JP6809701B2 - Monomer compounds, polymer compounds, polymer composites, their manufacturing methods, electrolyte materials, and applications using them. - Google Patents

Description

The present invention relates to a monomer compound capable of synthesizing an anionic polymer, a polymer compound thereof, a polymer composite obtained from the polymer compound, a method for producing them, an electrolyte material using the polymer compound, and a lithium ion battery and its use. Regarding air batteries.

Polymer electrolytes are being studied as electrolytes for all-solid-state lithium-ion batteries. For example, it is known that a polymer having an anionic polymer as a main chain and Li ions as counter cations can be used as a polymer electrolyte of a lithium ion battery (see, for example, Non-Patent Document 1). However, in Non-Patent Document 1, since a triblock copolymer is used, the Li ion density is not sufficient, and further improvement in conductivity is required. In addition, it cannot be used in a low temperature environment because its conductivity decreases.

On the other hand, it is known that a flame-retardant ionic liquid is used as an electrolyte of a lithium ion battery. For example, an ionic liquid in which Li ions are complexed with glyme has been developed, and application of a lithium ion battery to an electrolyte has been studied (see, for example, Non-Patent Document 2 and Non-Patent Document 3). According to Non-Patent Documents 2 and 3, the bond between Li ion and grime is relatively weak, and high conductivity due to Li ion is expected. However, such an ionic liquid cannot be applied to an all-solid-state lithium-ion battery as it is.

R. Bouchet et al., Nature Materials, Vol. 12, May 2013, 452-457 K. Yoshida et al., J. Mol. Am. Chem. Soc. 2011, 133, 13121-13129 Ce Zhang et al., J. Mol. Phys. Chem. B 2014,118,514-5153

An object of the present invention is a monomer compound for producing a polymer composite exhibiting excellent conductivity even in a low temperature environment such as 0 ° C. or lower, a polymer compound thereof, a polymer composite using these, and their production. It is to provide a method, an electrolyte material using it, and an application using it.

The monomer compound according to the present invention is represented by the general formula (1), thereby solving the above-mentioned problems.


Here, Tf represents a trifluoromethanesulfonyl group (-SO ₂ CF ₃ ), and R ₁ is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, which has or does not have a hydrogen or a substituent. n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec-pentyl group, 3-pentyl group, tert-pentyl group, n-hexyl group, isohexyl group, sec-hexyl group , 3-Hexyl group, tert-Hexyl group or Cyclohexyl group.
The R ₁ may be a hydrogen or a methyl group.
The substituent may be selected from the group consisting of halogen groups, hydroxyl groups, amino groups and epoxy groups. The polymer compound according to the present invention is represented by the general formula (2), thereby solving the above-mentioned problems.

Here, Tf represents a trifluoromethanesulfonyl group (-SO ₂ CF ₃ ), and R ₁ is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, which has or does not have a hydrogen or a substituent. n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec-pentyl group, 3-pentyl group, tert-pentyl group, n-hexyl group, isohexyl group, sec-hexyl group , 3-Hexyl group, tert-Hexyl group or cyclohexyl group, where n is an integer of 10 or more and 100,000 or less.

The R ₁ may be a hydrogen or a methyl group. The polymer composite according to the present invention has an anionic polymer compound represented by the general formula (3) as a main chain.
The complex represented by the general formula (4) is used as a counter cation, thereby solving the above-mentioned problem.

Here, Tf represents a trifluoromethanesulfonyl group (-SO ₂ CF ₃ ), and R ₁ is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, which has or does not have a hydrogen or a substituent. n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec-pentyl group, 3-pentyl group, tert-pentyl group, n-hexyl group, isohexyl group, sec-hexyl group , 3-Hexyl group, tert-Hexyl group or Cyclohexyl group, n is an integer of 10 or more and 100,000 or less, and R ₂ and R ₃ have or do not have the same or different substituents. , Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec-pentyl group, 3-pentyl group, tert- It is a pentyl group, an n-hexyl group, an isohexyl group, a sec-hexyl group, a 3-hexyl group, a tert-hexyl group or a cyclohexyl group, and m is an integer of 1 or more and 4 or less.
The R ₁ may be a hydrogen or a methyl group, and the R ₂ and the R ₃ may be the same or different methyl or ethyl groups.
The method for producing the above-mentioned monomer compound according to the present invention comprises the first step of reacting NH ₂ SO ₂ CF ₃ with MH (M is an element selected from the group consisting of Li, Na, K and Cs). The second step of reacting the reaction product obtained in the first step with the compound represented by the general formula (I), and the reaction product obtained in the second step are lithium hydride and lithium hydroxide. , And a third step of reacting a lithium salt selected from the group consisting of lithium alkoxides, thereby solving the above problems.

Here, R ₁ is hydrogen, or has or does not have a substituent, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-. Pentyl group, isopentyl group, sec-pentyl group, 3-pentyl group, tert-pentyl group, n-hexyl group, isohexyl group, sec-hexyl group, 3-hexyl group, tert-hexyl group or cyclohexyl group, X Is an element selected from the group consisting of fluorine, chlorine, bromine and iodine.
The first step may be reacted in a polar solvent in a temperature range of −100 ° C. or higher and 30 ° C. or lower.
The second step may be reacted in a polar solvent in a temperature range of −100 ° C. or higher and 30 ° C. or lower.
The third step may be reacted in a polar solvent in a temperature range of −100 ° C. or higher and 30 ° C. or lower.
The method for producing the above-mentioned monomer compound according to the present invention comprises the first step of reacting NH ₂ SO ₂ CF ₃ with MH (M is an element selected from the group consisting of Li, Na, K and Cs). The reactant obtained in the first step, the compound represented by the general formula (I), and an amine selected from the group consisting of triethylamine, pyridine and 1,4-diazabicyclo [2.2.2] octane. It includes a second step of reacting with the class, thereby solving the above problems.

Here, R ₁ is hydrogen, or has or does not have a substituent, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-. Pentyl group, isopentyl group, sec-pentyl group, 3-pentyl group, tert-pentyl group, n-hexyl group, isohexyl group, sec-hexyl group, 3-hexyl group, tert-hexyl group or cyclohexyl group, X Is an element selected from the group consisting of fluorine, chlorine, bromine and iodine.
The method for producing the above-mentioned monomer compound according to the present invention includes NH ₂ SO ₂ CF ₃ , a compound represented by the general formula (I), triethylamine, pyridine and 1,4-diazabicyclo [2.2.2] octane. The present invention includes a first step of reacting with amines selected from the group consisting of the above, and a second step of reacting the reactant obtained in the first step with lithium halide. To solve.

Here, R ₁ is hydrogen, or has or does not have a substituent, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-. Pentyl group, isopentyl group, sec-pentyl group, 3-pentyl group, tert-pentyl group, n-hexyl group, isohexyl group, sec-hexyl group, 3-hexyl group, tert-hexyl group or cyclohexyl group, X Is an element selected from the group consisting of fluorine, chlorine, bromine and iodine.
In the method for producing the above-mentioned polymer compound according to the present invention, the above-mentioned monomer compound is polymerized by a polymerization method selected from the group consisting of radical polymerization, living radical polymerization, ion polymerization, living ion polymerization, photopolymerization and thermal polymerization. It includes steps to solve the above problems.
The living radical polymerization may be Atom Transfer Radical Polymerization (ATRP).
The method for producing the above-mentioned polymer composite in the present invention includes the step of mixing the above-mentioned polymer compound and grime represented by the general formula (II) in a polar solvent, thereby solving the above-mentioned problems. Resolve.

Here, R ₂ and R ₃ are the same or different, having or not having a substituent, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-. Butyl group, n-pentyl group, isopentyl group, sec-pentyl group, 3-pentyl group, tert-pentyl group, n-hexyl group, isohexyl group, sec-hexyl group, 3-hexyl group, tert-hexyl group or cyclohexyl It is a group, and m is an integer of 1 or more and 4 or less.
The mixing step may be performed in an inert gas atmosphere.
The electrolyte material according to the present invention contains at least the above-mentioned polymer composite, thereby solving the above-mentioned problems.
The lithium ion secondary battery according to the present invention includes a positive electrode, a negative electrode, and a polymer electrolyte layer located between the positive electrode and the negative electrode, and the polymer electrolyte layer is made of the above-mentioned electrolyte material. Solve the above problems.
The lithium-ion air battery according to the present invention includes an air electrode, a negative electrode, and a polymer electrolyte layer located between the air electrode and the negative electrode, and the polymer electrolyte layer is made of the above-mentioned electrolyte material. To solve the above problem.

Since nitrogen is directly bonded to the methacrylate group in the monomer compound according to the present invention, the monomer compound itself can be made compact. By using such a monomer compound, an anionic polymer compound can be obtained, but since a compact monomer compound is used, the density of the polymer compound can be improved. As a result, the density of Li ions contained is also improved. In the polymer composite obtained by using the monomer compound of the present invention as a starting material, the polymer compound of the present invention is used as the main chain of the anionic polymer compound, and the complex of Li ion and glyme or glyme derivative is used as the counter cation. , Li ions can easily move, and the degree of dissociation of Li ions and the transport rate of Li ions can be improved. Furthermore, as the crystallinity of the polymer composite of the present invention decreases, the glass transition temperature decreases dramatically, so that it is possible to have extremely excellent conductivity even at a particularly low temperature. When such a polymer composite is used for the polymer electrolyte layer of a lithium ion battery or an air battery, it can be used not only in a normal environment but also in a low temperature environment, which is advantageous without depending on the environment.

