JP2001084832A - High polymer solid electrolyte - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a high polymer soid electrolyte having a high ion conductivity which is chemically stable and has excellent moldability. SOLUTION: This high polymer solid electrolyte comprises [I] a polymer including (1) a hard segment comprising a polymer having a glass transition temperature of 105 deg.C or more, and (2) a soft segment comprising a polymer having a glass transition temperature of 30 deg.C or less, [II] a salt of a metal of group Ia in the periodic table, and [III] a solvent capable of dissolving the salt of a metal of group Ia in the periodic table, as necessary.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid polymer electrolyte, and more particularly to a solid polymer electrolyte suitable for use in electrochemical devices such as primary batteries, secondary batteries and capacitors.

[0002]

BACKGROUND OF THE INVENTION Conventionally, primary batteries, secondary batteries,
Liquid electrochemical solutions have been used for electrochemical devices such as capacitors. However, the electrolyte leaks,
There is a problem that batteries and capacitors lack long-term reliability. One solution to this problem is
A method using a solid electrolyte is known. When a solid electrolyte is used, a highly reliable element can be provided without liquid leakage, and the element itself can be reduced in size and weight, and the degree of freedom of a product shape can be increased. It has the advantage that.

[0003] Such a solid electrolyte comprises an inorganic solid electrolyte such as silver iodide, Li ₂ Ti ₃ O ₇ , β-alumina, RbAg ₄ I ₅ , phosphotungstic acid, a polymer matrix and an electrolyte salt. Polymer solid electrolytes are known. However, it is often difficult to form or form an inorganic solid electrolyte into an arbitrary shape, and the raw materials are expensive. Furthermore, in order to obtain sufficient ionic conductivity, a temperature higher than room temperature is required. There are many problems, such as the need for many.

On the other hand, since the polymer solid electrolyte has flexibility, it can be flexibly applied to a volume change caused in the ion-electron exchange reaction process between the electrode and the polymer solid electrolyte. It has the characteristics of such a solid electrolyte. For this reason, in recent years, various polymer solid electrolytes have been studied as solid electrolytes. As such a polymer solid electrolyte, specifically, a composite of a polyethylene oxide having a polyether structure and an alkali metal salt such as a lithium salt is known. Also, Japanese Patent Application Laid-Open No. 5-253
No. 53 discloses an ester compound of a polyoxyalkylene and a diester compound, an ester compound of a polymethoxyoxyalkylene, a crosslinked resin of a copolymer of an oxy compound having a double bond such as vinylene carbonate, and an inorganic salt. Is described as a main component. Furthermore, JP-A-6-223842 describes a polymer solid electrolyte comprising an organic polymer having a carbonate group as a functional group and a metal salt.

However, this polymer solid electrolyte generally has a lower ionic conductivity than the electrolytic solution, so that it has been difficult to obtain a primary battery and a secondary battery having excellent discharge characteristics. In addition, it is difficult to mold the crosslinkable resin, and when it is used as a component of the solid polymer electrolyte, there is a problem that the molding method is limited. Under such circumstances, there is a demand for a polymer solid electrolyte that satisfies requirements such as high ionic conductivity, excellent electrochemical stability, and excellent moldability.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and has a high ionic conductivity, is chemically stable, and has excellent moldability. It is intended to provide an electrolyte.

[0007]

SUMMARY OF THE INVENTION The solid polymer electrolyte according to the present invention comprises [I]
(1) a polymer containing a hard segment composed of a polymer having a glass transition temperature of 105 ° C. or higher and (2) a soft segment composed of a polymer having a glass transition temperature of 30 ° C. or lower, and [II] a periodic table And a salt of a Group Ia metal.

Further, the solid polymer electrolyte according to the present invention comprises:
[I] a polymer including (1) a hard segment composed of a polymer having a glass transition temperature of 105 ° C. or higher, and (2) a soft segment composed of a polymer having a glass transition temperature of 30 ° C. or lower, [II] A salt of a metal of Group Ia of the Periodic Table, [III]
A solvent capable of dissolving a salt of a metal of Group Ia of the periodic table.

The polymer (1) having a glass transition temperature of 105 ° C. or higher is a polymer having a cyclic structure in the main chain and / or
Alternatively, a polymer containing a structural unit derived from a (meth) acrylate monomer is preferred. In addition, (2) 30
The polymer having a glass transition temperature of not more than ° C. is preferably a polymer containing a structural unit derived from an alkylene oxide monomer structure and / or a (meth) acrylate monomer.

[I] The polymer comprises (1) a hard segment comprising a polymer having a glass transition temperature of 105 ° C. or higher and (2) a soft segment comprising a polymer having a glass transition temperature of 30 ° C. or lower. Weight ratio (hard segment /
Soft segment) is preferably 2/98 to 98/2. Further, the solvent capable of dissolving the salt of the metal of Group Ia of the Periodic Table [III] is preferably a carbonate ester.

[0011]

DETAILED DESCRIPTION OF THE INVENTION The solid polymer electrolyte according to the present invention will be specifically described below. In this specification, the term "(meth) acrylic acid" means acrylic acid and / or methacrylic acid, and the term "(meth) acrylate" means acrylate and / or methacrylate. . Further, in this specification, the term "polymerization" may be used to mean not only homopolymerization but also copolymerization, and the term "polymer" is used not only for homopolymers but also for copolymers. Is sometimes used in a sense that also includes

[Polymer] First, the polymer used in the present invention will be described. The polymer used in the present invention is
The same molecule has (1) a hard segment made of a polymer having a glass transition temperature of 105 ° C. or higher, and (2) a soft segment made of a polymer having a glass transition temperature of 30 ° C. or lower. Such polymers include, for example,
(1) a hard segment consisting of a polymer having a glass transition temperature of 105 ° C. or more, and (2) a block polymer of a soft segment consisting of a polymer having a glass transition temperature of 30 ° C. or less, (1) 105 ° C. or more Examples thereof include a graft polymer of a hard segment composed of a polymer having a glass transition temperature and (2) a soft segment composed of a polymer having a glass transition temperature of 30 ° C. or lower, or a mixture of the block polymer and the graft polymer.

The weight average molecular weight Mw of such a polymer
(In terms of standard polystyrene) 10,000 to 2,000,000, preferably 20,000 to 1,500,000, more preferably 30,000 to 1,0
Desirably it is in the range of 00,000. Hard segment The hard segment comprises a polymer having a glass transition temperature of 105 ° C or higher, preferably 110 to 250 ° C, more preferably 120 to 200 ° C. The polymer is not particularly limited as long as the glass transition temperature is within the above range. Specifically, a polymer having a cyclic structure in the main chain and a vinyl having a bulky substituent in a side chain And a polymer having a rigid structure such as a vinyl polymer and a vinylidene polymer.

As the polymer having a cyclic structure in the main chain,
A copolymer of a cyclic olefin having a structural unit represented by the following formula (Ia) and an olefin, and a hydrogenated product of a metathesis polymer of a cyclic olefin having a structural unit represented by the following formula (Ib) (the cyclic olefin) Hydrogenated product of the ring-opened polymer of the present invention).

