JPH1053626A - High-dielectric vinyl copolymer and ionically conductive resin composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject copolymer which manifests excellent ionic conductivity with improved resistance to polar solvent and can be used as a solid electrolyte by radical-polymerizing a specific cyanoethylated monomer and an epoxy group-bearing monomer. SOLUTION: This copolymer comprises the recurring units of formula I [R1 is H, methyl; R2 is the residue after removing the whole OH groups from a (1+a) polyhydroxy compound; a is an integer of 1 or more] and the recurring units of formula II (R3 is H, methyl; R4 is a single bond, carbonyl or an alkylene) at a molar ratio of 10/1-1/1 in which these recurring units are linearly and randomly arranged and its molecular weight is about 1,000-100,000. The objective copolymer is obtained by effecting radical copolymerization of a cyanoethylated monomer of formula III and an epoxy group-bearing monomer at a molar ratio of 10/1-1/1 in the presence of a polymerization initiator whereby the objective polymer acquires high dielectric constant and high ionic conductivity and can improve its resistance to polar solvents.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a highly dielectric vinyl copolymer and an ion-conductive resin composition containing the copolymer, and more particularly, to a radical polymerized vinyl polymer chain as a main chain and a side chain containing a cyanoethyl group and an epoxy resin. A high dielectric constant vinyl copolymer containing both a group and an ordinary amine curing agent for epoxy resin and / or a specific cyanoethylated amine compound as a curing agent. In addition to the ionic conductivity, especially improved the resistance to polar solvents, mainly as a binder resin for electrodes of lithium ion secondary batteries,
And a binder resin for organic dispersion type electroluminescence (EL); a dielectric material (dielectric film) for a capacitor; as a solid electrolyte used in polymer batteries, electrochromic devices, electrolytic capacitors, electric double layer capacitors, lithium ion secondary batteries, etc. The present invention relates to a useful ionic conductive resin composition, the above high dielectric vinyl copolymer, and a method for producing the same.

[0002]

BACKGROUND OF THE INVENTION Binder resins for electrodes of lithium ion secondary batteries and the above-mentioned solid electrolytes and the like need to have excellent ionic conductivity. In such a case, resistance to a polar solvent (such as ethylene carbonate or propylene carbonate) which is a main component of the electrolytic solution, current collection of the electrode, and high adhesion to a supporting metal surface are required. By the way, as a polymer material for obtaining good ionic conductivity, which is the most important property, for example, cyanoethylated cellulose, cyanoethylated polyvinyl alcohol, and cyanoethylated pullulan having a high dielectric constant and having a cyanoethyl group having a large dipole efficiency (see, for example, Acrylate / methacrylate polymers of partially cyanoethylated polyhydroxyl compounds (JP-A-5-140234, JP-A-6-336506, and Japanese Patent Application No. 6-280).
No. 337); polymers mainly composed of polyoxyethylene chains have been studied.

[0003] However, although these materials have an effect on ionic conductivity, the above-mentioned electrolyte has little resistance to polar solvents (dissolves when marked) (dissolution can be prevented by crosslinking between polymers, (Swelling and softening is remarkable) and cannot be used. For this reason, fluororesins (such as polytetrafluoroethylene) and polyvinylidene fluoride are used, but there is a problem with ionic conductivity, that is,
There are problems such as high internal resistance of the battery, heat generation during charge / discharge, and reduction in efficiency during discharge at a high discharge rate (when used at a large current, the extraction rate of charged power decreases).

