WO2013099224A1 - Polymère réticulé et électrolyte de gel de polymère - Google Patents

Polymère réticulé et électrolyte de gel de polymère Download PDF

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WO2013099224A1
WO2013099224A1 PCT/JP2012/008283 JP2012008283W WO2013099224A1 WO 2013099224 A1 WO2013099224 A1 WO 2013099224A1 JP 2012008283 W JP2012008283 W JP 2012008283W WO 2013099224 A1 WO2013099224 A1 WO 2013099224A1
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formula
group
network polymer
structure represented
partial structure
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PCT/JP2012/008283
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Japanese (ja)
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一大 山吹
大石　勉
鬼村　謙二郎
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国立大学法人山口大学
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
    • C08F222/1025—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate of aromatic dialcohols
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0085—Immobilising or gelification of electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a novel network polymer having a crown ether, a polymer gel electrolyte containing a network polymer, and a secondary battery containing the polymer gel electrolyte.
  • gel materials have been widely used in foods, medical products, daily necessities, industrial products, etc., and the types of polymer compounds used in these materials are also diverse. There are only two types: gels and chemical gels.
  • a physical gel is a gel that is often found in nature, such as gelatin and agar, and a large variety of physical gels occupy most of the living tissue. Since such a physical gel forms a network by physical attractive interaction acting between polymers, the stability to temperature and solvent is low.
  • a chemical gel is a huge single molecule in which the entire network is directly connected by a covalent bond. Therefore, the chemical gel is excellent in temperature and solvent stability, and is widely used in industrial applications.
  • the chemical gel has a drawback that since the cross-linking points are fixed, the non-uniform structure formed in the cross-linking reaction is permanently retained, and the mechanical strength is extremely low.
  • Non-patent Document 1 a gel composed of a polymer compound obtained by polymerizing pseudorotaxane. Since the polymer compound is easy to produce, further application is expected.
  • Japanese Patent No. 3475252 Japanese Patent Laying-Open No. 2005-068032 WO 2006/115255 WO2009 / 136618 JP 2009-270120 A JP 2009-051994 JP 2010-155880 A JP 2010-159336 A JP 2010-159337 A JP 2002-334690 A JP 2003-317692 A
  • the present invention has been made in view of such circumstances, and an object thereof is to obtain a novel network polymer having a rotaxane structure and to obtain a polymer gel electrolyte having both high safety and high ionic conductivity. .
  • the present inventors have succeeded in building a novel network polymer having a rotaxane structure using a crown ether, and the polymer gel electrolyte obtained from the network polymer has high safety. And the present invention has been completed.
  • R 1 and R 2 are the same or different and may have —O—, —CO—, —COO— or —CONH—, saturated or partially unsaturated, linear or branched
  • the hydrocarbon group having 1 to 15 carbon atoms n1 represents an integer of 3 or 4, and n2 represents an integer of 1 to 30.
  • R 3 and R 4 are the same or different and may have —O—, —CO—, —COO— or —CONH—, saturated or partially unsaturated, linear or branched chain, a hydrocarbon group having 1 to 15 carbon atoms, Z -. represents a counter anion), or the following formula (II ')
  • a network polymer having a unit (A), or a network polymer having a unit (B) derived from the unit (A) and a radical polymerizable monomer A network polymer in which the molar ratio ((I) / (II)) between the partial structure represented by the formula (I) and the partial structure represented by the formula (II) is 1/1 to 10/1 (however,
  • the unit (A) consists of a partial structure represented by the formula (I) and a partial structure represented by the formula (II), excluding a case where the unit (A) does not have the unit (B)), (2)
  • the molar ratio ((A) / (B)) between the unit (A) and the unit (B) derived from the radical polymerizable monomer is from 1/1 to 1/100 (1)
  • Network polymers (3) The network polymers
  • the radical polymerizable monomer is one or more compounds selected from the group consisting of methyl methacrylate, n-butyl methacrylate, 2-hydroxyethyl methacrylate, polyethylene glycol methacrylate, styrene and acrylonitrile. It is related with the network polymer as described in (1).
  • the present invention also provides: (6) Formula (V)
  • R 1 and R 2 are the same or different and may have —O—, —CO—, —COO— or —CONH—, saturated or partially unsaturated, linear or branched
  • the chain represents a hydrocarbon group having 1 to 15 carbon atoms
  • X 1 and X 2 are the same or different and represent a group that acts as a bonding site during the polymerization reaction
  • n1 represents an integer of 3 or 4.
  • R 1 and R 2 are the same or different and may have —O—, —CO—, —COO— or —CONH—, saturated or partially unsaturated, linear or branched
  • the chain represents a hydrocarbon group having 1 to 15 carbon atoms
  • X 1 and X 2 are the same or different and each represents a group that acts as a binding site during a polymerization reaction or a group that does not act as a binding site during a polymerization reaction, provided that When n2 is 1, it is limited to the case where X 1 and X 2 are groups acting as a binding site during the polymerization reaction.
  • n1 represents an integer of 3 or 4.
  • n2 represents an integer of 1 to 30.