[0015]

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In the above formula, n is an integer of 1 to 3. R ¹
-R ¹⁸ is a group consisting of elements selected from hydrogen, carbon, oxygen, nitrogen, silicon, and halogen, and specifically, for example, hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, Stearyl, an alkyl group such as cyclohexyl, a phenyl group, an aryl group such as a toluyl group, an aldehyde group, a carbonyl group,
Carboxyl group, ester group, amino group, amide group, silyl group, halogen, aldehyde group, carbonyl group, carboxyl group, ester group, amino group, amide group, silyl group, hydrocarbon group containing halogen and the like. Can be R ^{1 to} R ¹⁸ may be different or the same.

Of these, R ^{1 to} R ¹⁸ are preferably hydrogen or a hydrocarbon group such as a methyl group or an ethyl group. The polymer may contain other structural units as long as the glass transition temperature is 105 ° C. or higher, for example, 7-methyl
-1,6-octadiene, 5-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 8-epoxy-1-octene, 10-
Structural units derived from monomers such as epoxy-1-decene are preferred examples. The content of other structural units in the polymer is at most 15 mol%, preferably 1 mol%.
It is desirably 0 mol% or less.

As the vinyl polymer and vinylidene polymer having a bulky substituent in the side chain, the following polymers having a poly (meth) acrylate ester skeleton are preferable.

[0019]

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In the above formula, ^Ra is a hydrogen atom or a methyl group. R ^{20 to} R ²² are groups consisting of elements selected from hydrogen, carbon, oxygen, nitrogen, silicon, and halogen, and specifically include, for example, alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, and cyclohexyl;
Phenyl group, aryl group such as toluyl group, aldehyde group, carbonyl group, carboxyl group, ester group, amino group, amide group, silyl group, halogen, aldehyde group,
Examples include a carbonyl group, a carboxyl group, an ester group, an amino group, an amide group, a silyl group, and a hydrocarbon group containing halogen. Note that R ^{20 to} R ²² may be the same or different.

Particularly, a syndiotactic (meth) acrylate polymer is preferred because of its high glass transition temperature, and methyl (meth) acrylate and (meth) acrylate having a high syndiotacticity (syndiotactic regularity) are preferred. Polymers such as cyclohexyl acrylate and isopropyl (meth) acrylate are preferred. Further, the hard segment is a polycyclic (meth) acrylic acid ester polymer having a structural unit represented by the following formula (II) in addition to the polymer represented by the above formulas (Ia) and (Ib). Coalescing is also suitable.

[0022]

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In the above formula, n is an integer of 1 to 3. R ^b
Is a hydrogen atom or a methyl group. X ¹ represents a direct bond or a lower alkylene group which may have an oxygen atom, and specific examples of the lower alkylene group include a methylene group and an ethylene group, and an oxygen-containing lower alkylene group. Specific examples include an oxymethylene group and an oxyethylene group.

R ^{31 to} R ⁴⁷ represent hydrogen, carbon, oxygen, nitrogen,
A group consisting of an element selected from silicon and halogen; specifically, for example, a hydrogen atom, a methyl group, an ethyl group,
Alkyl groups such as propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, stearyl group, cyclohexyl group, aldehyde group, carbonyl group, carboxyl group, ester group, amino group, amide group, silyl Groups, halogens, and aldehyde groups, carbonyl groups, carboxyl groups, ester groups, amino groups, amide groups, silyl groups, and hydrocarbon groups containing halogen. Note that R ^{31 to} R ⁴⁷ may be different or the same.

R ^{31 to} R ^{47 each} represent a hydrogen atom or a methyl group,
Hydrocarbon groups such as ethyl groups are preferred. The weight average molecular weight of the above polymer (polymer constituting the hard segment) measured by GPC (in terms of polystyrene) is 3,000 to 6
00,000, preferably 5,000 to 400,000, particularly preferably 7,
It is desirable that it is 000-300,000, more preferably 3,000-200,000. Further, it is desirable that Mw (weight average molecular weight) / Mn (number average molecular weight) is in the range of 1 to 20, preferably 1 to 10, and more preferably 1 to 5.

The above polymer may contain a structural unit derived from another monomer as long as the glass transition temperature is 105 ° C. or higher. Specific examples of these include (meta)
Glycidyl acrylate, allyl (meth) acrylate,
Preferred examples include (meth) acrylates having a functional group in an ester group such as vinyl (meth) acrylate.

Soft segment The soft segment comprises a polymer having a glass transition temperature of 30 ° C or lower, preferably -200 to 25 ° C, more preferably -150 to 20 ° C. Such a polymer is not particularly limited as long as the glass transition temperature is within the above range, and specifically, an alkylene oxide polymer and a (meth) acrylate polymer are preferred.

Specific examples of the alkylene oxide polymer include polymers of ethylene oxide, propylene oxide, oxetane, and tetrahydrofuran, and copolymers thereof. Specifically, as the (meth) acrylate polymer,
Those having the following structures are preferred.

[0029]

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In the above formula, R ^c is a hydrogen atom or a methyl group. R ⁵⁰ is ether, carbonyl, carboxyl, carbonate, amino, amide, imino, imide,
It has a siloxy, halo bond, carbon, oxygen, hydrogen, nitrogen,
It is a group composed of elements selected from silicon and halogen. The above polymer may contain other monomer structures as long as the glass transition temperature is 30 ° C. or lower. Specific examples of these include glycidyl (meth) acrylate,
Preferred examples include (meth) acrylates having a functional group in an ester group such as allyl (meth) acrylate and vinyl (meth) acrylate.

The weight average molecular weight (in terms of polystyrene) of the above polymer measured by GPC is from 3,000 to 600,000, preferably from 5,000 to 400,000, particularly preferably from 7,000 to 300,000.
0, more preferably 3,000 to 100,000. Further, Mw (weight average molecular weight) / Mn (number average molecular weight) of such a polymer is 1 to 20, preferably 1 to 10, and more preferably 1 to 10.
It is desirably in the range of ~ 5.

Composition of Polymer The weight ratio of hard segment to soft segment (hard segment / soft segment) contained in the polymer used in the present invention is 2/98 to 98/2, preferably 4/96 to 96. / 4, more preferably 5 / 95-9
The ratio is preferably 5/5, particularly preferably 7/93 to 93/7.

Such a polymer may contain other components as long as the effects of the present invention are not impaired. When other components are contained, the total amount of the hard segment and the soft segment in the polymer is at least 20% by weight, preferably at least 30% by weight, more preferably at least 60% by weight, particularly preferably at least 80% by weight. % Is desirable. As other components, specifically, additives such as a heat stabilizer, a halogen absorber, an antistatic agent, a slip agent, and a filler, a (meth) acrylate polymer, an alkylene oxide polymer, a cyclic olefin polymer, Examples include polymers such as olefin polymers, nitrogen-containing polymers such as polyacrylonitrile, and halogen-containing polymers such as polyvinylidene fluoride. In addition, this polymer component,
It may be combined with the hard segment and / or the soft segment, or may be simply mixed.

The polymer used in the present invention may have a cyclic structure or a crosslinked structure, but preferably has a substantially linear structure. Having a substantially linear structure means that it is dissolved in an organic solvent under somewhat mild conditions,
For example, it can be confirmed by dissolving in tetrahydrofuran (THF), toluene or the like at the time of GPC measurement. The solvent-insoluble component is 50% by weight or less, preferably 40% by weight or less, more preferably 30% by weight or less, and particularly preferably 2% by weight or less.
It is at most 5% by weight, more preferably at most 20% by weight.