[0004] These problems are small when used under a relatively small current, such as a portable personal computer, a mobile phone, and a video movie, but are serious when used in an application requiring a large current, such as an electric vehicle. To solve such problems,
JP-A-6-131911, JP-A-6-184130, and JP-A-6-267329 disclose a material obtained by introducing a cyanoethyl group into a thermosetting epoxy resin resistant to the polar solvent to impart a dielectric constant. See)
It has a reasonable effect. The electrolyte solution should not be dissolved or softened by a polar solvent, but a slight swelling in a range where a decrease in mechanical strength or adhesion to a supporting metal foil or the like is allowed increases ionic conductivity. It is sometimes preferable. However, conventionally used fluororesins and polyvinylidene fluoride do not swell at all and are not preferred from the viewpoint of ionic conductivity.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies to provide a cyanoethylated polymer material having excellent ionic conductivity and improved polar solvent resistance, and found that a specific cyanoethylated polymer material was obtained. A vinyl copolymer obtained by radical polymerization of a monomer and an epoxy group-containing monomer and having a vinyl polymerization main chain and having both a cyanoethyl group and an epoxy group introduced into its side chain has a desired high dielectric constant and high ionic conductivity. If the copolymer is cross-linked or cured with an amine-based curing agent for an epoxy resin or the like, the intended polar solvent resistance can be improved. If a cyanoethylated epoxy compound is used in combination, the polar solvent resistance is greatly improved, and the above-mentioned swelling and mechanical strength and adhesion to the supporting metal foil are achieved. It found that can adjust to a wide range and and subtle degrees, thereby completing the present invention.

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

Embedded image Wherein R ₁ is H or CH ₃ ; R ₂ is a residue obtained by removing all OH groups from a (1 + a) -valent polyhydroxyl compound; and a is an integer of 1 or more. A] and the formula:

Embedded image Wherein R ₃ is H or CH ₃ ; and R ₄ is a single bond or a carbonyl group, an alkylene group or a carboxy mono-polyoxyalkylene group. A high dielectric vinyl copolymer having a molecular weight of about 1,000 to 100,000, which is linearly and irregularly arranged at a molar ratio of 1: 1; (2) the high dielectric vinyl copolymer, and an amine curing agent for an epoxy resin as a curing agent; And / or an amine compound having two or more active hydrogens of an amino group (—NH ₂ ) and / or an imino group (—NH—) in one molecule, the active hydrogen (but not more than A cyanoethyl group through a reaction of (meth) acryloyl group or glycidyl group with at least one active hydrogen of all active hydrogens, or directly Ion conductive resin composition characterized in that it consists of cyanoethylated amine compound consists of introduced; and (3):

Embedded image (Wherein R ₁ , R ₂ and a are as defined above), and a compound represented by the formula:

Embedded image (Wherein R ₃ and R ₄ have the same meanings as described above) in a molar ratio of 10: 1 to 1: 1 with a polymerization initiator and, if necessary, a chain transfer. A process for producing the above-mentioned highly dielectric vinyl copolymer, which is subjected to radical polymerization in the presence of an agent. In addition, in this specification, a (meth) acryloyl group means an acryloyl group or a methacryloyl group.

The cyanoethylated monomer [I] used in the present invention can be produced by the following procedure. That is, (1+) of the formula: R ₂ — (OH) _{1 + a} [III] (wherein R ₂ and a are as defined above)
a) 1 mol of the polyhydroxyl compound [III]
i) 1 mol of acrylic acid or methacrylic acid or their acid chlorides, usually in the presence of an acid catalyst, from 50 to 1
After the esterification reaction at 50 ° C. × 4 to 48 hours, a mole of acrylonitrile is usually subjected to a Michael addition reaction at 20 to 100 ° C. × 1 to 48 hours in the presence of an acid or alkali catalyst, Or ii) after a Michael addition reaction of a mole of acrylonitrile under the same conditions,
One mole of acrylic acid or methacrylic acid or their acid chlorides may be esterified under the same conditions.

The polyhydroxyl compound [III] is not particularly limited as long as it has two or more OH groups in one molecule. Examples thereof include ethylene glycol, propylene glycol, tetramethylene glycol and neopentyl glycol. Aliphatic low molecular weight polyhydroxyl compounds such as glycerin, trimethylolpropane, hexanetriol, pentaerythritol, xylitol, inositol, mannitol, sorbitol;
Polyphenols and polyphenols such as bisphenol A, bisphenol F, resorcin, hydroquinone, pyrogallol, and novolak phenol; glucose, fructose, sucrose, polyglycerin, polyoxyethylene glycol, polyoxypropylene glycol; low molecular weight polyhydroxyl ethylene Oxide or propylene oxide addition polymer; a compound having an OH group at a molecular terminal obtained by reacting a polyhydroxy compound with an overequivalent amount of a polybasic acid; polyvinyl alcohol; and the like, and an aliphatic low molecular weight polyhydroxyl compound is particularly preferable.

