TW201204755A - Sparingly water-soluble anion conductive resin - Google Patents

Abstract

Provided is an anion conductive resin which has high heat resistance and also high anion conductivity, low solubility in water, high adhesion to catalysts and barrier films, which is low cost and is highly soluble in solvents, and which can generate electricity and produce a high output when employed as a resin for joining catalyst and electrode layers in a solid polymer type fuel cell that uses an anion exchange film, and also provided is a method for producing the anion conductive resin. The sparingly water-soluble anion conductive resin is a non-crosslinked block copolymer which has aromatic rings, which has hydrophilic units in which the aromatic ring has an ammonium salt represented by formula (1) (1) -(CH2)n-N+R1R2R3(X)z (where n is an integer of 3-6, R1, R2 and R3 are each C1-5 straight-chain or branched alkyl groups, all or some of R1, R2 and R3 may form a ring by interconnection, X is a counter anion, and z is the reciprocal of the valency of X), and which has hydrophobic units that do not have said ammonium salt, and the method for producing the anion conductive resin is also provided.

Description

[Technical Field] The present invention relates to an anion conductive resin used at the time of forming or joining a catalyst electrode layer constituting a polymer electrolyte fuel cell. [Prior Art] The research and development of a cation exchange membrane type fuel cell using a cation exchange type electrolyte membrane (hereinafter referred to as a cation exchange membrane) as a solid polymer electrolyte membrane has been actively carried out. In recent years, an anion exchange membrane type fuel cell using an anion exchange type electrolyte membrane (hereinafter referred to as an anion exchange membrane) as a solid polymer electrolyte membrane has been proposed (Patent Documents 1 to 6). The anion exchange membrane type fuel cell has advantages not obtained by the following cation exchange membrane type fuel cell. (1) The reaction field is intensive, so it is possible to use a cheap transition metal touch ") a wide variety of catalysts to be used. Therefore, the use of high-battery batteries is possible. The movement of hydroxide ions in the ui electrolyte ( ) 乃 乃 乃 乃 的 的 的 的 氧化剂 氧化剂 氧化剂 逋 逋 逋 逋 逋 逋 逋 逋 逋 逋 逋 逋 逋 逋 逋 逋 逋 逋 逋 逋 逋 逋 逋 逋 逋 逋 逋 逋 逋 逋 逋 逋 逋 逋When the oxidant is passed through, the fuel and the oxidant gas JI 4 > -5Γ j. I are prevented from reacting to reduce the output voltage. Further, an inexpensive hydrocarbon-based material is used as the anion cost is lowered. 'In the anion exchange membrane type fuel cell, in addition to the & ion exchange membrane of 3 201204755, an electrode catalyst that causes a reaction of fuel or oxidant is necessary, and an electron conductor of a potential generated by the catalyst is necessary. Further, a bonding resin for forming an anion-conducting catalyst electrode layer for transporting an anion to the catalyst and for fixing the anion to the anion is necessary: these electrode catalysts, electron conductors, and catalysts The electrode for forming the electrode is formed into a tree, formed to form a catalytic electrode layer, and the catalyst electrode layer is fixed to the anion: the film is changed to form a membrane-electrode assembly. The anion exchange membrane type fuel is further In the anion exchange membrane used in the cell, in order to reduce the internal resistance of the battery, it is desirable to have high ion conduction, and the reaction between the feed and the oxygen (4) directly forms a decrease in the output voltage, requires the impermeability of the material, or the composition or treatment of the fuel cell. In addition, it is required to be low-cost, and the bonding resin for forming a catalyst electrode is used to suppress high internal ion resistance or low cost, and has different characteristics from the anion exchange membrane. Fuel or oxidation_phase combustion permeability or gas material (4) 、, * dissolve (4) 'The anion exchange membrane has a high adhesion, 妁 '5 7 , and the layer requires solvent solubility. The catalyst electrode of the hook-like fuel-like fuel cell has a high operating temperature, and the heat of the large-used material can be obtained. The fuel cell can be used in a high-temperature shovel and a cation exchange membrane type fuel cell. However, the heat resistance of the cell is poor. It is not possible to make the operation of 1 liter (four) sub-family change-type fuel electric wheel and to increase the operating temperature of the battery to the necessary use. It is remarkable in the 2-way drive power supply, etc. As in the vehicle 4 20 The review of 1204755 has heretofore reviewed the improvement of the heat resistance of anion exchange enthalpy of anion exchange membrane type fuel cell. However, according to the examination by the present inventors, it is understood that only the heat resistance of the anion exchange membrane is increased and the fuel cell is used as a fuel cell. Regardless of the increase in heat resistance, it is determined that the heat resistance of the catalyst electrode forming material of the one or more constituent materials is not increased. Thus, the anion conducting (four) catalyst electrode used in the anion exchange membrane type fuel cell is formed. The bonding resin is exemplified by amination of a chlorohydrazine compound of a copolymer of an aromatic poly(tetra) and an aromatic polythioxanthrene (Examples of Patent Document 11 and Examples of Patent Document 12), or has a chlorohydrazine group. The amine of the block copolymer of styrene is a tetramerized polymer (Patent Document 13) and the like. However, there has been no review of the increase in heat resistance of the bonding resin for forming these catalyst electrodes. Here, in the bonding resin for forming these catalyst electrodes, attention is given to the fourth-order secret of the anion exchange group, and in any case, the chloromethyl group is substantially aminated to introduce the anion exchange group to the aromatic ring. The knot is based on the base. It is generally known that because of the high reactivity of the nodal base, it is susceptible to nucleophilic attack, and it is judged that the nucleophilic attack of the hydroxide ion is weak. For example, according to Non-Patent Document 1, the benzylammonium salt is in acetic acid, and under milder conditions of sodium acetate, the ammonium salt falls off to form an acetate. On the other hand, a general crosslinked anion exchange resin used for adsorbent or desalting, water treatment, electrodialysis or the like has been reported, and there is no resin in the form of the above-mentioned benzyl group opening/amination. For example, a resin in which a fluorinated aldehyde is condensed to a crosslinked polyvinyl alcohol to quaternize an amine group (Patent Document 14), a resin obtained by etherifying glycidylation in the same manner to quaternize an amine group (Patent Document 15), A resin in which a 201204755 fluorine-based cation exchange resin is modified to form a quaternary ammonium salt (Patent Documents 16-18), and a resin obtained by halogenating a crosslinked polystyrene to quaternize an amine group (Patent Documents 7-10) And transesterification of an acrylate with an alcohol having a tertiary amine to obtain a polymer having a tertiary amine, a resin which quaternizes the polymer (Patent Documents 19 and 20), and an aromatic polyether ketone haloalkyl group A resin in which the amine group is quaternized (Patent Document 21), a resin having a 4-stage ammonium salt and an alkyl halide, and a polyethylene resin is occluded and further quaternized (Patent Document 22), and aromatic The polyether sulfone is halogenated, the tetrabasic resin is formed by a monoamine or a polyamine (Patent Documents 23 and 24), and the amino alkoxy styrene is polymerized with a crosslinkable monomer to obtain a phenyl ether. An amine-based parent polymer, which forms a quaternized resin with an organic compound (Patent Document 25), with a phase transition Halo hospital so stupid vinyl group formed of four resin (Patent Document 26) and the like. Further, an anion exchange membrane for a fuel cell is also known as an example of quaternizing a crosslinked pitch alkyl styrene resin (Patent Document 1). However, these resins are used as a bonding resin user for forming a catalyst electrode layer because the crosslinked polymer is insoluble in a solvent (Patent Documents 1, 7-10, 14, and 15) because the fluorine-based polymer is used. It is difficult to use because it has low oil repellency and low adhesion to a catalyst or anion exchange membrane and high cost (Patent Documents 16-18). The former has a solubility in a solvent by omitting the crosslinked structure. Since it has a large amount of ion-exchange groups and is dissolved in water, it is still difficult to use as a catalyst electrode-forming material-bonding resin. (4) Acid brewing (Patent Documents 19 and 20) is expected to be in the process of testing, aromatic poly _ (specialized literature 21) or aromatic poly (thio) ether milling system (Patent Documents 23, 2 approximately The ion exchange group is introduced only on the (thio) side, so the amount of anion 2 capacity 2 201204755 is insufficient, and anion conductivity is difficult. Polyethylene _ system (Patent Document 22), protonated (4) has a pKa value of 5, It is smaller than the calorific value of the other amides (the force 10), that is, the protons are easily dissociated, and therefore, the base is easily detached, so it remains in the test for heat. Similarly, the system having benzene (tetra) (Patent Document 25) "The stupid oxygen ion is easily detached, so the heat resistance is unstable during the test. The resin having a transalkylation group to form a tetraalkylated styrene resin (Patent Document 26) has The phase-shifted amine is relatively large in molecular weight, and the polymer of