The polymer used in the present invention preferably has thermoplasticity. The weight average molecular weight (standard polystyrene conversion) measured by GPC of the polymer comprising the hard segment and the soft segment used in the present invention is 10,000 to 2,000,000, preferably 20,000 to 1,50.
0,000, more preferably 30,000-1,000,000. The polymer used in the present invention has a substantially linear structure and exhibits thermoplasticity, and therefore has excellent moldability, injection molding, and T-
Molding can be performed by a conventionally known molding method such as die molding, press molding, extrusion molding, inflation molding, blow molding, and vacuum molding.

Synthesis of Polymer A method for synthesizing the polymer used in the present invention will be described. As a method for synthesizing the polymer according to the present invention, any conventionally known method can be applied. Specifically, (i) a polymer reaction method of synthesizing a polymer constituting a hard segment comprising a polymer having a reactive group and a polymer constituting a soft segment polymer and then copolymerizing them (a macromonomer method); After the polymer that constitutes the hard segment is synthesized by living polymerization, the monomer of the polymer that constitutes the soft segment is polymerized, or the polymer that constitutes the soft segment is synthesized by living polymerization, and then the hard segment is formed. (Iii) graft polymerization of the polymer of the soft segment onto the polymer of the soft segment or the addition of the hard segment on the polymer of the soft segment An example is a graft polymerization method in which a monomer of the constituting polymer is graft-polymerized. can do.

[(I) Polymer Reaction Method] The polymer reaction method will be described below. In the polymer reaction method, a polymer constituting a hard segment and a polymer constituting a soft segment are formed in advance. Examples of the method for synthesizing such a polymer include conventionally known methods such as a suspension polymerization method, an emulsion polymerization method, a solution polymerization method, and a bulk polymerization method, in which monomers corresponding to the hard segment and the soft segment are polymerized. It can be obtained by: As the polymerization method, a bulk polymerization method is desirable in order to avoid contamination with impurities, and a solution polymerization method is desirable for controlling the molecular weight, molecular weight distribution, composition distribution, and the like.

Synthesis of Polymer Constituting Hard Segment When the hard segment is composed of a copolymer of a cyclic olefin and an olefin, the copolymer is prepared by converting the cyclic olefin and the olefin in the presence of a Ziegler catalyst and a metallocene catalyst. It is synthesized by copolymerization. When the hard segment comprises a hydrogenated product of a metathesis polymer, the hydrogenated polymer is synthesized by subjecting a cyclic olefin to ring-opening polymerization using a metathesis polymerization catalyst, and hydrogenating this with a hydrogenation catalyst. You.

As the cyclic olefin, those having the following structure are used.

[0040]

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In the above formula, n is an integer of 1 to 3. R ¹
-R ¹⁷ is a group consisting of an element selected from hydrogen, carbon, oxygen, nitrogen, silicon, and halogen. Specifically, for example, hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, Stearyl, an alkyl group such as cyclohexyl, a phenyl group, an aryl group such as a toluyl group, an aldehyde group, a carbonyl group,
Carboxyl group, ester group, amino group, amide group, silyl group, halogen, aldehyde group, carbonyl group, carboxyl group, ester group, amino group, amide group, silyl group, hydrocarbon group containing halogen and the like. Can be R ^{1 to} R ¹⁷ may be different or the same. Among them, R ^{1 to} R ¹⁷ are preferably hydrogen or a hydrocarbon group such as a methyl group or an ethyl group.

As such a cyclic olefin, specifically,

[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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And the like. Two or more of these cyclic olefins may be used. The Ziegler catalyst is a catalyst comprising an organometallic compound component of Groups I, II, and III (excluding boron) of the periodic table and a metal compound component of Groups IV to VIII. A catalyst composed of vanadium, vanadyl halide or the like is used. Examples of the metallocene catalyst include a catalyst comprising a metallocene compound of a transition metal selected from Group 4 of the periodic table, an organic aluminum oxy compound and / or an ionized ionic compound.

Examples of the metathesis catalyst include tungsten (IV) halide and a system comprising a tungsten halide and an organic aluminum compound or an organic tin compound. Examples of the hydrogenation catalyst include nickel compounds such as Raney nickel, cobalt compounds such as Raney cobalt, platinum compounds such as platinum oxide, palladium compounds such as palladium carbon, and copper compounds such as copper chromite.

Examples of the olefin include ethylene, propylene, and butene. Of these, ethylene is preferably used. Further, two or more of these olefins may be used. Furthermore, if the glass transition temperature of the obtained copolymer is 105 ° C. or lower, other monomers may be copolymerized in addition to the above-mentioned olefin, and such a monomer may be 7-methyl-1. , 6-octadiene, 5-
Those having a functional group such as methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 8-epoxy-1-octene, and 10-epoxy-1-decene are preferable. These monomers are usually used in an amount of 20 to olefin or cyclic olefin.
It is desirable to use it in an amount of not more than 15 mol%, preferably not more than 15 mol%, more preferably not more than 10 mol%.

When the hard segment is derived from a vinyl polymer or a vinylidene polymer having a bulky substituent in the side chain, for example, the polymer may be a (meth) acrylic acid represented by the following formula: It is obtained by polymerizing an ester compound.

[0055]

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In the above formula, ^Ra is a hydrogen atom or a methyl group. R ^{20 to} R ²² are groups consisting of elements selected from hydrogen, carbon, oxygen, nitrogen, silicon, and halogen, and specifically include, for example, alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, and cyclohexyl;
Phenyl group, aryl group such as toluyl group, aldehyde group, carbonyl group, carboxyl group, ester group, amino group, amide group, silyl group, halogen, aldehyde group,
Examples include a carbonyl group, a carboxyl group, an ester group, an amino group, an amide group, a silyl group, and a hydrocarbon group containing halogen. Note that R ^{20 to} R ²² may be the same or different.

Specific examples of such compounds include t-butyl (meth) acrylate, cumyl (meth) acrylate,
Texyl (meth) acrylate, amyl (meth) acrylate, trityl (meth) acrylate, (meth) acrylic acid
Examples thereof include 1,1-diphenylethyl, diphenylpyridylmethyl (meth) acrylate, and admantyl (meth) acrylate. In addition, the syndiotactic (meth) acrylate polymer has a high glass transition temperature,
Polymers having high syndiotacticity such as methyl (meth) acrylate, cyclohexyl (meth) acrylate, and isopropyl (meth) acrylate can also be mentioned as preferable examples.

Further, in addition to the above, a polymer which induces a hard segment can be synthesized by polymerizing a cyclic (meth) acrylate compound represented by the following formula.

[0059]

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[0060] In the above formulas, n is an integer of 1-3, R ^b
Is a hydrogen atom or a methyl group. X ¹ is a lower alkylene group which may have a direct bond or may have an oxygen atom. Specific examples of the lower alkylene group include a methylene group and an ethylene group. Specific examples of the group include an oxymethylene group and an oxyethylene group.

R ^{30 to} R ⁴⁷ represent hydrogen, carbon, oxygen, nitrogen,
Silicon, a group consisting of elements selected from halogen, specifically, for example, a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a stearyl group, Alkyl groups such as cyclohexyl group, aldehyde group, carbonyl group, carboxyl group, ester group, amino group, amide group, silyl group, halogen, further hydroxy group, aldehyde group, carbonyl group, carboxyl group, ester group, amino group, Examples include an amide group, a silyl group, and a hydrocarbon group containing a halogen. Note that R ^{30 to} R ⁴⁷ may be different or the same. Among them, a hydrogen atom or a hydrocarbon group such as a methyl group or an ethyl group is preferable.