The epoxy group-containing monomer [II] used in the present invention includes, for example, glycidyl acrylate,
Glycidyl methacrylate, allyl glycidyl ether; ethylene glycol, diethylene glycol, triethylene glycol, polyoxyethylene glycol,
Propylene glycol, acrylate or methacrylate of monoglycidyl ether of mono-polyoxyalkylene glycol such as polyoxypropylene glycol; acrylate or methacrylate of monoglycidyl ether of alkanediol such as propanediol, butanediol, and hexanediol; Glycidyl methacrylate; acrylates or methacrylates of monoglycidyl ethers of mono to lower polyoxyethylene glycols such as ethylene glycol, diethylene glycol and triethylene glycol are preferred.

The high dielectric vinyl copolymer according to the present invention comprises the cyanoethylated monomer [I] and the epoxy group-containing monomer [II] in a ratio of 10: 1 to 1: 1, preferably 8: 1.
It is produced by subjecting it to solution polymerization, photopolymerization or the like at a molar ratio of 1-2: 1 according to a usual radical polymerization method, for example, in the presence of a polymerization initiator and, if necessary, a chain transfer agent. In the molar ratio of both monomers [I] and [II], when the ratio of the cyanoethylated monomer [I] is larger than the above range, the dielectric constant and ionic conductivity increase, but on the other hand, the crosslink density decreases, so the polarity If the resistance to the solvent is easily reduced, and if the amount is less than the above range, the resistance to the polar solvent increases, but the dielectric constant and the ionic conductivity decrease.

The above cyanoethylated monomer [I]
In addition to and the epoxy group-containing monomer (II), a copolymerization monomer may be used in combination as needed.Specifically,
For example, acrylates (methyl acrylate, ethyl acrylate, propyl acrylate, 2,2,3,
3-tetrafluoropropyl acrylate, n-butyl acrylate, isobutyl acrylate, amyl acrylate, octafluoropentyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, n-octyl acrylate, etc., methacrylic acid esters (methyl methacrylate, ethyl methacrylate) , N-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, tridecyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, octafluoropentyl methacrylate, etc.) ,Nothing Maleic acid, 4-methacryloxyethyl trimellitic acid anhydride, acid phosphoxyethyl methacrylate, styrene or its derivative (alpha-methyl styrene, etc. chloromethylstyrene),
Fumaric acid diesters (diethyl fumarate, dibutyl fumarate, dipropyl fumarate, etc.), vinyl halides (vinyl chloride, vinylidene chloride, ethylene fluoride, vinylidene fluoride, vinylene fluoride, etc.), vinyl acetate,
Examples thereof include vinyl propionate, vinyl versatate (manufactured by Shell Chemical Industries, Vova), acrylonitrile, acrylamide, N-methylolacrylamide, vinylpyridine, vinylpyrrolidone, and butadiene. These comonomers are usually combined with the cyanoethylated monomer [I] in an amount that does not degrade the high dielectric properties according to the adjustment of the mechanical strength, glass transition point (Tg), and other various physical properties of the copolymer. Epoxy group-containing monomer [II]
May be selected within a range of 100 parts or less, preferably 50 parts or less, based on 100 parts (total parts by weight, hereinafter the same).

Examples of the polymerization initiator include peroxides (ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxyester, peroxydicarbonate, etc.) and azo [ 2,2'-azobis
(4-methoxy-2,4-dimethylvaleronitrile), 2,
2'-azobis (2-cyclopropylpropionitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 2,2'-
Azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 1-[(1-
Cyano-1-methylethyl) azo] formamide, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile and the like. The amount used is usually 0.01 to 5 parts, preferably 0.1 part, per 100 parts of the total amount of the cyanoethylated monomer [I] and the epoxy group-containing monomer [II].
It may be selected within the range of ~ 1 part. If the amount used is larger than necessary, the molecular weight of the high dielectric vinyl copolymer may be reduced, or may remain as an impurity and adversely affect the electrical characteristics and the like.

