JP5245233B2 - Silicone rubber composition for polymer electrolyte and proton conductive polymer electrolyte membrane - Google Patents

Description

The present invention relates to a silicone rubber composition for a polymer electrolyte and a proton conductive polymer electrolyte membrane, and more specifically, a fuel cell, water electrolysis, hydrohalic acid electrolysis, salt electrolysis, oxygen concentrator, humidity sensor, gas sensor, etc. suitably the ion conductive membrane or the like used for a strength and ionic conductivity of the silicon combines - consisting of oxygen crosslinked structure ionically conductive materials polyelectrolyte silicone rubber composition using, as well as curing of the composition The present invention relates to a proton conductive polymer electrolyte membrane made of a material.

  Since the ion conductive material has the property of binding firmly to specific ions or selectively permeating cations or anions, it is formed into particles, fibers, or membranes, electrodialysis, It is used for various applications such as diffusion dialysis and battery diaphragm. For example, a polymer electrolyte fuel cell uses a polymer electrolyte membrane to electrochemically oxidize a fuel such as hydrogen or methanol in the cell, thereby converting the chemical energy of the fuel directly into electric energy and taking it out. In recent years, it has attracted attention as a clean electrical energy supply source. In particular, in the case of a polymer having a functional group such as a sulfonic acid group in a polymer chain as a proton conductive membrane, a high output density is obtained and a low-temperature operation is possible, which is expected as a power source for electric vehicles.

  The basic structure of such a fuel cell is composed of an electrolyte membrane and a gas diffusion electrode having a pair of catalyst layers bonded to both sides thereof, and further a current collector is disposed on both sides thereof. By supplying hydrogen or methanol as fuel to one electrode (anode), oxygen or air as oxidant to the other electrode (cathode), and connecting an external load circuit between both electrodes, the fuel When operating as a battery, protons produced at the anode move to the cathode side through the electrolyte membrane and react with oxygen at the cathode to produce water.

  The electrolyte membrane functions as a proton transfer medium and a hydrogen gas or oxygen gas diaphragm. Therefore, in addition to high proton conductivity, strength, and chemical stability, gas sealing properties are required. In particular, in the case of fuel cells and water electrolysis, peroxide is generated in the catalyst layer formed at the interface between the electrolyte membrane and the electrode, and the generated peroxide diffuses and becomes a peroxide radical, causing a deterioration reaction. Therefore, it is difficult to use a hydrocarbon-based electrolyte membrane having poor oxidation resistance. Therefore, in general, a perfluorosulfonic acid membrane having high oxidation resistance is used although it is expensive.

  As electrolyte membranes in practical use, fluorine-based membranes having perfluoroalkylene as the main skeleton and partially having ion-exchange groups such as sulfonic acid groups and carboxylic acid groups at the end of the perfluorovinyl ether side chain are mainly used. ing. As such a fluorine-based electrolyte membrane, Nafion membrane (registered trademark: Du Pont), Dow membrane (registered trademark: Dow Chemical), Aciplex membrane (registered trademark: Asahi Kasei Kogyo Co., Ltd.), Flemion membrane (registered trademark) : Asahi Glass Co., Ltd.).

  The current polymer electrolyte fuel cell is operated in a relatively low temperature range from room temperature to about 80 ° C. The limitation of the operating temperature is that the fluorine-based membrane used has a glass transition temperature (Tg) near 130 ° C., and the ion channel structure contributing to proton conduction is destroyed at a temperature higher than this. Therefore, it is due to such a factor that it can be practically used only at 100 ° C. or lower. The low operating temperature causes a demerit that the power generation efficiency is low for the fuel cell. If the operating temperature can be set to 100 ° C. or higher, the power generation efficiency is improved and the waste heat can be used, so that energy can be used more efficiently. Further, if the operating temperature can be raised to 120 ° C., not only the improvement of efficiency and utilization of waste heat but also the possibility of realizing an inexpensive fuel cell can be realized by expanding the range of catalyst material selection.

  In the current proton-conducting membrane, the presence of water is essential as a substance that plays a role in proton transmission, which is one of the causes that make high-temperature operation difficult. The proton conductive membrane represented by Nafion is greatly influenced by the proton conductivity depending on the water content in the membrane, and does not exhibit proton conductivity in the absence of water. In order to always have water, it is necessary to feed fuel such as hydrogen in a humidified state. The necessity of strict and complicated water content control in the membrane by fuel humidification complicates the structure of the fuel cell and causes failure and the like. At the same time, pressurization is required at a high temperature exceeding the boiling point of water, which is 100 ° C., and the burden on the apparatus becomes large, for example, the apparatus becomes large. In particular, when the temperature exceeds 150 ° C., a considerably high pressure is required, which not only increases the cost of the fuel cell but is not preferable from the viewpoint of safety.

  As described above, the fluorine-based electrolyte has the disadvantages that it is difficult to manufacture and is very expensive, and the current fluorine-based electrolyte has a problem that it cannot sufficiently cope with high-temperature operation of a fuel cell or the like. Therefore, development of an ion conductive / ion exchange material to replace the fluorine-based electrolyte has been desired, and silicon polymers having high heat resistance and oxidation resistance have already been proposed.

  One of them has an organic polymer having polytetramethylene oxide as a main skeleton, disclosed in JP-A No. 2001-307545 (Patent Document 1), and a three-dimensional crosslinked structure with a silicon-oxygen bond, A proton conductive membrane having a protonic substance and water in the membrane, and a proton conductive membrane having polysiloxane as a main skeleton disclosed in JP-A-2004-55165 (Patent Document 2).

  The proton conductive membranes disclosed in Patent Documents 1 and 2 are improved in heat resistance by an inorganic material component or polysiloxane, but on the other hand, the strength is not sufficient and is brittle. In particular, when operating as a fuel cell, the membrane is destroyed by gas pressure and impact. This is because the membrane material lacks tensile strength and flexibility. In addition, the three-dimensional crosslinked structure has a problem in that the proton conductivity is not sufficient, and the proton conductivity is low particularly at low humidity.

  In JP 2002-184427 A (Patent Document 3), a cross-linked product combining a mercapto group-containing alkoxysilane, a boron oxide and another alkoxysilyl compound is formed, and then oxidized to provide heat resistance. A method for producing a proton conducting membrane having the following is disclosed. However, in this method, the crosslinked structure of mercapto group-containing alkoxysilane and boron oxide and the crosslinked structure of mercapto group-containing alkoxysilane, boron oxide and other alkoxysilyl compounds are all obtained as powders. Therefore, it is impossible to form a film by itself. Therefore, it is necessary to form a composite with another polymer material for film formation, but even if the crosslinked body itself has high heat resistance, the heat resistance of the composite polymer material is inferior, so the heat resistance as a film is not necessarily high. It was not.

  Japanese Patent Application Laid-Open No. 2006-131770 (Patent Document 4) also discloses a method for producing a conductive film by forming a crosslinked body in which a mercapto group-containing alkoxysilane and another alkoxysilyl compound are combined, and then oxidizing. It is disclosed. However, in this method, only a conductive film having a surface resistance of at most 10Ω / □ level can be obtained, and its application is limited to the field of surface coating, and it cannot be used for an electrolyte film.