As such a cyclic (meth) acrylate compound, specifically,

[0063]

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[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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This polymer has a glass transition temperature of 105 ° C.
If so, other compounds may be polymerized in addition to the (meth) acrylate compound. Specific examples of the other compound include those having a functional group such as glycidyl (meth) acrylate, allyl (meth) acrylate, and vinyl (meth) acrylate. For the purpose of adjusting the glass transition temperature, a (meth) acrylate having a primary ester group such as methyl methacrylate or ethyl methacrylate may be copolymerized.
These are 20 mol% or less, preferably 15 mol% or less,
More preferably, it may be used in an amount of 10 mol% or less.

As the polymerization initiator, a radical polymerization initiator or an anionic polymerization initiator is usually used.
As the radical polymerization initiator, specifically, benzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, 3,3,5-trimethylhexanoyl peroxide, di-2-ethylhexyl peroxydicarbonate, Methyl ethyl ketone peroxide, t-butylperoxyphthalate, t-butylperoxybenzoate, di-t-butylperoxyacetate, t-butylperoxyisobutyrate, t-butylperoxy-2-hexanoate, t-butylperoxide Organic peroxides such as oxy-3,5,5-trimethylhexanoate, 1,1'-azobisisobutyronitrile, 1,1'-azobiscyclohexanecarbonitrile, 2-cyano-2-propylazo An azo compound such as formamide can be exemplified. It is also possible to generate radicals by irradiating light such as ultraviolet rays to carry out polymerization. Examples of the anionic polymerization initiator include n-butyl lithium, s-butyl lithium, t-butyl lithium, 1,1-diphenylhexyl lithium, fluorenyl lithium, α
Organic alkali metal compounds such as -methylstyryl lithium, Grignard reagents such as n-butylmagnesium halide, s-butylmagnesium halide, t-butylmagnesium halide, aluminum compounds such as methylaluminum tetraphenylporphyrin, diethylaluminum diphenylamide, bis Examples include metallocene compounds such as cyclopentadienyl samarium hydride and biscyclopentadienyl ytterbium hydride, and organic phosphorus compounds such as triethylphosphine and triphenylphosphine. These anionic polymerization initiators include triethylaluminum, tributylaluminum, trioctylaluminum, methylbis (2,6-di-
Addition of organic aluminum compounds such as (-t-butylphenoxy) aluminum, organic nitrogen compounds such as tetramethylethylenediamine, or irradiation with light makes it easier to accelerate the polymerization rate and control the molecular weight and composition. The effect may appear. In addition to the above catalyst,
Coordinating anionic polymerization initiators, group transfer polymerization initiators, and the like can also be used.

[0073] coordination known Ziegler as anionic polymerization initiator - Natta catalyst, and examples of the group transfer polymerization initiator, and various ketene silyl acetal compound, HF ₂ ^- Ya nucleophilic reagent such as And those comprising a Lewis acid such as bibenzoate. Further, as a polymerization initiator, carbon tetrachloride, benzyl chloride, halides such as glycidyl 2-bromo-2-methylbutanoate, glycidyl trichloroacetate, metal complexes such as ruthenium triphenylphosphine dichloride complex and Lewis such as aluminum alkoxide. A multi-component initiator in combination with an acid can also be used. When such an initiator is used, a functional group derived from the initiator can be introduced into a polymerization initiation terminal.

Other methods for introducing a functional group into the polymerization initiation terminal include, for example, radical polymerization using a radical polymerization initiator having a functional group stable to radicals, and an anion having a functional group stable to anions. Examples include anionic polymerization using a polymerization initiator and cationic polymerization using a cationic polymerization initiator having a functional group stable to cations. Examples of such an initiator include a radical polymerization initiator such as an azo compound having a cyclic ether structure such as an epoxy group, an oxetane group and a tetrahydrofurfuryl group and a peroxide, a vinyl ether group and a vinylidene type hydrocarbon group. Organic alkali metal compounds, Grignard compounds, anionic polymerization initiators such as Grignard compounds having a styrene type double bond such as vinylbenzyl group, Lewis acids having a (meth) acryloyl group, halogenated hydrocarbons and metal salts, A cationic polymerization initiator comprising an organic metal halide is exemplified.

In a system capable of living polymerization, a functional group can be introduced into the terminal at which polymerization is stopped. When performing a radical polymerization reaction, a chain transfer agent such as t-butyl mercaptan, n-butyl methyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, α-methyl styrene dimer or the like is used for the purpose of adjusting the molecular weight. It can be used in an amount of 1 mol or less based on the meth) acrylates.

In the case of polymerization using a Ziegler-Natta catalyst, hydrogen is a preferred chain transfer agent. The solvent used in the solution polymerization or the like is not particularly limited as long as the produced polymer is dissolved, but in the case of radical polymerization, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and t-butylbenzene are used. And ketones such as methyl ethyl ketone and methyl isobutyl ketone; esters such as diethyl carbonate and dimethyl carbonate; ethers such as tetrahydrofuran and dioxane; and amides such as dimethylformamide. In the case of anionic polymerization or coordination anionic polymerization, ketones, esters, and the like often react with the initiator, and thus the aromatic hydrocarbons and ethers described above are preferably used. These solvents can be used in combination of two or more kinds.

The polymerization temperature can be set arbitrarily. For example, in the case of radical polymerization, it is -20 ° C. to 200 ° C., preferably 0 ° C.
C. to 120.degree. C., more preferably 20 to 120.degree. C., particularly preferably 50 to 120.degree. In the case of anionic polymerization and coordination anionic polymerization, it is preferable to perform the polymerization at a low temperature because side reactions can be suppressed.
C. to 70.degree. C., preferably -90.degree. C. to 50.degree. C., particularly preferably -80.degree. C. to 30.degree.

Further, as a method for producing a polymer for deriving a hard segment, a method of preliminarily polymerizing (meth) acrylic acid and reacting a monomer which forms an ester may be employed. it can.
According to this method, a polycyclic olefin can be reacted with poly (meth) acrylic acid under an acid catalyst to synthesize a polymer represented by the above formula (II).

Synthesis of Polymer Constituting Soft Segment The polymer constituting the soft segment is prepared by converting an alkylene oxide such as ethylene oxide, propylene oxide, oxetane or tetrahydrofuran into an anion such as potassium hydroxide, t-butyl potassium or phosphazenium. It can be obtained by polymerization with an initiator, a coordinating anion initiator such as organozinc, tin and a phosphoric ester and a condensate, or a cationic initiator such as boron trifluoride, ethylaluminum dichloride, and aluminum trichloride. In the polymerization at this time, bulk polymerization is suitably used. Polymerization temperature is -100 to 200
° C, preferably -50 to 180 ° C, particularly preferably -20.
１５０150 ° C.

When the soft segment is derived from a (meth) acrylate polymer as described above, the polymer is obtained by polymerizing a (meth) acrylate represented by the following formula. .

