WO2004081068A1

WO2004081068A1 - Novel graft copolymer and process for producing the same

Info

Publication number: WO2004081068A1
Application number: PCT/JP2004/003055
Authority: WO
Inventors: Hiroo Muramoto; Takeshi Niitani
Original assignee: Nippon Soda Co. Ltd.
Priority date: 2003-03-14
Filing date: 2004-03-10
Publication date: 2004-09-23
Also published as: JPWO2004081068A1

Abstract

A novel graft copolymer which has polyether chains in branches and is usable as a base for solid electrolytes having high ionic conductivity; and a solid electrolyte comprising the graft copolymer and an electrolyte salt. The copolymer is characterized by having repeating units represented by the formula (I): (I) [wherein R2 represents a functional group capable of having an active halogen atom at an end and X represents the formula (II)] and repeating units comprising a nonpolar moiety.

Description

Specification

Novel graft copolymer and method for producing the same

Technical field:

The present invention relates to a polymer copolymer suitable for a polymer solid electrolyte suitable as a device material for electrochemical devices such as a battery, a capacitor, a sensor, a capacitor, an EC device, and a photoelectric conversion device.

Conventional technology:

As a polymer solid electrolyte, a composition is known from a polymer obtained by graft polymerization of a polyether chain and an electrolyte salt. For example, after a random copolymer is obtained from chloromethylstyrene and methyl methacrylate by a radical polymerization method, methoxy polyethylene glycol monomethacrylate is obtained by a living radical polymerization method using the random copolymer as an initiator and a copper complex as a catalyst. An intrinsic polymer solid electrolyte having a matrix of a random daraft copolymer obtained by graft copolymerization of a polyethylene oxide component with a polyethylene oxide component of around 40% by weight and an ionic conductivity of 10 · ⁴ S / It is on the order of cm, and its Young's modulus is said to be several MPa at room temperature. (See Polymer preprints, Japan Vol 51, No. 11, 2742 (2002))

However, as described later, the value of the ionic conductivity of the polymer solid electrolyte film was poor in reproducibility and could not be said to be sufficiently satisfactory. When the above film was observed with an electron microscope, no phase-separated structure was observed and the film had a uniform structure. It is known that the ionic conductivity of a polymer solid electrolyte having a polymer having a uniform structure as a matrix depends on the content of a polyethylene oxide component. is 4 about 0箪量% content, it ion conductivity at a content of the degree is 1 0- ⁴ S / cm order was expected that normally is not considered.

DISCLOSURE OF THE INVENTION:

The present invention provides a novel graft copolymer serving as a base for a solid electrolyte having high ionic conductivity having a polyether chain in a graft chain, and a solid electrolyte comprising the graft copolymer and an electrolyte salt. The purpose is to:

The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that In a graft copolymer having a polyethylene glycol mono (meth) acrylate unit as a graft chain, a non-polar and rigid repeating unit such as polystyrene is bonded as a block chain or the like to form a graft copolymer. It has been found that a separation structure is exhibited, and as a result, it is possible to achieve both high ionic conductivity and excellent membrane physical properties.Moreover, by using two kinds of living radical polymerization methods together, such a graft copolymer can be obtained. It has been confirmed that it can be manufactured, and the present invention has been completed. That is, the present invention basically includes the following invention units (1) to (24).

(1) Equation (I)

(In the formula, represents a hydrogen atom or a C 1 to C 10 hydrocarbon group which may have a substituent, R ₂ represents a functional group capable of having an active halogen atom, and R ₃ represents , A halogen atom or an organic group, and X is a group represented by the formula (II)

(In the formula, R ₄ represents a hydrogen atom or a C 1 to (: 10 hydrocarbon group which may have a substituent, and R ₅₁ and R ₅₂ each independently represent a hydrogen atom, or It represents C 1～C4 alkyl group, R ₆ represents a hydrogen atom, a hydrocarbon group, Ashiru group, a silyl group, a phosphoryl group, a hydrocarbon phosphoryl group or a hydrocarbon sulfonyl Le group,, d is 1 to 1,000 When d is 2 or more, R ₄ , R ₅₁ , R ₅₂ , R ₆ , and e may be the same or different, and e is It represents an integer of 1-100, when e is 2 or more, R ₅ i each other, and R ₅₂ each other, repeatedly expressed by may be the same or different.) Represents a polymer chain having a repeating unit, a represents an integer of any of 1 to 3, when a is 2 or more, R ₂ and X may be the same or different, b represents 1 or 2; b represents 2; X may be the same or different; c represents 0 or any integer from 1 to (4-1a); c represents In the case of two or more, R ₃ may be the same or different. A copolymer having a repeating unit represented by the formula: and a repeating unit comprising a nonpolar moiety.

(2) In the formula (I), R ₂ is the formula (IV)

(Wherein, R ₉ and R ₁₀ each independently represent a hydrogen atom, a halogen atom, or a C 1 -C 10 hydrocarbon group which may have a substituent, and b in the formula (I) represents (2 represents a bond to X.) The copolymer according to (1), which is a functional group represented by the following formula:

(3) The copolymer according to (1) or (2), wherein the degree of polymerization of the repeating unit represented by the formula (I) is 3 or more.

(4) The copolymer according to any one of (1) to (3), wherein the degree of polymerization of the repeating unit comprising the nonpolar moiety is 5 or more.

(5) In the polymer chain having the repeating unit represented by the formula (II), the degree of polymerization of the repeating unit represented by the formula (II) is 5 or more, (1) to (4). ) The copolymer according to any one of the above.

(6) The copolymer according to any one of (1) to (5), wherein the repeating unit represented by the formula (I) and the repeating unit comprising a nonpolar moiety are copolymerized in a block. .

(7) The block chains (B) and (C) having a repeating unit composed of a nonpolar moiety which may be the same as or different from the block chain (A) having a repeating unit represented by the formula (I) are represented by ( The copolymer according to any one of (1) to (6), which has an arrangement in the order of B), (A) and (C).

(8) The arrangement of (B), (A), and (C) is (B) — (A) one (C) combined sequence The copolymer according to (7), wherein

(9) With respect to the total number of moles of the repeating unit represented by the formula (I), the repeating unit represented by the formula (Π), and the repeating unit comprising a nonpolar moiety, the formula is represented by the formula (I) The copolymer according to any one of (1) to (8), wherein the number of moles of the repeating unit is 0.001 to 50%.

(10) With respect to the total number of moles of the repeating unit represented by the formula (I), the repeating unit represented by the formula (Π), and the repeating unit comprising a nonpolar moiety, the repeating unit represented by the formula (Π) Characterized in that the number of moles of the unit is in the range of 9.999 to 80%

The copolymer according to any one of (1) to (9).

(11) With respect to the total number of moles of the repeating unit represented by the formula (I), the repeating unit represented by the formula (Π), and the repeating unit composed of the nonpolar moiety, Characterized in that the number of moles is in the range of 19.999 to 90%

The copolymer according to any one of (1) to (10).

(12) The repeating unit comprising a nonpolar moiety is represented by the formula (III)

-cH ₂ -cf- (III)

I

R ₈

(In the formula, R ₇ represents a hydrogen atom or a C 1 -C 10 hydrocarbon group which may have a substituent, and R ₈ represents a hydrocarbon group which may have a substituent. The copolymer according to any one of (1) to (11), which is a repeating unit represented by the formula:

(13) The copolymer according to (12), wherein in the formula (III), R ₈ is an aromatic hydrocarbon group which may have a substituent.

(14) The repeating unit represented by the formula (III) is represented by the formula (V)

(Wherein represents a hydrogen atom or a methyl group.) The copolymer according to any one of (1) to (13), which is a repeating unit represented by the following formula:

(15) The copolymer according to any one of (1) to (14), wherein the number average molecular weight is in the range of 10,000 to 5,000,000.