  Non-patent document 1 (Solid State Ionics, Vol. 74, p. 105, 1994) also crosslinks a combination of a mercapto group-containing alkoxysilane and another alkoxysilyl compound, and oxidizes. A method for obtaining an electrolyte material is disclosed. However, although there is no detailed description of the material form and the like here, it has been clearly shown that it exhibits deliquescence at high humidity and cannot be used as a proton conductive membrane.

  Non-Patent Document 2 (Kaliaguine, Microporous and Mesoporous Materials, Vol. 52, pp. 29-37, 2002) is a mixture of mercapto group-containing alkoxysilane and tetraethoxysilane in various ratios, and the mixture is a surfactant. A method of obtaining an electrolyte material having microscopic pores that function as ion channels by crosslinking in the presence of the like and subsequent oxidation is disclosed. However, even the membrane obtained by this method does not sufficiently exhibit the effect on proton conductivity under low humidity.

JP 2001-307545 A JP 2004-55165 A JP 2002-184427 A JP 2006-131770 A Solid State Ionics, 74, 105, 1994 Kaliaguine, Microporous and Mesoporous Materials, 52, 29-37, 2002

The present invention has been made in view of the above circumstances, and is a material for a proton conductive membrane that is excellent in sealability due to high elasticity, has little fluctuation in proton conductivity due to changes in humidity, and is particularly excellent in proton conductivity under low humidity. obtained silicon - oxygen comprising a crosslinked structure ion conducting materials polyelectrolyte silicone rubber composition using, to provide the proton-conducting polymer electrolyte membrane having rubber elasticity formed of a cured product of the composition Objective.

  As a result of intensive investigations to achieve the above object, the present inventors have determined that an alkoxysilane having an epoxy group and an alkoxysilane having a sulfur atom-containing group such as a mercapto group are present in the presence of water and an oxidizing agent. Reaction is carried out to cause co-hydrolysis / condensation of both alkoxysilanes, conversion of a sulfur atom-containing group to a sulfonic acid group by the oxidizing agent, ring opening of the epoxy group, and condensation of a hydroxyl group generated based on this. The resulting silicon-oxygen crosslinked structure is a good proton conductive material, and is further composed of a cured silicone rubber composition containing a vinyl group-containing organopolysiloxane blended with the proton conductive material. The highly functional polymer electrolyte membrane is easy to manufacture, low in cost, excellent in strength, has rubber elasticity, maintains gas seal characteristics, and has high heat resistance. High proton conductivity even at low humidity, found that it is possible to realize a fuel cell that may correspond to the high temperature operation, the present invention has been accomplished.

Accordingly, the present invention provides the following silicone rubber composition for polymer electrolyte and proton conductive polymer electrolyte membrane.
[1] (A) The following average composition formula (1)
R _a SiO _{(4-a) / 2} (1)
(In the formula, R is the same or different unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, provided that the total number of vinyl groups in one molecule is 2 or more, and a is 1.95 to 2 .05 represents a positive number.)
A vinyl group-containing organopolysiloxane having a terminal end blocked with a triorganosilyl group or a diorganohydroxysilyl group: 100 parts by mass,
(B) An alkoxysilane having an epoxy group and an alkoxysilane having a sulfur atom-containing group are reacted in the presence of water and an oxidizing agent to co-hydrolyze / condense both alkoxysilanes, and a sulfur atom by the oxidizing agent. Ion conductive material comprising a silicon-oxygen cross-linked structure obtained by converting a contained group into a sulfonic acid group, ring opening of the epoxy group and condensation of a hydroxyl group generated based on the ring opening: 20 to 400 Parts by mass,
(C) Crosslinking agent: A silicone rubber composition for polymer electrolyte membranes, containing 0.1 to 10 parts by mass.
[2] The polymer electrolyte membrane according to [1], wherein the component (B) is further added with a nitrogen-containing compound to form a salt of the nitrogen-containing compound and the sulfonic acid group of the ion conductive material. Silicone rubber composition.
[3] The silicone rubber composition for a polymer electrolyte membrane according to [2], wherein the nitrogen-containing compound is a nitrogen-containing heterocyclic compound selected from the group consisting of imidazole, pyrazole, triazole, and tetrazole.
[4] A proton conductive polymer electrolyte membrane having rubber elasticity made of a cured product of the silicone rubber composition for a polymer electrolyte membrane according to any one of [1] to [3].

According to the present invention, it is possible to obtain a silicon-oxygen crosslinked structure that can be a polymer electrolyte material that is excellent in ion conductivity, easy to manufacture, low in cost, excellent in strength, and high in heat resistance. The cured product of the above-mentioned silicone rubber composition is excellent in sealing properties due to its high elasticity, has little fluctuation in proton conduction performance due to changes in humidity, and can be a proton-conducting polymer electrolyte membrane that is particularly excellent in proton conduction performance under low humidity. .
The proton conductive polymer electrolyte membrane of the present invention can be widely used in fuel cells, water electrolysis, hydrohalic acid electrolysis, salt electrolysis, oxygen concentrators, humidity sensors, gas sensors and the like.

  The polymer electrolyte membrane of the present invention includes a first step of preparing a mixture solution of an alkoxysilane having an epoxy group and an alkoxysilane having a sulfur atom-containing group such as a mercapto group, and water and an oxidizing agent are added to the solution. The both alkoxysilanes are cohydrolyzed / condensed, the sulfur atom-containing group is converted into a sulfonic acid group by the oxidizing agent, the epoxy group is opened, and the hydroxyl group generated based on this is condensed to form silicon. A second step of producing an oxygen-crosslinked structure, and the silicon-oxygen crosslinked structure is mixed with a vinyl group-containing organopolysiloxane to form a mixture in which the silicon-oxygen crosslinked structure is dispersed in the organopolysiloxane. And a proton conductive polymer electrolyte membrane having rubber elasticity by curing a silicone rubber composition obtained by adding a crosslinking agent to the mixture. It is produced from the fourth step of forming.

  The silicon-oxygen crosslinked structure of the present invention includes a first step of preparing a mixture solution of the above-described alkoxysilane having an epoxy group and an alkoxysilane having a sulfur atom-containing group such as a mercapto group, and water and oxidation in the solution. An agent is added to cause both the alkoxysilanes to co-hydrolyze and condense, to convert the sulfur atom-containing group into a sulfonic acid group by the oxidizing agent, to ring-open the epoxy group, and to condense the hydroxyl group generated based on this. And the second step of producing a silicon-oxygen cross-linked structure.

  The raw material of the silicon-oxygen crosslinked structure used in the first step is composed of the following alkoxysilane having an epoxy group and alkoxysilane having a sulfur atom-containing group.

