JP2009287012A - Ionic polymer and method of manufacturing the same - Google Patents

Abstract

（式中、Ｒ¹は水素原子又はメチル基、Ｒ²は炭素数１〜８のアルキレン基、Ｒ³は炭素数１〜８のアルキル基、Ｘ^-はアニオン成分を示す。）で表される繰り返し単位を含む。
【選択図】なしDisclosed is a novel ionic polymer which hardly causes leaching of ions and has high ionic conductivity.
The following formula (1)

Wherein R ¹ is a hydrogen atom or a methyl group, R ² is an alkylene group having 1 to 8 carbon atoms, R ³ is an alkyl group having 1 to 8 carbon atoms, and X ⁻ represents an anion component. Includes repeat units.
[Selection figure] None

Description

  The present invention relates to an ionic polymer and a method for producing the same.

As an electrolyte material used for electrochemical devices such as lithium ion batteries, lithium ion capacitors, and electric double layer capacitors, an electrolytic solution in which an electrolyte is mainly dissolved in an organic solvent has been used so far. However, there is a problem that the electrolytic solution may ignite or leak.
In order to prevent this problem, polymer solid electrolytes and gel electrolytes have been actively developed. However, even in these materials, it is difficult to completely prevent electrolytes and gel plasticizers from leaking out, and practical application is difficult. There is a problem that it is difficult.

  On the other hand, ionic liquids are liquid molten salts at room temperature, and are non-volatile, non-flammable and exhibit ionic conductivity, and thus are expected to be applied to various electrochemical devices. For example, the development of impregnating an ionic liquid into a separator, a film, or the like is underway, but there is a problem that the convenience as a material is significantly impaired due to a bleeding phenomenon.

  From these technical backgrounds described above, attempts have been made to encapsulate ionic liquids in various polymer materials in order to solidify them while maintaining the properties of the ionic liquid as an electrolyte (Patent Documents 1 and 2). For example, an attempt has been made to encapsulate an ionic liquid using an epoxy resin that is a thermosetting resin. However, in the obtained formed body, deterioration due to elution of the ionic liquid during the processing process or use of the formed body is avoided. It was a problem.

  As another solidification method, for example, an ionic polymer obtained by polymerizing an ionic monomer is disclosed (Non-Patent Document 1). However, this ionic polymer has a problem that the glass transition temperature is high.

JP 2007-70420 A

J Polym Sci Part A: Polym Chem 2005, 5477-5489

  Therefore, the present invention provides a novel ionic polymer having a low glass transition temperature and immobilizing an ionic functional group in the polymer, which hardly causes leaching of ions and exhibits ionic conductivity as a self-supporting film. This is the issue.

  The inventors of the present invention have conducted intensive studies on a polymer having ion conductivity, and found that it has a low glass transition by copolymerizing a (meth) acrylate having an imidazolinium cation group and another specific (meth) acrylate. The present invention was completed by finding that a novel ionic polymer having a high temperature and having a high ionic conductivity with which ions do not easily exude.

  That is, 1) The present invention provides the following formula (1)

(Wherein R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkylene group having 1 to 8 carbon atoms, R ³ represents an alkyl group having 1 to 8 carbon atoms, and X ⁻ represents an anion. Indicates ingredients.)
A repeating unit represented by the following formulas (2), (3) and (4):

(Wherein R ⁴ , R ⁶ and R ^{8 to} R ¹¹ each independently represents a hydrogen atom or a methyl group, R ⁵ represents an alkyl group having 1 to 8 carbon atoms, and R ⁷ represents carbon. An alkylene group having 2 to 8 carbon atoms, R ¹² represents a trivalent hydrocarbon group having 4 to 25 carbon atoms, and n represents an integer of 1 or more.)
An ionic polymer containing at least one of the repeating units represented by the formula:

  2) Moreover, this invention provides the molded object containing the ionic polymer of said 1) description.

