JP2002275234A - Cross-linked material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cross-linked material produced by containing a polycarbonate compound, used as a polymer electrolyte or a binding agent for an electrode and capable of improving characteristics such as environmental stability and weather resistance. SOLUTION: This cross-linked material is obtained by polymerizing a polycarbonate compound containing a recurring structural unit expressed by the following formula (1) and a recurring structural unit expressed by the following formula (2) [wherein, R1 is a 2-10C alkylene which may be substituted by a hetero atom; R2 is a branched chain or a cyclic 2-10C alkylene which may be substituted by a hetero atom; and (m) and (n) are each a positive integer].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a crosslinked product produced by polymerizing a polycarbonate compound, and more particularly, to a crosslinked product formed by polymerizing a polycarbonate compound containing a repeating structural unit of different polyols, and The present invention relates to a crosslinked product having improved properties and weather resistance.

[0002]

2. Description of the Related Art Polycarbonate compounds have been used in various applications because of their high chemical resistance, environmental stability, and weather resistance. In recent years, in particular, in recent years, polymer compounds for lithium secondary batteries and electrodes have been used. Attention has been focused on its use as a binder for cosmetics. When the polycarbonate compound is used as the above-mentioned polymer electrolyte or as a binder for a lithium secondary battery electrode, the polycarbonate compound is polymerized alone or together with another polymer to obtain desired properties. In many cases.

[0003] Among the above-mentioned uses, when a polycarbonate compound is used as a polymer electrolyte, it is a crosslinked product with a conductive polymer having high ionic conductivity such as polyalkylene oxide, particularly polyethylene oxide. Polyethylene oxide is used alone or in combination with so-called dopants such as alkali metal salts to further improve the conductivity due to its high ionic conductivity, and is used in applications such as antistatic agents and polymer electrolytes. .

[0004] For this reason, in order to provide a polymer electrolyte having good characteristics, for example, it is necessary to provide a crosslinked product having a good hydrophobic segment introduced therein without adversely affecting the ionic conductivity of the polyalkylene oxide. Is needed. Also, for example, for the electrodes of a lithium secondary battery,
2. Description of the Related Art An electrode is used in which a powder such as an electrode active material powder or a conductive powder is mixed with various binders on a current collector to form a film. These electrodes are required to be used in a wide potential range, to play a role in reducing the distortion in response to expansion and contraction caused by charging and discharging, and to have heat resistance in heating and drying during manufacturing. Will be done. Furthermore, it is also necessary to provide stable characteristics in a wide environment.

[0005]

Accordingly, the present invention can be produced containing a polycarbonate compound and used as a polymer electrolyte or a binder for an electrode to improve properties such as environmental stability and weather resistance. It is an object of the present invention to provide a highly crosslinked product.

[0006]

Means for Solving the Problems As a result of intensive studies, the present inventors have provided a crosslinked product containing a specific polycarbonate diol (hereinafter abbreviated as PCD), and particularly, a polymer electrolyte or an electrode. The present inventors have found that environmental stability and weather resistance can be improved as a binder, and have led to the present invention.

That is, according to the present invention, the following formula (1)

[0008]

Embedded image And a repeating structural unit represented by the following formula (2)

[0009]

Embedded image Is provided by polymerizing a polycarbonate compound containing a repeating structural unit represented by the formula (in the above formulas (1) and (2), R ₁ may be substituted with a hetero atom) A divalent group having 2 to 10 carbon atoms, R ₂ is a branched or cyclic divalent group having 2 to 10 carbon atoms which may be substituted by a hetero atom, and m and n are Is an integer).

In the present invention, the ratio (m: n) of the repeating structural unit represented by the formula (1) to the repeating structural unit represented by the formula (2) is 0.5: 99.
It can be in the range of 5-99.5 to 0.5.

Further, in the present invention, the above formula (1)
And the ratio (m: n) of the repeating structural unit represented by the formula (2) to 5: 95-95.
-5.

In the present invention, R _{1 in the} above formula (1) is a straight-chain hexylene group, and R ₁ in the above formula (2)
Preferably, ₂ is a methylpentylene group.

Further, the polycarbonate compound is
It contains at least a hydroxyl group or a group having an ethylenically unsaturated bond, and is produced by radical polymerization or polycondensation.

The crosslinked product of the present invention preferably further contains a dopant and a polyalkylene oxide, and preferably has an ionic conductivity of 10 ⁻⁵ Scm ⁻¹ to 10 ⁻² Scm ⁻¹ .

Further, the crosslinked product of the present invention is particularly preferably used as a binder for an electrode.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The crosslinked product of the present invention has the following formula (1)

[0018]

Embedded image And a repeating structural unit represented by the following formula (2)

[0019]

Embedded image And is obtained by polymerizing a polycarbonate compound containing a repeating structural unit represented by Equation (1) above
R ₁ in the repeating structural unit represented by is preferably a divalent group having 2 to 10 carbon atoms which may be optionally substituted with a hetero atom such as N, O, or S. Further, N, O And a straight-chain alkylene or oxyalkylene group having 3 to 8 carbon atoms which may be optionally substituted with a hetero atom such as S, S.