As the alkoxysilane having an epoxy group, those represented by the following general formula (I) can be used.
Y-SiX _n R _3-n (I)
(In formula (I), X represents an alkoxy group or an aryloxy group, Y represents an epoxy group-containing group, R represents a monovalent organic group, and n represents an integer of 1 to 3)

  In the formula (I), X is an alkoxy group or an aryloxy group. Specific examples thereof include a methoxy group, an ethoxy group, a propanoxy group, a butoxy group, a methoxymethyl group, an ethoxymethyl group, a methoxyethyl group, an ethoxyethyl group, and a phenoxy. Groups and the like. The number of carbon atoms of the alkoxy group is usually 1 or more and 10 or less, preferably 6 or less, more preferably 4 or less. The carbon number of the aryloxy group is 6 or more and 12 or less. If the number of carbon atoms of the alkoxy group or aryloxy group is large, the molecular weight of the hydrolyzed product increases, making it difficult to remove the hydrolyzed product, and when water is used as the solvent, the compatibility with water becomes poor. Since there is a possibility that the number of carbon atoms is small, an alkoxy group is more preferable, and a methoxy group, an ethoxy group, and the like are particularly preferable.

Y is an epoxy group-containing group, and is preferably the following (A) or (B).

  R is a monovalent organic group, and the carbon number of the organic group is usually 6 or less, preferably 3 or less, more preferably 1. The types of hydrocarbon groups include methyl groups, ethyl groups, propyl groups, butyl groups, pentyl groups, hexyl groups and other alkyl groups, methoxyethyl groups, ethoxyethyl groups, butoxyethyl groups, methoxypropyl groups, ethoxypropyl groups. And the like, and a methyl group is most preferable.

Examples of the alkoxysilane represented by the formula (I) include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltripropoxysilane, and 3-glycidoxy. Propyltri (2-methoxyethoxy) silane, 3-glycidoxypropyldimethoxymethylsilane, 3-glycidoxypropyldiethoxymethylsilane, 3-glycidoxypropyldibutoxymethylsilane, 3-glycidoxypropyldimethylmethoxy Silane, 3-glycidoxypropyldimethylpropoxysilane, 5,6-epoxyhexyltrimethoxysilane, 5,6-epoxyhexyltriethoxysilane, β- (3,4-epoxycyclohexyl) -ethyltrimethoxysilane , 3- Glycidoxypropyl Chill - di - include isopropenoxysilane alkoxy Sila down. The most preferred specific examples include 3-glycidoxypropyltrimethoxysilane (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.) and 3-glycidoxypropylmethyldimethoxysilane (KBM-402).

On the other hand, as the alkoxysilane having a sulfur atom-containing group, those represented by the following general formula (II) can be used.
Z- (R ′)-SiX _n R ¹ _3-n (II)
(In the formula (II), X is an alkoxy group or aryloxy group, Z is a sulfur atom-containing group that can be converted to a sulfonic acid group by oxidation, R ′ is a divalent hydrocarbon group, and R ¹ is a monovalent hydrocarbon group. N represents an integer of 1 to 3.)

  X is an alkoxy group or an aryloxy group, and specific examples include a methoxy group, an ethoxy group, a propanoxy group, a butoxy group, a methoxymethyl group, an ethoxymethyl group, a methoxyethyl group, an ethoxyethyl group, and a phenoxy group. . The requirements for the alkoxy group and the aryloxy group are the same as in the formula (I), and an alkoxy group having a small number of carbon atoms is preferred, and among them, a methoxy group, an ethoxy group, and the like are preferred.

  Z is a sulfur atom-containing group that can be converted to a sulfonic acid group by oxidation. Usually, it is a substituent containing a functional group containing a sulfur atom having a sulfur oxidation number of 5 or less, and specific examples include a substituent containing a mercapto group, a sulfite group, etc. Among these, a substituent containing a mercapto group Is preferred. The number of sulfur atoms is not limited, but is usually one.

  R 'is a divalent hydrocarbon group, and includes a group having a low reactivity with an oxidizing agent or a solvent by linking the above-described functional group such as mercapto group or sulfite group with silicon. The carbon number of the hydrocarbon group is usually 12 or less, preferably 6 or less, more preferably 4 or less, and most preferably 3 or less and 1 or more. Examples of the hydrocarbon group include an alkylene group, an arylene group, an alkenylene group and an alkynylene group, preferably an alkylene group and an arylene group, and most preferably an alkylene group. These groups may contain a substituent that does not affect the oxidation reaction of the sulfur atom. The alkylene group preferably has 4 or less carbon atoms, and preferred examples include a methylene group, an ethylene group, a propylene group, and a butylene group. The arylene group preferably has 9 or less carbon atoms, and preferred examples include a phenylene group, a methylphenylene group, and a dimethylphenylene group.

  Preferred groups for Z— (R ′) — include a mercaptoalkyl group and a mercaptoaryl group, with a mercaptoalkyl group being particularly preferred. Examples of the mercaptoalkyl group include a mercaptomethyl group, a 2-mercaptoethyl group, and a 3-mercaptopropyl group. Examples of the mercaptoaryl group include a mercaptophenyl group, and an alkyl mercaptophenyl group in which a benzene ring is substituted with a methyl group or an ethyl group.

R ¹ is a monovalent hydrocarbon group. The number of carbon atoms of the hydrocarbon group is usually 6 or less, preferably 3 or less, and usually 1. Examples of the hydrocarbon group include an alkyl group, and a methyl group is most preferable.
The number of n is 1 to 3, but if n is small, the strength of the proton conductor may not increase, so 2 or 3 is more preferable. When n is plural, the types of hydrolyzable substituents may be the same or different.

  The most preferred specific examples of the alkoxysilane represented by the formula (II) include 3-mercaptopropyltrimethoxysilane (KBM-803 manufactured by Shin-Etsu Chemical Co., Ltd.) and 3-mercaptopropylmethyldimethoxysilane (KBM). -802).

  The use ratio of the epoxy group-containing alkoxysilane and the sulfur atom-containing group-containing alkoxysilane is, as a mass ratio, epoxy group-containing alkoxysilane: sulfur atom-containing group-containing alkoxysilane = 9: 1 to 1: 9, particularly 8: 2-2. : 8 is preferable. If the proportion of the epoxy group-containing alkoxysilane is too large, proton conductivity may be reduced, and if it is too small, water-solubilization is likely to occur and the membrane may be dissolved out of the system.

  In the first step, first, the alkoxysilane having an epoxy group and the alkoxysilane having a sulfur atom-containing group are sufficiently mixed in the presence of an organic solvent.

  Here, as the organic solvent, one or more of alcohols, glycol derivatives, hydrocarbons, esters, ketones, ethers and the like are mixed and used. The organic solvent usually has 1 to 10 carbon atoms, preferably 8 or less, and more preferably 6 or less.

  Examples of alcohols include methanol, ethanol, isopropyl alcohol, n-butanol, isobutyl alcohol, octanol, n-propyl alcohol, and acetylacetone alcohol. As glycol derivatives, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-propyl ether, ethylene glycol mono n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, Examples include ethylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate. Examples of the hydrocarbons include benzene, kerosene, toluene, xylene and the like. Examples of the esters include methyl acetate, ethyl acetate, butyl acetate, methyl acetoacetate, and ethyl acetoacetate. Examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, and acetyl acetone. Examples of ethers include ethyl ether, butyl ether, 2-α-methoxyethanol, 2-α-ethoxyethanol, dioxane, furan, and tetrahydrofuran.