  3) Further, the present invention provides the following formula (5)

(Wherein R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkylene group having 1 to 8 carbon atoms, R ³ represents an alkyl group having 1 to 8 carbon atoms, and X ⁻ represents an anion. Indicates ingredients.)
And the following formulas (6), (7) and (8)

(Wherein R ⁴ , R ⁶ and R ^{8 to} R ¹¹ each independently represents a hydrogen atom or a methyl group, R ⁵ represents an alkyl group having 1 to 8 carbon atoms, and R ⁷ represents carbon. An alkylene group having 2 to 8 carbon atoms, R ¹² represents a trivalent hydrocarbon group having 4 to 25 carbon atoms, and n represents an integer of 1 or more.)
The method for producing an ionic polymer as described in 1) above, wherein at least one of the monomers represented by formula (1) is polymerized.

  4) Following formula (9)

(Wherein R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkylene group having 1 to 8 carbon atoms, R ³ represents an alkyl group having 1 to 8 carbon atoms, and X ⁻ represents di Represents a sulfonylamino anion.)
The compound represented by these is provided.

  The ionic polymer of the present invention has a low glass transition temperature, hardly exudes ions, has high ionic conductivity, and has high ion stability and high thermal stability. Therefore, the ionic polymer of the present invention is useful as a molded product used for a solid electrolyte layer of a capacitor, a capacitor, a battery, an antistatic agent, or the like.

Table ¹ H-NMR spectrum of the obtained by the copolymerization of Example 2 of 1 copolymer (400MHz, acetone -d ₆₎ is a diagram showing a. It is a figure which shows the monomer consumption rate with respect to superposition | polymerization time. It is a figure which shows the < ¹ > H-NMR spectrum of the obtained polymer. It is a figure which shows the monomer consumption rate with respect to superposition | polymerization time.

In the ionic polymer of the present invention, in formula (1), R ¹ is preferably a methyl group.
R ² is preferably a linear or branched alkylene group having 1 to 8 carbon atoms, and preferred specific examples include a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, and a pentamethylene group. And a hexamethylene group, and a methylene group is particularly preferable.

Moreover, as R < ³ >, a C1-C8 linear or branched alkyl group is preferable, As a suitable specific example, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, Examples thereof include an n-pentyl group and an n-hexyl group, and a methyl group is particularly preferable.

In the ionic polymer of the present invention, the anion component represented by X ⁻ is not particularly limited as long as it is negatively charged. For example, a carboxylate anion, a sulfonate anion, a disulfonylamino anion, an inorganic acid anion, Lewis An acid anion and the like, and a disulfonylamino anion is particularly preferable.
Specific examples of the anion component include Br ⁻ , AlCl ₄ ⁻ , Al ₂ Cl ₇ ⁻ , NO ₃ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , CH ₃ COO ⁻ , CF ₃ COO ⁻ , CF ₃ SO ₃ −. , (CF ₃ SO ₂ ) ₂ N ⁻ , (CF ₃ SO ₂ ) ₃ C ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , F (HF) _n ⁻ , CF ₃ CF ₂ CF ₂ CF ₂ SO ₃ ⁻ , (CF ₃ CF ₂ SO ₂ ) ₂ N ⁻ , CF ₃ CF ₂ CF ₂ COO ^{− and the} like. BF ₄ ⁻ , PF ₆ ⁻ , (CF ₃ SO ₂ ) ₂ N are low in melting point and high in heat resistance. ^- it is _{^{preferred, PF 6 -, (CF 3}} SO 2) 2 N - ( hereinafter, TFSI ^-. and also referred to) is more _{preferable, (CF 3 SO 2) 2} N - is particularly preferred.
The disulfonylamino anion is preferably a di (perfluoroalkanesulfonyl) amino anion, further a di (C _1-6 perfluorosulfonyl) amino anion, particularly a di (trifluoromethanesulfonyl) amino anion.

Moreover, in formula (2)-(4), as R < ⁴ >, R < ⁶ > and R < ⁸ > -R < ¹¹ >, a methyl group is preferable.
R ⁵ is preferably a linear or branched alkyl group having 1 to 8 carbon atoms. Preferred specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, Examples thereof include an n-pentyl group and an n-hexyl group, and a methyl group is particularly preferable.

R ⁷ is preferably a linear or branched alkylene group having 2 to 8 carbon atoms, and preferred specific examples include ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group. Group etc. are mentioned, An ethylene group is especially preferable.

