JPH0551632B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a block-graft copolymer composition useful as a functional polymer material such as a fixed polymer electrolyte. (Prior Art) Recently, organic conductors have been discovered that have electronic conductivity comparable to that of metals, and their use has already begun to be considered in some areas. However, although progress has been made in the development of ionic conductors, mainly inorganic crystals, glasses, and ceramics, organic polymer solids have not yet been put into practical use. Compared to inorganic ionic conductors, polymeric ones (i) have a lower specific gravity; (ii)
It has the following characteristics: (iii) flexible and thin films can be easily obtained; and (iv) relatively high ionic conductivity at room temperature. On the other hand, the required properties for general solid electrolytes, including polymer electrolytes, are (i) film-forming properties, (ii) high ionic conductivity, (iii) ionic ring ratio, and (iv) control of low water content. In particular, (ii) is emphasized. The mainstream of polymer materials currently being researched is matrix materials containing polyethylene oxide. (Problem to be solved by the invention) However, homopolyethylene oxide has a high degree of polymerization.
If it is less than 20, the cohesive force is too weak to form a film, and if it is more than 20, crystallization will begin and the performance as a solid electrolyte will deteriorate. Therefore, there is a limitation that the performance as a solid electrolyte cannot be improved with the currently available polymer materials. An object of the present invention is to provide a new highly functional polymeric material that solves this problem. (Means for Solving the Problems) The functional polymer material according to the present invention has the general formula () (Here, R ¹ is a hydrogen atom, a methyl group, or an ethyl group, R ² is a hydrogen atom or a methyl group, R ³ is a hydrogen atom, an alkyl group, an aryl group, an acyl group, or a silyl group, and n is 1 to 45 is an integer in the expression The number average molecular weight of the graft chain shown by is 45 or more
A block chain A of at least one polymer having a degree of polymerization of 10 or more and consisting of repeating units represented by (less than 2000); (Here, R ⁴ is a hydrogen atom, a methyl group, or an ethyl group, M is a formula -CH=CH ₂ , -C(CH ₃ )=CH ₂ ,
_A group represented by _-COOCH3 or _-COOC2H5 ,
It is composed of a block chain B of at least one kind of polymer having a degree of polymerization of 300 or more, which is composed of repeating units represented by phenyl group or substituted phenyl group, and the component ratio of block chain A and block chain B is A block-graft copolymer having a polymerization degree of 310 or more with a ratio of 1:30 to 30:1 has a ratio of 0.05 to 80 to the alkylene oxide unit (n) of the general formula ().
The composition is a mixture of inorganic salts containing at least one element selected from Li, Na, K, Cs, Ag, Cu, and Mg in mol%. The block-graft copolymer used here has at least one polymer block chain A, B consisting of the same or different repeating units represented by the general formulas () and ((), for example, A ¹ B ¹ , B ¹ A ¹ , B ¹ A ¹ B ¹ , B ¹ A ¹ B ² ,
They can be arbitrarily arranged as B ¹ A ¹ B ² A ¹ B ¹ . The polymerization degree of block chain A of the polymer is 10 or more, and the polymerization degree of B is 300 or more, and the component ratio of both block chains A and B is 1:30 to 30:1, so that the obtained block-graft copolymer The polymerization degree of the combination is 310 or more. Since the polymer block chain A functions as a polymer electrolyte, if the degree of polymerization is less than 10,
This polymer does not exhibit the characteristic microphase separation structure, and since the block chain B is a portion that maintains mechanical strength, if the degree of polymerization is less than 300, the mechanical strength of the polymer will decrease. Furthermore, if the component ratio of block chain A to block chain B is less than 1:30, the graft component will be too small and it will be difficult to maintain the function as a polymer electrolyte, and if it is more than 30:1, the graft component will not function as the main molecule of the block chain. This is because it becomes difficult to maintain mechanical strength. The block-graft copolymer composition according to the present invention is obtained by mixing the above-mentioned block-graft copolymer with the following inorganic salt. The inorganic ionic salts used here include Li, Na, K,
Contains at least one element among Cs, Ag, Cu, and Mg, specifically LiClO ₄ , LiI,
LiSCN, LiBF ₄ , LiAsF ₆ , LiCF ₃ SO ₃ , LiPF ₆ ,
NaI, NaSCN, NaBr, _NPF6 , KI, KSCN,
KPF ₆ , KAsF ₆ , CsSCN, CsBF ₄ , CsPF ₆ ,
Examples include AgNO ₃ , CuC ₁₂ Mg(ClO ₄ ) ₂ , RbCu ₄ I _1.75 Cl _3.25 , and these may be used alone or in combination of two or more thereof. By forming metal complexes with polyalkylene oxide,
The transfer rate of metal ions is increased, and properties as a solid electrolyte are obtained. In addition, the ratio of this to the block-graft copolymer is 0.05 to 80% relative to the alkylene oxide unit (n) of this copolymer.
