JPH0649213A - Ionic electrically conductive material - Google Patents

Abstract

(57) [Summary] [Object] To provide an ion conductive material which exhibits high ion conductivity at room temperature and is suitably used as a solid electrolyte of electronic devices such as batteries and display elements. [Structure] Formula (—SO ₃ ⁻ ) nM ^{n +} bonded to a polymer skeleton through a hydrocarbon group (wherein, M ^{n +} represents a metal ion of Group I or Group II of the periodic table, and n is 1 Or 2.) An ion conductive material comprising a cross-linked polymer copolymer composed of an organopolysiloxane chain containing a metal sulfonate group represented by 2) and a polyoxyalkylene chain.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to ionically conductive materials.

[0002]

2. Description of the Related Art In recent years, electronic devices such as batteries and display elements (ECD, etc.)
Higher performance, smaller size, and thinner have been further advanced. Along with this, the ion conductive materials used therefor are required not only to have high performance, but also to have various high requirements such as solidification, high reliability, high flexibility, high moldability, and moisture resistance. Conventionally, as such an ion conductive material, a solid electrolyte material in which a salt of a metal of group I or group II of the periodic table is dissolved and dispersed in a polymer resin matrix is known.
Among them, attempts have been actively made to synthesize a solid electrolyte in which an organopolysiloxane chain and a polyethylene oxide (PEO) chain are combined. The presence of the organopolysiloxane chain has the effect of activating the molecular motion of the PEO chain, and is very effective in improving the ionic conductivity. However, many of the ionic conductive materials that have been proposed to date that consist of cross-linked products of polysiloxane and PEO are those in which negative ions move at the same time as positive ions (metal ions) because the metal salt is dispersed. Met. (Japanese Patent Laid-Open No. 62-
209169 gazette). The migration of negative ions is often a detriment. For example, when an ion conductive material is incorporated as an electrolyte in a device such as a battery, the internal resistance increases over time due to polarization in the electrolyte due to the movement of negative ions, and the steady current of metal ions does not flow. . Negative ions must be present for charge compensation with positive ions, but it is necessary to reduce their mobility as much as possible, that is, a positive ion single conduction type ion conductive solid material. On the other hand, it has been reported that, particularly in a lithium battery or the like, when the charging and discharging cycles are repeated, lithium dendrites tend to be generated from the lithium metal negative electrode, resulting in short circuit of the battery. In this case, if a positive ion single conduction type ion conductive material, especially a solid one, is used as the electrolyte, the distribution of negative ions is almost uniformly dispersed regardless of the process of charging and discharging, and therefore the conduction of lithium ions Since the paths are not localized, there is an effect that the generation of dendrites is significantly suppressed. As an attempt to produce such a positive ion single conduction type ion conductive material, for example, octamethylcyclotetrasiloxane and benzenesulfonic acid methyl ester are plasma-polymerized, and then PEO is compounded,
Further, a lithium ion single conduction type ion conductive thin film in which sulfonate ions are fixed by treatment with lithium iodide has been proposed (see Lecture No. 2XIIC08, Annual Meeting of the Chemical Society of Japan 1988 Spring Annual Meeting). But in this case
Since it is difficult to preserve 100% of the structure of the monomer in plasma polymerization, it is not a perfect lithium ion single conduction type ionic conductor, and there is a drawback that the range of application is limited due to plasma polymerization. As described above, all of the solid electrolytes proposed up to the present, which are composed of crosslinked products of polysiloxane and other polymer materials, have problems in their properties or manufacturing methods, and are not satisfactory for application to the above-mentioned electronic devices. It wasn't kimono. As a result of diligent studies to solve such problems, the present inventors have found that a material obtained by dispersing a specific metal ion in a specific crosslinked product of a high molecular weight copolymer does not have the above-mentioned drawbacks and has an ionic conductivity. It has been found that the present invention can be a positive ion single conduction type ion conductive material, and has reached the present invention. An object of the present invention is to provide an ion conductive material which exhibits high ion conductivity at room temperature and is suitably used as a solid electrolyte for electronic devices such as batteries and display elements.