R ¹² is a trivalent hydrocarbon group having 4 to 25 carbon atoms, preferably a trivalent alkyl group having 4 to 25 carbon atoms. Furthermore, as R ¹² , the following formula (10)
Following formula (10)

(In the formula, R ^{13 to} R ¹⁵ independently represent an alkylene group having 1 to 8 carbon atoms, and R ¹⁶ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.)
The group represented by these is preferable.

As said R < ¹³ > -R < ¹⁵ >, a C1-C8 linear alkylene group is preferable, As a specific example, a methylene group, ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, Although a hexamethylene group etc. are mentioned, a methylene group is especially preferable.

R ¹⁶ is preferably a linear alkyl group having 1 to 8 carbon atoms, and preferred specific examples include a methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n- Although a hexyl group etc. are mentioned, a methyl group and an ethyl group are especially preferable.

  Moreover, as formula (3), as n, 1-200 are preferable and 1-20 are more preferable.

  The repeating unit represented by the formula (1) and the repeating units represented by the formulas (2) to (4) are (1) 1 to 99 mol% and (2) to (4) 99 mol%, respectively. -1 mol% is preferable, (1) 20-99 mol%, (2)-(4) 80 mol%-1 mol% is more preferable, (1) 50 mol%-95 mol%, ( 2) to (4) 5 to 50 mol% is particularly preferable.

  The ionic polymer of the present invention includes, as exemplified by the following formula, a monomer represented by the formula (5) and at least one of the monomers represented by the formulas (6), (7) and (8): Is obtained by polymerizing.

(Wherein R ^{1 to} R ¹² , X ⁻ and n are the same as above)

  The monomer represented by the formula (5) used in the production method of the present invention can be produced according to the following reaction formula (A).

(In the formula, R ¹ , R ² , R ³ and X ⁻ are the same as above. Y represents a halogen atom.)

  In Reaction Formula (A), Y represents a halogen atom, preferably a bromine atom and a chlorine atom, and more preferably a bromine atom.

The reaction of the compound (11) and the compound (12) can be carried out in the presence / absence of a catalyst, but is preferably carried out in the presence of a catalyst. The catalyst may be a basic catalyst, but triethylamine, tripropylamine, tributylamine and pyridine are preferable, and triethylamine and pyridine are more preferable. The amount of the catalyst added is preferably 1 to 2 equivalents, more preferably about 1.1 equivalents, relative to compound (11).
The reaction of compound (11) and compound (12) can be carried out in the presence / absence of a solvent, but is preferably carried out in the presence of a solvent. As the solvent, a nonpolar organic solvent is suitably used, dichloromethane, chloroform and toluene are more preferable, and dichloromethane is more preferable. The addition amount of the solvent is preferably about 4 to 10 times by volume with respect to the compound (11).

  The reaction of the compound (13) and the imidazole compound can be carried out in the presence / absence of a solvent, but is preferably carried out in the absence of a solvent. In the reaction, it is preferable to use a phenol derivative as a polymerization inhibitor, preferably 2,6-dibutyl-4-methylphenol, dihydroquinone, p-methoxyphenol, 2,6-dibutyl-4-methylphenol, Dihydroquinone is more preferred. The addition amount of the polymerization inhibitor is preferably about 0.1 to 5 mol% with respect to the compound (13).

Compound (14), X ^- in the anion component is reacted represented By isolating and purifying a monomer represented by the formula (5) is obtained. This reaction is carried out, for example, by reacting the compound corresponding to X ⁻ in an aqueous solution in equimolar amounts in principle.

  Of the monomers represented by the formula (5) obtained by the reaction formula (A), the following formula (9)

(Wherein R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkylene group having 1 to 8 carbon atoms, R ³ represents an alkyl group having 1 to 8 carbon atoms, and X ⁻ represents di Represents a sulfonylamino anion.)
Is a novel compound.

  Moreover, the monomer represented by Formula (6), (7) and (8) which is another raw material used for this invention is obtained by a well-known method.

  In the production method of the present invention (hereinafter also referred to as the present invention production method), the amount of the monomer represented by the formulas (6), (7) and (8) is the same as the monomer represented by the formula (5). On the other hand, about 5 mol% to 100 mol% is preferable.