mol %, preferably 0.1 to 50 mol %. This block-graft copolymer has, for example, the general formula () (wherein R ¹ is the same as above) and at least one block chain C of a polymer having a degree of polymerization of 10 or more; 1 degree of polymerization
Component ratio of block chain B of polymer of 300 or more is 1:
A block copolymer T having a polymerization ratio of 30 to 30:1 and having a polymerization degree of 310 or more is synthesized, and then the hydroxyl group of the side chain of this block copolymer is substituted with the general formula RMe ( Here, R is t-butyl ether, diphenylethylene, benzyl, naphthalene, or cumyl group, and Me is sodium, potassium, or cesium atom).
Add to this the general formula () (Here, R ² is the same as above) is added to grow the graft chain,
Then the acid or the general formula R ⁵ X (where R ⁵ is an alkyl group, aryl group, acyl group or silyl group,
is a halogen atom) by adding a halogen compound to stop the polymerization. At this time, the block copolymer T as a main molecular chain consisting of block chains C and B used as starting materials is firstly 4-hydroxystyrene, 4-(1
For a monomer compound containing a residue represented by the general formula (), exemplified by -methylethenyl)phenol, the phenolic hydroxyl group is protected with a trialkyl group or a trialkylsilyl group. Synthesized from monomer compounds exemplified by vinyl compounds such as α-methylstyrene; diene compounds such as butadiene and isoprene; acrylic acid esters and methacrylic acid esters such as methyl acrylate, ethyl acrylate, metal methacrylate, and ethyl methacrylate; It can be obtained by polymerizing a block polymer having a repeating unit represented by the general formula () by a living anionic polymerization method and then hydrolyzing it with an acid or the like. Examples of initiators used in this polymerization include organometallic compounds such as n-butyllithium, sec-butyllithium, tert-butyllithium, and 2-methylbutyllithium. -Butyllithium is preferred. The amount used, together with the amount of the compound to be charged, determines the molecular weight of the resulting polymer, and is therefore selected depending on the desired molecular weight. Since it is preferable that the degree of polymerization of the block chains C constituting the obtained block copolymer T is 10 or more, the concentration in the reaction solution is usually on the order of 10 ^-2 to 10 ^-4 mol/. . Polymerization is generally carried out in an organic solvent, and examples of organic solvents that can be used include benzene,
Solvents for anionic polymerization such as toluene, n-hexane, and tetrahydrofuran are preferred. The appropriate concentration of the monomer compound to be subjected to polymerization in the reaction solution is 1 to 10% by weight, and the polymerization reaction is carried out under a high vacuum with a stress of 10 ^-5 Torr or less, or purified to remove harmful substances such as moisture. It is preferable to carry out the reaction under stirring at room temperature in an inert gas atmosphere such as argon or nitrogen. The elimination reaction of the protecting group can be easily carried out by dropping an acid such as hydrochloric acid or hydroiodic acid in a solvent such as dioxane, acetone, methyl ethyl ketone, or acetonitrile while heating. Carbanionization of the hydroxyl groups of the block copolymer T thus obtained is carried out by dissolving it in an anionic polymerization solvent such as tetrahydrofuran at a concentration of 1 to 30% by weight, preferably 1 to 10% by weight.
Add the organic alkali metal dissolved in a suitable solvent such as tetrahydrofuron to this, and add it for 30 minutes at 0 to 25℃.
