JP2000351843A - Polycarbonate polyol, polycarbonate polyol (meth) acrylate, and their use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate polyol good in solubility in solvents, a polycarbonate (meth)acrylate derived therefrom and improved in storage stability, and a solid electrolyte utilized the acrylate. SOLUTION: This polycarbonate polyol is manufactured by polycondensation of two kinds of glycol and a carbonic acid diester, phosgene, or a chloroformic acid ester. The glycols are represented by the formulae HO-(CH2CH2O)n-H (n is an integer 2-10), and HO-R-OH (R is a C4-20 alkylene group). To the hydroxyl group of the polycarbonate polyol, a (meth)acrylic acid is reacted to obtain (meth)acrylate. By incorporating an alkali metal salt, to the resin prepared by polymerization of the polycarbonate (meth)acylate, a polymer solid electrolyte having a high ion conductivity and excellent electrochemical stability is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel polycarbonate polyol, a polycarbonate (meth) acrylate obtained by esterifying a hydroxyl group thereof, a polycarbonate (meth) acrylate resin obtained by polymerizing the same, and a resin thereof. The present invention relates to a solid polymer electrolyte which is useful for a primary battery, a secondary battery, a capacitor and the like using the same.

[0002]

2. Description of the Related Art Conventionally, a liquid electrolyte has been used for an electrochemical element such as a primary battery, a secondary battery, and a capacitor. However, there has been a concern that the liquid electrolyte leaks from a container during long-term use. Therefore, in order to enhance the long-term reliability of these electrochemical devices, the practical use of solid electrolytes instead of liquid electrolytes has been considered. If such solid electrolytes are realized, highly reliable devices can be provided, and the devices themselves can be provided. It is expected that the size and weight will be reduced.

As a kind of the solid electrolyte, a polymer solid electrolyte has been studied in recent years. Since the polymer solid electrolyte has flexibility, it has an advantage that it can flexibly cope with a volume change occurring in the ion-electron exchange reaction process between the electrode and the polymer solid electrolyte.

As such a polymer solid electrolyte, a complex of a polyethylene oxide having a polyether structure and an alkali metal salt such as a lithium salt is known.
Japanese Patent Application Laid-Open No. 1-241764 discloses a solid electrolyte prepared by mixing a polar aprotic liquid and an alkali metal salt with a crosslinked polymer obtained by polymerizing a methacrylate such as poly (diethylene glycol carbonate) dimethacrylate. Is described.

However, poly (diethylene glycol carbonate), which is a raw material for producing the above-mentioned poly (diethylene glycol carbonate) dimethacrylate, has a strong polarity, and thus has low solubility in solvents such as toluene used in ordinary esterification reactions and the like. Although the methacrylate of this is not clear whether it is due to its chemical structure or not, its storage stability is lacking because it is easily polymerized.

[0006]

Accordingly, the present invention provides a novel polycarbonate polyol having improved solubility in a solvent such as toluene, a novel polycarbonate (meth) acrylate having improved storage stability,
It is another object of the present invention to provide a flexible solid polymer electrolyte using the polymer, which has high ionic conductivity, is excellent in electrochemical stability, and is flexible.

[0007]

That is, the present invention relates to at least one kind of glycol represented by the general formula (1) HO- (CH ₂ CH ₂ O) _n -H (1) (Wherein, n is an integer of 2 to 10), and at least one kind of glycol HO-R-OH represented by the general formula (2). (2) (wherein, R is an alkylene group having 4 to 20 carbon atoms,
It may contain an ether bond therein, except for an oxyethylene group, and R may be linear or branched, and may form a ring structure). The present invention relates to a polycarbonate polyol which is a polycondensate with a carbonyl compound selected from the group consisting of diester, phosgene and chloroformate.

The polycarbonate polyol has a constituent ratio (weight) of the diol represented by the general formula (1) and the diol represented by the general formula (2) of 5:95 to 95: 5, and the weight average molecular weight of the polycondensate is from 500 to 100,000.
It is preferably 0.

The present invention also relates to a polycarbonate (meth) acrylate resin obtained by polymerizing the above-mentioned polycarbonate (meth) acrylate, and a polymer solid electrolyte using the same.