[0003]

Means for Solving the Problem and Its Action The present invention is of the formula (—SO ₃ ^— ) n, which is bonded to a polymer skeleton via a hydrocarbon group.
M n ⁺ (wherein, M n ⁺ represents a periodic table Group I or Group II metal ion, n represents 1 or 2.) Containing a metal sulfonate group represented by organopolysiloxane chain and polyoxy The present invention relates to an ion conductive material, which comprises a crosslinked high molecular weight copolymer composed of an alkylene chain. In order to explain this, the above-mentioned cross-linked polymer copolymer is an alkylene group having 1 to 8 carbon atoms such as methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, Formula (—SO ₃ ⁻ ) nM ^{n +} (wherein M ^{n +} is bonded to the polymer skeleton through a hydrocarbon group exemplified by an arylene group having 6 to 20 carbon atoms such as a phenylene group and a naphthylene group.
Is a metal ion of Group I or Group II of the periodic table exemplified by lithium, sodium, potassium, magnesium, calcium and the like, and n is 1 or 2. ) Is composed of a sulfonate group-containing organopolysiloxane chain having a chemical structure represented by the formula) and a polyoxyalkylene chain. Here, the type, morphology,
The crosslink density and the like are not particularly limited. The ion conductive material of the present invention has a group (-SO) containing a negative ion as described above.
₃ ^-) is because it is coupled to the polymer backbone via a hydrocarbon group, the mobility of the negative ions extremely low. Therefore, in the crosslinked product of the high molecular weight copolymer, the metal ion is dissociated from the negative ion, and the metal ion moves to develop ionic conductivity. If the type of negative ions present in the crosslinked polymer copolymer is only —SO ₃ ⁻ , the ion conductive material of the present invention functions as a metal ion homoconductor.

Regarding the method for producing the ion conductive material of the present invention, the following method is desirable. In order to obtain a final crosslinked product, it is roughly divided into two steps, a reaction of introducing a metal sulfonate structure and a crosslinking reaction. Final desired (-SO ₃ ^-) because it is sufficient that the crosslinked product having nM n ⁺ structure, the order of the two steps are not limited, and may be performed simultaneously. That is, the prepolymer or monomer before crosslinking (-SO ₃ ^-) nM ^{n +} or structure crosslinked after introducing, into the crosslinked product (-SO ₃ ^-) nM
^{An n +} structure may be introduced. Further, the reaction of introducing the (—SO ₃ ⁻ ) nM ^{n +} structure into the prepolymer or the monomer and the crosslinking reaction may be simultaneously performed. As the elementary reaction for introducing the (—SO ₃ ⁻ ) nM ^{n +} structure, it is preferable to use the following reactions.

(1) A reaction for forming a metal sulfonate by reacting a metal sulfite with an epoxy group. Epoxy group is directly bonded to silicon atom or has 1 to 2 carbon atoms
It may be bonded to the silicon atom via an alkylene group of 0 and / or an arylene group. In addition, they may be bonded via an ether bond or the like on the way. Further, the non-silicon compound may be further subjected to such a sulfonation reaction and then bonded to the silicon compound. Examples of the sulfite metal salt include lithium sulfite, sodium sulfite, potassium sulfite, calcium sulfite and the like. It is efficient to carry out the reaction in a water dispersion system at a reaction temperature of about 60 to 80 ° C., but it may be carried out in a polar solvent such as alcohol. Also,
The addition of metal bisulfite as a buffer improves the reaction conversion rate. When the reaction is carried out with the ratio of the metal equivalent to the epoxy group equivalent exceeding 1, in order for the final crosslinked product (ion conductive material) to function as a metal ion single conductor,
Excessive metal ions need to be removed by some method before crosslinking.

(2) A reaction of reacting a chlorine atom bonded to a carbon atom with a metal sulfite to form a metal sulfonate. The chlorine atom must be bonded to the silicon atom via an alkylene group having 1 to 20 carbon atoms or an arylene group via an alkylene group having 1 to 5 carbon atoms. Representative examples are a propylene group and a benzyl group. In addition, they may be bonded via an ether bond or the like on the way. Further, the non-silicon compound may be further subjected to such a sulfonation reaction and then bonded to the silicon compound. As the metal sulfite, lithium sulfite,
Examples thereof include sodium sulfite, potassium sulfite, calcium sulfite and the like. The reaction is a water dispersion system and the reaction temperature is 60 to 80.
Although it is efficient to carry out at about ° C, it may be carried out in a polar solvent such as alcohol. When the reaction is carried out with the ratio of metal equivalent to chlorine equivalent exceeding 1, in order for the final cross-linked product (ion conductive material) to function as a metal ion single conductor,
Excessive metal ions need to be removed by some method before crosslinking.