  • R 3 and R 4 are the same or different and may have —O—, —CO—, —COO— or —CONH—, saturated or partially unsaturated, linear or branched
  • the chain represents a hydrocarbon group having 1 to 15 carbon atoms
  • X 3 and X 4 are the same or different and each represents a group that acts as a binding site during the polymerization reaction
  • Z ⁇ represents a counter anion
  • R 3 and R 4 are the same or different and may have —O—, —CO—, —COO— or —CONH—, saturated or partially unsaturated, linear or branched
  • the novel network polymer having a rotaxane structure of the present invention is a polymer gel electrolyte having both high safety and high ionic conductivity, and the polymer gel electrolyte is used as an electrolyte for a non-aqueous electrolyte secondary battery such as a lithium ion secondary battery. Is possible.
  • the network polymer of the present invention includes a network polymer having a —N + H 2 — group and a network polymer in which a —N + H 2 — group is neutralized with an electrophile.
  • the network polymer before neutralization of the present invention is a unit (A) in which a partial structure represented by the following formula (II) is clasped into an annular portion of a partial structure represented by the following formula (I) (A ) Having a network polymer (hereinafter referred to as “network polymer A-1”) or a network polymer having the unit (A) and a unit (B) derived from a radical polymerizable monomer (hereinafter referred to as “network polymer A-2”). ).
  • R 1 and R 2 are the same or different and may have —O—, —CO—, —COO— or —CONH—, saturated or partially unsaturated, linear or branched
  • n1 represents an integer of 3 or 4
  • n2 represents an integer of 1 to 30.
  • R 2 is bonded to the 3rd or 4th position as viewed from the carbon atom to which the alkylene group having an ether bond is bonded, and may be either the 3rd or 4th position, or a mixture thereof. There may be.
  • R 3 and R 4 are the same or different and may have —O—, —CO—, —COO— or —CONH—, saturated or partially unsaturated, linear or branched Represents a hydrocarbon group having 1 to 15 carbon atoms, and Z ⁇ represents a counter anion.
  • the present invention does not include the network polymer A-1 consisting only of the unit (A).
  • “chain hydrocarbon group having 1 to 15 carbon atoms” includes methylene group, dimethylene group, trimethylene Group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, tridecamethylene group, tetradecamethylene group, pentadecamethylene group Alkylene groups such as: ethylidene, propylidene, isopropylidene, sec-butylidene, tert-butylidene, n-pentylidene, n Examples
  • the counter ion represented by Z ⁇ is not particularly limited, but is represented by the formula (II) in the cyclic portion of the partial structure represented by the formula (I). It is possible to construct a rotaxane structure or pseudo-rotaxane structure in which the partial structure is included in a skewered manner, and in the unit derived from the partial structure represented by the formula (II) in the rotaxane structure or pseudo-rotaxane structure— Any monovalent anion capable of converting an N + H 2 — group into an —NR 5 — group (R 5 represents a residue derived from an electrophile) may be used.
  • m represents a numerical value of 1 or more and 4 or less.
  • N (RfSO 3 ) 2 ⁇ C (RfSO 3 ) 3 ⁇ , RfSO 3 ⁇ , RfCO 2 ⁇ , N (SO 2 F) 2 — and the like
  • Rf contained in the anion represented by N (RfSO 3 ) 2 ⁇ , C (RfSO 3 ) 3 ⁇ , RfSO 3 — or RfCO 2 — represents a fluoroalkyl group having 1 to 12 carbon atoms, trifluoromethyl, Examples include fluorinated alkyl groups such as pentafluoroethyl, heptafluoropropyl and nonafluorobutyl.
  • the “unit (B) derived from radically polymerizable monomer” is a structure contained in the network polymer A-2, and the radically polymerizable monomer is not particularly limited as long as it is a compound having radical polymerizability.
  • the radically polymerizable monomer is not particularly limited as long as it is a compound having radical polymerizability.
  • R a R b CR c R d (Wherein R a , R b and R c are the same or different and each represents a hydrogen atom or a halogen-substituted or unsubstituted lower alkyl, and R d represents an alkyl group, an alkenyl group, an alkyloxycarbonyl group, an aryl group, carbamoyl) 1 type or a mixture of 2 or more types of compounds such as a group represented by
  • radical polymerizable monomer examples include styrene and styrene derivatives, (meth) acrylic acid and (meth) acrylic acid derivatives, (meth) acrylamide and (meth) acrylamide derivatives, (meth) acrylonitrile, isoprene, and 1,3-butadiene. , Ethylene, vinyl acetate, vinyl chloride, vinylidene chloride and the like.
  • styrene and derivatives thereof include styrene, tert-butylstyrene, tert-butoxystyrene, hydroxystyrene, vinyltoluene, chlorostyrene, and salts thereof.
  • (meth) acrylic acid and derivatives thereof include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and (meth) acrylic acid.
  • Examples of (meth) acrylamide and derivatives thereof include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nn-butyl (meth) acrylamide, N -N-alkyl (meth) acrylamides such as tert-butyl (meth) acrylamide; N, N-dialkylacrylamides such as N, N-dimethylacrylamide and the like.
  • methyl methacrylate, n-butyl methacrylate, 2-hydroxyethyl methacrylate, polyethylene glycol methacrylate, styrene and acrylonitrile are preferred.
  • the unit (A) in which the partial structure represented by the formula (II) is clasped into the annular portion of the partial structure represented by the formula (I) is a rotaxane structure.
  • Rotaxane refers to a ring in which a rod-like molecule penetrates a macrocyclic molecule and a bulky site is bonded to both ends of the shaft so that the ring cannot be removed from the shaft due to steric hindrance.