DETAILED DESCRIPTION OF THE INVENTION Polycarbonate Polyol The polycarbonate polyol according to the present invention is a polymer having a carbonate bond in a polymer main chain and having a hydroxyl group at a terminal. This polycarbonate polyol is
It is a polycondensate obtained by subjecting at least two types of glycols described below to a polycondensation reaction with a carbonyl compound selected from the group consisting of carbonic acid diester, phosgene, and chloroformate.

As the glycol, two types of glycol (A) represented by the general formula (1) and glycol (B) represented by the general formula (2) are used. Next, each of them will be described.

The glycol (A) is a compound represented by the following general formula (1). HO- (CH ₂ CH ₂ O) _n -H (1) where n is an integer of 2 to 10. Specific examples of the glycol include diethylene glycol, triethylene glycol, polyethylene glycol having n of 4 or more, and among them, diethylene glycol is preferable.
These glycols may be used alone or as a mixture of two or more.

The glycol (B) is a compound represented by the following general formula (2). HO-R-OH (2) where R is an alkylene group having 4 to 20 carbon atoms, and the group may contain an ether bond. However, oxyethylene groups are excluded. R may have a linear structure or a branched structure, and may further form a ring structure.

Specific examples of the glycol (B) include:
(A) 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6
-Hexanediol, 1,8-octanediol, neopentyl glycol, 2-methyl-1,8-octanediol, 1,9-nonanediol, (b) dipropylene glycol, tripropylene glycol, polypropylene glycol, (c) 1,3-bis (2-hydroxyethoxy) benzene, 1,4-bis (2-hydroxyethoxy) benzene, 1,4-cyclohexanediol,
1,4-cyclohexanedimethanol and the like can be mentioned.

Of these, 1,4-butanediol, 3-methyl-1,5 pentanediol, 1,6-hexanediol and dipropylene glycol are preferred. These glycols can be used alone or Two or more kinds may be used as a mixture.

The composition ratio of the glycol component (A) and the glycol component (B) in the polycarbonate polyol is from 5:95 to 95: 5, preferably from 20:80 to 90:10 by weight ratio. Glycol component (A)
When the composition ratio of (B) and (B) is within the above range, the polarity of the produced polycarbonate polyol is optimized, so that good solubility in the esterification reaction solvent in the next step is obtained and storage stability is obtained. And a high electrolyte performance is finally obtained when the polymer solid electrolyte material is finally obtained.

In the reaction with the carbonyl compound, a trihydric or higher polyhydric alcohol may be added and mixed as the third component in addition to the glycol (A) and the glycol (B). Specific examples of polyhydric alcohols include polyols such as trimethylolpropane, trimethylolethane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, glycerin, sorbitol, and tris (2-hydroxyethyl) isocyanurate. Can be mentioned. Alternatively, alcohols having a hydroxyl group obtained by adding 1 to 5 equivalents of ethylene oxide, propylene oxide, or other alkylene oxide to the hydroxyl group of these polyhydric alcohols may be used. These polyhydric alcohols may be used alone or as a mixture of two or more.
The use ratio is preferably from 1 to 40% by weight based on the total amount of glycol (A) and glycol (B).

Examples of the carbonyl compound include (a) diester carbonate such as dimethyl carbonate, diethyl carbonate, diisopropyl carbonate, diphenyl carbonate, ethylene carbonate and propylene carbonate; and (b) chloroformate such as methyl chloroformate, ethyl chloroformate and phenyl chloroformate. Acid ester or (c) phosgene.
These carbonyl compounds may be used alone or as a mixture of two or more.

The polycarbonate polyol is synthesized by subjecting at least two kinds of glycols and a carbonyl compound to a polycondensation reaction under general conditions. 64
These are described in JP-A-1726 and JP-A-4-7327. The amount of the reaction ratio of the carbonyl compound to the glycol component is based on the hydroxyl group of the glycol,
It is preferably 0.2 to 2 equivalents. The terminal functional group of the polycarbonate polyol after the reaction is usually an OH group, but a part thereof may be a carbonate group.

