JP6273742B2 - Ether type network polymer and polymer gel electrolyte - Google Patents

Description

  The present invention relates to a novel ether type network polymer, in particular, the network polymer using a trifunctional benzene derivative as a monomer, and a polymer gel electrolyte containing the network polymer.

  One of the batteries expected as a next-generation secondary battery is a multivalent ion battery. For example, a magnesium ion secondary battery using divalent (polyvalent) magnesium as the negative electrode active material can be expected to improve energy density compared to a lithium ion secondary battery using monovalent lithium as the negative electrode active material. . In current electric vehicles, the travel distance by the lithium ion secondary battery is about 150 km, but the travel distance can be extended by increasing the energy density of the secondary battery.

On the other hand, magnesium metal has a problem that it forms a passive film at room temperature and does not lead to a reversible dissolution and precipitation reaction, and a magnesium ion secondary battery has not yet reached a practical stage. As one of the solutions, Patent Document 1 discloses that a Grignard reagent is mixed with an organometallic compound (for example, C ₆ H ₅ MgCl) or a salt other than magnesium (for example, (C ₂ H ₅ ) ₂ AlCl) in tetrahydrofuran. An electrolytic solution dissolved in is disclosed.

  The inventors have so far used a non-aqueous ammonium ionic liquid solution of a Grignard reagent as an electrolyte solution, which is superior to the case of a Grignard reagent alone, has high ionic conductivity, and is excellent. Have found an electrolyte solution for magnesium ion secondary batteries that exhibits reversibility of dissolution and precipitation of magnesium (Non-Patent Document 1).

  Furthermore, the inventors have also found an electrolytic solution for a magnesium ion secondary battery comprising an imidazolium-based ionic liquid or a pyrrolidinium-based ionic liquid and a Grignard reagent (Patent Document 2, etc.).

  However, the Grignard reagent has a problem of high reactivity and high possibility of causing a major accident due to liquid leakage. In order to prevent liquid leakage, it is effective to use a polymer gel electrolyte as in the case of the lithium ion secondary battery. However, a network polymer such as a normal acrylic resin has a low resistance to a Grignard reagent and decomposes.

JP 2007-188709 A JP 2012-48874 A

J. Power Sources, 2010, 195, 2096

  The present invention has been made in view of such circumstances, and an object thereof is to provide a network polymer that is resistant to the Grignard reagent and does not decompose and a polymer gel electrolyte containing the network polymer.

  As a result of intensive studies to solve the above problems, the present inventor succeeded in the construction of a new ether type network polymer using a monomer having a polymerizable functional group at positions 1, 3, and 5 of benzene, and The present inventors have found that a polymer gel electrolyte obtained from a network polymer has both high safety and high ionic conductivity, and has completed the present invention.

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

(Where
Y ^a , Y ^b and Y ^c each independently represent CR ₂ , —O— or —S—, and each R in CR ₂ independently represents H or an alkyl group having 1 to 4 carbon atoms. Represent,
R ^1a , R ^1b and R ^1c each independently represent a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms,
R ^2a , R ^2b and R ^2c each independently represent a substituted or unsubstituted alkylene group having 2 to 10 carbon atoms,
R ^3a , R ^3b and R ^3c each independently represent H or an alkyl group having 1 to 4 carbon atoms)
A network polymer obtained by polymerizing a compound represented by the following formula by olefin metathesis reaction; and
(2) The compound represented by the formula (I) is represented by the following formula (II)

It is related with the network polymer as described in (1) characterized by the above-mentioned.

The present invention also provides:
(3) The following formula (I)

(Where
Y ^a , Y ^b and Y ^c each independently represent CR ₂ , —O— or —S—, and each R in CR ₂ independently represents H or an alkyl group having 1 to 4 carbon atoms. Represent,
R ^1a , R ^1b and R ^1c each independently represent a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms,
R ^2a , R ^2b and R ^2c each independently represent a substituted or unsubstituted alkylene group having 2 to 10 carbon atoms,
R ^3a , R ^3b and R ^3c each independently represent H or an alkyl group having 1 to 4 carbon atoms)
It relates to a method for producing a network polymer as described in (1) or (2), wherein the compound represented by formula (1) is polymerized by an olefin metathesis reaction.

Furthermore, the present invention provides
(4) A polymer gel electrolyte comprising the network polymer according to (1) or (2) in an electrolytic solution,
(5) The electrolytic solution is represented by the following formula (M)

(Where
R is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, a substituted or unsubstituted carbon A cyclic alkyl group of formula 3-6, a substituted or unsubstituted thiophene group, a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group,
X represents Cl, Br or I)
The polymer gel electrolyte according to (4), wherein the polymer gel electrolyte is a solution of one or more halogenated organomagnesium compounds represented by:
(6) The polymer gel electrolyte according to (4) or (5), wherein the electrolytic solution is a diethylmethylmethoxyethylammonium bis (trifluoromethane) sulfonimide salt solution of ethylmagnesium bromide, and
(7) A secondary battery comprising the polymer gel electrolyte according to any one of (4) to (6).