The figure which shows the process of manufacturing the monomer compound of this invention. The figure which shows another process for producing the monomer compound of this invention. The figure which shows still another process for producing the monomer compound of this invention. The figure which shows the process of producing the polymer compound of this invention. The figure which shows the process of manufacturing the polymer composite of this invention. Schematic diagram showing the lithium ion secondary battery of the present invention Schematic diagram showing the air battery of the present invention The figure which shows the process of synthesizing the monomer compound in Example 1. The figure which shows the appearance of the product obtained in Example 1. The figure which shows ^{1 1} H NMR spectrum of the product of Example 1. The figure which shows the ¹³ C NMR spectrum of the product of Example 1. The figure which shows the FT-IR spectrum of the product of Example 1. The figure which shows the process of synthesizing the polymer compound in Example 2. The figure which shows the relationship between the consumption ratio of a monomer compound and time in the synthesis of the polymer compound of Example 2. The figure which shows the dependence of the conversion rate of the monomer compound of the molecular weight of a polymer compound in the synthesis of the polymer compound of Example 2 The figure which shows the dependence of the conversion rate of the monomer compound of the molecular weight distribution of a polymer compound in the synthesis of the polymer compound of Example 2 The figure which shows the process of synthesizing a polymer composite in Example 3. The figure which shows ^{1 1} H NMR spectrum of the product of Example 3. The figure which shows the DSC behavior of the product of Example 3. The figure which shows the temperature dependence of the conductivity of the product of Example 3. The figure which shows the process of synthesizing the monomer compound in Example 5. The figure which shows the process of synthesizing the monomer compound in Example 6.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. The same elements are given the same numbers, and the description thereof will be omitted.

(Embodiment 1)
In the first embodiment, the monomer compound of the present invention and a method for producing the same will be described.

The monomer compound according to the present invention is represented by the general formula (1).

Here, Tf represents a trifluoromethanesulfonyl group (-SO ₂ CF ₃ ), and R ₁ is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, which has or does not have a hydrogen or a substituent. n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec-pentyl group, 3-pentyl group, tert-pentyl group, n-hexyl group, isohexyl group, sec-hexyl group , 3-Hexyl group, tert-Hexyl group or Cyclohexyl group.

In the monomer compound according to the present invention, nitrogen is directly bonded to the methacrylate group, and a trifluoromethanesulfonyl group is bonded to this nitrogen. Conventionally, those having a trifluoromethanesulfonyl group at both ends of nitrogen and those in which various alkyl groups and then nitrogen are bonded to a methacrylate group via an ester bond are known for ease of synthesis (for example, A. See S. Shaplov et al., Esterochimica Acta 2011, 57, 74-90). However, the inventors of the present application have succeeded in miniaturizing the monomer compound as a result of ingenuity in the synthesis method described later based on the idea of directly binding nitrogen to the methacrylate group.

R ₁ is preferably a hydrogen or methyl group. These are advantageous because they are easy to synthesize and the monomer compound becomes more compact.

The substituent that modifies R ₁ is not limited as long as it is a reactive substituent, but is exemplifiedly selected from the group consisting of a halogen group, a hydroxyl group, an amino group and an epoxy group. These substituents do not significantly affect the properties of the monomer compound, but the substituents can impart further properties.

Next, a method for producing the monomer compound of the present invention will be described.
FIG. 1 is a diagram showing a process of producing the monomer compound of the present invention.

Step S110: NH ₂ SO ₂ CF ₃ (trifluoromethanesulfonylamine: NH ₂ Tf) is reacted with MH (M is an element selected from the group consisting of Li, Na, K and Cs) (also in the first step). Call). As a result, the alkali metal trifluoromethanesulfonylamide (NHMTf) 110 (FIG. 1) is obtained. Here, M is an element selected from the group consisting of Li, Na, K and Cs.

In the first step, specifically, NH ₂ Tf and MH are reacted in a polar solvent in a temperature range of −100 ° C. or higher and 30 ° C. or lower. Preferably, by setting the temperature in the temperature range of −100 ° C. or higher and 0 ° C. or lower, side reactions can be suppressed and the desired product can be obtained with high purity. There is no particular limitation as long as it is a polar solvent in which NH ₂ Tf and MH are dissolved, but examples thereof include methanol, ethanol, tetrahydrofuran (THF), acetonitrile (AcN), N, N-dimethylformamide (DMF) and dimethyl sulfoxide. (DMSO), dimethylacetamide (DMAc), acetone, dioxane, ethyl acetate, chloroform, methyl ethyl ketone, propanol and the like. With these, NH ₂ Tf and MH are surely dissolved.

The reaction is completed in 1 hour or more and 48 hours or less, and NHMTf110 is obtained as a powdery product by removing the polar solvent with an evaporator or the like. The MH should be mixed so as to be at least the same as the molar equivalent of NH ₂ Tf. MH may be used more than NH ₂ Tf, as long as they are at least the same.

Step S120: The reaction product 110 (that is, NHMTf) obtained in step S110 is reacted with compound 120 (FIG. 1) represented by the general formula (I) (also referred to as a second step). As a result, the reactant 130 (FIG. 1) is obtained.

Here, R ₁ is hydrogen, or has or does not have a substituent, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-. Pentyl group, isopentyl group, sec-pentyl group, 3-pentyl group, tert-pentyl group, n-hexyl group, isohexyl group, sec-hexyl group, 3-hexyl group, tert-hexyl group or cyclohexyl group, X Is an element selected from the group consisting of fluorine, chlorine, bromine and iodine. As described above, the substituent that modifies R ₁ is not limited as long as it is a reactive substituent, but exemplary, it is selected from the group consisting of a halogen group, a hydroxyl group, an amino group and an epoxy group. Will be done.

In the second step, specifically, NHMTf110 and compound 120 of the general formula (I) are reacted in a polar solvent in a temperature range of −100 ° C. or higher and 30 ° C. or lower. Preferably, by setting the temperature in the temperature range of −100 ° C. or higher and 0 ° C. or lower, side reactions can be suppressed and the desired product can be obtained with high purity. There is no particular limitation as long as it is a polar solvent in which NHMTf110 and compound 120 are dissolved, but exemplary examples thereof include acetonitrile, acetone, tetrahydrofuran (THF), N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and dimethylacetamide. (DMAc), dioxane, ethyl acetate, chloroform, methyl ethyl ketone and the like. With these, NHMTf110 and compound 120 are surely dissolved.

The compound 120 of the general formula (I) may be added to the polar solvent containing NHMTf110 over a period of 1 hour or more and 5 hours or less, and the mixture may be stirred. As a result, the reaction is initiated and MX (M is an element selected from the group consisting of Li, Na, K and Cs, and X is selected from the group consisting of fluorine, chlorine, bromine and iodine. Is an element) is precipitated. By removing the MX precipitate by filtration and removing the polar solvent from the filtrate by an evaporator or the like, the reaction product 130 is obtained as a powdery product.

The compound 120 of the general formula (I) may be mixed so as to be at least the same as the molar equivalent of NH ₂ Tf used in step S110. When the solvent is added at a temperature of 0 ° C. or lower, the temperature of the solvent may be raised to room temperature after the addition. This promotes the reaction. As used herein, room temperature is intended to be in a temperature range above 0 ° C and below 30 ° C.

Step S130: The reactant 130 (FIG. 1) obtained in step S120 is reacted with a lithium salt selected from the group consisting of lithium hydride, lithium hydroxide, and lithium alkoxide (also referred to as a third step). .. As a result, the monomer compound 140 (FIG. 1) of the present invention represented by the general formula (1) is obtained. Examples of the lithium alkoxide include lithium methoxydo, lithium ethoxydo, lithium tert-butoxide and the like, but there is no particular limitation as long as it is a lithium compound having an alkoxide group.

In the third step, specifically, the reactant 130 and the lithium salt are reacted in a polar solvent in a temperature range of −100 ° C. or higher and 30 ° C. or lower. Preferably, by setting the temperature in the temperature range of −100 ° C. or higher and 0 ° C. or lower, the formation of side reactants can be suppressed and the desired product can be obtained with high purity. There is no particular limitation as long as it is a polar solvent in which the reaction product 130 and the lithium salt are dissolved, but exemplary examples thereof include tetrahydrofuran (THF), water, methanol, ethanol, acetonitrile (AcN), N, N-dimethylformamide (DMF). , Dimethyl sulfoxide (DMSO), dimethylacetoamide (DMAc), acetone, dioxane, ethyl acetate, chloroform, methylethylketone, propanol and the like. With these, the reactant 130 and the lithium salt are surely dissolved. The polar solvent containing the reactant 130 may be added to the polar solvent containing the lithium salt over a period of 0.5 hours or more and 3 hours or less, and the mixture may be stirred. Here, the lithium salt is added so as to be at least equal to the molar equivalent of the reactant 130. When the mixture is added at a temperature of 0 ° C. or lower, the temperature of the mixture may be raised to room temperature after the addition. This further accelerates the reaction.

By removing the polar solvent with an evaporator or the like, the monomer compound 140 represented by the general formula (1) can be obtained as a powdery product.

FIG. 2 is a diagram showing another process for producing the monomer compound of the present invention.

Step S210: NH ₂ SO ₂ CF ₃ (NH ₂ Tf) is reacted with MH (M is an element selected from the group consisting of Li, Na, K and Cs) (also referred to as the first step). Since this step is the same as the first step (S110) described with reference to FIG. 1, the description thereof will be omitted.