  In the production method of the present invention, the reaction is preferably performed in the presence of a polymerization initiator. Examples of the polymerization initiator include azobisisobutyronitrile, benzoyl peroxide, and azobiscyclohexane-1-carbonitrile. Azobisisobutyronitrile and benzoyl peroxide are preferable, and azobisisobutyronitrile is preferable. More preferred. The addition amount of the polymerization initiator is preferably about 0.1 to 5 mol% with respect to the total amount of the monomer represented by the formula (5) and the monomers represented by the formulas (6), (7) and (8). .

  In the production method of the present invention, the reaction can be carried out in the presence / absence of a solvent, but the reaction is preferably carried out in the presence of a solvent. The solvent is not particularly limited as long as it dissolves the reaction product and the product, but is preferably an ionic liquid, dimethylformamide, dimethyl sulfoxide, acetone, or methyl ethyl ketone, more preferably an ionic liquid, dimethylformamide, or acetone, and dimethyl Formamide (hereinafter also referred to as DMF) and ionic liquid are more preferable. The addition amount of the solvent is preferably about 0.5 to 20 times the total amount of the monomer represented by the formula (5) and the monomers represented by the formulas (6), (7) and (8).

Of the above solvents, an ionic liquid is preferred in that the ionic conductivity of the ionic polymer is improved. The ionic liquid is a molten salt which is liquid at room temperature and is composed of a cation component and an anion component.
Examples of the cation component include metal ions such as lithium ion, sodium ion, and potassium ion, 1-ethyl-3-methylimidazolium cation, 1-n-hexyl-3-methylimidazolium cation, and the like. 1-ethyl-3-methylimidazolium cation is preferred.
As anion components, Br ⁻ , AlCl ₄ ⁻ , Al ₂ Cl ₇ ⁻ , NO ₃ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , CH ₃ COO ⁻ , CF ₃ COO ⁻ , CF ₃ SO ₃ −, (CF ₃ SO ₂ ) ₂ N ⁻ , (CF ₃ SO ₂ ) ₃ C ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , F (HF) _n ⁻ , CF ₃ CF ₂ CF ₂ CF ₂ SO ₃ ⁻ , (CF ₃ CF ₂ SO ₂ ) ₂ N ⁻ , CF ₃ CF ₂ CF ₂ COO ^{− and the} like can be mentioned, and (CF ₃ SO ₂ ) ₂ N ⁻ is preferable.
That is, as the ionic liquid, 1-ethyl-3-methylimidazolium bistrifluoromethanesulfonimide (hereinafter also referred to as EMImTFSI) is preferable, and EMImTFSI is particularly preferable.

  In the production method of the present invention, a catalyst may be used in addition to the polymerization initiator, and examples of the catalyst include trialkylborane, trialkylaluminum, and dialkylzinc.

  In the production method of the present invention, the reaction time is preferably 10 minutes to 48 hours, more preferably 30 minutes to 24 hours, and even more preferably 30 minutes to 3 hours. The reaction temperature is preferably 60 to 90 ° C, more preferably 70 to 80 ° C.

  In the present invention, the target ionic polymer can be isolated and purified by a method such as reprecipitation. In addition, the ionic polymer of this invention obtained by the said manufacturing method is a novel compound.

  As a weight average molecular weight of the ionic polymer of this invention, 500-1 million are preferable, 1000-500,000 are more preferable, 1000-200,000 are further more preferable. Moreover, as Mw / Mn, 1-10 are preferable and 1-5 are more preferable.

  The ionic polymer of the present invention has a low glass transition temperature, hardly exudes ions, has high ionic conductivity, and further has an ion dissociable site and high thermal stability, as shown in Examples below. Have Therefore, the ionic polymer can be used as an electrolyte film as it is or by forming it into a film, so as to form a solid electrolyte layer such as a capacitor (lithium ion capacitor, battery double layer capacitor, etc.), capacitor, battery (lithium ion battery, etc.) Can be applied to a wide range of applications such as antistatic agents, and other places where, for example, polythiophene, ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide) are used as alternative technologies for transparent conductive films It can be used as a molded body such as a film that can be widely used, and can be used for producing the molded body.

  In addition, the molded body may be blended with an antioxidant for improving chemical stability, may be blended with an inorganic filler for increasing mechanical strength and flame retardancy, and further conductive. In order to improve the property, a conductive material such as carbon black, fullerene, or carbon nanotube may be blended. In the molded article, the content of the ionic polymer of the present invention is not particularly limited, but is preferably 30 to 100%.

