided into 8 portions and added every 1 hour, and the mixture was heated and stirred overnight at 200 ° C.

On the next day, 6.9 g (10.6 mmol) of IC ₈ F ₁₆ I and 2.3 g ( ₁₆ mmol) of (t-BuO) ₂ dissolved in 18 ml of trichlorobenzene were added in 8 portions every other hour, and 200 overnight. Heated and stirred at ℃.

On the next day, a mixture of 3.9 g (27 mmol) of (t-BuO) ₂ and 5.7 ml of trichlorobenzene was added in 8 portions every other hour, followed by heating and stirring at 200 ° C. overnight.
On the next day (3 days after the start of the reaction), the temperature of the oil bath was set to 150 ° C., and trichlorobenzene was distilled off under reduced pressure, followed by drying under reduced pressure at 150 ° C. for 1 hour. After returning to room temperature, the residue in the flask was washed 5 times with 50 ml of chloroform and the insoluble material was collected by filtration. The resulting solid material (insoluble material) was dried under reduced pressure at room temperature overnight and reacted as a black solid. The product was obtained.

(Hydrolysis step)
The reaction product as a black solid was pulverized in a mortar and transferred to a 2 L four-necked flask, to which 50 ml of THF and 260 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, 70 ml of concentrated hydrochloric acid was added, and this liquid was subjected to a HITACHI cooling centrifuge HIMAC CR20B3 (setting 10 ° C., 7000 rpm × 15 min, the same applies hereinafter) to separate the precipitate and the supernatant, and the supernatant Was removed.

  After adding 150 ml of 10% hydrochloric acid to the precipitate and mixing well, the mixture was similarly centrifuged to separate the precipitate and the supernatant, and the supernatant was removed. This operation was repeated twice in total.

  Add 150 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, centrifuge again to separate the precipitate from the supernatant, The supernatant was removed.

After adding 150 ml of 10% hydrochloric acid to the precipitate and mixing well, the mixture was similarly centrifuged to separate the precipitate and the supernatant, and the supernatant was removed.
After adding 150 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. This operation 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 3 days.
After the dried precipitate was pulverized in a mortar, it was further vacuum-dried overnight in a sample oven set at 40 ° C. to obtain 23 g of ion-dissociative functional polymer (I).
Incidentally, the above hydrolysis step, the sulfonyl fluoride groups -SO ₂ F are converted to sulfonic acid groups (-SO ₂ OH).

[Example 2]
(Process (1))
In a glass 2 L four-necked flask equipped with a stirrer, 50 g (corresponding to 19 mmol) of the ion dissociable functional molecule precursor (I) is taken, 130 ml of 1,2,4, -trichlorobenzene is added, and nitrogen is added. The mixture was heated and stirred in an oil bath at 200 ° C. in an air flow atmosphere. A solution prepared by dissolving 11.5 g (17.6 mmol) of IC ₈ F ₁₆ I and 3.9 g (27 mmol) of (t-BuO) _{2 in} 25 ml of trichlorobenzene was added in 8 portions every 1 hour. One hour after the completion of the addition, 3.0 g (corresponding to 1.5 mmol) of the ion dissociative functional molecule precursor (II) was further added and stirred overnight.

The next day, 6.9 g (10.6 mmol) of IC ₈ F ₁₆ I, 2.3 g ( ₁₆ mmol) of (t-BuO) ₂ and 18 ml of trichlorobenzene were added in 8 portions every other hour, and everything was completely added. After 1 hour from the beginning, 1.0 g (corresponding to 0.5 mmol) of the ion dissociative functional molecule precursor (II) was further added and stirred overnight.

On the next day, a mixture of 3.9 g (27 mmol) of (t-BuO) ₂ and 5.7 ml of trichlorobenzene was added in 8 portions every other hour and stirred at 200 ° C. overnight.
On the next day (3 days after the start of the reaction), the temperature of the oil bath was set to 150 ° C., and trichlorobenzene was distilled off under reduced pressure, followed by drying under reduced pressure at 150 ° C. for 1 hour. After returning to room temperature, the residue in the flask was washed 5 times with 50 ml of chloroform and the insoluble material was collected by filtration. The resulting solid material (insoluble material) was dried under reduced pressure at room temperature overnight and reacted as a black solid. The product was obtained.