[0081]

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In the above formula, R ^c is a hydrogen atom or a methyl group. R ⁵⁰ is ether, carbonyl, carboxyl, carbonate, amino, amide, imino, imide,
It has a siloxy, halo bond, carbon, oxygen, hydrogen, nitrogen,
It is a group composed of elements selected from silicon and halogen. Specific examples of such compounds include 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, diethylene glycol methyl (meth) acrylate, diethylene glycol ethyl (meth) acrylate, and (meth) acrylic acid. Triethylene glycol methyl acid, triethylene glycol ethyl (meth) acrylate, tetraethylene glycol methyl (meth) acrylate, tetraethylene glycol ethyl (meth) acrylate, nonaethylene glycol methyl (meth) acrylate, (meth) acrylic Nonaethylene glycol ethyl acid, ethylene glycol carbonyloxymethyl (meth) acrylate, ethylene glycol carbonyloxyethyl (meth) acrylate, diethylene glycol carbonyloxymethyl (meth) acrylate , Diethylene glycol carbonyloxyethyl (meth) acrylate,
Ethylene glycol carbonyl methyl (meth) acrylate, ethylene glycol carbonyl ethyl (meth) acrylate, diethylene glycol carbonyl methyl (meth) acrylate, diethylene glycol carbonyl ethyl (meth) acrylate, triethylene glycol carbonyl methyl (meth) acrylate, ( Triethylene glycol carbonyl ethyl (meth) acrylate, 2-methyl 2-methoxyethyl (meth) acrylate, 2- (meth) acrylate
Methyl 2-ethoxyethyl, dipropylene glycol methyl (meth) acrylate, dipropylene glycol ethyl (meth) acrylate, tripropylene glycol methyl (meth) acrylate, tripropylene glycol ethyl (meth) acrylate, (meth) acryl Tetrapropylene glycol methyl acrylate, tetrapropylene glycol ethyl (meth) acrylate, nonapropylene glycol methyl (meth) acrylate, nonapropylene glycol ethyl (meth) acrylate, propylene glycol carbonyloxymethyl (meth) acrylate, (meth) Propylene glycol carbonyloxyethyl acrylate,
Dipropylene glycol carbonyloxymethyl (meth) acrylate, dipropylene glycol carbonyloxyethyl (meth) acrylate, propylene glycol carbonylmethyl (meth) acrylate, propylene glycol carbonylethyl (meth) acrylate, di (meth) acrylate Propylene glycol carbonyl methyl,
Examples thereof include dipropylene glycol carbonyl ethyl (meth) acrylate, tripropylene glycol carbonyl methyl (meth) acrylate, and tripropylene glycol carbonyl ethyl (meth) acrylate. Two or more of these may be used.

As long as the polymer has a glass transition temperature of 30 ° C. or lower, other monomers may be copolymerized. Specific examples of such other monomers include glycidyl (meth) acrylate, Those having a functional group in the ester group such as allyl (meth) acrylate and vinyl (meth) acrylate are exemplified. Further, (meth) acrylates such as methyl methacrylate and ethyl methacrylate can be used for the purpose of adjusting the glass transition temperature. These may be used in an amount of 20 mol% or less, preferably 15 mol% or less, more preferably 10 mol% or less.

The method for synthesizing the polymer constituting such a soft segment is the same as that for the (meth) acrylate polymer corresponding to the hard segment. Polymer Synthesis Method (i) In the polymer reaction method, the polymer is obtained by copolymerizing the polymer constituting the hard segment and the polymer constituting the soft segment.

At this time, the weight ratio (hard segment / soft segment) of the hard segment and the soft segment is 2/98 to 98/2, preferably 4/96 to 98/98.
It is preferably used at 96/4, more preferably 5/95 to 95/5, particularly preferably 7/93 to 93/7, and the solvent is 2 to 100 liters, preferably 2 to 70 liters per kilogram of the polymer. , Particularly preferably 2-
50 liters are used. If the amount of the solvent is too large, the reaction rate and the molecular weight may be reduced. If the amount of the solvent is too small, phase separation may occur between the polymers, and copolymerization may not easily occur. As the solvent, the same solvents as those exemplified when performing the solution polymerization are used. At this time, although the polymerization initiator varies depending on the functional group, when the functional group is an epoxy group, boron trifluoride, ethyl aluminum dichloride, a cationic initiator such as aluminum trichloride, an alkyl zinc compound,
Condensates of a tin compound and a phosphorus compound, alkoxy compounds of alkali metals, phosphazeniums and the like are used.

The reaction temperature is -100 to 200 ° C, preferably -50 to 180 ° C, more preferably -20 to 150 ° C.
° C, particularly preferably -10 to 100 ° C. When copolymerizing the polymer constituting the hard segment and the polymer constituting the soft segment, another monomer may be copolymerized as necessary. Such other monomers, hard segments, depending on the functional group contained in the polymer constituting the soft segment, ethylene oxide, epoxy compounds such as propylene oxide,
Examples thereof include vinylidene-type hydrocarbons such as oxetanes, tetrahydrofurans, and isobutene, and vinyl ethers such as isobutyl vinyl ether. [(Ii) Living polymerization method] In addition to the above-described polymer reaction method, as a polymer synthesis method, a soft segment is formed on a hard segment living polymer obtained by living-polymerizing a monomer corresponding to a polymer constituting the hard segment. It can also be synthesized by a living polymerization method in which a monomer corresponding to a polymer is polymerized. In addition, the monomer corresponding to the polymer constituting the hard segment may be polymerized into a living polymer obtained by soft segment living polymerization of the monomer corresponding to the polymer constituting the soft segment, and the living polymerization may be repeated. .

The catalyst used at this time includes halides such as carbon tetrachloride, benzyl chloride, glycidyl 2-bromo-2-methylbutanoate and glycidyl trichloroacetate, and metal complexes such as ruthenium triphenylphosphine complex with ruthenium. A multi-system initiator in combination with a Lewis acid such as aluminum alkoxide, the Grignard reagent described above, an organic alkali metal, a metallocene compound,
Porphyrin compounds, phosphine compounds, and organoaluminum compounds are exemplified. As the solvent, those described above can be used. The polymerization conditions such as monomer concentration and temperature are the same as described above. [(Iii) Graft polymerization method] As another synthesis method, there is a method of graft-polymerizing a monomer of a polymer constituting a soft segment to a polymer constituting a hard segment.

Specifically, a method of dissolving the polymer constituting the hard segment in a solvent and adding a radical initiator and a monomer corresponding to the polymer constituting the soft segment to polymerize the polymer or a method of polymerizing the soft segment can be used. A method of dissolving the coalesced solvent in a solvent, adding a radical initiator and a monomer corresponding to the hard segment, and polymerizing the mixture can be exemplified. In addition to the solvent and the radical initiator, the reaction conditions such as the temperature are the same as described above.

This method is preferably applied when an olefin polymer having a cyclic structure is used. [Preparation of Polymer Solid Electrolyte] The polymer solid electrolyte according to the present invention comprises [I] the polymer described above and [II] a salt of a metal of Group Ia of the periodic table.

The metal salt of Group Ia of the periodic table includes Li
ClO ₄ , LiBF ₄ , LiPF ₆ , LiAsF ₆ , LiCF ₃ S
One or more Li salts selected from O ₃ , LiN (CF ₃ SO ₂ ) ₂ , LiC (CF ₃ SO ₂ ) _{3 and the} like are desirable. In the solid polymer electrolyte according to the present invention, the metal salt of Group Ia of the periodic table is contained in an amount of 1 to 50% by weight, preferably 5 to 20% by weight based on the total weight of the solid polymer electrolyte. Is preferred.

