JP2000302861A - Polycarbonate composition, preparation thereof and polymeric solid electrolyte using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymerizable polycarbonate which is useful as a raw material for a functional resin material, a preparation process thereof and also provide a solid electrolyte comprising the polycarbonate which has a high ionic conductivity, an electrochemical stability and a flexibility. SOLUTION: This composition contains a polycarbonate of the formula (wherein, X is a 2-20C bivalent hydrocarbon group), wherein preferably from 10 to 99% of the R1 and R2 at the molecular ends are (meth)acryloyl groups. A polymeric solid electrolyte is prepared by blending a salt of a group Ia metal of the periodic table with a polymer of the composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polycarbonate composition and a method for producing the same, and also relates to a polymer solid electrolyte useful for a primary battery, a secondary battery, a capacitor and the like using a polymer of the polycarbonate composition. is there.

[0002]

2. Description of the Related Art It is known that polycarbonate (meth) acrylate obtained by esterifying terminal hydroxyl groups of polycarbonate polyol with acrylic acid or methacrylic acid is useful as a raw material for various resins. For example,
JP-A-63-270641 discloses 3-methyl-
It is described that di (meth) acrylates of polycarbonate of 1,5-pentanediol can be used as vehicles for printing inks and paints. JP-A-3-181517 describes that a polycarbonate (meth) acrylate resin has photocurability and forms a cured coating film having excellent wet heat resistance.

As a method for producing the polycarbonate (meth) acrylate, as described in the above publication, 1) a polycarbonate polyol and (meth) acrylic acid are azeotropically dehydrated in the presence of an acid catalyst. A method of esterification and a method of condensing a polycarbonate polyol with a (meth) acrylic halide in the presence of a base catalyst are disclosed. However, all of these methods use highly corrosive (meth) acrylic acid or (meth) acrylic halide as a raw material,
Corrosion resistant reactors are used.

[0004] On the other hand, in the field of electrolytes, liquid electrolytes have been used in electrochemical devices such as primary batteries, secondary batteries and capacitors. However, there is a concern that the liquid electrolyte may leak from the container during long-term use. Therefore, in order to enhance long-term reliability, practical use of a solid electrolyte has been considered. If the solid electrolyte is realized, a highly reliable device can be provided, and the size and weight of the device itself can be expected to be reduced. In recent years, polymer solid electrolytes have been studied as a kind of solid electrolyte, and when a flexible polymer solid electrolyte is used, it is also flexible to the volume change that occurs during the ion-electron exchange reaction process between the electrode and the polymer solid electrolyte. There is an advantage that can be handled. Therefore, a solid polymer electrolyte having high ionic conductivity, flexibility, and excellent discharge characteristics is strongly demanded.

[0005]

Accordingly, an object of the present invention is to provide a novel polymerizable polycarbonate composition useful as a raw material for various resins, and to further use a special corrosion-resistant reactor. It is another object of the present invention to provide a method for producing a polycarbonate composition which can be produced by a general reactor. It is another object of the present invention to provide a flexible solid electrolyte having high ionic conductivity and electrochemical stability composed of a polymer of a polycarbonate composition.

[0006]

That is, the present invention relates to a polycarbonate composition containing a polycarbonate body represented by the general formula (1).

[0007]

Embedded image (Wherein, X is a divalent hydrocarbon group having 2 to 20 carbon atoms, and the group may contain a double bond, an aromatic ring or an ether bond, and some of R ¹ and R ² are (meth) an acryloyl group, the remaining R ¹ and R ² are at least alkoxycarbonyl group, a phenoxycarbonyl group, and one group selected from the group consisting of a hydrogen atom, R ¹ and R ² May be the same or different, and the average value of n is from 1 to 1000.) In the above polycarbonate composition, R ¹ and R ²
Of the (meth) acryloyl group as 10 to 9
It is preferably 9 mol%.