This is done by stirring for 4 hours. Examples of organic alkali metals used in this reaction include t-butoxypotassium, naphthalene potassium, diphenylethylene potassium, benzyl potassium, cumyl potassium, naphthalene sodium, and cumyl cesium. Among these, t-butoxypotassium is particularly preferred. preferable. To confirm this reaction, the product was reacted with trimethylsilyl chloride, then precipitated in methanol, purified, dried, and isolated.
This can be done by measuring the disappearance of hydroxyl groups and the amount of increase in trimethylsilyl groups by ¹ H-NMR, and it is possible to quantitatively understand the reaction of organic alkali metals to hydroxyl groups. It can also be confirmed by GPC that the block chains have not undergone cross-linking or decomposition reactions. Next, to the carbanionized block copolymer T, an alkylene soxide represented by the general formula (), such as ethylene oxide, propylene oxide, etc., is added in vapor or liquid form, and the mixture is heated at 0 to 80°C for 1 to 10 minutes, depending on the amount. After stirring for 48 hours, a block-graft copolymer can be obtained. The polymerization solution containing alkylene oxide is n-
Pouring into hexane produces a precipitate that can be isolated by filtering and drying. For characterization, the number average molecular weight is measured using a membrane osmometer, and the structure and composition are measured using infrared absorption spectroscopy and ¹ H-NMR. From the results, the length and number of graft chains can be determined. In addition, GPC can be used to determine whether the target product has been isolated and to estimate its molecular weight distribution. The polymerization of the block copolymer T, which becomes the main molecular chain, and the reaction for growing its branch molecular chains are usually carried out in an organic solvent. Examples of organic solvents that can be used for this are tetrahydrofuran, dioxane, Solvents for anionic or ring-opening polymerization, such as tetrahydropyran and benzene, are preferred. Compounds used to terminate polymerization include, for example, acids such as acetic acid; alkyl groups and aryl groups represented by the general formula R ⁵ halogenated compounds having a group, an acyl group, or a silyl group; and the like. The length of the graft chain is controlled by the number of moles of block chain C contained in the block-graft copolymer,
It is determined by the amount of organic alkali metal and the amount of alkylene oxide during carbanionization.
That is, the amount of organic alkali metal must not exceed the number of moles of block chain C, and the length of the graft chain is expressed as: number of moles of alkylene oxide/number of moles of organic alkali metal×molecular weight of alkylene oxide. For example, the length of the graft chain is the number average molecular weight.
To produce a block-graft copolymer of 2000, a block containing 7 x 10 ^-3 mol of block chain C is
Add organic alkali metal 5x to graft copolymer
After adding 10 ^-3 mol and performing carbanionization, 10 g of alkylene oxide may be added. Further, in order to produce a block-graft copolymer having a number average molecular weight of 45, all of the above-mentioned components may be used in equimolar amounts. Furthermore, those with a number average molecular weight of 45 to 2000,
This can be achieved by arbitrarily selecting an intermediate number of moles. The block-graft copolymer thus obtained is then added with the above-mentioned inorganic salt to obtain the composition of the present invention, but there are no particular restrictions on the method. A method in which an inorganic salt is dissolved in a solvent such as methyl ethyl ketone as necessary and mixed uniformly, a method in which an inorganic salt is added to a block-graft copolymer and mechanically kneaded at room temperature or under heat, and a method in which an inorganic salt is dissolved Any method can be selected, such as a method in which the membrane of the block-graft copolymer is impregnated in a solvent such as methanol to swell the membrane, and the inorganic salt is uniformly dispersed therein. (Examples) Hereinafter, specific embodiments of the present invention will be described in more detail based on Examples and Comparative Examples. In addition,
The block copolymer in the example is made by connecting each component with [-b-], for example, a ternary block copolymer of polystyrene, poly-p-hydroxystyrene, and polystyrene, and poly(styrene-b-). p-
hydroxystyrene-b-styrene). Example 1-1 [Poly(styrene-b-p-hydroxystyrene-b-styrene)...Synthesis of block copolymer T serving as the main molecular chain] Tetrahydrofuran 540 under high vacuum of 10 ^-5 Torr
1.1x of n-butyllithium as initiator in ml
10 ^-4 mol was charged. This mixed solution was kept at -78°C and diluted with 80ml of tetrahydrofuran. 5.6g
of styrene was added and polymerized with stirring for 30 minutes. This reaction solution took on a red color. Next, 4.1 g of p-tert-butoxystyrene diluted with 90 ml of tetrahydrofuran was added and polymerized for 15 minutes with stirring. This solution took on a red color. To this was added 5.6 g of styrene diluted with 80 ml of tetrahydrofuran, and polymerization was continued for an additional 10 minutes with stirring. This solution also took on a red color. After the polymerization was completed, the reaction mixture was poured into methanol to precipitate the resulting polymer, which was then separated and dried to obtain 15.3 g of a white polymer. According to the ¹ H-NMR results, this is 73% styrene.