In the present invention, a solvent capable of dissolving the salt of the above-mentioned polymer [I] with the above-mentioned polymer and the metal of the group [IIa] Ia with the group [II] is included. It may be. As a solvent capable of dissolving the salt of the metal of Group Ia of the periodic table, a carbonate ester is suitably used. Specific examples of the carbonate include ethylene carbonate, propylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, dipropyl carbonate, vinylene carbonate, divinyl carbonate and the like.

When a solvent is used, it is used in an amount of 50 parts by weight or less, 0 to 30 parts by weight or less, more preferably 0 to 10 parts by weight or less based on 1 part by weight of the polymer. The solid polymer electrolyte according to the present invention is in a solid state or a gel state. The polymer solid electrolyte comprises the polymer, a salt of a metal of Group Ia of the periodic table, and a solvent capable of dissolving a salt of a metal of Group Ia of the periodic table, if necessary, at -20 to 20. 200 ° C, preferably -10 to 170 ° C,
More preferably, it is prepared by mixing at 0 to 150 ° C. If necessary, a solvent that easily dissolves the metal salt can be used as an auxiliary. It is preferable that this auxiliary agent is finally removed by a method such as reduced pressure. Since the above-mentioned polymers are often amorphous, they are excellent in the absorbability of the metal salt solution, and can often absorb the metal salt solution relatively quickly even at room temperature. In this case, various shapes of polymer solid electrolytes can be easily obtained by molding the matrix resin by various molding methods and then absorbing the metal salt solution.

The solid polymer electrolyte according to the present invention has high ionic conductivity and is electrochemically stable. Such a polymer solid electrolyte can be used for, for example, primary batteries, secondary batteries, capacitors, electrochemical devices such as electrochromic display devices, medical actuators, and the like. Further, the solid polymer electrolyte according to the present invention can be used as a substitute for an organic electrolyte solution of a lithium ion secondary battery. In addition, the powdered electrode material is dispersed into a current collector.
It can also be used as a binder for fixing.

When such a solid polymer electrolyte is used for a battery, the battery can be manufactured by forming the solid polymer electrolyte into a film in advance and sandwiching it between a positive electrode and a negative electrode. Further, since the polymer used in the present invention is excellent in absorbency of a metal salt solution, in a conventional battery manufacturing process having a step of forming a three-layer structure of a positive electrode, a separator, and a negative electrode and then impregnating with an electrolytic solution,
It is only necessary to use the polymer of the present invention instead of the separator, and a battery containing the solid polymer electrolyte of the present invention can be manufactured without newly remodeling the conventional process.

[0095]

The polymer solid electrolyte according to the present invention comprises, as a polymer matrix, (1) a hard segment composed of a polymer having a glass transition temperature of 105 ° C. or higher, and (2) a glass transition temperature of 30 ° C. or lower. And a polymer having a soft segment consisting of a polymer having high ionic conductivity and high electrochemical stability. Such a polymer solid electrolyte can be used for, for example, primary batteries, secondary batteries, capacitors, electrochemical devices such as electrochromic display devices, medical actuators, and the like. In addition, since the solid polymer electrolyte of the present invention is thermoplastic, molding is easy and conventional molding methods can be used. Further, since the polymer constituting the matrix of the solid polymer electrolyte is amorphous and contains a low glass transition temperature component, the polymer solid electrolyte is excellent in absorption of metal salts and electrolytes.

[0096]

The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

[0097]

[Synthesis Example 1] (Synthesis of each segment polymer) Synthesis of hard segment polymer [I-1] A 500 ml five-neck glass reactor equipped with a stirrer, a cooling tube, a temperature sensor, and a nitrogen blowing tube was subjected to nitrogen. After the replacement, 190 ml of purified toluene, 9.6 ml of tetracyclododecyl methacrylate (TDMA), and 0.1 ml of glycidyl methacrylate (GMA) were added.
4 ml, dimethyl azobisisobutyrate (trade name:
V-601) 1 mol / l toluene solution 2.23
Milliliter was charged, and nitrogen bubbling was performed at 0 ° C. for about 30 minutes. Next, the reactor was heated to a reaction temperature of 80.
C. for 1.5 hours to carry out polymerization.

After a predetermined time, the reactor was cooled in an ice bath and poured into a large excess of methanol to precipitate a polymer. This is filtered off with a glass filter, and 5
After washing twice, it was dried under reduced pressure at 80 ° C. to obtain 7.09 g of a polymer (hard segment component [I]). The weight average molecular weight (standard polystyrene conversion) measured by GPC was Mw = 11,
400, Mw / Mn = 2.38, glass transition temperature measured by DSC is 15
5 ° C.

Synthesis of Hard Segment Polymer [I-2] 100 ml of toluene, 9.8 ml of TDMA, 0.2 ml of GMA, and 0.86 ml of a 1 mol / liter toluene solution of V-601 were used. Except for the above, polymerization was carried out in the same manner as for hard segment polymer [I-1] to obtain 8.45 g of a polymer. The weight average molecular weight (standard polystyrene conversion) measured by GPC was Mw = 23,800 and Mw / Mn = 2.74.

Synthesis of Hard Segment Polymer [I-3] Using 50 ml of toluene, 9.8 ml of TDMA, 0.25 ml of GMA, and 0.89 ml of a 1 mol / liter toluene solution of V-601, Polymerization was carried out in the same manner as for the hard segment polymer [I-1] except that the polymerization time was changed to 43 minutes, and 7.94.
Grams of polymer were obtained. The weight average molecular weight (standard polystyrene conversion) measured by GPC was Mw = 46,200 and Mw / Mn = 2.04.

Synthesis of Hard Segment Polymer [I-4] 30 ml of toluene, 9.8 ml of TDMA, 0.2 ml of GMA, and 1 part of V-601
Polymerization was carried out in the same manner as for the hard segment polymer [I-1] except that 0.44 ml of a mol / liter toluene solution was used and the polymerization time was 33 minutes, to obtain 8.32 g of a polymer. Weight average molecular weight measured by GPC
(In terms of standard polystyrene) Mw = 76,100 and Mw / Mn = 1.93.

Synthesis of Hard Segment Polymer [I-5] 380 ml of toluene, 19.2 ml of TDMA, 0.8 ml of GMA, V-601
Was polymerized in the same manner as in the hard segment polymer [I-1] except that 2.23 ml of a 1 mol / liter toluene solution of was used to obtain 14.08 g of a polymer. The weight average molecular weight (standard polystyrene conversion) measured by GPC was Mw = 1,800 and Mw / Mn = 2.47.

Synthesis of Soft Segment Polymer [II-1] A 500 ml five-necked glass reactor equipped with a stirrer, a cooling tube, a temperature sensor, and a nitrogen blowing tube was purged with nitrogen. , Triethylene glycol methyl methacrylate (trade name: MT
9.55 mL of G), 0.45 mL of GMA, and 2.29 mL of a 1 mol / L toluene solution of V-601 were charged, and nitrogen bubbling was performed at 0 ° C. for about 30 minutes. Next, the reactor was heated and the reaction temperature was kept at 80 ° C. for 1.5 hours to carry out polymerization.