  • the bulky part is called a stopper, cap, or end group.
  • the bulkiness is insufficient, which is called pseudorotaxane.
  • the network polymer of the present invention has no stopper component and is constructed only from a ring and a shaft.
  • the unit (A) can be said to be a pseudorotaxane.
  • another pseudo-rotaxane unit or another pseudo-rotaxane unit bonded via a radical polymerizable monomer serves as a stopper, so that the ring and the axis are not separated.
  • Network polymer A-1 contains unit (A) in its structure.
  • the molar ratio of the partial structure represented by the formula (I) to the partial structure represented by the formula (II) is 1 to 10: 1, preferably 1 to 3: 1, more preferably 1: 1.
  • Network polymer A-2 contains unit (A) and unit (B) in its structure.
  • the molar ratio of the partial structure represented by the formula (I) and the partial structure represented by the formula (II) is 1 to 10: 1, preferably 1 to 3: 1, more preferably 1: 1.
  • the molar ratio of the unit (A) to the unit (B) is 1: 1 to 100, preferably 1: 2 to 50, more preferably 1: 5 to 10.
  • the network polymer A is composed of hydrocarbons such as water and n-hexane; halogenated hydrocarbons such as chloroform and dichloromethane; aromatic hydrocarbons such as benzene and toluene; alcohols such as methanol and ethanol; acetone Ketones such as tetrahydrofuran; ethers such as diethyl ether; insoluble in solvents such as acetonitrile, N, N-dimethylformamide and ethyl acetate.
  • hydrocarbons such as water and n-hexane
  • halogenated hydrocarbons such as chloroform and dichloromethane
  • aromatic hydrocarbons such as benzene and toluene
  • alcohols such as methanol and ethanol
  • acetone Ketones such as tetrahydrofuran
  • ethers such as diethyl ether
  • solvents such as acetonitrile, N, N-dimethylformamide and e
  • Non-patent Document 1 As the compound represented by the formula (I) and the compound represented by the formula (II), commercially available ones can be used, and the compound can be produced by a conventionally known method (Non-patent Document 1).
  • the partial structure represented by the formula (I) is preferably a partial structure represented by the following formula (III).
  • n2 is the same as defined in formula (I).
  • the partial structure represented by the formula (II) is preferably a partial structure represented by the following formula (IV).
  • y is an integer of 1 to 12
  • Z ⁇ is a counter anion, and examples thereof are the same as those in formula (II).
  • Network polymer after neutralizing —N + H 2 — group (network polymer B)
  • the network polymer after neutralization of the network polymer A of the present invention (hereinafter referred to as “network polymer B”) is obtained by reacting the above-described network polymer A with an electrophile (R 5 X) to obtain the formula (II)
  • the —N + H 2 — group in the partial structure represented by the formula (II ′) is replaced with the —NR 5 — group (R 5 represents a residue derived from an electrophile) in the partial structure represented by the formula (II ′). It is a converted network polymer.
  • the interaction between the partial structure represented by the formula (I) and the partial structure represented by the formula (II ′) is weakened at the cross-linked site of the rotaxane structure in the polymer, and the mobility of the network polymer is reduced. It increases and the ion electric power improves.
  • R 3 and R 4 are the same or different and may have —O—, —CO—, —COO— or —CONH—, saturated or partially unsaturated, linear or branched
  • Examples of the hydrocarbon group having 1 to 15 carbon atoms are the same as those in the formula (II).
  • an electrophile capable of converting the —N + H 2 — group in the repeating unit derived from the compound represented by the formula (II) into a —NR 5 — group
  • R 5 preferably has about 1 to 11 carbon atoms.
  • alkyl group examples include methyl group, ethyl group, n-propyl group, i-propyl group, cyclopropyl group, n-butyl group, sec-butyl group, i-butyl group, tert-butyl group, and cyclobutyl.
  • alkenyl group specifically, vinyl group, allyl group, methacryl group, crotonyl group, butenyl group, pentenyl group, cyclopentenyl group, hexenyl group, cyclohexenyl group, heptenyl group, octenyl group, nonenyl group, decanenyl group, An undecanenyl group etc. are mentioned.
  • arylalkyl group examples include a benzyl group, a cinnamyl group, a hydrocinnamyl group, and a naphthalenemethyl group.
  • alkylcarbonyl group examples include formyl group, acetyl group, propionyl group, acryloyl group, propioyl group, butyryl group, isobutyryl group, methacryloyl group, crotonoyl group, isocrotonoyl group, valeryl group, isovaleryl group, and pivaloyl group. Can be mentioned.
  • alkoxycarbonyl group examples include methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, i-propoxycarbonyl group, n-butoxycarbonyl group, tert-butoxycarbonyl group, pentoxycarbonyl group, neopentyloxy A carbonyl group, an amyloxycarbonyl group, a hexyloxycarbonyl group, etc. are mentioned.
  • arylcarbonyl group examples include a benzoyl group, a toluoyl group, a naphthoyl group, a furoyl group, a thiophenecarbonyl group, a nicotinoyl group, and an isonicotinoyl group.
  • aryloxycarbonyl group examples include a phenoxycarbonyl group, a tolyloxycarbonyl group, and a naphthyloxycarbonyl group.
  • arylalkylcarbonyl group examples include a benzylcarbonyl group, a cinnamoyl group, a hydrocinnamoyl group, and a naphthalenylacetyl group.