Step S220: the reaction product obtained in step S210 (i.e., NHMTf110) and, in the general formula (I) compound represented by 120 (Fig. 2), triethylamine _(Et 3 N), pyridine and 1,4-diazabicyclo [ 2.2.2] React with amines selected from the group consisting of octane (DABCO) (also called the second step). As a result, the monomer compound 140 (FIG. 2) of the present invention represented by the general formula (1) is obtained.

Here, R ₁ is hydrogen, or has or does not have a substituent, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-. Pentyl group, isopentyl group, sec-pentyl group, 3-pentyl group, tert-pentyl group, n-hexyl group, isohexyl group, sec-hexyl group, 3-hexyl group, tert-hexyl group or cyclohexyl group, X Is an element selected from the group consisting of fluorine, chlorine, bromine and iodine. As described above, the substituent that modifies R ₁ is not limited as long as it is a reactive substituent, but exemplary, it is selected from the group consisting of a halogen group, a hydroxyl group, an amino group and an epoxy group. Will be done.

In the second step, specifically, NHMTf110, compound 120 of the general formula (I), and amines are reacted in a polar solvent in a temperature range of −100 ° C. or higher and 30 ° C. or lower. Preferably, by setting the temperature in the temperature range of −100 ° C. or higher and 0 ° C. or lower, side reactions can be suppressed and the product can be obtained with high purity. There is no particular limitation as long as it is a polar solvent in which NHMTf110, compound 120 and amines are dissolved, but exemplary examples thereof include tetrahydrofuran (THF), methanol, ethanol, acetonitrile (AcN), N, N-dimethylformamide (DMF), and the like. There are dimethyl sulfoxide (DMSO), dimethylacetamide (DMAc), acetone, dioxane, ethyl acetate, chloroform, methyl ethyl ketone, propanol and the like. With these, the above-mentioned compounds can be dissolved.

The amines and then the compound 120 of the general formula (I) may be added to the polar solvent containing NHMTf110 over a period of 1 hour or more and 5 hours or less, and the mixture may be stirred. As a result, the reaction is started, and the monomer compound 140 of the present invention can be obtained via an intermediate. The production method shown in FIG. 2 is suitable for mass production because it requires fewer steps and has a higher yield than the production method described with reference to FIG. 1.

Compound 120 and amines of the general formula (I) may be mixed so as to be at least the same as the molar equivalent of NH ₂ Tf used in step S210. When the mixture is added at a temperature of 0 ° C. or lower, the temperature of the mixture may be raised to room temperature after the addition. This further accelerates the reaction and can produce amine halides as precipitates. By removing the polar solvent with an evaporator or the like, the monomer compound 140 represented by the general formula (1) can be obtained as a powdery product.

FIG. 3 is a diagram showing still another process for producing the monomer compound of the present invention.

Step S310: NH ₂ SO ₂ CF ₃ (NH ₂ Tf), compound 120 represented by the general formula (I) (FIG. 3), triethylamine (Et ₃ N), pyridine and 1,4-diazabicyclo [2. 2.2] React with amines selected from the group consisting of octane (DABCO) (also called the first step). This gives the product 310 (FIG. 3). In FIG. 3, for ease understanding of the product 310 shows the product when using Et 3 _N as amines.

Here, R ₁ is hydrogen, or has or does not have a substituent, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-. Pentyl group, isopentyl group, sec-pentyl group, 3-pentyl group, tert-pentyl group, n-hexyl group, isohexyl group, sec-hexyl group, 3-hexyl group, tert-hexyl group or cyclohexyl group, X Is an element selected from the group consisting of fluorine, chlorine, bromine and iodine. As described above, the substituent that modifies R ₁ is not limited as long as it is a reactive substituent, but exemplary, it is selected from the group consisting of a halogen group, a hydroxyl group, an amino group and an epoxy group. Will be done.

Specifically, in the first step, NH ₂ Tf, compound 120 of the general formula (I) and amines are reacted in a polar solvent in a temperature range of −100 ° C. or higher and 30 ° C. or lower. Preferably, by setting the temperature in the temperature range of −100 ° C. or higher and 0 ° C. or lower, side reactions can be suppressed and the product 310 can be obtained with high purity. There is no particular limitation as long as it is a polar solvent in which NH ₂ Tf, compound 120 and amines are dissolved, but exemplary examples thereof include tetrahydrofuran (THF), acetonitrile (AcN), methanol, ethanol, N, N-dimethylformamide ( DMF), dimethyl sulfoxide (DMSO), dimethylacetonitrile (DMAc), acetone, dioxane, ethyl acetate, chloroform, methyl ethyl ketone, propanol and the like. With these, the above-mentioned compounds can be dissolved.

The amines and then the compound 120 of the general formula (I) may be added to the polar solvent containing NH ₂ Tf over a period of 1 hour or more and 5 hours or less, and the mixture may be stirred. As a result, the reaction is started and the reactant 310 can be obtained. When the mixture is added at a temperature of 0 ° C. or lower, the temperature of the mixture may be raised to room temperature after the addition. This promotes the reaction.

Step S320: Lithium halide is reacted with the reactant 310 obtained in step S310 (also referred to as a second step). The lithium halide is lithium chloride, lithium fluoride, lithium bromide, lithium iodide and the like.

In the second step, specifically, the compound 310 and lithium halide are reacted in a polar solvent in a temperature range of −100 ° C. or higher and 30 ° C. or lower. Preferably, by setting the temperature in the temperature range of −100 ° C. or higher and 0 ° C. or lower, side reactions can be suppressed and the product can be obtained with high purity. There is no particular limitation as long as it is a polar solvent in which compound 310 and lithium halide are dissolved, but exemplary examples thereof include tetrahydrofuran (THF), methanol, ethanol, acetonitrile (AcN), N, N-dimethylformamide (DMF) and dimethyl. There are sulfoxide (DMSO), dimethylacetamide (DMAc), acetone, dioxane, ethyl acetate, chloroform, methylethyl ketone, propanol and the like. With these, the above-mentioned compounds can be dissolved.

Lithium halide may be added to compound 310 in a polar solvent and stirred. As a result, the reaction is started, a halide of amine is produced as a precipitate, and the monomer compound 140 (FIG. 3) of the present invention can be obtained. The production method shown in FIG. 3 is suitable for mass production because it requires fewer steps and has a higher yield than the production method described with reference to FIG. 1. By removing the polar solvent with an evaporator or the like, the monomer compound 140 represented by the general formula (1) can be obtained as a powdery product.

(Embodiment 2)
In the second embodiment, the polymer compound of the present invention and a method for producing the same will be described.

The polymer compound of the present invention is represented by the general formula (2).

Here, Tf represents a trifluoromethanesulfonyl group (-SO ₂ CF ₃ ), and R ₁ is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, which has or does not have a hydrogen or a substituent. n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec-pentyl group, 3-pentyl group, tert-pentyl group, n-hexyl group, isohexyl group, sec-hexyl group , 3-Hexyl group, tert-Hexyl group or cyclohexyl group, and n is an integer of 10 or more and 100,000 or less.

The polymer compound of the present invention has a repeating unit in which nitrogen is directly bonded to a methacrylate group and a trifluoromethanesulfonyl group is bonded to this nitrogen. Since such a structure is asymmetrical with respect to nitrogen, the crystallinity is lowered and the glass transition temperature is lowered.

n is the number of repeating units, but if n is less than 10, the crystallinity does not decrease and the glass transition temperature may not decrease. When n exceeds 100,000, the solubility in a solvent decreases, and it becomes difficult to synthesize a polymer composite described later. Preferably, n is an integer in the range of 10 or more and 50,000 or less. Within this range, a polymer compound having reduced crystallinity can be obtained. More preferably, n is an integer in the range of 50 or more and 10,000 or less.

The weight average molecular weight (M _w ) of the polymer compound of the present invention represented by the general formula (2) is preferably in the range of 5,000 to 1,000,000. If the weight average molecular weight is 5,000 or more, a decrease in crystallinity is expected, and if it is 1,000,000 or less, it can be dissolved in a solvent. More preferably, the weight average molecular weight is in the range of 15,000 to 40,000.

The number average molecular weight (M _n ) of the polymer compound of the present invention represented by the general formula (2) is preferably in the range of 5,000 to 1,000,000. If the weight average molecular weight is 5,000 or more, a decrease in crystallinity is expected, and if it is 1,000,000 or less, it can be dissolved in a solvent. More preferably, the weight average molecular weight is in the range of 15,000 to 40,000.

The molecular weight distribution (M _w / M _n ) of the polymer compound of the present invention represented by the general formula (2) is preferably in the range of 1 or more and 3 or less. This makes it possible to synthesize the polymer composite of the present invention described later. Preferably, M _w / M _n is in the range of 1 or more and 1.5 or less. More preferably, M _w / M _n is in the range of 1 or more and 1.2 or less.

R ₁ is preferably a hydrogen or methyl group. These are advantageous because they are easy to synthesize and the polymer compound becomes more compact.

The substituent that modifies R ₁ is not limited as long as it is a reactive substituent, but is exemplifiedly selected from the group consisting of a halogen group, a hydroxyl group, an amino group and an epoxy group. These substituents do not significantly affect the properties of the polymer compound, but the substituents can impart additional properties.

In the general formula (2), R ₁ may be the same or different for all n. When R ₁ is the same, it is preferable because synthesis is easy. If R ₁ is different, it may be possible to impart various functions to the polymer compound.

Further, the terminal of the polymer compound in the general formula (2) is variable by a polymerization method (or termination method) described later, and thus is not limited, but is exemplified by a hydrocarbon group such as hydrogen or a methyl group. ..