The above chain transfer agent controls the molecular weight,
It is used to prevent gelation during polymerization, and specific examples thereof include generally used mercaptans (for example, aliphatic and aromatic compounds such as n-butyl mercaptan, octyl mercaptan, lauryl mercaptan, benzyl mercaptan, and cyclohexyl mercaptan). Group, alicyclic group). The amount used is usually 1 in total of the cyanoethylated monomer [I] and the epoxy group-containing monomer [II].
The amount may be selected within the range of 5 parts or less, preferably 1 part or less with respect to 00 parts.

The high-dielectric vinyl copolymer produced in this manner contains the repeating unit [A] (containing a cyanoethyl group in the side chain) and the repeating unit [B] (containing an epoxy group in the side chain) of 10: 1-1: 1 (preferably 8: 1 to 2:
It is of a structure that is linearly and irregularly arranged in the molar ratio of 1),
Molecular weight of about 1000 to 100,000 (preferably about 10
(0000 to 50,000), and generally shows a solid or lump at room temperature.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The ionic conductive resin composition according to the present invention is obtained by blending a general amine-based curing agent for epoxy resin and / or a cyanoethylated amine compound as a curing agent with the above-mentioned highly dielectric vinyl-based copolymer. Consists of a system. Here, the compounding amount of the curing agent (the total amount when the two groups of curing agents are used in combination) is usually the epoxy equivalent of the high dielectric vinyl copolymer and the amino group and / or imino group of the curing agent. What is necessary is just to select so as to be around the reaction equivalent calculated from the number of active hydrogens, and such a compounding amount is often allowed within about ± 10 to 20% of the above reaction equivalent. If the value falls outside the upper and lower limits of the allowable range, curing will be incomplete, mechanical properties will not be exhibited, and resistance to polar solvents will tend to be poor. As the amine-based curing agent for the epoxy resin, 1
A compound having two or more active hydrogens of an amino group (—NH ₂ ) and / or an imino group (—NH—) in a molecule (hereinafter referred to as an amine compound), for example, ethylamine, n-propylamine, n Aliphatic monoamines such as butylamine, isobutylamine, monoethanolamine and diethylaminopropylamine; ethylenediamine, 1,3-propylenediamine, 1,6-hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine And aliphatic polyamines such as polyethyleneimine;
Alicyclic mono- to polyamines such as cyclohexylamine, menthanediamine, isophoronediamine; benzylamine, m-xylenediamine, m-phenylenediamine,
o-toluidine, 4,4′-diaminodiphenylmethane,
Aromatic mono-, such as 4,4'-diaminodiphenyl sulfone
Polyamine; terminal O of polyoxyalkylene glycol
Polyoxyalkylene mono- or diamines in which the H group has been converted to NH ₂ groups; other compounds in which alkylene oxides such as ethylene oxide and propylene oxide have been partially added to these amine compounds; Examples include a compound obtained by reacting a compound having a group (such as an epoxy group, a carboxyl group, or a vinyl group) that reacts with a group in an excess amount, and an aliphatic polyamine is particularly preferable.

The above-mentioned cyanoethylated amine compound is characterized in that the active hydrogen (excluding at least one active hydrogen of all active hydrogens) and (meth) acryloyl are added to the amino group and / or imino group of the amine compound. Or the direct introduction of a cyanoethyl group via a reaction with a glycidyl group or a glycidyl group, specifically from the amine compound and acrylonitrile, or from an amine compound and a compound of the formula: R ₅ — (OH) _{1 + f} [IV] (wherein R ₅ is a residue obtained by removing all OH groups from a (1 + f) -valent polyhydroxyl compound; and f is an integer of 1 or more) [IV], (meth) prepared from acrylic acid or epichlorohydrin and acrylonitrile, and the formula: A- (B) _c in the formulas, a is involved in the cyanoethyl group introduced from an amine compound Residues were removed that active hydrogen; B is _{-R 6 'O-R 5 -} (OCH 2 CH 2 CN) f or -CH ₂ CH ₂ CN (where, R _6' is

Embedded image R ₅ and f are as defined above); and c is an integer of 1 or more. The (meth) acrylic acid means acrylic acid or methacrylic acid.