  Hereinafter, embodiments of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

Synthesis Example 1 Synthesis of 1- [2- (methacryloyloxy) ethyl] 3-methyl-imidazolium-bis (trifluoromethanesulfonyl) imide (hereinafter referred to as Met-IL-TFSI)

To a solution of 2-bromoethanol (8.0 mL, 110 mmol) and methacryloyl chloride (9.8 mL, 100 mmol) in dichloromethane (60 mL) cooled in an ice bath was added a solution of triethylamine (15 mL, 110 mmol) in dichloromethane (10 mL) over 15 minutes. And dripped. After stirring at room temperature for 12 hours, the reaction mixture was filtered, and the obtained filtrate was washed three times with distilled water (100 mL). After the dichloromethane layer was dried with magnesium sulfate, the solvent was removed under reduced pressure. The obtained crude product was purified by silica gel chromatography (eluent: ethyl acetate-hexane (volume ratio 1: 4)) to obtain colorless liquid 2-bromoethyl methacrylate (17 g, 89.0 mmol) in a yield of 89. %.

  2-Bromoethyl methacrylate (2.96 g, 15.40 mmol) and 2,6-ditert-butyl-4-methylphenol (20 mg) were dissolved in 1-methylimidazole and then stirred at 40 ° C. for 48 hours. By washing the obtained crude product with diethyl ether, white solid 1- [2- (methacryloyloxy) ethyl] 3-methyl-imidazolium bromide (hereinafter referred to as Met-IL-Br) ( 3.96 g, 14.45 mmol) was obtained with a yield of 94%.

After adding an aqueous solution (4 mL) of bis (trifluoromethanesulfonyl) imide lithium (LiTFSI, 4.40 g, 15.40 mmol) to an aqueous solution (4 mL) of Met-IL-Br (3.96 g, 14.45 mmol) at room temperature. , And stirred at 45 ° C. for 24 hours. The product was extracted with ethyl acetate (20 mL), and the organic layer was washed with water (15 mL). The organic layer was dried over magnesium sulfate, and then the solvent was removed under reduced pressure to obtain colorless liquid Met-IL-TFSI (5.28 g, 11.10 mmol) in a yield of 77%.
The structure of Met-IL-TFSI was confirmed by ¹ H-NMR, ¹³ C-NMR, IR, and elemental analysis.

¹ H NMR (400 MHz, CDCl ₃ ): δ = 9.1 (s, 1H), 7.6-7.9 (d, 2H), 5.6-6.15 (d, 4H), 4.5-4.6 (t, 2H), 4.7-4.8 (t, 2H), 4.0 (3H, S), 1.8 (3H, S).
¹³ C NMR (CDCl ₃ ): δ = 163.0, 148, 138, 124, 64, 49.62, 37.46, 19.41.
IR (KBr): 3160, 3123, 3000, 1722, 1637, 1577,1568, 1500, 1400, 1300, 1200, 1141, 1100, 950, 845, 815, 791, 742, 706, 653, 618, 571, 514 , 483, 449, 423, cm ^-1
Elemental Analysis: Calcd for C ₁₂ H ₁₅ F ₆ N ₃ O ₆ S ₂・ 0.5H ₂ O: C, 29.75; H, 3.33; N, 8.67; S, 13.24; F, 23.53. Found: C, 29.43; H, 3.02; N, 8.80; S, 13.03; F, 24.29.

Examples 1-4 Copolymerization of Met-IL-TFSI and methyl methacrylate (MMA) in dimethylformamide (DMF)

Met-IL-TFSI (150 mg, 0.32 mmol), methyl methacrylate (MMA, 0.034 mL. 0.32 mmol), azobisisobutyronitrile (AIBN, 0.6 mg, 0.0032 mmol) and dimethylformamide (0. 21 mL) ([Met-IL-TFSI] / [MMA] = 1/1). Dissolved oxygen was removed by freeze degassing, followed by heating at 70 ° C. for 30 minutes under nitrogen. The reaction mixture was poured into a large amount of methanol, and the precipitated white precipitate was filtered off and washed with methanol. The white solid copolymer was obtained by making it dry under reduced pressure at room temperature (121 mg).
In Examples 2-4, it carried out like Example 1 except having made the copolymerization ratio of Met-IL-TFSI and methyl methacrylate show in Table 1. The results are shown in Table 1. The ¹ H-NMR spectrum (400 MHz, acetone-d ₆ ) of the copolymer obtained by copolymerization in Example 2 in Table 1 is shown in FIG.