[0007] (3) a compound having an unsaturated aliphatic hydrocarbon group or a mercapto group, at one end (-SO ₃ ^-) nM n ⁺
A reaction in which a compound having a group and having a mercapto group or an unsaturated aliphatic hydrocarbon group at the other end is converted to a metal sulfonate by an addition reaction by ultraviolet irradiation. The former compound having an unsaturated aliphatic hydrocarbon group or a mercapto group is an unsaturated aliphatic hydrocarbon group or a mercapto group directly bonded to a silicon atom, or an alkylene group having 1 to 20 carbon atoms and / or an arylene group. It may be bonded to the silicon atom via In addition, they may be bonded via an ether bond or the like on the way. Examples of the unsaturated aliphatic hydrocarbon group include vinyl group, allyl group, propenyl group and the like. Further, even if the present compound is a non-silicon compound, it may be bonded to the silicon compound after such a sulfonation reaction. In the latter compound having a (—SO ₃ ⁻ ) nM ^{n +} group at one end and a mercapto group or an unsaturated aliphatic hydrocarbon group at the other end, the above-mentioned groups are available as the unsaturated aliphatic hydrocarbon group. It is illustrated. The main chain is composed of an alkylene group having 1 to 20 carbon atoms and / or an arylene group. In addition, a silicon atom, an ether bond or the like may be included in the middle. These two
For the addition reaction of the unsaturated aliphatic hydrocarbon group and the mercapto group between the various compounds, a reaction means for irradiating an energy beam such as an electron beam, X-ray or ultraviolet ray can be used, but it is economical and convenient. Therefore, ultraviolet rays are preferable. This reaction can be carried out in the absence of solvent when the two kinds of compounds are well compatible with each other, but otherwise, it is dissolved in a polar organic solvent such as tetrahydrofuran, dioxane, acetonitrile, dimethylformamide or dimethylsulfoxide, and then dissolved. Irradiation with ultraviolet rays is preferred. Further, it is efficient to carry out the reaction in the presence of the photosensitizer exemplified below. Examples include acetophenone, benzophenone, trimethylsilylbenzophenone and the like. The addition amount of the photosensitizer is in the range of 0.001 to 30 parts by weight, preferably in the range of 0.05 to 20 parts by weight, based on 100 parts by weight of the total amount of the two kinds of compounds. The reaction temperature is not particularly limited, but is usually room temperature to heating. The source of ultraviolet rays may be a conventionally known one, and examples thereof include a hydrogen discharge tube, a xenon discharge tube, a low pressure, medium pressure or high pressure mercury lamp.

(4) Unsaturated aliphatic hydrocarbon group or SiH
A reaction in which a compound having a (—SO ₃ ⁻ ) nM ^{n +} group at one end and a SiH group or an unsaturated aliphatic hydrocarbon group at the other end is converted into a metal sulfonate by an addition reaction using a platinum catalyst. The former unsaturated aliphatic hydrocarbon group or S
In a compound having an iH group, an unsaturated aliphatic hydrocarbon group is directly bonded to a silicon atom, or has 1 to 2 carbon atoms.
It may be bonded to the silicon atom via an alkylene group of 0 and / or an arylene group. In addition, they may be bonded via an ether bond or the like on the way. Examples of the unsaturated aliphatic hydrocarbon group include vinyl group, allyl group, propenyl group and the like. The latter, at one end (-SO ₃ ^-) nM ^{n +}
In the compound having a group and a SiH group or an unsaturated aliphatic hydrocarbon group at the other end, the unsaturated aliphatic hydrocarbon group is exemplified by the above groups. Main chain has 1 to 2 carbon atoms
It is composed of 0 alkylene group and / or arylene group. In addition, a silicon atom, an ether bond or the like may be included in the middle. The addition reaction between the unsaturated aliphatic hydrocarbon group and the SiH group between these two kinds of compounds can be easily carried out in the presence of a general hydrosilylation reaction catalyst. Examples of the catalyst include solid catalysts carrying a metal such as chloroplatinic acid, potassium chloroplatinate, palladium chloride, iridium chloride, iron carbonyl complex, ruthenium chloride, nickel chloride, platinum and ruthenium. This reaction can be carried out in the absence of a solvent when the two kinds of compounds are well compatible with each other, but in the other case, it is preferable to dissolve them in an appropriate organic solvent and then to carry out the reaction. The amount of the catalyst used is in the range of 0.0001 to 0.1 part by weight, preferably 0.001 to 20 part by weight, based on 100 parts by weight of the total amount of the two kinds of compounds. The reaction temperature is not particularly limited, but it is usually performed at room temperature to 150 ° C.