  • arylalkyloxycarbonyl group examples include a benzyloxycarbonyl group and a 9H-fluoren-9-ylmethoxycarbonyl group.
  • alkylsulfonyl group examples include a methanesulfonyl group, a trifluoromethanesulfonyl group, a camphorsulfonyl group, and the like.
  • arylsulfonyl group examples include a benzenesulfonyl group, a toluenesulfonyl group, and a naphthalenesulfonyl group.
  • the first step for producing the network polymer A of the present invention is to mix a cyclic compound represented by the following formula (V) and a linear compound represented by the following formula (VI).
  • the mixing conditions are not particularly limited, but they are usually mixed at room temperature in an organic solvent such as chloroform and toluene.
  • R 1 and R 2 are the same or different and may have —O—, —CO—, —COO— or —CONH—, saturated or partially unsaturated, linear or branched
  • X 1 and X 2 are the same or different and each represents a group that acts as a bonding site during the polymerization reaction.
  • n1 represents an integer of 3 or 4.
  • R 3 and R 4 are the same or different and may have —O—, —CO—, —COO— or —CONH—, saturated or partially unsaturated, linear or branched
  • X 3 and X 4 are the same or different and each represents a group that acts as a bonding site during the polymerization reaction.
  • Z ⁇ represents a counter anion.
  • “chain hydrocarbon group having 1 to 15 carbon atoms” includes methylene group, dimethylene group, trimethylene Group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, tridecamethylene group, tetradecamethylene group, pentadecamethylene group Alkylene groups such as: ethylidene, propylidene, isopropylidene, sec-butylidene, tert-butylidene, n-pentylidene, n Examples
  • the “group that acts as a binding site during the polymerization reaction” of X 1 to X 4 is not particularly limited as long as it is a group that acts as a binding site during the polymerization reaction.
  • cationic polymerization, anionic polymerization, radical polymerization, coordination Examples thereof include polymerizable functional groups used for polymerization, metathesis polymerization, ring-opening polymerization and the like.
  • the counter ion represented by Z ⁇ is not particularly limited, but the moiety represented by the formula (VI) is added to the cyclic part of the partial structure represented by the formula (V).
  • -N in a unit derived from the partial structure represented by the formula (VI) in the rotaxane structure or pseudo-rotaxane structure, in which a rotaxane structure or pseudo-rotaxane structure in which the structure is included in a skewered manner can be constructed Any monovalent anion capable of converting a + H 2 — group into a —NR 5 — group (R 5 represents a residue derived from an electrophile) may be used.
  • m represents a numerical value of 1 or more and 4 or less.
  • N (RfSO 3 ) 2 ⁇ C (RfSO 3 ) 3 ⁇ , RfSO 3 ⁇ , RfCO 2 ⁇ , N (SO 2 F) 2 — and the like
  • Rf contained in the anion represented by N (RfSO 3 ) 2 ⁇ , C (RfSO 3 ) 3 ⁇ , RfSO 3 — or RfCO 2 — represents a fluoroalkyl group having 1 to 12 carbon atoms, trifluoromethyl, Examples include fluorinated alkyl groups such as pentafluoroethyl, heptafluoropropyl and nonafluorobutyl.
  • the N + in the compound represented by the formula (VI) is added to the crown ether ring in the formula (V).
  • a structure (A) in which an H 2 group is included, that is, a pseudo-rotaxane structure is formed. That is, the compound represented by the formula (V) functions as a macrocyclic compound, and the compound represented by the formula (VI) functions as a linear compound.
  • the mixing ratio of the compound represented by the formula (V) and the compound represented by the formula (VI) is 1 to 10: 1, preferably 1 to 3: 1, more preferably 1: 1 in molar ratio. is there.
  • the formation of the pseudorotaxane complex can be confirmed by 1 H-NMR measurement.
  • the compound represented by the formula (V) can be polymerized in advance.
  • This polymer is a compound represented by the above formula (VII), and the polymerization reaction is not particularly limited as long as the compound represented by the formula (V) can be polymerized.
  • the polymerization can be carried out by radical polymerization, coordination polymerization, metathesis polymerization, ring-opening polymerization, etc., with metathesis polymerization being particularly preferred.
  • the network polymer of the present invention can be produced.
  • 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.
  • the solvent that can be used is not limited as long as it can dissolve the compound represented by the formula (VII) in which n2 is 1 and the catalyst used in the reaction, and preferably include dichloromethane, chloroform, tetrahydrofuran, toluene, and the like. More preferably, it is dichloromethane.
  • X 1 and X 2 at the end of the polymer are groups that act as binding sites during the polymerization reaction. Therefore, the X 1 and X 2, in order to convert into a group that does not act as a binding site during the polymerization reaction, after the polymerization reaction, an alkyl group in X 1 and X 2, alkoxy group, alkyloxycarbonyl group, an aryl group And the like. In addition to this, it is conceivable to saturate the carbon-carbon double bonds of X 1 and X 2 by a catalytic hydrogenation reaction after completion of the polymerization reaction, but the conversion method is not limited to this.
  • the compound represented by the formula (V) or the formula (VII) and the compound represented by the formula (VI) When the compound represented by the formula (V) or the formula (VII) and the compound represented by the formula (VI) are mixed, the compound represented by the formula (V) or the formula (VII) has a formula (V) A structure (A) in which an N + H 2 group in the compound represented by VI) is included, that is, a pseudo-rotaxane complex is formed.