It was found to be a block copolymer consisting of 27% p-tert-butoxystyrene. Furthermore, the GPC solution curve showed a sharp single peak, confirming that it was a single polymer. n of this polymer is 14
It was ×10 ⁴ . Next, the block copolymer was dissolved in a mixed solvent of acetone and benzene, and dissolved at 30℃ using hydrogen iodide.
Poly(styrene-b-p-hydroxystyrene-b-
Styrene) was synthesized. In addition, styrene/in this poly(styrene-b-p-hydroxystyrene-b-styrene)
The ratio and molecular weight of p-hydroxystyrene/styrene can be arbitrarily selected depending on the amount charged and the concentration of the initiator. Example 1-2 [Poly(styrene-b-p-hydroxystyrene-b-styrene)...carbanionization of block copolymer T serving as the main molecular chain with an organic alkali metal] Poly(styrene obtained in the previous example) -b-p-hydroxystyrene-b-styrene) was dissolved in 200 ml of tetrahydrofuran under vacuum. To this solution was added 0.07 mol of potassium t-butoxy at 25°C. After stirring this solution for 1 hour, an additional 0.5
After adding mol of trimethylsilyl chloride to react, the reaction solution was poured into methanol, and the resulting polymer was precipitated and separated. When this polymer was analyzed by ¹ H-NMR, it was confirmed that potassium reacted with the hydroxyl groups, so that the hydroxyl group peak disappeared and the trimethylsilyl group peak increased. Also
From the GPC elution curve, it was confirmed that the molecular weight distribution was unchanged from before carbanionization, and that neither crosslinking nor decomposition reactions had occurred. In this example, carbanionization of the hydroxyl groups of the block copolymer proceeded completely quantitatively, and
This indicates that there are no side reactions such as main chain decomposition or crosslinking. Example 1-3 [Poly(styrene-
b-p-hydroxystyrene-b-styrene)
Synthesis of block-graft copolymer from
Production of the composition of the present invention incorporating NaSCN] The poly(styrene-b-
10g of p-hydroxystyrene (b-styrene)
was dissolved in 250 ml of tetrahydrofuran under high vacuum at 10 ⁻⁶ Torr. 8.3×10 ^-3 in this solution at 25℃
A mole of potassium t-butoxy was added. After stirring this solution for 1 hour, 4.15 g of ethylene oxide was added. This was kept at 65°C and stirred for 24 hours. Thereafter, acetic acid was added to stop the polymerization, and the reaction mixture was poured into n-hexane to precipitate and separate the polymer, which was then dried. The obtained polymer is 14.15
It was hot at g. This GPC elution curve is shown in Figure ¹ .
The results of NMR analysis are shown in Figure 2. Since the GPC elution curve is sharp and has a single peak,
It was confirmed that this was a single polymer. Further, n of this polymer was 20×10 ⁴ . This ¹ H
-From NMR and n, the length of the graft chain is 500
The composition of polyethylene oxide was found to be 30%. In addition, this IR spectrum is
Shown in the figure. FIG. 4 shows an electron micrograph of a film prepared by dissolving this block-graft copolymer in methyl ethyl ketone. From this, the phase of the trunk molecular chain (fine white streaks) and the phase of the branch molecular chains (black streaks)
It can be seen that these are microscopically separated. The absorption position of this graft chain in IR and ¹ H-NMR is IR (cm ^-1 ): C-O-C: 1115 cm ^-1 , ¹ H-
NMR (δ, ppm): OCH ₂ CH ₂ : 3.6 ppm. 1 g of the block-graft copolymer thus obtained was dissolved in 25 ml of methyl ethyl ketone. 5ml of 0.03g NaSCN dissolved in this solution
of methyl ethyl ketone was added and mixed uniformly.
