JP2002097272A - Polysiloxane, method for producing the same, and proton conductive material - Google Patents

Abstract

(57) [Problem] To provide a polysiloxane which becomes a self-supporting membrane material, has excellent proton conductivity, and has a small decrease in proton conductivity even under a high-temperature dry atmosphere, a method for producing the same, and a proton-conductive material. A silane compound (A) represented by the following general formula (1), a silane compound (B) represented by the following general formula (2), and at least one kind selected from phosphoric acid and sulfuric acid. A polysiloxane obtained by hydrolyzing and condensing a mixture with an acid component (C) and, if necessary, heating at 100 to 300 ° C. R ¹ _a Si (OR ² ) _4-a (1) (wherein, R ¹ is a monovalent functional group, R ² is a monovalent organic group, and a is an integer of 1 or 2. .) R ³ _b Si (OR ² ) _4-b ... (2) (wherein, R ³ represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group, and R ² represents a monovalent organic group.) , B is 0
Indicates an integer of 2. A proton conductive material comprising the above polysiloxane.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polysiloxane having excellent proton conductivity, a method for producing the same, and a proton conductive material comprising the polysiloxane. More specifically, even under high temperature and low humidity conditions, a polysiloxane having a high proton conductivity, a small decrease in the proton conductivity, and excellent film forming properties, a method for producing the same, and a proton conductive material comprising the polysiloxane About the material.

[0002]

2. Description of the Related Art Substances in which ions move in a solid have been energetically studied as materials for electrochemical devices such as batteries, and currently various materials such as Li ⁺ , Ag ⁺ , H ⁺ , and F ⁻ are used. Ionic conductors of various conductive ionic species have been found.
Among them, those using proton (H ⁺ ) as a conductive ionic species
It is expected to be applied to various electrochemical devices such as fuel cells, capacitors, and electrochromic display devices.
A proton conductor can be used as an electrolyte of the electrochemical device as described above.

[0003] Proton conductors can be used at temperatures as low as 0 ° C or lower.
Ideally, it shows high proton conductivity at a high temperature of 00 ° C. or higher and also in a low humidity to high humidity region. At present, as a proton conductor, organic substances such as a polymer ion exchange membrane having a side chain containing a perfluorosulfonic acid group in a perfluoroalkane polymer, or uranyl phosphate hydrate or molybdo phosphate hydrate, etc. Although inorganic substances are known, these materials cannot exhibit proton conductivity under such a wide range of environmental conditions.

For example, organic proton conductors, particularly perfluoroalkyl sulfonic acids, which have been studied for common use, have many problems in production technology such as yield because they are produced by complex organic synthesis, and are expensive materials. In addition to the production problem, under high-temperature or low-humidity conditions, water in the conductive membrane that functions as a proton conductor tends to be desorbed, and the proton conductivity under these conditions is significantly reduced. There was a problem.

Also, in the above-mentioned inorganic proton conductor, protons in the crystallization water are involved in conduction, so that the crystallization water is desorbed at high temperatures, especially under low humidity conditions, and the proton conductivity is reduced. There is a problem. Furthermore, inorganic materials also have complicated film-forming and brittleness problems. Therefore, the present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, a silane compound (A) represented by a specific chemical formula (1) described below and a silane compound represented by a specific chemical formula (2) A polysiloxane obtained by adding sulfuric acid and / or phosphoric acid to a mixture with the compound (B) and hydrolyzing and condensing the mixture has high proton conductivity even under high temperature and low humidity conditions, and furthermore, has a high proton conductivity. The inventors have found that the film has a small degree of decrease and is a flexible self-supporting film that can avoid complicated film-forming properties and brittleness problems, and has completed the present invention. Proton conductive materials made of such polysiloxane can be suitably used.

[0006]

SUMMARY OF THE INVENTION The present invention relates to a conventional inorganic material which cannot prepare a brittle and self-supporting film as described above,
It solves the technical problem of conventional organic materials that causes a decrease in proton conductivity under low humidity conditions.
An object of the present invention is to provide a polysiloxane capable of obtaining a self-supporting film having excellent proton conductivity, a small decrease in proton conductivity even under conditions of high temperature and dry atmosphere, a method for producing the same, and a proton conductive material obtained therefrom. And

[0007]

The polysiloxane of the present invention comprises a silane compound (A) represented by the following general formula (1), a silane compound (B) represented by the following general formula (2), phosphoric acid and sulfuric acid. At least one acid component (C) selected from
Is hydrolyzed and condensed, and if necessary,
It is characterized by being obtained by heat treatment at ~ 300 ° C.