Patent Document 4 is blended with the "cationic" conductive catalyst electrode layer, but the purpose is to capture The metal is dissolved in the anode (as an anion), and the hair In the solid polymer fuel cell using the anion exchange membrane, the heat resistance of the anion conductive resin used as the binder resin of the catalyst electrode layer is increased, and the heat resistance can be increased. It is a big problem to generate electricity at high temperatures and to obtain high output. In addition to this, it is necessary to satisfy high anion conductivity or low water solubility, high adhesion to catalyst or separator, cost, and solvent dissolution. Therefore, the present inventors have made it easy to establish both ion conductivity and poor solubility in water due to dissolution in a solvent and phase separation structure, and are superior to fluorine in terms of quality or cost. Patent Document 13 discloses a block copolymer system of styrene having an aromatic ring at a base bond and a quaternary ammonium group, and it is judged that the chain length of the extended base between the fourth-order and the aromatic ring can be increased. Heat resistance. A method for obtaining a chain length polymer of an alkyl group between a 4-stage ammonium group and an aromatic ring has been proposed to make chloromethyl styrene and ruthenium 201204755 Grignard reagent. The Gerry The reagent is reacted with a recarburizing agent such as dihalogenation to synthesize a styrene monomer having a carbon number of 2 or more, and a method of quaternizing the amine after polymerization (Patent Document 8); The Grignard reagent reaction 'synthesis of a method of quaternizing an amine by polymerizing a stupid ethylene monomer having a halogenated ordinal group of 2 or more (Patent Document 28); after introducing a olefin chain into the chloroquinone-based polystyrene A method of adding a brominated polymer compound to the olefin chain to obtain a brominated polymer compound and reacting the brominated polymer compound with an amine compound to form a quaternary amine (Patent Document 29), etc. However, according to Patent Document 8, 28. Even if a styrene monomer having a carbonization number of 2 or more is synthesized and a block polymer is produced using the same, the monomer is first reacted with a functionalized alkyl group under anionic polymerization conditions, and thus cannot be δ, and The monomer which is first reacted with an amine to form a salt is not soluble in the anionic polymerization solvent', so that the block polymer is not obtained in this case. Further, the methods of extending the alkyl group in Patent Documents 8 and 28 are not easily applied to the block copolymer-based joining resin. That is, 'when a strange amount of the block polymer of the raw material is subjected to conventional gas thiolation or gasification to react with magnesium, a Grignard reagent, a gas methyl group or a different polymer is prepared. The gas methyl group of the chain undergoes a coupling reaction to deactivate or crosslink the Grignard reagent to form an insoluble polymer, and thus the desired resin cannot be obtained. Further, according to Patent Document 29, a chloromethylated block polymer is introduced into a rare hydrocarbon in the block polymer via an aryl magnesium toothing.

In the case of 虱, the end bromide will form an internal bromide, a polymer that is not desirable. I 先前 先前 2012 2012 2012 2012 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 [Patent Document 5] Japanese Laid-Open Patent Publication No. JP-A No. 20 0-9-93975 [Patent Document 5] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. 2000-349941 (Patent Document No. JP-A No. Hei. Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. JP-A-61-098708 (Patent Document No.) JP-A-63-042389 [Patent Document 19] JP-A 02-21-9801 [Patent Literature] [Patent Document No. 2] [Patent Document No. 2003-053965] [Patent Document 23] Japanese Laid-Open Patent Publication No. 2003-038965 [Patent Document 25] Japanese Laid-Open Patent Publication No. Hei. No. 2009- 126 728 [Patent Document 27] JP-A-2009-026690 (Patent Document 28) Japanese Patent Laid-Open No. Hei No. 2009-62452 [Non-Patent Document] [Non-Patent Document 1] Norman Rabjohn, Organic Synthesis

Collective Volume, Volume 4 (USA), John Wiley & Sons

Issued by Inc., 1963, p. 582~584. SUMMARY OF THE INVENTION [Problems to be Solved by the Invention] The present invention solves the problems of the above-mentioned prior art to provide heat resistance, low conductivity to anions or water, and adhesion to a catalyst or a separator. High-efficiency anion conduction that can generate electricity at room temperature, low-cost, high solubility to solvents, and a bonding electrode layer of a catalyst electrode layer in a polymer electrolyte fuel cell using an anion exchange film The resin and its manufacturing method are for the purpose. [Technical means for solving the problem] " The present inventors have conducted active research on the above-mentioned subject. In other words, it has been found that a block polymer having a gas methyl group as a precursor polymer of an anion conductive resin for forming a catalyst electrode in the past is effective in extending the calcination method, and the above problems may be satisfactorily solved. The present invention has been proposed to develop an anion conductive resin composed of a block. 201204755, that is, 'the water-insoluble anion conductive resin having a non-crosslinked block copolymer having an aromatic ring' has a hydrophilic unit having an ammonium salt represented by the following formula (1) in the aromatic ring; a hydrophobic unit having no such ammonium salt, -(CH2)„-N+R'R2R3(X)z (1) (wherein η is an integer of 3 to 6', R1, R2 and R3 are each a carbon number 1~5 linear or branched chain alkyl groups, R2 and R3 may be bonded to each other in whole or in part to form a coating 'X is a relative anion (counter anj_on), and z is the reciprocal of the X valence). The present invention is a method for producing an anion conductive resin composed of the above block copolymer, that is, a compound which protects a radical by a protecting group, Η9Κ〇Η2)η.χ-〇γ (2) (wherein Y represents a protecting group of a hydroxyl group, Hal represents chlorine, bromine or iodine, η is the same as defined in the formula (1), and 乂 is an integer of i or more and n-丨 or less) reacts with a magnesium or an alkyllithium compound to form Gliner reagent or organolithium compound' is insoluble in the Grignard reagent or organolithium compound and non-crosslinked block copolymer with aromatic ring Resin reaction, the poorly water-soluble resin has a unit having a substituent represented by formula (3) in the aromatic ring and a hydrophobic unit, -(CH2)X-Hal' (3) (wherein Hal' represents Gas, bromine or iodine, X is an integer of 1 or more and nl or less (but η is the same as defined in formula (1))) 201204755 After removing the protecting group of the radical, the hydroxyl group is converted to a _ or a sulfonate, followed by a level 3 Further, the present invention is a bonding resin for forming a catalyst electrode layer composed of the anion conductive resin. The present invention is an ion conduction for forming a catalyst electrode layer including an organic solvent and the above-mentioned bonding resin. The agent and the composition for forming a solid high-concentration + type fuel cell containing the ion conductivity imparting agent, the electrode catalyst, and the solvent are used as a catalyst. The catalyst for forming the composition for the catalyst electrode layer is used. The electrode layer, the membrane-electrode assembly including the catalyst electrode layer, and the fuel cell including the membrane-electrode assembly are also included in the scope of the present invention. [Effect of the Invention] The anion value of the present invention Shengshu Yueqi has a better knowledge The anion-conducting resin has a high heat resistance, and an anion exchange membrane made of a second electrode layer made of an ion conductivity imparting agent containing a binder resin for forming a catalyst electrode layer composed of the anion conductive resin is used as an electrolyte. Solid 咼 molecular fuel cell, compared with the solid anion exchange membrane used as an electrolyte, its eight-worker 丨 φ ^ ^ knife-type fuel cell, making it possible to generate electricity at higher temperatures, thus enabling lightning strikes The activity of the medium is increased, and the light battery can be obtained. In addition, it does not extend to water nj " horse water is difficult to be pure, because it is non-crossing soluble in solvent, can be chatted with electricity F, so 43L -f ^ ^ When W - and the catalyst particles are mixed, an ion conductivity imparting agent for dispersing the south of the electrode catalyst particles is produced. Catalyst [Formation of the Invention] The present invention is a non-parental block copolymer having a coating, having a hydrophilic unit having an ammonium salt represented by the formula (1) in the ring of 2012 12,055,55 and A poorly water-soluble anion conductive resin having a hydrophobic unit of the ammonium salt -(CH2)„-N+R!R2R3(X)z (!) (wherein η is an integer of 3 to 6, R1 The ruler 2 and the R3 are each a linear or branched chain alkyl group having a carbon number of 5, and {^ and R3 may be bonded to each other in whole or in part to form a ring, and X is a relative anion (c〇unter ani〇n). , z is the reciprocal of the X valence), and there is a methyl group having a carbon number of 3 to 6 between the 4-stage ammonium group and the aromatic ring, so the anion of the 4th-order group is bonded to the node group at the aromatic ring. The conductive resin has high stability to the nucleophilic reaction of the four-stage group, and is excellent in the heat-generating property. Therefore, the joint for forming the catalyst electrode layer composed of the anion-conductive resin of the