Next, a method for producing the polymer compound of the present invention will be described.
FIG. 4 is a diagram showing a process of producing the polymer compound of the present invention.

Step S410: The monomer compound 140 (FIG. 4) of the present invention described in the first embodiment is polymerized. As a result, the polymer compound 410 of the present invention represented by the general formula (2) is obtained. Since the miniaturized monomer compound 140 is used, the density of the obtained polymer compound 410 can be improved. Naturally, the density of Li ions contained can also be improved.

As the polymerization, any method of polymerization under a metal complex is adopted, and for example, it is selected from the group consisting of radical polymerization, living radical polymerization, ionic polymerization, living ionic polymerization, photopolymerization and thermal polymerization. When atom transfer radical polymerization (ATRP) is adopted as a polymerization method among living radical polymerizations, monovalent or divalent copper, divalent to tetravalent titanium, using an organic halide as an initiator. A metal complex such as divalent or trivalent iron, divalent cobalt, divalent nickel, trivalent or pentavalent molybdenum, or trivalent ruthenium can be used as the catalyst.

Exemplary organic halides are tert-butyl α-bromoisobutyrate, methyl α-bromoisobutyrate, ethyl 2-bromoisobutyrate, 2-hydroxyethyl 2-bromoisobutyrate, ethylbis (2-bromoisobutyrate). , 1,1,1-Tris (2-bromoisobutyryloxomethyl) ethane, dodecyl2-bromoisobutyrate, octadecyl2-bromoisobutyrate, etc., which can be used as a radical polymerization initiator. For example, it is not limited to this.

Among the above-mentioned metal complexes, from the viewpoint of reactivity, monovalent copper metal complexes such as cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, and cuprous oxide, A combination with a metal complex of divalent copper such as cupric chloride, cupric bromide, cupric iodide, cupric cyanide, and cupric oxide is preferable.

Further, in addition to the initiator and metal complex, 2,2'-bipyridyl derivatives such as 2,2'-bipyridyl, 4,4'-dimethyl-2,2'-bipyridyl, N- Ligsins such as butyl-2-pyridylmethaneimine, N-octyl-2-pyridylmethaneimine, and Tris (2-pyridylmethyl) amine may be used.

Specifically, a monomer compound 140 represented by the formula (1) described in the first embodiment, an initiator, and if necessary, a ligand are added to the polar solvent, and a metal complex is added thereto. , Just react. Here, the polar solvents are N, N-dimethylformamide (DMF), tetrahydrofuran (THF), methanol, ethanol, acetonitrile (AcN), dimethyl sulfoxide (DMSO), dimethylacetamide (DMAc), acetone, dioxane, ethyl acetate, Chloroform, methyl ethyl ketone, propanol and the like. The reaction is accelerated by heating at a relatively mild temperature above room temperature and below 100 ° C. The product is recovered as a solid powder by washing and centrifugation.

(Embodiment 3)
In the third embodiment, the polymer composite of the present invention and a method for producing the same will be described.

The polymer composite of the present invention contains a polymer having an anionic polymer compound represented by the general formula (3) as a main chain and a complex represented by the general formula (4) as a counter cation.

Here, Tf represents a trifluoromethanesulfonyl group (-SO ₂ CF ₃ ), and R ₁ is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, which has or does not have a hydrogen or a substituent. n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec-pentyl group, 3-pentyl group, tert-pentyl group, n-hexyl group, isohexyl group, sec-hexyl group , 3-Hexyl group, tert-Hexyl group or cyclohexyl group, and n is an integer of 10 or more and 100,000 or less.

R ₂ and R ₃ are the same or different, having or not having a substituent, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-Pentyl group, isopentyl group, sec-pentyl group, 3-pentyl group, tert-pentyl group, n-hexyl group, isohexyl group, sec-hexyl group, 3-hexyl group, tert-hexyl group or cyclohexyl group. , M is an integer of 1 or more and 4 or less.

n is the number of repeating units, but if n is less than 10, the crystallinity does not decrease and the glass transition temperature may not decrease. When n exceeds 100,000, the solubility in a solvent decreases, and it becomes difficult to synthesize a polymer complex. Preferably, n is an integer in the range of 10 or more and 50,000 or less. Within this range, a polymer composite having reduced crystallinity can be obtained. More preferably, n is an integer of 50 or more and 10,000 or less.

The weight average molecular weight (M _w ) of the polymer composite of the present invention is preferably in the range of 5,000 to 1,000,000. When the weight average molecular weight is 5,000 or more, the crystallinity is expected to decrease, and it is preferably 1,000,000 or less from the handling characteristics at the time of film formation. More preferably, the weight average molecular weight is in the range of 15,000 to 40,000.

The number average molecular weight (M _n ) of the polymer composite of the present invention is preferably in the range of 5,000 to 1,000,000. When the number average molecular weight is 5,000 or more, the crystallinity is expected to decrease, and it is preferably 1,000,000 or less from the handling characteristics at the time of film formation. More preferably, the number average molecular weight is in the range of 15,000 to 40,000.

The molecular weight distribution (M _w / M _n ) of the polymer composite of the present invention is preferably in the range of 1 or more and 1.5 or less. When an electrolyte membrane is obtained using the polymer composite of the present invention, an electrolyte membrane having excellent mechanical strength can be provided as long as the above-mentioned narrow molecular weight distribution is satisfied. More preferably, (M _w / M _n ) is in the range of 1 or more and 1.2 or less. This makes it possible to produce an electrolyte membrane that reliably exhibits excellent ionic conductivity at a low temperature of 0 ° C. or lower and has a stable film morphological holding power. For example, the polymer composite (film-like) of the present invention has a conductivity of 2.0 × ^10-6 S / cm or more and a thin film-like flume form even at room temperature or lower.

When m is 5 or more, it may inhibit the movement of Li ions from the counter cation represented by the general formula (4), causing a decrease in conductivity.

R ₁ is preferably a hydrogen or methyl group, and R ₂ and R ₃ are preferably the same or different methyl or ethyl groups. These are advantageous because they are easy to synthesize and form a high-density polymer composite. The substituents that R _{1 to} R ₃ can have are not limited as long as they are reactive substituents, but are exemplifiedly selected from the group consisting of halogen groups, hydroxyl groups, amino groups and epoxy groups. To.

According to the polymer composite of the present invention, the Li ion has a structure surrounded by a glyme or a glyme derivative as represented by the general formula (4), and therefore is represented by the general formula (3). The bond between the anion of the anionic polymer compound and the cation of the Li ion is weakened, the Li ion can be easily moved, and the degree of dissociation of the Li ion and the transport number of the Li ion can be improved.

Further, in the polymer composite of the present invention, a repeating unit is one in which nitrogen is directly bonded to a methacrylate group and a trifluoromethanesulfonyl group is bonded to this nitrogen. Since such a structure is asymmetrical around nitrogen, the crystallinity is reduced and the glass transition temperature is dramatically reduced. Therefore, it can have extremely excellent conductivity not only at room temperature but also at a low temperature of 0 ° C. or lower (for example, −70 ° C. to 0 ° C.). Further, since the polymer composite of the present invention is an ionic liquid polymer, it has the flame retardancy characteristic of an ionic liquid.

The polymer composite of the present invention is usually a solid material, but THF, N, N-dimethylformamide (DMF), methanol, ethanol, acetonitrile (AcN), dimethyl sulfoxide (DMSO), dimethylacetamide (DMAc), acetone. , Dioxane, ethyl acetate, chloroform, methyl ethyl ketone, propanol and other polar solvents, and become a viscous liquid. Therefore, the polymer composites of the present invention may be used in viscous liquids. By applying a viscous liquid to a substrate, electrodes, or the like and removing the solvent, a film made of the polymer composite of the present invention can be easily obtained.

If the polymer composite of the present invention having the above characteristics is used as an electrolyte material in a polymer electrolyte of a lithium ion battery or an air battery, it can be used not only in a normal environment but also in a low temperature environment, so that it depends on the environment. It is possible to provide an all-solid-state lithium-ion battery or an all-solid-state air battery that can be used without any problems and has high safety.

In the general formula (3), R ₁ may be the same or different for all n. When R ₁ is the same, it is preferable because synthesis is easy. If R ₁ is different, it may be possible to impart various functions to the polymer compound.

Further, since the end of the main chain of the anionic polymer compound in the general formula (3) is variable by the polymerization method (or termination method), there is no limitation, but exemplary examples are hydrocarbons such as hydrogen or a methyl group. It becomes the basis.

Further, the value of m in the counter cation represented by the general formula (4) may be the same or different for all n. When m is the same, it is preferable because synthesis is easy. If m is different, the binding property of Li ions in the counter cation changes, so that the conductivity, the degree of dissociation of Li ions, or the transport number can be controlled.

Next, the method for producing the polymer composite of the present invention will be described.
FIG. 5 is a diagram showing a process of producing the polymer composite of the present invention.

Step S510: The polymer compound 410 (FIG. 5) represented by the formula (2) described in the second embodiment and the grime or grime derivative 510 (FIG. 5) represented by the general formula (II) are placed in a polar solvent. Mix with. The description of the polymer compound 410 will be omitted. The grime or grime derivative 510, sometimes referred to as symmetric or asymmetric glycol ethers, is usually a liquid.

Here, R ₂ and R ₃ are the same or different, having or not having a substituent, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-. Butyl group, n-pentyl group, isopentyl group, sec-pentyl group, 3-pentyl group, tert-pentyl group, n-hexyl group, isohexyl group, sec-hexyl group, 3-hexyl group, tert-hexyl group or cyclohexyl It is a group, and m is an integer of 1 or more and 4 or less. The substituents that R ₂ and R ₃ can have are not limited as long as they are reactive substituents, but are exemplifiedly selected from the group consisting of halogen groups, hydroxyl groups, amino groups and epoxy groups.