R ¹ _a Si (OR ² ) _4-a (1) wherein R ¹ is a monovalent functional group, R ² is a monovalent organic group, and a is 1-2 R ³ _b Si (OR ² ) _4-b ... (2) (wherein, R ³ represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group, and R ² is monovalent) An organic group of b is 0 to
Indicates an integer of 2. R ¹ in the general formula (1) is preferably a group having a carbon-carbon double bond in the molecule or an epoxy group.

The proton conductive material of the present invention is characterized by comprising the above polysiloxane. The method for producing a polysiloxane of the present invention comprises the steps of: mixing a mixture of a silane compound (A) represented by the following general formula (1) and a silane compound (B) represented by the following general formula (2) with phosphoric acid and sulfuric acid; And hydrolysis and condensation in the presence of at least one acid component selected from the group consisting of:

R ¹ _a Si (OR ² ) _4-a (1) (wherein, R ¹ is a monovalent functional group, R ² is a monovalent organic group, and a is 1-2) R ³ _b Si (OR ² ) _4-b ... (2) (wherein, R ³ represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group, and R ² is monovalent) An organic group of b is 0 to
Indicates an integer of 2. In the method for producing the polysiloxane, the general formula (1)
R ¹ in the above is preferably a group having a carbon-carbon double bond in the molecule or an epoxy group.

Further, in the method for producing a polysiloxane, it is preferable to heat-treat a hydrolyzed / condensed product obtained by hydrolysis and condensation at 100 to 300 ° C.

[0012]

DETAILED DESCRIPTION OF THE INVENTION Next, the polysiloxane of the present invention,
The production method and the proton conductive material will be specifically described. The polysiloxane of the present invention is selected from a silane compound (A) represented by the following general formula (1), a silane compound (B) represented by the following general formula (2), and phosphoric acid and sulfuric acid. At least one acid component (C)
Is hydrolyzed and condensed, and if necessary,
It is characterized by being obtained by heat treatment at ~ 300 ° C.

R ¹ _a Si (OR ² ) _4-a (1) wherein R ¹ is a monovalent functional group, R ² is a monovalent organic group, and a is 1-2 R ³ _b Si (OR ² ) _4-b ... (2) (wherein, R ³ represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group, and R ² is monovalent) An organic group of b is 0 to
Indicates an integer of 2. ) Polysiloxane / Proton Conductive Material The polysiloxane of the present invention comprises a silane compound (A) having an organic functional group and a plurality of alkoxysilyl groups represented by the general formula (1), Represented,
A compound obtained by hydrolyzing and condensing a mixture of a silane compound (B) having no organic functional group and having a plurality of alkoxysilyl groups, and an acid component (C) composed of phosphoric acid and / or sulfuric acid. It is considered that the above-mentioned acid component is involved not only as a catalyst component in the hydrolysis / condensation reaction, but also as a condensation component, and is incorporated in the polysiloxane.

When the above-mentioned acid component is incorporated into the polysiloxane, the proton conductivity is improved, and the decrease in proton conductivity can be reduced even under high temperature and low humidity conditions.
The incorporation of an acidic component into the polysiloxane can be suitably performed mainly by using the silane compound (A). By using the silane compounds (A) and (B) together, a crosslinked structure for obtaining a self-supporting film can be formed in the polysiloxane.

