JP2010116503A - Production method of block copolymer using reactive oligomer - Google Patents

Abstract

The present invention efficiently provides a block copolymer comprising a hydrophilic aromatic polymer compound having a proton acid group and a hydrophobic aromatic polymer compound having no proton acid group.
(A) a step of preparing a first aromatic polymer compound having a perfluorobiphenyl group at a terminal and a protonic acid group; and (b) a perfluorobiphenyl group of (a) at a terminal. Preparing a second aromatic polymer compound having a reactive group capable of reacting with the protonic acid group, and (c) a first aromatic polymer compound and a second aromatic polymer It is produced by a step of preparing a copolymer to which molecular compounds are bound.
[Selection figure] None

Description

  The present invention relates to a method for producing a block copolymer, a block copolymer obtained by the production method, a polymer electrolyte composition containing the block copolymer, and a polymer electrolyte membrane containing the electrolyte composition.

Fuel cells have high power generation efficiency and excellent environmental performance, and are expected as next-generation power generation devices that can contribute to solving environmental problems and energy problems, which are now major issues.
Among these fuel cells, solid polymer fuel cells are smaller and have higher output than any other system, and they are the next generation as small-scale on-site, mobile (on-vehicle) and portable fuel cells. It is said to be the main force.
At present, solid polymer fuel cells are not yet in practical use, but as polymer electrolyte membranes for fuel cells used in trial production or testing, perfluoroalkylene groups are the main skeleton, and some "Nafion (registered trademark)", "Flemion (registered trademark)" and the like are known as fluorine-based polymer electrolyte membranes having ion-exchange groups such as sulfonic acid groups and carboxylic acid groups at the end of perfluorovinyl ether side chain. Yes.
However, in the currently used fuel cell polymer electrolyte membrane “Nafion (registered trademark)” and the like, when the operation is performed at a temperature exceeding 100 ° C., the moisture content of the polymer electrolyte membrane drops rapidly, The softening of the polymer electrolyte membrane is also remarkable, especially in the direct methanol fuel cell where the future is expected, when a fluorine-based proton conductive polymer material such as the conventional “Nafion (registered trademark)” is used as the electrolyte , Methanol that has passed through the anode diffuses in the electrolyte and reaches the cathode, where it causes a short circuit phenomenon (crossover) in which it directly reacts with the oxidant (O ₂ ) on the cathode catalyst, thereby significantly improving battery performance. There is a problem in that sufficient performance cannot be exhibited because of lowering.
In addition, when an electrolyte containing a halogen such as fluorine is used in a fuel cell, there is a concern about the generation of a halide such as hydrogen halide during disposal or recycling, which causes an increase in processing cost and an environmental load.
In order to solve these problems, various studies have been made on polymer electrolyte membranes in which a sulfonic acid group for imparting proton conductivity is introduced to a heat-resistant aromatic polymer used as a substitute for a fluorine-based membrane. From the viewpoint of heat resistance and chemical stability of the polymer electrolyte membrane, sulfonated aromatic polyether ketones (Patent Document 1), sulfonated aromatic polyether sulfones (Patent Document 2), and sulfonated polyphenylene (Patent Document 3) and the like.
Among these, the sulfonated aromatic polymer is also studied to further increase proton conductivity by making it a block copolymer blocked into a hydrophilic segment into which a sulfonic acid group has been introduced and a hydrophobic segment into which the sulfonate group has not been introduced. It has been broken.
As a method for synthesizing a block copolymer composed of a hydrophilic part segment and a hydrophobic part segment, first, a polymerization reaction is performed on either the hydrophilic part segment or the hydrophobic part segment to increase the molecular weight, and then the other segment. A sequential addition method is known in which the monomers are added and polymerized sequentially. The sequential addition method is easy to operate because a block copolymer can be synthesized with One-Pot, but it is problematic in that randomization is likely to occur and block chain length is difficult to control.
Further, it is possible to synthesize a block copolymer by a method in which a hydrophilic part segment and a hydrophobic part segment are separately synthesized and then both are reacted. However, there are problems that the synthesis operation is complicated and that the polarities of the hydrophilic part segment and the hydrophobic part segment are greatly different, so that the compatibility is poor and the blocking reaction is difficult to proceed.
As a method for solving the compatibility problem, Patent Document 4 discloses a method of obtaining a block copolymer by using a solvent obtained by mixing two types of good solvents for hydrophilic segments and good solvents for hydrophobic segments. .

JP-A-6-93114 Japanese Patent Laid-Open No. 10-45913 JP 2001-329053 A JP 2007-106986 A

In view of the above circumstances, an object of the present invention is to provide a method for producing a block copolymer which can prepare a polymer electrolyte excellent in proton conductivity and does not contain a halogen.
Moreover, an object of this invention is to provide the block copolymer obtained from this manufacturing method, the polymer electrolyte composition containing this, and the polymer electrolyte membrane containing this.

  As a result of intensive research, the present inventors have determined that proton conductivity is obtained by bonding between a first aromatic polymer compound containing a proton acid group and a second aromatic polymer compound containing no proton acid group. In preparing a block copolymer excellent in the above and a polymer electrolyte composition containing the same, a monovalent hydrophobic aromatic halogen group was previously introduced into the first aromatic polymer compound containing a protonic acid group. It is found that the first aromatic polymer compound and the second aromatic polymer compound can be reliably bonded to each other and a block copolymer containing no halogen can be produced. It came to complete.

The present invention
[1]
(A) a step of preparing a first aromatic polymer compound having a monovalent hydrophobic aromatic halogen group at a terminal and having a protonic acid group; and the monovalent hydrophobic aromatic halogen, wherein The group is not a perfluorobiphenyl group,
(B) a second aromatic polymer compound having a reactive group capable of reacting with a monovalent hydrophobic aromatic halogen group of the first aromatic polymer compound at the terminal and having no proton acid group A step of preparing
(C) A method for producing a block copolymer, comprising the step of preparing the block copolymer by bonding the first aromatic polymer compound and the second aromatic polymer compound. About.
[2]
The method according to [1], wherein the reactive group of the second aromatic polymer compound is a phenolic hydroxyl group.
[3]
It is related with the method of [1] description whose mass average molecular weight of said 1st aromatic polymer compound is 2000-150,000, and whose mass average molecular weight of said 2nd aromatic polymer compound is 2000-150,000.
[4]
In the step (c) of preparing the block copolymer, the mass ratio of the first aromatic polymer compound and the second aromatic polymer compound [first aromatic polymer compound] / [second Block copolymerization is performed by mixing the first aromatic polymer compound and the second aromatic polymer compound so that the value of the aromatic polymer compound is 0.1 or more and 10.0 or less. The method according to [1], which is a step of preparing a block copolymer.
[5]
The first aromatic polymer compound is divalent having at least one protonic acid group selected from the group consisting of the following formulas (1), (3), (4) and (5): The method according to [1], which comprises a group of


[In the formula (1), A represents a direct bond, —O—, —S—, —S (O) —, —S (O) ₂ —, —C (O) —, —P (O) (C _{6 H 5) -, - C} (CH 3) 2 -, - CH 2 -, - C (C 6 H 5) 2 -, or,


[In Formula (2), X is a protonic acid group which may be the same or different, and is a sulfonic acid group, a phosphoric acid group, an alkylsulfonic acid group having 1 to 6 carbon atoms, or 1 carbon atom. Represents an oxyalkyl sulfonic acid group of -20, an alkyl phosphoric acid group of 1 to 6 carbon atoms, or an oxyalkyl phosphoric acid group of 1 to 20 carbon atoms, m represents the number of substituents of 1 to 4, and n represents 1 to 1 The number of substituents of 4 is shown. ]
Indicate
R may be the same or different and each represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. An aryloxy group or an acyl group having 2 to 20 carbon atoms;
X is a protonic acid group which may be the same or different, and is a sulfonic acid group, a phosphoric acid group, an alkylsulfonic acid group having 1 to 6 carbon atoms, or an oxyalkylsulfonic acid having 1 to 20 carbon atoms. A group, an alkyl phosphate group having 1 to 6 carbon atoms, or an oxyalkyl phosphate group having 1 to 20 carbon atoms,
m represents the number of substituents 1 to 4,
f represents the number of substituents 1 to (4-m);
n represents the number of substituents 1 to 4,
j represents the number of substituents of 1 to (4-n). ]


[In the formula (3), Rs may be the same or different and are each hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. , An aryloxy group having 6 to 20 carbon atoms, or an acyl group having 2 to 20 carbon atoms,
X is a protonic acid group which may be the same or different, and is a sulfonic acid group, a phosphoric acid group, an alkylsulfonic acid group having 1 to 6 carbon atoms, or an oxyalkylsulfonic acid having 1 to 20 carbon atoms. A group, an alkyl phosphate group having 1 to 6 carbon atoms, or an oxyalkyl phosphate group having 1 to 20 carbon atoms,
m represents the number of substituents 1 to 4,
f represents the number of substituents 1 to (4-m);
n represents the number of substituents 1 to 4,
j represents the number of substituents of 1 to (4-n). ]


[In the formula (4), A represents a direct bond, -O-, -S-, -S (O)-, -S (O) _2- , -C (O)-, -P (O) (C _{6 H 5) -, - C} (CH 3) 2 -, - CH 2 -, - C (C 6 H 5) 2 -, or shows an alkylidene group having 1 to 10 carbon atoms,
R may be the same or different and each represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 6 to 20 carbon atoms. An aryloxy group or an acyl group having 2 to 20 carbon atoms;
X is a protonic acid group which may be the same or different, and is a sulfonic acid group, a phosphoric acid group, an alkylsulfonic acid group having 1 to 6 carbon atoms, or an oxyalkylsulfonic acid having 1 to 20 carbon atoms. A group, an alkyl phosphate group having 1 to 6 carbon atoms, or an oxyalkyl phosphate group having 1 to 20 carbon atoms,
m represents the number of substituents of 1 to 5,
f represents the number of substituents 1 to (5-m);
n represents the number of substituents of 1 to 5,
j represents the number of substituents of 1 to (5-n). ]


[In formula (5), Z represents a direct bond, —NH—, a divalent alkylamino group having 1 to 10 carbon atoms, —N (C ₆ H ₅ ) —, —O—, or —S—. ,
R is hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, or an acyl having 2 to 20 carbon atoms. Group,
X is a protonic acid group, which is a sulfonic acid group, a phosphoric acid group, an alkylsulfonic acid group having 1 to 6 carbon atoms, an oxyalkylsulfonic acid group having 1 to 20 carbon atoms, or an alkylphosphoric acid group having 1 to 6 carbon atoms. Group, or an oxyalkyl phosphate group having 1 to 20 carbon atoms,
m represents the number of substituents of 1 to 5,
f represents the number of substituents of 1 to (5-m). ]
[6]
The second aromatic polymer compound includes at least one aromatic ring or heterocyclic ring selected from the group consisting of the following formulas (6), (8), (9), and (10): 1] The method described above.