(Hydrolysis step)
The hydrolysis step was performed in the same manner as in Example 1 to obtain 29 g of ion dissociable functional polymer (II).

[Comparative Example 1]
(Process (1))
In a glass 2 L four-necked flask equipped with a stirrer, 10 g (corresponding to 3.7 mmol) of the ion dissociable functional molecule precursor (I) is added, and 26 ml of 1,2,4, -trichlorobenzene is added, The mixture was heated and stirred in an oil bath at 200 ° C. in a nitrogen stream atmosphere. Thereto, 2.3 g (3.5 mmol) of IC ₈ F ₁₆ I and 0.8 g (5.4 mmol) of di-t-butyl peroxide (hereinafter sometimes referred to as (t-BuO) ₂ ) were added to trichlorobenzene. The solution dissolved in 5 ml was added in 8 portions every 1 hour, and heated and stirred at 200 ° C. overnight.

The next day, IC ₈ F ₁₆ I 1.4 g (2.1 mmol) and (t-BuO) ₂ 0.5 g (3.2 mmol) dissolved in 3.6 ml of trichlorobenzene were divided into 8 portions every 1 hour. In addition, the mixture was heated and stirred overnight at 200 ° C.

On the next day, a mixture of 0.8 g (5.4 mmol) of (t-BuO) ₂ and 1 ml of trichlorobenzene was added in 8 portions every 1 hour, and heated and stirred at 200 ° C. overnight.
On the next day (3 days after the start of the reaction), the temperature of the oil bath was set to 150 ° C., and trichlorobenzene was distilled off under reduced pressure, followed by drying under reduced pressure at 150 ° C. for 1 hour. After returning to room temperature, the residue in the flask was washed 5 times with 10 ml of chloroform and the insoluble material was collected by filtration. The resulting solid material (insoluble material) was dried under reduced pressure at room temperature overnight and reacted as a black solid. The product was obtained.

(Hydrolysis step)
The hydrolysis step was performed in the same manner as in Example 1 to obtain 3.7 g of an ion dissociative functional polymer (C1).

Example 3
(Process (1))
Into a glass 2 L four-necked flask equipped with a stirrer, 50 g (equivalent to 21 mmol) of the ion dissociable functional molecule precursor (III) is taken, 130 ml of 1,2,4, -trichlorobenzene is added, and nitrogen is added. The mixture was heated and stirred in an oil bath at 200 ° C. in an air flow atmosphere. A solution prepared by dissolving 11.5 g (17.6 mmol) of IC ₈ F ₁₆ I and 3.9 g (27 mmol) of (t-BuO) _{2 in} 25 ml of trichlorobenzene was added in 8 portions every 1 hour.

One hour after the completion of all additions, 0.5 g (equivalent to 0.7 mmol) of fullerene (nanom (registered trademark) purple ST (C _60: 99%) manufactured by Frontier Carbon Co., Ltd.) was further added and stirred overnight.

The next day, 6.9 g (10.6 mmol) of IC ₈ F ₁₆ I, 2.3 g ( ₁₆ mmol) of (t-BuO) ₂ and 18 ml of trichlorobenzene were added in 8 portions every other hour, and everything was completely added. 1 hour later, 0.2 g (corresponding to 0.3 mmol) of fullerene (nanom (registered trademark) purple ST (C ₆₀ approx. 99%) manufactured by Frontier Carbon Co., Ltd.) was added and stirred overnight.