The molecular weight of the polycarbonate polyol after the polycondensation reaction is measured by GPC analysis, and the weight-average molecular weight in terms of standard polystyrene is 500 to 500.
100,000, preferably 1,000 to 50,000
Is advantageous in finally obtaining a flexible polymer solid electrolyte.

Such a polycarbonate polyol can be used as a raw material for a polycarbonate (meth) acrylate described later, and is also useful as a plasticizer for an electrolyte of a Li-ion secondary battery or as a urethane raw material.

Polycarbonate (meth) acrylate The polycarbonate (meth) acrylate according to the present invention is a compound obtained by converting a part or all of the hydroxyl groups of the above-mentioned polycarbonate polyol into an acrylate or methacrylate. In the book, both are described as polycarbonate (meth) acrylate.

This esterified product can be produced under the same conditions as in the usual esterification reaction. For example, (a) a method of condensing a polycarbonate polyol with acrylic acid or methacrylic acid in the presence of an acid catalyst, and (b) a method of transesterifying a polycarbonate polyol with an acrylate or methacrylate in the presence of a catalyst. (C) a method in which a polycarbonate polyol is condensed with an acrylic acid halide or a methacrylic acid halide in the presence of a base compound, (d) or a method in which the polycarbonate polyol and an acrylic acid anhydride or a methacrylic acid anhydride are reacted in the presence of a catalyst. Examples of the method include condensation.

The reaction ratio of acrylic acid, methacrylic acid, or a derivative thereof used in these esterification reactions is 0.1 to 1.0 with respect to the hydroxyl groups of the polycarbonate polyol.
It is 2 to 10, preferably 0.5 to 6 equivalents.

First, details of the case of manufacturing by the method (a) will be described. Examples of the acid catalyst used in the reaction include sulfuric acid, methanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, hydrochloric acid, phosphoric acid, phosphotungstic acid, and phosphomolybdic acid. Among them, sulfuric acid or toluenesulfonic acid is preferable, and the amount of use thereof is usually 0.01 to 10% by weight, preferably 0.1 to 10% by weight based on the raw material polycarbonate.
5% by weight.

The reaction can be carried out without solvent, but solvents inert to the reaction, for example, halogenated hydrocarbons such as dichloromethane, chloroform and dichloroethane, aromatic hydrocarbons such as benzene, toluene and xylene, hexane, heptane , Decane, cyclohexane and other saturated hydrocarbons, and ethers such as diethyl ether, diisopropyl ether and tetrahydrofuran can also be used as solvents. In this case, the amount of the solvent used is usually 0.1 to 10 with respect to the raw material polycarbonate polyol.
The weight is twice, preferably 0.2 to 5 times by weight.

The reaction temperature is usually from 25 to 180 ° C, preferably from 50 to 150 ° C. It is preferable that water generated as the reaction proceeds is distilled off from the reaction system by azeotropic distillation with a solvent, and a polymerization inhibitor may be added during the reaction. After the completion of the reaction, the resultant is treated according to a conventional method to isolate the desired polycarbonate (meth) acrylate.

Next, details of the case of manufacturing by the method (b) will be described. Examples of the (meth) acrylic ester as a raw material include acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, and butyl acrylate, and methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate. Can be used.

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 amount of these catalysts used is usually 0.0
It is 1 to 10% by weight, preferably 0.1 to 5% by weight.

The type of the reaction solvent, the amount of the solvent used and the reaction temperature are the same as in the above (a). It is preferable that the alcohol generated in the reaction is quickly distilled out of the reaction system,
Thereby, the breaking of the polycarbonate chain by the produced alcohol can be prevented. Further, a polymerization inhibitor may be added during the reaction.

Next, the method (c) will be described. Examples of the raw material (meth) acrylic acid halide include acrylic acid chloride and methacrylic acid chloride. Examples of the base compound to be added during the reaction include organic bases such as triethylamine, pyridine, dimethylaminopyridine, and diazabicycloundecene (DBU), and inorganic bases such as sodium carbonate, potassium carbonate, sodium hydroxide, and potassium hydroxide. It is preferable to use 1 to 5 equivalents to the raw material acid halide. The reaction solvent is the same as in the above (a). The reaction temperature is usually -20 to 100C, preferably -5 to 50C.