(5) A reaction in which a concentrated sulfuric acid or fuming sulfuric acid is caused to act on an aromatic ring which is not directly connected to a silicon atom so as to be sulfonated, and then neutralized to thereby form a metal sulfonate. Examples of the aromatic ring include a phenylene group, a naphthylene group and derivatives thereof, that is, those in which hydrogen on the aromatic ring is partially substituted with another organic group. The compound containing an aromatic ring may be a polymer having a silicon skeleton or a non-silicon compound, but the sulfonated compound needs to be incorporated as a side chain of the silicone polymer by some method in the end. There is. At this time, when the aromatic ring and the silicon atom are directly bonded, this bond is broken during the treatment with concentrated sulfuric acid or fuming sulfuric acid, which is not preferable.
An alkylene group having 1 to 20 carbon atoms and / or an arylene group and the like must be interposed between the aromatic ring and the silicon atom. In order for sulfuric acid not to remain in the system after the reaction, the amount of sulfuric acid added should be 1: 1 with respect to the equivalent amount of the aromatic ring in terms of sulfur atoms.
Up to a degree is desirable. When concentrated sulfuric acid (that is, a sulfuric acid aqueous solution) is used as the sulfuric acid, the concentration is preferably 96% (saturated), but needs to be 80% or more. The reaction temperature is preferably room temperature or slightly heated. It is advisable not to use a solvent or to use an organic solvent other than aromatic. After the sulfonation is performed as described above, it may be neutralized with a corresponding metal-containing base to form a sulfonic acid metal salt. As the base, a very ordinary one, that is, I of the Periodic Table
Examples thereof include hydroxides and hydrides of group III or group II metal elements. It is necessary to accurately measure the oxidation of the sulfonic acid beforehand and to add an equivalent amount of the base accordingly. The neutralization reaction proceeds reliably when it is carried out in a mixed system of a polar organic solvent such as tetrahydrofuran, dimethylsulfoxide, dimethylformamide and water.

The crosslinking reaction is not limited, but the following methods are preferred. (1) A method of condensing an organopolysiloxane containing a silanol group or an alkoxysilyl group and a polyoxyalkylene containing a silanol group or an alkoxysilyl group. Examples of alkoxy include methoxy and ethoxy. In order to carry out crosslinking, it is necessary that at least three silanol groups or alkoxysilyl groups be present in both the organopolysiloxane and the polyoxyalkylene, but it may be at any of the terminal and side chain sites. Alternatively, the two types of prepolymers of organopolysiloxane and polyoxyalkylene may be previously combined by some means, and then the silanol group or alkoxysilyl group present at an appropriate site may be condensed to crosslink. This reaction requires heating without a solvent or under a polar organic solvent, and finally vacuum heat drying to completely remove the produced water and / or alcohol. The reaction proceeds rapidly when an acid or a base is added as a catalyst, but it is necessary to devise such that the catalyst does not remain in the system in the end, for example, an operation of using a volatile catalyst and removing it by vacuum drying. (2) A method in which either or both of the two types of prepolymers of organopolysiloxane and polyoxyalkylene contain a chlorobenzyl group and are crosslinked by ultraviolet rays. In order to carry out crosslinking, at least three chlorobenzyl groups must be present in both the organopolysiloxane and the polyoxyalkylene, but it may be at either the terminal or side chain site. Alternatively, the two types of prepolymers of organopolysiloxane and polyoxyalkylene may be previously bound by some means, and then the chlorobenzyl groups present at appropriate sites may be condensed to crosslink them. Regarding the conditions necessary for this reaction, the UV sensitizer, etc., the above-mentioned sulfonated method (3) can be applied. (3) A mercapto group is contained in either of the two types of prepolymers of organopolysiloxane and polyoxyalkylene,
On the other hand, a method in which an unsaturated aliphatic group is contained and crosslinking is carried out by ultraviolet rays in the presence of a suitable sensitizer. In order to carry out the crosslinking, it is necessary that at least three functional groups are present in both the organopolysiloxane and the polyoxyalkylene.
It may be either at the end or at the side chain. Alternatively, the two types of prepolymers of organopolysiloxane and polyoxyalkylene may be previously bound by some means, and then the above functional groups present at appropriate sites may be added to crosslink. In this case, the above-mentioned sulfonated method (3) can be applied to examples of unsaturated aliphatic groups, conditions necessary for the reaction, UV sensitizers and the like. (4) A method in which one of two types of prepolymers of organopolysiloxane and polyoxyalkylene contains a SiH group and the other contains an unsaturated aliphatic group, and crosslinks in the presence of a suitable hydrosilylation reaction catalyst. In order to carry out the crosslinking, it is necessary that at least three functional groups are present in both the organopolysiloxane and the polyoxyalkylene.
It may be either at the end or at the side chain. Alternatively, the two types of prepolymers of organopolysiloxane and polyoxyalkylene may be previously bound by some means, and then the above functional groups present at appropriate sites may be added to crosslink. Examples of unsaturated aliphatic groups in this case, conditions necessary for the reaction, hydrosilylation reaction catalyst, etc.,
The above-mentioned sulfonation method (4) can be applied. (5) A carboxyl group is contained in either one of the two types of prepolymers of organopolysiloxane and polyoxyalkylene, and a carbinol group is contained in the other prepolymer, which is heated and vacuum-crosslinked in the presence of a suitable esterification catalyst. The carboxyl group and the carbinol group are preferably bonded to the prepolymer through a hydrocarbon group such as an alkylene group having 1 to 20 carbon atoms and / or an arylene group. In order to carry out crosslinking, it is necessary that at least three functional groups are present in both the organopolysiloxane and the polyoxyalkylene, but it may be at any of the terminal and side chains. Further, the two types of prepolymers of organopolysiloxane and polyoxyalkylene may be previously bound by some means, and then the functional groups present at appropriate sites may be condensed to be crosslinked. This reaction requires heating without solvent or under a polar organic solvent, and finally vacuum heating and drying to completely remove the produced water. When an acid or a base is added as a catalyst, the reaction proceeds rapidly, but it is necessary to devise such that the catalyst does not remain in the system in the end, for example, an operation of using a volatile catalyst and removing it by vacuum drying.