Such a polysiloxane of the present invention is excellent in proton conductivity and has a small decrease in proton conductivity even under conditions of high temperature and low humidity, so that it can be suitably used as an excellent proton conductive membrane material. In addition, since a self-supporting membrane is obtained, a flexible proton conductive membrane material can be easily produced from this polysiloxane. The ratio of the amount of the silane compound (A) to the amount of the silane compound (B) used is such that the silane compound (A) is usually 30 to 90 mol%, preferably 5 to 80 mol%, more preferably 10 to 75 mol. %, The silane compound (B) is usually 10 to 70 mol%,
Preferably it is 20 to 95 mol%, more preferably 25 to 95 mol%.
90 mol% (however, (A) + (B) = 100 mol%)
It is desirable that

The amount of sulfuric acid to be added is generally 0.001 to 3 equivalents, preferably 0.03 equivalents, per equivalent of the alkoxysilyl group of the total of the silane compound (A) and the silane compound (B).
01 to 1.5 equivalents. The amount of phosphoric acid to be added is generally 0.001 to 3 equivalents, preferably 0.001 to 1.5 equivalents, per equivalent of the alkoxysilyl group, which is the total of the silane compound (A) and the silane compound (B). .

Silane compound (A) The silane compound (A) usable in the present invention is a compound represented by the following general formula (1). R ¹ _a Si (OR ² ) _4-a (1) (wherein, R ¹ is a monovalent functional group, R ² is a monovalent organic group, and a is an integer of 1 or 2. In particular, R ¹ is a vinyl functional group, an allyl functional group, a methacrylic functional group, an acrylic functional group, an epoxy functional group, a mercapto functional group, an ether functional group, an acetoxy functional group, a benzoyl functional group. Preferred are a functional group, a ketone-based functional group, a urea-based functional group, a cyano-based functional group, a thiocyanate-based functional group, a carbamate-based functional group, an acid anhydride-based functional group, and a phosphorus-based functional group.

R ² is preferably an organic group selected from an alkyl group, an aryl group and an arylalkyl group. Specifically, vinyl trimethoxy silane, vinyl triethoxy silane, butenyl trimethoxy silane, butenyl triethoxy silane, styryl ethyl trimethoxy silane, vinyl of styryl ethyl triethoxy silane, allyl dimethoxy silane, allyl diethoxy silane Allyl, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane such as, allyltrimethoxysilane, allyltriethoxysilane, 2- (chloromethyl) allyltrimethoxysilane and 2- (chloromethyl) allyltriethoxysilane , Acryloxymethyltrimethoxysilane, acryloxymethyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane,
3-methacryloxypropyltriethoxysilane, (3
-Methacryloxypropyl) methyldimethoxysilane,
(3-methacryloxypropyl) methyldiethoxysilane, 3-acryloxypropyltrimethoxysilane,
-Acryloxypropyltriethoxysilane, (3-acryloxypropyl) methyldimethoxysilane, (3-
Acryloxypropyl) methyldiethoxysilane, O-
(Methacryloxyethyl) -N- (triethoxysilylpropyl) urethane, O- (methacryloxyethyl) -N- (trimethoxysilylpropyl) urethane,
Methacryl such as O- (acryloxyethyl) -N- (triethoxysilylpropyl) urethane, O- (acryloxyethyl) -N- (trimethoxysilylpropyl) urethane, or acrylic, 3-glycidoxy Propyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane , 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane,
5,6-epoxyhexyltrimethoxysilane, 5,6
An epoxy type such as epoxyhexyltriethoxysilane, a mercapto type such as mercaptoethyltrimethoxysilane, mercaptoethyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-mercaptopropyltriethoxysilane; a 3-methoxypropyltrimethoxysilane 3-methoxypropyltriethoxysilane, (furfuryloxymethyl) trimethoxysilane, (furfuryloxymethyl) triethoxysilane,
3- (heptafluoroisopropoxy) propyltrimethoxysilane, 3- (heptafluoroisopropoxy)
Ether-based such as propyltriethoxysilane, acetoxy-based such as acetoxymethyltrimethoxysilane, acetoxymethyltriethoxysilane, acetoxypropyltrimethoxysilane, acetoxypropyltriethoxysilane, benzoyloxypropyltrimethoxysilane, benzoyloxypropyltriethoxysilane Benzoyl, 2-hydroxy-4- (3-trimethoxypropoxy) diphenyl ketone, 2-hydroxy-
Ketones such as 4- (3-triethoxypropoxy) diphenyl ketone, urea such as bis (3- (trimethoxysilyl) propyl) urea, bis (3- (triethoxysilyl) propyl) urea, 2-cyanoethyltri Methoxysilane, 2-cyanoethyltriethoxysilane, 2-
Cyano-based compounds such as cyanopropyltrimethoxysilane, 2-cyanopropyltriethoxysilane, 11-cyanoundecyltrimethoxysilane, 11-cyanoundecyltriethoxysilane, 3-thiocyanatepropyltrimethoxysilane, and 3-thiocyanatepropyltriethoxy Thiocyanates such as silane, (3-trimethoxysilylpropyl) -t-butyl carbamate, (3-
Carbamates such as trimethoxysilylpropyl) -t-butyl carbamate, 3- (trimethoxysilyl)
Propyl succinic anhydride, 3- (triethoxysilyl)
Acid anhydrides such as propylsuccinic anhydride, 2- (diphenylphosphino) ethyltrimethoxysilane,
Phosphorus such as (diphenylphosphino) ethyltriethoxysilane is exemplified.