[In the formula (6), A represents a direct bond, —O—, —S—, —S (O) —, —S (O) ₂ —, —C (O) —, —P (O) (C _{6 H 5) -, - C} (CH 3) 2 -, - CH 2 -, - C (C 6 H 5) 2 -, or


Indicate
B, C, D and E may be the same as or different from each other, hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, An aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, or a cyano group. ]


[In Formula (8), F and G may be the same as or different from each other, hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and 6 to 20 carbon atoms. An aryl group, an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, or a cyano group is shown. ]


[In the formula (9), A represents a direct bond, -O-, -S-, -S (O)-, -S (O) _2- , -C (O)-, -P (O) (C ₆ H ₅ ) —, —C (CH ₃ ) ₂ —, —CH ₂ —, —C (C ₆ H ₅ ) ₂ — or an alkylidene group having 1 to 10 carbon atoms,
R may be the same or different and each represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. An aryloxy group or an acyl group having 2 to 20 carbon atoms;
f and j each independently represent 1 to 5 substituents. ]


[In the formula (10), Z represents a direct bond, —NH—, an alkylamino group having 1 to 10 carbon atoms, —N (C ₆ H ₅ ) —, —O—, or —S—;
R is hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, or an acyl having 2 to 20 carbon atoms. Group,
f shows the number of substituents of 1-5. ]
[7]
The method according to [1], wherein the protonic acid group is a sulfonic acid group and / or a phosphoric acid group.
[8]
The method according to [1], wherein the first aromatic polymer compound is the following formula (11).

(11)

[In Formula (11), A's may be the same or different, and may be a direct bond, -O-, -S-, -S (O)-, -S (O) _2- , -C. (O) -, - P ( O) (C 6 H 5) -, - C (CH 3) 2 -, - CH 2 -, or _{-C (C 6 H 5) 2} - indicates,
X represents a halogen group,
n represents an integer of 3 or more. ]
[9]
It is related with the block copolymer prepared by the method of any one of [1]-[8].
[10]
[9] A polymer electrolyte composition comprising the block copolymer according to [9].
[11]
[10] A polymer electrolyte membrane comprising the polymer electrolyte composition according to [10].

The method for producing a block copolymer according to the present invention comprises the following steps: a segment having significantly different polarities (the first aromatic polymer compound having a proton acid group and the first aromatic polymer compound reactive with the proton acid group It is possible to block the second aromatic polymer compound that does not have. In particular, by introducing a monovalent hydrophobic aromatic halogen group which is a reactive group into the first aromatic polymer compound in advance, the first aromatic polymer compound and the second aromatic polymer compound are introduced. Reaction with a high molecular compound can be performed reliably. In particular, for example, the polymer obtained in Patent Document 4 is a series of hydrophobic blocks or hydrophilic blocks such as [-A-A-B-B-A-B-] (A is a hydrophilic block, B is a hydrophobic block). In contrast to a block polymer having a bonding mode, the method for producing a block copolymer of the present invention reliably produces [-A-B-A-B-A-B-] (specifically, A Is a block polymer having a bonding mode of the first aromatic polymer compound (hydrophilic block) and B is the second aromatic polymer compound (hydrophobic block).
The block copolymer synthesized using the production method of the present invention can be suitably used as a material for a polymer electrolyte membrane that exhibits high proton conductivity.
Further, the method for producing a block copolymer of the present invention can easily control the segment chain length of each of the first aromatic polymer compound and the second aromatic polymer compound, and The block copolymer can have a high molecular weight regardless of the chain length.
Moreover, the polymer electrolyte containing this and a polymer electrolyte membrane can be provided using the block copolymer obtained from the manufacturing method of this invention.
Moreover, the method for producing a block copolymer of the present invention can provide a block copolymer containing no halogen group in the molecule.
In addition, since the polymer electrolyte membrane of the present invention does not contain halogen, it is possible to reduce processing costs and environmental burdens that occur during disposal and recycling.
In addition, the polymer electrolyte membrane of the present invention has excellent properties that the production process is simple, the quality is stable, and the production cost is low.

Hereinafter, the present invention will be described in detail.
(1) Block copolymer The block copolymer of the present invention has (a) a monovalent hydrophobic aromatic halogen group at the terminal (provided that the monovalent hydrophobic aromatic halogen group is perfluorobiphenyl). A first aromatic polymer compound (hydrophilic segment) having a protonic acid group, and (b) a monovalent hydrophobic aromatic halogen group of the first aromatic polymer compound at the terminal, It is obtained by reacting and bonding with a second aromatic polymer compound (hydrophobic segment) having a reactive group capable of reacting and not having a protonic acid group. The block copolymer of the present invention does not contain halogen in the molecule. Therefore, as the first aromatic polymer compound and the second aromatic polymer compound, a polymer compound containing no halogen group other than at least the terminal group is selected.
Usually, when two polymer segments each having a functional group capable of reacting with each other are copolymerized, a block copolymer is obtained. However, when trying to obtain a block copolymer by polymerizing polymer segments having greatly different polarities, the polymer segments having different polarities are not compatible with each other, and simply mixing both polymer segments. Even in the block copolymerization, the same polymer segments often react with each other, and the reactions between different polymer segments often do not proceed sufficiently.
Therefore, a hydrophilic and highly active monovalent hydrophobic aromatic halogen group is previously bonded to the end of the hydrophilic polymer segment (first aromatic polymer compound), thereby making the hydrophilic polymer segment (first aromatic polymer compound) hydrophilic. At the end of the polymer segment, compatibility with the hydrophobic polymer segment (second aromatic polymer compound) and reaction activity were imparted. As a result, the block copolymer reaction by different polymer segments proceeds sufficiently, and the block copolymer obtained as necessary is used as a block copolymer precursor, and a plurality of block copolymer precursors are Can be crosslinked to obtain a block copolymer having a higher molecular weight.
Hereinafter, the structure and ratio of the first aromatic polymer compound and the second aromatic polymer compound, the preparation method thereof, and the like will be described in detail.

(1-1) Structure of the first aromatic polymer compound The (a) first aromatic polymer compound of the present invention comprises a terminal monovalent hydrophobic aromatic halogen group and a protonic acid group introduced. And a valent group.
(1-1-1) Terminal monovalent hydrophobic aromatic halogen group The terminal monovalent hydrophobic aromatic halogen group present in the first aromatic polymer compound of the present invention is a group other than a perfluorobiphenyl group. It is highly hydrophobic and has high reaction activity. By introducing a hydrophobic reactive group into the hydrophilic segment, the compatibility of the terminal with the hydrophobic segment becomes good, and the blocking reaction easily proceeds. By using a reactive group with high reaction activity, the reaction temperature for blocking can be lowered. By performing the blocking reaction at a lower temperature, an effect of suppressing randomization of the block copolymer can be expected. In the present invention, the reaction activity refers to the activity for the polymerization reaction, and the activity is high when the polymerization reaction proceeds at 80 ° C. to 180 ° C., preferably 80 ° C. to 160 ° C.
The terminal monovalent hydrophobic aromatic halogen group has a direct bond, -O-, -S-, -S (O)-, -S with an adjacent group (such as a divalent group having a protonic acid group introduced). (O) _2- , -C (0)-, -P (O) (C ₆ H ₅ )-, -C (CH ₃ ) _2- , -CH _2- , or -C (C ₆ H ₅ ) ₂ -May be combined.
Examples of terminal monovalent hydrophobic aromatic halogen groups include:


Etc.

(1-1-2) Divalent Group Introduced with Protic Acid Group The first aromatic polymer compound of the present invention has the following divalent group (α) and / or proton introduced with a protonic acid group: The main chain contains a divalent group (β) into which an acid group has been introduced.
The divalent group (α) having a proton acid group introduced therein preferably contains a structural unit having an aromatic ring having a proton acid group introduced into the following formula (1) and / or the following formula (3). .


In the formula (1), A is a direct bond, -O -, - S -, - S (O) -, - S (O) 2 -, - C (O) -, - P (O) (C 6 _{H 5) -, - C (} CH 3) 2 -, - CH 2 -, - C (C 6 H 5) 2 -, or,


[In Formula (2), X is the proton acid group which may be the same or different, respectively, Comprising: A sulfonic acid group, a phosphoric acid group, C1-C20, Preferably C1-C10, More preferably an alkylsulfonic acid group having 1 to 6 carbon atoms, 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably an oxyalkylsulfonic acid group having 1 to 6 carbon atoms, 1 to 20 carbon atoms, preferably An alkyl phosphate group having 1 to 10 carbon atoms, more preferably an alkyl phosphate group having 1 to 6 carbon atoms, an oxyalkyl phosphate group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms. . m represents the number of substituents of 1 to 4, preferably 1 to 2, more preferably 1. n represents 1 to 4, preferably 1 to 2, more preferably 1 substituent. ]
Indicates.

R may be the same or different, and hydrogen, an alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and preferably 1 to 20 carbon atoms, preferably Is an alkoxy group having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, 6 to 20 carbon atoms, preferably 6 to 16 carbon atoms, more preferably an aryl group having 6 to 14 carbon atoms, 6 to 20 carbon atoms. , Preferably an aryloxy group having 6 to 16 carbon atoms, more preferably an aryloxy group having 6 to 14 carbon atoms, or an acyl group having 2 to 20 carbon atoms, preferably 6 to 14 carbon atoms, more preferably 2 to 14 carbon atoms.
X is a protonic acid group which may be the same or different, and is a sulfonic acid group, a phosphoric acid group, 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 1 carbon atoms. 6 represents an oxyalkylsulfonic acid group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms.
m represents the number of substituents of 1 to 4, preferably 1 to 2, more preferably 1.
f represents the number of substituents of 1 to (4-m), preferably 1 to 2, more preferably 1.
n represents 1 to 4, preferably 1 to 2, more preferably 1 substituent.
j represents 1- (4-n), preferably 1-2, more preferably 1 substituent number.

Examples of the divalent group (α) introduced with the protonic acid group of the formula (1) include:















Etc.

In the formula (3), R may be the same or different from each other, and is hydrogen, an alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and carbon. An aryl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, 6 to 20 carbon atoms, preferably 6 to 16 carbon atoms, and more preferably 6 to 14 carbon atoms. An aryloxy group having 6 to 20 carbon atoms, preferably 6 to 16 carbon atoms, more preferably 6 to 14 carbon atoms, 2 to 20 carbon atoms, preferably 2 to 16 carbon atoms, more preferably 2 to 14 carbon atoms. An acyl group of
X is a proton acid group which may be the same or different, and is a sulfonic acid group, a phosphoric acid group, 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 1 carbon atoms. 6 alkyl sulfonic acid groups, 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon oxyalkyl sulfonic acid groups, 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, More preferably, it represents an alkyl phosphate group having 1 to 6 carbon atoms, or an oxyalkyl phosphate group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms.
m represents the number of substituents of 1 to 4, preferably 1 to 2, more preferably 1.
f represents the number of substituents of 1 to (4-m), preferably 1 to 2, more preferably 1.
n represents 1 to 4, preferably 1 to 2, more preferably 1 substituent.
j represents 1- (4-n), preferably 1-2, more preferably 1 substituent number.

Examples of the divalent group (α) introduced with the protonic acid group of the formula (3) include:









Etc.

The divalent group (β) having a proton acid group introduced therein preferably contains a structural unit having a heterocyclic ring having a proton acid group introduced by the following formula (4) and / or formula (5).


Wherein (4), A is a direct bond, -O -, - S -, - S (O) -, - S (O) 2 -, - C (O) -, - P (O) (C 6 H ₅ ) —, —C (CH ₃ ) ₂ —, —CH ₂ —, —C (C ₆ H ₅ ) ₂ —, or C 1-10, preferably C 1-8, more preferably C 1-6 alkylidene groups are shown.
R may be the same as or different from each other, and hydrogen, an alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and 1 to 20 carbon atoms, preferably Is an alkoxy group having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, 6 to 20 carbon atoms, preferably 6 to 16 carbon atoms, more preferably an aryl group having 6 to 14 carbon atoms, 6 to 20 carbon atoms. , Preferably an aryloxy group having 6 to 16 carbon atoms, more preferably an aryloxy group having 6 to 14 carbon atoms, and an acyl group having 2 to 20 carbon atoms, preferably 2 to 16 carbon atoms, and more preferably 2 to 14 carbon atoms.
X is a proton acid group which may be the same or different, and is a sulfonic acid group, a phosphoric acid group, 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 1 carbon atoms. 6 alkyl sulfonic acid groups, 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon oxyalkyl sulfonic acid groups, 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, More preferably, it represents an alkyl phosphate group having 1 to 6 carbon atoms, or an oxyalkyl phosphate group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms.
m represents the number of substituents of 1 to 5, preferably 1 to 2, more preferably 1.
f represents the number of substituents of 1 to (5-m), preferably 1 to 2, more preferably 1.
n represents 1 to 5, preferably 1 to 2, more preferably 1 substituent.
j represents 1- (5-n), preferably 1-2, more preferably 1 substituent number.