(16) Equation (VI)

(Wherein, R „represents a hydrogen atom or a C 1 to (: 10 hydrocarbon group which may have a substituent, R ₁₂ represents a functional group capable of having an active halogen atom, Represents a halogen atom, R ₁₃ represents a halogen atom or an organic group, al represents any integer from 1 to 3, and when al is 2 or more, R ₁₂ and Y are the same. And bl may be the same or different, and bl represents 1 or 2. When bl is 2, Y may be the same or different, and 1 is 0 or 1. And (13-1 al), wherein when cl is 2 or more, R ₁₃ 's may be the same or different from each other.) And a compound represented by the formula (VII)

(In the formula, R ₁₇ represents a hydrogen atom or a C 1 -C 10 hydrocarbon group which may have a substituent, and R ₁₈ represents an aromatic hydrocarbon group which may have a substituent. Is subjected to living radical polymerization using a stable radical polymerization initiator to obtain a copolymer, and then the obtained copolymer is used as an initiator, and a transition metal complex is used to obtain a copolymer. (VIII)

(Wherein, R ₁₄ represents a hydrogen atom or an optionally substituted C 1 to (: 10 hydrocarbon group, and R ₁₅₁ and R ₁₅₂ each independently represent a hydrogen atom, or or represents C 1～C4 alkyl group, R ₁₆ is a hydrogen atom, a hydrocarbon group, Ashiru group, a silyl group, a phosphoryl group, a hydrocarbon phosphoryl group or a hydrocarbon sulfonyl group, el is 1 Represents an integer of 100 or more, and when el is 2 or more, R ₁₅₁ and R ₁₅₂ may be the same or different from each other.) A method for producing a copolymer.

(17) In the formula (VI), R ₁₂ is the formula (IX)

(Wherein! ^^ and! ^ ^ Independently represent a hydrogen atom, a halogen atom, or a C 1-10 (optionally substituted hydrocarbon group; In the above (2), when bl is 2, it represents a bond to Y.) The method according to (16), wherein the functional group is represented by the following formula:

(18) The copolymer according to (16) or (17), wherein the copolymer obtained from the compound represented by the formula (VI) and the compound represented by the formula (VII) is a block copolymer. A method for producing the copolymer according to the above.

(19) The copolymer according to any one of (16) to (18), wherein the stable radical initiator comprises a stable free radical compound and a radical polymerization initiator or alkoxyamines. Production method.

(20) The method for producing a copolymer according to (19), wherein the stable free radical compound is a nitroxyl compound.

(21) It is characterized in that the radical polymerization initiator is an organic peroxide or an azo compound. The method for producing a copolymer according to (19) or (20).

(22) A polymer solid electrolyte comprising the copolymer according to any one of (1) to (15) and an electrolyte salt.

(23) The electrolyte according to (22), wherein the electrolyte salt is at least one selected from the group consisting of an alkali metal salt, a quaternary ammonium salt, a quaternary phosphonium salt, a transition metal salt, and a protonic acid. The solid polymer electrolyte according to the above.

(24) The polymer solid electrolyte according to (23), wherein the electrolyte is a lithium salt.

Hereinafter, the present invention will be described in detail.

(1) The block-graft copolymer of the present invention

The block graft copolymer of the present invention is a copolymer having a repeating unit represented by the formula (I) and a repeating unit composed of a nonpolar moiety. In the formula (I), 1 ^ represents a hydrogen atom or a C 1 to C 10 hydrocarbon group which may have a substituent, and specifically, a hydrogen atom, a methyl group, an ethyl group, —Propyl group, isopropyl group, n-butyl group, sec—butyl group, isobutyl group, t-butyl group, phenyl group, naphthyl group, benzyl group and the like.

Further, 1 ^ may have a substituent on an appropriate carbon atom, and specific examples of such a substituent include a halogen atom such as a fluorine atom, a chlorine atom, or a bromo atom, a methyl group, Hydrocarbon groups such as ethyl group, n-propyl group, phenyl group, naphthyl group, benzyl group, etc .; hydrocarbon groups such as acetyl group, benzoyl group, etc .; nitrile group, nitro group, nitro group, methoxy group, phenoxy group, etc. , A methylthio group, a methylsulfinyl group, a methylsulfonyl group, an amino group, a dimethylamino group, an argino group and the like.

In the formula (I), R ₂ represents a functional group capable of having an active halogen atom. Here, the “functional group capable of having an active halogen atom” is a functional group having a structure such that when a halogen atom is bonded to a constituent carbon atom, the halogen atom becomes an active halogen atom. Specifically, a functional group capable of having a halogen atom in a position such as an electron-withdrawing group such as a carbonyl group, an ester group, an amide group, a sulfonyl group, a nitrile group, or a nitro group. Examples can be given. Examples of the halogen atom bonded to R ₂ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom and a bromine atom are particularly preferable.

Specific examples of R ₂ include the following functional groups.

_{_{S-- CH 2 - -NH- CH 2 -}} - - CH 2 - CH 3

_{-S- C- CH 2 - NH- C-- CH} 2 - - - C-- CH 2 "

II ² II I II

o o CH30

CN

-CH ₂ —— CH- -CH ₂ ― CH- -CH ₂ 1 C 1

I

C0 ₂ Me CN C0 ₂ Me

-CH? ——

Particularly, as R ₂ , a functional group represented by the formula (IV) can be preferably exemplified. In the formula (IV), R ₉ and R _{1 Q} each independently represent a hydrogen atom, a halogen atom, or a C 11 hydrocarbon group which may have a substituent, and in the formula (I) When b is 2, it represents a bond with X.

R ₉ , and. Specifically, a hydrogen atom, a chlorine atom, a bromine atom, or To halogen atom such as nitrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, t-butyl group, n-benzyl group, n- Examples thereof include hydrocarbon groups having 1 to 10 carbon atoms, such as a xyl group, a cyclohexyl group, a phenyl group, a naphthyl group, and a benzyl group.

Further, similarly to, a substituent can be provided on an appropriate carbon atom, and similar substituents can be exemplified.

Specific examples of the formula (IV) include functional groups represented by the following formula.

CH.

c-

Formula (I) R ₃ represents a halogen atom or an organic group, c represents 0 or any integer from 1 to (4-a), and when c is 2 or more, R ₃ is the same or May be different. Specific examples of R ₃ include a halogen atom such as a chlorine atom, a bromine atom, or an iodine atom, or a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group. Group, t-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group, phenyl group, naphthyl group, benzyl group and other hydrocarbon groups having 1 to 10 carbon atoms, methoxy group, ethoxy group, etc. Organic groups such as an alkoxy group, a methylthio group and an acetyl group can be exemplified.

In addition, similarly to the above, a substituent can be provided on an appropriate carbon atom, and similar substituents can be exemplified.

In the formula (I), X represents a polymer chain having a repeating unit represented by the formula (II). In the formula (Π), R ₄ represents a hydrogen atom or a C 1 to (: 10 hydrocarbon group which may have a substituent, and specifically, is the same as the specific example represented by 1 ^ The following functional groups can be exemplified.

R _{5 1,} and R _{5 2} are each independently a hydrogen atom or or C 1 through C 4, Represents an alkyl group. Examples of such a functional group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group and a t-butyl group. Examples can be given. e represents an integer of from 1 to 1 0 0, if e is 2 or more, R _{5 1} together and, and R _{5 2} together may also be different from one phase in the same.

R ₆ represents a hydrogen atom, a hydrocarbon group, an acyl group, a silyl group, a phosphoryl group, a hydrocarbon phosphoryl group, or a hydrocarbon sulfonyl group, specifically, a methyl group, an ethyl group, an n-propyl Group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, t_butyl group, n-hexyl group, phenyl group, substituted phenyl group, hydrocarbon group such as naphthyl group, formyl group, acetyl group, Acyl groups such as propionyl group and butylyl group, trimethylsilyl group, silyl groups such as t-butyldimethylsilyl group, dimethylphenylsilyl group, hydrocarbon phosphoryl groups such as dimethylphosphoryl group and diphenylphosphoryl group, methylsulfonyl group, Examples thereof include a hydrocarbon sulfonyl group such as a phenylsulfonyl group.

d represents an integer of from 1 to 1 0 0 0, if d is 2 or more, R ₄ together, R _{5 1} together, R _{5 2} together, R ₆ to each other, and e each other are the same or or different phases, e represents an integer of from 1 to 1 0 0, if e is 2 or more, R ₅ i and between, and R _{5 2} each other, are identical or different You may.

Specific examples of the repeating unit represented by the formula (II) include the following compounds. However, it is exemplified by a monomer which is considered to be derived from the repeating unit represented by the formula (II).

These repeating units may be used alone or in a combination of two or more.