The case of manufacturing by the method (d) will be described. Examples of the acid anhydride as a raw material include acrylic acid anhydride and methacrylic anhydride. Examples of the catalyst used for the reaction include sulfuric acid, methanesulfonic acid, toluenesulfonic acid, pyridine, and dimethylaminopyridine. Such a catalyst is usually added in an amount of 0.01 to 0.5 equivalent based on the acid anhydride. The reaction can be carried out in the presence or absence of a solvent in the same manner as in the method (a), and the reaction temperature is as follows:
Usually, it is desirable to be in the range of −5 to 120 ° C., preferably 25 to 100 ° C.

After the esterification reaction is completed by the methods (a) to (d), if some of the hydroxyl groups of the starting polycarbonate polyol still remain without being esterified, the acid anhydride is further added. It is desirable to convert to an ester group by reacting with the above, so that the battery performance can be enhanced when finally used as a battery electrolyte. Examples of the acid anhydride include acetic anhydride, propionic anhydride, and benzoic anhydride, and among them, acetic anhydride is preferable. In this case, the amount of the acid anhydride to be used is 1 to 10 equivalents, preferably 1 to 5 equivalents, based on the remaining hydroxyl groups.

The polycarbonate (meth) acrylate thus obtained can be used as a polymerizable monomer for producing a polymer substance by utilizing a double bond of an acrylate group or a methacrylate group. It can be effectively used as a raw material for electrolytes, adhesives, paints, and the like.

Polycarbonate (meth) acrylate tree
Polycarbonate (meth) acrylate resins produced from fatty polycarbonate (meth) acrylates include:
(A) a homopolymer of the polycarbonate (meth) acrylate, (b) a copolymer of two or more of the polycarbonate (meth) acrylates, (c) the polycarbonate (meth) acrylate, and the polycarbonate (meth) acrylate. And copolymers with other copolymerizable monomers.

This polycarbonate (meth) acrylate resin can be obtained as a polymer by polymerizing polycarbonate (meth) acrylate by a radical polymerization method or an ionic polymerization method. In the case of the radical polymerization method, polymerization is performed using a means such as heating or irradiation with radiation such as an ultraviolet ray or an electron beam in the presence or absence of a radical initiator such as an organic or inorganic peroxide or an azo compound. The reaction can proceed. In the case of ionic polymerization, the polymerization reaction can be advanced using a nucleophilic reagent such as an alkali metal, an electrophilic reagent such as a Lewis acid, or the like.

The monomers copolymerizable with the polycarbonate (meth) acrylate include vinyl monomers,
There are vinylidene monomer, vinylene monomer and the like. Specifically, ethyl (meth) acrylate, ethoxyethyl (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate, polyester (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.

It is desirable that such a copolymerizable monomer be contained in the polycarbonate (meth) acrylate resin in an amount of usually 1 to 90% by weight, preferably 1 to 50% by weight as a monomer unit.

Polymer Solid Electrolyte The polymer solid electrolyte according to the present invention contains the above-mentioned polycarbonate (meth) acrylate resin in the periodic table I.
It is a solid electrolyte containing a group a metal salt as an electrolyte.

The metal salt of Group Ia of the periodic table includes salts of lithium, sodium, potassium, etc.
_{ClO 4, LiBF 4, LiPF 6} , LiAsF 6, LiC
F ₃ SO ₃ , LiN (CF ₃ SO ₂ ) ₂ , LiC (CF ₃ SO
₂ ) One or more lithium salts selected from ₃ are preferred. The metal salt concentration in the solid electrolyte is desirably 0.1 to 10 (mol / l) in order to exhibit appropriate ionic conductivity.

The production of the solid electrolyte is carried out by mixing a previously produced polycarbonate (meth) acrylate resin with the Ia of the periodic table.
A method of uniformly mixing a group III metal salt, or a copolymerizable monomer with at least one of polycarbonate (meth) acrylate, if necessary, and Ia of the periodic table.
The method can be carried out by, for example, a method of uniformly mixing the group III metal salt and then proceeding the polymerization reaction. Particularly, the latter method is preferable because a solid electrolyte in which a metal salt is uniformly dispersed in a polycarbonate (meth) acrylate resin can be easily obtained in a desired shape. As the polymerization method at this time, the above-described polymerization method for polycarbonate (meth) acrylate can be similarly used.