present invention having the above-described composition is used. The catalyst electrode layer of the tree vinegar can stabilize the power generation even at a high temperature above the order. In addition, there is a hydrophilic green that serves as a salt-conducting structure for ion conduction. Forming a block with a hydrophobic unit to carry out block block a, m slave, and polymerization' thus having a phase separation structure, excellent ion conductivity, and poorly soluble in water. Further, the anion conductive resin of the present invention does not have = The structure is therefore soluble in the solvent, and is superior to the gas system in terms of adhesion to the separator or cost. The anion conductive resin of the present invention is a non-crosslinked inlay with an aromatic ring. The copolymer has a hydrophilic single π which is an ammonium salt represented by the formula _ 瑕 _ a octagonal in the aromatic ring and a hydrophobic resin which does not have the ammonium salt. The ring-block copolymer of the ring from the * & heart into the father's 'anion-conducting peppers as the catalyst layer for the formation of the catalyst layer, the newspaper layer used to make the catalyst electrode from the private 7 ± He Yuet The ion conductivity imparting electrode 4' for layer formation is insoluble in a solvent, and the output of the battery is lowered in combination with the electrode catalyst due to 201204755. In general, the dispersibility of the electrode catalyst is reduced, which leads to Rong Jiantian. The polymer is insoluble once formed into a crosslink. Thus, the anion conductive resin of the present invention is non-crosslinked. Further, in the side chain, the right-handed, _ _ s ^, the hydrophilic unit of the ammonium salt represented by the formula (1), 盥 not =: salt: hydrophobic unit, and any copolymerization without block copolymerization In addition, if the ionic property of the ion-conductive resin is added and the hydrophilic 罝s having the salt are added, the solubility of the ion-conductive resin to water is improved, and the gate is The bonding resin for forming the catalyst electrode layer is eluted from the catalyst electrode layer using the bonding resin for forming the catalyst electrode layer, and the battery output is unstable. Conversely, if the solubility in water is lowered and the hydrophobic unit is increased, the ion conduction of the ion conductive resin is lowered, and the resistance of the catalyst electrode layer is increased to lower the battery output. Further, the anion conductive resin of the present invention is a block copolymer in which the hydrophilic unit and the hydrophobic unit form a part (a hydrophilic portion and a hydrophobic portion), respectively. Hereinafter, the anion conductive resin according to a preferred embodiment of the present invention will be exemplified by the block copolymer described above. In the invention of the present invention, the anion conductive resin is poorly soluble in water, and is defined as a solubility in water of 2 Gt (concentration of an anion conductive resin in a saturated aqueous solution) of less than i% by weight, preferably. · 8 wt%. The anion conductive resin of the present invention is used as a bonding resin for forming a catalyst electrode layer for a high-concentration sub-fourth battery, and the anion conductive resin is insoluble in water. When the polymer electrolyte fuel cell is used, the anion conductive resin used as the bonding resin for forming the catalyst electrode layer is eluted from the catalyst electrode layer to lower the battery output. 14 201204755 η in the above formula (1) represents the number of methyl groups extending between the 4-stage ammonium group and the aromatic ring of the main chain, and is an integer of 3 to 6. η is! At the time of hydrogen formation at the base of the node, the valley is easily decomposed. When n is 2, the hydrogen at the benzyl group is an active hydrogen, which is pulled out to desorb the amine and is therefore unstable. Therefore, the effect of improving the heat resistance is obtained: n is 3 or more. On the other hand, at t... or more, the ion exchange capacity of the anion-conducting f Μ 曰 倾向 is lowered, so that the anion conductivity of the oxy-ion ion is lowered. From the viewpoint of heat resistance and negative conductivity, it is preferable that η is 3 to 5. In the above formula (1), each of R1, R2 and R3 is a linear or branched alkyl group selected from the group consisting of carbon atoms of 1 to 5, and is not particularly limited, and R1, R2 and R3 may be bonded to each other in whole or in part. Ring 'but in the case of importance ion conductivity, ion = change capacity can be higher, so R1, R2 and R3 are all better than the methyl group with relatively good ion conductivity. Also in the case of stability, R1, R2, and R3 are all bonded to each other, and the "stone" of the "sub-formation ring" (qui) is not in the reverse-orientation (antiperipUnar) ring system, or ^ and V are bonded to each other. , a 3' 3' 5' 5-tetramethyl π-pyridyl ring in which the N-former forms a ring and the stone-hydrogen is all substituted with a f group, because it is easy to cause Hoffmann decomposition of the ammonium salt. Further, in the above formula (1), X is a relative anion (counter ani〇n), and there is no particular limitation that Z is a reciprocal of the X valence. For example, X is an i-valent anion, z is an anion of z 2 h, z & i When the anion conductive resin of the present invention is used as a bonding resin for forming a catalyst electrode layer, the XA hydroxide ion nucleus ion and the hydrogencarbonate ion are not inhibited by the electrode catalyst reaction. 15 201204755 The idea of constituting an aromatic ring having a hydrophilic structure of a hydrophilic structure having no ammonium salt, preferably two: but from the test, it is stable, synthetic or ^Polymerized part 4 of the part of the present ethylene must be completely substituted into the formula, (: structure. - and constitute the hydrophilic For the good ion conductivity, u) the non-ammonium salt. The amount of the anion conduction introduced from the viewpoint that the aromatic ring in the resin can be difficult to be formed from the viewpoint of water is desired to be an anion (::: part of the ammonium salt) The polymerization monomer 〇.3~4.2ramc)1/g, the ratio of the hydrophilicity unit in the ion exchange capacity of the primary resin is: two-sub-conductivity, water-insoluble, two special; The skeleton structure of the hydrophobic portion of the money salt shown in (1) is a hydrophobic portion, and is not particularly limited. From the warp-knitted polymer which is stable in the test, for example, a polyfluorene or an ethylene aromatic compound can be used for synthesis. Or easy to obtain, Polyethylene, Polypropylene, Polybutylene, Polyisoethylene, and copolymers containing hydrogenated polybutadiene or polyisoprene A polyolefin such as a olefinic structure of a diene is preferred. The two parts may also form a diblock copolymer, or a triblock copolymer, or an intercalation copolymer, but are readily synthesized or obtained. The viewpoint is that a two-year-old or triblock copolymer is preferred. The molecular weight (degree of polymerization) of the individual blocks or the length ratio between the blocks, etc., is not particularly limited, and may be in the form of a block copolymer (diblock, triblock, multiblock) or an important property (ion conductivity). It is determined by the insoluble water. 201204755 Block copolymers suitable for the above conditions, such as polystyrene-poly(ethylene tert-butyl) polystyrene three-segment copolymer (sebs), polystyrene-poly ( Ethyl ethyl propyl) _ polystyrene ethylene triblock copolymer (Qing s), polystyrene (extended ethyl - stretching ethyl _ propyl ethylene triblock copolymer (EEPS), etc. The stupid ethylene unit has a salt represented by the formula (1) as a substituent hydrophilic II. A file, and a block copolymer having no hydrophobic portion of the ammonium salt. The method for producing an anion conductive resin of the present invention is effective in the production of the following method, and is also preferable in terms of cost. (i) a compound of the following formula (2), which protects the transdentate tooth compound Ha,-(CH2)nx-〇Y (2) (wherein Y represents a protecting group of a hydroxyl group, and Hal represents chlorine, bromine Or iodine, η" is the same as defined in formula (1), X is an integer of 1 or more and η_ι or less) reacts with a smectic or pyridyl compound to form a Grignard reagent or an organic chain compound, (ii) the Grina reagent or The organolithium compound reacts with a non-crosslinking block copolymer having an aromatic ring and a resin having a substituent represented by the following formula (3) in the aromatic ring and a poorly water-soluble resin of the hydrophobic unit - (CH2) X-Har (3) (In the formula, 'Hal' means chlorine, bromine or iodine, X is an integer of 1 or more and nl or less (but η is the same as defined in the formula (1)), and after removing the protecting group of the hydroxyl group, the hydroxyl group is converted. After halogen or sulfonate, 17 201204755 (ill), react with a tertiary amine to form an ammonium salt. Hundreds of first, a halogen compound represented by the above formula (2) protecting a hydroxyl group with a protecting group, and a town or a burning base The compound is reacted to form a Grignard reagent or an organic compound. In the oxime (), γ is a radical protecting group, and can be combined with a Grignard reagent or an organic lithium. The reactants are not particularly limited. For example, "a" can be used.

Greene, Protective Groups in Organic Synthesis, Wiley "〇ns, Jane, Chapter n, p l"8, such as the i-type, light-based protective groups, etc., especially in order to guide the protective group under acidic conditions, preferably Methoxymethyl m-tetrapyranyi, tetrafuranyi, ethoxyethyl, butyl and the like.