If it is a polar solvent, it dissolves the polymer compound 410 and grime or grime derivative 510. Specifically, the polar solvent is tetrahydrofuran (THF), N, N-dimethylformamide (DMF), methanol, ethanol, acetonitrile (AcN), dimethyl sulfoxide (DMSO), dimethylacetamide (DMAc), acetone, dioxane, acetic acid. There are ethyl, chloroform, methylethylketone, propanol and the like.

The polymer compound 410 and grime or grime derivative 510 may be added to the polar solvent and stirred. If the viscous substance is visually uniform after stirring, it can be said that the polymer composite 520 (FIG. 5) of the present invention represented by the general formula (3) and the general formula (4) is formed. The polymer compound 410 is a powder and the grime or grime derivative 510 is a liquid, but if the polymer composite 520 is not formed, a uniform viscous substance cannot be obtained. In this way, since it is only necessary to mix and stir, expensive equipment and the like are not required, and it can be provided at low cost.

Here, the glyme or the glyme derivative 510 is preferably mixed with the polymer compound 410 so as to be at least the same as the molar equivalent of Li in the monomeric compound 120 (FIG. 4) for producing the polymer compound 410. The mixing is preferably carried out in an atmosphere of an inert gas such as nitrogen, argon, helium, neon, krypton, or xenon. This promotes the reaction.

Further, preferably, as the polymer compound 410, if a polymer compound having a molecular weight distribution (weight average molecular weight (M _w ) / number average molecular weight (M _n )) of 1.2 or less is used, it is reliable at a low temperature of 0 ° C. or less. It is possible to produce an electrolyte membrane which exhibits excellent ionic conductivity and has a stable film morphological holding power.

In the third embodiment, the polymer composite 520 (FIG. 5) in which the Li ion has a structure surrounded by grime or a grime derivative as represented by the general formula (4) has been described in detail. In step S510 of step S510, in place of grime or grime derivative 510 (FIG. 5) or with grime or grime derivative 510 (FIG. 5), tetrahydrofuran, acetone, dioxane, dimethyl sulfoxide, morpholine, hexamethylphosphate triamide, diethyl ether , N, N-dimethylformamide, ethylenediamine, pyridine and triethylamine may be used as a solvent selected from the group. Thereby, a polymer composite having a structure in which Li ions are surrounded by these solvents or a combination of these solvents and grime or grime derivative 510 may be formed. In this case as well, since the Li ion and these solvents form a complex, the anionic polymer compound represented by the general formula (3) is used as the main chain, and the complex composed of the Li ion and at least these solvents is used as the counter cation. It becomes a polymer composite.

Even when these solvents are used, the movement of Li ions in the polymer complex is facilitated, and the degree of dissociation of Li ions and the transport number of Li ions are improved, as in the case of using a glyme or a glyme derivative. As a result, the crystallinity of the polymer composite is lowered, the glass transition temperature is lowered, and it is possible to have extremely excellent conductivity not only at room temperature but also at low temperature.

Another method for producing the polymer composite of the present invention will be described. The monomer compound 140 of the present invention described in the first embodiment (FIGS. 1 to 3) and the grime or grime derivative 510 represented by the general formula (II) (FIG. 5) are mixed to form Li of the monomer compound 140. A monomer compound in which grime or a grime derivative is complexly formed may be synthesized and polymerized. The polymerization can be carried out in the same manner as in step S410 of the second embodiment, for example.

(Embodiment 4)
In the fourth embodiment, a lithium ion secondary battery and an air battery will be described as applications in which the polymer composite described in the third embodiment is used as an electrolyte material.
FIG. 6 is a schematic view showing the lithium ion secondary battery of the present invention.

The lithium ion secondary battery 600 of the present invention includes at least a positive electrode 610, a negative electrode 620, and a polymer electrolyte 630 located between the positive electrode 610 and the negative electrode 620. Here, the polymer electrolyte 630 is made of an electrolyte material containing the polymer composite 520 (FIG. 5) represented by the general formulas (3) and (4) described in the third embodiment. The description of the polymer composite 520 is omitted because it overlaps.

The positive electrode 610 contains at least any positive electrode active material capable of occluding and releasing lithium. An exemplary positive electrode active material is a Li—Ni-based composite oxide represented by LiNiO ₂ , a Li—Ni—Mn-based composite oxide represented by LiNi _0.5 Mn _0.5 O _2, and a representative LiFePO ₄ . Although there are lithium-transition metal composite oxides such as Li-iron phosphate-based composite oxides, positive electrode active materials usually used for lithium ion secondary batteries can be adopted.

The positive electrode 610 may have a positive electrode active material layer formed by further containing a conductive material for improving conductivity in addition to the positive electrode active material, and a binder or the like for binding these. Examples of conductive materials include acetylene black, Ketjen black (registered trademark), carbon black such as carbon nanofibers, and carbon materials such as graphene. Binders include, but are not limited to, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), epoxy resin, styrene-butadiene rubber (SBR), and the like.

The positive electrode 610 may further have a positive electrode current collector on the surface of the positive electrode active material layer, and may be configured to enable electrical connection with the outside. The positive electrode current collector is typically made of a metal material such as aluminum, stainless steel, iron, chromium, nickel, manganese, etc., but any conductive material is used. The shape can be foil-like, plate-like, or mesh-like.

The negative electrode 620 contains at least any negative electrode active material capable of occluding and releasing lithium. Examples of the negative electrode active material include elemental metals such as Li, Sn, Si, Sb, Ge, and C, alloys containing these, and the like, and negative electrode active materials usually used for lithium ion secondary batteries can be adopted.

The negative electrode 620 may have a negative electrode active material layer formed by further containing a conductive material for improving conductivity in addition to the negative electrode active material, and a binder or the like for binding these. Exemplary conductive materials and binders are as described above.

The negative electrode 620 may further have a negative electrode current collector on the surface of the negative electrode active material layer, and may be configured to enable electrical connection with the outside. The negative electrode current collector is also the same as the positive electrode current collector.

An exemplary method for producing a lithium ion secondary battery 600 is to form a positive electrode 610, coat it with a solution containing a polymer composite 520 (FIG. 5), and form a polymer electrolyte layer 630. A negative electrode 620 may be formed on the negative electrode. If necessary, the solvent is removed by heating or leaving.

FIG. 7 is a schematic view showing the air battery of the present invention.

The air battery 700 of the present invention includes at least an air electrode 710 that functions as a positive electrode, a negative electrode 720, and a polymer electrolyte 730 located between the air electrode 710 and the negative electrode 720. Here, the polymer electrolyte 730 is made of an electrolyte material containing the polymer composite 520 (FIG. 5) represented by the general formulas (3) and (4) described in the third embodiment. The description of the polymer composite 520 is omitted because it overlaps.

As the air electrode 710, the air electrode of an existing air battery can be used. Illustratively, the air electrode 710 serves as a catalyst for metals such as platinum, rhodium, palladium, silver, ruthenium, and / or perovskite oxide, manganese oxide, cobalt oxide, iron oxide, nickel oxide, copper oxide. , A carbon material carrying an oxide such as ruthenium oxide. Carbon materials include acetylene black, Ketjen black (registered trademark), carbon black such as carbon nanofibers, and graphene.

The air pole 710 may further have an air pole current collector on its surface and may be configured to allow electrical connection to the outside. The air electrode current collector is typically made of a metal material such as aluminum, stainless steel, iron, chromium, nickel, manganese, etc., but any conductive material is used and has a mesh shape.

The negative electrode 720 contains at least any negative electrode active material capable of occluding and releasing lithium. Exemplary negative electrode active materials include Li metals, lithium alloys, Si alloys, Sn alloys, lithium-containing oxides, metal oxides such as tin oxide, metal sulfides such as nickel sulfides, metal nitrides such as lithium nitride, and the like. However, a negative electrode active material usually used for an air secondary battery can be adopted.

The negative electrode 720 may have a negative electrode active material layer formed by further containing a conductive material for improving conductivity in addition to the negative electrode active material, and a binder or the like for binding these. The exemplary conductive material and binder are similar to the conductive material and binder described for lithium ion secondary batteries.

The negative electrode 720 may further have a negative electrode current collector on the surface of the negative electrode active material layer, and may be configured to enable electrical connection with the outside. The negative electrode current collector is also made of a metallic material such as aluminum, stainless steel, iron, chromium, nickel, manganese and the like, but any conductive material is used. The shape can be foil-like, plate-like, or mesh-like.

An exemplary method of manufacturing the air battery 700 is to form an air electrode 710, coat it with a solution containing a polymer composite 520 (FIG. 5), form a polymer electrolyte layer 730, and onto it. The negative electrode 720 may be formed. If necessary, the solvent is removed by heating or leaving.

In FIGS. 6 and 7, a single cell is shown as the lithium ion secondary battery 600 and the air battery 700 for the sake of clarity, but a plurality of such cells may be connected. Such a lithium ion secondary battery is housed in a battery case (not shown) and is a chip type, coin type, button type, mold type, pouch type, laminated type, cylindrical type, square type or the like capacitor. You may.

According to the lithium ion secondary battery 600 and the air battery 700 of the present invention, the polymer electrolyte layers 630 and 730 are composed of the electrolyte material composed of the polymer composite 520 (FIG. 5) of the present invention, and thus are under normal environment. Not only can it be used in low temperature environments.