This solution was cast onto a Teflon plate. The sample was allowed to stand at room temperature for 24 hours to remove excess solvent, and then dried under reduced pressure at 60° C. for 24 hours to form a film. This membrane is
NaSCN was uniformly dispersed. This is 15mm in diameter
The electrodes were formed by applying conductive silver paste to both sides of the disk, and using an AC impedance measuring device (Yokogawa-Hewlett Packard) with a frequency of 5 Hz to 13 MHz.
Multi-frequency LCR meter
Ion conductivity was calculated by computer processing the complex impedance display using model 4192A). As a result, a value of 7×10 ⁻⁵ S/cm at 23° C. was obtained. Examples 2 to 3 and Comparative Example 1 [Same as the previous example] The same procedure as in the previous example was performed except that the amounts of ethylene oxide and inorganic salts added and the polymerization conditions were changed as shown in Table 1, and the results were as shown in the table. The results were obtained. In addition, in Comparative Example 1, a block-graft copolymer with a graft chain length of 5000 was obtained, and the polyethylene oxide chains were crystallized.
NaSCN was precipitated in the upper layer, and it was not possible to obtain a product in which NaSCN was uniformly dispersed.

[Synthesis of block-graft copolymer from poly(styrene-b-p-hydroxystyrene-b-styrene) using propylene oxide and production of a composition incorporating LiClO ₄ therein]

Poly(styrene-b-
10g of p-hydroxystyrene (b-styrene)
was dissolved in 250 ml of tetrahydrofuran under high vacuum at 10 ⁻⁶ Torr. 0.02 mol of cumyl potassium was added to this solution, and after stirring at 25° C. for 1 hour, 6.3 g of propylene oxide was added. This was kept at 65°C and stirred for 24 hours, and trimethylsilyl chloride was added to stop the polymerization. After the polymerization was completed, the reaction mixture was poured into n-hexane to precipitate the polymer, which was separated and dried. The obtained polymer was white in color and weighed 16.3 g.
The n of this polymer is 23 x ¹⁰⁴ , and the GPC elution curve consists of a single sharp peak similar to that in Figure 1, confirming that this is a single polymer and making it ideal. It was found that grafting had taken place. IR of the grafted chain of this, ¹ H−
The absorption position in NMR is IR (cm ^-1 ): C-O-
C: 1115 cm ^-1 , ¹ H-NMR (δ, ppm): OCH ₂ CH
(CH ₂ ): 3.6 ppm. In addition, from the above n and ¹ H-NMR, it was found that the length of the graft chain was 315 and the composition of polypropylene oxide was 39%. 1 g of the obtained copolymer was dissolved in 25 ml of tetrahydrofuran. Add 0.03g LiClO ₄ to this solution
5 ml of tetrahydrofuran was added thereto, mixed uniformly, and cast onto a Teflon plate. This membrane was also allowed to stand at room temperature for 24 hours to remove excess solvent.
Further, it was dried under reduced pressure at 60°C for 24 hours to form a film. In this film, LiClO ₄ was uniformly dispersed. When the specific conductivity of this was measured in the same manner as in Example 1-3, a value of 7.5×10 ⁻⁵ S/cm (25° C.) was obtained. Example 5 [Block copolymer: poly(styrene-b-p
-Hydroxystyrene-b-methyl methacrylate) and ethylene oxide, and KPF ₆
[Preparation of a composition incorporating
3.6×10 ^-5 mol of n-butyllithium was charged,
Keep this at -78℃ and add 5.2g of styrene, p.