For example, a homogeneous mixture is prepared by adding a polycarbonate (meth) acrylate, a metal salt of Group Ia of the Periodic Table, and a solvent if necessary. The mixture is applied on a flat substrate. When polymerization is started by irradiation with radiation such as an electron beam or heating, the thickness is 0.1 to 10
A 00 μm solid electrolyte thin film can be formed directly on a substrate.

In the case of thermal polymerization, a thermal polymerization initiator can be used, and depending on the polymerization mode, peroxides such as benzoyl peroxide and peroxycarbonate, and 2,2'-
Azo compounds such as azobisisobutyronitrile, nucleophiles such as alkali metals, and electrophiles such as Lewis acids can be used alone or in combination. The polymerization temperature at this time is 0 to 100 ° C, preferably 20 to 90 ° C.
This is performed in a temperature range where the metal salt as the electrolyte is not decomposed.

In the polymerization by ultraviolet irradiation, benzophenone, acetophenone, 2,2-dimethoxy-2-
A photosensitizer such as phenylacetophenone can be added.

The solid polymer electrolyte according to the present invention comprises:
In addition to the polycarbonate (meth) acrylate resin and the metal salt of Group Ia of the periodic table, a non-aqueous solvent such as a carbonate ester is added to the polycarbonate (meth) acrylate resin 100
The electrolyte may preferably contain 0 to 1000 parts by weight, particularly preferably 100 to 700 parts by weight, based on parts by weight. As a method for containing a non-aqueous solvent, for example, when producing a solid polymer electrolyte, polymerization may be carried out in the presence of a non-aqueous solvent, or the non-aqueous solvent may be impregnated after polymerization.

As a nonaqueous solvent that can be used, a carbonate ester or a lactone is preferably used. Examples of the carbonic ester include linear or cyclic carbonates such as ethylene carbonate, propylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, and dipropyl carbonate. Examples of the lactone include γ-butyrolactone, δ-valerolactone, ε-caprolactone, and the like.

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, and medical actuators.

Further, the solid polymer electrolyte according to the present invention comprises:
It can be used as an alternative to an organic electrolyte for a lithium ion secondary battery. Further, the powdery electrode material can be used as a binder used for dispersing and fixing the powdered electrode material on a current collector.

When this polymer solid electrolyte is used in a battery, the battery can be manufactured by forming the polymer solid electrolyte into a film and sandwiching it between the positive electrode and the negative electrode. In the conventional battery manufacturing method,
After forming a three-layer structure of a positive electrode, a separator, and a negative electrode, a process of impregnating with an electrolytic solution was performed. Instead of the electrolytic solution impregnation, a polycarbonate (meth) acrylate and a metal salt of Group Ia of the periodic table were used. It is also possible to change to a manufacturing process in which a mixed solution comprising a non-aqueous solvent is impregnated and then polymerize the polycarbonate (meth) acrylate, and this method can minimize the process modification.

[0050]

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

Example 1 159.2 g of diethylene glycol and 118.2 g of 1,6-hexanediol were placed in a glass reaction vessel equipped with a stirrer, thermometer, rectification tower and the like.
g, 270.2 g of dimethyl carbonate, and 28 as a catalyst.
% Sodium methoxide methanol solution 0.48 g was charged and mixed.

Next, the solution was kept at 95 ° C. under normal pressure for 2 hours, then heated to 150 ° C. over 5 hours, and further heated at 150 ° C. for 4 hours, during which time methanol produced by the reaction was distilled off. . Then, 150 mm under a reduced pressure of 5 mmHg.
The temperature was maintained at １５155 ° C., and 45.0 g of glycol produced during the polymerization reaction was distilled off.

After cooling to 70 ° C., 200 ml of toluene and 4.8 g of activated clay were added, and the mixture was stirred at this temperature for 1 hour. Thereafter, the mixture was cooled to room temperature, the activated clay was filtered, and the filtrate was concentrated to obtain a polycarbonate polyol 27.
0 g was obtained as a viscous oil. As a result of analysis by GPC, the weight average molecular weight of this oily substance was 6,600. This polycarbonate polyol was soluble in an equal volume of toluene at room temperature.