Next, the present invention will be described in detail with reference to specific examples, but it should be noted that the present invention is not limited to these examples.

[Reagents used for synthesis]
The reagents used in the subsequent examples and comparative examples were all special grade reagents. Trifluoromethanesulfonamide (NH ₂ SO ₂ CF ₃ , purity 98%), methanol, lithium hydride (LiH, purity 95%), acetonitrile (AcN), tetrahydrofuran (THF), N, N-dimethylformamide (DMF), ethyl 2-bromoisobutyrate (EBIB), 2,2'-bipyridine (bipy), chloroform, tetraglyme (G4), triethylamine _(Et 3 N, 99% purity), and lithium chloride, from Tokyo Chemical industry Co., Ltd. I bought it. Methacryloyl chloride (purity 97%), cuprous chloride (Cu (I) Cl), and cupric chloride (Cu (II) Cl ₂ ) were purchased from Wako Pure Chemical Industries, Ltd. Methanol, G4, AcN, DMF and THF were dried before use.

[Example 1]
In Example 1, a monomer compound in which R ₁ is a methyl group was synthesized in the general formula (1).
FIG. 8 is a diagram showing a process of synthesizing the monomer compound in Example 1.

NH ₂ SO ₂ CF ₃ (NH ₂ Tf) was reacted with LiH as MH (M is an element selected from the group consisting of Li, Na, K and Cs) (step S110 in FIGS. 1 and 8). .. Specifically, NH ₂ SO ₂ CF ₃ (15.2 g, 0.1 mol) was dissolved in methanol (20 mL) as a polar solvent. To this solution was added a methanol solution of CH ₃ OLi obtained from LiH (0.837 g, 0.1 mol) and methanol (30 mL). At this time, the temperature at the time of mixing was set to −40 ° C. After mixing and stirring, methanol was removed by a rotary evaporator.

Then, the resulting product _{(NHLiSO 2 CF 3, NHLiTf)} , R 1 in the general formula (I) is obtained by reacting methacryloyl chloride is a methyl group (step S120 of FIG. 1 and FIG. 8). Specifically, the product (NHLiTf) was dissolved in AcN (70 mL) as a polar solvent and cooled to 0 ° C. Methacryl chloride (12.1 g, 0.12 mol) was added to this solution over 3 hours with stirring. After the addition, the mixture was stirred for an additional hour and heated to room temperature. After stirring at room temperature for 24 hours, the precipitate lithium chloride (LiCl) was separated by filtration, and AcN was removed from the filtrate by a rotary evaporator. It was confirmed by nuclear magnetic resonance (NMR, JEOL, JEM-ECX400) that the obtained product was trifluoromethanesulfonylmethacrylamide (TFSMA in FIG. 8).

Next, TFSMA was further reacted with LiH as a lithium salt (step S130 in FIGS. 1 and 8). Specifically, LiH (20 mmol) was dissolved in THF (70 mL) as a polar solvent cooled to −40 ° C. with stirring. A solution prepared by dissolving TFSMA (20 mmol) in THF (30 mL) was added dropwise to this solution over 1 hour. The mixture was heated to room temperature and held for 24 hours. The solution was then filtered and THF was removed by rotary evaporator.

In this way, a product (15.4 g, yield 71%) was obtained. Observe the resulting product and perform NMR, Fourier transform infrared spectroscopy (FT-IR, Thermo Scientific, Nicolet iS50) and liquid chromatography-mass spectrometry (LC / MS, Waters, Xevo G2-S QTof). Identified. The ¹ H NMR spectrum, using tetramethylsilane (TMS) as internal standard, added acetonitrile -D ₃ to the product, dissolved, 400 MHz, measured at room temperature. The ¹³ C NMR spectrum, using methanol as an internal standard, and methanol -D ₄ was added to the product, dissolved, 100 MHz, measured at room temperature. The FT-IR spectrum was measured by the transmission method with the product dissolved in KBr. For LC / MS, a standard solution using polyethylene glycol (PEG) as a standard substance (organic solvent contains LiBr: 3.5 g / L, Acetonitrile: H ₂ O = 2: 3) was used, and the peak area of the product was used. The calibration curve was obtained from the ratio with the peak area of the standard solution, and the weight average molecular weight and the number average molecular weight were calculated. These results are shown in FIGS. 9 to 12.

FIG. 9 is a diagram showing the appearance of the product obtained in Example 1.

Although shown in gray scale in FIG. 9, it was confirmed that the portion of the sample container in which the contrast was brightly shown was the product and was a white solid powder.

FIG. 10 is a diagram showing a ¹ H NMR spectrum of the product of Example 1.
FIG. 11 is a diagram showing a ¹³ C NMR spectrum of the product of Example 1.

According to FIG. 10, the signals A and B derived from the terminal hydrogen of the vinyl group are at 6.07 (2H) ppm and 5.49 (2H) ppm, respectively, and the signal C derived from the hydrogen of the methyl group is displayed. It was observed at 1.86 (3H) ppm.

According to FIG. 11, the carbon-derived signals (1) to (5) of (1) to (5) are changed to 176.32 ppm, 144.33 ppm, 123.72 ppm, 120.65 ppm and 18.53 ppm, respectively. It was observed.

FIG. 12 is a diagram showing an FT-IR spectrum of the product of Example 1.

The absorption peaks a to e observed in the FT-IR spectrum could be assigned to the vibration / rotation of the molecule shown in FIG. 12, respectively. Notably, since the peak of 1320 cm ^-1 and 1590 cm ^-1 attributable respectively to the stretching vibration of S = O and C = O sulfonamide group (CO-N-SO ₂₎ were observed, sulfonamide It was confirmed that it was grafted.

Further, according to LC / MS, the m / z of the product was 215.9913, while the theoretical value of C ₅ H ₅ F ₃ NO ₃ S as the anion of the monomer compound was 216.1542.

From the above results, the product obtained in Example 1, in the general formula (1) wherein R ₁ is a methyl group, is a monomer compound which nitrogen is directly bonded to methacrylate group (LiTFSMA in FIG. 8), Small It was shown that the conversion was successful. Hereinafter, the monomer compound obtained in Example 1 will be referred to as LiTFSMA.

[Example 2]
In Example 2, a polymer compound in which R ₁ is a methyl group was synthesized in the general formula (2).
FIG. 13 is a diagram showing a process of synthesizing the polymer compound in Example 2.

The monomeric compound LiTFSMA obtained in Example 1 was polymerized (step S410 in FIGS. 4 and 13). Here, as the polymerization method, atom transfer radical polymerization (ATRP), which is one of the living radical polymerizations, was adopted. DMF was placed in the Schlenk tube as a polar solvent, and LiTFSMA, a halide which is EBIB as an initiator, and a ligand which is BICY were added. Then, the inside of the Schlenk tube was purged with argon gas and deoxidized for 20 minutes. Filling with argon gas was performed in the glove box. Next, cuprous chloride and cupric chloride were added as metal complexes to these mixed solutions, and a three-way stopcock was attached to the Schlenk tube. The molar ratios of LiTFSMA, EBIB, metal complex and BICY used here are shown in Table 1.

M in the upper part of Table 1 is the molecular weight of each reagent, and [M] in the lower part represents the molar ratio when 1 mol of EBIB is taken.

The Schlenk tube was then stirred in an oil bath at 60 ° C. to initiate polymerization. The polymerization time was 1 to 7 hours. A constant volume of solution was taken out from the Schlenck tube every hour, and the monomer conversion rate was determined by NMR, and the weight average molecular weight, number average molecular weight, and molecular weight distribution were determined by gel permeation chromatography (GPC, Shodex, GPC-101). In GPC, a standard solution using PEG (organic solvent contains LiBr: 3.5 g / L, acetonitrile: H ₂ O = 2: 3) is used, and the ratio of the peak area of the product to the peak area of the standard solution is used. The calibration curve was calculated. The results are shown in FIGS. 14 to 16.

After polymerizing for 7 hours, the reaction product was diluted with a mixed solvent of AcN and chloroform and recovered by a centrifuge. The dilution and centrifugation were repeated 3 times to obtain a white powder product (4.83 g, yield 97%). It was confirmed by NMR and FTIR that the product was a polymer compound in which R ₁ was a methyl group in the general formula (2) (PLiTFSMA in FIG. 13).

FIG. 14 is a diagram showing the relationship between the consumption ratio of the monomer compound and the time in the synthesis of the polymer compound of Example 2.

In FIG. 14, [M] ₀ is the concentration of the monomer compound at the time of charging, [M] is the concentration of the residual monomer compound, and the vertical axis represents the consumption ratio of the monomer compound. According to FIG. 14, since the consumption ratio of the monomer compound was linear, it was confirmed that ATRP was performed well.

FIG. 15 is a diagram showing the dependence of the molecular weight of the polymer compound on the conversion rate of the monomer compound in the synthesis of the polymer compound of Example 2.
FIG. 16 is a diagram showing the dependence of the conversion rate of the monomer compound on the molecular weight distribution of the polymer compound in the synthesis of the polymer compound of Example 2.

In FIG. 15, M _{n on} the vertical axis represents a number average molecular weight. According to FIG. 15, it was confirmed that ATRP was performed well because the change in the molecular weight of the polymer compound with the conversion of the monomer compound was linear. In particular, by carrying out the polymerization for 7 hours, 80% of the monomer compounds at the time of charging were converted into polymer compounds, and the number average molecular weight at that time was 29,176.