14.7 g of -tert-butoxystyrene and 5.2 g of methyl acrylate were successively added, and poly(styrene-b-p-tert-butoxystyrene-b-methyl methacrylate) was obtained in a polymerization time of 3 hours. Next, this block copolymer was dissolved in a mixed solvent of acetone and benzene, and hydrolyzed using hydrogen iodide to form a polyester containing 30 parts of styrene/40 parts of p-hydroxystyrene/30 parts of methyl methacrylate. (Styrene-b-p-hydroxystyrene-b-methyl methacrylate) was synthesized. From the results of ¹ H-NMR, GPC, and membrane osmotic pressure, this is 40% hydroxystyrene, and n is 20×10 ⁴
It was confirmed that 10g of this block copolymer was 10 ^-6 mm/Hg
Dissolved in 250 ml of tetrahydrofuran under high vacuum. To this solution was added 0.03 mol of potassium naphthalene at 25°C. After stirring this solution for 1 hour, 14 g of ethylene oxide was added. This was heated to 65℃ for 24 hours.
After stirring for an hour, methyl bromide was added to stop the polymerization. After the polymerization was completed, the reaction mixture was poured into n-hexane to precipitate the polymer, which was separated and dried.
The obtained polymer was white and weighed 24 g. The n of this polymer is 47 x 10 ⁴ , and the GPC solution curve consists of a single sharp peak, similar to that in Figure 1, confirming that this is a single polymer, and that it is ideal. It was found that grafting had taken place. This IR spectrum is shown in FIG. The absorption position of this graft chain in IR and ¹ H-NMR is IR (cm ^-1 ):C-O-C:
1115cm ^-1 , C=O: 1730cm ^-1 , C-CH ₃ : 1390,
1480cm ^-1 , ¹ H-NMR (δ, ppm): OCH ₂ CH ₂ :
3.6 ppm, α-methyl group: 1.2 ppm. In addition, from the above n and ¹ H-NMR, it was found that the length of the graft chain was 450, and the composition of polyethylene oxide was 58%. 1 g of the obtained copolymer and 0.06 g of KPF ₆ were dissolved in tetrahydrofuran and cast on a Teflon plate. This membrane was allowed to stand at room temperature for 24 hours to remove excess solvent, and then dried under reduced pressure at 60° C. for 24 hours to form a membrane. In this film, KPF ₆ was uniformly dispersed. When the specific conductivity of this was measured in the same manner as in Example 1-3, it was found to be 8×10 ^-5 S/cm.
(25℃) was obtained. Example 6 [Block copolymer: poly(styrene-b-p
- Synthesis of a block-graft copolymer from hydroxystyrene-b-butadiene and ethylene oxide and production of a composition incorporating _CsBF4 ] In 500 ml of tetrahydrofuran, 1.0 x 10 ^- as an initiator. Prepare ⁴ moles of n-butyllithium,
Keep this at -78℃ and add 5.6g of styrene, p.
- Butoxystyrene 7.0g and butadiene 5.2g were added sequentially, styrene and p-tert-butoxystyrene were polymerized for 1 hour each, butadiene was polymerized for 3 hours, and poly(styrene-b-p
-tert-xystyrene-b-butadiene) was obtained. Next, this block copolymer was dissolved in a mixed solvent of acetone and benzene, and hydrolyzed using hydrogen iodide. Poly(styrene) containing 35 parts of styrene/30 parts of p-hydroxystyrene/35 parts of butadiene was -bp-hydroxystyrene-b-butadiene) was synthesized. From the results of ¹ H-NMR, GPC, and membrane osmotic pressure, the composition of this p-hydroxystyrene is 30% by weight,
It was confirmed that Mn was 15×10 ⁴ . 10g of this block copolymer was 10 ^-6 mm/Hg
Dissolved in 250 ml of tetrahydrofuran under high vacuum. To this solution was added 0.02 mol of cumyl cesium. After stirring this solution at 25° C. for 2 hours, 10 g of ethylene oxide was added. This was stirred at 65°C for 24 hours, and acetic acid was added to stop the polymerization. After the polymerization was completed, the reaction mixture was poured into n-hexane to precipitate the polymer, which was separated and dried. The obtained polymer was white and weighed 20 g. The n of this polymer is 30 × 10 ⁴ , and the GPC solution curve consists of a single peak with a sharp sharpness similar to that in Figure 1, confirming that this is a single polymer and making it ideal. It was found that grafting had taken place. This IR spectrum is shown in FIG. The absorption position of this graft chain in IR and ¹ H-NMR is IR (cm ^-1 ):C-O-C:
1115cm ^-1 , -CH=CH ₂ :905, 990cm ^-1 , C=O:
1640cm ^-1 , ¹ H-NMR (δ, ppm): OCH ₂ CH ₂ :
3.6ppm, -CH= _CH2 : 5.4, 5.0ppm. In addition, from the above n and ¹ H-NMR, it was found that the length of the graft chain was 500, and the composition of polyethylene oxide was 50%. 1 g of the obtained copolymer and 0.08 g of CsBF ₄ were dissolved in tetrahydrofuran and cast on a Teflon plate. This membrane was allowed to stand at room temperature for 24 hours to remove excess solvent, and then dried under reduced pressure at 60° C. for 24 hours to form a membrane. In this film, CsBF ₄ was uniformly dispersed. When the specific conductivity of this was measured in the same manner as in Examples 1 to 3, it was found to be 7×10 ^-5 S/cm (25°C).