R ₂ in the repeating structural unit represented by the above formula (2) is particularly preferably a branched or cyclic alkylene or oxyalkylene group having 3 to 10 carbon atoms.

More preferably, in the present invention, R ₁ in the repeating structural unit represented by the above formula (1) is
A hexylene group is preferable because it can give appropriate flexibility to the crosslinked product and also give appropriate hydrophobicity. R ₂ in the above formula (2) is
It has been found that a branched alkylene group, particularly a methylpentylene group, is preferred.

The ratio (m: n) of the repeating structural unit represented by the formula (1) to the repeating structural unit represented by the formula (2) in the crosslinked structure of the present invention is 0.5: 9.
9.5 to 99.5 to 0.5, and the ratio (m:
It is preferable that n) be 5:95 to 95: 5 from the viewpoint of simultaneously improving ionic conductivity and environmental stability. Further, when the ratio (m: n) is 5:95 to 70:30, it is preferable because it becomes liquid at ordinary temperature and becomes easy to handle.

The above-described PCD of the present invention specifically includes
It has a structural formula represented by the following general formula (3) and the following general formula (4).

[0024]

Embedded image

[0025]

Embedded image

The ratio of repeating structural units in the present invention means the ratio of m and n in the repeating structural units represented by the above general formula (3) or (4) (m and n are positive Is an integer).

The P which can be used in the present invention described above
If the molecular weight of CD becomes too large, it becomes high viscosity,
If the handleability is reduced, and too small, environmental stability,
In some cases, the weather resistance cannot be sufficiently improved. For this reason, the molecular weight of PCD used in the present invention can be in the range of 250 to 2,000 in number average molecular weight (Mn), more preferably in the range of 250 to 1500, and In order to balance the properties with the environmental stability, it is preferable to be in the range of 300 to 1,000.

The PCD that can be used in the present invention is
It can be manufactured by any method known so far. In particular, in the present invention, it is preferable to use a transesterification reaction represented by the following formula between a diol and a low molecular weight carbonate.

[0029]

Embedded image

[0030] In the present invention, in producing a PCD by transesterification, as the compound capable of providing a suitable R _1, there may be mentioned polyhydric alcohols linear low molecular weight, specifically Is, for example, ethylene glycol, 1,1′-oxybis-2-propanol, triethylene glycol, tetraethylene glycol,
1,6-pentanediol, 1,3-propanediol, 1,4-butanediol, 1,4-butenediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, diethylene glycol,
Examples thereof include dipropylene glycol and glycerin.

In the present invention, compounds capable of providing R ₂ suitable for the present invention include 1,2-propanediol, 1,2-butanediol, 1,3-butanediol, dipropylene glycol, tripropylene glycol, Cyclohexanediol, 3-methyl-1,5-pentanediol, cyclohexane-1,2,4-trimethanol, cyclohexane-1,3,5-trimethanol, 1,4-cyclohexanedimethanol, 1,2,6
-Hexanetriol trimethylolmethane, trimethylolethane, trimethylolpropane, trimethylolbutane and the like.

The PCD that can be used in the present invention can be a random copolymer, but can also be used as a block copolymer in which each repeating structural unit is a block.

Examples of the low molecular weight carbonate which can be used for the transesterification for producing the PCD of the present invention include, for example, alkylene carbonates such as ethylene carbonate and propylene carbonate, dimethyl carbonate, diethyl carbonate and the like. And dialkyl carbonates such as ethylmethyl carbonate, and diaryl carbonates such as diphenyl carbonate.

The crosslinked product of the present invention is obtained by combining the above-mentioned PCD or polycarbonate (di) acrylate with an essentially ion-conductive polymer segment such as polyalkylene glycol or polyalkylene glycol (poly) acrylate. The resulting mixture can be produced as a conductive crosslinked product by polycondensation or radical polymerization.

The polyalkylene glycols that can be used when the crosslinked product of the present invention is made conductive include:
Specifically, polyethylene glycol, polypropylene glycol, alkylene glycol adduct of glycerin represented by the following formula,

[0036]

Embedded image (In the above formula, p, q, and r are positive integers which may be the same or different.)

In the present invention, the above-mentioned polycarbonate polyol and polyalkylene glycol are
By acryloylation or methacryloylation, polymerization can be performed as an acrylate or methacrylate derivative. Examples of the acrylate or methacrylate that can be used in this case include compounds in which an acryloyl group or a methacryloyl group is bonded to a terminal hydroxyl group such as polyalkylene glycol monoacrylate, polyalkylene glycol diacrylate, or an alkylene glycol adduct of glycerin. Can be used.

In the present invention, ionic conductive polymers that can be used to further impart ionic conductivity include polyester, polyethylene succinate, poly-β-propiolactone, polyethyleneimine, and polyalkylene sulfide. Can be used in place of the polyalkylene glycol, or can be used as a mixture with the polyalkylene glycol. Further, a polymer having an acryloyl group or a methacryloyl group bonded thereto by an appropriate method can also be used.