  The network polymer of the present invention contains a repeating unit composed of a benzene ring and an ether chain, and therefore has higher chemical stability to a negative electrode active material and a solvent than a conventional network polymer. Because of its high chemical stability, the network polymer gel of the present invention can be used as a polymer gel electrolyte using an organic magnesium halide such as a Grignard reagent as a negative electrode active material. A polymer gel electrolyte using halogenated organomagnesium as a negative electrode active material can obtain a higher energy density than conventional network polymer gel electrolytes, and can be used for a highly safe secondary battery.

It is a diagram showing the ¹ H-NMR spectrum of 1,3,5-tris (10-undecenyl) benzene. It is a figure which shows IR spectrum of the network polymer which uses 1,3,5-tris (10-undecenyloxy) benzene as a monomer. It is a figure which shows the result of the cyclic voltammetry (CV) measurement of the polymer gel electrolyte using the network polymer of this invention.

(Network polymer)
The network polymer of the present invention contains a structural unit derived from a monomer represented by the following formula (I) in its structure.

In the formula, Y ^a , Y ^b and Y ^c each independently represent CR ₂ , —O— or —S—, and each R in CR ₂ is independently H or a group having 1 to 4 carbon atoms. Represents an alkyl group,
R ^1a , R ^1b and R ^1c each independently represent a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms,
R ^2a , R ^2b and R ^2c each independently represent a substituted or unsubstituted alkylene group having 2 to 10 carbon atoms,
R ^3a , R ^3b and R ^3c each independently represent H or an alkyl group having 1 to 4 carbon atoms.

  In the compound represented by the formula (I), specific examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, 2-butyl. Group and tert-butyl group.

In the compound represented by the formula (I), the alkylene group having 1 to 10 carbon atoms and the alkylene group having 2 to 10 carbon atoms include methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, Examples include a heptylene group, an octylene group, a nonylene group, and a decylene group.

  As the substituent of the alkylene group having 1 to 10 carbon atoms, any substituent may be used as long as the compound represented by the formula (I) becomes a network polymer and is stable with respect to the Grignard reagent or the like. Includes the alkyl group having 1 to 4 carbon atoms.

In the compound represented by formula (I), each of Y ^a , Y ^b and Y ^c is preferably CR ₂ , and R is more preferably H.

In the compound represented by the formula (I), R ^1a , R ^1b and R ^1c are preferably a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, and a butylene group, a pentylene group, A xylene group is more preferable, and a butylene group is most preferable. Similarly, in the compound represented by the formula (I), R ^2a , R ^2b and R ^2c are preferably a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, a butylene group, a pentylene group, More preferred is a hexylene group, and most preferred is a butylene group.

Furthermore, in the compound represented by the formula (I), R ^1a , R ^1b and R ^1c and R ^2a , R ^2b and R ^2c are preferably unsubstituted alkylene groups, and R ^1a = R ^1b = R ^1c Most preferably, R ^2a = R ^2b = R ^2c .

Furthermore, in the compound represented by formula (I), R ^3a , R ^3b and R ^3c are preferably H or a methyl group, and most preferably R ^3a = R ^3b = R ^3c = H.

  Among the monomers represented by the formula (I), preferred are compounds represented by the following formula (I ′),

  In the formula, na, nb and nc are integers of 2 to 9, more preferably, in the compound represented by the formula (I ′), na = nb = nc is an integer of 2 to 9, most preferably Includes compounds represented by the following formula (II).

Examples of the method for synthesizing the compound represented by formula (I) include the following methods.
By substituting substituted or unsubstituted 1,3,5-benzenetriol into a base, dissolving it in an aprotic polar solvent, and reacting this with a chain portion having a terminal double bond, that is, Williamson's ether The target compound represented by formula (I) can be synthesized by the reaction (Scheme 1). At this time, if necessary, a phase transfer catalyst may be used.

Wherein Y ^a , Y ^b and Y ^c , R ^1a , R ^1b and R ^1c , R ^2a , R ^2b and R ^2c , and R ^3a , R ^3b and R ^3c have the same definitions as in formula (I), Z ^a , Z ^b and Z ^c are the same or different and represent a leaving group.

  Specific examples of the base include lithium hydride, sodium hydride, potassium hydride, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, cesium hydrogen carbonate and the like. Can be mentioned.

  As the aprotic polar solvent, any solvent may be used as long as the reaction proceeds. Specifically, acetonitrile, dimethylformamide, dimethylacetamide, N, N-dimethylimidazolidinone, hexamethylphosphate triamide , Tetrahydrofuran and the like.