  • the mixing ratio of the compound represented by the formula (V) or the formula (VII) and the compound represented by the formula (II) is 1 to 10: 1, preferably 1 to 3: 1 in terms of molar ratio. Preferably it is 1: 1.
  • the formation of the pseudorotaxane complex can be confirmed by 1 H-NMR measurement.
  • the structure (A) is formed when a compound represented by the formula (V) or the formula (VII) and a compound represented by the formula (VI) are mixed in a solvent and their 1 H-NMR is measured.
  • the chemical shift of protons near the ammonium salt of the compound represented by the formula (VI) can be confirmed by shifting to a low magnetic field.
  • the structure (A) formed in the first stage is polymerized (production of the network polymer A-1), or the structure (A) and the radical polymerizable monomer are polymerized.
  • the pseudo-rotaxane complex formed in the first step has a structure in which the polymerizable functional groups of X 1 to X 4 are oriented in four directions, or a structure in which the polymerizable functional groups of X 3 and X 4 are oriented in two directions. .
  • the structure of the network polymer after polymerization can be controlled by selecting the reactivity of the polymerizable functional groups X 1 to X 4 or the polymerization method.
  • the polymerization method is not limited as long as the structure (A) is polymerized and the resulting network polymer includes the partial structures represented by the formulas (I) and (II).
  • the olefin metathesis is not limited. Reaction or radical polymerization reaction is preferred.
  • the network polymer produced by the polymerization by olefin metathesis reaction has a structure in which a rotaxane unit is incorporated in the polymer main chain, while the network polymer by radical polymerization has a structure in which a rotaxane unit is incorporated in the polymer side chain.
  • the structure in which the rotaxane unit is incorporated in the polymer main chain means a structure in which the rotaxane units are arranged along the extending direction of the polymer, and “the structure in which the rotaxane unit is incorporated in the polymer side chain”. Means that the rotaxane unit is located in a direction perpendicular to the direction of elongation of the polymer.
  • the polymerization reaction between the structure (A) and the radically polymerizable monomer is a partial structure represented by the formula (I) and the formula (II) in the network polymer produced by the polymerization.
  • the polymerization method is not limited, but a radical polymerization reaction is preferred.
  • the radical polymerization reaction is not limited as long as the polymerizable functional group and the radical polymerizable monomer in the formula (V) and the formula (VI) react to generate a polymerization active site.
  • a method of exposing to heat or light And a method of adding other active species, and a polymerization initiator, a reactive active species stabilizer, and the like may be added during the polymerization reaction.
  • the mixing ratio of the pseudorotaxane complex and the radical polymerizable monomer is 1: 1 to 100, preferably 1: 2 to 50, more preferably 1: 5 to 10 in terms of molar ratio.
  • the reaction conditions are not particularly limited, but the reaction is usually carried out in an organic solvent such as chloroform and toluene at room temperature to 100 ° C. for 1 to 24 hours.
  • the structure of the network polymer produced by the above method can be confirmed by 1 H-NMR measurement, IR measurement or the like.
  • the polymerization reaction is not limited as long as the polymerizable functional group in Formula (V) or Formula (VII) and Formula (VI) reacts to generate a polymerization active site.
  • Examples thereof include a method of exposing to heat and light, a method of adding other active species, and the like, and a polymerization initiator, a stabilizer of reactive active species, and the like may be added during the polymerization reaction.
  • the polymerization initiator used may be a conventionally known polymerization initiator such as 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylpropionamidine) disulfate, 2,2 '-Azobis (2-methylpropionamidine) dihydrochloride, 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane] Azo initiators such as dihydrochloride; persulfate initiators such as potassium persulfate and ammonium persulfate; peroxide initiators such as benzoyl peroxide, t-butyl hydroperoxide and hydrogen peroxide It is done.
  • a conventionally known polymerization initiator such as 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylpropionamidine) disulfate, 2,2 '-Azobis (2-methylpropionamidine
  • a —N + H 2 — group having a partial structure represented by the formula (II) can be converted into a —NR 5 — group having a partial structure represented by the formula (II ′).
  • the electrophile preferably has about 1 to 11 carbon atoms.
  • linear or branched alkyl halide as the electrophile include methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, ethyl iodide, n-propyl chloride, N-propyl bromide, n-propyl iodide, i-propyl chloride, i-propyl bromide, i-propyl iodide, cyclopropyl chloride, cyclopropyl bromide, cyclopropyl iodide, n-butyl chloride, bromide n-butyl, n-butyl iodide, sec-butyl chloride, sec-butyl bromide, sec-butyl iodide, i-butyl chloride, i-butyl bromide, i-butyl iodide, tert-but
  • Examples thereof include a method in which a nitrogen anion is generated using a metal hydride after being converted to-, and reacted with a linear or branched alkyl halide, a linear or branched alkenyl halide, or an arylalkyl halide. At this time, the reactivity between the nitrogen anion and the nucleophile may be increased by adding a metal iodide or the like.