[0011]

The present invention will be described in more detail with reference to the following examples. The ionic conductivity was measured by the following method.
The ion conductive material was molded into a film and used as a measurement sample. After measuring the thickness of this sample with a micrometer, a circular plate-shaped platinum electrode with a diameter of 1 cm was adhered to both sides of the sample, and the whole was placed in a decompression container where the temperature could be set to an arbitrary temperature, and 10 ^-5 Torr. After decompressing to the following high vacuum and the sample state has reached a sufficient equilibrium, an AC voltage of 5 Hz to 13 MHz is applied by an LCR meter (Yokogawa Hewlett Packard 4192A), and the conductivity is measured by the complex impedance method. did.

[0012]

Example 1 As the ion conductive material, a material according to the present invention (Sample 1) and a material according to the prior art (Sample 2) were prepared for the purpose of characteristic comparison. Sample 1 10.0 g of 3-glycidoxypropyl-trimethoxysilane and 3.98 g of lithium sulfite were reacted in 14 g of pure water with stirring at 75 ° C. for 2 hours. Then, the reaction product was poured into 100 ml of acetone with stirring to obtain a white precipitate. The white precipitate was isolated to obtain the compound (1) shown below. Similarly, 3-glycidoxypropyl-methyldimethoxysilane was used as a starting material to obtain a compound (2) shown below. Compound (1) 0.
1 g, compound (2) 0.2 g, compound (3) 0.3 shown below
g, 0.4 g of the compound (4) shown below, 0.5 g of pure water, and 0.5 g of tetrahydrofuran were stirred and mixed to sufficiently dissolve them. Pass this solution through a weakly acidic cation exchange resin,
Excessive lithium ions were removed. 2 g of the passed solution was poured into a 3 cm square Teflon dish, heated on a hot plate at 120 ° C. for 2 hours, and then dried in a vacuum drier.
After vacuum drying at 0 ° C. for 4 days, a transparent film having a thickness of 0.3 mm was obtained. When the infrared absorption spectrum of this film was examined, it was found that the condensation reaction was almost completely carried out because no absorption of silanol groups was observed. The ionic conductivity of this film was measured and found to be 2.0 × 10 ⁻⁶ S · cm ⁻¹ at 25 ° C. Compound (1):

[Chemical 1] Compound (2):