  Among these organic solvents, alcohols that have high solubility in epoxy groups and sulfonic acid groups and are completely compatible with water are preferable. From the viewpoint of compatibility with water and ease of solvent removal later, the number of carbons in the alcohols is preferably from 1 to 6, more preferably 4 or less, and even more preferably 2 or less. Specifically, methanol, ethanol, isopropyl alcohol or butanol is preferable, and methanol or ethanol is particularly preferable.

  The amount of the organic solvent used is preferably 20 to 2000 parts by mass, particularly 80 to 200 parts by mass with respect to 100 parts by mass in total of the epoxy group-containing alkoxysilane and the sulfur atom-containing group-containing alkoxysilane. If the amount of the organic solvent added is too large, the composition may be combined with the organopolysiloxane to remove the solvent, which may be economically disadvantageous. If the amount is too small, gelation may occur during the production of the crosslinked structure, and stirring may occur. It may be insufficient and the reaction may not proceed sufficiently.

  Next, in the second step, water and an oxidant are added to the mixture solution to co-hydrolyze and condense the both alkoxysilanes, and the oxidant converts the sulfur atom-containing group into a sulfonic acid group. The ring opening of the epoxy group and the condensation of the hydroxyl group generated based on the ring opening are performed.

Here, the oxidizing agent is not particularly limited as long as it can oxidize a sulfur atom-containing group to a sulfonic acid group. However, an oxidizing agent soluble in a solvent such as alcohol or water is preferable, and hydrogen peroxide solution is particularly preferable. .
The oxidizing agent can also be added as water or an alcohol solution. In this case, as the alcohol, the same alcohols as described above can be used.

  The amount of the oxidizing agent is preferably 3 molar equivalents or more and more preferably 3 molar equivalents or less and 5 molar equivalents or less as an oxide equivalent with respect to 1 mol of the sulfur atom-containing group in the alkoxysilane. If the amount of the oxidizing agent is too small, there are cases where oxidation to the sulfonic acid is difficult to proceed and the hydrolysis / condensation products of both alkoxysilanes described above do not form a uniform solution. The upper limit of the amount of the oxidizing agent is not particularly limited, but is usually 5 molar equivalents or less, preferably 4 molar equivalents or less as an acid equivalent per 1 mol of the sulfur atom-containing group in the alkoxysilane. If the amount of the oxidizing agent is too large, an undesirable oxidation reaction may occur such as poor economic efficiency or oxidation of the neutralizing agent used in the subsequent process.

In addition, when an oxidizing agent such as H ₂ O ₂ is diluted, the reaction efficiency of sulfur oxidation is significantly reduced. At the same time, the diluted solvent may be oxidized to give undesirable by-products, while avoiding the danger of decomposition and explosion. For this reason, it is usually most desirable to use a commercially available 30% hydrogen peroxide solution as it is.
In this case, the amount of water used for hydrolysis must be equal to or greater than the total alkoxy groups of the alkoxysilane. From this point, the amount of water is selected. The amount of water to be added can be determined in consideration of the amount of water contained therein and the amount of water generated when hydrogen peroxide oxidizes sulfur atom-containing groups such as mercapto groups. Sometimes it is not necessary.

  In this reaction, the temperature and time for bringing both alkoxysilanes into contact with the oxidizing agent and water are not particularly limited, but are usually 0 to 100 ° C. for 2 hours to 3 days. It is preferable to hold or agitate for a time until a uniform solution is obtained. However, depending on conditions, the solution is solidified or gelled when all or a part of a predetermined amount of the oxidizing agent to be contacted is contacted. May cause solids to precipitate. Even in such a case, a uniform solution of the silicon-oxygen crosslinked structure can be obtained by bringing all of the predetermined amount of oxidant into contact with each other and maintaining the solvent in a state where the solvent does not evaporate.

By adding water and an oxidizing agent to the alkoxysilane mixture solution, the sulfur atom-containing group in the alkoxysilane having a sulfur atom-containing group is oxidized to a sulfonic acid group, and at the same time, hydrolysis and condensation of both alkoxysilanes are performed. The reaction proceeds, and further, a part or all of the epoxy group becomes acidic due to the formation of a sulfonic acid group, which causes the epoxy group to ring open and be converted to —CH (OH) —CH ₃ , resulting in a hydroxyl group. The hydroxyl group is involved in the condensation reaction, and the hydroxyl group is condensed with the hydroxyl group generated by hydrolysis of the alkoxysilane to produce a silicon-oxygen crosslinked structure.

  The molecular structure of the silicon-oxygen crosslinked structure is not particularly limited, and specific examples include linear, partially branched linear, branched, and network, preferably linear and branched. . Further, the viscosity of the solution is not particularly limited because it greatly varies depending on the concentration. For example, the viscosity value at 25 ° C. is preferably in the range of 1 to 50,000 mPa · s, and more preferably 5 to 1,000 mPa · s. A range is preferable. Here, this viscosity is a value measured by a rotational viscometer.

  The sulfonic acid group of the silicon-oxygen crosslinked structure of the present invention is chemically bonded to a silicon atom via a group R ′ having low reactivity with an oxidizing agent such as a hydrocarbon group or a solvent. Therefore, even when it is uniformly dissolved in a solvent such as water, the sulfonic acid group is not liberated as sulfuric acid.

  The concentration of the silicon-oxygen crosslinked structure in the solution is usually 10% by mass or more, preferably 40% by mass or more, and usually 99% by mass or less, preferably 95% by mass or less, more preferably 80% by mass or less. A higher concentration is preferable as long as siloxanes are dissolved. The concentration of the siloxanes in the solution and the silicon concentration derived from the siloxanes can be adjusted to a predetermined concentration by adding the above-described water and / or organic solvent as necessary, or removing only the solvent by vacuum distillation or the like. As an organic solvent here, the thing similar to the organic solvent mentioned above can be used.

Next, the silicone rubber composition for polymer electrolyte membrane of the present invention comprises the following components (A), (B), and (C).
(A) A vinyl group-containing organopolysiloxane represented by the following average composition formula (1) and having a terminal blocked with a triorganosilyl group or a diorganohydroxysilyl group:
R ² _a SiO _{(4-a) / 2} (1)
(In the formula, R ² is the same or different unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, provided that the total number of vinyl groups in one molecule is 2 or more, and a is 1.95 to Represents a positive number of 2.05.)
(B) the silicon-oxygen crosslinked structure produced above,
(C) Crosslinking agent

The vinyl group-containing organopolysiloxane (A) used in the present invention is a main component of the composition and has a great influence on the strength. The vinyl group-containing organopolysiloxane (A) is represented by the following average composition formula (1), and the terminal is a triorganosilyl group R: It is blocked with ² ₃ Si- or a diorganohydroxysilyl group R ² ₂ Si (OH)-.
R ² _a SiO _{(4-a) / 2} (1)
(In the formula, R ² is the same or different unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, provided that the total number of vinyl groups in one molecule is 2 or more, and a is 1.95 to Represents a positive number of 2.05.)