Hal indicates that gas, desert or moth ' is preferably bromine from the balance of easy availability and reactivity. η is the same as the formula (1), and represents the length of the methyl chain extending between the ammonium salt group of the obtained anion conductive resin and the aromatic ring of the main chain, and is an integer of Η. X represents the length of the methyl group chain of the substituent represented by the formula (8) in which the non-crosslinked block copolymer having an aromatic ring is substituted as described below, and is an integer of n-1 or less. The (tetra) compound having a protecting group as shown in the formula (2) can be synthesized by a known method such as the above-mentioned book on the protective group. Nanhua alcohol, when the methyl chain is 2 or 3, is a vapor, a desert, an iodide, or a gasification of 4, a halogenated alcohol which is cut by Sigma Aldrich and the like. Chess Baigudu ^ ^ 咚 仵 仵 市 市 仵 仵 仵 仵 仵 仵 仵 仵 仵 仵 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 醚 醚 醚 醚 醚 醚 醚 醚 醚 醚 醚 醚 醚 醚 醚 醚 醚 醚 醚 醚 醚 醚 醚 醚 醚 醚 醚 醚 醚· Synthetic method shown in 64η43. The formula of thiol can be selected from commercially available reagents depending on the type of protecting group. If it is methoxymethion, the base is commercially available with dimethoxymethane, if it is four oximes: Nanji's are commercially available. Hydrogen. Compared with argon, if it is tetrahydrofuranyl, it is commercially available as Fengfunan. If it is ethoxyethyl, it is commercially available as ethyl acetonate. If it is t-butyl, it is commercially available as methyl butyl ether. The toothed alcohol of the raw material reacts the complex under strong conditions, so it is desirable to protect the base of the functional alcohol which should be protected under acidic conditions under the conditions of neutralization to acidic conditions. The compound of the group increases the double bond to form the 1-methoxymethyl group or the butyl group which is introduced under the acidic condition by the exchange reaction. The group is protected as the vaporized compound having the protected sulfhydryl group in the Grignard reagent. 'The desert or hardened material can be prepared by reacting with the town in a solution such as strontium or tetranitrogen. The town used here is usually coated with an oxide film. The film is removed for pretreatment to activate. Necessary. Pretreatment can use well-known methods, such as in solvents (4) Magnesium collides with each other or magnesium collides with the mixing wing or container wall, or is activated by hydration, or activated by ultrasonic vibration or reacted with a small amount of active agent such as sputum or Erqinyuan. Two times the following modulation of the Griina reagent, a small amount of --modulated Grignard reagent is saved. This Grignard reagent can also be used as an active agent. The activated town is usually not taken out and protected with the warp group. Tooth reaction. Usually, the m-based protected compound is dissolved in the solvent to be used, and it is desirable to add it in small amounts at a time. The temperature at this time is preferably based on the type of dentate but the inhibition coupling reaction carried out under 19 201204755. When it is high, it is not possible to react with the halogen-protected halide which is added with a small amount of hydroxyl group after the formation of the internal D-type agent, and the desired Grignard reagent can be obtained. The southing compound of m is prepared by reacting with a butyl group such as an organic organic compound or a metal. In this case, it is usually preferred to suppress the coupling reaction below room temperature. The resulting Grignard reagent or organolithium The compound is reacted with a non-crosslinked block having an aromatic ring and is further reacted with a water-insoluble resin having a hydrophilic portion and a hydrophobic portion having the above-described substituent in the aromatic ring. In the case of 3), Hal, ± A, and nal are not gas, bromine or iodine, and are preferably gas for reasons of easy synthesis. The number of excision base chains of X-substituents is 1 or more and n-1 or less. From the viewpoint of easy synthesis, χ is preferably the same as defined in the formula (1), and 'the number of methyl groups extending between the (4) salt group and the aromatic ring in the obtained anion conductive resin is 3~ An integer of 6 is a non-crosslinked block copolymer having an aromatic % and having a hydrophilic portion and a hydrophobic portion of the substituent represented by the 'wherein' a non-crosslinked block copolymer, a hydrophilic portion of an aromatic ring having a substituent represented by the above formula (3), and a water-insoluble resin having a hydrophobicity (hereinafter referred to as a raw material resin) The aromatic ring is obtained by haloalkylation. The raw material resin is a non-crosslinked block copolymer having an aromatic ring, and has a hydrophilic portion of an aromatic ring having a substituent represented by the formula (3) and a water-soluble portion of the 201204755 aqueous portion. There is no special limit to the introduction of the above formula (8). The raw material resin has a hydrophilic portion of the aromatic ring which is determined by the stability of the bone, and the hydrophilic portion of the aromatic ring which is substituted by the accepting group is preferably an electron reaction for the W which is substituted by the attracting group. The idea that the basicization is easy to synthesize or obtain is preferably in the test - (four). The portion which is also poorly soluble in water is preferably a skeleton structure' which is preferably a tobacco-based polymer such as a polydisperse polymer or a rare aromatic polymer. From the standpoint of easy synthesis or acquisition, #enepolypropylene, polybutylene, polyisoprene and copolymers thereof (polymers containing deuterated polybutadiene or polyisoprene) The portion composed of the polyolefin such as the skeleton structure is more preferable. Two. The file may also form a diblock copolymer, or a triblock copolymer, or a succinyl copolymer, but a diblock or diblock copolymer is preferred from the standpoint of ease of synthesis or availability. The individual block molecular weight (degree of polymerization) or the length ratio between the blocks, etc., are not particularly limited, depending on the form of the block copolymer (diblock, three-stage, multi-block) or physical properties (ion conduction) Degree, water is difficult to dissolve) to decide. As the raw material resin, a block copolymer suitable for the above conditions, such as polystyrene-poly(ethylene-tert-butyl)-polystyrene triblock copolymer (SEBS), polystyrene-poly(stretch) Ethyl-extended propyl)-polystyrene triblock copolymer (SEPS), polystyrene-poly(extended ethyl-extended ethyl-propyl polystyrene triblock copolymer (SEEPS), etc. The halogen-based method of the raw material resin can be synthesized by using a known method, for example, by dissolving a solution of a raw material resin, a paraformaldehyde (paraf〇rmaldehyde) 21 201204755 or a trioxane (trioxane) with a toothing reaction or the like. In this case, it is also possible to use (4) Lewis acid as a catalyst for the addition of vaporized tin and a gas methyl group. The use of the Lewis acid catalyst is described in JP-A-A-5-126532. The next, and the agent, slowed by "miao / shrinking compound and toothing: two by the action of the gas methylation agent in the reaction enthalpy, so that the side of the South methylation" according to the Chemical Society's new experimental chemistry lecture 19th volume, the first edition of the "I" of the polymer science (the third brush), Maruzen Co., Ltd., Showa 53 years (Showa 60 years 5 (1G), as described in the following page, a method of using a thiol methyl ether under a tin chloride catalyst to methylate a halide, etc. A resin having a substituent represented by the above formula (3) and The Grignard reagent or the organic clock compound obtained by protecting the radical group of the protecting group represented by the formula (7) is reacted to remove the hydroxyl protecting group to regenerate the hydroxyl group. Any of the reaction occasions will have the formula (3). The substituent resin is dissolved in a solvent such as tetrahydrofuran, and the reaction is carried out by slowly dropping a Grignard reagent or an organic chemical σ. The temperature is usually from room temperature to about 1 Torr, and the reaction time is usually About 1 hour to 24 hours. Regarding the detachment of the protective group, the method described in the above-mentioned book can also be used according to the type of the leaving group. Usually, the acid hydrolysis method is used to contact the excess amount of the diluted hydrochloric acid, because the operation is simple. The regenerated base is converted into a complex or a mesylate by a known method. For example, in a halogenated hydrocarbon solvent such as a gas imitation, it is heated with a sulfuryl chloride or a thionyl chloride to obtain a vapor. The bromide is obtained by reacting with phosphorus tribromide or the like. Further, the sulfonate can be formed by reacting the benzenesulfonic acid gas or the methyl sulphuric acid gas in the presence of a base. The ammonium sulphate after the passage of 22 201204755 is easily converted into The bromide is preferred. After the reaction with the tertiary amine, a quaternary salt is obtained. The reaction is carried out by contacting the tertiary amine with a solvent, and it is not necessary to dissolve the resin in the solvent. The tertiary amine is preferably used in the resin. Sulfonic acid vinegar is used in excess of 'usually 1-〇5 moles to 1 moles'. In view of the cost of the tertiary amine used, it can also be used at 100 moles or more if it does not become uneconomical. The temperature may be pressurized depending on the boiling point of the tertiary amine used, but usually from room temperature to about 10 "C'. Excessive use of 6"amines, because the resin is insoluble in water, it can be easily removed by washing with hydrochloric acid or the like. The anion-conductive resin thus obtained usually has a 4-stage ammonium group having a ruthenium ion-xamate ion as a relative ion (e_ter-), but this anion-conductive resin is used as a junction for a hydroxide ion-conductive fuel cell. In the case of using a resin, it is preferred to exchange the relative ion ions of the four-stage recording group into any one of a gas ion ion, a carbonate ion, and a hydrogencarbonate ion from the viewpoint of easily obtaining a high output of the fuel cell. The method of changing the relative ions of the ion enthalpy to the fourth stage can be carried out according to the conventional conditions. (4) In the case where the ion exchange is a hydroxide ion, the upper = anion conductive resin is impregnated into an aqueous alkali hydroxide solution such as an aqueous solution of sodium hydroxide or a water-cooled liquid. The concentration of the aqueous alkali hydroxide solution is particularly limited, and is generally about Q•b~. Bu rl, and the immersion temperature is ~6 〇C, and the immersion time is about 〜5~48 hours. 