[Chemical 2] Compound (3):

[Chemical 3] Compound (4):

[Chemical 4] Sample 2 0.278 g of the compound (5) shown below and 0.52 of the compound (6)
7 g, 0.195 g of the compound (7) and 30.8 mg of lithium perchlorate were mixed with stirring, irradiated with ultrasonic waves to be sufficiently dissolved, and 3 μl of 0.1 N hydrochloric acid ethanol solution was added. This solution was passed through a weakly acidic cation exchange resin to remove excess lithium ions. 2 g of the solution that passed through 3
Pour into a Teflon dish with a size of 1 cm square and heat it on a hot plate at 120 ° C for 2 hours, then use a vacuum dryer to 140
After vacuum drying at 4 ° C. for 4 days, a transparent film having a thickness of 0.3 mm was obtained. When the infrared absorption spectrum of this film was examined, peaks derived from hydroxyl groups and free carboxylic acids were not observed, and a stretching vibration peak of the carbonyl group due to ester formation was observed at 1740 cm ^-1, which indicates that the esterification reaction Turned out to be almost complete. The ionic conductivity of this film was measured and found to be 4.8 × 10 ⁻⁵ S · cm ⁻¹ at 25 ° C. Compound (5):

[Chemical 5] Compound (6):

[Chemical 6] Compound (7): HO (CH ₂ CH ₂ O) ₁₂ CH ₃ DC voltage application test 1 mm diameter on both surfaces of Sample 1 and Sample 2 with a thickness of 0.3 mm,
A 0.14 mm-thick lithium foil was adhered, and the whole was placed in a decompression container and decompressed to a high vacuum of 10 ⁻⁵ Torr or less at 25 ° C., and after the sample state reached a sufficient equilibrium, A direct current voltage of 1 V was applied to both lithium foils, and the change over time of the flowing current was observed. In Sample 1, the initial current of 52 μA lasted for about 2 days, and it was confirmed that this ionic conductive material was a positive ion single conduction type ionic conductive material. On the other hand, in the sample 2, the initial current of 79 μA dropped to 4.4 μA after 2 days.

[0013]

Example 2 10.0 g of 3-glycidoxypropyl-
Trimethoxysilane and 5.33 g of sodium sulfite were reacted in 15 g of pure water by stirring at 75 ° C. for 2 hours.
The reaction product was then poured into 100 ml of acetone with stirring to give a white precipitate. The reaction product was isolated to obtain the compound (8) shown below.
Similarly, 3-glycidoxypropyl-methyldimethoxysilane was used as a starting material to obtain a compound (9) shown below. 0.1 g of compound (8), 0.2 g of compound (9), 0.3 g of compound (3) used in Example 1, 0.4 g of compound (4), pure water of 0.
5 g and tetrahydrofuran 0.5 g were mixed by stirring to sufficiently dissolve them. This solution was passed through a weakly acidic cation exchange resin to remove excess sodium ions. Pour 2 g of the passed solution into a 3 cm square Teflon dish,
After heating on a hot plate at 120 ° C for 2 hours, it was vacuum dried at 140 ° C for 4 days in a vacuum dryer.
A transparent film with a thickness of 3 mm was obtained. When the infrared absorption spectrum of this film was examined, it was found that the condensation reaction was almost completely carried out because the absorption of silanol groups was not observed. When the ionic conductivity of the film was measured, a value of 2.8 × 10 ⁻⁶ S · cm ⁻¹ was obtained at 25 ° C. Further, when a DC voltage application test similar to that in Example 1 was performed, a current of 73 μA continued for about 2 days. Compound (8):

[Chemical 7] Compound (9):

[Chemical 8]

[0014]

Example 3 10.0 g of 3-glycidoxypropyl-
Trimethoxysilane and 5.08 g of calcium sulfite were reacted in 15 g of pure water by stirring at 75 ° C. for 2 hours.
Then, the reaction product was poured into 100 ml of acetone with stirring to obtain a white precipitate. The reaction product was isolated to obtain the compound (10) shown below. Similarly, 3-glycidoxypropyl-methyldimethoxysilane was used as a starting material to obtain a compound (11) shown below. Compound (10) 0.1 g, Compound (11) 0.2 g, Compound (3) 0.3 g used in Example 1, Compound (4) 0.4
g, pure water 0.5 g and tetrahydrofuran 0.5 g were mixed with stirring to sufficiently dissolve them. This solution was passed through a weakly acidic cation exchange resin to remove excess calcium ions. 2 g of the passed solution was poured into a 3 cm square Teflon dish, heated on a hot plate at 120 ° C. for 2 hours, and then vacuum-dried at 140 ° C. for 4 days in a vacuum dryer to give a thickness of 0.3 mm. A transparent film was obtained. When the infrared absorption spectrum of this film was examined, it was found that the condensation reaction was almost completely carried out because the absorption of silanol groups was not observed. When the ionic conductivity of the film was measured, a value of 8.7 × 10 ⁻⁷ S · cm ⁻¹ was obtained at 25 ° C. Further, when a DC voltage application test similar to that in Example 1 was performed, a current of 23 μA was maintained for about 2 days. Compound (10):