Further, the present invention provides a polycarbonate body represented by the general formula (2):

Embedded image (In the formula, X is a divalent hydrocarbon group having 2 to 20 carbon atoms, which may contain a double bond, an aromatic ring or an ether bond, R ³ and R ^{4 each} represent a hydrogen atom, At least one group selected from the group consisting of an alkoxycarbonyl group and a phenoxycarbonyl group, wherein R ³ and R ⁴ may be the same or different, and the average value of n is 1
~ 1000)

The present invention relates to a method for producing the above polycarbonate composition by subjecting a transesterification reaction with an alkyl (meth) acrylate represented by the general formula (3) in the presence of a catalyst.

Embedded image (Wherein, R ⁵ is a hydrogen atom or a methyl group, and R ⁶ is an alkyl group having 1 to 4 carbon atoms)

Further, the present invention relates to a solid polymer electrolyte comprising a polymer of a composition containing a polycarbonate represented by the general formula (4) and a metal salt of Group Ia of the periodic table.

Embedded image (Wherein, X is a divalent hydrocarbon group having 2 to 20 carbon atoms, and the group may contain a double bond, an aromatic ring or an ether bond, and some of R ¹ and R ² are (meth) an acryloyl group, the remaining R ¹ and R ² are at least alkoxycarbonyl group, a phenoxycarbonyl group, and one group selected from the group consisting of a hydrogen atom, R ¹ and R ² May be the same or different, and the average value of n is 1 to 1000)

In the present invention, acrylic acid and methacrylic acid are combined, and (meth) acrylic acid, acryloyl group and methacryloyl group are combined, (meth) acryloyl group, acrylic ester and methacrylic ester are combined (meth) This is referred to as an acrylate ester.

[0012]

Next, the present invention will be described in detail. Polycarbonate Composition The polycarbonate composition according to the present invention contains a polycarbonate body represented by the following general formula (1).

Embedded image

Here, X is a divalent hydrocarbon group having 2 to 20 carbon atoms, and the group may contain a double bond, an aromatic ring or an ether bond. For example, it may be a linear or branched alkylene group, cyclohexylene group, phenylene group, or a mixture thereof.

Part of R ¹ and R ² is a (meth) acryloyl group (CH ₂ ＣＨCH—CO—, CH ₂ ＣC (CH ₃ ) —C
O-), and the content ratio of the (meth) acryloyl group is usually 10 to 99 mol%, preferably 50 to 99 mol%. When the proportion of the (meth) acryloyl group is within the above range, the polymerization reaction during the production of the resin proceeds smoothly and can be adjusted to an appropriate molecular weight.

The remaining R ¹ and R ² are at least an alkoxycarbonyl group (RO—CO—: R is an alkyl group having 1 to 10 carbon atoms) and a phenoxycarbonyl group (Ph—O—CO
-: Ph is a phenyl group) and one kind of group selected from the group consisting of hydrogen atoms, which may be the same or different. The remaining R ¹ and R ² may also be ester groups.

N indicates the degree of polymerization, and the average value is 1 to
It is a number of 1000, preferably 2 to 500. The number average molecular weight of the polycarbonate body represented by the formula (1) measured by GPC and converted into standard polystyrene is 200 to 100,000, preferably 400 to 5
It is 0000. When n and the number average molecular weight are in this range, a flexible film can be formed.

Since the polycarbonate composition has a polymerizable double bond such as radical polymerization or ionic polymerization, it can be used as a photopolymerizable or thermopolymerizable prepolymer. It can be used as a raw material for chemicals and other functional materials. In particular, it can be suitably used as a material for a polymer solid electrolyte described below.

Method for Producing Polycarbonate Composition A composition containing a polycarbonate body represented by the general formula (1) comprises a polycarbonate body represented by the general formula (2) and a (meth) acrylic acid represented by the general formula (3) It can be produced by subjecting an alkyl ester to a transesterification reaction in the presence of a catalyst.

The polycarbonate body as a raw material is represented by the general formula (2).

Embedded image

Here, X is a divalent hydrocarbon group having 2 to 20 carbon atoms, which may contain a double bond, an aromatic ring or an ether bond, as described in the general formula (1). As you did. R ³ and R ⁴ are a hydrogen atom, an alkoxycarbonyl group (RO—CO—: R is an alkyl group having 1 to 10 carbon atoms) and a phenoxycarbonyl group (Ph—O—CO
-: Ph is a phenyl group), and R ³ and R ⁴ may be the same or different. The average value of n is 1 to 1000, preferably 2 to 500.