2, an anion-conductive resin of the invention can be used as a catalyst electrode layer for forming a sigma. The bonding resin 23 for forming a catalyst electrode layer of a solid molecular fuel cell using an anion exchange membrane as an electrolyte is preferably 201204755. use. The bonding of the catalyst electrode layer formed of the anionic conductive resin of the present invention can be formed by selecting an early-resin from the anion-conducting dendritic raft of the present invention. The anion conductive resin of the present invention having a different capacity, molecular weight, and skeleton structure is exchanged, and is not particularly limited thereto. In the anion conduction of the present invention, a bonding resin for forming a catalyst electrode layer composed of a t-amp; &<>, and a v-resin is used for the solid 円 molecular fuel in the field. The catalyst electrode layer of the battery is dissolved or dispersed in a single solvent or a solvent of two or more kinds of solvents contained in the following ruthenium or ruthenium as a binder resin for forming a solvent and a catalyst electrode layer. The ion conductivity imparting agent for forming a thunder electrode layer is preferably used. The ionic conductivity imparting agent for the catalyst ray and the electrode layer is specifically coated with an electrode catalyst which is coated on the surface of the solid surface of the pharyngeal electrode layer and the surface of the pharyngeal electrode layer. The composition for the catalyst electrode layer of the particles is used. The solvent for modulating the layer shape of the catalyst electrode is not particularly limited, and the ion exchange of the bonding resin can be used, for example, in the case of an ion conductivity imparting agent for use in a solvent described below, but in view of the capacity of the catalyst electrode layer to be dissolved, The molecular weight, the composition ratio of the skeleton, and the like are appropriately selected. ^Alcohols such as sterol L alcohol, propanol, 2-propanol, butanol, butanol, cyclohexanol, 2-ethoxyethanol; acetone, methyl ethyl ketone, etc. _ class; esters such as ethyl acetate and isobutyl acetate; nitriles such as acetonitrile and acetonitrile (1113 1011:^116); ^_Dimethylcarnitine, 曱-mercaptoamine, N-review: a. / 'Methyl-2-pyrrolidone (pyrr〇Hdin〇ne), etc.; amines; dimethyl sulfonate, sulfone, sulfone, etc.; diethyl ether 24 201204755 dimethoxy Alkane, tetrahydrofuran, dioxane (4). ·. A solvent such as an ether; a hydrocarbon such as an alkane or a stupid; a gasified hydrocarbon such as a gas or a methane; These can be used individually or in combination of 2 or more types. In combination of two or more cases, water may also be used as one of the solvents. In the ion conductivity imparting agent for forming a catalyst electrode layer of the present invention, the most suitable solvent composition is appropriately selected in accordance with the physical properties of the bonding resin for forming the catalyst electrode layer, so that the bonding resin for forming the catalyst electrode layer is not aggregated. And evenly loosened or dispersed. In order to form a uniform catalyst electrode layer, the catalyst electrode layer of the present invention forms (4) a material-imparting agent which is dispersed in a state in which the resin does not settle, and is more preferably dissolved. The solubility and dispersibility of the bonding resin for forming a catalyst electrode layer of a solvent can be confirmed by centrifugation or pressurization to separate insoluble components, or by measurement of the prepared ion conductivity imparting agent, or the like. . In the ion conductivity imparting agent for forming an electrode catalyst layer, the anion conductive resin is used as an interface tree for forming a catalyst electrode layer, and there is no thickener. Therefore, the catalyst electrode layer may be formed. The bonding resin to be used has a high concentration, and the bonding resin for the catalyst electrode layer is a high concentration region of 5 to 1 G by weight in the melted "00 weight portion, and the bonding resin for forming the catalyst electrode layer is not It will solidify 'providing an ion conductivity imparting agent that dissolves. The concentration of the bonding resin for forming the catalyst electrode layer in the ion conductivity imparting agent for forming the electrode catalyst layer of the present invention is not particularly limited, and the combination of the solvent and the bonding resin for forming the catalyst electrode layer can be used for the electrode contact. The composition for the use of the medium, the viscosity, and the formation of the catalyst electrode layer are appropriately determined at the time of the creation of 25 201204755. Further, the adjustment of the viscosity is based on the formation of the catalyst electrode layer = the use form of the composition at the time of preparation, 35 when the solvent type and the use of ^ are selected. Usually, the concentration of the bonding resin for forming the catalyst electrode layer is from 0% by weight to 30% by weight, preferably from 1% by weight to 10% by weight. In addition to the bonding resin and solvent for forming the catalyst electrode layer, the ion conductivity imparting agent for forming the above-mentioned catalyst electrode layer of the present invention may contain an adhesive or a viscosity without departing from the scope of the invention. Adding ingredients such as a regulator of oxidation, a heat stabilizer, and the like. When these additions are made to 2, it is desirable to use a ratio of 5 parts by weight to the total weight of 100 parts by weight of the solvent, preferably 1 part by weight or less. The car is also preferably used as an adhesive resin, such as polytetrafluoroethylene, polyfluoroethylene = olefin (? ^ 1401 * 0 ^ 1 ^ 11 (16116), tetrafluoroethylene _ perfluoroalkyl vinyl ether polymer Fluorine-based polymer, etc.; (4) polymer such as 6-air, styrene-butadiene copolymer, etc.; #-polymer, etc. These may be used alone or in combination of two or more. The adhesive has the effect of enhancing the physical strength of the catalytic electrode layer 'drying and dampening can alleviate the stretching tension of the catalytic electrode layer'. The long-term continuous stability of the power generation performance of the excellent battery is obtained. The viscosity adjuster can be used alone or Mixing an organic solvent such as decyl alcohol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tetrahydrofuran, 14-dioxane, n-propyl ether, or carboxymethyl fiber Polyethylene glycol, polyvinyl alcohol, polyethylene, etc., such as ketone, methyl cellulose, hydroxyethyl cellulose, or cellulose, etc., each ketone, or polydecyl vinyl ether, etc. Antioxidants such as (obstruction) Phenol, monovalent or divalent sulfur, trivalent ~ 26 201204755 pentavalent phosphorus, phenol, stupid = alpha It is preferable to block each of the compounds of the amine oxime, the cyanoacrylate type, the salicylic acid type, and the oxalic acid aniline system. The ion conductivity imparting agent for forming the catalyst electrode layer of the present invention is composed of a catalyst electrode layer. The bonding resin for formation, the solvent, and the additional component to be added as needed are obtained by mixing in an ordinary manner, and the anion conductive resin is dissolved or dispersed in a solvent to obtain an ion conductivity for forming a catalyst electrode layer. The dissolution or dispersion time of the bonding resin for forming the catalyst electrode layer at the time of the agent is not limited, and the bonding ion exchange capacity for forming the catalyst electrode layer to be dissolved or dispersed, the molecular unit, the genomic frame, and the like. The composition ratio of the composition and the nature of the solvent to be used are appropriately adjusted. When the catalyst electrode is used to form the ion conductivity imparting agent for the formation of the electrode layer, the dissolution or dispersion temperature of the bonding resin for layer formation is also There is no particular limitation on the ratio of the ion exchange capacity of the conjugated tree that can be formed from the dissolved or dispersed catalyst electrode layer, the composition ratio of the molecular structure, the crystallization structure, and the dissolution of the structure. Nature, etc., suitable for 锢敕 / D whole, but