Further, in the crosslinked product of the present invention, a compound which functions as a so-called dopant that gives an ion for improving ionic conductivity can be appropriately mixed and used. As these dopants, specifically, for example, lithium fluoride, lithium chloride, lithium bromide, lithium iodide, lithium nitrate, lithium thiocyanate, lithium perchlorate, trifluoromethyllithium sulfonate, tetrafluorolithium borate, Tetraphenyl lithium borate, LiPF ₆ , sodium fluoride, sodium chloride, sodium bromide, sodium iodide, sodium nitrate, sodium thiocyanate, sodium perchlorate, trifluoromethyl sodium sulfonate, tetrafluoro sodium borate, tetraphenyl sodium borate , NaPF ₆ , potassium fluoride, potassium chloride, potassium bromide, potassium iodide, potassium nitrate, potassium thiocyanate, potassium perchlorate, trifluoromethyl potassium sulfone Salt, tetrafluoro potassium borate, tetraphenyl potassium borate, KP
A compound such as F ₆ , LiN (CF ₃ SO ₂ ) ₂ , L
A perfluoroalkanesulfonic acid compound such as iN (CF ₃ SO ₂ ) ₂ can be used.

Further, in the present invention, as a cation,
Rb ⁺ , Cs ⁺ , ammonium ion, Mg ²⁺ , Ca
A compound of a cation such as ²⁺ , Zn ²⁺ , Cu ²⁺ and Rb ²⁺ and the above-mentioned anion can be used as a dopant.

The crosslinked product of the present invention is not mixed with an ionic conductive polymer such as polyethylene oxide in order to impart conductivity, and the above-mentioned polycarbonate diol is subjected to polycondensation or radical polymerization to form a crosslinked product. By doing so, it is possible to produce a binder for an electrode, particularly a binder for an electrode for a lithium secondary battery. In order to use the crosslinked product of the present invention as a binder for an electrode, a metal oxide such as cobalt oxide, manganese oxide, vanadium oxide, nickel oxide, and molybdenum oxide, molybdenum sulfide, Titanium sulfide,
Metal sulfides such as vanadium sulfide, lithium cobalt oxide (Li _x CoO ₂ ), and lithium molybdate (Li
_x MnO ₂ ) or the like can be dispersed or mixed.

When the crosslinked product of the present invention is used as a binder for an electrode, the crosslinked product of the present invention contains polyethylene oxide, polypropylene oxide, polyacrylonitrile, polybutadiene, polyacrylate, polymethacrylate, and polystyrene. , Poly (styrene-
Polymers such as (meth) acrylate) copolymer, polyphosphazene, polysiloxane, polyamide, polyvinylidene fluoride, and polytetrafluoroethylene can be appropriately mixed and used. Further, a conductive polymer such as polyaniline, polyacetylene, polyparaphenylene, polypyrrole, polythienylene, polypyridinediyl, polyisothianaphthenylene, polyselenophene, or a derivative thereof can be mixed.

In the present invention, when a crosslinked product is formed using a polycarbonate compound, the crosslinked product of the present invention is formed by polycondensation reaction of the above-mentioned PCD containing a hydroxyl group with, for example, polyisocyanate. In the form of a polyurethane. In the present invention, as described above, PCD is acrylic-modified by an appropriate method to obtain a polycarbonate diacrylate, and a crosslinked product in the form of an acrylic crosslinked product formed by radical polymerization using an appropriate initiator. Can be.

Examples of the polyisocyanate which can be used for performing the polycondensation reaction include, for example, tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI) , Tolidine diisocyanate, naphthylene diisocyanate, xylylene diisocyanate (XDI), 3-isocyanatomethyl-3,
5,5-trimethylcyclohexyl isocyanate (I
PDI).

The radical initiators which can be used in the above-mentioned acrylic polymerization include dimethyl 2,2'-azobisisobutyrate, azobiscyanovaleric acid and 1,1 '
-Azobis- (cyclohexane-1-carbonitrile), 2,2'-azobis- (2,4-dimethylvaleronitrile), azobismethylbutyronitrile, 2,2 '
Azo-based initiators such as -azobis- (4-methoxy-2,4-dimethylvaleronitrile) and 2,2'-azobisisobutyronitrile can also be used as appropriate.

In the present invention, the initiator may be a compound selected from the group consisting of methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, or a mixture thereof.

Further, in the present invention, isobutyryl peroxide, 3,5,5
-A compound selected from the group consisting of trimethylhexanoyl peroxide, lauroyl peroxide, benzoyl peroxide, p-chlorobenzoyl peroxide or a mixture thereof.

Further, in the present invention, di-tert-butyl peroxide, t-
Butyl-α-cumyl peroxide, di-α-cumyl peroxide, 1,4-bis (t-butylperoxyisopropyl) benzene, 1,3-bis (t-butylperoxyisopropyl) benzene, 2,5- Dimethyl-
2,5-bis (t-butylperoxy) hexane,
5-dimethyl-2,5-bis (t-butylperoxy)
It is also possible to use a compound selected from the group consisting of -3-hexyne or a mixture thereof.