In the above formula (1), R ² is the same or different monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, and preferably 1 to 8 carbon atoms. Is an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group or a hexyl group; an aryl group such as a phenyl group, a tolyl group or a xylyl group; an aralkyl group such as a benzyl group or a phenethyl group; Examples thereof include monovalent hydrocarbon groups such as halogen-substituted alkyl groups such as propyl group and 3,3,3-trifluoropropyl group, preferably methyl group and phenyl group.

R ² has at least two or more vinyl groups in one molecule, and the content of vinyl groups in R ² is 0.01 to 10 mol%, particularly 0.05 to 5 mol%. It is preferable. The bonding position of the vinyl group is not particularly limited, and examples thereof include molecular chain end, molecular chain side chain, molecular chain end and molecular chain side chain.

  The molecular structure of the organopolysiloxane (A) is preferably linear or partially branched, and one type is used alone, or two or more types having different degrees of polymerization and molecular structures are used in combination. It's okay.

The degree of polymerization of the component (A) is an integer of 100 or more as R ² _a SiO _{(4-a) / 2} units, and preferably 200 to 100,000. If this unit is less than 100, the rubber strength characteristics are poor and the object of the present invention may not be achieved. Specifically, the component (A) is preferably an organopolysiloxane usually in the form of silicone raw rubber.

  Specifically, as the component (A), molecular chain both ends trimethylsiloxy group-capped dimethylsiloxane / methylvinylsiloxane copolymer, molecular chain both ends trimethylsiloxy group-capped methylvinylpolysiloxane, molecular chain both ends trimethyl Siloxy group-blocked methylvinylsiloxane / diphenylsiloxane copolymer, trimethylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane / diphenylsiloxane copolymer, both ends of molecular chain dimethylvinylsiloxy group-blocked dimethylpolysiloxane, both molecular chains Terminal dimethylvinylsiloxy-blocked methylvinylpolysiloxane, molecular chain both ends dimethylvinylsiloxy-blocked methylphenylpolysiloxane, molecular chain both ends dimethylvinylsiloxy-blocked dimethylsiloxane methylvinyl Roxane copolymer, dimethylvinylsiloxy group-blocked dimethylvinylsiloxy group copolymer at both ends of molecular chain, dimethylvinylsiloxy group-blocked dimethylsiloxane / diphenylsiloxane copolymer at both chain ends, silanol-blocked dimethylol at both ends of molecular chain Siloxane / methylvinylsiloxane copolymer, silanol-blocked dimethylsiloxane / diphenylsiloxane copolymer, silanol group-blocked methylvinylpolysiloxane, silanol-blocked methylvinylpolysiloxane, silanol-blocked dimethylsiloxane / methylvinylsiloxane -A methylphenylsiloxane copolymer is illustrated.

  The component (B) is the above-described silicon-oxygen crosslinked structure or a solution thereof. Since this solution is in the form of a strong acid, in order to cause peripheral corrosion and deterioration of the coexisting polymer, it is necessary to neutralize the sulfonic acid group with a basic compound to form a sulfonate.

As a basic compound, it can be neutralized with an aqueous solution of ammonia water, potassium hydroxide, an alcohol solution of sodium methoxide, etc., but this silicon-oxygen crosslinked structure is obtained by adding a nitrogen-containing compound to form a nitrogen-containing compound. By using a salt form of the compound and the sulfonic acid group of the silicon-oxygen crosslinked structure, it can be used as an ion conductive material even under low humidity. Especially, nitrogen-containing compounds, imidazole, pyrazole, triazole, it is preferable to use a nitrogen-containing heterocyclic compound selected from Tetorazo Le or Ranaru group.

  In conventional proton conductive materials and proton conductive material membranes, water is mostly used as an ion transfer aid. However, when high temperature operability is improved as in the present invention, at 100 ° C. or higher, While evaporation of water occurs and the performance as a sufficient ion transfer aid cannot be achieved, when a nitrogen-containing heterocyclic compound is used, the ion transfer aid can be made to work simultaneously with neutralization. it can.

The amount of the basic compound used for neutralizing the silicon-oxygen crosslinked structure is preferably not less than the equivalent of the number of moles of the sulfonic acid group and not more than 10 equivalents, and more preferably 2 to 5 equivalents. If the amount is less than the equivalent, it is acidic, and degradation due to cutting of the organopolysiloxane may occur. If the amount exceeds 10 equivalents, the rubber physical properties of the film may be deteriorated.
Moreover, the neutralization method can be quickly neutralized by adding a basic compound to the silicon-oxygen crosslinked structure solution with stirring. Since heat is generated at this time, it is desirable to cool in a water bath or the like.

  In particular, the blending amount of the component (B) that plays an important role in ion conduction is in the range of 20 to 400 parts by mass with respect to 100 parts by mass of the component (A) in terms of the pure component excluding the solvent in calculation, More preferably, it is the range of 50-200 mass parts. This is because, when the blending amount of the component (B) is less than 20 parts by mass with respect to 100 parts by mass of the component (A), the ionic conductivity of the obtained silicone rubber may be remarkably lowered, and 400 masses. When it exceeds the part, the fluidity of the obtained composition is remarkably lowered, and the handling workability of the composition may be extremely difficult.

The crosslinking agent (C) has a function as a curing agent. There are no limitations on the curing mechanism, and various conventionally known curing agents can be used as long as they are crosslinked and cured using radical reactions, addition reactions, etc., which are usually used for crosslinking of silicone rubber compositions. . For example, an organic peroxide is used in the radical reaction, and a combination of a platinum catalyst and an organohydrogenpolysiloxane can be used in the addition reaction.
The compounding amount of the component (C) is an amount capable of curing the organopolysiloxane of the component (A) and may be the same as that of a normal silicone rubber composition.

Among these, when using nitrogen-containing compounds such as amines, it is preferable to use organic peroxides that do not inhibit crosslinking. More specifically, examples of the organic peroxide curing agent include benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, o-methylbenzoyl peroxide, p-methylbenzoyl peroxide, and 2,4-dicumyl peroxide. 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, di-t-butyl peroxide, t-butyl perbenzoate and the like.
The compounding amount of the organic peroxide is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the component (A). In particular, the amount is preferably 1 to 5 parts by mass. If the addition amount is less than 0.1 parts by mass, the crosslinking density tends to be low and the rubber strength tends to decrease. If the amount exceeds 10 parts by mass, peroxide decomposition residues remain. It may be easier.

The method of cross-linking the silicone rubber composition used in the present invention into a conductive silicone rubber irradiates an uncured film with electromagnetic waves such as ultraviolet rays, electron beams, X-rays and γ rays having a wavelength shorter than that of visible light. It can also be done. Case of irradiation with ultraviolet light may be used a high-pressure mercury lamp, irradiation energy, for example in quantity of ultraviolet wavelength of 365nm, 20~20,000mJ / cm ^2, and more desirably 50~5,000mJ / cm ² irradiated be able to. Alternatively, irradiation with ultraviolet rays or the like and heat treatment can be used in combination. In this case, curing of the film forming component is promoted, and the hardness of the obtained transparent film may be increased. A photopolymerization initiator necessary for curing can be appropriately added.
Specific examples of the photopolymerization initiator include acylphosphine oxide (Lucirin TPO, manufactured by BASF), Darocur 1173 (hydroxyketone, manufactured by Ciba Specialty Chemicals), Irgacure 907 (aminoketone, Ciba Specialty Chemicals) Manufactured) and the like. In this case, an organopolysiloxane having at least two mercaptoalkyl groups in one molecule is used as a crosslinking agent.