preferably 20eC ~ 18〇t, especially 4 (TC ~ 15 (TC is better. And Wei Tian di ~ Do not use the boiling point of the agent is more soluble or When the dispersion temperature is low, the solvent may be heated to a temperature above the boiling point by using a pressurized container such as a gas pressure regulator, a gas cylinder, or the like; and the solvent may be dissolved or dispersed in a pressurized state. In the catalyst, the composition for the layer contains the ion conductivity of the above-mentioned catalyst electrode layer, and the electrode is provided to the electrode, the electrode catalyst and the solvent. Here, the catalyst electrode layer is formed. The composition used for the composition is not a composition (coating liquid) for a catalyst electrode layer of a polymer electrolyte fuel cell. The electrode catalyst particles are supported by an electrode catalyst supported on carbon or a metal oxide 27 201204755 Electronic conductors, or thunder and heroes. / Early body of the electrode catalyst. In order to reduce the amount of catalyst used and to have high electron conductivity of the catalyst electrode layer, it is preferred to use a metal conductor previously supported. The electrode catalyst is a substance that promotes the oxidation reaction of hydrogen and the reduction reaction of oxygen, such as Ming, Jin, Yin, Ji, Yin, Qian, Nail, Tin, Iron, Ming, Record, Pin, Crane, Hunger or Alloys and the like synthesized by these. The electron conductor is an electron conductive material, and is not limited to, for example, conductive carbon black, carbon nanotube, activated carbon, metal oxide or the like. The particle volume of the electrode catalyst is 特别, and the meaning is particularly limited. Further, the amount of the electrode catalyst supported on the electron conductive material 3 is an amount effective to exhibit the catalytic activity, and there is no particular limitation on the amount of the catalyst, but the amount of the electrode catalyst supported on the electronically conductive substance 1 〇 01 to 9. 〇 G-metal/g_carbon, flat and live in the stable. 〇2~4. Og-metal/g_carbon range. The solvent used in the composition for the catalyst electrode layer of the present invention may be a solvent: the anion conductivity imparting agent for forming the electrode layer is dissolved or dispersed, and is particularly limited, but for example, The solvent is selected as the appropriate one of the alcohols: "alcohol 6 alcohol, propanol, 2-propanol, butanol, butanol, -, cyclohexanol, 2-ethoxyethanol, etc.; Ketones such as acetone ketone; ethyl esters, esters of 7 绐s Τ 乙 - - isobutyl acetate; nitriles such as acetonitrile and malonitrile; U-...carbamidine : Yin Jiyi, amine, " base_2, sulfones such as sulfolane, ketones, etc.; diethyl ether, 28 201204755 1' Ethers such as 2-dimethoxyethane, tetrahydrofuran, and dioxane, etc.. Hydrocarbons such as hexane or toluene; solvents such as gasification and gasification such as gas and gas. It may be used alone or in combination of two or more. In combination of two or more kinds, water may be used as one of the solvents. ° The composition for the catalyst electrode layer of the present invention may optionally contain a dispersant or carbon. Other components such as vitamins, adhesives, water repellents, etc. Dispersing agents such as anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, etc. surfactants: the contact electrode layer of the present invention The composition is added to the composition, and is excellent in storage stability and fluidity, and productivity in coating work. Carbon fiber can be used as ray (R) carbon fiber, pAN carbon fiber, and lignin carbon fiber. Carbon fiber, vapor-grown carbon fiber or the like is preferably a vapor-grown carbon fiber. Addition of carbon fiber to the composition for the catalyst electrode layer lowers the electric resistance due to an increase in electron conductivity in the electrode, and increases the diffusibility of the fuel gas or oxygen by increasing the pore volume in the electrode, thereby improving the cause. The flooding caused by the generated water increases the power generation performance. A resin which can be used for an adhesive or a water repellent, for example, a fluorine-based polymer such as polytetrafluoroethylene, polyfluoroethylene (P〇lyflUOrovinylidene), tetrafluoroethylene-perfluoro-vinyl ether copolymer; A hydrocarbon-based polymer such as ether ether ketone 'polyether sulfone or styrene-butadiene copolymer; a fluorene-based polymer. These may be used singly or in combination of two or more. The adhesive has the effect of enhancing the physical strength of the catalytic electrode layer, and the drying and wetting can alleviate the stretching tension of the catalytic electrode layer, and the % conductivity of the power generation b of the long-term continuous excellent battery output can be obtained. The water-repellent agent can efficiently discharge the water generated by the battery. 29 201204755 The effect of the power generation is improved. The total amount of the electrode catalyst particles of the present invention is 0.1 to 20% by weight, preferably 0 5 to 15% by weight, based on the total amount of the composition for the catalyst electrode layer, and the content of the bonding resin for forming the catalyst electrode layer. 1 to 20% by weight, preferably 5% to 15% by weight, and the solvent content is 5 Å to 99% by weight, preferably 7 Å to 95% by weight. If necessary, the dispersant is used in an amount of 〇~1〇% by weight, preferably 0% to 5% by weight, and the carbon fiber content is 〇~2〇% by weight, preferably "% by weight" of the adhesive is 〇〜25重量%, preferably 〇2〇2% by weight. Further, the content of the above components is not more than 1% by weight. When the content of the catalyst particles is less than the above range, the electrode reaction rate is lowered, thereby The fuel cell output is lowered. On the other hand, when the above range is exceeded, the viscosity of the composition for the catalyst electrode layer is increased, paint spots are generated when the transfer substrate is applied, and a fuel cell output cannot be stably obtained. When the content of the bonding resin for forming the catalyst electrode layer is less than the above range, the ion conductivity is lowered to increase the electric resistance, the output of the fuel cell is lowered, and the ability to bond the electrode catalyst particles is insufficient. Therefore, the catalyst electrode layer may not be formed. On the other hand, when the above range is exceeded, the pore volume in the catalyst electrode layer tends to decrease, and the gas diffusion in the catalyst electrode layer When the content of the solvent is within the above range, the pore volume of the catalyst electrode layer required for power generation can be sufficiently ensured, and the treatment for forming the catalyst electrode layer is suitable. The content of the dispersant is within the above range. When the composition of the electrode catalyst layer which is excellent in the stability of 30 201204755 is obtained, the content of the above-mentioned fiber is not more than the above range, and the electric quantity is too long. The effect of increasing the amount of pores is reduced, and the electrode reaction enthalpy is lowered when the surface is over-tacked. The composition for the catalyst electrode layer of the invention can be kneaded and adjusted, for example, by the above-mentioned methods. Such as _ stirrer, ultrasonic „ = L does not 'mize the device (nanomizer) and other devices. The conditions such as the mixing order and the temperature of each component are not particularly limited. For example, mixing all the components for a predetermined period of time, or mixing the components other than the dispersing agent for a predetermined period of time, it is necessary to add a dispersing agent and then proceeding. It is better to stir the 仃-疋 time. The amount of solvent is also adjusted as needed, and the viscosity of the catalyst electrode layer composition is also adjusted. The catalyst electrode layer of the present invention can be obtained by forming a desired shape of the composition for forming the catalyst electrode layer and then removing the solvent. For example, a composition for forming a catalyst electrode layer is applied onto a transfer substrate to remove a solvent. In other words, the electrode catalyst layer of the present invention comprises a bonding resin for forming a catalyst electrode layer composed of the anion conductive resin of the present invention and the electrode catalyst particles. As the transfer substrate, a sheet made of a fluorine-based polymer such as polytetrafluoroethylene or a glass plate treated with a release agent on the surface, a metal plate, a polyethylene terephthalate sheet or the like can be used. Further, the composition for forming the catalyst electrode layer may be applied directly to an anion exchange membrane or a gas diffusion layer or to a carbon paper to form a catalyst electrode layer. 31 201204755 A method of applying a composition for forming a catalyst electrode layer to a transfer substrate, such as brush coating, squeegee coating, coating bar coating, knife coating, doctor blade method , screen printing, smear coating, etc. The membrane-electrode assembly of the present invention has the above-described catalyst electrode layer on at least one surface of the solid polymer electrolyte membrane. The method for producing a membrane-electrode assembly of the present invention can be carried out by using a known method, an electrode catalyst and a catalyst f-layer forming a bonding resin and an anion present on the surface of the catalyst electrode layer and the solid polymer electrolyte membrane. The method of exchanging the membrane contact is not particularly limited.