Of these alkoxysilanes having an organic functional group, vinyl, allyl, methacrylic, acrylic and epoxy-based compounds, which easily incorporate an acid component into the polysiloxane, are preferred. In particular, methacrylic,
Acrylic and epoxy are particularly preferred. Silane compound (B) The silane compound (B) that can be used in the present invention is a compound represented by the following general formula (2).

R ³ _b Si (OR ² ) _4-b ... (2) (wherein, R ³ represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group, and R ² represents a monovalent organic compound) Group, b is 0
Indicates an integer of 2. In particular, R ³ is preferably an alkyl group or an aryl group, or a group obtained by halogenating them.

Specific examples of the silane compound represented by the general formula (2) include methyltrimethoxysilane, methyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyl Triethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane , Cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, (3-cyclopentadienyl Pills) trimethoxysilane, (3
-Cyclopentadienylpropyl) triethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, tolyltrimethoxysilane, tolyltriethoxysilane, benzyltrimethoxysilane, benzyltriethoxysilane, phenethyltrimethoxysilane, phenethyltriethoxysilane Bromophenyltrimethoxysilane, bromophenyltriethoxysilane, 3-bromopropyltrimethoxysilane, 3-bromopropyltriethoxysilane, 11-bromoundecyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3
-Chloropropyltriethoxysilane, chlorophenyltrimethoxysilane, chlorophenyltriethoxysilane, chloropropyltrimethoxysilane, chloropropyltriethoxysilane, chlorophenyltrimethoxysilane, ((chloromethyl) phenylethyl) trimethoxysilane, ((chloromethyl ) Phenylethyl) triethoxysilane, (tridecafluoro-1,1,2,2-
(Tetrahydrooctyl) trimethoxysilane, (tridecafluoro-1,1,2,2-tetrahydrooctyl)
Trialkoxysilanes such as triethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, 1,3-dimethyltetramethoxydisiloxane, 1,3-dimethyltetraethoxydisiloxane, 1,3-dioctyl Tetraalkoxysilanes such as tetramethoxydiloxane and 1,3-dioctyltetraethoxydiloxane, 1,3-divinyltetraethoxydisiloxane, bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, bis (trimethoxy) (Silyl) ethane, bis (triethoxysilyl) ethane, bis (trimethoxysilyl) hexane, bis (triethoxysilyl) hexane, bis (trimethoxysilyl) octane, bis (triethoxysilyl) octane, (Trimethoxysilyl) nonane, bis (triethoxysilyl) nonane, bis (trimethoxysilyl) ethylene, bis (triethoxysilyl)
Ethylene, 1,4-bis (trimethoxysilylethyl)
Benzene, 1,4-bis (triethoxysilylethyl)
Hexaalkoxysilanes such as benzene can be mentioned.

Of these, trialkoxysilane and tetraalkoxysilane are suitable for forming a crosslinked structure for obtaining a self-supporting film as a hybrid material of polysiloxane. Particularly, tetraalkoxysilane is preferable. Method for Producing Polysiloxane / Proton Conductive Material The above polysiloxane can be produced by a sol-gel method.

For example, a mixture of the silane compound (A) represented by the general formula (1) and the silane compound (B) represented by the general formula (2) is mixed with at least one of phosphoric acid and sulfuric acid. A polysiloxane can be produced by hydrolysis and condensation in the presence of various acid components. In this method, an aqueous solution of phosphoric acid and / or sulfuric acid which also serves as a component of a hydrolysis / condensation catalyst and a polysiloxane is added to a mixture solution of the silane compound (A) and the silane compound (B), and mixed. Then, a sol is prepared, the obtained sol is cast, dried and gelled, and a predetermined heat treatment is performed to obtain a polysiloxane.