2-Methoxyethyl (meth) acrylate, 2-ethoxyxetyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, 2-ethoxypropyl (meth) acrylate, methoxypolyethylene glycol (The number of units of ethylene glycol is 2 to 10 0) (meth) acrylate, ethoxy polyethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, methoxy polypropylene glycol (the number of units of propylene glycol is 2 1100) (meth) acrylate, ethoxy polypropylene glycol (meth) acrylate, phenoxypolypropylene glycol (meth) acrylate, poly (ethylene glycol mono (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polypropylene glycol Mono (meth) acrylate, polyethylene glycol-polypropylene glycol mono (meth) acrylate, octoxypolyethylene glycol-polypropylene glycol mono (meth) acrylate, lauroxypolyethylene glycol mono (meth) acrylate, stearoxypolyethylene glycol mono (meth) Akurireto, "BLEMMER PME series" [1 in formula (I) ^ = 1 ^ = hydrogen atom, R ₃ = methyl, single corresponding to m = 2 to 9 0 Body) (Nippon Oil & Fats), acetyloxy polyethylene glycol (methyl) acrylate, benzoyloxy polyethylene glycol (meta) acryle-t-butyldimethyloxysilyloxy polyethylene dalicol (meth) acrylate, methoxy polyethylene glycol 1-cyclohexene-1-potoxy propylate, methoxypolyethylene glycol-cinnamate.

The repeating unit comprising a non-polar moiety contained in the copolymer of the present invention includes a functional group containing no polar group represented by a hydrocarbon group such as a phenyl group, a naphthyl group, a methyl group, and an ethyl group, and the entire repeating unit. As long as it is a functional group containing a polar group as long as it is not affected, or a functional group having a difference in polarity as compared with the repeating unit represented by the formula (I), there is no particular limitation. Specifically, a repeating unit represented by the formula (III) can be preferably exemplified.

In the repeating unit represented by the formula (III), R ₇ represents a hydrogen atom or a C 1 to C 10 hydrocarbon group which may have a substituent. Functional groups similar to the examples can be exemplified.

R ₈ represents a hydrocarbon group which may have a substituent, and specific examples include a methyl group, an ethyl group, a phenyl group, a naphthyl group, and an anthracenyl group. Preferred examples include aromatic hydrocarbon groups. R ₈ may have a substituent on an appropriate carbon atom. Examples of such a substituent include a halogen atom such as a fluorine atom, a chlorine atom, or a bromo atom, a methyl group, and a Hydrocarbon groups such as tyl group, n-propyl group, phenyl group, naphthyl group, benzyl group, etc., hydrocarbon groups such as acetyl group, benzoyl group, etc., nitrile group, nitro group, methoxy group, phenoxy group, etc. , Methylthio, methylsulfinyl, methylsulfonyl, amino, dimethylamino, anilino and the like.

Specific examples of the repeating unit represented by the formula (III) include the following repeating units, and particularly preferably a repeating unit represented by the formula (V). However, a monomer which is considered to be derived from the repeating unit represented by the formula (III) will be exemplified.

The repeating unit represented by the formula (III) may be a single type or a mixture of two or more types.

Styrene, o-methylstyrene, p-methylstyrene, p-t-butylstyrene, α-methylstyrene, ρ-t-butoxystyrene, mt-butoxystyrene, 2,4-dimethylstyrene, m-chlorostyrene, p-Chlorostyrene, 1-vinylnaphthalene, 9-vinylanthracene, etc.

The degree of polymerization of the repeating unit represented by the formula (I) (which represents the number of moles of the repeating unit; the same applies hereinafter) is not particularly limited, but is preferably 3 or more. If it is less than 3, sufficient ion conductivity cannot be obtained.

The degree of polymerization of the repeating unit comprising a nonpolar moiety represented by the formula (III) is not particularly limited, but is preferably 5 or more. If it is less than 5, there is a problem that the film quality is degraded, and the film does not have a clear microphase separation structure at the time of film formation.

The degree of polymerization in the repeating unit represented by the formula (II) in the polymer chain having the repeating unit represented by the formula (II) is not particularly limited, but is preferably 5 or more. If it is less than 5, sufficient ionic conductivity cannot be obtained.

The copolymer of the present invention comprises a repeating unit represented by the formula (I), a repeating unit represented by the formula (II), and a total mole of a repeating unit composed of a nonpolar moiety represented by the formula (ΠΙ) and the like. The number of moles of the repeating unit represented by the formula (I) is preferably in the range of 0.001 to 50% based on the number (hereinafter referred to as the total mole number). If the content is less than 0.001%, sufficient ionic conductivity cannot be obtained, and if the content is more than 50%, a formed film is formed. Quality may be reduced.

Further, the number of moles of the repeating unit represented by the formula (II) is preferably in the range of 9.999 to 80% based on the total number of moles. 9. If it is less than 999%, ion conductivity may be reduced, and if it is more than 80%, the film quality may be reduced.

Further, the number of moles of the repeating unit composed of the nonpolar moiety represented by Formula (III) or the like is preferably in the range of 19.999 to 90% based on the total number of moles. 19. If less than 999%, the film quality deteriorates and a clear microphase separation structure cannot be obtained, and if it exceeds 90%, ion conductivity may decrease.

In the present invention, the bonding state of the polymer chain (A) containing a repeating unit represented by the formula (I) and the polymer chain (B) containing a repeating unit composed of a nonpolar moiety represented by the formula (III) are particularly Although not limited, it is preferable that they are linked by a block. By bonding with blocks, they exhibit a microphase-separated structure when formed or formed into a film, and exhibit good ionic conductivity even in a solid state. In addition, being linked by a block means that the polymer chains (A;) and (B) are linked directly or indirectly by another polymer chain or a linking group. In addition, a taper block in which the component ratio between repeating units constituting each polymer chain gradually changes is also included in the block connection in the present invention. At this time, the other polymer chain may be a homopolymer or a binary or higher copolymer. In the case of a copolymer, the bonding state therein is not particularly limited, and may be random, tapered block, It may be a block. Further, the polymer chain (A) containing a repeating unit represented by the formula (I) or the like means a polymer chain consisting only of the repeating unit represented by the formula (I) or the like and a polymer chain represented by the formula (I) or the like. Means a copolymerized polymer chain consisting of a repeating unit and another component.

In the copolymer of the present invention, the polymer chains (A) and (B) and the polymer chain (C) which may be the same as or different from the polymer chain (B) are (B), (A), It is preferable to have the arrangement in the order of (C), and it is particularly preferable that the arrangement is a combination of (B)-(A)-(C).

[(A)-(B)] j, [(B)-(A)-(C)] j, [(A)-(B) one (A)] j ( j represents any integer of 1 or more.) and the like. In addition, each of the above block polymers is The copolymer may be a block copolymer in which the segments are extended or branched, as represented by the following formulas (1) to (3) via the residue of the drug. In the formula, w represents an integer of 1 or more, and X represents a residue of a coupling agent.

[(A) ― (B)] w— X · · · (1)

[(B)-(A)-(C)] w-X · · · (2)

[(A) (B) one (A)] w-X

The number average molecular weight of the copolymer having a repeating unit comprising a nonpolar moiety represented by formulas (I) and (III) is not particularly limited, but is preferably in the range of 10,000 to 5,000, 000. can do. If it is less than 10,000, thermal and physical properties may be reduced, and if it is more than 5,000,000, moldability or film formability may be reduced.

In the polymer chain having a repeating unit composed of a nonpolar moiety represented by the formula (1), the formula (11), and the formula (III) of the present invention, or between polymer chains, as necessary. In addition, other repeating units can be included, and as such a repeating unit, a repeating unit derived from the following monomer can be exemplified. These repeating units can be used singly or as a mixture of two or more.

(Meth) methyl acrylate, (meth) ethyl acrylate, (meth) acrylic acid n-butyl, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate,

Benzyl (meth) acrylate, Isopolnyl (meth) acrylate, Dicyclopentenyl (meth) acrylate, 1-adamantyl (meth) acrylate, 2-methyl-2-methadenyl (meth) acrylate, (meth) acrylic Acid 1-methylene adamantyl, (meth) acrylic acid 1-ethylene adamantyl, (meth) acrylic acid 3,7-dimethyl-1-adamantyl, (meth) tricyclodecanyl acrylate, (meth) acrylic acid Norpornan, Menthyl (meth) acrylate, n-Propyl (meth) acrylate, Isopropyl (meth) acrylate, 2-Ethylhexyl (meth) acrylate, Isodecyl (meth) acrylate, (meth) acrylic acid Isooctyl,

Lauryl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofuranyl (meth) acrylate, tetrahydropyrael (meth) acrylate, 3-methyl oxocyclohexyl (meth) acrylate, (meta) ) Petyrolactone acrylate, (Meth) acrylic acid derivatives such as (meth) acrylic acid meparonic lactone,

1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentane, 2-methyl-1,3-pentene, 1,3-hexadiene, 1,6 —Hexadiene, 4, 5-Jetyl-1,3-octadiene, 3-Butyl-1,3-octadiene, conjugated gens such as chloroprene, α such as N-methylmaleimide and N-phenylmaleimide , / 3-unsaturated carboxylic imides,

(Meth) α, / 3-unsaturated nitriles such as acrylonitrile.