  • Examples of the acid anhydride as the electrophile include formic anhydride, acetic anhydride, propionic anhydride, acrylic anhydride, propiolic anhydride, butanoic anhydride, isobutanoic anhydride, methacrylic anhydride, crotonic anhydride, isocrotonic anhydride , Barrelic anhydride, isovaleric anhydride, pivalic anhydride, benzoic anhydride, tolyric anhydride, naphthalene anhydride, furan carboxylic anhydride, thiophene carboxylic anhydride, nicotinic anhydride, isonicotinic anhydride, cinnam anhydride, hydrocinnam anhydride
  • Examples include acid and naphthalenyl acetic anhydride.
  • Carbonic acid halides as the electrophiles include methoxycarbonyl chloride, ethoxycarbonyl chloride, n-propoxycarbonyl chloride, i-propoxycarbonyl chloride, n-butoxycarbonyl chloride, tert-butoxycarbonyl chloride, pentoxycarbonyl chloride, neopentyl.
  • Examples thereof include oxycarbonyl chloride, amyloxycarbonyl chloride, hexyloxycarbonyl chloride, phenoxycarbonyl chloride, naphthyloxycarbonyl chloride, benzyloxycarbonyl chloride, tolyloxycarbonyl chloride, 9H-fluoren-9-ylmethoxycarbonyl chloride and the like.
  • anhydrous carbonic acid diester as the electrophile
  • examples of the anhydrous carbonic acid diester as the electrophile include dimethyl carbonate, diethyl carbonate, di-n-propyl carbonate, di-i-propyl carbonate, di-n-butyl carbonate, di-tert-butyl carbonate, dipentyl carbonate, dineopentyl carbonate, diamyl carbonate , Dihexyl carbonate, diphenyl carbonate, ditolyl carbonate, dinaphthyl carbonate, dibenzyl carbonate, di (9H-fluoren-9-ylmethyl) carbonate, and the like.
  • alkylsulfonyl halide and arylsulfonyl halide as the electrophile examples include methanesulfonyl chloride, trifluoromethanesulfonyl chloride, camphorsulfonyl chloride, benzenesulfonyl chloride, toluenesulfonyl chloride, naphthalenesulfonyl chloride and the like.
  • the —N + H 2 — group of the partial structure represented by the formula (II) is represented by the formula (II ′
  • the method for converting the partial structure represented by (II) to the —NR 5 — group is not particularly limited as long as it can be converted.
  • a base and the above acid halide, acid anhydride, carbonate halide, carbonate anhydride In the presence of a diester, an alkylsulfonyl halide, an arylsulfonyl halide, or the like, a —N + H 2 — group can be converted to a —NR 5 — group.
  • the base used at this time may be either an inorganic base or an organic base, but an organic base is preferable and a tertiary amine is preferable. More specifically, triethylamine, tri-n-butylamine, diazabicycloundecene (1,8-diazabicyclo [5.4.0] undec-7-ene) and the like can be mentioned.
  • the reaction solvent is not particularly limited as long as it is an aprotic solvent, and preferred solvents include acetonitrile, dichloromethane, N, N-dimethylformamide and the like.
  • the amount of the electrophile used is preferably 1.0 molar equivalent or more, more preferably 1.0 to 100.0 molar equivalent based on the formula (II).
  • -NR 5 only part - - -N + H 2 in the repeating units derived from Formula (II) - All groups -NR 5 also converted polymer network based on, Included in the present invention.
  • the conversion rate of the —N + H 2 — group to the —NR 5 — group may be 10% or more, preferably 30% or more, more preferably 50% or more.
  • the network polymer A before reacting with the electrophile attracts the crown ether ring in the partial structure represented by the formula (I) and the —N + H 2 — group in the partial structure represented by the formula (II). Fit. Therefore, the movement of the crown ether ring in the axial direction in the solution or gel is limited to some extent. However, the mobility of the crown ether ring is improved by converting the —N + H 2 — group to the —NR 5 — group by reaction with the electrophile. The gelation ability with respect to the organic solvent is the same as that of the network polymer A. It can be confirmed by IR measurement that at least part of the —N + H 2 — group is converted to the —NR 5 — group.
  • gelation means that the fluidity of a fluid liquid is lost.
  • a conventionally known inorganic ion salt used for a non-aqueous electrolyte solution can be used.
  • lithium chloride (LiCl) lithium perchlorate (LiClO 4 )
  • LiAsF 6 lithium hexafluoroarsenate
  • Lithium hexafluorophosphate LiPF 6
  • LiBF 4 lithium tetrafluoroborate
  • LiB (C 6 H 5 ) 4 lithium methanesulfonate
  • LiCF 3 SO 3 Lithium trifluoromethanesulfonate
  • bis (pentafluoroethanesulfonyl) imide lithium Li (C 2 F 5 SO 2 ) 2 N
  • bis (trifluoromethanesulfonyl) imide lithium Li (CF 3 SO 2) ) 2 N
  • tris trifluoromethanesulfonyl
  • Mechirurichi Beam LiC (CF 3 SO 2) 3
  • it is possible to use lithium bromide (LiBr) may be used by mixing two or more of these.
  • a conventionally known solvent used for a non-aqueous electrolyte solution can be used.
  • a conventionally known solvent used for a non-aqueous electrolyte solution can be used.
  • a solvent containing at least one selected from the group consisting of 1,2-dimethoxyethane, diethyl carbonate, and methyl ethyl carbonate, and ethylene carbonate or propylene carbonate a solvent containing at least one selected from the group consisting of 1,2-dimethoxyethane, diethyl carbonate, and methyl ethyl carbonate, and ethylene carbonate or propylene carbonate
  • an electrolyte solution in which at least one inorganic ion salt selected from the group consisting of LiClO 4 , LiBF 4 , LiPF 6 and LiCF 3 SO 3 is dissolved is preferable.