In the preparation of the sol, as described above, phosphoric acid and / or sulfuric acid are added to a mixed solution of the silane compound (A) and the silane compound (B) and mixed to cause hydrolysis and condensation. It is possible to do
It may be performed in stages. For example, in the presence of water containing an acidic condensation catalyst, the silane compound (A) and the silane compound (B) are partially hydrolyzed and, if necessary, partially condensed, and then phosphoric acid or sulfuric acid is added and mixed. And hydrolysis and condensation are further performed to prepare a sol.

By performing the reaction in a plurality of stages as described above, the incorporation of the acid component into the gel can be controlled, and the gel having the above specific structural composition can be efficiently produced. As the hydrolysis / condensation catalyst, various acids such as hydrochloric acid, nitric acid, acetic acid, formic acid, phosphoric acid, and sulfuric acid can be used, but phosphoric acid and sulfuric acid, which are acid components incorporated into polysiloxane, are preferred. Is preferred. The acidity of water is preferably about 0 to 4 in terms of pH. Silane compound (A)
And the amount of water added to the mixture of the silane compound (B)
0.1 to 10 equivalents, preferably 0.1 to 10 equivalents, based on 1 equivalent of the total alkoxysilyl group of the silane compounds (A) and (B).
It is 2 to 8 equivalents, more preferably 0.5 to 5 equivalents, and most preferably 0.5 to 3 equivalents.

After a predetermined amount of an acid component consisting of sulfuric acid and / or phosphoric acid is added to the mixture of the above silane compounds, the reaction system is stirred.
00 rpm, preferably 50 to 100 rpm. The addition of the acid component is preferably performed by partially hydrolyzing the alkoxysilyl group and, if necessary, partially condensing the resulting partially decomposed product.

After completion of the stirring, the resulting reaction solution is usually applied to a substrate, air-dried at room temperature to 50 ° C. or vacuum-dried, and further heat-treated (calcined) to give a self-supporting film of polysiloxane gel. Is obtained. The heat treatment temperature is usually 50 to 500C, preferably 100 to 300C, more preferably 150 to 250C, and the heat treatment time is 0.2 to 24 hours, preferably 0.5 to 10 hours.

The polysiloxane obtained as described above can be used as a proton conductive membrane material. Also,
The obtained polysiloxane can be used as a composite with an organic polymer-based proton conductive membrane material.

[0029]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples.
As a starting material, 3-methacryloxypropyltrimethoxysilane (CH ₂ ＣC (CH ₃ ) — (CH ₂ ) ₃ —Si
(OCH ₃ ) ₃ (manufactured by Chisso Corporation, hereinafter abbreviated as TMSPM), 3-glycidoxypropyltrimethoxysilane (CH (O) CH—CH ₂ —O— (CH ₂ ) ₃ —Si (OC
H ₃ ) ₃ (manufactured by Chisso Corporation, hereinafter abbreviated as GPTMS),
Tetramethoxysilane (Si (OCH ₃ ) ₄ ) (Tokyo Kasei Kogyo Co., Ltd .; hereinafter abbreviated as TMOS), ethyl alcohol (Wako Pure Chemical Industries, Ltd.), sulfuric acid (Wako Pure Chemical Industries, Ltd.), phosphoric acid (Manufactured by Wako Pure Chemical Industries, Ltd.). Water used was distilled ion-exchanged water.

The obtained proton conductive membrane material was sandwiched between platinum electrodes, and the conductivity was measured and evaluated by an alternating current method at a temperature of 30 ° C. and a relative humidity (RH) of 60%. Further, the conductive film was subjected to a temperature of 130 ° C. and a relative humidity of 0% (under a nitrogen stream) for 0 minute, 100 minutes, 200 minutes, and 300 minutes.
Minutes, measure the proton conductivity after 400 minutes,
The stability of proton conductivity at low humidity was evaluated.