In FIG. 16, M _{w on} the vertical axis represents a weight average molecular weight, M _n represents a number average molecular weight, and M _w / M _n represents a molecular weight distribution. According to FIG. 16, it can be seen that the variation in molecular weight decreases as the polymerization progresses. In particular, when the monomer conversion rate is 50% or more, there is almost no molecular weight distribution, that is, M _w / M _n is 1. A polymer compound satisfying 2 or less can be obtained.

The weight average molecular weight, number average molecular weight, and molecular weight distribution of the polymer compounds obtained at various monomer conversion rates are summarized in Table 2 from FIGS. 15 and 16. Hereinafter, the polymer compound obtained in Example 2 will be referred to as PLiTFSMA.

[Example 3]
In Example 3, a polymer complex was synthesized in which R ₁ was a methyl group in the general formula (3), R ₂ and R ₃ were methyl groups in the general formula (4), and m was 4.
FIG. 17 is a diagram showing a process of synthesizing the polymer composite in Example 3.

The PLiTFSMA synthesized in Example 2 and tetraglyme (G4, tetraethylene glycol dimethyl ether) in which R ₂ and R ₃ are methyl groups and m is 4 in the general formula (II) are mixed in THF as a polar solvent. (Step S510 in FIGS. 5 and 17). At this time, PLiTFSMA and G4 were mixed in a glove box purged with argon gas so as to satisfy 1: 1 (molar equivalent). When the mixture was stirred, it became a uniform viscous liquid. THF was then removed by rotary evaporator. As a result, a white solid powder was obtained.

The obtained uniformly viscous liquid was observed, and it was identified as a complex by NMR. ^{1 1} H NMR spectrum was measured at 400 MHz at room temperature by adding CDCl ₃ to the liquid using tetramethylenesilane (TMS) as an internal standard. The results are shown in FIG.

FIG. 18 is a diagram showing a ¹ H NMR spectrum of the product of Example 3.

FIG. 18 also shows the NMR spectrum of G4 for comparison. According to FIG. 18, in the product of Example 3, signals (1) to (3) derived from hydrogens (1) to (3) of G4 were observed, but all the signals were completely shifted. Therefore, it was confirmed that by mixing in step S510, PLiTFSMA and G4 formed a polymer complex (hereinafter, the product of Example 3 is referred to as PLi (G4) TFSMA).

Differential scanning calorimetry (DSC, manufactured by Shimadzu, DTG-60) was performed on PLi (G4) TFSMA to determine the glass transition temperature and heat capacity. The measurement was carried out using an empty platinum cell as a standard substance, from -100 ° C to 100 ° C, and then from 100 ° C to -100 ° C at a temperature raising / lowering rate (10 ° C./min) in a nitrogen atmosphere. The results are shown in FIG.

FIG. 19 is a diagram showing DSC behavior of the product of Example 3.

FIG. 19 also shows the DSC behavior of PLiTFSMA, the product of Example 2, for comparison. According to the DSC behavior of PLi (G4) TFSMA in FIG. 19, a baseline shift (region 1910 in FIG. 19) was observed near about −74 ° C. On the other hand, according to the DSC behavior of PLiTFSMA in FIG. 19, a baseline shift (region 1920 in FIG. 19) was observed around about 32 ° C. When the glass transition temperature was calculated in detail from these, the glass transition temperatures of PLi (G4) TFSMA and PLiTFSMA were calculated to be −74.2 ° C. and 32.3 ° C., respectively. Moreover, when the specific heat capacity was calculated, the specific heat capacities of PLi (G4) TFSMA and PLiTFSMA were 0.35537 mJ / deg · mg and 0.094161 mJ / deg · mg, respectively. From this, it was shown that the glass transition temperature decreased dramatically as the crystallinity decreased.

Next, the temperature dependence of the conductivity of PLi (G4) TFSMA was investigated. The battery cell for measurement was adjusted as follows. A THF solution (10 wt%) in which PLi (G4) TFSMA was dissolved was added dropwise to one side of a stainless steel disk-shaped electrode polished on both sides, and the solution was maintained under vacuum for 5 hours to remove THF. Next, the stainless steel electrode to which PLi (G4) TFSMA was applied was heat-treated at 120 ° C. for 2 hours. Then, this was sandwiched between stainless steel electrodes as counter electrodes to form a battery cell for measurement. At this time, the thickness of PLi (G4) TFSMA was 100 μm.

The measuring battery cell was placed in an oven chamber with a thermostat, and AC impedance was measured using a multi-frequency LCR meter (E4980A Precision LCR manufactured by Agilent Technologies) and a resistor (R). The measurements were made at various frequencies in the range of 20 Hz to 2 MHz and at various temperatures from -5 ° C to 125 ° C (-5 ° C, 15 ° C, 35 ° C, 55 ° C, 75 ° C, 95 ° C and 115 ° C). .. The results are shown in FIG.

FIG. 20 is a diagram showing the temperature dependence of the conductivity of the product of Example 3.

FIG. 20 also shows the temperature dependence of the conductivity of PLiTFSMA, the product of Example 2, for comparison. According to FIG. 20, in the region from 55 ° C. or lower to near room temperature, the conductivity of PLi (G4) TFSMA was higher than that of PLiTFSMA without a decrease associated with glass transition. This means that in the polymer composite of the present invention, since the complex of Li ion and glyme or glyme derivative is used as a counter cation, Li ion easily moves even in a temperature range near room temperature, and the degree of dissociation of Li ion is high. And show that high Li ion transport rates are maintained.

It was found that the conductivity of PLi (G4) TFSMA has a higher value than that of PLiTFSMA in the extremely low temperature region below room temperature (for example, 25 ° C.). Of particular note, the conductivity of PLi (G4) TFSMA in the extremely low temperature range below room temperature (eg, −5 ° C.) was 2.0 × ^10-6 S / cm. As the crystallinity of the polymer composite of the present invention decreases, the glass transition temperature decreases dramatically, so that it has extremely excellent conductivity even at low temperatures, which is the polymer electrolyte layer of a lithium ion battery or an air battery. It was shown that it can be used not only in a normal environment but also in a low temperature environment. The above results are summarized in Tables 3 and 4.

[Comparative Example 4]
Instead of PLiTFSMA, the polymer shown in FIG. 1 of Non-Patent Document 1 (Sample A-BCE_3 of Table 1 of Non-Patent Document 1) was used and mixed with G4. The mixing and stirring conditions were the same as in Example 3. When mixed and stirred, the state in which the polymer was dispersed was visually confirmed, and the liquid did not have a uniform viscosity. From the results of Example 3 and Comparative Example 4, any polymer having an anionic polymer as a main chain and Li ions as a counter cation did not form a complex with a grime or a grime derivative represented by G4, and the general formula (2). It has been shown that the polymer compound represented by) is effective for complex formation with grime or a grime derivative, and further for the synthesis of a polymer complex.

[Example 5]
In Example 5, a monomer compound in which R ₁ is a methyl group was synthesized in the general formula (1).
FIG. 21 is a diagram showing a process of synthesizing the monomer compound in Example 5.

NH ₂ SO ₂ CF ₃ (NH ₂ Tf) was reacted with LiH as (M is an element selected from the group consisting of Li, Na, K and Cs) (step S210 in FIGS. 2 and 21). Specifically, NH ₂ Tf (7.6 g, 0.05 mol) was dissolved in methanol (10 mL) as a polar solvent. To this solution was added a methanol solution of CH ₃ OLi obtained from LiH (0.4184 g, 0.05 mol) and methanol (15 mL). At this time, the temperature at the time of mixing was set to −40 ° C. After mixing and stirring, methanol was removed by a rotary evaporator.

Then, the resulting product _{(NHLiSO 2 CF 3, NHLiTf)} , in the general formula (I) _{R 1} is reacted with methacryloyl chloride is a methyl group, and a triethylamine _(Et 3 N) as the amine ( Step S220 of FIGS. 1 and 21). Specifically, the product (NHLiTf) was dissolved in THF (70 mL) as a polar solvent and cooled to 0 ° C. To this _{solution, Et 3 N (5.11g, 0.05mol} ), then methacryloyl chloride (6.0 g, 0.06 mol) with stirring, was added over 3 hours. After the addition, the mixture was stirred for an additional hour and heated to room temperature. After stirring at room temperature for 24 hours, the precipitate triethylamine chloride (Et ₃ NCl) was separated by filtration, and THF was removed from the filtrate by a rotary evaporator. The product was washed 3 times with THF (100 mL) to remove THF.

In this way, a product (10.05 g, yield 90%) was obtained. When the obtained product was observed, it was a white solid powder. Similar to Example 1, it was identified by NMR, FT-IR and LC / MS.

¹ According to the ¹ H NMR spectrum, a characteristic peak was detected as in Example 1. Signals A and B derived from the terminal hydrogen of the vinyl group are 6.07 (2H) ppm and 5.49 (2H) ppm, respectively, and signal C derived from the hydrogen of the methyl group is 1.86 (3H). Observed at ppm.

According to the ¹³ C NMR spectrum, a characteristic peak was detected as in Example 1. Signals (1) to (5) derived from the carbons (1) to (5) (FIG. 11) were observed at 176.32 ppm, 144.33 ppm, 123.72 ppm, 120.65 ppm and 18.53 ppm, respectively. It was.

From the above results, the product obtained in Example 5 is a monomer compound in which R ₁ is a methyl group in the general formula (1) and nitrogen is directly bonded to the methacrylate group (LiTFSMA in FIG. 21). Shown. From this, it is shown that the monomer compound of the present invention is effective in the production method shown in FIG. 2 in addition to the production method shown in FIG. 1, and is produced in a small number of steps and in a higher yield. It was.