[Chemical 9] Compound (11):

[Chemical 10]

[0015]

Example 4 5.00 g of compound (12) shown below and p-
1.77 g of chloromethylstyrene was dissolved in 10 ml of toluene, then 1.6 mg of p-methoxyphenol as a polymerization inhibitor, and 2% by weight of chloroplatinic acid hexahydrate (H ₂ PtCl ₆ .6H ₂ O) as a hydrosilylation catalyst. After adding 24.7 μl of the isopropyl alcohol solution, the temperature was raised to 70 ° C. and the reaction was carried out at this temperature for about 2 hours. Further, 3.50 g of the compound (13) shown below was added dropwise to this reaction solution at 70 ° C. and reacted at this temperature for about 2 hours, and then the solvent was removed. The resulting product (10.4 g) and 0.545 g of lithium sulfite were reacted in 11 g of pure water by stirring at 75 ° C. for 2 hours. Then, the reaction product was poured into 100 ml of acetone with stirring to obtain a white precipitate. The reaction product was isolated to obtain the compound (14) shown below. Excessive lithium ions were removed by passing through a weakly acidic cation exchange resin. Compound obtained above
(14) Pour 1 g into a 3 cm square Teflon dish, and irradiate 160 W / cm ultraviolet rays from a high-pressure mercury lamp from a vertically upper position at a distance of 5 cm for 6 seconds to obtain a transparent film having a thickness of 0.3 mm. Got Further, after drying this under reduced pressure at 70 ° C. for 2 days, the ionic conductivity was measured.
The measured value was 1.5 × 10 ⁻⁶ S · cm ⁻¹ at 25 ° C.
Further, when a DC voltage application test similar to that in Example 1 was performed, a current of 39 μA continued for about 2 days. Compound (12):

[Chemical 11] Compound _{(13): CH 2 = CH} -CH 2 O (CH 2 CH 2 O) 12 CH 3 Compound (14):

[Chemical 12]

[0016]

Example 5 0.634 g of compound (15) shown below, 0.275 g of compound (16) shown below, and sodium bisulfite 0.09.
1 g, pure water 0.5 g and tetrahydrofuran 0.5 g were added and uniformly mixed. As a photosensitizer, (4-
After adding about 20 mg of isopropyl) phenyl-11 hydroxyisopropylketone, it was poured into a 3 cm square Teflon dish and heated on a hot plate at 120 ° C. for 2 hours, then 160 W from a high pressure mercury lamp from above vertically.
By irradiating UV rays of / cm at a distance of 5 cm for 6 seconds,
A transparent film with a thickness of 0.3 mm was obtained. The film was further dried under reduced pressure at 70 ° C for 2 days, and the ionic conductivity of this film was measured. The measured value was 25 ° C at 1.
It was 8 × 10 ⁻⁶ S · cm ⁻¹ . Further, when a DC voltage application test similar to that in Example 1 was performed, a current of 47 μA continued for about 2 days. Compound (15):

[Chemical 13] Compound _{(16): CH 2 = CH} -CH 2 O (CH 2 CH 2 O) 12 CH 2 -CH
= CH ₂

[0017]

Example 6 Compound (12) 0.53 used in Example 4
9 g, 0.291 g of the compound (16) used in Example 5,
Lithium styrenesulfonate 0.176g, pure water 0.5g
And 0.5 g of tetrahydrofuran were added and homogeneously mixed. 2 g of this solution was poured into a 3 cm square Teflon dish and heated on a hot plate at 120 ° C. for 2 hours.
2 wt% chloroplatinic acid 6 as a hydrosilylation catalyst
After adding 2.47 μl of hydrate (H ₂ PtCl ₆ · 6H ₂ O) isopropyl alcohol solution, the temperature was raised to 70 ° C. and the reaction was carried out at this temperature for about 2 hours. I got a film. Further, this was dried under reduced pressure at 70 ° C. for 2 days, and the ionic conductivity was measured.
A value of 1.6 × 10 ⁻⁶ S · cm ⁻¹ was obtained at ° C. Further, when a DC voltage application test similar to that in Example 1 was performed, it was 42 μm.
The current of A lasted for about 2 days.