(2) Method for producing block / graft copolymer of the present invention

The method for producing a block / graft copolymer of the present invention is characterized by using two types of living radical polymerization methods described in detail below. That is, a stable radical initiator is used.After obtaining a block copolymer by a living radical polymerization method, the obtained block copolymer is grafted by a living radical polymerization method using a macroinitiator and a transition metal complex as a catalyst. This is a method of performing copolymerization.

The monomer used in the method for producing a copolymer of the present invention is a compound represented by the formula (VI), the formula (VII), and the formula (VIII), and the compound represented by the formula (VI), the formula (VIII) The compound represented by the formula (VII) corresponds to the repeating unit represented by the formula (I) and the repeating unit represented by the formula (II), and the compound represented by the formula (VII) is represented by the formula (III) , The contents of the functional groups represented by Ru to R ₁₄ , R ₁₅ or R ₁₅₂ , and R _{16 to} R ₁₈ are 1 ^ to 1 ^ ₄ , R ₅₁ , respectively. corresponds to the content of the functional group represented by R _52, R ₆ ~R _8, specific examples of each compound, may be exemplified the same compound and compounds exemplified as a monomer induced to each repeat unit . In addition, d corresponds to a, bl, b, b, cl, c, and el corresponds to e. Further, in the compound represented by the formula (VI), Y represents a halogen atom, and specifically represents a chloro atom, a bromo atom, an iodine atom, or the like.

Moreover, the functional group represented by formula (IX) corresponds to the functional group represented by the formula _{(IV), R 19,:} . The content of the functional group represented by R ₉ ,. Corresponds to the content of the functional group represented by.

The method for producing the block / graft copolymer of the present invention will be described in more detail corresponding to the monomers. The compound represented by the formula (VI) and the compound represented by the formula (VII) Are block copolymerized by a living radical polymerization method using a stable radical initiator, and then the obtained block copolymer is subjected to a living radical polymerization method using a macroinitiator and a transition metal complex as a catalyst to obtain a compound represented by the formula (VIII). ) Is graft-polymerized.

Specific examples of the compound represented by the formula (VI) include 4-chloromethylstyrene, 3-chloromethylstyrene, 4-chloromethyl-10! -Methylstyrene, 3-chloromethyl-<<-methylstyrene, and 4-chloromethylstyrene. Dichloromethylstyrene and the like can be exemplified.

Examples of the stable radical initiator include a mixture of a stable free radical compound and a radical polymerization initiator, or various alkoxyamines.

A stable free radical compound is one that exists as a stable free radical alone at room temperature or under polymerization conditions, and that can react with a growing terminal radical to form a re-dissociable bond during the polymerization reaction. Yes, for example, 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMP〇), 4-amino-1,2,2,6,6-tetramethyl-1-piberidinyloxy, 4- Hydroxy-2,2,6,6-tetramethyl-1-biperdinyloxy, 4-oxo-2,2,6,6-tetramethyl-1-piberidinyloxy, 4,4'-dimethyl 1,3-oxazoline-3-yloxy, 2,2,5,5-tetramethyl-11-pyridinyloxy, di-t_butyl nitroxide, 2,2-di (4_t-octylphenyl) _1-picrylhydrazyl Nitroxide radical hydrazinyl Compounds 1 to plurality generate radical are exemplified.

The radical polymerization initiator may be any compound that decomposes to generate free radicals. Specifically, 2,2′-azobisisobutyronitrile, 2,2′-azobis mono (2,4- Azo compounds such as dimethylvaleronitrile), diacyl peroxides such as benzoyl peroxide, ketone oxides such as methyl perketone peroxide, oxides, 1,1-bis (t-butyl peroxy) ) — Peroxyketals such as 3,3,5-trimethylcyclohexane; hydroperoxides such as cumene hydroperoxide; dialkyl peroxides such as dicumylperoxide; t-butyl peroxybivalate, t-butyl peroxybivalate Organic peroxides of peroxyesters such as benzoate can be exemplified. In addition, a known polymerization accelerator used in combination with an organic peroxide such as dimethylaniline-cobalt naphthenate may be used in combination.

These radical polymerization initiators are generally used in an amount of 0.05 to 5 mol, preferably 0.2 to 2 mol, per 1 mol of the aforementioned stable free radical compound. Specific examples of the alkoxyamines include the following compounds.

The polymerization can be performed by various known polymerization methods, for example, bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization.The polymerization temperature is 50 to 200 in an atmosphere of an inert gas such as nitrogen or argon. C., preferably at 100 to 150.degree. The organic solvent used in the solution polymerization is not particularly limited, and aromatic hydrocarbons such as benzene, toluene, and xylene; alicyclic hydrocarbons such as cyclohexane; methyl ethyl ketone; Ketones such as butyl ketone and cyclohexanone; ethers such as dioxane; esters such as ethyl acetate and butyl acetate; alcohols such as ethanol and n-butanol; ethylene glycol monomethyl ether and ethylene glycol monomethyl ether acetate And the like polyhydric alcohol derivatives.

As a method for producing a copolymer by living radical polymerization using the above stable radical initiator, specifically,

(1) For example, after the conversion of the first monomer reaches 100%, the second monomer is added. A method of sequentially adding monomers to obtain a block copolymer by repeating this,

(2) Even if the conversion of the first monomer does not reach 100%, the polymerization is continued by adding the second monomer at the stage when the target degree of polymerization or molecular weight has been reached, and between the block chains. A method for obtaining a gradient copolymer having a random portion,

(3) Even if the conversion of the first monomer does not reach 100%, the reaction is stopped once when the target degree of polymerization or molecular weight has been reached, the polymer is taken out of the system, and the obtained polymer is obtained. Is used as a macroinitiator and other monomers are added to intermittently proceed with copolymerization to obtain a block copolymer.

And the like.

When the stable free radical compound used is monofunctional, copolymers of A—B type, B—A type, and B—A—C type are basically obtained. In this case, basically, A-B-A type and B-A-B type copolymers are obtained.

As another method for obtaining a gradient copolymer, a gradient copolymer is also obtained by ordinary radical polymerization in which polymerization is carried out only with a radical polymerization initiator without using a stable free radical compound in the above method (2). This is also possible, and this method is also included in the method for producing a graft copolymer of the present invention.

Tracking of the copolymerization process and confirmation of the completion of the reaction can be easily performed by gas chromatography, liquid chromatography, gel permeation chromatography, membrane osmometry, NMR, and the like. After completion of the copolymerization reaction, the copolymer can be purified by column purification, vacuum purification, or by applying ordinary separation and purification methods such as, for example, pouring into water or a poor solvent, filtering and drying the precipitated polymer. Can be obtained.

In the present invention, graft polymerization is carried out by a living radical polymerization method in which a block copolymer obtained by the above-mentioned lipinal radical polymerization using a stable free radical initiator is used as a macroinitiator and a transition metal complex is used as a catalyst. It is characterized.

For the graft polymerization, various known polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization can be adopted.The polymerization temperature is 50 to 200 in an atmosphere of an inert gas such as nitrogen or argon. C., preferably at 100 to 150.degree. A place for solution polymerization The organic solvent used in the combination is not particularly limited, but may be aromatic hydrocarbons such as benzene, toluene and xylene, alicyclic hydrocarbons such as cyclohexane, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Ketones; ethers such as dioxane; esters such as ethyl acetate and butyl acetate; alcohols such as ethanol and n-butanol; polyvalents such as ethylene glycol monomethyl ether and ethylene glycol monomethyl ether acetate. Examples thereof include alcohol derivatives.

The central metals constituting the transition metal complex used in the present invention include manganese, rhenium, iron, ruthenium, rhodium, nickel, copper, etc., elements of Group 7 to 11 of the Periodic Table (edited by the Chemical Society of Japan, Chemical Handbook). Basic Edition I, Revised 4th Edition ”(based on the periodic table described in 1993). Preferred examples of the metal species include zero-valent and monovalent copper, divalent ruthenium, and divalent iron. More specifically, examples include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous acetate, cuprous perchlorate, and the like. be able to. When these copper compounds are used, for example, 2,2-pipyridyl and its derivatives, 1,10-phenanthroline and its derivatives, alkylamines such as triptylamine, tetramethylethylenediamine, pentamethylethylenediethylenetriamine, hexane It is preferable to add a polyamine such as methyltriethylenetetramine or the like as a ligand for enhancing the catalytic activity. Further, ruthenium tris triphenyl phosphine chloride complex _{(R u C l 2 (PP} h 3) 3) may divalent ruthenium complex suitably used, such as. When a ruthenium complex is used, it is preferable to add an aluminum compound such as trialkoxyaluminum to enhance the activity of the catalyst. Further, a divalent iron complex such as an iron chloride tristriphenylphosphine complex (FeCl ₂ (PPh ₃ ) ₃ ) can also be suitably used. These transition metal complexes can be used alone or in combination of two or more.