Examples of the divalent group (β) introduced with the protonic acid group of the formula (4) include:










Etc.

In formula (5), Z represents a direct bond, —NH—, a divalent alkylamino group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, —N (C ₆ H ₅ ) —, —O—, or —S—.
R is hydrogen, an alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably a carbon number. 1 to 6 alkoxy groups, 6 to 20 carbon atoms, preferably 6 to 16 carbon atoms, more preferably aryl groups having 6 to 14 carbon atoms, 6 to 20 carbon atoms, preferably 6 to 14 carbon atoms, more preferably An aryloxy group having 6 to 14 carbon atoms, an acyl group having 2 to 20 carbon atoms, preferably 2 to 16 carbon atoms, and more preferably 2 to 14 carbon atoms is shown.
X is a protonic acid group, and is a sulfonic acid group, a phosphoric acid group, an alkylsulfonic acid group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and 1 to 1 carbon atoms. 20, preferably an oxyalkylsulfonic acid group having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, an alkyl phosphate group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, or 1 to 20 carbon atoms , Preferably an oxyalkyl phosphate group having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms.
m represents the number of substituents of 1 to 5, preferably 1 to 2, more preferably 1.
f represents the number of substituents of 1 to (5-m), preferably 1 to 2, more preferably 1.

Examples of the divalent group (β) introduced with the protonic acid group of the formula (5) include:






Etc.
Here, the structural units of the divalent groups (α) and (β) into which protonic acid groups are introduced are not necessarily limited to one type, and two or more types of structural units may be included.

(1-1-3) Other divalent groups Further, the first aromatic polymer compound of the present invention includes other than the divalent groups (α) and (β) into which the protonic acid group is introduced. These divalent groups may be included. Other divalent groups other than the divalent groups (α) and (β) into which the protonic acid group is introduced in the present invention are not particularly limited, but are used for the second aromatic polymer compound, for example. Divalent groups not having a protonic acid group, divalent alkylene ether groups derived from ethylene oxide, propylene oxide, tetramethylene oxide, etc., divalent aromatic ether groups having bonds such as aromatic imides, amides, etc. .
The divalent groups (α) and (β) into which the protonic acid group is introduced and the other divalent groups are a direct bond, —O—, —S—, —S (O) —, —S. _{(O) 2 -, - C} (O) -, - P (O) (C 6 H 5) -, - C (CH 3) 2 -, - CH 2 -, or -C (C ₆ H _{5) 2} -May be combined.

(1-1-4) Amount of protonic acid group contained in the first aromatic polymer compound The content of the protonic acid group contained in the first aromatic polymer compound of the present invention is not particularly limited, The total amount of protonic acid groups in the first aromatic polymer compound is adjusted in the range of 200 to 600, preferably 200 to 550, more preferably 200 to 500 in terms of ion exchange equivalent mass (EW value). It is preferable. Here, the ion exchange equivalent mass (EW value) refers to the mass (g) of the polymer compound per mole of protonic acid groups. If the EW value of the first aromatic polymer compound is 250 or more, the solvent resistance of the block copolymer is not drastically lowered, and if it is 600 or less, the proton conductivity of the block copolymer is reduced. There is no decline.

(1-1-5) Molecular weight of the first aromatic polymer compound The mass average molecular weight of the first aromatic polymer compound is preferably 2000 or more and 150,000 or less, more preferably 7000 or more and 120,000 or less, and 7000 or more and 100,000. The following is more preferable. If the mass average molecular weight is 2000 or more, the molecular chain length of the first aromatic polymer compound will not be insufficient, and if it is 150,000 or less, the block copolymerization reaction will not be insufficient.
Further, the number average molecular weight of the first aromatic polymer compound is preferably from 5,000 to 100,000, more preferably from 8,000 to 80,000, and further preferably from 10,000 to 50,000. If the mass average molecular weight is 5000 or more, the molecular chain length of the first aromatic polymer compound will not be insufficient, and if it is 100000 or less, the block copolymerization reaction will not be insufficient.

Specifically, the first aromatic polymer compound of the present invention more preferably includes the structure of the following formula (11).


In formula (11), A's may be the same or different, and are each a direct bond, -O-, -S-, -S (O)-, -S (O) _2- , -C ( O) -, - P (O ) (C 6 H 5) -, - C (CH 3) 2 -, - CH 2 -, or _{-C (C 6 H 5) 2} - shows a.
n is an integer of 3 or more, preferably 5 or more, more preferably 5 to 50, and still more preferably 5 to 50.
X represents a halogen group, preferably fluorine, chlorine, bromine, iodine, more preferably fluorine.

Examples of the first aromatic polymer compound represented by the formula (11) include:




















Can be mentioned.

(1-2) Structure of the second aromatic polymer compound (b) The second aromatic polymer compound of the present invention reacts with the perfluorobiphenyl group of the first aromatic polymer compound at the terminal. It has a reactive group to be obtained and a divalent group having no proton acid group.
(1-2-1) Terminal Reactive Group The reactive group present at the terminal of the second aromatic polymer compound of the present invention can react with the perfluorobiphenyl group of the first aromatic polymer compound. . Although there is no restriction | limiting in particular as this reactive group, For example, an aromatic amino group, an aromatic thiol group, a phenolic hydroxyl group etc. are preferable, and a phenolic hydroxyl group is especially preferable from a viewpoint of reactivity and the ease of handling. Specifically, as an aromatic amino group, for example,

Is mentioned. Moreover, as an aromatic thiol group, for example,


Is mentioned. Furthermore, as a phenolic hydroxyl group, for example,

Is mentioned.
The terminal reactive group includes an adjacent group (such as a divalent group having no proton acid group), a direct bond, -O-, -S-, -S (O)-, -S (O) _2- , -C (O) -, - P (O) (C 6 H 5) -, - C (CH 3) 2 -, - CH 2 -, or _{-C (C 6 H 5) 2} - have been coupled with Also good.

(1-2-2) Divalent group not having a protonic acid group The first aromatic polymer compound of the present invention comprises a divalent group (γ) and / or a heterocyclic ring containing an aromatic ring shown below. The main chain contains a divalent group (δ).
The divalent group (γ) containing an aromatic ring preferably contains a structural unit having an aromatic ring of the following formula (6) and / or the following formula (8).


Wherein (6), A is a direct bond, -O -, - S -, - S (O) -, - S (O) 2 -, - C (O) -, - P (O) (C 6 _{H 5) -, - C (} CH 3) 2 -, - CH 2 -, - C (C 6 H 5) 2 -, or


Indicates.
B, C, D, and E may be the same or different, and are hydrogen, an alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and carbon. An aryl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, 6 to 20 carbon atoms, preferably 6 to 16 carbon atoms, and more preferably 6 to 14 carbon atoms. An aryloxy group having 6 to 20 carbon atoms, preferably 6 to 16 carbon atoms, more preferably 6 to 14 carbon atoms, 2 to 20 carbon atoms, preferably 2 to 16 carbon atoms, more preferably 2 to 14 carbon atoms. An acyl group or a cyano group.

Examples of the divalent group (γ) containing an aromatic ring of the formula (6) include



Etc.

In the formula (8), F and G are hydrogen or an alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and 1 to 20 carbon atoms, preferably 1 carbon atom. -10, more preferably an alkoxy group having 1 to 6 carbon atoms, 6 to 20 carbon atoms, preferably 6 to 16 carbon atoms, more preferably an aryl group having 6 to 14 carbon atoms, 6 to 20 carbon atoms, preferably carbon An aryloxy group having 6 to 16 carbon atoms, more preferably an aryloxy group having 6 to 14 carbon atoms, or an acyl group having 2 to 20 carbon atoms, preferably 2 to 16 carbon atoms, more preferably 2 to 14 carbon atoms, and a cyano group.
As the divalent group (γ) containing the aromatic ring of the formula (8), for example,




Etc.

The divalent group (δ) containing a heterocyclic ring preferably contains a structural unit having a heterocyclic ring of the following formula (9) and / or formula (10).


In the formula (9), A represents a direct bond, —O—, —S—, —S (O) —, —S (O) ₂ —, —C (O) —, —P (O) (C ₆ H ₅ ) —, —C (CH ₃ ) ₂ —, —CH ₂ —, —C (C ₆ H ₅ ) ₂ —, or 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 carbon atom. -6 alkylidene groups are shown.
R may be the same or different, but hydrogen, an alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, 1 to 20 carbon atoms, Preferably it is C1-C10, More preferably, it is C1-C6 alkoxy group, C6-C20, Preferably it is C6-C16, More preferably, it is C6-C14 aryl group, C6-C6 20, preferably an aryloxy group having 6 to 16 carbon atoms, more preferably 6 to 14 carbon atoms, an acyl group having 2 to 20 carbon atoms, preferably 2 to 16 carbon atoms, more preferably 2 to 14 carbon atoms. .
f and j each independently represent 1 to 5, preferably 1 to 2, more preferably 1 substituent.

Examples of the divalent group (δ) containing a heterocyclic ring of the formula (9) include:





Etc.

In formula (10), Z is a direct bond, —NH—, an alkylamino group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, —N (C ₆ H ₅ )-, -O-, or -S-.
R is hydrogen, an alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably a carbon number. An alkoxy group having 16 to 16 carbon atoms, preferably 6 to 16 carbon atoms, more preferably an aryl group having 6 to 14 carbon atoms, 6 to 20 carbon atoms, preferably 6 to 16 carbon atoms, more preferably carbon An aryloxy group having 6 to 14 carbon atoms, an acyl group having 2 to 20 carbon atoms, preferably 2 to 16 carbon atoms, and more preferably 2 to 14 carbon atoms are shown.
f represents the number of substituents of 1 to 5, preferably 1 to 2, more preferably 1.
Examples of the divalent group (δ) containing a heterocyclic ring of the formula (10) include



Etc.
Here, the structural unit of the divalent group (γ) containing an aromatic ring and the divalent group (δ) containing a heterocyclic ring is not necessarily limited to one type, and includes two or more types of structural units. It may be.

(1-2-3) Other divalent groups Further, the second aromatic polymer compound of the present invention includes the above divalent group (γ) containing an aromatic ring and a divalent group containing a heterocyclic ring. Other divalent groups other than (δ) may be contained. The divalent group other than the divalent group (γ) containing an aromatic ring and the divalent group containing a heterocyclic ring (δ) in the present invention is not particularly limited, and examples thereof include ethylene oxide, propylene oxide, There are groups that do not contain a halogen group such as a divalent alkylene ether group derived from tetramethylene oxide or the like, a divalent aromatic ether group having a bond such as an aromatic imide, or an amide.
The divalent group (γ) containing an aromatic ring and the divalent group (δ) containing a heterocyclic ring and the other divalent group are a direct bond, -O-, -S-, -S (O )-, -S (O) _2- , -C (O)-, -P (O) (C ₆ H ₅ )-, -C (CH ₃ ) _2- , -CH _2- , or -C (C ₆ H ₅ ) _2- may be bonded.