[0031]

Example 1 1.5 mol (372.5 g) of TMSPM and 1 mol (152.2 g) of TMOS were mixed at room temperature for 10 minutes. To this, 0.0125 mol of concentrated sulfuric acid (1.23
g) and 7.5 mol (135 g) of water were added, and the mixture was stirred at room temperature for 2 hours to prepare a sol. The obtained sol was cast on a Teflon (registered trademark) petri dish,
After being left at room temperature for 1 hour, it was dried at 50 ° C. for 24 hours, and heat-treated at 150 ° C. for 5 hours.

As a result, the obtained gel has a transparent crack.
It was a 100 μm-thick self-supporting film without any. The resulting membrane
Has a proton conductivity of 1 × at 30 ° C. and 60% RH.
10 ^-6S / cm. At a temperature of 130 ° C., relative humidity
Proton conduction under the condition of 0% (under nitrogen flow)
Table 1 shows changes over time in the degree.

[0033]

Example 2 (Example in which the composition of the organic / inorganic component and the acid component in Example 1 was changed) TMSPM 2.0 mol (496.
7 g) and 1 mol of TMOS (152.2 g) were mixed in 10 mol (460 g) of ethanol at room temperature for 10 minutes. An aqueous solution consisting of 0.081 mol (8 g) of concentrated sulfuric acid, 9 mol (162 g) of water and 5 mol (230 g) of ethanol was added thereto, and the mixture was stirred at room temperature for 2 hours to prepare a sol. The obtained sol was cast on a Teflon petri dish,
After being left at room temperature for 1 hour, it was dried at 50 ° C. for 24 hours, and heat-treated at 150 ° C. for 5 hours.

As a result, the obtained gel was a transparent, crack-free, free-standing film having a thickness of 75 μm. The proton conductivity of the obtained membrane at 30 ° C. and 60% RH was 4 × 1.
It was 0 ^-6 S / cm. Table 1 shows the time-dependent change in proton conductivity at a temperature of 130 ° C. and a relative humidity of 0% (under a nitrogen stream).

[0035]

Example 3 (Example of Example 2 using phosphoric acid instead of concentrated sulfuric acid) TMSPM 2.0 mol (496.7)
g) and 1 mol of TMOS (152.2 g)
Mix for 10 minutes at room temperature in 0 mol (460 g).
0.081 mol of phosphoric acid (8 g) and 9 mol of water (16
An aqueous solution consisting of 2 g) and 5 mol (230 g) of ethanol was added, and the mixture was stirred at room temperature for 2 hours to prepare a sol.

The obtained sol was cast on a petri dish made of Teflon, left at room temperature for 1 hour, dried at 50 ° C. for 24 hours, and further heat-treated at 150 ° C. for 5 hours. As a result, the obtained gel was a transparent free-standing film having a thickness of 80 μm without cracks. The proton conductivity of the obtained membrane at 30 ° C. and 60% RH was 2 × 10 ⁻⁵ S / cm. Also,
Table 1 shows the time-dependent changes in proton conductivity at a temperature of 130 ° C. and a relative humidity of 0% (under a nitrogen stream).

[0037]

Example 4 (Example in which the amount of phosphoric acid used in Example 3 was changed) In Example 3, 0.16 mol of phosphoric acid (1
A membrane was prepared in the same manner as in Example 3 except that the amount used was 6 g). As a result, the obtained gel was a transparent free crack-free film having a thickness of 85 μm. The proton conductivity of the obtained membrane at 30 ° C. and 60% RH was 8 × 1.
It was 0 ^-5 S / cm. Table 1 shows the time-dependent change in proton conductivity at a temperature of 130 ° C. and a relative humidity of 0% (under a nitrogen stream).

The results of examining the near-infrared absorption spectra of the obtained polysiloxane and the gel before heat treatment and the gel after heat treatment at 150 ° C. for 5 hours are shown in FIG. 1 (gel before heat treatment) and FIG. Gel). 1 and 2, in the gel before the heat treatment, the absorption peak of the C = C group is A;
The absorption peak was large around 1.6 μm, but in the gel after heat treatment, the absorption peak was small.