The value of was obtained. Examples 7 to 23 and Comparative Example 2 [Production of compositions of the present invention using different types of inorganic salts] In Examples 1-3, the types and amounts of inorganic salts added were changed as shown in Table 2. Do the same for the rest,
When the composition of the present invention was manufactured, the results shown in Table 2 were obtained. Note that Comparative Example 2 is a case where no inorganic salt was added.

[Table] (Effects of the Invention) The block-graft copolymer composition according to the present invention has (1) a block copolymer as a backbone molecule, and amorphous polyalkylene oxide arranged in a concentrated manner at a specific location. (2) Because the molecular structure has been specified, it exhibits a precise microphase-separated structure.
Therefore, functions can be shared between the main molecular chain and the branch molecular chains. In particular, by selecting mechanical strength for the block chain (stem molecule) and by selecting amorphous polyalkylene oxide for the graft chain, by forming a complex with an inorganic salt, and by incorporating an inorganic salt into the polymer. By uniformly distributing , it is possible to impart functions such as high metal ion mobility, resulting in a functional polymer material with higher performance than conventional polymers containing polyalkylene oxide. Normally, when the number average molecular weight of polyalkylene oxide is 2000 or more, crystallization begins and the high mobility of metal ions and the content of metal ions cannot be increased, so blocks with graft chains of such length are - Although a graft copolymer cannot be used as a solid polymer electrolyte, the polyalkylene oxide of the present invention, which has a number average molecular weight of less than 2000, is in a liquid state, resulting in high metal ion mobility and metal ion content. allows for an increase in the amount of
It ensures high ionic conductivity and provides properties as a solid electrolyte.

[Brief explanation of the drawing]

Figures 1 to 4 show the block-graft copolymer obtained in Example 1, respectively.
FIGS. 5 and 6 are graphs and electron micrographs showing GPC elution curves, ¹ H-NMR spectra, and IR spectra, respectively. It is a graph showing an IR spectrum.

Claims (1)

[Claims] 1 General formula () (Here, R ¹ is a hydrogen atom, methyl group or ethyl group, R ² is a hydrogen atom or methyl group, R ³ is a hydrogen atom, alkyl group, aryl group, acyl group or silyl group, n is an integer from 1 to 45) , and in the formula The number average molecular weight of the grafted chain is 45 or more.
a block chain A of at least one polymer having a degree of polymerization of 10 or more and consisting of repeating units represented by the formula (less than 2000); (Here, R ⁴ is a hydrogen atom, methyl group or ethyl group, M is a formula -CH=CH ₂ , -C(CH ₃ )=CH ₂ , -
Consisting of at least one type of polymer block chain B having a degree of polymerization of 300 or more and consisting of repeating units represented by a group represented by COOCH ₃ or -COOC ₂ H ₅ , a phenyl group, or a substituted phenyl group. A block-graft copolymer having a degree of polymerization of 310 or more and having a component ratio of block chain A and block chain B of 1:30 to 30:1 is added to the alkylene oxide unit (n) of the general formula (). A block-graft copolymer composition mixed with an inorganic salt containing 0.05 to 80 mol% of at least one element selected from Li, Na, K, Cs, Ag, Cu and Mg.