After a predetermined time, the reactor was cooled in an ice bath and poured into a large excess of hexane, whereby a viscous liquid polymer adhered to the bottom and walls of the vessel. The supernatant was decanted, washed with hexane five times, and then recovered by dissolving the viscous liquid in toluene, and concentrated and dried at 80 ° C. under reduced pressure to give 6.84 g of a viscous liquid. (Soft segment polymer [II]) was obtained. Weight average molecular weight (standard polystyrene conversion) measured by GPC is Mw = 10,400, Mw / Mn
= 2.31.

Synthesis of Soft Segment Polymer [II-2] 100 ml of toluene, 9.8 ml of MTG, 0.2 ml of GMA, and 1 part of V-601
Polymerization was carried out in the same manner as for the soft segment polymer [II-1] except that 1.13 ml of a mol / liter toluene solution was used to obtain 8.16 g of a polymer.
Weight average molecular weight measured by GPC (standard polystyrene conversion)
Was Mw = 19,900 and Mw / Mn = 2.25.

Synthesis of Soft Segment Polymer [II-3] 50 ml of toluene, 9.8 ml of MTG, 0.26 ml of GMA, and 1 part of V-601
Polymerization was carried out in the same manner as for the soft segment polymer [II-1], except that 0.91 ml of a mol / liter toluene solution was used and the polymerization time was 41 minutes, to obtain 5.53 g of a polymer. Weight average molecular weight measured by GPC
(In terms of standard polystyrene) Mw = 51,000, Mw / Mn = 1.97.

Synthesis of Soft Segment Polymer [II-4] 30 ml of toluene, 9.8 ml of MTG, 0.26 ml of GMA and 1 part of V-601
Polymerization was carried out in the same manner as for the soft segment polymer [II-1], except that 0.46 ml of a mol / liter toluene solution was used and the polymerization time was 1 hour, to obtain 8.62 g of a polymer. Weight average molecular weight measured by GPC
(In terms of standard polystyrene) Mw = 79,400 and Mw / Mn = 2.79.

Synthesis of Soft Segment Polymer [II-5] 20 ml of toluene, 9.8 ml of MTG, 0.26 ml of GMA, 1 part of V-601
Polymerization was carried out in the same manner as for the soft segment polymer [II-1] except that 0.46 ml of a mol / liter toluene solution was used and the polymerization time was 30 minutes to obtain 7.37 g of a polymer. Weight average molecular weight measured by GPC
(In terms of standard polystyrene) Mw = 215,900 and Mw / Mn = 4.64.

Synthesis of Soft Segment Polymer [II-6] 50 ml of toluene, 3 ml of MTG, and 2 ml of methoxycarbonyloxyethyl methacrylate
Ml, GMA 0.14 ml, V-6
Polymerization was carried out in the same manner as for the soft segment polymer [II-1], except that 0.65 ml of a 1 mol / l toluene solution of 01 was used and the polymerization time was 1 hour.
3.85 grams of polymer were obtained. Weight average molecular weight (standard polystyrene conversion) measured by GPC is Mw = 20,900, Mw / Mn
= 2.07.

Synthesis of Soft Segment Polymer [II-7] 50 ml of toluene, 9.8 ml of diethylene glycol methyl methacrylate instead of MTG, 0.3 ml of GMA, 1 mol of V-601
Using 0.55 ml / liter toluene solution,
Polymerization was carried out in the same manner as for the soft segment polymer [II-1] except that the polymerization time was changed to 1 hour, to obtain 8.39 g of a polymer. The weight average molecular weight (in terms of standard polystyrene) measured by GPC was Mw = 107,600 and Mw / Mn = 3.89.

[0111]

[Synthesis Example 2] (Synthesis of base polymer) 0.3 g of hard segment polymer [I-1] was placed in a three-necked glass reactor equipped with a polymer [III-1] synthetic cooling tube and thermometer. 0.7 g of the soft segment polymer [II-1] was charged with a stirrer chip, and dried under reduced pressure for 1 hour. Next, 3 ml of purified toluene was added under a nitrogen stream to dissolve the polymer, and then 0.1 ml of a 1.0 mol / l toluene solution of a boron trifluoride diethyl ether complex was added with stirring, and the temperature was raised to 60 ° C. Warmed and held for 2 hours. The reactor was cooled with an ice bath, and aqueous ammonia / methanol 10%
The reaction was stopped by adding 1 ml of the solution. The reaction solution was once concentrated, dissolved in toluene, and then separated by centrifugation to remove a precipitate (residue of the initiator), and then concentrated again, and dried at 80 ° C. under reduced pressure to obtain a rubbery polymer. The polymer yield was 0.96 grams. The weight average molecular weight (standard polystyrene conversion) measured by GPC is Mw = 68,600,
Mw / Mn = 9.19.

Synthesis of Polymer [III-2] Polymer [III-1] except that 0.5 g of hard segment polymer [I-1] and 0.5 g of soft segment polymer [II-1] were used. Copolymerization was carried out in the same manner as described above. The yield was 0.95 grams. The weight average molecular weight (in terms of standard polystyrene) measured by GPC is Mw = 73,80.
0, Mw / Mn = 1.10.18.

Synthesis of Polymer [III-3] Polymer [III-1] except that 0.3 g of hard segment polymer [I-1] and 0.7 g of soft segment polymer [II-2] were used. Copolymerization was carried out in the same manner as described above. The yield was 0.94 grams. The weight average molecular weight (standard polystyrene conversion) measured by GPC is Mw = 80,30.
0, Mw / Mn = 8.65.

Synthesis of Polymer [III-4] 5 ml of toluene was mixed with a hard segment polymer [I
-2], 0.3 g of a soft segment polymer [II-
Copolymerization was carried out in the same manner as in the polymer [III-1] except that 0.7 g of [3] was used. The yield was 0.97 grams. The weight average molecular weight (in terms of standard polystyrene) measured by GPC is Mw = 104,400, Mw / Mn = 5.18.
Met.

Synthesis of polymer [III-5] 7.9 ml of toluene, 0.3 g of hard segment polymer [I-4] and soft segment polymer [II
-4] was used in the same manner as in the polymer [III-1], except that 0.7 g of propylene oxide and 0.12 ml of a 0.4 mol / l toluene solution of propylene oxide were used. The yield was 0.93 grams. After drying under reduced pressure,
When an attempt was made to prepare a 0.5 g / liter THF solution, an insoluble portion of 19% by weight was present.

The weight-average molecular weight (in terms of standard polystyrene) of the soluble portion measured by GPC was Mw = 211,900, Mw /
Mn was 5.18. Synthesis of Polymer [III-6] 7.9 ml of toluene, 0.3 g of hard segment polymer [I-4], and soft segment polymer [II
-5-5] and 0.12 ml of a 0.4 mol / l toluene solution of propylene oxide were copolymerized in the same manner as in the polymer [III-1]. The yield was 0.92 grams. After drying under reduced pressure,
When an attempt was made to prepare a 0.5 g / liter THF solution, an insoluble portion of 19% by weight was present.

The weight average molecular weight (in terms of standard polystyrene) of the soluble portion measured by GPC was Mw = 102,300, Mw /
Mn = 2.65. Synthesis of polymer [III-7] 4 ml of toluene, hard segment polymer [I
-5] and 0.3 g of the soft segment polymer [II-
Copolymerization was carried out in the same manner as in the polymer [III-1] except that 0.7 g of [6] was used. The yield is 0.99 grams. After drying under reduced pressure, an attempt was made to prepare a 0.5 g / liter THF solution, and as a result, a 17% by weight insoluble portion was present.