Further, in the present invention, t-butyl hydroperoxide, cumene hydroperoxide, di-isopropylbenzene hydroperoxide, p-menthane hydroperoxide, 1,1,3,3- It is also possible to use a compound selected from the group consisting of tetramethylbutyl hydroperoxide or a mixture thereof.

Further, in the present invention, 1,1-bis (t-butylperoxy)-is used as the above-mentioned radical initiator.
3,3,5-trimethylcyclohexane, n-butyl =
4,4-bis (t-butylperoxy) valerate,
It is also possible to use a compound selected from the group consisting of 2,2-bis (t-butylperoxy) butane or a mixture thereof.

Furthermore, in the present invention, t-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxyoctoate, t-butyl peroxypivalate, t-butyl peroxy acetate,
Butyl peroxy neodecanoate, t-butyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxybenzoate, t-butyl peroxy laurate, 2,5-dimethyl-2,5- It is also possible to use a compound selected from the group consisting of bis (benzoylperoxy) hexane or a mixture thereof.

Further, in the present invention, bis- (2-ethylhexyl) peroxydicarbonate, diisopropylperoxydicarbonate, di-sec-butylperoxydicarbonate,
Di-n-propylperoxydicarbonate, bis (3
-Methoxybutyl) peroxydicarbonate, bis (2-ethoxyethyl) peroxydicarbonate, bis (4-t-butylcyclohexylperoxydicarbonate, OO-t-butyl-O-isopropylperoxycarbonate It can also be a selected compound or a mixture thereof.

In the present invention, the above radical initiator may be a water-soluble compound comprising azobiscyanovaleric acid, bis (2-ethoxyethyl) peroxydicarbonate, potassium persulfate, ammonium persulfate, or a mixture thereof. Is also possible. The above-mentioned radical initiators can be used by mixing plural kinds of any combination of the above-mentioned radical initiators.

Further, when a crosslinked product is produced by radical polymerization, methacrylic acid esters, acrylic acid esters, styrene, α-methylstyrene, urethane acrylate, acrylic acid or methacrylic acid ester having an oxyfluorocarbon chain, carbonate chain Or methacrylate, fluorinated alkyl ester of acrylic acid, acrylamide, methacrylamide, methylacrylamide on N, N, N, N-dimethylmethacrylamide, N-vinylpyrrolidone, acryloylmorpholine, methacrylmorpholine, N, N-dimethylamino Polymerizable compounds such as propyl (meth) acrylamide, N-vinylacetamide, N-vinylformamide, and alkyl vinyl ether can be appropriately mixed.

The crosslinked product of the present invention can also be used after forming the above-mentioned PCD and the crosslinked product, then doping with a dopant and then molding and processing. Furthermore, the crosslinked body of the present invention can be diluted with an appropriate solvent to form a film, and then polymerized to form a crosslinked body.

Various solvents can be used as the solvent that can be used at this time. These solvents include, for example, amylbenzene, isopropylbenzene,
Ethylbenzene, xylene, diethylbenzene, cyclohexene, cyclopentane, dipentene, dimethylnaphthalene, cymes, camphor oil, petroleum ether, petroleum benzine, solvent naphtha, decalin, decane, tetralin, turpentine oil, kerosene, dodecane, dodecylbenzene,
Examples include hydrocarbon solvents such as toluene, naphthalene, nonane, pine oil, pinene, methylcyclohexane, p-menthane, and ligroin.

Examples of the solvent further include 2-ethylhexyl chloride, amyl chloride, isopropyl chloride, ethyl chloride, naphthalene chloride, butyl chloride, hexyl chloride, methyl chloride, methylene chloride, o-chlorotoluene, p-chlorotoluene, chlorobenzene, Carbon tetrachloride, dichloroethane, dichloroethylene, dichlorotoluene, dichlorobutane, dichloropropane, dichlorobenzene, dibromoethane, dibromobutane, dibromopropane, dibromobenzene, dibromopentane, allyl bromide, isopropyl bromide, ethyl bromide, octyl bromide , Butyl bromide,
Propyl bromide, methyl bromide, lauryl bromide, tetrachloroethane, tetrachloroethylene, tetrabromoethane, tetramethylenechlorobromide, trichloroethane, trichloroethylene, trichlorobenzene, bromochloroethane, 1-bromo-3-chloropropane, bromonaphthalene, bromobenzene, Hexachloroethane,
It is possible to use a halogenated hydrocarbon solvent such as pentamethylenechlorobromide.