Examples 5-7 Copolymerization of Met-IL-TFSI and MMA in 1-ethyl-3-methylimidazolium bistrifluoromethanesulfonimide (EMImTFSI)

Met-IL-TFSI (150 mg, 0.32 mmol), methyl methacrylate (MMA, 0.034 mL, 0.32 mmol), azobisisobutyronitrile (AIBN, 0.6 mg, 0.0032 mmol) in 1-ethyl It was dissolved in -3-methylimidazolium bistrifluoromethanesulfonimide (EMImTFSI, 129 mg) ([Met-IL-TFSI] / [MMA] = 1/1). Dissolved oxygen was removed by freeze degassing, followed by heating at 70 ° C. for 30 minutes under nitrogen. The reaction mixture was poured into a large amount of methanol, and the precipitated white precipitate was filtered off and washed with methanol. The white solid copolymer was obtained by making it dry under reduced pressure at room temperature (110 mg).
In Examples 6-7, it carried out like Example 5 except having set it as the ratio of Met-IL-TFSI and methyl methacrylate as shown in Table 2. The results are shown in Table 2.

For the copolymer obtained by copolymerization in Example 7 in Table 2, the glass transition temperature T _g and 5% thermal decomposition temperature T _d-5 measured by DSC and TG were 75 ° C. and 345 ° C., respectively. .

Reference Example 1 Homopolymerization of Met-IL-TFSI in DMF

Met-IL-TFSI (250 mg, 0.53 mmol) and azobisisobutyronitrile (AIBN, 1.6 mg, 0.010 mmol) were dissolved in DMF (0.35 mL). Dissolved oxygen was removed by freeze degassing, followed by heating at 70 ° C. for 2 hours under nitrogen. The reaction mixture was poured into a large amount of methanol, and the precipitated white precipitate was filtered off and washed with methanol. By drying under reduced pressure at room temperature, a white solid-soluble polymer was obtained (210 mg, 84%) in dimethylsulfoxide, dimethylformamide, acetonitrile and acetone. The monomer consumption rate relative to the polymerization time is shown in FIG. The ¹ H-NMR spectrum (400 MHz, acetone-d ₆ ) of the obtained polymer is shown in FIG.
With respect to the obtained copolymer, the glass transition temperature T _g and the 5% thermal decomposition temperature T _d-5 were 177 ° C. and 345 ° C. by DSC and TG.

Reference Example 2 Homopolymerization of Met-IL-TFSI in 1-ethyl-3-methyl-imidazolium bistrifluoromethanesulfonimide (EMImTFSI)

Met-IL-TFSI (250 mg, 0.53 mmol) and azobisisobutyronitrile (AIBN, 1.6 mg, 0.010 mmol) were combined with 1-ethyl-3-methyl-imidazolium bistrifluoromethanesulfonimide (EMImTFSI, 206 mg). ). Dissolved oxygen was removed by freeze degassing, followed by heating at 70 ° C. for 2 hours under nitrogen. The reaction mixture was poured into a large amount of methanol, and the precipitated white precipitate was filtered off and washed with methanol. By drying under reduced pressure at room temperature, a white solid polymer soluble in dimethyl sulfoxide, dimethylformamide, acetonitrile and acetone was obtained (205 mg, 82%). The monomer consumption rate with respect to the polymerization time is shown in FIG.
The ¹ H-NMR spectrum (400 MHz, acetone-d ₆ ) of the obtained polymer showed the same spectrum as the polymer obtained by polymerization in dimethylformamide.
With respect to the obtained copolymer, the glass transition temperature T _g and the 5% thermal decomposition temperature T _d-5 were 175 ° C. and 370 ° C. by DSC and TG.