  Z is a moiety that becomes a leaving group, and examples thereof include chlorine, bromine, iodine, methanesulfonyloxy group, trifluoromethanesulfonyloxy group, benzenesulfonyloxy group, toluenesulfonyloxy group, and the like.

  As the phase transfer catalyst, crown ether, quaternary ammonium salt and the like can be used. Specifically, 12-crown-4-ether, 15-crown-5-ether, 18-crown-6-ether, etc. And tetraalkylammonium halides such as tetraethylammonium chloride, tetraethylammonium bromide, tetra-n-butylammonium chloride and tetra-n-butylammonium bromide. These phase transfer catalysts can be appropriately selected by those skilled in the art depending on the type of the base and the type of the solvent.

Further, the reaction between the 1,3,5-benzenetriol moiety and the chain moiety can be carried out as a one-pot reaction as described in Reaction Scheme 1, or the hydroxyl group of the 1,3,5-benzenetriol moiety Different protecting groups can be introduced, and different chain portions can be introduced step by step. For such protecting groups, see Green & Wuts, “PROTECTIVE GROUPS in ORGANIC SYNTHESIS” 4 ^th ed. John Wiley & Sons, Inc.

  Formula (III) which is a chain part of the compound represented by Formula (I)

(In the formula, Y, R ¹ and R ² are respectively the same as Y ^a to Y ^c , R ^{1a to} R ^1c and R ^{2a to} R ^{2c in} the formula (I). Z represents a leaving group. Represents.)
Can be purchased as a reagent, or can be synthesized, for example, by the method shown below.

  After protecting one hydroxyl group of the diol with a protecting group PG, the other hydroxyl group is oxidized and converted to an aldehyde. By performing a Wittig reaction on this aldehyde, an olefin is introduced, and after deprotection, the remaining hydroxyl group is converted to a leaving group Z, thereby synthesizing a compound represented by the formula (III). (Scheme 2).

For the protecting group PG, reference can be made to Green & Wuts, “PROTECTIVE GROUPS in ORGANIC SYNTHESIS” 4 ^th ed. John Wiley & Sons, Inc. Specifically, acyl groups such as an acetyl group and a pivaloyl group, silyl groups such as a tert-butyldimethylsilyl group, a triisopropylsilyl group, and a triethylsilyl group can be used.

  As the method for oxidizing the hydroxyl group, any method can be used as long as it selectively oxidizes a primary alcohol to an aldehyde, and specific examples include Dess-Martin oxidation and TEMPO oxidation.

  Examples of the method for converting the hydroxyl group after deprotection to the leaving group Z include a method of introducing chlorine or bromine by reacting carbon tetrachloride or carbon tetrabromide in the presence of triphenylphosphine. In addition, a method of leading to a sulfonyl ester by reacting with an alkyl or aryl sulfonyl chloride in the presence of a base such as a tertiary amine can be mentioned. Moreover, the method etc. which halogenate the sulfonyl ester part by making the alkali metal salt of halogen react in polar solvents, such as acetone, etc. can be mentioned.

  When Y is O or S, the left side part (A) of the chain part represented by the formula (III) can be synthesized, for example, by the following method (Scheme 3). Similar to the synthesis procedure of Reaction Scheme 2, one hydroxyl group of the diol is selectively protected, and the unprotected hydroxyl group is converted into an olefin moiety through an oxidation step. Thereafter, the protecting group is removed and converted to a leaving group Z '(wherein Z' has the same definition as Z). Here, when a sulfonyl ester is used as a protecting group, the step of removing the protecting group and converting it to a leaving group can be omitted. In this way, the left part (A) of the chain part represented by the formula (III) can be synthesized.

  Furthermore, the right side portion of the chain portion represented by the formula (III) can be synthesized, for example, by the following method (Scheme 4). One of the hydroxyl groups of the diol can be selectively protected, and the right portion (B) of the chain portion represented by the formula (III) in which Y is O can be synthesized. When Y is S, this hydroxyl group is converted to halogen by the same method as described above, and thiourea is allowed to act on the base condition and then hydrolyzed, whereby the chain represented by the formula (III) The right part (C) of the shaped part can be synthesized.

  The left part (A) and the right part (B) or (C) of the chain part represented by the formula (III) obtained by the above method are subjected to basic conditions in the same manner as the method shown in the reaction formula 1. By performing etherification or thioetherification, removing the protecting group and converting the hydroxyl group to the leaving group Z, a chain portion represented by the formula (III) can be synthesized (Reaction Formula 5).

  Formula (IV) which is a cyclic moiety of the compound represented by Formula (I)

(Wherein R ^{3a to} R ^3c have the same definition as in formula (I).)
Can be purchased as a reagent, or can be synthesized, for example, by the following method (Scheme 6).