(1-2-4) Molecular Weight of Second Aromatic Polymer Compound The mass average molecular weight of the second aromatic polymer compound is, for example, 2,000 to 150,000, preferably 5,000 to 150,000, preferably 7,000 to 120,000. The following are more preferable, and 7000 or more and 100,000 or less are more preferable. If the mass average molecular weight is 5000 or more, the segment length will not be insufficient, and if it is 150,000 or less, the block copolymerization reaction will not be insufficient.
The number average molecular weight of the second aromatic polymer compound is preferably from 2,000 to 100,000, more preferably from 3,000 to 80,000, and even more preferably from 4,000 to 50,000. If the mass average molecular weight is 2000 or more, the molecular chain length of the second aromatic polymer compound will not be insufficient, and if it is 100000 or less, the block copolymerization reaction will not be insufficient.

Specifically, the second aromatic polymer compound of the present invention more preferably includes the structure of the following formula (12).
(12)

(1-3) Ratio of the first aromatic polymer compound and the second aromatic polymer compound The block copolymer of the present invention comprises the first aromatic polymer compound and the second aromatic polymer compound. It is obtained by block copolymerization with a molecular compound. Specifically, the first aromatic polymer compound and the second aromatic polymer compound are mixed in a mass ratio between the first aromatic polymer compound and the second aromatic polymer compound [first The value of [one aromatic polymer compound] / [second aromatic polymer compound] is, for example, 0.1 or more and 10.0 or less, preferably 0.2 or more and 5.0 or less, more preferably 0.2. It is preferable to perform block copolymerization by mixing so as to be 3.0 or more. Proton conductivity is good when the value of the mass ratio [first aromatic polymer compound] / [second aromatic polymer compound] is 0.1 or more, and block weight is less than 10.0. The durability of coalescence is not lowered.

(1-4) Other compounds The block copolymer of the present invention is polymerized by including any other compound in addition to the first aromatic polymer compound and the second aromatic polymer compound. May be obtained. Such other compounds are not particularly limited as long as they can react with the first aromatic polymer compound and / or the second aromatic polymer compound. For example, ethylene oxide, propylene oxide, tetra Examples thereof include a divalent alkylene ether group derived from methylene oxide and the like, a divalent aromatic ether group having a bond such as a perfluoroalkylene ether, an aromatic imide, and an amide.

(1-5) Amount of Protic Acid Group of Block Copolymer The block copolymer of the present invention has a proton acid group derived from the first aromatic polymer compound. The amount of the protonic acid group is not particularly limited, but from the viewpoint of proton conductivity and durability, the ion exchange equivalent mass (EW value) is preferably from 300 to 1,000, more preferably from 400 to 900, more preferably 500 More preferable is 800 or less. Here, the ion exchange equivalent mass (EW value) refers to the mass (g) of the block copolymer per mole of protonic acid groups. If the EW value is 300 or more, the durability does not decrease, and if it is 1000 or less, the proton conductivity is good.

(2) Production of block copolymer The block copolymer of the present invention comprises the following steps:
(A) a step of preparing a first aromatic polymer compound having a monovalent hydrophobic aromatic halogen group at the terminal and having a protonic acid group (provided that the monovalent hydrophobic aromatic halogen group is Not a perfluorobiphenyl group),
(B) a second aromatic polymer compound having a reactive group capable of reacting with a monovalent hydrophobic aromatic halogen group of the first aromatic polymer compound at the terminal and having no proton acid group And (c) combining the first aromatic polymer compound and the second aromatic polymer compound to prepare a block copolymer,
Manufactured by.

(2-1) Preparation of First Aromatic Polymer Compound The preparation method (step (a)) of the first aromatic polymer compound of the present invention will be described.
The first aromatic polymer compound of the present invention has a monovalent hydrophobic aromatic halogen group other than a perfluorobiphenyl group at the terminal and a protonic acid group. Therefore, the first aromatic polymer compound is synthesized by introducing a monovalent hydrophobic aromatic halogen group at the end of the main chain containing a divalent group having a proton acid group introduced. Examples of the method for introducing a terminal monovalent hydrophobic aromatic halogen group include the following methods.
(1) It is obtained after (co) polymerizing a precursor monomer containing a terminal protecting group that protects a portion that reacts with a compound having a hydrophobic aromatic halogen group and a divalent group into which a protonic acid group has been introduced. The terminal protective group of the (co) polymer was removed, and the (co) polymer and a compound having a monovalent hydrophobic aromatic halogen group were reacted to form a monovalent at the terminal of the (co) polymer. A method of introducing a hydrophobic aromatic halogen group.
(2) preparing a precursor monomer containing a divalent group having a proton acid group introduced therein and another precursor monomer capable of reacting with a compound having a hydrophobic aromatic halogen group in excess of the precursor monomer; Then, these precursor monomers are copolymerized, and then the obtained copolymer is reacted with a compound having a monovalent hydrophobic aromatic halogen group to give a monovalent hydrophobic aromatic at the terminal of the copolymer. To introduce a halogen group.
Here, the method (2) will be described as an example.

First, the precursor polymer compound (I) for preparing the first aromatic polymer compound is synthesized. The precursor polymer compound (I) includes at least one precursor monomer (η) containing a divalent group (α) and / or (β) into which a protonic acid group is introduced in the present invention, and the other divalent group. It is synthesized by copolymerization with a precursor monomer (θ) containing a group of The precursor monomer (η) has two or more reactive functional groups capable of reacting with the end group of the precursor monomer (θ) at its end. The precursor monomer (θ) has two or more reactive functional groups capable of reacting with the precursor monomer (η) and a compound having a hydrophobic aromatic halogen group at its terminal. Here, the precursor monomer (θ) is added in excess with respect to the precursor monomer (η) in order to leave a reaction site used for the subsequent reaction with the compound having a monovalent hydrophobic aromatic halogen group. There is no restriction | limiting in particular in the method to manufacture a copolymer here, The appropriate well-known method according to each combination of precursor monomer can be used.
As the precursor monomer (η), for example, a dihalogenated compound containing a divalent group (α) and / or (β) into which a protonic acid group is introduced is preferable. Examples of the halogen include fluorine, chlorine, bromine and iodine. The reactive functional groups may be the same or different from each other.

Examples of the precursor monomer (θ) include diphenol compounds, triphenol compounds, tetraphenol compounds, dithiophenol compounds, trithiophenol compounds, tetrathiophenol compounds, diamino compounds containing other divalent groups, Triamino compounds, tetraamino compounds, di-substituted amino compounds, tri-substituted amino compounds, tetra-substituted amino compounds and the like can be mentioned. The precursor monomer (θ) may be used alone or in combination of two or more. Examples of the reactive functional group of the precursor monomer (θ) include a phenol group, a thiophenol group, and an amino group. The reactive functional groups may be the same or different from each other.
The precursor monomer (θ) is preferably 1.01 to 1.30 equivalents, more preferably 1.01 to 1.25 so as to be in an excess amount (molar equivalent) with respect to the precursor monomer (η). It is preferable to add in an amount of equivalent, more preferably 1.01-1.20 equivalent.

  A monovalent hydrophobic aromatic halogen group is further introduced into the terminal of the precursor polymer compound (I) thus obtained to obtain a first aromatic polymer compound. Examples of the method for introducing a monovalent hydrophobic aromatic halogen group include a method of adding a compound having a monovalent hydrophobic aromatic halogen group to the precursor polymer compound (I), for example, difluorodiphenyl sulfone. As for difluorodiphenyl sulfone, it is appropriate to add about 2 equivalents of difluorodiphenyl sulfone with respect to the amount of excess precursor monomer (θ) added in the synthesis of precursor polymer compound (I).

The synthesis of the first aromatic polymer compound of the present invention is suitably performed in a solvent in the presence of a catalyst.
As the catalyst, alkali catalysts such as potassium carbonate, calcium carbonate and cesium carbonate and metal halides such as cesium fluoride can be used. The amount of the catalyst is suitably 1 to 10 times, preferably 1 to 5 times, more preferably 1 to 2 times the number of moles of the precursor monomer to be reacted.

As the solvent, an appropriate one can be selected from aprotic polar solvents such as N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, hexamethylphosphonamide, and γ-butyrolactone. However, it is not limited to these. A plurality of these solvents may be used as a mixture within a possible range.
The amount of solvent can be used in the range of 1 to 100 times, preferably 1 to 70 times, and more preferably 10 to 250 times the total mass of the precursor monomer and catalyst to be reacted.
The reaction temperature is, for example, 0 ° C to 350 ° C, preferably 40 ° C to 260 ° C. The reaction time can be, for example, 2 hours to 500 hours, preferably 10 hours to 250 hours.

As a more specific introduction method of the monovalent hydrophobic aromatic halogen group of the present invention, for example, a precursor of a first aromatic polymer compound having a phenolic hydroxyl group at the terminal is prepared, and the precursor terminal is prepared. Can be obtained by reacting 2 equivalents of difluorodiphenylsulfone.
The amount of the monovalent hydrophobic aromatic halogen group introduced is not particularly limited, but is preferably 0.5% to 30%, preferably 1% to 25% with respect to the first aromatic polymer compound. It is more preferable that it is 2% or more and 20% or less. If it is 0.5% or more, the block copolymerization reaction will not be insufficient, and if it is 30% or less, the molecular chain length of the first aromatic polymer compound will not be insufficient.

(2-2) Preparation of Second Aromatic Polymer Compound A method for preparing the second aromatic polymer compound of the present invention (step (b)) will be described.
The second aromatic polymer compound (b) of the present invention can be prepared in the same manner as the methods (1) and (2) described in the preparation of the first aromatic polymer compound. Here, the method (2) will be described as an example.
First, a precursor polymer compound (II) for preparing the first aromatic polymer compound is synthesized. The precursor polymer compound (II) is a precursor containing one or more precursor monomers (ρ) containing an aromatic ring (γ) and / or a heterocyclic ring (δ) in the present invention and the other divalent group. It is preferably synthesized by copolymerizing with the monomer (σ). The precursor monomer (ρ) has two or more reactive functional groups capable of reacting with the terminal group of the precursor monomer (σ) at its terminal. The precursor monomer (σ) has at least two reactive functional groups capable of reacting with the monovalent hydrophobic aromatic halogen group at the terminal of the precursor monomer (ρ) and the first aromatic polymer compound. . Here, the precursor monomer (σ) is added to the precursor monomer (ρ) in order to leave a reactive site used for the reaction with the monovalent hydrophobic aromatic halogen group at the end of the first aromatic polymer compound later. Too much is added. Here, the method for producing the copolymer is not particularly limited, and a known method suitable for each combination of precursor monomers can be used.
Further, the precursor monomer (ρ) and a precursor monomer (σ) having two or more functional groups capable of reacting with the precursor monomer (ρ) may be subjected to a condensation reaction to form a copolymer. Can be synthesized.
Here, examples of the precursor monomer (ρ) include a dihalonated compound containing an aromatic ring (γ) and / or a heterocyclic ring (δ). As the two or more reactive functional groups present at the terminal of the precursor monomer (ρ), for example, a halogen group is preferable. Examples of the halogen include fluorine, chlorine, bromine and iodine. The reactive functional groups may be the same or different from each other.

  Examples of the precursor monomer (σ) include diphenyl compounds, triphenyl compounds, tetraphenyl compounds, dithiophenol compounds, trithiophenol compounds, tetrathiophenol compounds, diamino compounds, and triaminos containing other divalent groups. Examples thereof include compounds, tetraamino compounds, di-substituted amino compounds, tri-substituted amino compounds, tetra-substituted amino compounds and the like. The precursor monomer (σ) may be used alone or in combination of two or more. Examples of the reactive functional group of the precursor monomer (σ) include a phenyl group, a thiophenyl group, and an amino group. The reactive functional groups may be the same or different from each other.