Examples of the solvent include amyl alcohol, allyl alcohol, isoamyl alcohol, isobutyl alcohol, isopropyl alcohol, undecanol, ethanol, 2-ethylbutanol, 2-ethylhexanol, 2-octanol, n-octanol,
Glycidol, cyclohexanol, 3,5, -dimethyl-1-hexyn-3-ol, n-decanol, tetrahydrofurfuryl alcohol, α-terpineol,
Neopentyl alcohol, nonanol, fusel oil, butanol, furfuryl alcohol, propargyl alcohol, propanol, hexanol, heptanol, benzyl alcohol, pentanol, methanol, methylcyclohexanol, 2-methyl-1-butanol, 3-
Methyl-2-butanol, 3-methyl-1-butyne-3
Alcohols such as -ol, 4-methyl-2-pentanol and 3-methyl-1-pentyn-3-ol can also be mentioned.

Examples of the solvent further include anisole, ethyl isoamyl ether, ethyl-t-butyl ether, ethyl benzyl ether, epoxybutane, crown ethers, cresyl methyl ether, diisoamyl ether, diisopropyl ether, diethyl acetal, diethyl ether, Dioxane, 1,8-cineole, diphenyl ether, dibutyl ether, dipropyl ether, dibenzyl ether, dimethyl ether,
Tetrahydropyran, tetrahydrofuran, trioxane, bis (2-chloroethyl) ether, phenetole, butylphenylether, furan, furfural,
Ether-acetal solvents such as methylal, methyl-t-butyl ether, methyl furan and monochlorodiethyl ether can also be mentioned.

As the above-mentioned solvent, acetylacetone,
Acetaldehyde, acetophenone, acetone, isophorone, ethyl-n-butyl ketone, diacetone alcohol, diisobutyl ketone, diisopropyl ketone, diethyl ketone, cyclohexanone, di-n-propyl ketone, holon, mesityl oxide, methyl-n-amyl ketone, methyl isobutyl Ketone, methyl ethyl ketone,
Methylcyclohexanone, methyl-n-butyl ketone,
Ketone / aldehyde solvents such as methyl-n-propyl ketone, methyl-n-hexyl ketone, and methyl-n-heptyl ketone can also be used.

Solvents that can be used in the present invention include diethyl adipate, dioctyl adipate, triethyl acetyl citrate, tributyl acetyl citrate, ethyl acetoacetate, allyl acetoacetate, methyl acetoacetate, methyl abietate, and benzoate. Ethyl acid,
Butyl benzoate, propyl benzoate, benzyl benzoate, methyl benzoate, isoamyl isovalerate, ethyl isovalerate, isoamyl formate, isobutyl formate, ethyl formate, butyl formate, propyl formate, hexyl formate, benzyl formate, methyl formate, Tributyl citrate, cinnamate, methyl cinnamate, ethyl cinnamate, amyl acetate, allyl acetate, isoamyl acetate, isobutyl acetate, isopropyl acetate, ethyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, butyl acetate, acetic acid Propyl,
Benzyl acetate, methyl acetate, methyl cyclohexyl acetate, isoamyl salicylate, benzyl salicylate, methyl salicylate, ethyl salicylate, diamyl oxalate, diethyl oxalate, dibutyl oxalate, diethyl tartrate, dibutyl tartrate, amyl stearate, ethyl stearate, ethyl stearate, butyl stearate, sepacin Dioctyl acid, dibutyl sebacate, diethyl carbonate, diphenyl carbonate, dimethyl carbonate, amyl lactate, ethyl lactate, methyl lactate, diethyl phthalate, dioctyl phthalate, dibutyl phthalate, dimethyl phthalate, γ-butyrolactone, isoamyl propionate, propion Ethyl acid, butyl propionate, ethyl propionate, benzyl propionate, methyl propionate, borates, dioctyl maleate,
Dibutyl maleate, diisopropyl malonate, diethyl malonate, dimethyl malonate, isoamyl butyrate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl butyrate,
Ester solvents such as phosphoric esters can also be mentioned.

Examples of the solvent include ethylene glycol, ethylene glycol dibutyl ether, ethylene glycol diacetate, ethylene glycol dibutyl ether, ethylene glycol dimethyl ether, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, and ethylene glycol monoethyl ether. , Ethylene glycol monoethyl ether acetate, ethylene glycol monophenyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monomethoxymethyl Ether, ethylene black Hydrin, 1,3-octylene glycol, glycerin, glycerin 1,3-diacetate, glycerin dialkyl ether, glycerin fatty acid esters, glycerol triacetate, glycerin laurate, glycerin monoacetate, 2-chloro -
Examples include polyhydric alcohols such as 1,3-propanediol, 3-chloro-1,2-propanediol, diethylene glycol, diethylene glycol ethyl methyl ether, and polypropylene glycol, and derivatives thereof.