[Example 6]
In Example 6, a monomer compound in which R ₁ is a methyl group was synthesized in the general formula (1).
FIG. 22 is a diagram showing a process of synthesizing the monomer compound in Example 6.

NH ₂ SO ₂ CF ₃ (NH ₂ Tf), methacryloyl chloride in which R ₁ is a methyl group in the general formula (I), and triethylamine (Et ₃ N) as amines were reacted (FIGS. 3 and 22). Step S310). Specifically, NH ₂ Tf (15.2 g, 0.1 mol) was dissolved in THF (50 mL) as a polar solvent and cooled to −41 ° C. To this _{solution, Et 3 N (20.5g, 0.2mol} ), then methacryloyl chloride (10.8 g, 0.1 mol) with stirring, was added over 3 hours. After the addition, the mixture was stirred for an additional hour and heated to room temperature. After stirring at room temperature for 24 hours, THF was removed by a rotary evaporator.

Next, the obtained product was reacted with LiCl as a lithium salt (step S320 in FIGS. 3 and 22). Specifically, a THF solution (0.05 mol / L, 200 mL) containing LiCl as a lithium salt was added to the obtained product, and the mixture was stirred at 0 ° C. for 48 hours. The precipitate triethylamine chloride (Et ₃ NCl) was separated by filtration, and THF was removed from the filtrate by a rotary evaporator. The product was washed 3 times with THF (150 mL) to remove THF.

In this way, a product (21.94 g, yield 98%) was obtained. When the obtained product was observed, it was a white solid powder. Similar to Example 1, it was identified by NMR, FT-IR and LC / MS.

¹ According to the ¹ H NMR spectrum, a characteristic peak was detected as in Example 1. Signals A and B derived from the terminal hydrogen of the vinyl group are 6.07 (2H) ppm and 5.49 (2H) ppm, respectively, and signal C derived from the hydrogen of the methyl group is 1.86 (3H). Observed at ppm.

According to the ¹³ C NMR spectrum, a characteristic peak was detected as in Example 1. Signals (1) to (5) derived from the carbons (1) to (5) (FIG. 11) were observed at 176.32 ppm, 144.33 ppm, 123.72 ppm, 120.65 ppm and 18.53 ppm, respectively. It was.

From the above results, the product obtained in Example 6 is a monomer compound in which R ₁ is a methyl group in the general formula (1) and nitrogen is directly bonded to the methacrylate group (LiTFSMA in FIG. 22). Shown. From this, it is shown that the monomer compound of the present invention is effective in the production method shown in FIG. 3 in addition to the production method shown in FIG. 1, and is produced in a small number of steps and in a higher yield. It was.

Since the polymer compound obtained by using the monomer compound of the present invention has a high density of Li ions and a low glass transition temperature, it achieves high conductivity not only in a normal use environment but also in a low temperature environment of 0 ° C. or lower. To do. Such a polymer compound becomes an electrolyte for a lithium ion secondary battery and an air battery, and such a lithium ion secondary battery and an air battery can be used for portable electronic devices such as notebook computers and mobile phones.

600 Lithium-ion secondary battery 610 Positive electrode 620, 720 Negative electrode 630, 730 Polymer electrolyte layer 700 Air battery 710 Air electrode

Claims (20)

A monomer compound represented by the general formula (1).


Here, Tf represents a trifluoromethanesulfonyl group (-SO ₂ CF ₃ ), and R ₁ is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, which has or does not have a hydrogen or a substituent. n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec-pentyl group, 3-pentyl group, tert-pentyl group, n-hexyl group, isohexyl group, sec-hexyl group , 3-Hexyl group, tert-Hexyl group or Cyclohexyl group. The monomer compound according to claim 1, wherein R ₁ is a hydrogen or methyl group. The monomer compound according to claim 1, wherein the substituent is selected from the group consisting of a halogen group, a hydroxyl group, an amino group and an epoxy group. A polymer compound represented by the general formula (2).

Here, Tf represents a trifluoromethanesulfonyl group (-SO ₂ CF ₃ ), and R ₁ is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, which has or does not have a hydrogen or a substituent. n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec-pentyl group, 3-pentyl group, tert-pentyl group, n-hexyl group, isohexyl group, sec-hexyl group , 3-Hexyl group, tert-Hexyl group or cyclohexyl group, where n is an integer of 10 or more and 100,000 or less. The polymer compound according to claim 4, wherein R ₁ is a hydrogen or methyl group. The main chain is an anionic polymer compound represented by the general formula (3).
A polymer composite having a complex represented by the general formula (4) as a counter cation.

Here, Tf represents a trifluoromethanesulfonyl group (-SO ₂ CF ₃ ), and R ₁ is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, which has or does not have a hydrogen or a substituent. n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec-pentyl group, 3-pentyl group, tert-pentyl group, n-hexyl group, isohexyl group, sec-hexyl group , 3-Hexyl group, tert-Hexyl group or Cyclohexyl group, n is an integer of 10 or more and 100,000 or less, and R ₂ and R ₃ have or do not have the same or different substituents. , Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec-pentyl group, 3-pentyl group, tert- It is a pentyl group, an n-hexyl group, an isohexyl group, a sec-hexyl group, a 3-hexyl group, a tert-hexyl group or a cyclohexyl group, and m is an integer of 1 or more and 4 or less. The polymer composite according to claim 6, wherein R ₁ is a hydrogen or a methyl group, and R ₂ and R ₃ are the same or different methyl or ethyl groups. A method for producing the monomer compound according to claim 1.
The first step of reacting NH ₂ SO ₂ CF ₃ with MH (M is an element selected from the group consisting of Li, Na, K and Cs) and
The second step of reacting the reaction product obtained in the first step with the compound represented by the general formula (I), and
A method comprising the third step of reacting the reactant obtained in the second step with a lithium salt selected from the group consisting of lithium hydride, lithium hydroxide, and lithium alkoxide.

Here, R ₁ is hydrogen, or has or does not have a substituent, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-. Pentyl group, isopentyl group, sec-pentyl group, 3-pentyl group, tert-pentyl group, n-hexyl group, isohexyl group, sec-hexyl group, 3-hexyl group, tert-hexyl group or cyclohexyl group, X Is an element selected from the group consisting of fluorine, chlorine, bromine and iodine. The method according to claim 8, wherein the first step is to react in a polar solvent in a temperature range of −100 ° C. or higher and 30 ° C. or lower. The method according to claim 8, wherein the second step is to react in a polar solvent in a temperature range of −100 ° C. or higher and 30 ° C. or lower. The method according to claim 8, wherein the third step is to react in a polar solvent in a temperature range of −100 ° C. or higher and 30 ° C. or lower. A method for producing the monomer compound according to claim 1.
The first step of reacting NH ₂ SO ₂ CF ₃ with MH (M is an element selected from the group consisting of Li, Na, K and Cs) and
The reactant obtained in the first step, the compound represented by the general formula (I), and an amine selected from the group consisting of triethylamine, pyridine and 1,4-diazabicyclo [2.2.2] octane. A method comprising a second step of reacting with a class.

Here, R ₁ is hydrogen, or has or does not have a substituent, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-. Pentyl group, isopentyl group, sec-pentyl group, 3-pentyl group, tert-pentyl group, n-hexyl group, isohexyl group, sec-hexyl group, 3-hexyl group, tert-hexyl group or cyclohexyl group, X Is an element selected from the group consisting of fluorine, chlorine, bromine and iodine. A method for producing the monomer compound according to claim 1.
The NH ₂ SO ₂ CF ₃ is reacted with the compound represented by the general formula (I) with amines selected from the group consisting of triethylamine, pyridine and 1,4-diazabicyclo [2.2.2] octane. The first step and
A method comprising the second step of reacting the reactant obtained in the first step with lithium halide.

Here, R ₁ is hydrogen, or has or does not have a substituent, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-. Pentyl group, isopentyl group, sec-pentyl group, 3-pentyl group, tert-pentyl group, n-hexyl group, isohexyl group, sec-hexyl group, 3-hexyl group, tert-hexyl group or cyclohexyl group, X Is an element selected from the group consisting of fluorine, chlorine, bromine and iodine. The method for producing the polymer compound according to claim 4.
A method comprising the step of polymerizing the monomer compound according to claim 1 by a polymerization method selected from the group consisting of radical polymerization, living radical polymerization, ion polymerization, living ion polymerization, photopolymerization and thermal polymerization. The method according to claim 14, wherein the living radical polymerization is atom transfer radical polymerization (ATRP). The method for producing a polymer composite according to claim 6.
A method comprising mixing the polymer compound according to claim 4 with the grime represented by the general formula (II) in a polar solvent.

Here, R ₂ and R ₃ are the same or different, having or not having a substituent, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-. Butyl group, n-pentyl group, isopentyl group, sec-pentyl group, 3-pentyl group, tert-pentyl group, n-hexyl group, isohexyl group, sec-hexyl group, 3-hexyl group, tert-hexyl group or cyclohexyl It is a group, and m is an integer of 1 or more and 4 or less. The method of claim 16, wherein the mixing step is performed in an inert gas atmosphere. An electrolyte material containing at least the polymer composite according to claim 6. A lithium ion secondary battery including a positive electrode, a negative electrode, and a polymer electrolyte layer located between the positive electrode and the negative electrode.
The polymer electrolyte layer is a lithium ion secondary battery made of the electrolyte material according to claim 18. A lithium-ion air battery including an air electrode, a negative electrode, and a polymer electrolyte layer located between the air electrode and the negative electrode.
An air battery in which the polymer electrolyte layer is made of the electrolyte material according to claim 18.