A glass reaction vessel equipped with a stirrer, thermometer, Dean Stark, etc. was charged with 40.0 g of polycarbonate polyol, 3.93 g of acrylic acid, 0.8 g of p-toluenesulfonic acid monohydrate and 40 ml of toluene. The mixture was heated under reflux for an hour, and 0.9 ml of water produced by the esterification reaction was separated. After cooling to 80 ° C., 0.37 g of acetic anhydride was added and the mixture was stirred for 1 hour to acetylate the remaining hydroxyl groups without esterification. 50
After cooling to ° C., 4 g of magnesium oxide was added and stirred for 1 hour. After cooling to room temperature, the reaction solution was filtered, and the filtrate was concentrated under reduced pressure to obtain 41.4 g of a viscous oil. The proton NMR chart of this viscous oily substance is shown in FIG.

Example 2 127.3 g of diethylene glycol, 127.3 g of 1,4-butanediol were placed in a glass reaction vessel equipped with a stirrer, a thermometer, a rectification tower and the like.
258.9 g of dimethyl carbonate and 0.34 g of a 28% sodium methoxide methanol solution as a catalyst were charged and mixed.

Next, this solution was kept at 95 ° C. under normal pressure for 2 hours, then heated to 150 ° C. over 5 hours, and further heated at 150 ° C. for 4 hours, during which time methanol produced by the reaction was distilled off. . Then, 150 mm under a reduced pressure of 5 mmHg.
The temperature was kept at １５155 ° C., and 54.8 g of glycol produced during the polymerization reaction was distilled off.

After cooling to 70 ° C., 200 ml of toluene and 3.4 g of activated clay were added, and the mixture was stirred at this temperature for 1 hour. Thereafter, the mixture was cooled to room temperature, the activated clay was filtered, and the filtrate was concentrated to obtain a polycarbonate polyol 27.
0 g was obtained as a viscous oil. As a result of analysis by GPC, the weight average molecular weight of this oily substance was 7,200. The polycarbonate polyol was soluble at 50 ° C. in an equal volume of toluene.

A glass reaction vessel equipped with a stirrer, thermometer, Dean Stark, etc. was charged with 40.0 g of polycarbonate polyol, 3.1 g of acrylic acid, 0.4 g of sulfuric acid and 40 ml of toluene, and heated under reflux for 4 hours to carry out esterification. 0.8 ml of water produced by the reaction was separated. After cooling to 80 ° C., 0.53 g of acetic anhydride was added, and the mixture was stirred for 1 hour to acetylate hydroxyl groups that had not been esterified. After cooling to 50 ° C., 4 g of magnesium oxide was added and stirred for 1 hour. By cooling to room temperature, filtering the reaction solution, and concentrating the filtrate under reduced pressure,
39.3 g of a viscous oil were obtained. FIG. 2 shows a proton NMR chart of the viscous oily substance.

Example 3 In a glass reaction vessel equipped with a stirrer, a thermometer, a rectification column and the like, 240.0 g of diethylene glycol, 60.0 g of 3-methyl-1,5-pentanediol, 299.0 g of dimethyl carbonate, And 28% methanol solution of sodium methoxide 0.5 as a catalyst.
3 g were charged and mixed.

Next, this solution was kept at 95 ° C. under normal pressure for 2 hours, then heated to 150 ° C. over 5 hours, and further heated at 150 ° C. for 4 hours, during which time methanol produced by the reaction was distilled off. . Then, 150 mm under a reduced pressure of 5 mmHg.
The temperature was kept at １５155 ° C., and 50.4 g of glycol produced during the polymerization reaction was distilled off.

After cooling to 70 ° C., 300 ml of toluene and 5.3 g of activated clay were added, and the mixture was stirred at this temperature for 1 hour. Thereafter, the mixture was cooled to room temperature, the activated clay was filtered, and the filtrate was concentrated to obtain a polycarbonate polyol 267.
g was obtained as a viscous oil. As a result of the analysis by GPC,
The weight average molecular weight of this oily substance was 5,600. The polycarbonate polyol was soluble at 50 ° C. in an equal volume of toluene.