[0039]

Embodiment 5 (Example using organic component GPTMS) GPT
2.0 mol (472.7 g) of PM and 1 mol of TMOS (1
52.2 g) and 10 mol (460 g) of ethanol at room temperature for 10 minutes. To this, phosphoric acid 0.6
An aqueous solution consisting of 6 mol (64.7 g), 9 mol (162 g) of water and 5 mol (230 g) of ethanol was added and stirred at room temperature for 2 hours to prepare a sol. The obtained sol was cast on a Teflon petri dish and left at room temperature for 1 hour.
It was dried at 50 ° C. for one day, and heat-treated at 150 ° C. for 5 hours.

As a result, the obtained gel was a transparent free crack-free film having a thickness of 75 μm. The proton conductivity of the obtained membrane at 30 ° C. and 60% RH was 1 × 1.
It was 0 ^-5 S / cm. Table 1 shows the time-dependent change in proton conductivity at a temperature of 130 ° C. and a relative humidity of 0% (under a nitrogen stream).

[0041]

Embodiment 6 (Example in which the composition of the organic / inorganic component and the acid component in Embodiment 5 is changed) 3.0 mol (709.1 g) of GPTPM and 1 mol (152.2 g) of TMOS are combined with 15 mol (690 g) of ethanol. Medium at room temperature
Mix for minutes. To this, 1.72 mol of phosphoric acid (168.
6 g), an aqueous solution composed of 12 mol (216 g) of water and 5 mol (230 g) of ethanol was added, and the mixture was stirred at room temperature for 2 hours to prepare a sol. The obtained sol was cast on a Teflon petri dish, allowed to stand at room temperature for 1 hour, dried at 50 ° C. for 24 hours, and further heat-treated at 150 ° C. for 5 hours.

As a result, the obtained gel was a transparent, crack-free, self-supporting film having a thickness of 70 μm. The proton conductivity of the obtained membrane at 30 ° C. and 60% RH was 2 × 1.
It was 0 ^-4 S / cm. Table 1 shows the time-dependent change in proton conductivity at a temperature of 130 ° C. and a relative humidity of 0% (under a nitrogen stream). About the obtained polysiloxane, the near-infrared absorption spectra of the gel before heat treatment and the gel after heat treatment at 150 ° C. for 5 hours were measured in the same manner as in Example 4. FIG. 3 (gel before heat treatment) FIG. 4 (gel after heat treatment) is shown.

3 and 4, the gel before the heat treatment had H ₂
The absorption peak of the OH group of O is B: 3200 to 3550 cm
⁻¹ , the absorption peak of the —Si—O—Si— group is C;
In the vicinity of 1130, 1035 cm ^-1 , an epoxy group or S
An absorption peak of the i-OH group is observed around D; 900 cm ^-1 . Similarly, in the gel after the heat treatment, absorption peaks of B, C, and D were also observed.

[0044]

Example 7 (in Example 5, the amount of phosphoric acid used was changed).
Further example) In Example 5, 4 mol of phosphoric acid (392
g) except that it was used in the amount of g)
Prepared. As a result, the resulting gel has clear cracks.
It was a free-standing film having a thickness of 180 μm. Of the resulting membrane
The proton conductivity under the condition of 30 ° C. and 60% RH is 8 × 1
0 ^-FourS / cm. Also, at a temperature of 130 ° C, the relative humidity
Is 0% (under nitrogen flow)
Are shown in Table 1.

[0045]

[Table 1]

[0046]

Comparative Example 1 (Example in which only TMSPM was used as the silane compound) The following method was used in accordance with Example 1. 1.5 moles (372.5 g) of TMSPM at room temperature
Mix for 0 minutes. To this, 0.015 mol of concentrated sulfuric acid (1.5
g) and an aqueous solution consisting of 3 moles (54 g) of water were added and stirred at room temperature for 2 hours to prepare a sol. The obtained sol was cast on a Teflon petri dish and left at room temperature for 1 hour.
It was dried at 0 ° C. for a day and a night, and further heat-treated at 150 ° C. for 5 hours. However, no gel-like product was obtained.

[0047]

[Comparative Example 2] (Example using only TMOS as silane compound)
Example 1 was repeated except that MOS was used in an amount of 1 mol (152.2 g), and an aqueous solution consisting of 0.006 mol (0.006 g) of concentrated sulfuric acid and 3.5 mol (63.5 g) of water was added thereto. A sol-gel reaction was performed in the same manner as in Example 1. The gel was cast on a petri dish to progress the gelation, but a number of cracks were generated and a self-supporting film could not be obtained.