  The precursor monomer (ρ) is preferably 1.01 to 1.30 equivalent, more preferably 1.01 to 1.25 so as to be in an excess amount (molar equivalent) with respect to the precursor monomer (σ). It is preferable to add in an amount of equivalent, more preferably 1.01-1.20 equivalent.

The synthesis of the second aromatic polymer compound of the present invention is suitably performed in a solvent in the presence of a catalyst.
As the catalyst, alkali catalysts such as potassium carbonate, calcium carbonate and cesium carbonate and metal halides such as cesium fluoride can be used. The amount of the catalyst is suitably 1 to 10 times, preferably 1 to 5 times, more preferably 1 to 2 times the number of moles of the precursor monomer to be reacted.
As the solvent, an appropriate one can be selected from aprotic polar solvents such as N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, hexamethylphosphonamide, and γ-butyrolactone. However, it is not limited to these. A plurality of these solvents may be used as a mixture within a possible range.
The amount of solvent can be used in the range of 1 to 100 times, preferably 1 to 70 times, and more preferably 1 to 50 times the total mass of the precursor monomer and catalyst to be reacted.
The reaction temperature is, for example, 0 ° C to 350 ° C, preferably 40 ° C to 260 ° C.
The reaction time can be, for example, 2 hours to 500 hours, preferably 10 hours to 250 hours.

  The amount of terminal reactive groups introduced is not particularly limited, but is preferably 0.5% or more and 30% or less, more preferably 1% or more and 25% or less with respect to the second aromatic polymer compound. Preferably, it is 2% or more and 20% or less. If it is 0.5% or more, the block copolymerization reaction will not be insufficient, and if it is 30% or less, the molecular chain length of the second aromatic polymer compound will not be insufficient.

(2-3) Preparation of block copolymer The synthesis method of the block copolymer of the present invention is the first aromatic polymer compound (hydrophilic segment) and the second aromatic polymer compound prepared by the above method. (Block (hydrophobic segment) is mixed and bonded to prepare a block copolymer (step (c)).
As a method for mixing the first aromatic polymer compound and the second aromatic polymer compound used in the block copolymer of the present invention, the reaction solution containing each compound obtained by synthesis of each compound is used as it is. There is a method of mixing, a method of mixing the first aromatic polymer compound and the second aromatic polymer compound, which are purified and taken out after synthesis of each compound, adding a solvent, and dissolving in the solvent again. . The method of mixing the reaction solution containing each compound as it is is preferably used from the viewpoint of ease of reaction operation.
The solvent used for the synthesis of the block copolymer is not particularly limited as long as it dissolves the first aromatic polymer compound and the second aromatic polymer compound, but the first aromatic polymer compound is not limited. And a solvent used in the synthesis of the second aromatic polymer compound is preferably used. At this time, a solvent used for synthesis or other solvent may be added to adjust the solution concentration and solubility. Specific solvents include those suitable from aprotic polar solvents such as N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, hexamethylphosphonamide, and γ-butyrolactone. You can choose, but is not limited to these. A plurality of these solvents may be used as a mixture within a possible range.

The amount of the solvent can be used in the range of 1 to 100 times, preferably 1 to 70 times, more preferably 1 to 50 times the total mass of the monomer to be reacted and the catalyst.
The reaction temperature of the block copolymer is preferably 100 ° C. or higher and 220 ° C. or lower, more preferably 120 ° C. or higher and 200 ° C. or lower, further preferably 140 ° C. or higher and 180 ° C. or lower. If it is 220 ° C. or less, randomization does not proceed excessively.
The reaction time of the block copolymer is preferably 0.1 hours or more and 12 hours or less, preferably 0.2 hours or more and 8 hours or less, more preferably 0.5 hours or more and 4 hours or less, and more preferably 0.1 hours or more. For example, the block copolymerization reaction does not become insufficient, and if it is 12 hours or less, randomization does not proceed excessively.

(2-4) Purification method of block copolymer As a method of purifying the block copolymer of the present invention from the reaction solution, a conventionally known polymer purification method can be preferably used. If the copolymer is solid, it is washed with a solvent after filtration and dried. If it is oily, it is separated, and if it is dissolved in the reaction solution, the organic solvent is removed by evaporation. It can be purified by reprecipitation.
Alternatively, the block copolymer of the present invention is prepared by adding water to the reaction solution containing the block copolymer, adding an alkali component as necessary, stirring, and separating into a solvent phase and an aqueous phase. The precipitate is obtained from the aqueous phase by a method such as acid precipitation or salting out, and the precipitate is filtered, and then the filtered precipitate is washed with a solvent and dried.
The obtained block copolymer includes a hydrophilic segment derived from the first aromatic polymer compound and a hydrophobic segment derived from the second aromatic polymer compound. The molar ratio of these hydrophilic segment to hydrophobic segment is, for example, 100: 20 to 100: 500, preferably 100: 50 to 100: 400, and more preferably 100: 70 to 100: 300.

(3) Polymer electrolyte composition The polymer electrolyte composition of this invention contains the said block copolymer and arbitrary other resin components.
(3-1) Other resin components The block copolymer of the present invention may contain other types of resin components having different structures as long as the properties of the block copolymer are not significantly deteriorated.
Specific examples of the resin component include polyethylene (PE), polypropylene (PP), polystyrene (PS), polymethyl methacrylate (PMMA), ABS resin, AS resin, and other general-purpose resins, polyacetate (POM). , Polycarbonate (PC), polyamide (PA: nylon), engineering plastics such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), and polyphenylene sulfide (PPS), polyethersulfone (PES), polyketone (PK), polyimide (PI), thermoplastic resins such as polycyclohexanedimethanol terephthalate (PCT), polyarylate (PAR), and various liquid crystal polymers (LCP), epoxy resins, phenol resins, novolac resins And the like of the thermosetting resin, but is not limited thereto.
Further, when such other types of resin components are contained, the block copolymer of the present invention is preferably contained in an amount of 50% by mass or more and less than 100% by mass of the entire polymer electrolyte composition of the present invention. . More preferably, it is 70 mass% or more and less than 100 mass%. When the content of the block copolymer of the present invention is 50% by mass or more of the entire polymer electrolyte composition of the present invention, proton acid groups in the block copolymer of the polymer electrolyte composition containing the block copolymer It is preferable because good proton conductivity can be obtained without lowering the concentration, and the mobility of protons conducted by the block copolymer contained in the polymer electrolyte composition of the present invention as a discontinuous phase is high. It is preferable because it does not decrease.

In addition, the polymer electrolyte composition of the present invention includes, for example, an antioxidant, a heat stabilizer, a lubricant, a tackifier, a plasticizer, a crosslinking agent, a viscosity modifier, an antistatic agent, an antibacterial agent, Various additives such as an antifoaming agent, a dispersing agent, and a polymerization inhibitor may be included.
The polymer electrolyte composition of the present invention can be prepared by mixing the block copolymer and any other resin component and various additives. At this time, the block copolymer can be used alone or in combination of two or more.

The polymer electrolyte composition containing the block copolymer of the present invention can be formed into a molded body such as a fiber or a film by any method such as extrusion, spinning, rolling, or casting. Among them, a solution dissolved in an appropriate solvent It is preferable to form from.
Suitable solvents include aprotic polar solvents such as N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone and hexamethylphosphonamide, and alcohols such as methanol and ethanol. You can choose, but is not limited to these. A plurality of these solvents may be used as a mixture within a possible range.
The total concentration of the block copolymer of the present invention, other resin components and various additives contained in the solvent solution is preferably in the range of 0.1% by mass to 50% by mass. If the said density | concentration is 0.1 mass% or more, a moldability will not deteriorate, and if it is 50 mass% or less, since workability will not deteriorate, it is preferable.

  A method for obtaining a molded product by removing the solvent from the solvent solution can be performed using a conventionally known method. Examples of the method for removing the solvent include a method of heating, a method of drying under reduced pressure, and a method of immersing in a solvent that is miscible with the solvent used in the solvent solution but not dissolved in the polymer electrolyte composition. When the solvent used in the solvent solution is an organic solvent, the solvent is preferably distilled off by heating or drying under reduced pressure. At this time, it can be formed into various shapes such as a fiber shape, a film shape, a pellet shape, a plate shape, a rod shape, a pipe shape, a ball shape, and a block shape in a form combined with other compounds as necessary. . As other compounds, it is preferable to use a compound having a solvent solubility behavior similar to the solvent solubility behavior of the polymer electrolyte composition of the present invention in that good molding can be performed.

A polymer electrolyte membrane can also be produced from the polymer electrolyte composition of the present invention. The most preferable method for forming the polymer electrolyte membrane is a cast from a solution containing the polymer electrolyte composition, and the polymer electrolyte membrane can be obtained by removing the solvent from the cast solution as described above. .
The removal of the solvent is preferably by drying in view of the uniformity of the polymer electrolyte membrane. Specifically, it is preferable to perform drying at 25 to 300 ° C, preferably 30 to 250 ° C under normal pressure. Moreover, in order to avoid decomposition and alteration of the polymer electrolyte composition and the added solvent, it can be dried at the lowest possible temperature under reduced pressure. Further, when the viscosity of the solvent solution is high, when the substrate or the solution is heated and cast at a high temperature, the viscosity of the solution is lowered and the casting can be easily performed.
The thickness of the solution at the time of casting is not particularly limited, but is preferably 0.1 μm or more and 1000 μm or less, and more preferably 50 μm or more and 750 μm or less.
If the thickness of the solution is 0.1 μm or more, the form as a polymer electrolyte membrane can be sufficiently maintained, and if it is 750 μm or less, a uniform polymer electrolyte membrane can be formed.
A conventionally known method can be used as a method for controlling the thickness of the solution. For example, the thickness can be controlled to a constant thickness using an applicator, a doctor blade, or the like, or the thickness can be controlled by the amount and concentration of the solution with a cast area constant using a glass petri dish or the like. The cast solution can obtain a more uniform polymer electrolyte membrane by adjusting the solvent removal rate. For example, in the case of heating, the evaporation rate can be reduced by lowering the temperature in the first stage. When immersed in water or the like, the coagulation rate of the compound can be adjusted by leaving the solution in air or an inert gas for an appropriate time.
The polymer electrolyte membrane of the present invention can have any film thickness depending on the purpose, but is preferably as thin as possible from the viewpoint of proton conductivity. Specifically, it is preferably 5 to 200 μm or less, more preferably 5 to 75 μm or less, and most preferably 5 to 50 μm or less.
If the thickness of the polymer electrolyte membrane is 5 μm or more, it is preferable because handling of the polymer electrolyte membrane does not become difficult, and a short circuit or the like does not occur when a fuel cell is produced. If the thickness of the polymer electrolyte membrane is 200 μm or less, it is preferable because the electric resistance value of the polymer electrolyte membrane becomes too high and the power generation performance of the fuel cell does not deteriorate.
The proton conductivity of the polymer electrolyte membrane is 0.009 S / cm or more, preferably 0.03 to 1.0 S / cm, and more preferably 0.05 to 1.0 S / cm. is there. When the proton conductivity is 0.01 S / cm or more, a good output tends to be obtained in a fuel cell using the polymer electrolyte membrane.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these. The evaluation method of the polymer electrolyte membrane obtained in this example is shown below.
<Measurement method and evaluation method>
(1) Evaluation of swelling rate The swelling rate was determined by immersing a polymer electrolyte membrane having a thickness described in Table 2 cut into 3 cm × 3 cm in water at 80 ° C. for 1 hour, Obtained from the formula. The area after immersion was obtained by wiping the surface of the electrolyte membrane lightly with filter paper (5A), measuring the lengths of the vertical and horizontal sides, and calculating the product.
Formula: {[long side of the film after immersion (cm)] × [short side of the film after immersion (cm)] × 100} / 9
(2) Evaluation of methanol permeability In order to evaluate the amount of methanol permeation, a self-made evaluation cell shown in FIG. 1 was used. The polymer electrolyte membrane of the present invention was placed between the A cell and the B cell. In order to prevent deformation of the polymer electrolyte membrane, steel filters (mesh 1000) were disposed on both sides of the membrane at the cell opening. The solution inside the cell was stirred with a magnetic stirrer to suppress the concentration distribution in the vicinity of the electrolyte and in the vicinity of the sample outlet as much as possible.
180 g of purified water was added to the A cell, and 200 g of purified water was added to the B cell, and the evaluation cell was placed in a thermostatic bath (60 ° C.) and left for 30 minutes. 20 g of methanol was added to the A cell and stirred at 400 rpm. The methanol concentration in the B cell was quantified by gas chromatography every 30 minutes, and the methanol permeation amount against time was plotted. Methanol permeability was evaluated from the slope of this plot (methanol permeation flux).