First, a Friedel-Crafts alkylation reaction is performed on 1,3,5-trimethoxybenzene using an alkyl halide represented by R ³ -X ′ in the presence of a Lewis acid, so that R is added to the benzene ring. ³ can be introduced. Here, X ′ is selected from chlorine, bromine and iodine. Subsequently, the compound represented by the formula (IV) can be synthesized by deprotecting the methoxy group to a hydroxyl group using boron tribromide.

  As a Lewis acid that can be used in Friedel-Crafts alkylation, any Lewis acid can be used as long as Friedel-Crafts alkylation reaction proceeds. Specifically, aluminum chloride, secondary chloride can be used. Examples thereof include iron and titanium tetrachloride. Examples of the reaction solvent include chlorobenzene, dichlorobenzene, trichlorobenzene, nitrobenzene and the like. As the reaction temperature, the reaction can be carried out between room temperature and the boiling point of the reaction solvent.

  In the deprotection reaction using boron tribromide, dichloromethane, carbon tetrachloride, or the like can be used as a solvent, and a reaction temperature between −78 ° C. and room temperature can be selected.

In the case of the substituent R ³ in 2,4,6-position two or more, by the following method to introduce R ³ sequentially benzene ring, can be synthesized compound represented by the formula (IV) (Scheme 7). Orthotrithiolation of 1,3,5-trimethoxybenzene is performed, an alkyl halide represented by R ^3a -X ′ is added thereto, and alkylation is performed to introduce R ^3a into the benzene ring. Subsequently, ortho trithiolation is performed in the same manner, an alkyl halide represented by R ^3b -X ′ is added, and R ^3b is introduced into the benzene ring. Finally, R ^3c is introduced into the benzene ring and deprotected with boron tribromide to obtain a compound represented by the formula (IV).

  Orthotrithiolation followed by alkylation is performed as a one-pot reaction. As the lithiating agent, any lithiating agent may be used as long as ortho-lithiation proceeds. Specifically, methyllithium, ethyllithium, propyllithium, isopropyllithium, n-butyllithium, sec- Examples include butyl lithium, tert-butyl lithium, hexyl lithium and the like. Examples of the reaction solvent include tetrahydrofuran, diethyl ether, dioxane, dimethoxyethane, 2-methyltetrahydrofuran, cyclopentylmethyl ether, and the like. A reaction temperature between −78 ° C. and room temperature can be selected as the reaction temperature.

(Manufacture of network polymer)
The method for producing a network polymer of the present invention can be obtained by polymerizing a compound represented by the formula (I). The polymerization reaction is not particularly limited as long as the compound represented by the formula (I) can be polymerized, but olefin metathesis polymerization is preferable.

The olefin metathesis polymerization reaction is a reaction in which the double bond site of the compound represented by the formula (I) is polymerized by a cross metathesis reaction in which the double bond part is recombined by the action of a catalyst. The catalyst is not particularly limited as long as the metathesis reaction proceeds, but is preferably a Grubbs catalyst, more preferably a first generation Grubbs catalyst, and most preferably benzylidenebis (tricyclohexylphosphine) dichlororuthenium. It is.
The solvent used is not limited as long as it can dissolve the compound represented by formula (I) and the catalyst used in the reaction, and is preferably dichloromethane, chloroform, tetrahydrofuran, toluene, or the like, more preferably dichloromethane, chloroform. Most preferred is dichloromethane. As the reaction temperature, the reaction can be carried out between room temperature and the boiling point of the reaction solvent.

  The carbon-carbon double bond after the metathesis polymerization reaction may generate both a cis form and a trans form, and the polymer of the present invention includes both. The produced carbon-carbon double bond can partially or completely saturate the carbon-carbon double bond, for example, by catalytic hydrogenation reaction.

  Furthermore, further substituents can be introduced into the carbon-carbon double bond after the metathesis polymerization reaction. As an example, a Diels-Alder reaction to react with a diene compound or the like, or a pericyclic reaction such as an ene reaction can be performed. As another example, an alkenyl group or an aryl group can be introduced by performing a Heck reaction using a palladium catalyst.

  The network polymer of the present invention has very low solubility in a solvent, and it is extremely difficult to measure the number average molecular weight, weight average molecular weight, viscosity average molecular weight, etc. of the synthesized polymer.

  The glass transition point of the network polymer of the present invention is preferably 10 ° C to -40 ° C, more preferably 0 ° C to -30 ° C, and further preferably -10 ° C to -30 ° C. The glass transition point of the network polymer of the present invention can be measured by a well-known technique such as differential scanning calorimetry (DSC).

  Furthermore, in the network polymer of the present invention, the degree of swelling with respect to diethylmethylmethoxyethylammonium bis (trifluoromethane) sulfonimide salt at 25 ° C. is preferably 100% to 250%, more preferably 150% to 200%, still more preferably. 170% to 190%, most preferably about 180%.

The degree of swelling [%] was calculated by the following formula.