As the polycarbonate body, a commercially available product as polycarbonate diol can be used, or it can be produced, for example, by the method described in the following publication. 1) A diol and a carbonic acid diester or an equivalent thereof are subjected to a polycondensation reaction as described in JP-A-63-75030 and JP-A-64-1726. 2) Japanese Patent Application Laid-Open No. Hei 3-18151
No. 7, as described in JP-A-7, a crosslinkable trihydric or higher polyhydric alcohol is added in addition to the dihydric alcohol,
It is reacted with a carbonic acid diester or the like.

Next, a more specific method for producing the polycarbonate body represented by the general formula (2) will be described. The polycarbonate body is synthesized by reacting a diol with a carbonyl component such as carbonic acid diester, phosgene, or chloroformate by a well-known method, and a number of hydroxyl groups are formed at the molecular terminals of the product. A carbonyl group or a phenoxycarbonyl group may be contained.

Specific examples of the diol used as a raw material include ethylene glycol, 1,2-propylene glycol, diethylene glycol, dipropylene glycol,
Triethylene glycol, polyethylene glycol, polypropylene glycol, neopentyl glycol,
1,3-propanediol, 1,4-butanediol,
1,5-pentanediol, 3-methyl-1,5 pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,3-bis (2-hydroxyethoxy) benzene, 1,4-bis ( 2-hydroxyethoxy) benzene, 1,4-cyclohexanediol, 1,
4-cyclohexanedimethanol and the like. These may be used alone or in combination of two or more,
You may mix and use.

Specific examples of the carbonyl component include diester carbonates such as dimethyl carbonate, diethyl carbonate, diisopropyl carbonate, diphenyl carbonate, ethylene carbonate and propylene carbonate; chloroformate esters such as methyl chloroformate, ethyl chloroformate and phenyl chloroformate; Phosgene and the like.

The charging ratio of the carbonyl component such as carbonic acid diester to the diol is preferably 0.5 to 2 moles. The molecular weight of the produced polycarbonate body is preferably measured by GPC, and the weight average molecular weight in terms of standard polystyrene is preferably in the range of 200 to 100,000.

React with polycarbonate body (meth)
The acrylic acid alkyl ester is represented by the general formula (3).

Embedded image

In the formula, R ⁵ is a hydrogen atom or a methyl group, and R ⁶ is an alkyl group having 1 to 4 carbon atoms. Specific examples of the alkyl (meth) acrylate include acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, and butyl acrylate, or methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate. And methacrylic acid esters.

The reaction ratio of the (meth) acrylic acid alkyl ester to the polycarbonate body is 0.1 to 100 times, preferably 0.5 to 50 times, in terms of the charged molar ratio.
It is twice the mole.

As the catalyst used for the transesterification reaction,
Protic acids such as sulfuric acid, methanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, hydrochloric acid, phosphoric acid, phosphotungstic acid, phosphomolybdic acid, or sodium methoxide, lithium methoxide, potassium butoxide, aluminum triisopropoxide, and titanium Metal alkoxides such as tetraisopropoxide can be mentioned, and among them, toluenesulfonic acid or aluminum triisopropoxide is preferable. The addition amount of these catalysts is usually 0.01 to 10% by weight, preferably 0.1 to 5% by weight, based on the raw material polycarbonate body.

The reaction can be carried out without a solvent, but a solvent inert to the reaction, for example, a halogenated hydrocarbon such as dichloromethane, chloroform or dichloroethane, an aromatic hydrocarbon such as benzene, toluene or xylene, hexane or heptane , Decane, saturated hydrocarbons such as cyclohexane, and ethers such as diethyl ether, diisopropyl ether, and tetrahydrofuran (THF) can also be used as the solvent. In this case, the amount of the solvent used is usually 0.1 to
It is 10 times by weight, preferably 0.2 to 5 times by weight.