  The silicone rubber composition for a polymer electrolyte membrane of the present invention can be obtained by the following steps (third and fourth steps). That is, in the third and fourth steps, (B) a silicon-oxygen crosslinked structure solution and (A) a vinyl group-containing organopolysiloxane are mixed. After mixing, a silicone rubber composition can be prepared by dissolving the silicon-oxygen crosslinked structure, removing the solvent that has helped uniform dispersion with the vinyl group-containing organopolysiloxane, and adding (C) a crosslinking agent.

First, the concentration of the siloxanes in the solution or the silicon concentration derived from the siloxanes of the component (B) neutralized with the basic compound is added by adding water or an organic solvent as described above, or by vacuum distillation or the like. Adjust to a predetermined concentration by removing only the solvent. Here, the concentration is desirably 30 to 90% by mass, and more desirably 40 to 80% by mass. If the amount is less than 30% by mass, the amount of mixing increases, so the mixing time becomes long and economically disadvantageous. If it exceeds 90% by mass, uniform dispersion of the silicon-oxygen crosslinked structure and the vinyl group-containing organopolysiloxane becomes difficult. May be.
Then, this (B) component and (A) component are mixed, and a siloxane mixture can be obtained by removing a solvent further. Drying at the time of removing the solvent is performed at a temperature of 60 ° C. or higher and 200 ° C. or lower, more preferably 80 ° C. or higher and 180 ° C. or lower, and further preferably 80 to 120 ° C. for 0.5 to 5 hours. In drying, known methods such as natural drying, heat drying, and pressure heating with an autoclave may be used.
Subsequently, after cooling to room temperature, (C) component is added to this mixture, and it is set as a composition.

  Alternatively, in the preparation of the silicone rubber composition of the present invention, the components (A) and (B) are mixed uniformly using a rubber kneader such as a two-roll, Banbury mixer, or dough mixer (kneader). The mixture can be mixed with the component (C) using two rolls.

  In the silicone rubber composition of the present invention, in addition to the above essential components, other conductive agents, reinforcing agents, foaming agents, flame retardants, and heat resistance are improved as necessary as long as they do not interfere with the effects of the present invention as optional components. Various additives such as an agent, a reaction control agent, a release agent, or a filler dispersant can be added.

As the reinforcing agent, reinforcing silica powder can be suitably used. The silica powder is added to obtain a silicone rubber having excellent mechanical strength. For this purpose, the specific surface area is 50 m ² / g or more, preferably 100 to 300 m ² / g. Preferably there is. If the specific surface area is less than 50 m ² / g, the mechanical strength of the cured product may be lowered. Examples of such reinforcing silica include fumed silica, precipitated silica, and the like, and those whose surfaces are hydrophobized with chlorosilane, hexamethyldisilazane, or the like are also preferably used. The addition amount of the reinforcing agent such as reinforcing silica powder is preferably 0 to 70 parts by mass, particularly 3 to 50 parts by mass with respect to 100 parts by mass of the organopolysiloxane of the component (A).

Further, a coloring agent such as Bengala, and a bulking agent such as pulverized quartz and calcium carbonate may be added. The flame retardant contains platinum-containing material, platinum compound and titanium dioxide, platinum and manganese carbonate, platinum and γ-Fe ₂ O ₃ , ferrite, mica to make the silicone rubber composition of the present invention flame retardant and fire resistant. Further, known additives such as glass fiber and glass flake may be added.

  As the dispersant, usual ones such as diphenylsilane diol, various alkoxysilanes, carbon functional silane, silanol group-containing low molecular weight siloxane can be used, but the amount is the minimum addition amount so as not to impair the effects of the present invention. It is preferable to stop.

The silicone rubber composition thus obtained can be molded into silicone rubber required by various molding methods such as injection molding, cast molding, mold pressure molding (hot press), and extrusion molding. it can.
In addition, although hardening conditions can be adjusted suitably, it is 80-200 degreeC, Preferably it is 100-180 degreeC, 5 seconds-60 minutes, Preferably it is about 20 seconds-30 minutes.

  The proton conductive polymer electrolyte membrane of the present invention comprises a cured product of the silicone rubber composition obtained above, and the silicone rubber composition is cross-linked and cured to achieve both mechanical strength and conductive properties. A proton conductive polymer electrolyte membrane having rubber elasticity can be obtained (fourth step).

General conditions for obtaining a proton conductive polymer electrolyte membrane can be obtained by crosslinking and forming the silicone rubber composition by hot pressing at a temperature of 100 to 200 ° C, preferably 120 to 180 ° C. . Here, the hot press conditions can be 1 to 30 minutes, particularly 5 to 20 minutes at a pressure of 10 to 100 kgf / cm ² , particularly 30 to 80 kgf / cm ² .

  Furthermore, the film | membrane with improved electroconductivity is obtained by immersing this film | membrane in acidic aqueous solution as needed. This step is a step of introducing protons into the sulfonic acid group in the membrane obtained up to the fourth step. Examples of the acidic solution include a phosphoric acid aqueous solution, a hydrochloric acid aqueous solution, and a sulfuric acid aqueous solution. The concentration of the acidic solution is preferably 0.05 to 5N. The immersion temperature is preferably 15 to 35 ° C., and the immersion time is preferably 1 to 60 minutes.

  The thickness of the proton conductive polymer electrolyte membrane of the present invention thus obtained is not particularly limited, but is preferably 0.001 to 1 mm, more preferably 0.01 to 0.5 mm.

The proton conductive polymer electrolyte membrane of the present invention is excellent in ion conductivity, easy to manufacture and low in cost, excellent in strength, and high in heat resistance. The fluctuation of proton conduction performance due to changes in humidity is small, and the proton conduction performance is particularly excellent under low humidity.
The proton conductive polymer electrolyte membrane of the present invention can be widely used in fuel cells, water electrolysis, hydrohalic acid electrolysis, salt electrolysis, oxygen concentrators, humidity sensors, gas sensors and the like.

  EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.

[Examples 1-4, Comparative Examples 1-3]
[Synthesis of silicon-oxygen crosslinked structure]
[Synthesis Example 1]
(1) Production of epoxy sulfonic acid group-containing resin (silicon-oxygen crosslinked structure) (Ep25)
3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-803) 156.8 parts by mass (0.8 mol) and γ-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM) -403) To 63.0 parts by mass (0.267 mol), 260 parts by mass of ethanol and 40 parts by mass of distilled water were added and dissolved at room temperature. When 288 parts by mass of a 30% aqueous hydrogen peroxide solution (2.54 mol) was added dropwise with stirring over 3 hours, the temperature gradually increased and at the same time the viscosity increased, oxidation of the sulfur atom-containing group and trimethoxysilane. The hydrolysis proceeded simultaneously to form a gel.