On the next day, a mixture of 3.9 g (27 mmol) of (t-BuO) ₂ and 5.7 ml of trichlorobenzene was added in 8 portions every other hour and stirred at 200 ° C. overnight.
On the next day (3 days after the start of the reaction), the temperature of the oil bath was set to 150 ° C., and trichlorobenzene was distilled off under reduced pressure, followed by drying under reduced pressure at 150 ° C. for 1 hour. After returning to room temperature, the residue in the flask was washed 5 times with 50 ml of chloroform and the insoluble material was collected by filtration. The resulting solid material (insoluble material) was dried under reduced pressure at room temperature overnight and reacted as a black solid. The product was obtained.

(Hydrolysis step)
The hydrolysis step was performed in the same manner as in Example 1 to obtain 45 g of ion dissociable functional polymer (III).

[Comparative Example 2]
(Process (1))
Into a glass 2 L four-necked flask equipped with a stirrer, 50 g (equivalent to 21 mmol) of the ion dissociable functional molecule precursor (III) is taken, 130 ml of 1,2,4, -trichlorobenzene is added, and nitrogen is added. The mixture was heated and stirred in an oil bath at 200 ° C. in an air flow atmosphere. Then, 11.5 g (17.6 mmol) of IC ₈ F ₁₆ I and 3.9 g (27 mmol) of (t-BuO) ₂ dissolved in 25 ml of trichlorobenzene were divided into 8 portions and added every other hour. Heated and stirred at ℃.

The next day, 6.9 g (10.6 mmol) of IC ₈ F ₁₆ I, 2.3 g ( ₁₆ mmol) of (t-BuO) ₂ and 18 ml of trichlorobenzene were added in 8 portions and added every other hour at 200 ° C. overnight. And heated and stirred. Heated and stirred at 200 ° C. overnight.

On the next day, a mixture of 3.9 g (27 mmol) of (t-BuO) ₂ and 5.7 ml of trichlorobenzene was added in 8 portions every other hour and stirred at 200 ° C. overnight.
On the next day (3 days after the start of the reaction), the temperature of the oil bath was set to 150 ° C., and trichlorobenzene was distilled off under reduced pressure, followed by drying under reduced pressure at 150 ° C. for 1 hour. After returning to room temperature, the residue in the flask was washed 5 times with 50 ml of chloroform and the insoluble material was collected by filtration. The resulting solid material (insoluble material) was dried under reduced pressure at room temperature overnight and reacted as a black solid. The product was obtained.

(Hydrolysis step)
The hydrolysis step was performed in the same manner as in Example 1 to obtain 37 g of an ion dissociative functional polymer (CII).

(Ion conductivity measurement)
The ion-dissociative functional polymers synthesized in the examples and comparative examples were vacuum-dried at room temperature for 12 hours, respectively, and 200 mg of the obtained powder was pressed with a tablet molding machine so as to form a circular pellet having a diameter of 1.3 cm. Pressure molding was performed at 300 MPa. 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.

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.
Yield and yield of ion-dissociative functional molecule precursor (A), compound (B), obtained ion-dissociative functional polymer used in Examples and Comparative Examples, and ion conductivity determined by the above measurement method Is shown in Table 2.

原料としてイオン解離性機能分子前駆体（Ｉ）を用いた、本発明の実施例１、２と比較例１とを比較すると、実施例１、２の方が、比較例１よりも明らかに収率が向上していることがわかる。また、実施例１、２で得られたイオン解離性機能高分子のイオン伝導度は、比較例１で得られたイオン解離性機能高分子と同等以上であった。

When Examples 1 and 2 of the present invention using Comparative Example 1 using the ion-dissociative functional molecule precursor (I) as a raw material were compared, Examples 1 and 2 clearly showed better results than Comparative Example 1. It can be seen that the rate has improved. Moreover, the ion conductivity of the ion dissociative functional polymer obtained in Examples 1 and 2 was equal to or higher than that of the ion dissociative functional polymer obtained in Comparative Example 1.

  When Example 3 of the present invention and Comparative Example 2 using the ion dissociative functional molecule precursor (III) as a raw material were compared, the yield of Example 3 was clearly improved over that of Comparative Example 2. You can see that Moreover, the ionic conductivity of the ion dissociative functional polymer obtained in Example 3 was superior to that of the ion dissociative functional polymer obtained in Comparative Example 2.