For example, the above-mentioned method for cracking bamboo, t, and I k, for example, coating a composition for forming a catalyst electrode on the above-mentioned transfer substrate, or applying a pressure before drying. A method of forming a membrane-electrode assembly by bonding a solid molecular electrolyte membrane and a gas diffusion layer, or applying a composition for forming the catalyst electrode layer to a gas diffusion layer and drying it, or The method of forming a membrane-electrode assembly by σ is carried out by a method such as an invitation method before drying and a gas diffusion layer. As a solid polymer electric boat, a solid electrolyte is still a sub-electrolyte membrane, and there is no - ^夂. In particular, the anion exchange membrane described in the above Patent Document 6 can also be used to generate electricity. The anion exchange membrane is preferably used in the heat resistance of the two, and is contained in the two. The diffusion layer is not particularly limited. A commercially available material can be used. The membrane-electrode assembly of the catalyst electrode layer of the solid == is a material in which an electrode composed of a catalyst electrode layer and a gas diffusion layer is disposed on both sides of the === ,, and the fuel cell of the side structure has a spacer holding For electrodes outside the electrode, use in layers. 32 201204755 [Embodiment] Hereinafter, the present invention will be described in detail based on the embodiments, but the present invention is not limited to the examples described herein. In addition, the properties of the anion conductive resin, the catalyst electrode layer forming resin, and the catalyst electrode layer forming ion conductivity imparting agent shown in the examples and the comparative examples are measured by the following methods. 1) Anion exchange capacity An anion conductive resin was dissolved in a solution of 1-propanol and poured into a container made of Teflon (trademark) to prepare an anion-removing film made of an anion conductive resin. The membrane was immersed in an aqueous solution of 〇5m〇i.L^-NaCl for more than 1 hour to form a chloride ion type, and then replaced with a P-NaNO3 aqueous solution of 〇. 2mo, replaced with a nitrate ion type, and the 帛s After the potentiometric titration apparatus COMTITE-9G0, manufactured by Hiranuma Sangyo Co., Ltd., quantified the free gas ions (Am〇1), the titrated film was immersed in a 5 m aqueous solution of L NaCl for 4 hours or more at 25 ° C to After the ion-exchanged water is sufficiently washed with water, the surface of the film, such as W-paper, is removed, and then the surface is dehydrated and dried under reduced pressure for 5 hours, 彳, and weight (Dg). Based on the above measured values, the ionic anion exchange capacity is calculated by the following formula, I 〇〇〇 / D [mol.g' dry weight] 2) The durability of the anion exchange group 阴离子 eight f relative ion formation after the hydroxide ion type Sex tree:: Two containers made of Teflon are placed in the container, and the yin and valley are measured separately after 5 小时 °C or C ionic & The anion exchange rate formed by the ratio of the anion exchange capacity of the treated resin to the anion exchange capacity of the resin before the treatment was calculated, and the capacity retention rate was evaluated to evaluate the durability of the anion exchange group. 3) Method for determining the solubility of water. The log anion-conducting resin is immersed in a 20-ton ion-exchanged water 1 〇〇mi with a magnetic H-mixer and immersed for 丨 hours, decompressed H, and removed from ion-exchanged water. An anion conductive resin. The residual ion-exchanged water was placed in a miscellaneous bottle and concentrated under reduced pressure. After 5 (TC vacuum drying for 3 hours, the residual weight was measured. According to the above measured value, the weight % of the anion conductive resin dissolved in water was calculated] It is evaluated as water resistance of 0.5% by weight or less. 4) Evaluation of solubility of anion conductive resin (actual concentration/dissolution ratio) The solubility evaluation method of an anion conductive resin is carried out by a supernatant known by centrifugation. In the actual concentration measurement, the actual concentration ratio of the dissolved concentration is used as an index for solubility evaluation. In this embodiment, the solvent used was propanol. First, the ion conductivity imparting agent 1 〇ml was placed in a centrifuge tube having a capacity of 15 ml, and a centrifuge (H-3H manufactured by Kokusan) was set. The number of revolutions of the centrifuge was 2,500 rpm, 3000 rpm, and 5 000 rpm, respectively. Centrifuge the insoluble ingredients for a minute. After centrifugation at 5000 rpm, about 2 g of the supernatant was taken, placed in a weighing bottle, and naturally dried for 5 hours. Thereafter, the solvent was removed by vacuum drying, the weight of the remaining resin was weighed, and the actual concentration of the anion conductive resin in the supernatant was measured, and the ratio of the actual concentration to the dissolved concentration was calculated. 5) Evaluation method of fuel cell The obtained membrane-electrode assembly was placed in a fuel cell for evaluation (FC05-01SP-REF, manufactured by Electrochem Co., Ltd.) to form a single cell, and oxygen 34 201204755 (four) into rnmi/min pure oxygen' At the same time, the fuel is passed into the Qing 1/min pure wind to generate electricity. The battery temperature is 9 (rc, the humidification temperature of the two poles and the temperature of the battery - the 'degree of 1Gn. The open circuit voltage of the battery that has been operated for π hours beforehand is measured. This value is in the pool. 〇. 9V or more is evaluated as good. Fuel electricity production example 1 (manufacture of a resin containing a gas methyl group) Commercially available polystyrene-poly(ethylene-terminated butyl polystyrene triblock copolymer (weight average molecular weight 50,000, styrene content 30 weight) %) 15.6g (containing 61mmol of stupid ring) dissolved in 2〇〇mi gas and 2i2g of chloromethyl decyl ether (263 with 〇1), and then added tin (IV) gas 3.95g (15mmol , 25 mol%), reacted at 35 to 40 ° C for 2 hours, and introduced the gas methyl group into the resin. 50 ml of the 1H-saturated and water-mixed solution of hydrazine was added to the reaction solution, and after the reaction was terminated, the aqueous decyl alcohol solution was introduced. The resin is precipitated, washed with a non-alcoholic alcohol several times, and dried to form a resin containing a gas methyl group to obtain a polystyrene-poly(extended ethyl-extended propyl)-polystyrene triad introduced into the benzene ring. 16.2 g of a segment copolymer. Production Example 2 (Production of 2 - (3 - "Styry Propoxyl) Tetrahydroanthracene B South)) 3-Dipropanol 25 g (180 Methyl) was dissolved in 10 ml of a gas mixture, and 3 g (17 mmol) of p-toluenesulfonic acid was added thereto, and the mixture was stirred at room temperature, and a solution of dihydropyran 16 g (190 mol) in chloroform was added thereto, and the mixture was stirred overnight at room temperature. The aqueous solution of sodium carbonate was washed, and the chloroform layer was distilled off under reduced pressure to give 33 g of 2-(3-bromopropyloxy)tetrahydropyran ( 142 mmol, 79%). Example 1 〇· i4g magnesium (shaving sheet 35 201204755) (60 mmol) was added to tetrahydrofuran. 'A very small amount of iodine was added to activate magnesium. Here, in order to prepare a Grignard reagent, 2_(3_bromo) manufactured in Production Example 2 was slowly dropped. A solution of tetrahydrofuran in a tetrahydrofuran solution of 14 g (60 mmol) was added to the tetrahydrofuran solution immediately after the start of the dropwise addition. After the completion of the dropwise addition, 16 g of tetrahydroanthracene containing the gas methyl group-containing resin produced in Production Example 1 was dropped. The mixture was stirred overnight at room temperature. Thereafter, 0.11 hydrochloric acid was added to the solution. 200 ml 'Removing the protecting group while precipitating the resin. The resin was washed with decyl alcohol, and after drying, it was dissolved in 2 ml of gas. Here, 17 g of three deserts (63 nm 〇l) were dropped, and stirred at room temperature overnight. The gas-like solution was dripped into the vigorous stirring. 1 mol / L sodium carbonate aqueous solution 5 〇〇 m 1 , decomposition of the remaining phosphorus tribromide. After that, the resin was filtered off under reduced pressure to remove the resin. The resin was washed with methanol and dried. The resin was added to the mixed tridecylamine. 3 〇 〇 重量% aqueous solution 144g (triamylamine is 731mm 〇 1), acetone i 〇 4g, ion exchange water 448g in an aqueous solution, stirred at room temperature overnight to form a 4-stage ammonium salt. After the hydrochloric acid, it was stirred for 1 hour, and after removing excess trimethylamine, the resin was filtered. The obtained resin is suspended in an excess of 0.5-Bu 1 /]-aqueous sodium hydroxide solution, and the relative ions of the 4-stage ammonium group are ion-exchanged from the bromide ion to the hydroxide ion, and then washed with ion-exchanged water and dried to obtain 14 g of an anion conductive resin. The anion exchange capacity of the obtained anion conductive resin, the water solubility in 2{rc, and the durability of the anion parent group are shown in Table 1. The bonding resin 0 for forming a catalyst electrode layer made of a synthetic anion conductive resin is mixed with 75 g of propanol and dissolved to obtain an ion conductivity imparting agent for forming a catalytic electrode layer. The dissolution of the anion conductive resin of the ion conductivity imparting agent for forming the obtained catalyst electrode is used. 201204755 I. Raw, flattening, 'fruit (actual concentration / ratio of dissolved concentration) is shown in the table. To the 3 g of the ion conductivity imparting agent for forming the catalyst electrode layer, a commercially available carbon supporting 45 5% knob AA ^ ^ · and autumn 4 b. 5 / ° platinum (Tianzhong Precious Metal Industrial Co., Ltd., fuel cell) was added. Using catalyst TFP ! np κ np, beer 蜾 [ECl 〇 E5 〇 E) 〇 _5g with a small amount of ion-exchanged water and 0. 5 g of 1-propanol, the method of $ >> Paste, modulation catalyst electrode layer