The cyanoethylated amine compound can be produced according to the following procedure. i) First, one mole of the above (1 + f) -valent polyhydroxyl compound [IV] is reacted with one mole of (meth) acrylic acid or epichlorohydrin, and then f mole of acrylonitrile is subjected to a Michael addition reaction, or A mole of acrylonitrile is subjected to a Michael addition reaction followed by a reaction of one mole of (meth) acrylic acid or epichlorohydrin to obtain the formula: R ₆ O—R ₅ — (OCH ₂ CH ₂ CN) _f [V] (wherein , R ₆

Embedded image R ₅ and f are as defined above) to obtain an amine-reactive cyanoethyl compound [V], and then reacting the amine-reactive cyanoethyl compound [V] with the amino group and / or imino group of the amine compound. With the active hydrogen (excluding at least one active hydrogen of all the active hydrogens) to introduce a cyanoethyl group. ii) Acrylonitrile is directly reacted with active hydrogen (excluding at least one active hydrogen among all active hydrogens) of the amine compound to introduce a cyanoethyl group.

Specific examples of the polyhydroxyl compound [IV] may be selected from the polyhydroxyl compounds [III] used in the production of the cyanoethylated monomer [I] described above. The above-mentioned reaction (i) of (meth) acrylic acid or epichlorohydrin is usually carried out in the presence of an acid or alkali catalyst under the conditions of 50 to 150 ° C. for 4 to 48 hours or room temperature to 150 ° C. for 4 to 48 hours. It can be carried out by reaction or glycidyl etherification (dehydrochlorination reaction). The Michael addition reaction of acrylonitrile of the above (i) is usually carried out in the presence of an acid catalyst, an alkali catalyst, a quaternary ammonium base or the like in the range of 20 to 10
Cyanoethylation can be carried out under the conditions of 0 ° C. × 1 to 48 hours. The reaction of the amine-reactive cyanoethyl compound of the above (i) is usually carried out at room temperature to 120 ° C. × 1.
It can be performed under the conditions of ~ 48 hours. The reaction of acrylonitrile of the above (ii) is usually carried out at room temperature to 120 ° C. × 1.
It can be performed under the condition of 48 hours.

After compounding such a curing agent, by cross-linking or curing, a highly dielectric vinyl copolymer having a high dielectric constant and high ionic conductivity can be imparted with polar solvent resistance. By adding an epoxy resin and / or a cyanoethylated epoxy compound, it is possible to ensure a significant improvement in polar solvent resistance. The amount of addition (the total amount when the two groups of addition substances are used in combination) is usually 900 parts or less, preferably 10 to 500 parts per 100 parts of the high dielectric vinyl copolymer. . If it exceeds 900 parts, although it depends on the whole composition, it is generally too hard and brittle, and when it is used as an electrode binder for a lithium ion secondary battery, cracks and peeling of the electrode film tend to occur.

As the epoxy resin, 2 per molecule is used.
There is no particular limitation as long as the compound has two or more epoxy groups, and examples thereof include bisphenol A, bisphenol F, resorcin, catechol, hydroquinone,
Glycidyl ethers of polyphenols and polyphenols such as phenols such as pyrogallol and condensates of cresol and formaldehyde; ethylene glycol, propylene glycol, glycerin, pentaerythritol,
Glycidyl ethers of polyhydroxyl compounds such as trimethylolpropane; ethylenediamine, 1,3-
Glycidylated products of amines such as propanediamine and 4,4'-diaminodiphenylmethane; phenols, polyphenols, polyhydroxyl compounds, and glycidyl etherified products of OH terminal at the end by adding ethylene oxide or propylene oxide to these amines. And those obtained by modifying these epoxy resins with another functional group or atomic group.