(3) Measurement of proton conductivity An evaluation cell shown in FIG. 2 was prepared for measurement of proton conductivity. A platinum electrode was used as the electrode, and the electrode interval was 1 cm. It was put in a constant temperature and humidity chamber, the relative humidity was changed between 30% and 85% at 85 ° C., and the resistance of the electrolyte membrane was measured by the AC impedance method. The evaluation method is that the cell is connected to Solartron 1260FREQUENCY RESPONSE ANALYSER with four terminals and the real and imaginary parts of the total impedance detected when the AC frequency is arbitrarily changed from 1.0 Hz to 0.1 Hz are complex. Curve fitting was performed for several points in the Cole-Cole plot plotted on the surface, and the resistance of the electrolyte membrane was obtained from the value of the intercept.
This was substituted into Equation 1 to calculate proton conductivity.
σ = L / (R × S) (Formula 1)
σ: proton conductivity (S / cm), L: distance between electrodes (cm), R: resistance (Ω),
S: membrane cross-sectional area (cm ² )

(4) Measurement of ion exchange equivalent mass The polymer electrolyte membrane of the present invention was reacted with a 10% aqueous sulfuric acid solution to obtain a sulfonic acid type polymer electrolyte membrane having a sulfonic acid group in the first aromatic polymer compound. The sulfonic acid type polymer electrolyte membrane was dried under reduced pressure at 100 ° C. for 24 hours, then transferred to a glove box in an argon atmosphere and allowed to stand for 30 minutes, and the mass was measured. This was added to 1.0 mol / l saline and titrated with a 0.05 mol / l ethanol solution of potassium hydroxide. The point when the pH reached 7 was taken as the equivalent point, and the ion exchange equivalent mass (EW value) was calculated from the amount of potassium hydroxide added at that time.
Formula for calculating ion exchange equivalent mass (EW value):
Ion exchange equivalent mass (EW value) [meq / g] = 0.05 [mmol / ml] × potassium hydroxide titration [ml] / mass of polymer film [g]
(5) TEM observation The polymer electrolyte membrane of the present invention is immersed in a CsCl aqueous solution (1 mol / l) at room temperature for 1 hour to stain protonic acid groups, washed with distilled water, and then sliced with a microtome for observation. Samples were prepared. This was observed with a transmission electron microscope (TEM), and the phase structure of the polymer electrolyte membrane of the present invention was confirmed.

Example 1
<Synthesis of the first aromatic polymer compound (hydrophilic segment)>
A 1000 ml four-necked separable flask equipped with a Dean-Stark trap, condenser, stirrer and nitrogen supply tube was charged with 4,4'-dichloro-3,3'-sodium diphenylsulfone monohydrate (SDCDPS, molecular weight). 509.25, 15.00 g, 0.0295 mol, 1.00 eq), 4,4'-dihydroxybiphenyl (Biphenol, molecular weight 186.21, 6. 58 g, 0.0353 mol, 1.12 equiv), potassium carbonate (K ₂ CO _3, molecular weight 138.21, 5.62 g, 0.0406 mol, 1.38 equivalents), 70 ml of N-methylpyrrolidone and 50 ml of toluene were added, heated and stirred at 160 ° C for 1 hour and 180 ° C for 1 hour to distill off the toluene, then heated to 200 ° C and heated for 24 hours did. After cooling the reaction solution to room temperature, difluorodiphenyl sulfone (DFDPS, molecular weight 254.25, 3.00 g, 0.0118 mol, 0.40 equivalent) was added, and the mixture was heated and stirred at 180 ° C. for 4 hours to react with the first aromatic polymer compound reaction solution. Got. The obtained first aromatic polymer compound had a number average molecular weight of 14400 and a weight average molecular weight of 23600. The ion exchange equivalent mass value (EW value) was 365. The structure of the obtained first aromatic polymer compound is as follows.

<Synthesis of second aromatic polymer compound (hydrophobic segment)>
To a 500 ml eggplant flask equipped with a Dean-Stark trap, condenser, magnetic stirrer and nitrogen supply tube, 4,4′-dichlorodiphenylsulfone (DCDPS, molecular weight 287.16, 8.46 g, 0.0295 mol, 1.00 eq), 4,4′- dihydroxybiphenyl (Biphenol, molecular weight 186.21, 6.58 g, 0.0353 mol, 1.20 equiv), potassium carbonate placed (K ₂ CO _3, molecular weight 138.21,5.62G, 0.0406 mol, 1.38 eq), N- methylpyrrolidone 70 ml, toluene 50 ml, After heating and stirring at 160 ° C for 1 hour and 180 ° C for 1 hour to distill off toluene, the temperature was raised to 200 ° C and stirred for 12 hours to obtain a reaction liquid of the second aromatic polymer compound. . The obtained second aromatic polymer compound had a number average molecular weight of 5,200 and a weight average molecular weight of 8,600. The structure of the obtained second aromatic polymer compound is as follows.

<Synthesis of block copolymer>
A reaction vessel for the first aromatic polymer compound obtained as described above and a reaction vessel for the second aromatic polymer compound obtained as described above are connected by a silicon tube, and the reaction is performed under a nitrogen atmosphere. All the reaction liquid of the second aromatic polymer compound was poured into the reaction vessel of the first aromatic polymer compound at room temperature. At this time, the reaction vessel of the second aromatic polymer compound was washed with 150 ml of anhydrous N-methylpyrrolidone in a nitrogen atmosphere, and all the cleaning liquid was poured into the reaction vessel of the first aromatic polymer compound. The reaction mixture was heated and stirred at 180 ° C. for 12 hours to obtain a block copolymer.

<Purification of block copolymer>
The reaction solution containing the block copolymer obtained as described above was cooled to room temperature, and then the reaction solution was poured into 2000 ml of water to precipitate the block copolymer. After the block copolymer was filtered, it was transferred to a 3000 ml beaker, 1500 ml of distilled water was added, and the mixture was heated from room temperature to 70 ° C. After the block copolymer was filtered off from the resulting solution, the block copolymer was transferred to a 3000 ml beaker, 1500 ml of a 10% sulfuric acid aqueous solution was added, and the mixture was heated from room temperature to 70 ° C. After the block copolymer was filtered off from the resulting solution, the block copolymer was thoroughly washed with purified water, transferred to a 3000 ml beaker, 1500 ml of distilled water was added, and the mixture was heated from room temperature to 70 ° C. After filtering the block copolymer from the obtained solution, it was washed thoroughly with purified water, transferred to a 3000 ml beaker, 1500 ml of distilled water and 500 ml of 5% aqueous sodium carbonate solution were added, and the mixture was heated from room temperature to 70 ° C. . The block copolymer was filtered from the resulting solution, washed thoroughly with purified water, and dried in a hot air dryer at 140 ° C. for 6 hours to obtain the target block copolymer.
The structural formula, yield, yield, mass average molecular weight, dispersity, and ion exchange equivalent mass (EW value) of the obtained block copolymer are as shown below.
Structural formula:

Yield: 31.5 g, Yield: 90%, Number average molecular weight 42900, Mass average molecular weight 170000, Ion exchange equivalent mass value (EW value) 626
<Preparation of block copolymer film>
In order to evaluate the block copolymer, a polymer electrolyte membrane made of the obtained block copolymer was prepared.
After 15 g of the obtained block copolymer was dissolved in 85 g of N-methylpyrrolidone, it was filtered under pressure using a 1000 mesh filter, and further defoamed with a planetary stirring type deaerator. This solution was cast on a glass plate using a bar coater having a gap of 400 μm, and then dried with a hot air dryer at 60 ° C. for 15 minutes, 80 ° C. for 15 minutes, and 100 ° C. for 15 minutes. After removing the dried polymer electrolyte membrane from the dryer, peel the polymer electrolyte membrane from the glass plate, fix it to a stainless steel frame, and throw it into the dryer again, 160 ° C for 30 minutes, 200 ° C 30 Dried for minutes. After cooling to room temperature, the polymer electrolyte membrane was removed from the frame and impregnated with 10% sulfuric acid aqueous solution for 12 hours at room temperature. After the obtained polymer electrolyte membrane was washed with distilled water, the water adhering to the polymer electrolyte membrane was wiped off with a filter paper (5A) to produce a polymer electrolyte membrane consisting only of the block copolymer of the present invention.

(Example 2)
<Synthesis of the first aromatic polymer compound (hydrophilic segment)>
Sodium 4,4′-dichloro-3,3′-disulfonate diphenylsulfone monohydrate (SDCDPS, molecular weight 509.25, 15.00 g, 0.0393 mol, 1.00 equivalent), 4,4′-dihydroxybiphenyl (Biphenol, molecular weight 186.21, 6.03 g, 0.0324 mol, 1.10 eq), potassium carbonate (K ₂ CO ₃ , molecular weight 138.21, 5.15 g, 0.0373 mol, 1.27 eq), N-methylpyrrolidone 70 ml, toluene 50 ml, difluorodiphenyl sulfone (DFDPS, molecular weight 254.25, 1.50) g, 0.0059 mol, 0.20 equivalent) was used in the same manner as in Example 1. The obtained first aromatic polymer compound had a number average molecular weight of 22900 and a weight average molecular weight of 41200. The ion exchange equivalent mass value (EW value) was 334. The structure of the obtained first aromatic polymer compound is as follows.

<Synthesis of second aromatic polymer compound (hydrophobic segment)>
4,4'-dichlorodiphenylsulfone (DCDPS, molecular weight 287.16, 8.46g, 0.0295mol, 1.00eq), 4,4'-dihydroxybiphenyl (Biphenol, molecular weight 186.21, 6.03g, 0.0324mol, 1.10eq), potassium carbonate ( K ₂ CO _3, molecular weight 138.21,5.15G, .0373 mol, 1.27 eq), N- methylpyrrolidone 70 ml, were carried out in the same manner as in example 1 except for using toluene 50 ml. The obtained second aromatic polymer compound had a number average molecular weight of 9,300 and a weight average molecular weight of 19,000. The structure of the obtained second aromatic polymer compound is as follows.