(Polymer gel electrolyte)
The polymer gel electrolyte of the present invention can be obtained by mixing the network polymer described above and an electrolyte solution. Since the network polymer has a gelation ability with respect to various solvents, the polymer gel electrolyte is formed by containing the network polymer and the electrolyte solution.
Examples of the gelling solvent include protic organic solvents such as fatty acids, aliphatic alcohols and phenol derivatives, glyme, alkene carbonate, alkyl carbonate, cyclic ether, amides, nitriles, ketones and esters. Examples include an aprotic organic solvent. Specifically, propylene carbonate, ethylene carbonate, diethyl carbonate, γ-butyrolactone, 1,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, dimethyl sulfoxide, 1,3-dioxolane, formamide, dimethylformamide, 1,4- Dioxane, acetonitrile, nitromethane, ethyl monoglyme, phosphate triester, trimethoxymethane, dioxolane derivative, sulfolane, 3-methyl-2-oxazolidinone, propylene carbonate derivative, tetrahydrofuran derivative, diethyl ether, 1,3-propane sultone And aprotic organic solvents such as These can also be used in mixture of 2 or more types.
Moreover, various ionic liquids can also be mentioned as a solvent which gelatinizes. The ionic liquid is not limited as long as the organomagnesium halide is stably dissolved, but is not limited to ammonium ionic liquid, imidazolium ionic liquid, phosphonium ionic liquid, pyrazolium ionic liquid, pyridinium ion. A liquid, a pyrrolidinium ionic liquid, a sulfonium ionic liquid, or the like can be used.
In the present invention, gelation means that the fluidity of a fluid liquid is lost.

  In the polymer gel electrolyte of the present invention, since the network polymer of the present invention is chemically stable, a solution of organomagnesium halide such as Grignard reagent can be used as the non-aqueous electrolyte solution. The halogenated organomagnesium compound is not limited to these, but a compound represented by the following formula (M) can be used.

  In the formula, R is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, substituted or non-substituted A substituted C3-C6 cyclic alkyl group, a substituted or unsubstituted thiophene group, a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group is represented, and X represents Cl, Br, or I. In the compound represented by the formula (M), R may have one or more sites represented by Mg—X.

  Examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, and 1-methylbutyl. Group, 2-methylbutyl group, 3-methylbutyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, 3-pentyl group, n-hexyl group, 1-methylpentyl Group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl Group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, 3,3-dimethylbutan-2-yl group, 2,3-dimethylbutan-2-yl group, 3-hexyl group, 2-ethylpen A til group, 2-methylpentan-3-yl group, heptyl group, octyl group, nonyl group, decyl group and the like can be mentioned.

  Examples of the alkenyl group having 2 to 10 carbon atoms include vinyl group, 1-propenyl group, allyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1,3-butanedienyl group, 1-ethylvinyl group, 1-methyl-1-propenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, pentenyl group, pentadienyl group, hexenyl group, hexadienyl group, hexatrienyl group, heptenyl Group, heptadienyl group, heptatrienyl group, octenyl group, octadienyl group, octatrienyl group, octatetraenyl group, nonenyl group, nonadienyl group, nonatrienyl group, nonatetraenyl group, decenyl group, decadienyl group, decatrienyl group, decatetraenyl group, A decapentaenyl group is mentioned.

  Examples of the alkynyl group having 2 to 10 carbon atoms include ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1,3-butanediynyl group, and 1-methyl. 2-propynyl group, pentynyl group, pentadiynyl group, hexynyl group, hexadiynyl group, hexatriinyl group, heptynyl group, heptadiynyl group, heptatriinyl group, octynyl group, octadiynyl group, octatriinyl group, octatetrinyl group, noninyl Group, nonadiynyl group, nonatriynyl group, nonatetrinyl group, decynyl group, decadiynyl group, decatriynyl group, decaterinyl group, decapentynyl group and the like.

  Examples of the cyclic alkyl group having 3 to 6 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

  Examples of the substituent for the alkyl group, alkenyl group, alkynyl group, cyclic alkyl group, thiophenyl group, phenyl group, and naphthyl group include fluorine, chlorine, bromine, iodine, alkyl group, alkenyl group, alkynyl group, cyclic alkyl group, alkoxy Group, alkenyloxy group, alkynyloxy group, cyclic alkoxy group, aryl group, aryloxy group, nitro group and the like.

  Specific examples of the compound represented by the formula (M) include methyl magnesium chloride, methyl magnesium bromide, methyl magnesium iodide, ethyl magnesium chloride, ethyl magnesium bromide, ethyl magnesium iodide, butyl chloride. Magnesium, butylmagnesium bromide, butylmagnesium iodide, benzylmagnesium chloride, benzylmagnesium bromide, benzylmagnesium iodide, and the like. More preferred are methylmagnesium chloride, methylmagnesium bromide, ethylmagnesium chloride, bromide. Examples include ethyl magnesium, butyl magnesium chloride, butyl magnesium bromide, benzyl magnesium chloride, and benzyl magnesium bromide, and more preferably methyl magnesium bromide, ethyl magnesium bromide, and butyl bromide. Magnesium and the like, most preferably include methyl magnesium bromide or ethyl magnesium bromide.