The graft chain X is obtained by polymerizing a compound represented by the formula (VIII), and if necessary, other polymerizable unsaturated monomers, for example, a compound represented by the formula (VII) And / or methyl (meth) acrylate, ethyl (meth) acrylate, t-butyl (meth) acrylate, benzyl (meth) acrylate, (meth) acrylic acid It may be a copolymer chain with (meth) acrylates such as sopolnyl and dicyclopentenyl (meth) acrylate.

As a method of forming the graft chain X, specifically,

(1) a method of obtaining a homopolymer chain using only the compound represented by the formula (VIII),

(2) a method of simultaneously adding a compound represented by the formula (VIII) and another polymerizable unsaturated monomer to a reaction system to obtain a random copolymer chain,

(3) a method of sequentially adding a compound represented by the formula (VIII) and another polymerizable unsaturated monomer to a reaction system to obtain a block copolymer chain;

(4) a method of obtaining a gradient copolymer chain by changing the composition ratio of the compound represented by the formula (VIII) to another unsaturated monomer over time and adding the compound;

And the like. Further, the graft polymerization may be carried out continuously or intermittently. For example, in the above method (3), after confirming that the polymerization of the compound represented by the formula (VIII) is completed, another polymerizable unsaturated monomer is added and the copolymerization is continuously performed. In addition, even when the polymerization of the compound represented by the formula (VIII) is not completed, the block-graft copolymer is once taken out of the system once it is confirmed that the desired degree of polymerization or molecular weight has been reached. The block / graft copolymer can be used as a macroinitiator and other polymerizable unsaturated monomers can be added to proceed intermittently. Tracking of the graft polymerization reaction process and confirmation of the completion of the reaction can be easily performed by gas chromatography, liquid chromatography, gel permeation chromatography, membrane osmometry, NMR, and the like. After the completion of the graft polymerization reaction, a common separation and purification method such as column purification, pressure-reduction purification, or filtration and drying of the polymer component precipitated by pouring into water or a poor solvent, for example, is applied to the graft polymerization. A polymer can be obtained.

The electrolyte used in the present invention is not particularly limited, and may be an electrolyte containing an ion that is desired to be the carrier by charge.The dissociation constant in a polymer solid electrolyte obtained by curing it is desirable large, alkali metal salts, (CH ₃₎ ₄ NBF ₄ grade Anmoniumu salts ₆ and the like, (CH ₃₎ 4 grade Hosuhoniumu salts such as ₄ PBF _6, or a transition metal salt such as a g C 1 0 ₄ Hydrotonic acid such as hydrochloric acid, perchloric acid, borofluoric acid, etc. can be used, alkali metal salt, quaternary ammonium salt, quaternary phosphonium The use of salts or transition metal salts is preferred.

Specific examples of the alkali metal salts can be used, for example, _{_{L i CF 3 S0 3, L}} i N (CF 3 S 0 2) 2, L i C (CF 3 S 0 2) 3 L i C (CH 3) (CF ₃ S0 ₂ ) ₂ , L i CH (CF ₃ S 0 ₂ ) ₂ , L i CH ₂ (CF ₃ S0 ₂ ), L i C ₂ F ₅ S 0 ₃ , L i N (C ₂ F ₅ S 〇 _{_{2) 2, L i B (}} CF 3 S 0 2) 2, L i PF 6,: L i C 1_Rei _{4, L i I, L i} BF 4, L i S CN, L i As F 6, NaCF _{_{_{3 S0 3, NaPF 6, N}}} a C 1_Rei _{_{4, Na l, Na BF 4}} , N aA s F 6, KCF 3 S0 3, KP F 6, KI, L i CF 3 C0 3, N a C 1_Rei _{3, N a S CN, KB} F 4, Mg (C 10 4) 2, Mg (BF 4) can it to illustrate _2, and these electrolyte salts is mixed, may be used, among them lithium salt Is preferred.

The amount of the electrolyte salt added is 0.005 to 80 mol%, preferably 0.01 to 50 mol%, based on the alkylene oxide unit in the multibranched polymer which is the base polymer of the polymer electrolyte. Range. There is no particular limitation on the method of adding and complexing, for example, a method of dissolving the copolymer and the electrolyte salt in a suitable solvent such as tetrahydrofuran, methyl ethyl ketone, acetonitrile, ethanol, dimethylformamide, and the like. And a method of mixing them mechanically at room temperature or under heating.

The solid polymer electrolyte is preferably in the form of a sheet or the like. Specific examples of the manufacturing method include various coating methods such as a roll-co-one-court method, a curtain-co-one-cow method, a spin coating method, a dip method, and a casting method. Examples of the method include a method in which a composition containing the copolymer of the present invention and an electrolyte is formed on a support by means of a film, solidified by heat or the like, and then removed by removing the support.

The solid polymer electrolyte of the present invention is expected to be used as a solid electrolyte having excellent thermal properties, physical properties, and ionic conductivity in electrochemical devices such as batteries.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples.

Example 1 (1) Synthesis of block and graft copolymer

4-Chloromethylstyrene (hereinafter referred to as 4CMS) 131. Ommo 1 and 1- (2,2,6,6-tetramethylpiperidinyloxy) 1-phenylamine 9.6mmo 1 After uniformly mixing and performing nitrogen publishing for 15 minutes, the mixture was heated to 125 ° C. in a nitrogen atmosphere to start a polymerization reaction. Twelve hours after the initiation of the polymerization reaction, the reaction solution was cooled to 0 ° C to stop the polymerization reaction. The reaction solution was diluted with tetrahydrofuran (THF) to form a homogeneous solution, and then poured into a large amount of methanol to precipitate a polymer, which was filtered, washed, and dried under reduced pressure at 60 ° C for 5 hours. The isolation yield of the obtained polymer was 56%. Further, GPC analysis was performed on the obtained poly CMS. The number average molecular weight (hereinafter, referred to as Mn) was 1,300, and the dispersity (the ratio of the weight average molecular weight (Mw) to Mn (MwZMn), PD) was 1.35.

Next, 0.7 mmo 1 of the obtained poly CMS and 40 Ommo 1 of styrene (hereinafter, referred to as St) were uniformly mixed, nitrogen bubbling was performed for 15 minutes, and the mixture was heated to 125 ° C. The polymerization reaction was started. 24 hours after the start of the copolymerization reaction, the reaction solution was cooled to 0 ° C to stop the copolymerization reaction. As a result of GC analysis, the polymerization conversion of St was 63%. After diluting the reaction solution with THF to make a homogeneous solution; poured into a large amount of methanol to precipitate a polymer, followed by filtration and washing, and the obtained polymer was dried under reduced pressure at 60 ° C for 5 hours. GPC analysis of this polymer revealed that it was a block copolymer [P-1] having a poly (4CMS-b-St) structure with Mn = 37,000 and PD = 1.48. .

Then, in a nitrogen atmosphere, 110 g of toluene previously subjected to a nitrogen bubbling treatment was added to 0.1 g of the block copolymer [P-1] 0.1 lmmo 1 and methoxypolyethylene render glycol monomethacrylate (manufactured by NOF Corporation, Blenmer Co., Ltd.). PME-1 000, e 1 in formula (VIII) = 23) 38mmo 1, cuprous chloride 0.1mmol, 2,2'-viviridine 0.2mmo 1 The mixture was heated to ° C to start the copolymerization reaction. Twenty hours after the start of the copolymerization reaction, the temperature of the reaction system was cooled to 0 ° C to stop the copolymerization reaction. As a result of GPC analysis, the polymerization conversion of PME-1000 was 70%. Perform column purification of the reaction solution After removing the metal complex and unreacted monomer, volatile components were removed under reduced pressure to obtain a polymer. GPC analysis of this polymer revealed that it was a polymer with Mn = 3,10,000 and PD = 1.52. Further, ¹³ CNMR analysis showed that it was based on the total number of moles of repeating units in the copolymer. , 4 CMS moles of repeating units, St moles of repeating units, and PME—Poly ((4CMS— g—PME—100) -bSt), which was a block-graft copolymer [BG-1].