<Synthesis of block copolymer, purification of block copolymer, and production of block copolymer film>
A block copolymer was synthesized from the first aromatic polymer compound and the second aromatic polymer compound obtained as described above, the obtained block copolymer was purified, and the purified block copolymer was purified. A polymer electrolyte membrane consisting only of a polymer was obtained. A series of methods up to obtaining the polymer electrolyte membrane were all carried out in the same manner as in Example 1. The structural formula, yield, yield, mass average molecular weight, dispersity, and ion exchange equivalent mass (EW value) of the obtained block copolymer are as shown below.
Structural formula:

Yield: 25.5 g, Yield: 78%, Number average molecular weight 27600, Mass average molecular weight 112000, Ion exchange equivalent mass value (EW value) 666

(Example 3)
<Synthesis of the first aromatic polymer compound (hydrophilic segment)>
Sodium 4,4′-dichloro-3,3′-disulfonate diphenylsulfone monohydrate (SDCDPS, molecular weight 509.25, 15.00 g, 0.0295 mol, 1.00 equivalent), 4,4′-dihydroxybiphenyl (Biphenol, molecular weight 186.21, 6.86 g, 0.0368 mol, 1.25 equivalent), potassium carbonate (K ₂ CO ₃ , molecular weight 138.21, 5.85 g, 0.0423 mol, 1.44 equivalent), N-methylpyrrolidone 70 ml, toluene 50 ml, difluorodiphenyl sulfone (DFDPS, molecular weight 254.25, 3.74) g, 0.0147 mol, 0.50 equivalent) was used in the same manner as in Example 1. The obtained first aromatic polymer compound had a number average molecular weight of 12,700 and a weight average molecular weight of 22,700. The ion exchange equivalent mass value (EW value) was 380. The structure of the obtained first aromatic polymer compound is as follows.

<Synthesis of second aromatic polymer compound (hydrophobic segment)>
4,4'-dichlorodiphenylsulfone (DCDPS, molecular weight 287.16, 10.15g, 0.0353mol, 1.20eq), 4,4'-dihydroxybiphenyl (Biphenol, molecular weight 186.21, 7.95g, 0.0427mol, 1.45eq), potassium carbonate ( K ₂ CO ₃ , molecular weight 138.21, 6.79 g, 0.0491 mol, 1.67 equivalent), 70 ml of N-methylpyrrolidone and 50 ml of toluene were all used in the same manner as in Example 1. The obtained second aromatic polymer compound had a number average molecular weight of 5,000 and a weight average molecular weight of 8,000. The structure of the obtained second aromatic polymer compound is as follows.

<Synthesis of block copolymer, purification of block copolymer, and production of block copolymer film>
A block copolymer was synthesized from the first aromatic polymer compound and the second aromatic polymer compound obtained as described above, the obtained block copolymer was purified, and the purified block copolymer was purified. A polymer electrolyte membrane consisting only of a polymer was obtained. A series of methods up to obtaining the polymer electrolyte membrane were all carried out in the same manner as in Example 1. The structural formula, yield, yield, mass average molecular weight, dispersity, and ion exchange equivalent mass (EW value) of the obtained block copolymer are as shown below.
Structural formula:

Yield: 35.6 g, Yield: 93%, Number average molecular weight 52300, Mass average molecular weight 158000, Ion exchange equivalent mass value (EW value) 672

Example 4
<Synthesis of the first aromatic polymer compound (hydrophilic segment)>
Sodium 4,4′-dichloro-3,3′-disulfonate diphenylsulfone monohydrate (SDCDPS, molecular weight 509.25, 15.00 g, 0.0295 mol, 1.00 equivalent), 4,4′-dihydroxybiphenyl (Biphenol, molecular weight 186.21, 6.86 g, 0.0386 mol, 1.25 equivalents), potassium carbonate (K ₂ CO ₃ , molecular weight 138.21, 5.85 g, 0.0373 mol, 1.44 equivalents), N-methylpyrrolidone 70 ml, toluene 50 ml, difluorodiphenyl sulfone (DFDPS, molecular weight 254.25, 3.74) g, 0.0147 mol, 0.50 equivalent) was used in the same manner as in Example 1. The obtained first aromatic polymer compound had a number average molecular weight of 8600 and a weight average molecular weight of 16,100. The ion exchange equivalent mass value (EW value) was 380. The structure of the obtained first aromatic polymer compound is as follows.

<Synthesis of second aromatic polymer compound (hydrophobic segment)>
4,4'-dichlorodiphenylsulfone (DCDPS, molecular weight 287.16, 12.69g, 0.0442mol, 1.50eq), 4,4'-dihydroxybiphenyl (Biphenol, molecular weight 186.21, 9.60g, 0.0515mol, 1.75eq), potassium carbonate ( K ₂ CO ₃ , molecular weight 138.21, 8.19 g, 0.0593 mol, 2.01 equivalent), N-methylpyrrolidone 70 ml, toluene 50 ml were all used in the same manner as in Example 1. The obtained second aromatic polymer compound had a number average molecular weight of 10,500 and a weight average molecular weight of 23,400. The structure of the obtained second aromatic polymer compound is as follows.

<Synthesis of block copolymer, purification of block copolymer, and production of block copolymer film>
A block copolymer was synthesized from the first aromatic polymer compound and the second aromatic polymer compound obtained as described above, the obtained block copolymer was purified, and the purified block copolymer was purified. A polymer electrolyte membrane consisting only of a polymer was obtained. A series of methods up to obtaining the polymer electrolyte membrane were all carried out in the same manner as in Example 1. The structural formula, yield, yield, mass average molecular weight, dispersity, and ion exchange equivalent mass (EW value) of the obtained block copolymer are as shown below.
Structural formula:

Yield: 37.7 g, Yield: 90%, Number average molecular weight 37800, Mass average molecular weight 93700, Ion exchange equivalent mass value (EW value) 762

(Example 5)
<Synthesis of the first aromatic polymer compound (hydrophilic segment)>
Sodium 4,4′-dichloro-3,3′-disulfonate diphenylsulfone monohydrate (SDCDPS, molecular weight 509.25, 15.00 g, 0.0295 mol, 1.00 equivalent), 4,4′-dihydroxybiphenyl (Biphenol, molecular weight 186.21, 6.86 g, 0.0386 mol, 1.25 equivalents), potassium carbonate (K ₂ CO ₃ , molecular weight 138.21, 5.85 g, 0.0373 mol, 1.44 equivalents), N-methylpyrrolidone 70 ml, toluene 50 ml, difluorodiphenyl sulfone (DFDPS, molecular weight 254.25, 3.74) g, 0.0147 mol, 0.50 equivalent) was used in the same manner as in Example 1. The obtained first aromatic polymer compound had a number average molecular weight of 14400 and a weight average molecular weight of 26,200. The ion exchange equivalent mass value (EW value) was 380. The structure of the obtained first aromatic polymer compound is as follows.

<Synthesis of second aromatic polymer compound (hydrophobic segment)>
4,4'-dichlorodiphenylsulfone (DCDPS, molecular weight 287.16, 15.48 g, 0.0539 mol, 1.83 eq), 4,4'-dihydroxybiphenyl (Biphenol, molecular weight 186.21, 11.41 g, 0.0613 mol, 2.08 eq), potassium carbonate ( K ₂ CO ₃ , molecular weights 138.21, 9.74 g, 0.0705 mol, 2.39 equivalents), N-methylpyrrolidone 70 ml and toluene 50 ml were all used in the same manner as in Example 1. The obtained second aromatic polymer compound had a number average molecular weight of 6,200 and a weight average molecular weight of 10,900. The structure of the obtained second aromatic polymer compound is as follows.

<Synthesis of block copolymer, purification of block copolymer, and production of block copolymer film>
All were carried out in the same manner as in Example 1. The structural formula, yield, yield, mass average molecular weight, dispersity, and ion exchange equivalent mass (EW value) of the obtained block copolymer are as shown below.
Structural formula:

Yield: 41.7 g, Yield: 91%, Number average molecular weight 27000, Mass average molecular weight 77400, Ion exchange equivalent mass value (EW value) 773

(Comparative Example 1)
<Synthesis of random copolymer>
A 500 ml four-necked separable flask equipped with a Dean-Stark trap, condenser, stirrer and nitrogen supply tube was charged with sodium 4,4′-dichloro-3,3′-disulfonate diphenylsulfone monohydrate (SDCDPS, molecular weight). 509.25, 67.90 g, 0.1333 mol, 1.00 equivalent), 4,4'-dichlorodiphenyl sulfone (DCDPS, molecular weight 287.16, 47.86 g, 0.1667 mol, 1.25 equivalent), 4,4'-dihydroxybiphenyl (Biphenol, molecular weight 186.21, 40.97) g, 0.3333 mol, 2.50 equivalents), potassium carbonate (K ₂ CO ₃ , molecular weight 138.21, 55.27 g, 0.400 mol, 3.00 equivalents), N-methylpyrrolidone 380 ml, toluene 300 ml, 160 ° C. for 1 hour, 180 ° C. After heating and stirring for 1 hour to distill off toluene, the mixture was heated at 200 ° C. for 38 hours. After the reaction solution was cooled to room temperature, decafluorobiphenyl (DFBP, molecular weight 334.11, 11.14 g, 0.0333 mol, 0.25 equivalent) was added, and the mixture was heated and stirred at 140 ° C. for 7 hours to obtain a random copolymer reaction solution.

<Purification of random copolymer>
After cooling to room temperature, the reaction solution was poured into 2000 ml of water to precipitate a block copolymer. After the block copolymer was filtered, it was transferred to a 3000 ml beaker, 1500 ml of distilled water was added, and the mixture was heated from room temperature to 70 ° C. The block copolymer was filtered, transferred to a 3000 ml beaker, 1500 ml of 10% sulfuric acid aqueous solution was added, and the mixture was heated from room temperature to 70 ° C. The block copolymer was filtered, washed thoroughly with purified water, transferred to a 3000 ml beaker, 1500 ml of distilled water was added, and the mixture was heated from room temperature to 70 ° C. The block copolymer was filtered, washed thoroughly with purified water, transferred to a 3000 ml beaker, 1500 ml of distilled water and 500 ml of 5% aqueous sodium carbonate solution were added, and the mixture was heated from room temperature to 70 ° C. The block copolymer was filtered, washed thoroughly with purified water, and dried in a hot air dryer at 140 ° C. for 6 hours to obtain the target block copolymer.

<Preparation of random copolymer film>
Membranes were made to evaluate block copolymers.
After 15 g of the obtained block copolymer was dissolved in 85 g of N-methylpyrrolidone, it was filtered under pressure using a 1000 mesh filter, and further defoamed with a planetary stirring type deaerator. This solution was cast on a glass plate using a bar coater having a gap of 400 μm, and then dried with a hot air dryer at 60 ° C. for 15 minutes, 80 ° C. for 15 minutes, and 100 ° C. for 15 minutes. After taking out from the dryer, the membrane was peeled off from the glass plate, fixed to a stainless steel frame, poured again into the dryer, and dried at 160 ° C. for 30 minutes and 200 ° C. for 30 minutes. After cooling to room temperature, the membrane was removed from the frame and impregnated with 10% aqueous sulfuric acid for 12 hours at room temperature. After washing with distilled water, the water adhering to the membrane was wiped off with filter paper (5A) to produce a block copolymer membrane.
The structural formula, yield, yield, mass average molecular weight, dispersity, and ion exchange equivalent mass (EW value) of the obtained random copolymer are as shown below.
Structural formula:

Yield: 170 g, Yield: 97%, Number average molecular weight 424000, Dispersion 6.4, Ion exchange equivalent mass value (EW value) 605

(Comparative Example 2)
Blocking when no hydrophobic aromatic halogen group is present at the end of the first aromatic polymer compound <Synthesis of the first aromatic polymer compound (hydrophilic segment)>
A 1000 ml four-necked separable flask equipped with a Dean-Stark trap, condenser, stirrer and nitrogen supply tube was charged with 4,4'-dichloro-3,3'-sodium diphenylsulfone monohydrate (SDCDPS, molecular weight). 509.25, 40.00 g, 0.0785 mol, 1.00 eq), 4,4'-dihydroxybiphenyl (Biphenol, molecular weight 186.21, 16.82 g, 0.0903 mol, 1.15 equiv), potassium carbonate (K ₂ CO _3, molecular weight 138.21, 138.21,14.36G , 0.1039 mol, 1.32 equivalents), 150 ml of N-methylpyrrolidone and 100 ml of toluene were added, and the mixture was heated and stirred at 160 ° C. for 1 hour and 180 ° C. for 1 hour to distill off the toluene. The reaction liquid of the 1st aromatic polymer compound was obtained by heating. The obtained first aromatic polymer compound had a number average molecular weight of 18,000 and a weight average molecular weight of 35,000. The structure of the obtained first aromatic polymer compound is as follows.