  The organic magnesium halide represented by the formula (M) can be prepared from a compound represented by R—X and magnesium by a conventional method. Where R is as defined above. When preparing a compound represented by the formula (M), which is difficult to prepare by a conventional method, by reacting the magnesium activated by the Reike method with the compound represented by the R—X, the formula (M) The represented compounds can also be prepared.

  The solvent of the electrolyte solution is not limited as long as the organic magnesium halide is stably dissolved. Alkane organic solvents such as pentane, hexane, and heptane, and aromatic organic solvents such as benzene and toluene. And ether-based organic solvents such as diethyl ether, dibutyl ether, methyl tert-butyl ether, tetrahydropyran, and dioxane. In addition to the organic solvent, an ionic liquid that is excellent in safety, has high ionic conductivity, and can exhibit good reversibility of magnesium dissolution and precipitation can be used.

  The ionic liquid is not limited as long as the organomagnesium halide is stably dissolved, but is not limited to ammonium ionic liquid, imidazolium ionic liquid, phosphonium ionic liquid, pyrazolium ionic liquid, pyridinium ion. A liquid, a pyrrolidinium ionic liquid, a sulfonium ionic liquid, or the like can be used. Among them, preferred are ammonium-based ionic liquids, imidazolium-based ionic liquids, and pyrrolidinium-based ionic liquids, and most preferred are ammonium-based ionic liquids.

  Specific examples of the ammonium-based ionic liquid include diethylmethylmethoxyethylammonium bis (trifluoromethane) sulfonimide salt, methyltri-n-octylammonium bis (trifluoromethane) sulfonimide salt, and ethyldimethylpropylammonium bis (trifluoromethane). Sulfonimide salt, tetrabutylammonium bis (trifluoromethane) sulfonimide salt, benzyltrimethylammonium tribromide, tetraoctylammonium chloride, and the like, more preferably diethylmethylmethoxyethylammonium bis (trifluoromethane) sulfonimide salt, Methyltri-n-octylammonium bis (trifluoromethane) sulfonimide salt, ethyldimethylpropylammonium Bis (trifluoromethane) sulfonimide salt, tetrabutylammonium bis (trifluoromethane) sulfonimide salt, and more preferably diethylmethylmethoxyethylammonium bis (trifluoromethane) sulfonimide salt, methyltri-n-octylammonium bis ( Trifluoromethane) sulfonimide salt, and most preferably, diethylmethylmethoxyethylammonium bis (trifluoromethane) sulfonimide salt.

In addition to the electrolyte using the organomagnesium halide, a conventionally known inorganic ion salt used in a non-aqueous electrolyte solution can be used as the electrolyte. For example, lithium chloride (LiCl), lithium perchlorate ( LiClO ₄ ), lithium hexafluoroarsenate (LiAsF ₆ ), lithium hexafluorophosphate (LiPF ₆ ), lithium tetrafluoroborate (LiBF ₄ ), lithium tetraphenylborate (LiB (C ₆ H ₅ ) ₄ ), Lithium methanesulfonate (LiCH ₃ SO ₃ ), lithium trifluoromethanesulfonate (LiCF ₃ SO ₃ ), lithium bis (pentafluoroethanesulfonyl) imide (Li (C ₂ F ₅ SO ₂ ) ₂ N), bis ( trifluoromethanesulfonyl) imide lithium _{(Li (CF 3 SO 2)} 2 N) Tris (trifluoromethanesulfonyl) methyl lithium _{(LiC (CF 3 SO 2)} 3), it is possible to use lithium bromide (LiBr), may be used by mixing two or more of these.

  As a solvent used for an electrolyte other than the electrolyte using the organomagnesium halide, a conventionally known solvent used for a nonaqueous electrolyte solution can be used. For example, 4-fluoro-1,3-dioxolane-2- ON, ethylene carbonate, propylene carbonate, vinylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, γ-butyrolactone, γ-valerolactone, 1,2-dimethoxyethane, 1,2-diethoxyethane, tetrahydrofuran, 2-methyl Tetrahydrofuran, 1,3-dioxolane, 4-methyl-1,3-dioxolane, diethyl ether, methyl acetate, methyl propionate, ethyl propionate, propyl propionate, acetonitrile, propionitrile, anisole, Acetate, butyrate, glutaronitrile, adiponitrile, methoxyacetonitrile, 3-methoxypropionitrile, N, N-dimethylformamide, N-methylpyrrolidinone, N-methyloxazolidinone, nitromethane, nitroethane, sulfolane, methylsulfolane, dimethylsulfoxide , Trimethyl phosphate, triethyl phosphate, ethylene sulfide, bistrifluoromethylsulfonylimide, trimethylhexylammonium, and the like can be used, and a mixture of two or more of these can also be used.