  • the concentration of the inorganic ion salt in the electrolytic solution is preferably about 0.2 to 3.0 mol / L, for example.
  • the polymer gel electrolyte of the present invention can be obtained by gelling an electrolyte solution with the network polymer A and / or B. Specifically, a production method in which a predetermined amount of network polymer A and / or B is dissolved in a predetermined amount of electrolyte solution by heating and then cooled is exemplified. Usually, it is preferable to dissolve completely by heating.
  • the content of the electrolyte solution can be reduced, but the polymer gel electrolyte using the network polymer B is more electrolyte solution than the polymer gel electrolyte using the network polymer polymer A. The content of can be further reduced.
  • the amount of the electrolyte solution used with respect to the network polymer A is 10 to 300 parts by mass, preferably 100 to 200 parts by mass with respect to 100 parts by mass of the network polymer A.
  • the amount of the electrolyte solution used for the network polymer B is 10 to 100 parts by mass, preferably 10 to 50 parts by mass with respect to 100 parts by mass of the network polymer B.
  • Nonaqueous electrolyte secondary battery The polymer gel electrolyte can be used as a nonaqueous electrolyte secondary battery such as 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.
  • the positive electrode is not particularly limited as long as it absorbs positive ions or discharges negative ions during discharge, and is not limited to metal oxides such as LiMnO 2 , LiMn 2 O 4 , LiCoO 2 , LiNiO 2 , or polyacetylene.
  • metal oxides such as LiMnO 2 , LiMn 2 O 4 , LiCoO 2 , LiNiO 2 , or polyacetylene.
  • Conventionally known materials for secondary batteries such as conductive polymers such as polyaniline, polypyrrole, polythiophene and polyparaphenylene, derivatives thereof, and disulfide compounds can be used.
  • 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
  • negative electrode active materials for secondary batteries such as amorphous carbon obtained by heat treatment of pitch coke, acetylene pitch coke, and lithium alloys such as metallic lithium and AlLi can be used.
  • these electrode active materials can be mixed with an appropriate binder or functional material to form an electrode layer.
  • a 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.
  • a polymer electrolyte, a composite thereof, and the like are examples of a polymer electrolyte, a composite thereof, and the like.
  • a polymer gel electrolyte can be supported on the separator substrate.
  • a separator base material what is normally used as a separator base material for nonaqueous electrolyte secondary batteries can be used.
  • the shape of the nonaqueous electrolyte secondary battery of the present invention is not particularly limited.
  • 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, etc. 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
  • Table 6 shows the results of measurement of swelling degree using methanol, dichloromethane (DCM) and dimethyl sulfoxide (DMSO) for the network polymer gels produced in Synthesis Examples 15, 19, 20, 21, 34, and 37. Show.
  • the network polymer gel swelled well when dichloromethane was used, and hardly swelled when methanol was used. Moreover, the difference of the swelling degree by the ratio of the linear compound in a network polymer gel, a cyclic compound, and a radical polysynthetic monomer was not seen so much.
  • Ionic conductivity was measured using the network polymer gel obtained in Synthesis Examples 14, 15, and 39.
  • Table 8 shows the results of immersing in an electrolyte solution of LiPF 6 / EC (1M) and then measuring the ionic conductivity at measurement temperatures of 25 ° C. and 50 ° C.
  • the ionic conductivity of the network polymer gel obtained in Synthesis Example 15 was 3.95 ⁇ 10 ⁇ 4 S / cm at a measurement temperature of 25 ° C. and 4.95 ⁇ 10 ⁇ 4 S / cm at 50 ° C. Since the electrolyte solution was taken in more than the obtained network polymer, it increased significantly.
  • the ionic conductivity of the network polymer obtained in Synthesis Example 39 was measured by adjusting the amount of the electrolytic solution. When the content of the electrolytic solution with respect to the polymer was 170%, it was 1.18 ⁇ 10 ⁇ 3 S / cm at a measurement temperature of 25 ° C. and 1.48 ⁇ 10 ⁇ 3 S / cm at 50 ° C., and was obtained in Synthesis Example 16.
  • the ionic conductivity of the network polymer obtained in Synthesis Example 39 is 4.16 ⁇ 10 ⁇ 3 S / cm at a measurement temperature of 50 ° C. when the content of the electrolytic solution is 100%. The value was similar to that of the network polymer obtained in Example 16. From these results, it is considered that by acetylating ammonium salt, the degree of freedom of the crosslinking point increased and the mobility of the network polymer increased.
  • the network polymer obtained in the present invention exhibits high ionic conductivity despite a small amount of electrolyte solution retained. Therefore, the problems of the liquid leakage and the manufacturing cost of the conventional nonaqueous electrolyte secondary battery can be solved, and it can be a safer and cheaper material for the nonaqueous electrolyte secondary battery.