The reaction is carried out at a temperature of usually from 40 to 200 ° C., preferably from 60 to 150 ° C., and it is preferred that the alcohol produced by the transesterification is quickly distilled out of the reaction system. If left in the reaction system, the polycarbonate chain may be cut by the alcohol, and the molecular weight may be reduced. Incidentally, a polymerization inhibitor may be added during the reaction. After completion of the reaction, the mixture is treated according to a conventional method to obtain a composition containing the polycarbonate body represented by the general formula (1).

Polymer Solid Electrolyte The polymer solid electrolyte according to the present invention is obtained by mixing a metal salt of Group Ia of the periodic table with a polymer of a composition containing a polycarbonate represented by the general formula (4): It is configured.

Embedded image (Wherein, X is a divalent hydrocarbon group having 2 to 20 carbon atoms, and the group may contain a double bond, an aromatic ring or an ether bond, and some of R ⁷ and R ⁸ are A (meth) acryloyl group, and the remaining R ⁷ or R ⁸ is at least one group selected from the group consisting of an alkoxycarbonyl group, a phenoxycarbonyl group and a hydrogen atom, and R ⁷ and R ⁸ are May be the same or different, and the average value of n is 1 to 1000)

The composition containing the polycarbonate body represented by the formula (4) is substantially the same as the composition containing the polycarbonate body represented by the formula (1). However, when used as a material for a polymer solid electrolyte, if the remaining R ⁷ and R ⁸ in the formula (4) are hydrogen atoms, the terminal hydroxyl group reacts with the metal and becomes electrochemically unstable. Because it is easy, it is desirable to minimize the remaining R ⁷ and R ^{8 from} being hydrogen atoms in order to minimize the influence on the electrolyte.

Therefore, by controlling the reaction conditions before polymerizing the composition containing the polycarbonate represented by the formula (4), the proportion of hydroxyl groups can be reduced to near zero or modified with an esterifying agent or the like. Is preferred. As an example of a specific method, after transesterification with a (meth) acrylic acid ester, an equivalent or more acid anhydride corresponding to the remaining hydroxyl group, for example, acetic anhydride,
There is a method of esterifying the remaining hydroxyl groups using propionic anhydride, butyric anhydride, benzoic anhydride and the like. Alternatively, after polymerization, the remaining hydroxyl groups may be esterified by the same method as described above.

The composition containing the polycarbonate represented by the general formula (4) can be polymerized by itself and used as an electrolyte, or can be used as an electrolyte by copolymerizing with another copolymerizable monomer. You can also. The other monomer copolymerizable with the polycarbonate body may be any of a vinyl monomer, a vinylidene monomer, and a vinylene monomer. Specifically, ethyl (meth) acrylate, ethoxyethyl (meth) acrylate, (meth) Ethoxyethoxyethyl acrylate, polyethylene glycol (meth) acrylate, allyl alcohol, vinyl acetate, styrene, α-methylstyrene, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, acrylonitrile, vinyl cyanoacetate, allylamine, isopropylacrylamide Vinylene carbonate, maleic anhydride and the like.

The polymerization can be carried out in the presence or absence of a solvent. When a solvent is used, carbonates, lactones or ethers are preferably used.
Examples of the carbonate solvent include ethylene carbonate, propylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, dipropyl carbonate and the like. As a lactone,
Examples of γ-butyrolactone include ethers, and examples of ether include dimethoxyethane.

The polymer solid electrolyte can also be obtained by preliminarily polymerizing a composition containing the polycarbonate represented by the formula (4), and blending the polymer with a metal salt of Group Ia of the periodic table. Alternatively, it can also be obtained by blending a metal salt of Group Ia of the periodic table with a composition containing the polycarbonate body represented by the formula (4), and then proceeding the polymerization reaction in the presence of the metal salt. The composition containing the polycarbonate body represented by the formula (4) can be polymerized by an appropriate means such as radical polymerization or ionic polymerization.