A composition for forming. The composition of the catalyst layer for the formation of the catalyst electrode layer is as shown in the patent example. The platinum adhesion amount on the anion exchange membrane carried by the sample is as follows: the screen is printed on the ground, and dried at room temperature for 15 hours. (4) An electrode catalyst layer for forming a fuel electrode. Similarly, in the anion, the electrode catalyst layer for the oxygen electrode is formed on the inner surface of the father's membrane, (., 5邶-platinum-2) is sandwiched between two sheets of carbon paper (Tonghe Corporation TGP-H-G60) An anion exchange membrane in which the electrode catalyst layer was formed on both surfaces was formed to form a membrane-electrode assembly. This joined body was incorporated into the fuel cell for evaluation, and the open circuit voltage of the fuel cell was measured. Examples 2 to 8 The types of polystyrene-poly(ethylidene-propyl)-polystyrene triblock copolymer in Production Example 1 and the gas introduced into the chloromethyl group were changed as shown in Table 1. The amount of the tin (IV) catalyst was used, and the produced chloromethyl group-containing resin was used, and the anion conductive resin was produced in the same manner as in the examples. The anion of the obtained anion conductive resin was hydrolyzed, and the durability of the water at 20 C and the durability of the anion exchange group were as shown in the table. The bonding resin 〇 5g# of the catalyst electrode layer formed of the anion conductive resin synthesized in Examples 2 to 8 was mixed and dissolved to obtain an ion conductivity imparting agent. Using the obtained catalyst electrode to open the evaluation result of the solubility of the anion conductive resin of the ion conductivity imparting agent of 2012 201255 (the ratio of the actual concentration to the dissolved concentration) is shown in Table 。. Thereafter, using the ion conductivity imparting agent, a composition for forming an electrode catalyst layer was prepared in the same manner as in Example ,, and the composition was used in the same manner as in Example 1 to form an anion exchange membrane and a catalyst electrode layer. The gas diffusion layer constitutes a (four)-electrode assembly, and the open circuit voltage test of the fuel cell is evaluated. The results are shown in Table 1. Comparative Example 1 * The chloromethyl group-containing resin produced in Production Example 1 was impregnated into an aqueous solution containing 2 G equivalent of trimethylamine relative to the gas amount of the gas-containing methyl group-containing resin, and a 4-stage ammonium saltation was formed as an anion. Conductive resin. The anion exchange capacity of the obtained anion conductive resin, the water solubility to the I 2 generation, and the durability of the anion exchange group are shown in the table. A bonding resin for forming a catalyst electrode layer composed of a synthetic anion conductive resin was used, and an ion conductivity imparting agent was obtained as in the same manner. The evaluation result of the solubility of the ion conductive anion conductive resin using the centripetal electrode of the obtained catalyst electrode (the actual concentration/dissolution concentration is shown in Table 1. After that, using this ion enthalpy filling, 14 secret 1 The conductivity imparting agent is the same as the method of the first embodiment, and the combination of the catalytic catalyst electrode layer is formed by using the composition 'the method of the first embodiment' to form an anion exchange, a catalyst electrode layer and a gas diffusion layer. The membrane-electrode junction 艚, ° estimated the fuel cell open circuit voltage test. The results are shown in Table 1. Comparative Example 2 38 201204755 In addition to the gas-containing sulfhydryl resin of Example 5, the same as Comparative Example 1 An anion conductive resin was produced, and the anion exchange capacity of the obtained anion conductive resin, the water solubility at 20 ° C, and the durability of the anion exchange group are shown in Table 1. The composition was composed of a synthetic anion conductive resin. The bonding resin for forming a catalyst electrode layer, and the ion conductivity imparting agent for forming a catalyst electrode layer are obtained by the same. The ion conductivity for forming the f-electrode of the obtained catalyst is used. The solubility evaluation result of the anion conductive resin of the pretreatment (the ratio of the actual concentration/dissolution concentration) is shown in Table 1. Then, using this ion conductivity imparting agent, the catalyst electrode layer was formed in the same manner as in Example 1. The composition used was the same as the method of Example 1 to form a tantalum electrode joint composed of an anion exchange membrane, a catalyst electrode layer, and a gas diffusion buffer, and the open circuit voltage test of the fuel cell was evaluated. 1 shows [Table 1] Example Copolymer type vaporized tin catalyst amount (mmol) 1 SEBS1 15 2 SEBS1 8 3 SEBS1 29 4 SEPS1 4 5 SEPS1 6 6 SEPS1 8 7 SEBS2 6 8 SEPS2 15 Comparative Example 1 SEBS1 15 Comparative Example 2 SEPS1 6 Anion exchange capacity (mmol/g) Anion exchange anion exchange actual base fuel exchange base resistance/dissolution pool open-time long-term concentration ratio road voltage _(50°〇, % (90°〇,% __(%) 99 99 92 Good 99 99 89 Good 99 99 81 Good 99 99 94 Good 99 99 92 Good 99 99 93 Good 99 99 91 Good 99 99 83 Good 99 87 92 Good 99 88 84 good Solubility to water (wt%) 0. 03 0.02 0.04 0.01 0. 02 0. 03 0.02 0.03 0. 05 0. 03 39 201204755 • SEBSl: polystyrene-poly(extended ethyl-butylene)-polystyrene The triblock copolymer has a weight average molecular weight = 50,000 and a styrene content of 30% by weight. • SEPS1: polystyrene-poly(ethyl-extended propyl)-polystyrene triblock copolymer having a weight average molecular weight = 700 00 and a styrene content of 65% by weight. • SEBS2: polystyrene-poly(ethylene-tert-butyl)-polystyrene triblock copolymer having a weight average molecular weight = 50,000 and a styrene content of 67% by weight. • SEPS2: polystyrene-poly(ethyl-extended propyl)-polystyrene triblock copolymer having a weight average molecular weight = 50,000 and a styrene content of 30% by weight. [Simple description of the diagram] None [Key component symbol description] None 40

Claims (1)

201204755 VII. Patent application scope: 1 _ A poorly water-soluble anion conductive resin which is a non-crosslinked block copolymer having an aromatic ring having an ammonium salt as shown in the following formula a hydrophilic unit of the group and a hydrophobic unit not having the ammonium salt, -(CH2)nN + R1R2R3(X)z (1) (wherein η is an integer of 3 to 6, and R1, ^ and R3 are each A linear or branched alkyl group having 15 carbon atoms, R1, R2 and R3 may be bonded to each other in whole or in part to form a ring 'X is a relative anion, and z is a reciprocal of the valence of X). 2. The method for producing an anion conductive resin according to claim 1, wherein the halogen compound having a protecting group as shown in the following formula (2) is reacted with a magnesium or an alkyllithium compound to form a lattice. Grignard reagents or organolithium compounds, HaK〇H2)nx-OY (2) (wherein Y represents a protecting group for a hydroxyl group, Ha 1 represents chlorine, bromine or iodine, and η is the same as defined in formula (1) , X is an integer of 1 or more and nl or less.) The Grignard reagents or organolithium compounds react with a water-insoluble tree stalk having a non-crosslinked intercalated copolymer of cristobalite. The water-soluble resin has a unit having a substituent represented by the following formula (3) in the aromatic ring and a hydrophobic unit, -(CH2)X-Hal' (3) (wherein Hal represents chlorine, bromine or Iodine, χ is an integer of i or more, π-1 or less 41 201204755 (but η is the same as defined in formula (1))) After removing the protecting group of the hydroxyl group, the hydroxyl group is converted into a γ or a sulfonate, and then reacted with a tertiary amine. . 3. A bonding resin for forming a catalyst electrode layer, which is composed of the resin described in the first aspect of the patent application. 4_ An ion conductivity imparting agent for forming a catalyst electrode layer, comprising a solvent and a bonding resin for forming a catalyst electrode layer according to claim 3 of the patent application. A composition for forming a catalyst electrode layer, which comprises the catalyst electrode layer forming agent, the electrode catalyst, and the solvent described in the fourth aspect of the patent application. A catalyst electrode layer is formed by a composition for forming a catalyst electrode layer according to item 5 of the patent scope. A membrane-electrode assembly comprising a catalyst electrode layer of the sixth aspect of the patent application as a member. 8. A fuel cell electrode assembly as a member, comprising the film of claim 7 - 42