<Synthesis of second aromatic polymer compound (hydrophobic segment)>
In a 500 ml eggplant flask equipped with a Dean-Stark trap, condenser, magnetic stirrer and nitrogen supply tube, 4,4'-dichlorodiphenylsulfone (DCDPS, molecular weight 287.16,, 22.56 g, 0.0785 mol, 1.00 equivalent), 4,4 ' - dihydroxybiphenyl (Biphenol, molecular weight 186.21, 16.82 g, 0.0903 mol, 1.15 eq) was placed potassium carbonate (K ₂ CO _3, molecular weight 138.21,14.36G, 0.1039 mol, 1.32 eq), N- methylpyrrolidone 150 ml, of toluene 100ml After heating and stirring at 160 ° C for 1 hour and 180 ° C for 1 hour to distill off toluene, the temperature was raised to 200 ° C and heated and stirred for 12 hours to obtain a reaction solution of the second aromatic polymer compound It was. The obtained second aromatic polymer compound had a number average molecular weight of 7000 and a weight average molecular weight of 13,000. The structure of the obtained second aromatic polymer compound is as follows.

<Synthesis of block copolymer>
The reaction vessel for the first aromatic polymer compound and the reaction vessel for the second aromatic polymer compound are connected by a silicon tube, and the reaction solution for the second aromatic polymer compound is completely removed at room temperature under a nitrogen atmosphere. One aromatic polymer compound was poured into a reaction vessel. At this time, the reaction vessel of the second aromatic polymer compound was washed with 200 ml of anhydrous N-methylpyrrolidone under a nitrogen atmosphere, and all of the cleaning liquid was poured into the reaction vessel of the first aromatic polymer compound. The reaction mixture was stirred with heating at 200 ° C. for 16 hours.
<Purification of block copolymer and production of block copolymer film>
All were carried out in the same manner as in Example 1. The structural formula, yield, yield, mass average molecular weight, dispersity, and ion exchange equivalent mass (EW value) of the obtained block copolymer are as shown below.
Unreacted hydrophilic segments were eluted in the polymer purification. A good block copolymer having a low yield and molecular weight could not be obtained.
Structural formula:

Yield: 57 g, Yield: 65%, Number average molecular weight 27000, Mass average molecular weight 72000, Ion exchange equivalent mass value (EW value) 872

Tables 1 and 2 collectively show physical property values of Examples 1 to 5 and Comparative Examples 1 and 2. Table 1 is a table showing the charged molar ratios and molecular weights of the hydrophilic segment and the hydrophobic segment of Examples 1 to 5 and Comparative Example 1. Table 2 is a table showing the EW values, proton conductivity, and methanol permeability of Examples 1 to 5 and Comparative Example 1.
3 to 7 show TEM images of the block copolymer films prepared in Examples 1 and 3 and Comparative Example 1. It can be seen that the polymer electrolyte membranes of Examples 1 and 3 exhibit a phase separation structure due to the blocking effect. 3 to 7 are dark field images, and the white portion indicates the protonic acid group portion.

It is a figure which shows the cell for methanol permeability coefficient evaluation. It is a figure which shows the structure of the cell for proton conductivity measurement. 2 is a diagram showing a phase separation structure of an electrolyte membrane of Example 1. FIG. 6 is a diagram showing a phase separation structure of an electrolyte membrane of Example 3. FIG. 6 is a diagram showing a phase separation structure of an electrolyte membrane of Comparative Example 1. FIG.

Claims (11)

(A) a step of preparing a first aromatic polymer compound having a monovalent hydrophobic aromatic halogen group at a terminal and having a protonic acid group; and the monovalent hydrophobic aromatic halogen, wherein The group is not a perfluorobiphenyl group,
(B) a second aromatic polymer compound having a reactive group capable of reacting with a monovalent hydrophobic aromatic halogen group of the first aromatic polymer compound at the terminal and having no proton acid group A step of preparing
(C) A method for producing a block copolymer, comprising the step of preparing the block copolymer by bonding the first aromatic polymer compound and the second aromatic polymer compound. . The method according to claim 1, wherein the reactive group of the second aromatic polymer compound is a phenolic hydroxyl group. The method according to claim 1, wherein the first aromatic polymer compound has a mass average molecular weight of 2,000 to 150,000 and the second aromatic polymer compound has a mass average molecular weight of 2,000 to 150,000. In the step (c) of preparing the block copolymer, the mass ratio of the first aromatic polymer compound and the second aromatic polymer compound [first aromatic polymer compound] / [second Block copolymerization is performed by mixing the first aromatic polymer compound and the second aromatic polymer compound so that the value of the aromatic polymer compound is 0.1 or more and 10.0 or less. The method according to claim 1, wherein the step is a step of preparing a block copolymer. The first aromatic polymer compound is divalent having at least one protonic acid group selected from the group consisting of the following formulas (1), (3), (4) and (5): The method of claim 1 comprising the group:


[In the formula (1), A represents a direct bond, —O—, —S—, —S (O) —, —S (O) ₂ —, —C (O) —, —P (O) (C _{6 H 5) -, - C} (CH 3) 2 -, - CH 2 -, - C (C 6 H 5) 2 -, or,


[In Formula (2), X is a protonic acid group which may be the same or different, and is a sulfonic acid group, a phosphoric acid group, an alkylsulfonic acid group having 1 to 6 carbon atoms, or 1 carbon atom. Represents an oxyalkyl sulfonic acid group of -20, an alkyl phosphoric acid group of 1 to 6 carbon atoms, or an oxyalkyl phosphoric acid group of 1 to 20 carbon atoms, m represents the number of substituents of 1 to 4, and n represents 1 to 1 The number of substituents of 4 is shown. ]
Indicate
R may be the same or different and each represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. An aryloxy group or an acyl group having 2 to 20 carbon atoms;
X is a protonic acid group which may be the same or different, and is a sulfonic acid group, a phosphoric acid group, an alkylsulfonic acid group having 1 to 6 carbon atoms, or an oxyalkylsulfonic acid having 1 to 20 carbon atoms. A group, an alkyl phosphate group having 1 to 6 carbon atoms, or an oxyalkyl phosphate group having 1 to 20 carbon atoms,
m represents the number of substituents 1 to 4,
f represents the number of substituents 1 to (4-m);
n represents the number of substituents 1 to 4,
j represents the number of substituents of 1 to (4-n). ]


[In the formula (3), Rs may be the same or different and are each hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. , An aryloxy group having 6 to 20 carbon atoms, or an acyl group having 2 to 20 carbon atoms,
X is a protonic acid group which may be the same or different, and is a sulfonic acid group, a phosphoric acid group, an alkylsulfonic acid group having 1 to 6 carbon atoms, or an oxyalkylsulfonic acid having 1 to 20 carbon atoms. A group, an alkyl phosphate group having 1 to 6 carbon atoms, or an oxyalkyl phosphate group having 1 to 20 carbon atoms,
m represents the number of substituents 1 to 4,
f represents the number of substituents 1 to (4-m);
n represents the number of substituents 1 to 4,
j represents the number of substituents of 1 to (4-n). ]


[In the formula (4), A represents a direct bond, -O-, -S-, -S (O)-, -S (O) _2- , -C (O)-, -P (O) (C _{6 H 5) -, - C} (CH 3) 2 -, - CH 2 -, - C (C 6 H 5) 2 -, or shows an alkylidene group having 1 to 10 carbon atoms,
R may be the same or different and each represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 6 to 20 carbon atoms. An aryloxy group or an acyl group having 2 to 20 carbon atoms;
X is a protonic acid group which may be the same or different, and is a sulfonic acid group, a phosphoric acid group, an alkylsulfonic acid group having 1 to 6 carbon atoms, or an oxyalkylsulfonic acid having 1 to 20 carbon atoms. A group, an alkyl phosphate group having 1 to 6 carbon atoms, or an oxyalkyl phosphate group having 1 to 20 carbon atoms,
m represents the number of substituents of 1 to 5,
f represents the number of substituents 1 to (5-m);
n represents the number of substituents of 1 to 5,
j represents the number of substituents of 1 to (5-n). ]


[In formula (5), Z represents a direct bond, —NH—, a divalent alkylamino group having 1 to 10 carbon atoms, —N (C ₆ H ₅ ) —, —O—, or —S—. ,
R is hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, or an acyl having 2 to 20 carbon atoms. Group,
X is a protonic acid group, which is a sulfonic acid group, a phosphoric acid group, an alkylsulfonic acid group having 1 to 6 carbon atoms, an oxyalkylsulfonic acid group having 1 to 20 carbon atoms, or an alkylphosphoric acid group having 1 to 6 carbon atoms. Group, or an oxyalkyl phosphate group having 1 to 20 carbon atoms,
m represents the number of substituents of 1 to 5,
f represents the number of substituents of 1 to (5-m). ] The second aromatic polymer compound includes at least one aromatic ring or heterocyclic ring selected from the group consisting of the following formulas (6), (8), (9), and (10). Item 2. The method according to Item 1.


[In the formula (6), A represents a direct bond, —O—, —S—, —S (O) —, —S (O) ₂ —, —C (O) —, —P (O) (C _{6 H 5) -, - C} (CH 3) 2 -, - CH 2 -, - C (C 6 H 5) 2 -, or


Indicate
B, C, D and E may be the same as or different from each other, hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, An aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, or a cyano group. ]

[In Formula (8), F and G may be the same as or different from each other, hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and 6 to 20 carbon atoms. An aryl group, an aryloxy group having 6 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, or a cyano group is shown. ]


[In the formula (9), A represents a direct bond, -O-, -S-, -S (O)-, -S (O) _2- , -C (O)-, -P (O) (C ₆ H ₅ ) —, —C (CH ₃ ) ₂ —, —CH ₂ —, —C (C ₆ H ₅ ) ₂ — or an alkylidene group having 1 to 10 carbon atoms,
R may be the same or different and each represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. An aryloxy group or an acyl group having 2 to 20 carbon atoms;
f and j each independently represent 1 to 5 substituents. ]


[In the formula (10), Z represents a direct bond, —NH—, an alkylamino group having 1 to 10 carbon atoms, —N (C ₆ H ₅ ) —, —O—, or —S—;
R is hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, or an acyl having 2 to 20 carbon atoms. Group,
f shows the number of substituents of 1-5. ] The method according to claim 1, wherein the protonic acid group is a sulfonic acid group and / or a phosphoric acid group. The method according to claim 1, wherein the first aromatic polymer compound is the following formula (11).

(11)

[In Formula (11), A's may be the same or different, and may be a direct bond, -O-, -S-, -S (O)-, -S (O) _2- , -C. (O) -, - P ( O) (C 6 H 5) -, - C (CH 3) 2 -, - CH 2 -, or _{-C (C 6 H 5) 2} - indicates,
X represents a halogen group,
n represents an integer of 3 or more. ] The block copolymer prepared by the method of any one of Claims 1-8. A polymer electrolyte composition comprising the block copolymer according to claim 9. A polymer electrolyte membrane comprising the polymer electrolyte composition according to claim 10.