The gel-like material was redissolved when heated at 80 ° C. using an oil bath. When this solution was heated and stirred at 80 ° C. for 3 hours, a uniform transparent solution having a low viscosity was obtained.
An ester condenser was attached to the reaction vessel, and the mixture was further heated and stirred at 80 ° C. for 3 hours under a nitrogen stream to remove alcohols from the ester condenser and concentrated to obtain 440 g of a colorless and transparent uniform solution.

  In this solution, an alkoxysilane having an epoxy group and an alkoxysilane having a sulfur atom-containing group are reacted in the presence of water and an oxidizing agent to co-hydrolyze / condense both alkoxysilanes and sulfur by the oxidizing agent. A silicon-oxygen crosslinked structure obtained by converting an atom-containing group into a sulfonic acid group, ring-opening the epoxy group, and condensing a hydroxyl group generated based on the ring opening is a solvent containing water as a main component. It is a solution dissolved in The non-volatile content in the obtained solution was quantitatively determined by holding it in a dryer at 105 ° C. for 3 hours, and it was 44%. 1 g of this solution was dissolved in 25 g of water, and the content of sulfonic acid group was determined by titration with 0.1N NaOH aqueous solution (f = 1.004) using phenolphthalein as an indicator, and found to be 4.2 mmol / g. . This uniform solution is referred to as an epoxysulfonic acid group-containing resin (Ep25).

  This solution is, as shown below, an aqueous ammonia solution or 1-methylimidazole, gradually added with stirring and cooling until neutral to weakly basic with litmus paper to make a non-acidic solution. Used as a proton conductive material.

[Synthesis Example 2]
(2) Production of epoxysulfonic acid group-containing resin (silicon-oxygen crosslinked structure) (Ep50)
The same operation was carried out except that 188.8 parts by mass (0.8 mol) was used instead of 63.0 parts by mass (0.267 mol) of γ-glycidoxypropyltrimethoxysilane in Synthesis Example 1, and colorless and transparent 690 g of a homogeneous solution was obtained. This uniform solution is referred to as an epoxysulfonic acid group-containing resin (Ep50).

[Comparative Synthesis Example 1]
(3) Production of sulfonic acid group-containing resin (silicon-oxygen crosslinked structure) (S100)
The same operation was performed except that γ-glycidoxypropyltrimethoxysilane of Synthesis Example 1 was not used at all, to obtain 340 g of a colorless and transparent uniform solution. This uniform solution is referred to as a sulfonic acid group-containing resin (S100) containing no epoxy group.

[Comparative Synthesis Example 2]
(4) Production of epoxy group-containing resin (silicon-oxygen crosslinked structure) (Ep100)
γ-Glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-403) is dissolved in 188.8 parts by mass (0.8 mol) of 260 parts by mass of ethanol and 40 parts by mass of distilled water at room temperature. I let you. When 110 parts by mass of 0.05N hydrogen chloride aqueous solution was added dropwise with stirring at a constant rate for 3 hours, the temperature gradually increased and at the same time the viscosity increased and trimethoxysilane hydrolysis proceeded. This solution was heated and stirred at 80 ° C. for 3 hours, then an ester condenser was attached, alcohols were removed under a nitrogen stream, and concentration was performed to obtain 250 g of a colorless and transparent uniform solution. This uniform solution is referred to as an epoxy group-containing resin (Ep100).

Table 1 shows the results of measuring the nonvolatile content (105 ° C., 3 hours), refractive index, specific gravity, viscosity, and sulfonic acid group content of the resin solutions (1) to (4).
The non-volatile content of the resin solution is measured under conditions of 105 ° C. × 3 hours in accordance with JIS C 2103, the refractive index is measured by Abbe refractometer method in accordance with JIS K 0062, and the specific gravity is in accordance with JIS Z 8804. In accordance with buoyometer method, viscosity is measured by capillary viscometer method in accordance with JIS Z 8803, sulfonic acid group content is 0.1N NaOH aqueous solution using phenolphthalein indicator. It was measured by the acid titration method.
Moreover, the glass plate was immersed in these solutions, pulled up, and formed into a film by holding in a dryer. When the surface resistance of this film was quantified at an applied voltage of 10 V using a surface resistor Hiresta-UP MCP-HT450 manufactured by Mitsubishi Chemical Corporation, as shown in Table 1, Comparative Synthesis Examples 1 and 2 had poor film forming properties. In contrast, either of the film surface resistance was poor or the synthesis examples 1 and 2 showed that both the film forming property and the film surface resistance were good.

＊１）：温度２５℃、湿度３９％ＲＨ中で測定
＊２）：１０５℃で保持し、デシケータ中で２５℃に放冷後、直ちに測定

* 1): Measured at a temperature of 25 ° C and humidity of 39% RH * 2): Hold at 105 ° C, measure immediately after cooling to 25 ° C in a desiccator

(5) Production of neutralized salt of resin (silicon-oxygen crosslinked structure) (5-1) Preparation of ammonium salt To 100 parts by mass of the resin solution of (2) and (3) above, aqueous ammonia (28 %) 8 parts by mass were added dropwise to neutralize the acid. An ester condenser was attached to this reaction vessel, and this solution was heated and stirred at 70 ° C. for 5 hours under a nitrogen stream to remove a part of ethanol, and concentrated until the nonvolatile content in the obtained solution became 60% by mass. . This uniform solution is referred to as sulfonic acid-containing resin siloxane ammonium salt (hereinafter abbreviated as NH ₄ salt).

(5-2) Preparation of imidazole salt 22.6 parts by mass of methylimidazole was added dropwise to 100 parts by mass of the resin solutions (1) and (2) under water cooling to neutralize the acid. An ester condenser was attached to this reaction vessel, and this solution was heated and stirred at 70 ° C. for 5 hours under a nitrogen stream to remove a part of ethanol, and concentrated until the nonvolatile content in the obtained solution became 60% by mass. . This uniform solution is referred to as a sulfonic acid-containing resin siloxane imidazole salt (hereinafter abbreviated as “Imid-salt”).

When the NH ₄ salt solution was concentrated and dried, a hard resinous solid was obtained, which became a powder when pulverized in a mortar. On the other hand, the above-mentioned Imid-salt solution was concentrated to dryness, and became a highly viscous liquid.

[Production of composition and physical properties of silicone rubber]
(6-1) Manufacture of silicone rubber compound (KE-MU)
(CH _{3) 2} SiO units 99.50 _{mol%, (CH 3) (CH} 2 = CH) SiO units 0.475 mol% and _{(CH 3) 2 (CH 2} = CH) SiO 1/2 units 0.025 100 parts by mass of diorganopolysiloxane raw rubber composed of mol%, 40 parts by mass of Aerosil R-972 (fumed silica, manufactured by Nippon Aerosil Co., Ltd.), 5 parts by mass of terminal hydroxyl group dimethyl silicone oil (polymerization degree 10, dispersion aid) And heat treated at 160 ° C. for 2 hours to obtain a compound. This is a compound for silicone rubber (hereinafter abbreviated as KE-MU) containing silica having a silica content of 27.5% of the total nonvolatile components including polysiloxane.