As the metal salt of Group Ia of the periodic table,
LiClO_Four, LiBF_Four, LiPF ₆, LiAsF₆, L
iCF_ThreeSO_Three, LiN (CF_ThreeSO_Two)_Two, LiC (CF_Three
SO _Two)_ThreeUse of one or more Li salts selected from the group consisting of
Is preferred. The metal salt concentration in the solid electrolyte is 0.1 to
It is preferably 10 (mol / liter).

A particularly preferred method for producing a polymer electrolyte is as follows:
By mixing the above-described polycarbonate composition and a metal salt of Group Ia of the periodic table, applying the mixed solution on a flat substrate, and irradiating it with ultraviolet rays, radiation such as an electron beam, or by heating. This is a method obtained by polymerizing a polycarbonate composition. The obtained polymer has a thickness of 0.1 to 1
000 μm, which can be molded into an arbitrary shape and used as an electrochemical element.

In the case of polymerization by irradiation with ultraviolet rays, the reaction can proceed efficiently by adding a photosensitizer. Preferred photosensitizers include benzophenone, acetophenone, and 2,2-dimethoxy-2-phenylacetophenone. Can be exemplified.

When the polymerization is carried out by heat, it is desirable to use a thermal polymerization initiator. Depending on the polymerization mode, peroxides such as benzoyl peroxide and peroxydicarbonate, azo compounds such as 2,2'-azobisisobutyronitrile, nucleophiles such as alkali metals, and electrophiles such as Lewis acids Can be added alone or in combination.

[0042]

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

(Example 1) In a glass reaction vessel equipped with a stirrer, a thermometer, a rectification tower and the like, 3-methyl-1,5-
25 g of polycarbonate diol (Kuraray product: hydroxyl value; 58, Mn; 2000) produced from pentanediol, 1,6-hexanediol (molar ratio: 90:10), and diethyl carbonate, 17.5 g of methyl acrylate, aluminum triacrylate Isopropoxide 0.4
1 g, 0.05 g of 4-methoxyphenol and 25 ml of toluene were charged, and the produced methanol was distilled out of the reaction system while heating for 10 hours. After cooling to room temperature,
25 ml of toluene and 5 g of silica gel were added, and the mixture was stirred for 1 hour. Next, the silica gel was filtered, and the filtrate was concentrated under reduced pressure to obtain a colorless oil. Yield 2
4.8 g.

The proton NMR chart of the product is shown in FIG. From the NMR chart, characteristic signals of the acrylate ester and the methyl carbonate group were both recognized, and the integral ratio showed that the ratio of the acrylate ester was about 70 mol%.

Accordingly, the obtained product is a polycarbonate acrylate represented by the above formula (1),
Is CH ₂ CH ₂ CH (CH ₃ ) CH ₂ CH ₂ or (C
In H _{2) 6,} the average value of n is 3.9, R ¹ and R ² was an acryloyl group or a methoxycarbonyl group.

Example 2 The same polycarbonate diol as used in Example 1 (Kuraray product: hydroxyl value; 58, Mn ;: 2000) was placed in a glass reaction vessel equipped with a stirrer, a thermometer, a rectification tower and the like. 120 g, methyl acrylate 51.7 g, p-toluenesulfonic acid monohydrate 2.
4 g, 0.24 g of 4-methoxyphenol and 60 ml of toluene were charged, and methanol produced was distilled out of the reaction system while heating for 12 hours. After lowering to 50 ° C,
20 g of magnesium oxide was added and stirred for 1 hour. After cooling to room temperature, insolubles were filtered, and the filtrate was concentrated under reduced pressure to obtain a pale yellow oil. Yield 12
6.3 g.

FIG. 2 shows a proton NMR chart of the product. From the NMR chart, characteristic signals of the acrylate ester and the methyl carbonate group were both recognized, and the integral ratio showed that the ratio of the acrylate ester was about 85 mol%.

Accordingly, the obtained product is a polycarbonate acrylate represented by the above formula (1),
Is CH ₂ CH ₂ CH (CH ₃ ) CH ₂ CH ₂ or (C
In H _{2) 6,} the average value of n is 13.2, R ¹ and R ² was an acryloyl group or a methoxycarbonyl group.