Test Example 1 Ionic conductivity and ion extraction
Five samples of conductive resin containing Met-IL were prepared, and the conductivity of each sample was measured. Methyl methacrylate (MMA), ethylene glycol dimethacrylate (EGDMA), and trimethylolpropane (TMPTMA) are purchased from Wako Pure Chemical Industries, washed with aqueous sodium hydroxide, dried over anhydrous sodium sulfate, and then over calcium hydride. Distilled from. Then, 4,4′-azobisisobutyronitrile (AIBN) was purchased from Wako Pure Chemical Industries, and purified by recrystallization from methanol.

1) Creation of mold for film adjustment Recessed PTFE sheet (thickness) with 18 mm x 55 mm cuts in two glass slides with polytetrafluoroethylene tape (PTFE) (Permacel P422) on the surface 0.5 mm) was used as a spacer to create a PTFE mold for film preparation.

2) Production of Met-IL / EGDMA film (Example 8)
Met-IL (998 mg, 2.66 mmol), EGDMA (351 mg, 1.77 mmol), AIBN (azobisisobutyronitrile, azobisisobutylonitrile) (10.2 mg, 0.062 mmol) are mixed, poured into a PTFE formwork, and placed in a 2L glass container. The inside of the container was replaced with nitrogen, and the entire container was heated at 70 ° C. for 4 hours to synthesize a Met-IL / EGDMA film sample.

3) Production of Met-IL / EGDMA / EMImTFSI (50) film (Example 9)
Met-IL (998 mg, 2.66 mmol), EGDMA (351 mg, 1.77 mmol), EMImTFSI (1-ethyl-3-methylimidazolium bistrifluoromethanesulfonimide) (1278 mg, 3.27 mmol), AIBN (10.2 mg, 0.062 mmol), poured into a PTFE mold, put into a 2 L glass container, and the inside of the container was purged with nitrogen.The whole container was heated at 70 ° C. for 4 hours, and Met-IL / EGDMA / EMImTFSI (50) Film samples were synthesized.

4) Production of Met-IL / TMPTMA / EMImTFSI (50) film (Example 10)
Met-IL (998 mg, 2.66 mmol), TMPTMA (535 mg, 1.77 mmol), EMImTFSI (1546 mg, 3.95 mmol), AIBN (13 mg, 0.080 mmol) are mixed, poured into a PTFE formwork, 2 L The inside of the container was replaced with nitrogen, and the entire container was heated at 70 ° C. for 4 hours to synthesize a Met-ILTMPTMA / EMImTFSI (50) film sample.

5) Manufacture of MMA / EGDMA film (Comparative Example 1)
MMA (600 mg, 6.00 mmol), EGDMA (792 mg, 4.00 mmol), AIBN (79 mg, 0.48 mmol) are mixed, poured into a PTFE mold, placed in a 2 L glass container, and the inside of the container is purged with nitrogen. The whole container was heated at 70 ° C. for 4 hours to synthesize MMA / EGDMA film samples.

6) Manufacture of MMA / EGDMA / EMImTFSI (50) film (Comparative Example 2)
MMA (2144 mg, 21.4 mmol), EGDMA (2830 mg, 14.3 mmol), EMImTFSI (4974 mg, 12.7 mmol), AIBN (82 mg, 0.50 mmol) are mixed, poured into a PTFE formwork, and 2L glass. Place in a container and purge with nitrogen, and heat the whole container at 70 ° C for 4 hours to synthesize a film sample of MMA / EGDMA / EMImTFSI (50).

7) Measurement of ionic conductivity of film A small piece (15 mm x 10 mm x 0.5 mm) of a film sample was cut out, impedance was measured by the AC four-terminal method, and ionic conductivity was obtained from the absolute value (HIOKI 3532- 80 Chemical impedance meter, 9140 4-terminal probe, voltage: 50 mV, measurement frequency: 4 Hz to 100 KHz).

8) Ion extraction experiment Cut out a small piece (about 15 mm x 7 mm) of an ionic liquid-containing film, weigh it (60-70 mg), add it to a sample tube with a 50 mL screw cap, and add acetone (40 mL). After shaking well, the mixture was allowed to stand at room temperature, and with the passage of time, the conductivity of the solution in the sample tube was measured using a conductivity meter (METTLER TOLEDO S30). The extraction amount of the ionic liquid from the film was measured using a calibration curve created from the ionic conductivity of an ionic liquid solution (0.050 mmol / L to 2.0 mmol / L) having a known concentration in the same solvent. The extraction amount of the ionic liquid was measured under the condition of energization for 48 hours. Based on the calibration curve of the film that was not cleaned with acetone, the conductivity of the sample after cleaning with acetone was compared with the ion The amount of elution of the liquid was measured. The experimental results are shown in Table 3.