  Among the electrolyte solutions, an electrolyte solution in which ethyl magnesium bromide is dissolved in a solvent containing diethylmethylmethoxyethylammonium bis (trifluoromethane) sulfonimide salt is preferable.

  The ratio of the solute and the solvent in the electrolytic solution may be any ratio as long as the solute is dissolved in the solvent, but the solute: solvent is a substance amount ratio of 0.1: 10 to 10: 0.1, More preferably, it is 1:10 to 10: 1, more preferably 1: 5 to 5: 1, and most preferably 1: 2 to 2: 1.

  The polymer gel electrolyte of the present invention can be obtained by gelling an electrolyte solution with a network polymer. Specifically, a production method in which a predetermined amount of network polymer is immersed in a predetermined amount of electrolyte solution is exemplified. Usually, since the organomagnesium halide reacts with moisture and oxygen in the air to form a non-moving substance, the above operation is preferably performed under an inert gas.

(Non-aqueous electrolyte secondary battery)
The polymer gel electrolyte can be used as a non-aqueous electrolyte secondary battery such as a magnesium secondary battery or a lithium ion secondary battery.

  The non-aqueous electrolyte secondary battery of the present invention has a conventionally known configuration except that the polymer gel electrolyte is used.

  For example, the positive electrode is not particularly limited as long as it absorbs positive ions or discharges negative ions during discharge, and has a high conductivity such as metal oxide, polyacetylene, polyaniline, polypyrrole, polythiophene, and polyparaphenylene. Conventionally known materials such as molecules, derivatives thereof, and disulfide compounds can be used as positive electrode materials for secondary batteries.

  The negative electrode is not particularly limited as long as it is a material capable of occluding and releasing cations. Crystalline carbon such as graphitized carbon obtained by heat treatment of natural graphite, coal / petroleum pitch, etc., coal, petroleum Conventionally known negative electrode active materials for secondary batteries, such as amorphous carbon obtained by heat treatment of pitch coke, acetylene pitch coke, etc., lithium alloys such as metallic lithium and AlLi, can be used.

  Furthermore, when forming an electrode, these electrode active materials can be mixed with an appropriate binder or functional material to form an electrode layer. As the binder, a halogen-containing polymer such as polyvinylidene fluoride is used, and as the functional material, a conductive polymer such as acetylene black, polypyrrole, or polyaniline for ensuring electronic conductivity, ion conductivity, or the like. For example, a polymer electrolyte, a composite thereof, and the like.

  The nonaqueous electrolyte secondary battery of the present invention can be obtained by assembling a battery using the polymer gel electrolyte, the positive electrode and the negative electrode. There is no restriction | limiting in particular about another component and structure, The various component and structure employ | adopted by the conventionally well-known nonaqueous electrolyte secondary battery are applicable.

  For example, a polymer gel electrolyte can be supported on the separator substrate. As a separator base material, what is normally used as a separator base material for nonaqueous electrolyte secondary batteries can be used. For example, polyethylene nonwoven fabric, polypropylene nonwoven fabric, polyester nonwoven fabric, PTFE porous film, kraft paper, rayon fiber / sisal fiber mixed paper, manila hemp sheet, glass fiber sheet, cellulosic electrolytic paper, paper made of rayon fiber, cellulose and glass fiber Can be used, or a combination of these can be used to form a plurality of layers.

  Moreover, in the nonaqueous electrolyte secondary battery of this invention, there is no restriction | limiting in particular also about the shape. For example, any of a coin shape, a button shape, a sheet shape, a laminated shape, a cylindrical shape, a flat shape, a square shape, a large size used for an electric vehicle and the like may be used. The polymer gel electrolyte of the present invention has a significantly lower content of the electrolyte solution than the conventional secondary battery, so that the effects of the present invention are remarkable in terms of safety and manufacturing cost, especially when manufacturing a large battery. Appear in

  Hereinafter, the present invention will be described in more detail with reference to Examples, but the technical scope of the present invention is not limited thereto.

1. Synthesis of Monomer 1,3,5-tris (10-undecenyloxy) benzene was synthesized by the following procedure.

1,3,5-Benzenetriol (0.5 g, 3.08 mmol), 11-bromo-1-undecene (2.877 g, 12.32 mmol), cesium carbonate (5.058 g, 18.84 mmol) in dimethylformamide solution (50 ml) was placed in a flask and heated and stirred at 120 ° C. for 24 hours. Thereafter, the reaction solution was filtered while hot, and the filtrate was distilled. After distillation, it was subjected to silica gel column chromatography (eluent: hexane / ethyl acetate = 40: 1 (v / v)), and 1,3,5-tris (10-undecenyloxy) benzene yellow viscous liquid was 1 Obtained in a yield of .62 g (90.1% yield). The ¹ H-NMR spectrum of this compound is shown in FIG.