Further, as the above-mentioned solvent, isovaleric acid,
Isobutyric acid, itaconic acid, 2-ethylhexanoic acid, 2-ethylacetic acid, oleic acid, caprylic acid, caproic acid, formic acid, valeric acid, acetic acid, lactic acid, pivalic acid, propionic acid,
Carboxylic acid derivatives such as ethylphenol, octylphenol, catechol, guaiacol, xylenol, p-cumylphenol, cresol, dodecylphenol, naphthol, nonylphenol, phenol,
Phenols such as benzylphenol and p-methoxyethylphenol, acetonitrile, acetone cyanohydrin, aniline, allylamine, amylamine, isoquinoline, isobutylamine, isopropanolamines, isopropylamine, imidazole, N-ethylethanolamine, 2-ethylhexylamine, N- Ethyl morpholine, ethylenediamine, caprolactam,
Quinoline, chloroaniline, ethyl cyanoacetate, diamylamine, isobutylamine, diisopropylamine,
Diisopropylethylamine, monoethanolamine,
Diethanolamine, monopropanolamine, dipropanolamine, N, N-diethylaniline, diethylamine, diethylbenzylamine, diethylenetriamine, dioctylamine, cyclohexylamine, triethylamine, triamylamine, trioctylamine,
Triethanolamine, triethylamine, trioctylamine, tri-n-butylamine, tripropylamine, trimethylamine, toluidine, nitroanisole, picoline, piperazine, pyrazine, pyridine, pyrrolidine, N-phenylmorpholine, morpholine, butylamine, heptylamine, lutidine And nitrogen-containing compounds such as N-methylpyrrolidone, and these solvents, as well as sulfur-containing compound-based solvents and fluorine-based solvents.

When the crosslinked product of the present invention is used as ionic conductivity, the ionic conductivity is 10%.
The range of ⁻⁵ Scm ⁻¹ to 10 ⁻² Scm ⁻¹ is preferable in that appropriate ionic conductivity can be imparted. In the present invention, the ionic conductivity can be measured by various methods. In the present invention, a particularly preferable and highly accurate ionic conductivity measuring method is a method using an impedance measured by impedance measurement. FIG. 1 shows a device configuration and a measurement principle of impedance measurement that can be used in the present invention. FIG. 1A shows a basic configuration of an impedance measuring apparatus according to the present invention. As shown in FIG. 1A, a conductive crosslinked body 1 in which the crosslinked body of the present invention is ion-conductive is sandwiched between two opposed electrodes 2a and 2b, and a high frequency voltage is applied from an AC power supply. I do.

Here, as shown in FIG. 1B, the ionic conductor can be represented by a model including a resistance R and a capacitance C. The ionic conductivity of the ionic conductor can be measured by measuring the value of the current flowing through both electrodes 2a and 2b with an ammeter A when a high-frequency voltage is applied from the AC power supply 1. FIG. 1 shows that the ion-conductive crosslinked body 3 of the present invention is sandwiched between the electrodes 2a and 2b, and a high-frequency AC voltage is applied from the AC power supply 1.

FIG. 2 is a graph showing the real part (Z ′) in the complex impedance when the AC frequency is changed, which is obtained when the conductive cross-linked body can be approximated by the model shown in FIG. It is the figure which showed the complex impedance plot which plotted the imaginary part (Z ") on the axis as an axis. The frequency which gives the local maximum value in a complex impedance plot, the electrical conductivity, and the capacitance have the following relationship. Known (eg, conductive polymers,
(Edited by Naoya Ogata, Kodansha Co., Ltd., published on February 10, 1990).

[0067]

(Equation 1) Therefore, the ionic conductivity can be obtained from the value of the AC frequency giving the highest imaginary part based on the complex impedance plot and the value of the capacitance of the conductive cross-linked body measured separately. Further, in the present invention, it is possible to extrapolate to the real part (R ′) from the complex impedance plot, obtain R ′, and obtain the ionic conductivity using the following equation.

[0068]

(Equation 2) (Where σ is the ionic conductivity (Scm ⁻¹ ),
d is the distance between the electrodes, that is, the thickness (cm) of the crosslinked body, and A is the electrode area (cm ² ).

When the crosslinked product of the present invention is made ionically conductive, the change in ionic conductivity from high temperature and high humidity to low temperature and low humidity depends on the ionic conductivity σ _{h at} high temperature and high humidity and the ionic conductivity at low temperature and low humidity. The ratio σ ₁ / σ _h to the ionic conductivity σ _l is
The following range

[0070]

(Equation 3) Is preferable because suitable environmental stability can be imparted. In the present invention, high temperature and high humidity refer to an environment of 30 ° C. and 80% RH, and low temperature and low humidity refer to
It refers to an environment of 5 ° C. and 10% RH. Furthermore, when the crosslinked product of the present invention is used as ionic conductivity,
Furthermore, the conductivity can be improved by swelling with a compound such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, or diphenyl carbonate, and further adding the above-described dopant.

Further, the crosslinked product of the present invention can be used for controlling various properties whether it is used as a conductive material or as a binder for electrodes.
Any known inorganic fine particles, organic fine particles, additives such as surfactants and the like can be mixed and used within a range that does not adversely affect the properties of the crosslinked product of the present invention.

Hereinafter, the present invention will be described with reference to specific examples. However, the following examples do not limit the present invention.