The above cyanoethylated epoxy compound is
formula:

Embedded image (Wherein, R is a residue obtained by removing all OH groups from a (m + n) -valent polyhydroxyl compound; m is 1 or 2; and n is an integer of 1 or more). May be carried out according to the above-mentioned production procedure for the amine-reactive cyanoethyl compound [V] using epichlorohydrin.

Further, the preferred specific composition of the composition of the present invention is as follows. For example, when it is actually used as a binder resin for an electrode of a lithium ion secondary battery, the positive electrode usually contains lithium cobaltate and lithium manganate as active materials. Since a lithium compound such as lithium nickelate is used, these active material particles and, if necessary, a solvent for facilitating the coating, a fluidity adjusting material, a film-forming property improving agent for uniforming a coated film, and an active Acetylene black, graphite and the like for further improving the conductivity between the material particles are blended, usually applied to an aluminum foil for a positive electrode, and then subjected to thermosetting at the above-mentioned temperature. Also, in the negative electrode, carbon powder and graphite are usually used frequently as the active material. Therefore, these active materials and various additive materials used in the case of the positive electrode are compounded as necessary, and the same as in the case of the copper foil for the negative electrode. And then subjected to a crosslinking or curing treatment.

On the other hand, solid electrolytes for lithium ion secondary batteries have been developed as sheet batteries.
Compared with a liquid electrolyte, there is an advantage that a separator is unnecessary, safety is high, a laminated structure is easy, and a high-voltage laminated battery can be easily produced. To apply the composition of the present invention to such a solid electrolyte, lithium salts such as lithium perchlorate, lithium tetrafluoroborate, and lithium trifluoromethanesulfonate are blended, and ethylene carbonate such as ethylene carbonate and propylene carbonate if necessary. By adding a polar solvent, crosslinking or curing, the composition of the present invention can be a solid or gel-like semi-solid while containing these polar solvents,
It is also very suitable for a solid electrolyte of a lithium ion secondary battery.

[0024]

Next, the present invention will be described more specifically with reference to examples and comparative examples. Example 1 (1) Production of cyanoethylated monomer 204 g of 2% NaOH aqueous solution, pentaerythritol 6
8.08 g (0.5 mol) and 136 ml of methylene chloride
(181.7 g) was placed in a three-necked flask, and 84.9 g (1.6 mol) of acrylonitrile was added dropwise over 4 hours while vigorously stirring and refluxing (internal temperature 35 to 40 ° C.). Thereafter, the mixture is further stirred and reacted at the same temperature for 3 hours.
After the reaction, if left standing, the reaction solution separates into two layers (upper layer:
Aqueous layer, lower layer: methylene chloride layer), the aqueous layer was removed, and the methylene chloride layer was thoroughly washed with water until the alkalinity disappeared. Then, dehydration and methylene chloride were distilled off with a rotary pump, and tricyanoethylated pentane was removed. Obtain erythritol. Then, 52 g of methacrylic acid was added to 59 g (0.2 mol) of the tricyanoethylated pentaerythritol.
(0.6 mol), p-toluenesulfonic acid (3.2 g), hydroquinone (0.03 g) as a polymerization inhibitor and benzene (200 g) were added, and the mixture was reacted under reflux for 8 hours while removing generated water, followed by excess methacrylic acid. Wash off the acid with water,
A cyanoethylated monomer (tricyanoethylated pentaerythritol methacrylate) is obtained. The presence of -CN was confirmed in the infrared absorption spectrum of the cyanoethylated monomer, and the purity was confirmed to be 96.3% by GC analysis.

(2) Production of High Dielectric Vinyl Copolymer In a four-neck flask, 181.7 g (0.5 mol) of the cyanoethylated monomer of the above (1), 14.2 g (0.1 mol) of glycidyl methacrylate, methyl ethyl ketone 210.
1 g, 0.2 g of 2,2′-azobisisobutyronitrile and 0.1 g of lauryl mercaptan are charged, and polymerization is carried out at 75 to 80 ° C. for 4 hours under nitrogen gas introduction. Next, 500 g of methanol and 50 g of ion-exchanged water are added to precipitate a polymer component, and a liquid component is removed. The remaining precipitated polymer is washed several times with a mixed solution of methanol / ion-exchanged water (50/50 weight ratio). Thereafter, drying under reduced pressure is performed to obtain a high dielectric vinyl copolymer (hereinafter, referred to as copolymer A). The copolymer A was a white solid mass, and the presence of -CN and epoxy groups was confirmed by an infrared absorption spectrum,
Epoxy equivalent by hydrochloric acid-dioxane method is 1960,
When dissolved in THF and subjected to GPC analysis, the number average molecular weight in terms of polystyrene was about 9200.