The obtained block-graft copolymer [BG-1] was dissolved in acetone, cast on a Teflon (registered trademark) plate, left at room temperature for 24 hours, and dried under reduced pressure at 60 for 24 hours. A film having a thickness of 100 xm was obtained. A transmission electron micrograph of the obtained film was measured, and this block-graft copolymer had a sea-island-type microphase-separated structure in which a polystyrene phase was dispersed spherically in a polyethylene oxide phase. I understand.

(2) Preparation of resin composition for polymer solid electrolyte

Under an argon atmosphere, block graft copolymer obtained in the above procedure [BG-l] of 2 g was dissolved in acetone 1 8 g, homogeneously dissolved by adding _{L i C 1 O 4 0. 2} g Thus, a resin composition for a polymer solid electrolyte was prepared.

(3) Preparation of solid polymer electrolyte membrane and measurement of ionic conductivity

In an argon atmosphere, the above composition was cast on a Teflon (registered trademark) plate, left at room temperature for 24 hours, and dried under reduced pressure at 60 ° C for 24 hours to obtain a uniform polymer solid electrolyte membrane (membrane). Thickness 100 111). This polymer solid electrolyte membrane was sandwiched between white metal plates under an argon atmosphere, and the ionic conductivity was measured by complex impedance analysis using an impedance analyzer (Solartron-1260 type) with a frequency of 5 to 10 MHz. As a result, the ionic conductivity was 5x1 O ^ SZcm at 23 ° C. Example 2

(1) Synthesis of block / graft copolymer

4 CMS 13 1. Ommo 1 and bifunctional polymerization initiator having the following structure

After lmmo 1 was uniformly mixed and subjected to nitrogen publishing for 15 minutes, the mixture was heated to 125 ° C under a nitrogen atmosphere to start a polymerization reaction. Ten hours after the start of the polymerization reaction, the polymerization reaction was stopped by cooling the reaction solution to 0 ° C. The reaction solution was diluted with THF to make a homogeneous solution, and then poured into a large amount of methanol to precipitate a polymer. After filtration and washing, the obtained polymer was dried under reduced pressure at 60 ° C for 5 hours. The isolation yield of the obtained polymer was 65%. Furthermore, GPC analysis of the obtained poly-4CMS showed Mn = 1,800 and PD = 1.32.

Then, the obtained poly CMS 0.1 lmmo 1, St 65 mm ο 1 was uniformly mixed, nitrogen bubbling was performed for 15 minutes, and the copolymerization reaction was performed by heating to 125 ° C under a nitrogen atmosphere. Started. Twenty hours after the start of the copolymerization reaction, the reaction solution was cooled to 0 ° C to stop the copolymerization reaction. As a result of GC analysis, the polymerization conversion of St was 59%. The reaction solution was diluted with THF to form a homogeneous solution, and then poured into a large amount of methanol to precipitate a polymer. After filtration and washing, the obtained polymer was dried under reduced pressure at 60 ° C for 5 hours. GPC analysis of this polymer revealed that a block copolymer having the structure of poly (S t—b—4 CMS—b—S t) with Mn = 49, 000 and PD = 1.47 [ P—2].

Then, in a nitrogen atmosphere, 76 g of toluene which had been subjected to nitrogen publishing in advance was mixed with the block copolymer [P-2] 0.1 lmmo 1, Blemmer PME-1 000 25 mmo 1, and cuprous chloride 0.1 lmmo. l, 2,2′-Pypyridine 0.2 mmo 1 was added thereto, mixed uniformly, and then heated to 80 ° C. with stirring to start a copolymerization reaction. Eighteen hours after the start of the copolymerization reaction, the temperature of the reaction system was cooled to 0 ° C to stop the copolymerization reaction. As a result of GPC analysis, the polymerization conversion of Blemmer PME-1000 was 65%. The reaction solution was subjected to column purification to remove metal complexes and unreacted monomers, and then volatile components were removed under reduced pressure to obtain a polymer. This polymer When GPC analysis was carried out for one, Mn = 209,000 and PD = 1.52, and ¹³ CNMR was measured, the 4CMS repetition of the total number of repeating unit moles in the copolymer Unit, St repeat unit, and PME—Poly (St-b— (4 CMS) in which the molar ratio of 1000 repeat units is 13.3%, 61.8%, and 24.9%, respectively. -It was a block-graft copolymer [BG-2] having a structure of g-PME-1000) -b-St).

Further, the obtained block / graft copolymer [BG-2] was formed into a film in the same manner as in Example 1, and the obtained film was observed with a transmission electron microscope. The same result as in Example 1 was obtained. It had a sea-island type Miku mouth phase separation structure.

(2) Preparation of composition for polymer solid electrolyte

Under an argon atmosphere, block graft copolymer obtained in the above procedure [BG-2] to 2 g, was dissolved in acetone 1 8 g, was added to _{L i C 1 O 4 0. 1} 7 g uniform To prepare a resin composition for a solid polymer electrolyte.

In the same manner as in the composition in Example 1 to prepare a solid polymer electrolyte membrane, was measured I on conductivity was at ^{23 ° C 2x10- 4 S / cm} . -Example 3

(1) Synthesis of block / graft copolymer

Stol 90 mmol, 2,2,6,6-tetramethyl-1-piberidinyloxy 0.56 mmo 1 and benzoyl peroxide 0.47 mmol were uniformly mixed, and nitrogen bubbling was performed for 15 minutes. After maintaining at 95 ° C for 3.5 hours in a nitrogen atmosphere, the temperature was raised to 125 ° C to start the polymerization reaction. Thirty hours after the initiation of the polymerization reaction, the polymerization reaction was stopped by cooling the reaction solution to 0 ° C. The reaction solution was diluted with THF to form a homogeneous solution, and then poured into a large amount of methanol to precipitate a polymer. After filtration and washing, the obtained polymer was dried under reduced pressure at 60 ° C for 5 hours. The isolation yield of the obtained polymer was 64%. In addition, GPC analysis of the obtained poly-St revealed Mn = 43,100 and PD = 1.35. Next, the obtained poly Stlmmo 1 and 4 CMS 239 mmo 1 were uniformly mixed, nitrogen publishing was performed for 15 minutes, and then the temperature was increased to 125 ° C under a nitrogen atmosphere. To initiate the copolymerization reaction. Five hours after the start of the copolymerization reaction, the reaction solution was cooled to 0 to stop the copolymerization reaction. As a result of GC analysis, the polymerization conversion rate of 4 CMS was 20%. The reaction solution was diluted with THF to form a homogeneous solution, and then poured into a large amount of methanol to precipitate a polymer. After filtration and washing, the obtained polymer was dried under reduced pressure at 60 ° C for 5 hours. GPC analysis of this polymer revealed that it was a block copolymer [P-3] having the structure of poly (St-b-4CMS) with Mn = 50,000 and PD = 1.37. .

Then, in a nitrogen atmosphere, 70 g of toluene which had been subjected to nitrogen bubbling in advance, 70 ml of the above block copolymer [P-3], lmmo 1 and methoxypolyethylene glycol monomethacrylate (manufactured by NOF Corporation, PME-400, e 1 = 9) in formula (VIII) 5 lmmo 1, 0.1 mmo 1 of copper chloride [1], and 0.2 mmo 1 of viviridine are added and uniformly mixed. The copolymerization reaction was started by heating to ° C. After 15 hours from the start of the copolymerization reaction, the temperature of the reaction system was cooled to 0 ° C to stop the copolymerization reaction. As a result of GPC analysis, the polymerization conversion rate of PM E-400 was 60%. The reaction solution was subjected to column purification to remove the metal complex and unreacted monomer, and then volatile components were removed under reduced pressure to obtain a polymer. GPC analysis of this polymer revealed that it was a polymer with Mn = 185,000 and PD = 1.42, and ¹³ CNMR was measured. CMS repeat unit, St repeat unit, and PME—Poly (St-b— (CMS—) with a molar ratio of 400 repeat units of 6.2%, 56.6%, and 37.2%, respectively. g-PME-400)) and a block-graft copolymer [BG-3].

Further, the obtained block and graft copolymer [BG-3] were formed into a film in the same manner as in Example 1, and the obtained film was observed with a transmission electron microscope, and the same result as in Example 1 was obtained. It had a sea-island type Miku mouth phase separation structure.