Example 3 In a glass reaction vessel equipped with a stirrer, a thermometer, a rectification tower and the like, a polycarbonate diol containing 1,6-hexanediol as a main component (Daicel product: hydroxyl value; 58, Mn; 2000) ) 35.9
g, methyl acrylate 15.4 g, p-toluenesulfonic acid monohydrate 0.72 g, 4-methoxyphenol 0.4 g.
07 g and 35 ml of toluene were charged and methanol produced was distilled out of the reaction system while heating for 10 hours. After the temperature was lowered to 50 ° C., 2 g of magnesium oxide was added, and the mixture was stirred at 50 ° C. for 1 hour. After cooling to room temperature, the insolubles were filtered, and the filtrate was concentrated under reduced pressure,
A pale orange oil was obtained. Yield 36.6 g.

FIG. 3 shows a proton NMR chart of the product. From the NMR chart, both characteristic signals of the acrylate ester and the methyl carbonate group were recognized, and the integral ratio showed that the ratio of the acrylate ester was about 93 mol%.

Accordingly, the obtained product is a polycarbonate acrylate represented by the above formula (1),
Is (CH ₂ ) ₆ , the average value of n is 13.8, R ¹ and R ²
Was an acryloyl group or a methoxycarbonyl group.

(Example 4) Polycarbonate diol (Mn; 1400) synthesized from diethylene glycol and dimethyl carbonate as raw materials in a glass reaction vessel equipped with a stirrer, a thermometer, a rectification tower, and the like 46.15.
g, 26.38 g of methyl acrylate, 0.92 g of p-toluenesulfonic acid monohydrate, 0.07 g of 4-methoxyphenol and 46 ml of toluene, and methanol produced by heating for 7 hours was distilled out of the reaction system. did.
After the temperature was lowered to 50 ° C., 2 g of magnesium oxide was added, and the mixture was stirred at 50 ° C. for 1 hour. Next, after cooling to room temperature, insolubles were filtered, and the filtrate was concentrated under reduced pressure to obtain a colorless oil. Yield 24.8 g.

FIG. 4 shows a proton NMR chart of the product. From the NMR chart, characteristic signals of the acrylate ester and the methyl carbonate group were both recognized. Therefore, the obtained product is a polycarbonate acrylate represented by the above formula (1), wherein X is CH ₂ C
In H ₂ —O—CH ₂ CH ₂ , the average value of n is 10.0, R ¹
And R ² was an acryloyl group or a methoxycarbonyl group.

(Example 5) 20.0 parts by weight of the polycarbonate composition prepared in Example 1 was mixed with an equal mixture (weight ratio) of ethylene carbonate and propylene carbonate by L.
Electrolyte solution in which iPF ₆ is dissolved at a concentration of 1 mol / l
A solution containing 0 parts by weight was cast on a glass plate in an inert gas atmosphere, and an ultraviolet irradiation device (USHIO Inc.)
Made: UIS-25102, Optical fiber unit: SF
-101Q), polymerized and cured by irradiating ultraviolet rays for 30 minutes from a position 7 cm above the substrate, and having a thickness of about 0.5 mm
Was produced.

This polymer electrolyte was punched into a 10 mmφ disk shape, sandwiched between electrodes provided on a conductivity measurement holder, and controlled at 25 ° C. by a Peltier element to control the impedance of an impedance analyzer (HP4285A).
Was used to measure the complex impedance (measurement voltage: 10 mV), and the ionic conductivity was determined analytically. Pt (electrode area 0.5 cm ² ) as a working electrode, Li (electrode area 4 cm ² ) as a counter electrode, and Li (electrode area 0.5 cm ² ) as a reference electrode.
cm ² ) and the withstand voltage was measured by a potentiostat (Solartron 1286) by cyclic voltammetry. As a result, the ionic conductivity was 4.1 mS / cm ² and the withstand voltage was 5.6 V.

[0056]

The polycarbonate composition according to the present invention is a composition containing a polycarbonate having polymerizability and is useful as a raw material for various functional resin materials. Further, according to the method for producing a polycarbonate composition, the polycarbonate composition can be produced in a high yield with a general apparatus without using a special reaction apparatus having corrosion resistance.