Example 2 Preparation of High Dielectric Vinyl Copolymer: Example 1
In (2), 181.7 g of cyanoethylated monomer
(0.5 mol), 56.9 g of glycidyl methacrylate
(0.4 mol), 239 g of methyl ethyl ketone, 2,2 ′
-A high dielectric vinyl copolymer (hereinafter referred to as copolymer B) is produced in the same manner except that 0.2 g of azobisisobutyronitrile and 0.4 g of lauryl mercaptan are used. Similarly, according to the infrared absorption spectrum, -C
The presence of N and an epoxy group was confirmed, and the epoxy equivalent by the hydrochloric acid-dioxane method was 590.
As a result of C analysis, the number average molecular weight in terms of polystyrene was about 3,000.

Examples 3 to 7 Preparation of ionic conductive resin composition: (1) Production of cyanoethylated epoxy compound A four-necked flask was charged with 92.1 g (1 mol) of glycerin and 1.32 g of NaOH, and heated at 65 ° C. Heat and stir.
Next, 185.2 g (2 mol) of epichlorohydrin are added dropwise. After completion of the dropwise addition, the mixture is heated to 90 ° C. (5 hours). Thereafter, the mixture is stirred at room temperature overnight, heated again to 120 to 130 ° C., and stirred (2 to 3 hours). After cooling to room temperature, about 100 ml of toluene was added and 24.7 g of KOH powder was added under cooling.
(0.44 mol) are added. After heating to 30 ° C., 106.1 g (2 mol, excess) of acrylonitrile was added dropwise,
Stir overnight, extract with methylene chloride, wash with water, add magnesium sulfate and dry, distill off toluene with a rotary pump,
A cyanoethylated epoxy compound is obtained. The compound is a colorless and transparent viscous liquid, and the infrared absorption spectrum
The absorption of N and an epoxy group was confirmed, and the epoxy equivalent by the hydrochloric acid-dioxane method was 165.

(2) Production of cyanoethylated amine compound 37.8 g (0.2 mol) of tetraethylenepentamine was placed in a three-necked flask and stirred at room temperature while purging with nitrogen gas. ) Is gradually added and reacted. The first reaction is slightly exothermic and should be carried out under cooling if necessary. After the heat generation stops, the temperature is gradually increased, and the reaction is continued for 6 hours while continuing purging with nitrogen gas.
A cyanoethylated amine compound is obtained. The compound was a pale yellow viscous liquid, and disappearance of the double bond was confirmed by infrared absorption spectrum.

(3) Ion conductive resin composition and its performance evaluation An ion conductive resin composition is prepared by blending the components shown in Table 1 below. In the components, copolymers A and B were each used as a 50% by weight solution of N-methylpyrrolidone, and LiBF ₄ was used as a 10% by weight solution of ethylene glycol monoethyl ether. It corresponds to the solid content in the medium. Performance evaluation Immediately after compounding the ionic conductive resin composition, 60 mm ×
It is uniformly applied on a 100 mm × 1 mm aluminum plate using a 100 micron bar coater, dried and cured in a hot air oven at 120 ° C. for 60 minutes, aluminum is deposited as an upper electrode, and at 20 ° C. using an LCZ meter at 1 KHz. The dielectric constant and conductivity were measured. The resistance to polar solvents was determined by placing the cured test pieces in propylene carbonate at room temperature.
After immersion for 4 hours, the degree of swelling was observed and evaluated. These results are also shown in Table 1.