The weight-average molecular weight (in terms of standard polystyrene) of the soluble portion measured by GPC was Mw = 19,800, Mw / M
n = 4.18. Synthesis of Polymer [III-8] 5 ml of toluene, hard segment polymer [I
-3] and 0.3 g of the soft segment polymer [II-
[7-1] was copolymerized in the same manner as in the polymer [III-1] except that 0.7 g of [7] was used. The yield was 0.97 grams. The weight average molecular weight (standard polystyrene conversion) measured by GPC is Mw = 108,100, Mw / Mn = 3.55.
Met.

[0119]

COMPARATIVE SYNTHESIS EXAMPLE 1 A 500 ml five-necked glass reactor equipped with a copolymer synthesis stirrer, a cooling tube, a temperature sensor, and a nitrogen blowing tube was purged with nitrogen, and then 55.8 ml of purified toluene was added. 1.63 ml of tetracyclododecyl methacrylate and 4.63 ml of triethylene glycol methyl methacrylate.
58 ml, 0.5 of dimethyl azobisisobutyrate
0.5 ml of a mol / liter toluene solution was charged, and nitrogen bubbling was performed at 0 ° C. for about 30 minutes. Next, the reactor was heated and the reaction temperature was maintained at 80 ° C. for 1 hour to carry out polymerization.

After a predetermined time, the reactor was cooled in an ice bath and poured into a large excess of hexane, whereby a viscous liquid polymer adhered to the bottom and walls of the vessel. After the supernatant was decanted and washed five times with hexane, the viscous liquid was dissolved and recovered in toluene, concentrated, and dried at 80 ° C. under reduced pressure to obtain 3.91 g of a polymer. The weight average molecular weight (standard polystyrene conversion) measured by GPC is Mw = 45,
000, Mw / Mn = 1.90.

[0121]

Example 1 A high-pressure solid electrolyte polymer [III-1] was press-formed at 150 ° C. to produce a press sheet. To 1 part by weight of the press sheet was added 4 parts by weight of an electrolyte obtained by dissolving LiPF ₆ at a concentration of 1 mol / l in a mixed solvent of ethylene carbonate and propylene carbonate (weight ratio: 1: 1). After being sufficiently impregnated with the electrolytic solution, the resultant was allowed to stand for further 12 hours to produce a solid polymer electrolyte, but there was almost no change in the basic shape. The obtained polymer solid electrolyte is punched into a 10 mmφ disc shape,
The electrode was placed between electrodes provided in a conductivity measurement holder, and the electrode was controlled at 25 ° C. by a Peltier element, and complex impedance measurement (measurement voltage: 10 mV) was performed with an impedance analyzer (HP4285A), and ion conductivity was determined analytically. .

As a result, the ionic conductivity was 1.32 mS /
cm.

[0123]

Example 2 A solid polymer electrolyte was prepared and the ionic conductivity was measured in the same manner as in Example 1 except that the polymer [III-2] was used. As a result, the ionic conductivity is 1.23 m
S / cm.

[0124]

Example 3 A solid polymer electrolyte was prepared in the same manner as in Example 1 except that the polymer [III-3] was used, and the ionic conductivity was measured. As a result, the ionic conductivity was 2.74 m.
S / cm.

[0125]

Example 4 A solid polymer electrolyte was prepared in the same manner as in Example 1 except that the polymer [III-4] was used, and the ionic conductivity was measured. As a result, the ionic conductivity is 3.50 m
S / cm.

[0126]

Example 5 A solid polymer electrolyte was prepared and the ionic conductivity was measured in the same manner as in Example 1 except that the polymer [III-5] was used. As a result, the ionic conductivity was 3.73 m
S / cm.

[0127]

Example 6 A solid polymer electrolyte was prepared and the ionic conductivity was measured in the same manner as in Example 1 except that the polymer [III-6] was used. As a result, the ionic conductivity was 3.65 m.
S / cm.

[0128]

Example 7 A polymer solid electrolyte was prepared and the ionic conductivity was measured in the same manner as in Example 1 except that the polymer [III-7] was used. As a result, the ionic conductivity is 2.58 m
S / cm.

[0129]

Example 8 A solid polymer electrolyte was prepared and the ionic conductivity was measured in the same manner as in Example 1 except that the polymer [III-8] was used. As a result, the ionic conductivity was 2.81 m.
S / cm.

[0130]

Comparative Example 1 1 part by weight of the copolymer synthesized in Comparative Synthesis Example 1 was mixed with 1 mol / l of LiPF ₆ in a mixed solvent of ethylene carbonate and propylene carbonate (weight ratio 1: 1).
When 4 parts by weight of the electrolytic solution dissolved at a concentration of 2 was added, the polymer was completely dissolved, and a solid polymer electrolyte could not be prepared.

[0131]

Comparative Example 2 To 1 part by weight of a commercially available polyacrylonitrile, 4 parts by weight of an electrolyte obtained by dissolving LiPF ₆ at a concentration of 1 mol / l in a mixed solvent of ethylene carbonate and propylene carbonate (weight ratio 1: 1) was added. However, the impregnation of the electrolyte was very slow, and a solid polymer electrolyte could not be formed.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08L 33/10 C08L 33/10 45/00 45/00 71/02 71/02 101/12 101/12 H01G 9/025 H01M 6/18 E H01M 6/18 10/40 B 10/40 H01G 9/00 301G

Claims (6)

[Claims] 1. A polymer comprising (I) (1) a hard segment comprising a polymer having a glass transition temperature of 105 ° C. or higher, and (2) a soft segment comprising a polymer having a glass transition temperature of 30 ° C. or lower. And [II] a salt of a metal belonging to Group Ia of the periodic table. 2. A polymer comprising (I) (1) a hard segment comprising a polymer having a glass transition temperature of 105 ° C. or higher, and (2) a soft segment comprising a polymer having a glass transition temperature of 30 ° C. or lower. And [II] a polymer solid electrolyte comprising a salt of a metal of Group Ia of the periodic table and [III] a solvent capable of dissolving a salt of a metal of Group Ia of the periodic table. 3. The polymer (1) having a glass transition temperature of 105 ° C. or more comprises a polymer having a cyclic structure in the main chain and / or a structural unit derived from a (meth) acrylate monomer. 2. A polymer comprising:
Or the polymer solid electrolyte according to 2. 4. The composition (2) wherein the polymer having a glass transition temperature of 30 ° C. or lower is a polymer derived from an alkylene oxide monomer and / or a (meth) acrylate monomer. 3. The polymer solid electrolyte according to claim 1, wherein the polymer is a polymer containing units. 5. A hard segment comprising (1) a polymer having a glass transition temperature of 105 ° C. or higher and (2) a soft segment comprising a polymer having a glass transition temperature of 30 ° C. or lower contained in the polymer [I]. 3. The polymer solid electrolyte according to claim 1, wherein the weight ratio of the segments (hard segment / soft segment) is 2/98 to 98/2. 6. The solid polymer electrolyte according to claim 2, wherein the solvent capable of dissolving the salt of the metal of Group IIIa of the Periodic Table is a carbonic acid ester.