[0073]

EXAMPLE A Production of Polycarbonate Diol (Synthesis Example 1) 0.7 mol of 1,6-hexamethylenediol (molecular weight 118) and 0.3 mol of 3-methyl-1,5-pentanediol (molecular weight 118) , 0.9 mol of diethyl carbonate was charged into a 1-liter separable flask, and the ethanol removal reaction was carried out in an oil bath at a temperature of 180 ° C to 190 ° C under normal pressure. At the time when the amount of distilling out of ethanol began to decrease, 0.01 g of tetrabutyl titanate was charged and the pressure was reduced, and the reaction was further performed.
The degree of pressure reduction was gradually increased, and the reaction was continued until the pressure was finally reduced to 1 kPa. The end of the reaction was determined by analyzing the reaction product by ¹³ C-NMR, and when the peak of the terminal ethyl group could not be confirmed, the end of the reaction. By the above reaction, the number average molecular weight (Mn) is 500, and the hydroxyl value (OH)
v) is 224.4 mgKOH / g, average number of functional groups (f)
Was obtained as polycarbonate diol PCD-1.

(Synthesis Examples 2 to 4) The ratio of 1,6-hexamethylenediol to 3-methyl-1,5-pentanediol was 9.5 / 0.5 (PCD-2), 9/1 ( PCD
-2), 8/2 (PCD-3), 3/7 (PCD-4)
A polycarbonate diol was synthesized in the same manner as in Synthesis Example 1 except that the above conditions were changed to obtain a polycarbonate diol of the present invention.

(Synthesis 5) A polycarbonate diol of the present invention was synthesized in the same manner as in Synthesis Example 1 except that triethylene glycol was used instead of 1,6-hexanediol (PCD-5).

Synthesis Example 6 A polycarbonate diol of the present invention was synthesized in the same manner as in Synthesis Example 1 except that polytetramethylene glycol having Mn = 250 was used instead of 1,6-hexanediol (PCD). −
6).

Synthesis Example 7 The polycarbonate diol of the present invention was produced in the same manner as in Synthesis Example 1 except that cyclohexanediol was used instead of 3-methyl-1,5-pentanediol (PCD-7). ).

Table 1 shows the number average molecular weight (Mn), the composition ratio of repeating structural units (m / n), the hydroxyl value (OHv) of the polycarbonate diols of the present invention obtained in Synthesis Examples 1 to 6. The number average molecular weight and the average number of functional groups (f) calculated from OHv are shown.

[0079]

[Table 1] B. Manufacture of conductive crosslinked product Manufacture of polyurethane conductive crosslinked product Polycarbonate diol manufactured in A (PCD-1)
, MDI, and an ethylene oxide adduct of glycerin having the following structural formula (glycerin: ethylene oxide = 1:
75 (molar ratio)) in N-methylpyrrolidone to give a 20% by mass solution. LiCF is added to the above solution.
₃ SO ₃ was added as a dopant so as to be 20% by mass based on the solid content.

The above-mentioned solution was applied to an electrode of an impedance measuring device having the structure shown in FIG. 1, and after the solvent was dried at room temperature, it was cured by heating in a dryer at 150 ° C. for 1 hour. The crosslinked body formed on the electrode as described above was swollen with diethyl carbonate to produce a conductive crosslinked body.

C. Measurement of ionic conductivity In B, a high-frequency voltage (0.001 Hz) was applied to the conductive cross-linked body formed on the electrode of the impedance measuring device.
To 10 ⁷ Hz) was applied, and the ionic conductivity normal temperature and normal humidity (25 ° C., as measured in an environment of RH 55%). In the measurement of the ionic conductivity, the complex impedance plot described in FIG. 1B is performed, and the F ″ -F ′ plot is changed to F ′.
(Real axis). As a result, PCD-1
2 × 10 ⁻⁴ Scm for conductive crosslinked product using
An ionic conductivity of ^-1 was obtained.

The same measurement was carried out in a low-temperature and low-humidity environment (5
10% RH) and high temperature and high humidity environment (30 ° C, 80%
Performed in RH), respectively ionic conductivity, a humidity 5 × ¹⁰ -5 ^{Scm -1,} and high temperature and high at low temperature and low humidity 1 × 1
0 ^-3 Scm ^-1 was obtained.

When the above-mentioned conductive crosslinked products were prepared and measured for PCD-2 to PCD-7, conductive crosslinked products exhibiting good ionic conductivity and environmental stability were obtained. Table 2 shows the results.

[0084]

[Table 2]

D. Acrylic crosslinked product Polycarbonate diacrylate was produced using the polycarbonate diols of PCD-1 to 7 according to the production method described in JP-A-2000-86711. The produced polycarbonate diacrylate was replaced with polyethylene glycol diacrylate, LiCF ₃ SO
₃ and radical polymerization using benzoyl peroxide to form a conductive crosslinked product. Good ionic conductivity was obtained for the above-mentioned conductive crosslinked body, similarly to the polyurethane crosslinked body.