[0018]

Example 7: 0.3 g of the compound (5) used in Example 2,
0.5 g of compound (7), 0.5 of compound (1) used in Example 1.
2 g of pure water, 0.5 g of pure water and 0.5 g of tetrahydrofuran were evenly mixed, 3 μl of 0.1N hydrochloric acid ethanol solution was added, and then 2 g of the solution was poured into a 3 cm square Teflon dish and heated at 120 ° C. on a hot plate. After heating for 2 hours at 140 ° C. for 4 days under vacuum at 140 ° C., a transparent film having a thickness of 0.3 mm was obtained. When the ionic conductivity of this film was measured, a value of 1.7 × 10 ⁻⁶ S · cm ⁻¹ was obtained at 25 ° C. In addition, Example 1
When a DC voltage application test similar to the above was conducted, a current of 44 μA continued for about 2 days.

[0019]

Example 8 Compound (12) 10.0 used in Example 4
g, 2.41 g of styrene was dissolved in 20 ml of toluene, 3.2 mg of p-methoxyphenol as a polymerization inhibitor, and 2% by weight of chloroplatinic acid hexahydrate as a hydrosilylation catalyst (H
₂ PtCl ₆ · 6H ₂ O) After adding 49.4μl of isopropyl alcohol solution, the temperature was raised to 70 ° C., 2 at this temperature
Let it react for about the time. The solvent was removed from the reaction solution. After 10 g of the obtained polymer was contacted with 5 g of 96% sulfuric acid for sulfonation, excess sulfuric acid was removed by washing with water. After measuring the sulfonic acid value of the obtained oily substance, it was neutralized with an equivalent amount of lithium hydroxide to give the compound (1
7) was obtained. Next, 0.709 g of the compound (17), Example 5
0.291 g of the compound (16) used in 1., 0.5 g of pure water and 0.5 g of tetrahydrofuran were added and uniformly mixed.
Pour 2 g of this solution into a 3 cm square Teflon dish,
After heating at 120 ° C. for 2 hours on a hot plate, 2 wt% chloroplatinic acid hexahydrate (H 2
After adding 2.47 μl of ₂ PtCl ₆ .6H ₂ O) isopropyl alcohol solution, the temperature was raised to 70 ° C. and the reaction was carried out at this temperature for about 2 hours to obtain a transparent film having a thickness of 0.3 mm. It was Further, this film was dried under reduced pressure at 70 ° C. for 2 days and then its ionic conductivity was measured. As a result, a value of 1.8 × 10 ⁻⁶ S · cm ⁻¹ was obtained at 25 ° C. Further, when a DC voltage application test similar to that in Example 1 was performed, a current of 47 μA continued for about 2 days. Compound (17):

[Chemical 14]

[0020]

Industrial Applicability The ion conductive material of the present invention exhibits high ion conductivity at room temperature because metal ions are dispersed in a specific polymer copolymer crosslinked product, and depending on the operation of the composition, positive ion alone conductivity can be obtained. Type ion conductive material, and when it is applied to electronic devices etc., there are no problems such as liquid leakage, side effects, etc., prevention of internal resistance deterioration over time, generation of dendrites from metal electrodes, etc. Have. Therefore, a highly reliable product can be obtained, and since it is colorless and transparent, a wide range of applications can be expected. In addition, the manufacturing method has features that it is simple, the quality is constant, the environment is not deteriorated, the energy saving is excellent, and the cost required for capital investment can be reduced.

Claims (1)

[Claims] 1. A formula (—SO ₃ ⁻ ) nM ^{n +} bonded to a polymer skeleton via a hydrocarbon group (wherein, M ^{n +} represents a metal ion of Group I or Group II of the periodic table, and n Is 1 or 2.) An ion conductive material, characterized by comprising a crosslinked polymer copolymer composed of an organopolysiloxane chain containing a metal sulfonate group represented by 1) and a polyoxyalkylene chain. .