(2) Preparation of resin composition for polymer solid electrolyte

The block graft copolymer obtained by the above operation under an argon atmosphere

[BG-3] a 2 g was dissolved in acetone 1 8 g, was L i C L_〇 ₄ 0. 1 5 g was dissolved uniformly added to prepare a solid polymer electrolyte resin composition. (3) Preparation of solid polymer electrolyte membrane and measurement of ionic conductivity

A polymer solid electrolyte membrane was prepared from the above composition in the same manner as in Example 1, and the ion conductivity was measured. As a result, it was ⁸ × 10 -5 s Zcm at 23 ° C.

Example 4

(1) Synthesis of block / graft copolymer

Under a nitrogen atmosphere, 105 g of toluene previously subjected to a nitrogen bubbling treatment was added to 105 g of the block copolymer [P-2] produced in Example 2. 0.1 lmmol, PME-400 750 mmol, Add pentagenyl bis (triphenylphosphine) ruthenium (0.02 mmo1) and mix uniformly, then add di-n-butylamine (0.2 mmo1) and heat to 100 ° C under stirring to carry out the polymerization reaction. Started. Forty-five hours after the start of the polymerization reaction, the reaction solution was cooled to 0 ° C. to stop the copolymerization reaction. As a result of GC analysis, the polymerization conversion of PME-400 was 50%. The reaction solution was subjected to column purification to remove metal complexes and unreacted monomers, and then volatile components were removed under reduced pressure to obtain a polymer. GPC analysis of this polymer gave Mn = 230,000 and PD = 1.57. When ¹³ C NMR was measured, it was found that 4 CM relative to the total number of moles of repeating units in the copolymer was obtained. Poly (St-b- (4 CMS) in which the molar ratio of S repeating unit, St repeating unit, and PME-400 repeating unit is 9.5%, 44.2%, and 46.3%, respectively. — G— PME—400) -bSt) Block-graft copolymer [BG-4].

The obtained block graft copolymer [BG-4] was formed into a film in the same manner as in Example 1, and the obtained film was observed with a transmission electron microscope. Having a microphase-separated structure of

(2) Preparation of resin composition for polymer solid electrolyte

Under an argon atmosphere, the resulting block graph Bok copolymer steps above [BG-4] to 2 g was dissolved in acetone 1 8 g, L i C 1 Ο 4 0 · 1 5 g pressurized forte uniform To prepare a resin composition for a solid polymer electrolyte.

A polymer solid electrolyte membrane was prepared from the above composition in the same manner as in Example 1, and Its conductivity was 9 × ¹⁰ −5 sZcm at 23 ° C.

Comparative Example 1

(1) Synthesis of random-graph small copolymer

Methyl methacrylate (hereinafter referred to as MMA) 40 ml, 4 CMS 0.5 ml, 0.03 g of azobisisobutyronitrile are dissolved in 20 ml of toluene, and argon gas is bubbled for 15 minutes, followed by argon. Under an atmosphere, the temperature was raised to 8 O: to carry out a copolymerization reaction for 3 hours. After the reaction solution was cooled to room temperature, it was poured into a large amount of methanol to precipitate a polymer, which was filtered, dried, and dried under reduced pressure at 60 ° C. for 5 hours to obtain a polymer with an isolation yield of 41%. GPC analysis of this polymer revealed that Mn = l33,000, PD = 2.51, and that ¹³ CNMR was measured, the polymer containing 0.93 mol% of 4 CMS units (0.93 mol%) MMA—r—4 CMS).

Then, in an argon atmosphere, the obtained poly (MMA-r-4CMS) 0.1 lmmol, PME-400 7 Ommo 1, Add 0.1 mmo 1,4,4'-dimethyl-2,2'-dipyridyl copper 0.2 mmo 1 and mix uniformly, then heat to 90 ° C with stirring to start the copolymerization reaction. Was. Forty hours after the start of the copolymerization reaction, the temperature of the reaction system was cooled to 0 ° C. to stop the copolymerization reaction. As a result of GPC analysis, the polymerization conversion was 50%. The reaction solution was subjected to column purification to remove metal complexes and unreacted monomers, and then volatile components were removed under reduced pressure to obtain a polymer. GPC analysis of this polymer revealed that Mn = 283,000 and PD = 2.28, and ¹³ C NMR measurement showed that the polymer (MMA containing 42.4% by weight of a polyethylene oxide component) — R— (4CMS-g-PME-400)).

When the obtained random graft copolymer was dissolved in THF and the film formed in the same manner as in Example 1 was observed with a transmission electron microscope, a microphase-separated structure was not observed and a uniform structure was observed. Met.

(2) Preparation of resin composition for polymer solid electrolytic chamber

The random graft copolymer obtained by the above operation under an argon atmosphere The body 2 g was dissolved in THF 1 8 g, to prepare a solid polymer electrolyte resin composition was uniformly dissolved by adding L i C L_〇 ₄ 0. lg.

(3) Polymer solid electrolyte membrane preparation and ionic conductivity measurement

In an argon atmosphere, the above composition was cast on a Teflon (registered trademark) plate and dried under reduced pressure at room temperature for 24 hours to obtain a uniform polymer solid electrolyte membrane (polymer solid having a thickness of 100 m). The ionic conductivity of the electrolyte membrane was measured in the same manner as in Example 1. The solid polymer electrolyte membrane obtained in the same manner was dried at room temperature for 24 hours and further at 60 ° C. for 24 hours. The ionic conductivity of the polymer solid electrolyte membrane dried under reduced pressure was also measured, and as a result, the ion conductivity at 25 ° C was determined for both those dried at room temperature and those dried at room temperature and then heated. was ~ 2x10- ⁶ s Zcm.

Comparative Example 2

(1) Synthesis of block graft copolymer

t-Butyl acrylate (hereinafter referred to as tBA) 1 20mmol and 2,2,5-trimethyl-1-3-phenylethoxy) — 4-phenyl-3-azahexane 1.07 mm After uniformly mixing o and 1 and performing nitrogen publishing for 15 minutes, the mixture was heated to 125 ° C under a nitrogen atmosphere to start a polymerization reaction. After 15 hours from the start of the polymerization reaction, the reaction solution was cooled to 0 ° C to stop the polymerization reaction. After dissolving the reaction solution in THF, the polymer was poured into a large amount of methanol to precipitate a polymer, which was filtered, washed, and dried under reduced pressure at 60 ° C for 5 hours. The isolation yield of the obtained polymer was 78%. When GPC analysis was performed on the obtained poly-tBA, it was Mn = 10,800 and PD = 1.21.

Next, the obtained poly-tBA lmmo 1 and 4 CMS 10 Ommo 1 were uniformly mixed, nitrogen publishing was performed for 15 minutes, and the mixture was heated to 125 ° C. to start a copolymerization reaction. Five hours after the start of the copolymerization reaction, the reaction solution was cooled to 0 ° C to stop the copolymerization reaction. As a result of GC analysis, the polymerization conversion of 4CMS was 20%. The reaction solution was dissolved in THF and poured into a large amount of methanol to precipitate a polymer. After filtration and washing, the obtained polymer was dried under reduced pressure at 60 ° C for 5 hours. GPC analysis of this polymer showed that Mn = 13,700 and PD = 1.23. Block copolymer having the structure of poly (tBA-b-4CMS). Then, in a nitrogen atmosphere, 42 g of toluene previously subjected to a nitrogen publishing treatment was added to the above poly (t BA_b-4 CMS) 0.1 lmmo 1, PME 1000 1000 mmo 1, cuprous chloride 0.1 lmmol, After adding 0.2 mmol of 2,2, -biviridine and mixing uniformly, the mixture was heated to 80 with stirring to start the copolymerization reaction. Twenty hours after the start of the copolymerization reaction, the temperature of the reaction system was cooled to 0 ° C to stop the copolymerization reaction. As a result of GPC analysis, the polymerization conversion of PME-1000 was 68%. After column purification of the reaction solution to remove metal complexes and unreacted monomers, volatile components were removed under reduced pressure to obtain a polymer. GPC analysis of this polymer revealed that Mn = 12,000 and PD = 1.30. ¹³ CNMR analysis showed that the polymer had a value of 4 based on the total number of moles of repeating units in the copolymer. CMS repeat unit, tBA repeat unit, and PME—Poly (tBA—b— (), in which the molar ratio of 1000 repeat units is 9.5%, 42.3%, and 48.2%, respectively. It was a block / graft copolymer having the structure of 4CMS-g-PME-1000)).

The obtained block / graft copolymer was formed into a film in the same manner as in Example 1, and the obtained film was observed with a transmission electron microscope. As a result, no micro-mouth phase separation structure was observed and the film had a uniform structure. Was.