  In addition, when Examples 1 and 2 are compared with Comparative Example 2, Comparative Example 2 is superior in yield, but this is a raw material, which is an ion dissociative functional molecular precursor (I) and an ion dissociative function. It is thought to be due to the difference from the molecular precursor (III).

  In the production method of the present invention, when a similar ion dissociable functional molecule precursor is used, an ion dissociable functional polymer can be obtained with a higher yield than the conventional production method (comparative example).

Claims (10)

An ion dissociable functional molecule precursor (A) formed by bonding a precursor group of an ion dissociable group to fullerene via a spacer group at least partially fluorinated;
The number of moles of precursor group of ion dissociable group per gram is different from that of the ion dissociable functional molecule precursor (A), and the precursor of the ion dissociable group through a spacer group that is at least partially fluorinated with fullerene. At least one compound (B) selected from an ion dissociative functional molecule precursor formed by bonding body groups and fullerene;
React with the linking molecule (C),
It has the process (1) which obtains the reaction product which the said ion dissociative functional molecule precursor (A) and a compound (B) couple | bond together through the coupling chain derived from a coupling molecule (C). A method for producing an ion dissociative functional polymer.   The reaction includes a step of bringing the mixture containing the ion dissociative functional molecule precursor (A) and at least a part of the compound (B) into contact with at least a part of the linking molecule (C). The manufacturing method of the ion dissociation functional polymer of Claim 1.   In the reaction, the ion-dissociative functional molecule precursor (A) is contacted with at least a part of the linking molecule (C), and then the blend obtained by the contact and at least a part of the compound (B) The method for producing an ion dissociative functional polymer according to claim 1, further comprising a step of bringing the ion dissociation functional polymer into contact with each other.   The contact between the blend and at least a portion of the compound (B) is performed by adding the compound (B) to the blend in multiple portions. A method for producing an ion dissociative functional polymer.   Per 1 g of the compound (B) when the number of moles of precursor group of the ion dissociable group per gram of the ion dissociative functional molecule precursor (A) is a [mmol / g] 5. The ion dissociative functional polymer according to claim 1, wherein the number of moles of the precursor group of the ion dissociable group is from 0a to 0.9a [mmol / g]. Production method.   6. The linking molecule (C) is used in an amount of 100 to 500 mol% with respect to a total of 100 mol% of the ion dissociative functional molecule precursor (A) and the compound (B). A method for producing the ion dissociative functional polymer according to claim 1. In the ion dissociative functional molecule precursor (A) and the compound (B), the precursor group of the ion dissociable group is selected from the group consisting of —SO ₂ F, —SO ₂ Cl, —COF, and —COCl. It is at least 1 sort (s) of group, The manufacturing method of the ion dissociative functional polymer as described in any one of Claims 1-6 characterized by the above-mentioned. In the said connection molecule | numerator (C), the said connection chain | strand is a chain | strand represented by following General formula (1), The manufacture of the ion dissociative functional polymer as described in any one of Claims 1-7 characterized by the above-mentioned. Method.
_{- (CF 2) n- ··· (} 1)
(In the general formula (1), n is an integer of 5 to 10.) In the said ion dissociative functional molecule precursor (A) and a compound (B), the said spacer group has a structure represented by following General formula (2), It is any one of Claims 1-8 characterized by the above-mentioned. The manufacturing method of the ion dissociation functional polymer of description.
-(CF ₂ ) m- (2)
(In the general formula (2), m is an integer of 1 to 10.) In the said ion dissociative functional molecule precursor (A) and a compound (B), the said spacer group is group represented by following General formula (3), It is any one of Claims 1-9 characterized by the above-mentioned. The manufacturing method of the ion dissociation functional polymer of description.
_{- (CF 2) m-O-} (CF 2) m- ··· (3)
(In the above general formula (3), m is each independently an integer of 1 to 10.)