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Abstract

La présente invention a pour but d'obtenir un nouveau polymère réticulé ayant une structure de rotaxane et de proposer un électrolyte de gel de polymère qui peut être utilisé comme l'électrolyte pour une batterie secondaire telle qu'une batterie secondaire lithium-ion, et qui est à la fois hautement sans danger et présente une conductivité ionique élevée. Le polymère réticulé selon la présente invention est un polymère réticulé ayant une unité (A) formée par une structure partielle représentée par la formule (II) ou (II') ci-dessous qui est incluse de façon à être enfilée à travers la partie annulaire d'une structure partielle représentée par la formule (I) ci-dessous, ou, est un polymère réticulé ayant ladite unité (A) et une unité (B) qui est issue d'un monomère polymérisable par voie radicalaire. Le rapport molaire ((I)/(II)) de la structure partielle représentée par la formule (I) et de la structure partielle représentée par la formule (II) est de 1/1-10/1. (L'unité (A) est formée à partir de la structure partielle représentée par la formule (I) et de la structure partielle représentée par la formule (II), à l'exclusion des cas dans lesquels l'unité (B) n'est pas incluse).
PCT/JP2012/008283 2011-12-27 2012-12-25 Polymère réticulé et électrolyte de gel de polymère WO2013099224A1 (fr)

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JP2015063640A (ja) * 2013-09-26 2015-04-09 国立大学法人山口大学 エーテル型ネットワークポリマー及びポリマーゲル電解質
JP2015074657A (ja) * 2013-10-04 2015-04-20 国立大学法人山口大学 ネットワークポリマー及びポリマーゲル電解質
WO2015147282A1 (fr) * 2014-03-28 2015-10-01 富士フイルム株式会社 Pile rechargeable entièrement solide, feuille d'électrode de pile et composition d'électrolyte solide utilisées dans ladite pile, procédé de fabrication de feuille d'électrode de pile, et procédé de fabrication de pile rechargeable entièrement solide
JP2015227438A (ja) * 2014-05-02 2015-12-17 国立大学法人山口大学 含硫黄ポリマー
CN105367983A (zh) * 2015-11-18 2016-03-02 安徽雄亚塑胶科技有限公司 一种高回弹性热塑性弹性体组合物
CN105938916A (zh) * 2016-06-01 2016-09-14 中山大学 一种通过无机TiO2纳米粒子掺杂改性的丙烯腈-甲基丙烯酸甲酯共聚型凝胶电解质的制备方法
WO2016201335A1 (fr) * 2015-06-10 2016-12-15 The Regents Of The University Of California Conducteurs d'un seul type d'ions de réseau de polymères à séquence de liaison flexible
CN108288729A (zh) * 2017-12-26 2018-07-17 华中科技大学 一种可用于离子电池的复合凝胶电解质及其制备方法
WO2018124527A3 (fr) * 2016-12-28 2018-11-29 한국과학기술원 Liant polymère à base de rotaxane pour batterie secondaire au lithium, électrode en comprenant et batterie secondaire en comprenant
WO2020032056A1 (fr) * 2018-08-08 2020-02-13 株式会社トクヤマ Composition durcissable contenant un monomère de polypseudorotaxane
WO2020111086A1 (fr) * 2018-11-29 2020-06-04 日産化学株式会社 Composé (méth)acrylique et composition de film d'isolation photosensible

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JP2015063640A (ja) * 2013-09-26 2015-04-09 国立大学法人山口大学 エーテル型ネットワークポリマー及びポリマーゲル電解質
JP2015074657A (ja) * 2013-10-04 2015-04-20 国立大学法人山口大学 ネットワークポリマー及びポリマーゲル電解質
WO2015147282A1 (fr) * 2014-03-28 2015-10-01 富士フイルム株式会社 Pile rechargeable entièrement solide, feuille d'électrode de pile et composition d'électrolyte solide utilisées dans ladite pile, procédé de fabrication de feuille d'électrode de pile, et procédé de fabrication de pile rechargeable entièrement solide
JP2015227438A (ja) * 2014-05-02 2015-12-17 国立大学法人山口大学 含硫黄ポリマー
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WO2016201335A1 (fr) * 2015-06-10 2016-12-15 The Regents Of The University Of California Conducteurs d'un seul type d'ions de réseau de polymères à séquence de liaison flexible
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CN105367983A (zh) * 2015-11-18 2016-03-02 安徽雄亚塑胶科技有限公司 一种高回弹性热塑性弹性体组合物
CN105938916A (zh) * 2016-06-01 2016-09-14 中山大学 一种通过无机TiO2纳米粒子掺杂改性的丙烯腈-甲基丙烯酸甲酯共聚型凝胶电解质的制备方法
WO2018124527A3 (fr) * 2016-12-28 2018-11-29 한국과학기술원 Liant polymère à base de rotaxane pour batterie secondaire au lithium, électrode en comprenant et batterie secondaire en comprenant
US11296324B2 (en) 2016-12-28 2022-04-05 Korea Advanced Institute Of Science And Technology Rotaxane polymer binder for lithium secondary battery, electrode comprising same, and secondary battery comprising same
CN108288729A (zh) * 2017-12-26 2018-07-17 华中科技大学 一种可用于离子电池的复合凝胶电解质及其制备方法
WO2020032056A1 (fr) * 2018-08-08 2020-02-13 株式会社トクヤマ Composition durcissable contenant un monomère de polypseudorotaxane
WO2020111086A1 (fr) * 2018-11-29 2020-06-04 日産化学株式会社 Composé (méth)acrylique et composition de film d'isolation photosensible
JPWO2020111086A1 (ja) * 2018-11-29 2021-10-21 日産化学株式会社 （メタ）アクリル化合物および感光性絶縁膜組成物
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