Further, the polymer electrolyte comprising the polymer of the polycarbonate composition according to the present invention exhibits high ionic conductivity, becomes a stable electrochemical element, and is further added with flexibility, thereby providing a highly reliable primary battery. It can be used as an electrolyte for secondary batteries, capacitors and the like.

[Brief description of the drawings]

FIG. 1 is a proton NMR chart of the polycarbonate composition obtained in Example 1.

FIG. 2 is a proton NMR chart of the polycarbonate composition obtained in Example 2.

FIG. 3 is a proton NMR chart of the polycarbonate composition obtained in Example 3.

FIG. 4 is a proton NMR chart of the polycarbonate composition obtained in Example 4.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01G 9/028 H01M 10/40 B // H01M 6/18 H01G 9/00 301G 10/40 9/02 331G F term (reference) 4J002 CG001 DD006 DD036 DG046 DH006 DK006 FD206 GQ00 4J029 AA09 AB02 AB05 AC01 AD01 AE18 BA03 BA04 BA05 BA08 BA10 BB06A BD04A BD07A BF09 BF10 BF25 HA01 HC01 HC04A HC05A HC06 KB02 KH015 EJ14

Claims (6)

[Claims] 1. A polycarbonate composition comprising a polycarbonate represented by the general formula (1). Embedded image (Wherein, X is a divalent hydrocarbon group having 2 to 20 carbon atoms, and the group may contain a double bond, an aromatic ring or an ether bond, and some of R ¹ and R ² are (meth) an acryloyl group, the remaining R ¹ and R ² is at least an alkoxycarbonyl group, a single type of group selected from the group consisting of phenoxycarbonyl group and a hydrogen atom, R ¹ and R ² May be the same or different, and the average value of n is 1 to 1000) 2. The polycarbonate composition according to claim 1, wherein
^{2. The method according} to claim 1, wherein the content of the (meth) acryloyl group as R ¹ and R ² is 10 to 99 mol%.
The polycarbonate composition according to the above. 3. A polycarbonate body represented by the general formula (2): (In the formula, X is a divalent hydrocarbon group having 2 to 20 carbon atoms, which may contain a double bond, an aromatic ring or an ether bond, R ³ and R ^{4 each} represent a hydrogen atom, At least one group selected from the group consisting of an alkoxycarbonyl group and a phenoxycarbonyl group, wherein R ³ and R ⁴ may be the same or different, and the average value of n is 1
The method for producing a polycarbonate composition according to claim 1, wherein the transesterification reaction of the alkyl (meth) acrylate represented by the general formula (3) is carried out in the presence of a catalyst. Embedded image (Wherein, R ⁵ is a hydrogen atom or a methyl group, and R ⁶ is an alkyl group having 1 to 4 carbon atoms) 4. The method according to claim 3, wherein the transesterification catalyst is a protonic acid or a metal alkoxide.
A method for producing the polycarbonate composition described above. 5. A solid polymer electrolyte comprising a polymer of a composition containing a polycarbonate represented by the general formula (4), and a metal salt of Group Ia of the periodic table mixed with the polymer. Embedded image (Wherein, X is a divalent hydrocarbon group having 2 to 20 carbon atoms, and the group may contain a double bond, an aromatic ring or an ether bond, and some of R ⁷ and R ⁸ are A (meth) acryloyl group, and the remaining R ⁷ or R ⁸ is at least one group selected from the group consisting of an alkoxycarbonyl group, a phenoxycarbonyl group and a hydrogen atom, and R ⁷ and R ⁸ are May be the same or different, and the average value of n is 1 to 1000) 6. The metal salt of Group Ia of the periodic table, wherein the metal salt is Li
ClO_Four, LiBF_Four, LiPF₆, LiAsF₆, LiC
F_ThreeSO_Three, LiN (CF_ThreeSO_Two)_Two, LiC (CF_ThreeSO
_Two) _Three At least one metal salt selected from the group consisting of
The polymer solid electrolysis according to claim 5, wherein
quality.