(6-2) Mixing of KE-MU and resin solution In the formulations shown in Tables 2 and 3, to 100 parts by mass of the produced silicone rubber compound KE-MU, the NH ₄ salt solution 108 ~ of Ep50 and S100 obtained above. 167 parts by mass (65 to 100 parts by mass of polysiloxane as a nonvolatile component) and 5 parts by mass of fumed silica R-972 were kneaded with two rolls to prepare a mixture. The mixture was heat treated in a 120 ° C. hot oven for 2 hours to remove the solvent.

(7-1) Peroxide Crosslinking After kneading this mixture with two rolls, 4.0 parts by mass of C-8B (peroxide manufactured by Shin-Etsu Chemical Co., Ltd.) is added to 100 parts by mass of this compound, and these Was kneaded with two rolls to prepare a compound. Subsequently, this compound was press-molded at 165 ° C. for 10 minutes (pressure 70 kg / cm ² ) and post-cured at 120 ° C. for 4 hours to obtain a sheet having a thickness of 0.2 to 0.3 mm.

(7-2) UV crosslinking After kneading this mixture with two rolls, 1.2 parts by mass of (C) mercaptosiloxane obtained according to the following preparation example with respect to 100 parts by mass of this compound, Darocur 1173 as a sensitizer 0.6 parts by mass (ketone alcohol manufactured by Ciba Specialty Chemicals) was added, and these were kneaded with two rolls to prepare a compound. Subsequently, this compound was press-molded at room temperature (pressure 50 kgf / cm ² ) to obtain a sheet having a thickness of 0.2 to 0.3 mm.
The sheet was irradiated with ultraviolet rays using an ultraviolet irradiation device (high-pressure mercury lamp) manufactured by Igraphic (irradiation condition: irradiation energy of 200 mJ / cm ^{2 in the} 365 nm region twice, total 400 mJ / cm ² ), thickness 0. A 15 mm thin film silicone rubber sheet was obtained. The resulting silicone rubber sheet was post-cured at 120 ° C. for 4 hours.

[Preparation Example 1]
Synthesis of Mercapto Functional Group Polysiloxane Used at the Time of UV Crosslinking With respect to 19.6 parts by mass of 3-mercaptopropyltrimethoxysilane, 5.4 parts by mass (3 times equivalent) of water was added at room temperature and dissolved. The temperature of the mixture was cooled to 5 ° C., and 1.0 part by mass of 3.6% hydrochloric acid was added dropwise for hydrolysis. The temperature was raised to 15 ° C. and stirred for 1 hour, and further stirred at 70 ° C. for 3 hours. Neutralization was performed by adding dropwise 1.3 parts by mass of a 4.25% aqueous potassium hydroxide solution. After adding 20 parts by mass of butyl acetate and separating from the water layer, anhydrous magnesium sulfate was added for dehydration, followed by stripping at 60 ° C. and 2 mmHg to obtain 13.4 parts by mass of a mercapto functional group polysiloxane. The viscosity was 930 cs, the specific gravity was 1.175, the refractive index was 1.4935, and the non-volatile content was 99.2%. This oil is referred to as (C) mercaptosiloxane.

(8) Acid treatment The rubber sheet was immersed in a 1N phosphoric acid aqueous solution at room temperature for 30 minutes and then washed with water to introduce protons into the sheet.

The film strength of rubber properties was measured as the tensile strength (kgf / cm ² ) based on JIS K 6301.
An evaluation cell is prepared by sandwiching the obtained thin rubber sheet between stainless steel electrodes plated with gold, and resistance measurement is performed by an AC impedance method (LCR high tester manufactured by Hioki Electric, measurement frequency 0.1 Hz to 5 MHz). Proton conductivity was calculated. In addition, an electrical resistance value and electrical conductivity are values after phosphoric acid treatment.
These results are shown in Tables 2 and 3.
Moreover, when the dried sheet-like film of 2 cm in length and 4 cm in width was immersed in hot water at 80 ° C. for 1 hour and then dried and examined for the rate of change in weight, as shown in Table 2, in Example 1, Although the weight was reduced by 1%, the weight was reduced by 35% in Comparative Example 1.

  From the results shown in Tables 2 and 3, the polymer electrolyte membrane of the present invention shows excellent ionic conductivity with little decrease in strength even under high temperature and high humidity environments by comparing the comparative example with the examples. I understand that. Moreover, the film strength did not decrease significantly up to about 120 ° C., and materials suitable for various electrolyte membranes could be produced.

＊３） ＮＨ₄塩：アンモニアによる中和塩
＊４） Ｃ８Ｂ：信越化学工業（株）製パーオキサイド、純分４０％

* 3) NH ₄ salt: Neutralized salt with ammonia * 4) C8B: Peroxide manufactured by Shin-Etsu Chemical Co., Ltd., 40% pure

＊３） ＮＨ₄塩：アンモニアによる中和塩
＊５） Ｉｍｉｄ−塩：１−メチルイミダゾールによる中和塩
＊６） 飽和ＣａＣｌ₂・６Ｈ₂Ｏ水溶液を共存させたデシケータ中で制御した温度２５℃、湿度３１％ＲＨ中で測定
＊７） １０５℃で保持し、デシケータ中で２５℃に放冷後、直ちに測定

* 3) NH ₄ salt: neutralized salt with ammonia * 5) Imid-salt: neutralized salt with 1-methylimidazole * 6) Temperature controlled in a desiccator in the presence of a saturated aqueous CaCl ₂ · 6H ₂ O solution 25 ° C , Measured in a humidity of 31% RH * 7) Hold at 105 ° C, let cool to 25 ° C in a desiccator, and measure immediately

Claims (4)

(A) The following average composition formula (1)
R _a SiO _{(4-a) / 2} (1)
(In the formula, R is the same or different unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, provided that the total number of vinyl groups in one molecule is 2 or more, and a is 1.95 to 2 .05 represents a positive number.)
A vinyl group-containing organopolysiloxane having a terminal end blocked with a triorganosilyl group or a diorganohydroxysilyl group: 100 parts by mass,
(B) An alkoxysilane having an epoxy group and an alkoxysilane having a sulfur atom-containing group are reacted in the presence of water and an oxidizing agent to co-hydrolyze / condense both alkoxysilanes, and a sulfur atom by the oxidizing agent. Ion conductive material comprising a silicon-oxygen cross-linked structure obtained by converting a contained group into a sulfonic acid group, ring opening of the epoxy group and condensation of a hydroxyl group generated based on the ring opening: 20 to 400 Parts by mass,
(C) Crosslinking agent: A silicone rubber composition for polymer electrolyte membranes, containing 0.1 to 10 parts by mass.   The silicone rubber composition for a polymer electrolyte membrane according to claim 1, wherein the component (B) is further in the form of a salt of a nitrogen-containing compound and a sulfonic acid group of the ion conductive material to which a nitrogen-containing compound is added. object.   3. The silicone rubber composition for a polymer electrolyte membrane according to claim 2, wherein the nitrogen-containing compound is a nitrogen-containing heterocyclic compound selected from the group consisting of imidazole, pyrazole, triazole and tetrazole.   A proton conductive polymer electrolyte membrane having rubber elasticity made of a cured product of the silicone rubber composition for polymer electrolyte membrane according to any one of claims 1 to 3.