E. Production of Electrode for Lithium Secondary Battery (Production of Positive Electrode) Lithium carbonate powder and cobalt oxide powder are mixed, fired at 800 ° C. in an oxygen atmosphere, and then pulverized to obtain lithium cobalt oxide (Li ₂ CoO ₂ ) powder. Obtained. The lithium cobalt oxide powder thus obtained, conductive carbon, PCD-1 and MDI were mixed. The obtained composition was applied on an aluminum foil and cured at 180 ° C. for 1 hour to produce a positive electrode containing lithium cobalt oxide.

(Production of Negative Electrode) PCD-1 was mixed with conductive carbon black and MDI and applied on a copper foil.
The mixture was cured at 80 ° C. for 1 hour to produce a negative electrode.

F. Manufacture of lithium secondary battery The above-described positive electrode and negative electrode are impregnated with a hexafluorolithium / diethyl carbonate electrolyte solution, and a porous film impregnated with the above-mentioned electrolyte solution is interposed between the positive electrode and the negative electrode. A lithium oxide-based lithium secondary battery was manufactured. When the charge / discharge characteristics of the lithium secondary battery manufactured as described above were measured, the discharge capacity was large,
In addition, even when left in a high-temperature and high-humidity environment, almost no deterioration in characteristics was observed.

[0089]

As described above, according to the present invention, a crosslinked product having good environmental stability and weather resistance can be obtained.
The crosslinked product of the present invention is a polymer electrolyte for a lithium secondary battery, a binder for an electrode of a lithium secondary battery, a solid electrolyte for a solid electrolyte fuel cell, a photovoltaic cell, a sensor, an electrochromic device, and an electrolytic capacitor. It can be applied to various uses such as an electrolyte for use, an antistatic coating, and a conductive seal.

[Brief description of the drawings]

FIG. 1 is a diagram showing an impedance measuring device according to the present invention.

FIG. 2 is a diagram showing an impedance measuring method according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... AC power supply 2a, 2b ... Electrode 3 ... Crosslinked body A ... Ammeter

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) H01M 10/40 H01M 10/40 B 5H050 (72) Inventor Mamoru Akimoto 4530 Kaiseicho, Shinnanyo-shi, Yamaguchi Japan Japan Inside Polyurethane Industry Co., Ltd. Nanyo Plant (72) Inventor Takashi Nozu 4530 Kaisei-cho, Shinnanyo-shi, Yamaguchi Japan Japan Inside Polyurethane Industry Co., Ltd. Polyurethane Industry Co., Ltd. Nanyo Plant F-term (reference) 4J027 AB03 AB10 AB18 AB28 AC03 AC06 AJ08 BA05 BA07 BA13 BA14 BA15 CA26 CA33 CB04 CC02 CD00 4J034 DA01 DB04 DB07 DC07 DC35 DC50 DG14 HA01 HA06 HA07 HC03 HC12 HC13 HC17 HC22 HC46 HC52 HC52 HC52 HC52 HC52 HC52 HC64 HC67 HC71 HC73 JA24 MA15 QD06 RA14 5G301 CA30 CD01 5H026 AA06 CX05 EE18 HH06 5H029 AJ00 AJ 04 AJ14 AJ15 AK03 AL06 AM02 AM03 AM16 HJ02 HJ20 5H050 AA00 AA10 AA19 AA20 BA18 CA08 CB07 DA11 EA23 HA02 HA17

Claims (7)

[Claims] [Claim 1] The following formula (1) And a repeating structural unit represented by the following formula (2): A crosslinked product obtained by polymerizing a polycarbonate compound containing a repeating structural unit represented by the following formula (in the above formulas (1) and (2), R ₁ has 2 to 2 carbon atoms which may be substituted by a hetero atom) A divalent group of 10,
R ₂ is a branched or cyclic divalent group having 2 to 10 carbon atoms which may be substituted by a hetero atom, and m and n are positive integers). 2. The ratio (m: n) of the repeating structural unit represented by the formula (1) to the repeating structural unit represented by the formula (2) is 0.5: 99.5 to 99.5. The crosslinked product according to claim 1, wherein the range is from 0.5 to 0.5. 3. The ratio (m: n) of the repeating structural unit represented by the formula (1) to the repeating structural unit represented by the formula (2) is in the range of 5:95 to 95: 5. The crosslinked product according to claim 1. 4. The method according to claim 1, wherein R _{1 in the} formula (1) is a linear hexylene group, and R _{2 in the} formula (2) is a methylpentylene group. The crosslinked product according to the above. 5. The crosslinked product according to claim 1, wherein the polycarbonate compound contains at least a hydroxyl group or a group having an ethylenically unsaturated bond, and is produced by radical polymerization or polycondensation. 6. The composition further comprises a dopant and a polyalkylene oxide having a polymerizable functional group, and has an ionic conductivity of 10 ⁻⁵ Scm ⁻¹ to 10 ⁻² Scm ⁻¹ .
The crosslinked product according to claim 5. 7. The method according to claim 1, which is used as a binder for an electrode.
6. The crosslinked body according to any one of items 5 to 5.