As is clear from Table 1, TMSPM, G
A book obtained by hydrolyzing and condensing a mixture of a silane compound (A) such as PTMS, a silane compound (B) such as TMOS, and an acid component (C) selected from phosphoric acid and sulfuric acid. In the invention, the polysiloxane film is composed of 1
Despite the high temperature drying conditions of 30 ° C. and 0% relative humidity, the proton conductivity is high, and even after a long time,
The proton conductivity hardly decreases. Further, it can be seen that a transparent crack-free polysiloxane free-standing film can be obtained. Such an effect of the present invention is obtained when only one of the silane compounds (A) and (B) is used (Comparative Example 1,
It can be seen that 2) cannot be obtained.

[0049]

Industrial Applicability The polysiloxane of the present invention is obtained as a self-supporting membrane material, and the proton conductive membrane material comprising the same has excellent proton conductivity and lowers proton conductivity even under high temperature and dry conditions. Is small and stable. In addition, the production of the polysiloxane of the present invention and the proton conductive membrane material comprising the same is simple, and the polysiloxane and the proton conductive membrane material having excellent performance can be efficiently produced. Further, the proton conductor obtained by the production method of the present invention is useful as an electrolyte for various electrochemical devices such as fuel cells, capacitors, and electrochromic display devices.

[Brief description of the drawings]

FIG. 1 is a near-infrared absorption spectrum chart of a gel before heat treatment.

FIG. 2 is a near-infrared absorption spectrum chart of a gel after heat treatment.

FIG. 3 is a near infrared absorption spectrum chart of another gel before heat treatment.

FIG. 4 is a near infrared absorption spectrum chart of another gel after heat treatment.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Seiji Tadashi Nagaharu 6-998-3 Nakamozu Toricho-cho, Sakai City, Osaka Prefecture 1-192 Nakamozu Tontori Park Complex (130) Inventor Atsunori Matsuda Kawachinagano, Osaka 12-5 Midorigaoka Nakamachi, F-term (reference) 4J035 BA01 BA11 CA001 CA072 CA092 CA112 CA132 CA142 CA152 CA182 CA202 CA262 CA27N CA272 EA01 EB02 EB03 HA06 LA05 LB20 5G301 CA30 CD01 CE01

Claims (6)

[Claims] 1. A silane compound (A) represented by the following general formula (1), a silane compound (B) represented by the following general formula (2), and at least one selected from phosphoric acid and sulfuric acid. A polysiloxane obtained by hydrolyzing and condensing a mixture with a kind of acid component (C) and, if necessary, heating at 100 to 300 ° C. R ¹ _a Si (OR ² ) _4-a (1) (wherein, R ¹ is a monovalent functional group, R ² is a monovalent organic group, and a is an integer of 1 or 2. .) R ³ _b Si (OR ² ) _4-b ... (2) (wherein, R ³ represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group, and R ² represents a monovalent organic group.) , B is 0
Indicates an integer of 2. ) (2) R ¹ in the general formula (1) has a carbon atom in the molecule.
The polysiloxane according to claim 1, which is a group having a carbon double bond or an epoxy group. 3. A proton conductive material comprising the polysiloxane according to claim 1 or 2. 4. A mixture of a silane compound (A) represented by the following general formula (1) and a silane compound (B) represented by the following general formula (2) is selected from phosphoric acid and sulfuric acid. A method for producing a polysiloxane, comprising hydrolyzing and condensing in the presence of at least one acid component. R ¹ _a Si (OR ² ) _4-a (1) (wherein, R ¹ is a monovalent functional group, R ² is a monovalent organic group, and a is an integer of 1 or 2. .) R ³ _b Si (OR ² ) _4-b ... (2) (wherein, R ³ represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group, and R ² represents a monovalent organic group.) , B is 0
Indicates an integer of 2. ) 5. The compound of the formula (1) wherein R ¹ is a carbon
The method for producing a polysiloxane according to claim 4, wherein the polysiloxane is a group having a carbon double bond or an epoxy group. 6. The method for producing a polysiloxane according to claim 4, wherein the hydrolysis / condensation product obtained by hydrolysis and condensation is heat-treated at 100 to 300 ° C.