  As can be seen from the results of Example 8, conductivity was obtained by copolymerizing the ionic polymer Met-IL with bifunctional acrylic EGDMA, and the ionic liquid did not dissolve after washing with acetone. It was confirmed that it can be held for a long time.

  As can be seen from the results of Example 9, it was found that high conductivity can be obtained by copolymerizing the ionic polymer Met-IL with bifunctional acrylic EGDMA and impregnating the ionic liquid EMImTESI. From the confirmation of dissolution of the ionic liquid after washing with acetone, it was found that elution could be suppressed.

  As can be seen from the results of Example 10, it was found that high conductivity was obtained by copolymerizing the ionic polymer Met-IL with the trifunctional acrylic TMPTMA and impregnating the ionic liquid EMImTESI. From the confirmation of the dissolution of the ionic liquid after washing with acetone, it was found that elution can be suppressed.

  As can be seen from the results of Comparative Example 1, it was confirmed that conductivity was not obtained as a result of copolymerization of monofunctional acrylic MMA and bifunctional acrylic EGDMA.

  As can be seen from the results of Comparative Example 2, it was found that a polymer obtained by copolymerizing monofunctional acrylic MMA and bifunctional acrylic EGDMA was impregnated with ionic liquid EMImTESI to obtain high conductivity. However, when ionic liquid dissolution after washing with acetone was confirmed, 100% dissolution was confirmed in 15 minutes, and it was confirmed that it was difficult to maintain the function as a conductive polymer.

  From the above results, it was possible to obtain a film forming body capable of maintaining conductivity for a certain time by using the ionic polymer of the present invention.

  The molded body film of the present invention can be applied to, for example, a solid electrolyte layer of a lithium ion capacitor, a battery double layer capacitor, a capacitor, a lithium ion battery, and the like, as an alternative technique as another transparent conductive film. For example, it can be used in places where polythiophene, ITO (International Trade Organization), IZO (Idemitsu Indium Zinc Oxid) or the like is used.

Claims (6)

Following formula (1)

(Wherein R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkylene group having 1 to 8 carbon atoms, R ³ represents an alkyl group having 1 to 8 carbon atoms, and X ⁻ represents an anion. Indicates ingredients.)
A repeating unit represented by the following formulas (2), (3) and (4):

(Wherein R ⁴ , R ⁶ and R ^{8 to} R ¹¹ each independently represents a hydrogen atom or a methyl group, R ⁵ represents an alkyl group having 1 to 8 carbon atoms, and R ⁷ represents carbon. An alkylene group having 2 to 8 carbon atoms, R ¹² represents a trivalent hydrocarbon group having 4 to 25 carbon atoms, and n represents an integer of 1 or more.)
An ionic polymer comprising at least one repeating unit represented by: The ionic polymer according to claim 1, wherein the anion component X ⁻ of the chemical formula (1) is a disulfonylamino anion.   The molded object containing the ionic polymer of Claim 1 or 2.   The molded article according to claim 3, which is an electrolyte film. Following formula (5)

(Wherein R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkylene group having 1 to 8 carbon atoms, R ³ represents an alkyl group having 1 to 8 carbon atoms, and X ⁻ represents an anion. Indicates ingredients.)
And the following formulas (6), (7) and (8)

(Wherein R ⁴ , R ⁶ and R ^{8 to} R ¹¹ each independently represents a hydrogen atom or a methyl group, R ⁵ represents an alkyl group having 1 to 8 carbon atoms, and R ⁷ represents carbon. An alkylene group having 2 to 8 carbon atoms, R ¹² represents a trivalent hydrocarbon group having 4 to 25 carbon atoms, and n represents an integer of 1 or more.)
The method for producing an ionic polymer according to claim 1, wherein at least one of the monomers represented by formula (1) is polymerized. Following formula (9)

(Wherein R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkylene group having 1 to 8 carbon atoms, R ³ represents an alkyl group having 1 to 8 carbon atoms, and X ⁻ represents di Represents a sulfonylamino anion.)
A compound represented by

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