A glass reaction vessel equipped with a stirrer, thermometer, Dean Stark, etc. was charged with 40.0 g of polycarbonate polyol, 4.6 g of acrylic acid, 0.4 g of sulfuric acid and 40 ml of toluene, and heated under reflux for 4 hours to carry out esterification. 0.9 ml of water produced by the reaction was separated. After cooling to 80 ° C., 0.44 g of acetic anhydride was added and the mixture was stirred for 1 hour to acetylate unesterified hydroxyl groups. After cooling to 50 ° C., 4 g of magnesium oxide was added and stirred for 1 hour. After cooling to room temperature, the reaction solution was filtered, and the filtrate was concentrated under reduced pressure to give 4
0.1 g of a viscous oil was obtained. The proton NMR chart of this viscous oily substance is shown in FIG.

Example 4 106.1 g of diethylene glycol, 134.2 g of dipropylene glycol, 234.2 g of dimethyl carbonate and 28% sodium methoxide as a catalyst were placed in a glass reaction vessel equipped with a stirrer, a thermometer and a rectification column. 0.63 g of a methanol solution was mixed, kept at 95 ° C. under normal pressure for 2 hours, then heated to 155 ° C. in 5 hours, and further heated at 155 ° C. for 4 hours to distill off methanol generated in the reaction. . Then 5
Under a reduced pressure of mmHg, the temperature was maintained at 150 to 155 ° C., and 26.1 g of glycol produced during the polymerization reaction was distilled off.

After cooling to 70 ° C., 300 ml of toluene and 6.3 g of activated clay were added, and the mixture was stirred at this temperature for 1 hour. Thereafter, the mixture was cooled to room temperature, the activated clay was filtered, and the filtrate was concentrated to obtain 258 g of a polycarbonate polyol as a viscous oil. As a result of analysis by GPC, the product had a weight average molecular weight of 5,300. The polycarbonate polyol was soluble at 50 ° C. in an equal volume of toluene.

Next, the polycarbonate 66. was placed in a glass reaction vessel equipped with a stirrer, a thermometer and a dropping port.
7 g, 12.2 g of triethylamine and 87 ml of dichloromethane were mixed and cooled to 5 ° C. Acrylic chloride (9.12 g) was added dropwise from the dropping funnel over 10 minutes, and the mixture was further stirred at 5 ° C. for 1 hour. The temperature was gradually raised to room temperature, and the mixture was further stirred at room temperature for 2 hours. The reaction solution was filtered, the filtrate was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated to obtain 62.1 g of a viscous oil.
The proton NMR chart of this viscous oil is shown in FIG.

(Polymerization Initiation Temperature Measurement Test) The polycarbonate acrylates obtained in Examples 1 to 4
C analysis was performed. The temperature was raised at a rate of 2 ° C./min from 25 ° C., and the rise of the first observed exothermic peak was defined as the polymerization initiation temperature. The results are summarized in Table 1.

[0067]

[Table 1]

From these results, the polycarbonate acrylates synthesized in Examples 1 to 4 had a high polymerization initiation temperature,
It turned out that it was excellent in storage stability.

Example 5 LiPF ₆ was dissolved in a mixed solvent of ethylene carbonate and propylene carbonate (weight ratio: 1: 1) to a concentration of 1 (mol / l). 1.0 g of the polycarbonate acrylate produced in Example 1 was added to 3.0 g of this electrolytic solution, and mixed.
To prepare a homogeneous solution.

A silicone rubber mold having an inner diameter of 20 mm was attached on a glass substrate, and 150 μl of the previously prepared solution was placed in the mold.
1 was added dropwise. The substrate is placed on a hot plate placed in a nitrogen box and heated to 70 ° C., and irradiated with ultraviolet rays at an irradiation intensity of 300 (mW / cm ² ) for 30 minutes using a spot cure UIS-2502 manufactured by Ushio Inc. did. As a result, a cured polymer electrolyte thin film having a thickness of 423 μm was obtained. This thin film is punched into a 10 mm diameter,
The sample was sandwiched between US electrodes, the complex impedance was measured using Solartron 1255B, and the ionic conductivity was determined after analysis. Pt (electrode area, 0.5 c
m ^2), Li as the counter electrode (electrode area 4 cm ^2), using Li (electrode area 4 cm ²⁾ as a reference electrode, to measure the withstand voltage by cyclic voltammetry method at potentiostat (Solartron 1286). The results are shown in Table 2.