2. Synthesis of polymer film of 1,3,5-tris (undecenyloxy) benzene (40 mg, 0.069 mmol) and benzylidenebis (tricyclohexylphosphine) dichlororuthenium (2.83 mg, 3.41 × 10 ⁻³ mmol) The dichloromethane solution was dropped on a glass plate and heated at 50 ° C. for 24 hours. Thereafter, the reaction was stopped by adding ethyl vinyl ether, and the mixture was washed successively with methanol and ethyl acetate to obtain a network polymer film of a purple solid. The IR spectrum of the network polymer is shown in FIG.
The glass transition point of the network polymer measured by differential scanning calorimetry (DSC) was −21.6 ° C.

3. Network Polymer Film Stability Test The network polymer synthesized in 2 above was immersed in a 1M tetrahydrofuran solution of ethylmagnesium bromide in a glove box at room temperature in an argon atmosphere. Even after immersion for 24 hours, no tearing or deterioration of the film was observed, confirming stability.

4). Measurement of Ionic Conductivity of Electrolyte Using Network Polymer After the network polymer synthesized in 2 above is sufficiently dried, the mass ratio of ethylmagnesium bromide and diethylmethylmethoxyethylammonium bis (trifluoromethane) sulfonimide salt is 1. The polymer gel electrolyte was prepared by immersing in an electrolytic solution composed of a mixed solution of 1 in a glove box under an argon atmosphere. Table 1 shows the measurement results of the swelling degree and ionic conductivity of the prepared electrolyte.

5. Deposition / dissolution behavior of magnesium in network polymer electrolyte Cyclic voltammetry (CV) measurement was performed using the network polymer electrolyte prepared in 4 above. The results are shown in FIG. Oxidation / reduction behavior was observed in the network polymer electrolyte, which revealed that magnesium precipitation / dissolution occurred. In addition, when the measurement was performed three times in succession, there was almost no difference between the maximum oxidation potential and the reduction potential, indicating that the network polymer electrolyte of the present invention can be used as an electrolyte for a secondary battery.

  Since the network polymer obtained by the present invention does not have a site that reacts with a nucleophile, it has high stability with respect to a conventional network polymer. Accordingly, it is possible to supply a network polymer electrolyte having both high safety and high ionic conductivity, which is used as an electrolytic solution containing an organic magnesium halide containing a Grignard reagent, which cannot be handled by a conventional polymer gel electrolyte. By using this network polymer electrolyte, it becomes possible to supply a magnesium ion secondary battery having a higher energy density than a conventional lithium ion secondary battery.

Claims (7)

Formula (I)
(Where
Y ^a , Y ^b and Y ^c each independently represent CR ₂ , —O— or —S—, and each R in CR ₂ is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Represents
R ^1a , R ^1b and R ^1c each independently represent an alkylene group having 1 to 10 carbon atoms which may be substituted with an alkyl group having 1 to 4 carbon atoms,
R ^2a , R ^2b and R ^2c each independently represent an alkylene group having 2 to 10 carbon atoms which may be substituted with an alkyl group having 1 to 4 carbon atoms,
R ^3a , R ^3b and R ^3c each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)
A network polymer obtained by polymerizing a compound represented by the formula by olefin metathesis reaction. The compound represented by the formula (I) is represented by the following formula (II)
The network polymer according to claim 1, wherein the network polymer is a compound represented by the formula: Formula (I)
(Where
Y ^a , Y ^b and Y ^c each independently represent CR ₂ , —O— or —S—, and each R in CR ₂ is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Represents
R ^1a , R ^1b and R ^1c each independently represent an alkylene group having 1 to 10 carbon atoms which may be substituted with an alkyl group having 1 to 4 carbon atoms,
R ^2a , R ^2b and R ^2c each independently represent an alkylene group having 2 to 10 carbon atoms which may be substituted with an alkyl group having 1 to 4 carbon atoms,
R ^3a , R ^3b and R ^3c each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)
The method for producing a network polymer according to claim 1, wherein the compound represented by the formula is polymerized by an olefin metathesis reaction.   A polymer gel electrolyte comprising the network polymer according to claim 1 or 2 in an electrolytic solution. The electrolyte is the following formula (M)
(Where
R is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, a substituted or unsubstituted carbon A cyclic alkyl group of formula 3-6, a substituted or unsubstituted thiophene group, a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group,
X represents Cl, Br or I)
The polymer gel electrolyte according to claim 4, wherein the polymer gel electrolyte is a solution of one or more halogenated organomagnesium compounds represented by the formula:   6. The polymer gel electrolyte according to claim 4, wherein the electrolytic solution is a solution of ethyl magnesium bromide in diethylmethylmethoxyethylammonium bis (trifluoromethane) sulfonimide.   A secondary battery comprising the polymer gel electrolyte according to claim 4.