(1) Preparation of resin composition for polymer solid electrolyte

Under an argon atmosphere, 2 g of the block / graft copolymer obtained in the above procedure was dissolved in 18 g of acetone, and 0.2 g of LiClO ₄ was added to uniformly dissolve the polymer. A resin composition for a solid electrolyte was prepared.

(2) Preparation of solid polymer electrolyte membrane and measurement of ionic conductivity

A polymer solid electrolyte membrane was prepared from the above composition in the same manner as in Example 1, and the ion conductivity was measured. As a result, it was ³ × ¹⁰ −5 sZcm at 23 ° C.

Industrial applicability:

As described above, since the novel graft copolymer of the present invention has a sea-island structure phase separation structure in a thin film, it has high conductivity and excellent mechanical and physical properties in a composite with an electrolyte. Because of its properties, various electric devices such as batteries It is useful as a solid electrolyte for metals and has high industrial applicability.

Claims

The scope of the claims

Formula (I)

(In the formula, represents a hydrogen atom or a C 1 to (: 10 hydrocarbon group which may have a substituent, R ₂ represents a functional group capable of having an active halogen atom, and R ₃ represents , A halogen atom or an organic group, and X is a group represented by the formula (II)

(Wherein, R ₄ represents a hydrogen atom or a C 1 -C 10 hydrocarbon group which may have a substituent, and R ₅₁ and R ₅₂ each independently represent a hydrogen atom, or Represents a 1 to C4 alkyl group, R ₆ represents a hydrogen atom, a hydrocarbon group, an acyl group, a silyl group, a phosphoryl group, a hydrocarbon phosphoryl group, or a hydrocarbon sulfonyl group; represents Kano integer, when d is 2 or more, R ₄ together, each other R _51, R ₅₂ together, R ₆ to each other, and e each other, may be the same or different, e is 1 Represents an integer of 100, and when e is 2 or more, R ₅ _t and R ₅₂ may be the same or different from each other.) Represents a merging chain, a represents an integer of 1 to 3, when a is 2 or more, R ₂ and X May be the same or different; b represents 1 or 2; when b is 2, Xs may be the same or different; c is 0 or any of 1 to (4-a) And when c is 2 or more, R ₃ 's may be the same or different. A copolymer having a repeating unit represented by the formula: and a repeating unit comprising a nonpolar moiety.

2. In the formula (I), R ₂ is the formula αν)

(Wherein, R ₉ and R independently represent a hydrogen atom, a halogen atom, or a C 1 -C 10 hydrocarbon group which may have a substituent, and b in the formula (I) represents 2. In the case of 2, it represents a bond to X.) The copolymer according to claim 1, which is a functional group represented by the following formula:

3. The copolymer according to claim 1, wherein the degree of polymerization of the repeating unit represented by the formula (I) is 3 or more.

4. The copolymer according to any one of claims 1 to 3, wherein the degree of polymerization of the repeating unit comprising a nonpolar moiety is 5 or more.

5. The polymer chain having a repeating unit represented by the formula (Π), wherein the degree of polymerization of the repeating unit represented by the formula (Π) is 5 or more. Or the copolymer described in the above.

6. The copolymer according to any one of claims 1 to 5, wherein the repeating unit represented by the formula (I) and the repeating unit comprising a nonpolar moiety are in a block copolymer. .

7. Block chains (B) and (C) having a repeating unit composed of a nonpolar moiety which may be the same as or different from the block chain (A) having a repeating unit represented by the formula (I) are The copolymer according to any one of claims 1 to 6, wherein the copolymer has an arrangement of (B), (A), and (C).

8. The copolymer according to claim 7, wherein the arrangement in the order of (B), (A), and (C) is a combined sequence of (B)-(A)-(C). .

9. For the total number of moles of the repeating unit represented by the formula (I), the repeating unit represented by the formula (Π), and the repeating unit comprising a nonpolar moiety, the repeating represented by the formula (I) The mole number of the unit is in the range of 0.001 to 50%.

9. The copolymer according to any one of 1 to 8.

10. A repeating unit represented by the formula (I), a repeating unit represented by the formula (II), and And wherein the number of moles of the repeating unit represented by the formula (9.) is in the range of 9.999 to 80% based on the total number of moles of the repeating unit comprising a non-polar moiety. 10. The copolymer according to any one of 1 to 9.

1 1. The repeating unit consisting of the non-polar moiety relative to the total number of moles of the repeating unit represented by the formula (I), the repeating unit represented by the formula (II), and the repeating unit consisting of the non-polar moiety. The copolymer according to any one of claims 1 to 10, wherein the number of moles of the unit is in the range of 19.999 to 90%.

12. A repeating unit comprising a nonpolar moiety is represented by the formula (III)

(In the formula, R ₇ represents a hydrogen atom or a C 1 to (10 hydrocarbon group which may have a substituent, and R ₈ represents a hydrocarbon group which may have a substituent.) The copolymer according to any one of claims 1 to 11, which is a repeating unit represented by the following formula:

13. The copolymer according to claim 12, wherein in the formula (II), R ₈ is an aromatic hydrocarbon group which may have a substituent.

14. The repeating unit represented by the formula (III) is represented by the formula (V)

(Wherein represents a hydrogen atom or a methyl group.) The copolymer according to any one of claims 1 to 13, wherein the repeating unit is represented by the following formula:

15. The copolymer according to any one of claims 1 to 14, wherein the number average molecular weight is in the range of 10,000 to 5,000,000.

16. Equation (VI)

(In the formula, represents a hydrogen atom or a C 1 to (: 10 hydrocarbon group which may have a substituent, R ₁₂ represents a functional group capable of having an active halogen atom, and Y is Represents a halogen atom, R ₁₃ represents an octogen atom or an organic group, al represents an integer from 1 to 3, and when al is 2 or more, R ₁₂ and Y, and bl may be the same or different; bl represents 1 or 2; when bl is 2, Y may be the same or different; (1 is 0 or 1 to And R ₁₃ is the same or different when cl is 2 or more, and a compound represented by the formula (VII):

^ 17

H ₂ C = C ·,. (VII)

, 18

(In the formula, R ₁₇ represents a hydrogen atom or a C 1 -C 10 hydrocarbon group which may have a substituent, and R ₁₈ represents an aromatic hydrocarbon group which may have a substituent. The compound represented by the formula is subjected to living radical polymerization using a stable radical polymerization initiator to obtain a copolymer, and then the obtained copolymer is used as an initiator, and the compound represented by the formula (VIII)

(In the formula, R ₁₄ represents a hydrogen atom or a C 1 to (: 10 hydrocarbon group which may have a substituent, and R ₁₅₁ and R ₁₅₂ each independently represent a hydrogen atom, or or represents C 1～C4 alkyl group, R ₁₆ is a hydrogen atom, a hydrocarbon group, Ashiru group, Silyl group, a phosphoryl group, a hydrocarbon phosphoryl group or a hydrocarbon sulfonyl group, el represents a deviation integer of 1 to 100, if el is 2 or more, R ₁₅₁ to each other, and R ₁₅₂ Each may be the same or different. A method for producing a copolymer, comprising subjecting the compound represented by the formula to living radical polymerization.

1 7. In the formula (VI), R ₁₂ is the formula (IX)

(Wherein, R ₁₉ and R each independently represent a hydrogen atom, a halogen atom, or a C 1 -C 10 hydrocarbon group which may have a substituent. 17. The method for producing a copolymer according to claim 16, wherein, when bl is 2, it represents a bond to Y.)

18. The copolymer according to claim 16 or 17, wherein the copolymer obtained from the compound represented by the formula (VI) and the compound represented by the formula (VII) is a block copolymer. A method for producing a copolymer of

19. The method for producing a copolymer according to any one of claims 16 to 18, wherein the stable radical initiator comprises a stable free radical compound and a radical polymerization initiator or an alkoxyamine. .

20. The method for producing a copolymer according to claim 19, wherein the stable free radical compound is a nitroxyl compound.

21. The method for producing a copolymer according to claim 19, wherein the radical polymerization initiator is an organic peroxide or an azo compound.

22. A polymer solid electrolyte comprising the copolymer according to any one of claims 1 to 15, and an electrolyte salt.

23. The electrolyte according to claim 22, wherein the electrolyte salt is at least one selected from the group consisting of an alkali metal salt, a quaternary ammonium salt, a quaternary phosphonium salt, a transition metal salt, and a protonic acid. Molecular solid electrolyte.

24. The polymer solid electrolyte according to claim 23, wherein the electrolyte is a lithium salt.