(Examples 6 to 8) In Example 5, the polycarbonate acrylate produced in Example 2, 3 or 4 was used in place of the polycarbonate acrylate produced in Example 1, and the same operation was repeated to obtain a high level. A molecular electrolyte thin film was prepared, and the ionic conductivity and the withstand voltage were obtained in the same manner as in Example 5, and are shown in Table 2.

[0072]

[Table 2]

From the results of the ionic conductivity shown in Table 2, the polymer electrolytes using the polycarbonate acrylates produced in Examples 1 to 4 maintain high ionic conductivity and have excellent performance as a polymer electrolyte. It was found to have.

[0074]

In the present invention, since the glycol component constituting the polycarbonate polyol is selected from at least two kinds of glycols, an appropriate balance between the polarity and the solubility of the polycarbonate polyol is controlled. Was completed. Further, the polycarbonate (meth) acrylate produced from this polycarbonate polyol had a high polymerization initiation temperature and had improved storage stability.

The polycarbonate (meth) acrylate resin obtained by polymerizing the polycarbonate (meth) acrylate contains therein the periodic table Ia
Group metal salt, it has high ionic conductivity,
In addition, it is possible to obtain a polymer solid electrolyte having excellent withstand voltage, being electrochemically stable, and having flexibility. Such a solid polymer electrolyte can be used for a primary battery, a secondary battery, a capacitor, an electrochemical device such as an electrochromic display device, a medical actuator, and the like.

[Brief description of the drawings]

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

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

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

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

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) H01B 1/06 H01B 1/06 A // H01M 6/18 H01M 6/18 E 10/40 10/40 B F term ( (Reference) 4J027 AH03 BA04 BA05 BA07 BA08 BA13 BA14 CB02 CD01 4J029 AA09 AB02 AC02 AD01 BA01 BA02 BA05 BA07 BB06A BD04A BF09 BF10 BF17 BF19 BF25 HA01 HC01 HC02 HC04A HC05A HC06 KH01 5G301 AM16 AM04 A03AM04

Claims (9)

[Claims] At least one kind of glycol represented by the general formula (1) HO- (CH ₂ CH ₂ O) _n -H (1) wherein n is 2 to And at least one glycol represented by the general formula (2) HO-R-OH (2) (where R is An alkylene group having 4 to 20 carbon atoms,
It may contain an ether bond therein, except for an oxyethylene group, and R may be linear or branched, and may form a ring structure). A polycarbonate polyol, which is a polycondensate with a carbonyl compound selected from the group consisting of diester, phosgene and chloroformate. 2. The composition ratio of the diol component represented by the general formula (1) and the diol component represented by the general formula (2) is 5:95 to 95: 5 by weight ratio. The polycarbonate polyol according to claim 1, wherein: 3. The polycondensate has a weight average molecular weight of 500.
2. The polycarbonate polyol according to claim 1, wherein the amount is from 100,000 to 100,000. 4. A diol represented by the general formula (1):
2. The composition according to claim 1, wherein the composition is diethylene glycol.
Polycarbonate polyol as described. 5. A diol represented by the general formula (2):
1,4-butanediol, 1,6-hexanediol,
The polycarbonate polyol according to claim 1, which is at least one diol selected from the group consisting of 3-methyl-1,5-pentanediol and dipropylene glycol. 6. A polycarbonate (meth) acrylate which is an esterified product produced from the polycarbonate polyol according to any one of claims 1 to 5 and (meth) acrylic acid or a derivative thereof. 7. The polycarbonate (meth) according to claim 6,
A polycarbonate (meth) acrylate resin, which is an acrylate polymer. 8. The polycarbonate (meth) according to claim 7,
A polymer solid electrolyte comprising an acrylate resin containing a salt of a metal of Group Ia of the Periodic Table. 9. The solid polymer electrolyte according to claim 8, wherein the metal of Group Ia of the periodic table is lithium.