[0030]

[Table 1] In Table 1, Note 1: Bisphenol A-epichlorohydrin type liquid epoxy resin manufactured by Shell Chemical Company, "Epicoat 828",
Epoxy equivalent 192

Comparative Examples 1 and 2 (1) Production of Highly Dielectric Vinyl Homopolymer In Example 1 / (2), glycidyl methacrylate was not copolymerized, and a cyanoethylated monomer (tricyanoethylated pentaerythritol methacrylate) alone was used. To produce a homopolymer of Specifically, 218 g (0.6 mol) of the cyanoethylated monomer, 210 g of methyl ethyl ketone, and 0.2 g of 2,2′-azobisisobutyronitrile were used.
2 g and 0.1 g of lauryl mercaptan are charged and produced in the same manner as in Example 1 / (2). The obtained homopolymer was a white solid mass, and the presence of -CN was confirmed by an infrared absorption spectrum (the epoxy group was not confirmed). The homopolymer was dissolved in THF and subjected to GPC analysis. The average molecular weight was 8,600.

(2) Ion-conductive resin composition and evaluation of its performance An ionic-conductive resin composition is prepared by blending components of the number shown in Table 2 below. In the components, the homopolymer and LiBF ₄ were each contained in the same concentration as in the Example.
-Methylpyrrolidone solution and ethylene glycol monoethyl ether solution, polyvinylidene fluoride is a commercially available product in a 15% by weight solution of N-methylpyrrolidone, and the number of parts in Table 2 indicates the solid content in the solution. Is equivalent to The dielectric constant and the electrical conductivity were measured in the same manner as in the examples, and the resistance to polar solvents was evaluated. The results are also shown in Table 2.

[0033]

[Table 2]

[0034]

As is clear from the results of Tables 1 and 2, Examples 3 to 7 all have good ionic conductivity and polar solvent resistance, while Comparative Example 1 has good ion conductivity and polar solvent resistance. Although it exhibits excellent ionic conductivity, the polar solvent resistance is extremely poor. In Comparative Example 2, the polar solvent resistance is good, but the ionic conductivity is extremely low.

Continued on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical indication location C09J 151/06 C09J 151/06 H01M 4/62 H01M 4/62 Z

Claims (5)

[Claims] 1. The formula: embedded image Wherein R ₁ is H or CH ₃ ; R ₂ is a residue obtained by removing all OH groups from a (1 + a) -valent polyhydroxyl compound; and a is an integer of 1 or more. A] and the formula: Wherein R ₃ is H or CH ₃ ; and R ₄ is a single bond or a carbonyl group, an alkylene group or a carboxy mono-polyoxyalkylene group. A highly dielectric vinyl copolymer having a molecular weight of about 1,000 to 100,000, which is linearly and irregularly arranged at a molar ratio of 1: 1. 2. The highly dielectric vinyl copolymer according to claim 1, and an amine curing agent for an epoxy resin as a curing agent and / or an amino group (—NH ₂ ) and / or an imino group (−) in one molecule. NH-) with respect to the amino group and / or imino group of the amine compound having two or more active hydrogens, the active hydrogens (excluding at least one active hydrogen of all active hydrogens) and (meth) An ion conductive resin composition comprising a cyanoethylated amine compound obtained by introducing a cyanoethyl group through a reaction with an acryloyl group or a glycidyl group or directly. 3. An epoxy resin and / or a compound of the formula: (Wherein, R is a residue obtained by removing all OH groups from a (m + n) -valent polyhydroxyl compound; m is 1 or 2; and n is an integer of 1 or more). The ionic conductive resin composition according to claim 2. 4. An epoxy resin and / or a cyanoethylated epoxy compound in an amount of not more than 900 parts by weight based on 100 parts by weight of a high dielectric vinyl copolymer.
The ionic conductive resin composition according to the above. 5. The formula: (Wherein R ₁ , R ₂ and a have the same meanings as in claim 1) and a cyanoethylated monomer represented by the formula: (Wherein R ₃ and R ₄ are as defined in claim 1).
2. The process for producing a highly dielectric vinyl copolymer according to claim 1, wherein the polymerization is carried out in a radical polymerization at a molar ratio of 1: 1 in the presence of a polymerization initiator and, if necessary, a chain transfer agent.