JP3708733B2 - Polycarbonate (meth) acrylate and uses thereof - Google Patents

Description

【００８０】
【発明の効果】
本発明に係わるポリカーボネート（メタ）アクリレートは、原料として用いたポリカーボネートポリオールが有していたＯＨ基が、その一部は（メタ）アクリレートへとエステル化され、また残りのＯＨ基はエステル基、カーボネート基、エーテル基へと変更され、実質的に未反応のＯＨ基は残存していない。
【００８１】
従って、このポリカーボネート（メタ）アクリレートを重合して得られた樹脂は、適度の重合度と架橋度とに調整されており、ポリマー鎖のフレキシビリティーが確保されると共に、樹脂成形品としても可撓性がある。
【００８２】
それ故に、周期律表Ｉａ族の金属塩を均一分散させたこのポリカーボネート（メタ）アクリレート樹脂は、ポリマー鎖にフレキシビリティーがあるので金属イオンが動きやすく、高いイオン伝導度が得られる。また、このポリカーボネート（メタ）アクリレート樹脂にはフリーの水酸基が実質的にないので、金属との反応が起こらず、電気化学的な安定性にも優れている。さらに、このポリカーボネート（メタ）アクリレート樹脂は、適度な分子量と架橋度に調整されているので、可撓性のある高分子固体電解質となる。従って、一次電池、二次電池、コンデンサ等の電気化学素子の電解質として利用することができる。
【図面の簡単な説明】
【図１】 実施例１で得られたポリカーボネートアクリレートのプロトンＮＭＲチャートである。
【図２】 実施例２で得られたポリカーボネートアクリレートのプロトンＮＭＲチャートである。
【図３】 実施例３で得られたポリカーボネートメタクリレートのプロトンＮＭＲチャートである。
【図４】 比較例１で得られたポリカーボネートアクリレートのプロトンＮＭＲチャートである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel polycarbonate (meth) acrylate, a polycarbonate (meth) acrylate polymer resin obtained by polymerizing the same, and a polymer solid useful for a primary battery, a secondary battery, a capacitor and the like using the resin. It relates to the electrolyte.
[0002]
[Prior art]
Conventionally, a liquid electrolyte has been used in electrochemical elements such as a primary battery, a secondary battery, and a capacitor. However, there has been a concern that the liquid electrolyte may leak from the container during long-term use. Therefore, in order to improve long-term reliability, practical application of a solid electrolyte is considered. If the solid electrolyte is realized, a highly reliable element can be provided, and the element itself can be expected to be reduced in size and weight.
[0003]
In recent years, polymer solid electrolytes have been studied as a kind of solid electrolytes. Since the polymer solid electrolyte has flexibility, there is an advantage that it can flexibly cope with a volume change that occurs in the process of ion-electron exchange reaction between the electrode and the polymer solid electrolyte.
[0004]
As such a polymer solid electrolyte, a composite of polyethylene oxide having a polyether structure and an alkali metal salt such as a lithium salt is known. Japanese Patent Application Laid-Open No. 5-25353 discloses a polyoxyalkylene diester compound, a polymethoxyoxyalkylene monoester compound, a crosslinked resin of vinylene carbonate and an inorganic salt as main components. A polymer solid electrolyte is described. Further, JP-A-6-223842 discloses a polymer solid electrolyte comprising an organic polymer having a carbonate group as a functional group and a metal salt.
[0005]
Since these solid electrolytes generally have lower ionic conductivity than liquid electrolytes, further improvements are required to use them for primary batteries and secondary batteries with excellent discharge characteristics. Yes.
[0006]
[Problems to be solved by the invention]
Therefore, the present invention aims to provide a polymer solid electrolyte having high ionic conductivity, excellent electrochemical stability, and flexibility, and a novel polycarbonate (meth) acrylate compound therefor and The object is to provide the polymer.
[0007]
[Means for Solving the Problems]
That is, the present invention relates to a polycarbonate polyol having three or more hydroxyl groups in the molecule, a part of the hydroxyl group is converted to a (meth) acrylic acid ester group, and the remaining hydroxyl group has no polymerizable property, In particular, the present invention relates to a polycarbonate (meth) acrylate characterized by being converted to a substituent having no radical polymerizability or photopolymerizability.
[0008]
The polycarbonate polyol is preferably a polymer obtained by a polycondensation reaction with a diol compound, a trihydric or higher polyhydric alcohol, and a compound that becomes a carbonyl component. The substituent having no polymerizability is preferably a substituent in which any group selected from the group consisting of an ester group, a carbonate group, and an ether group is bonded to a hydrocarbon skeleton.
[0009]
The present invention also relates to a polycarbonate (meth) acrylate polymer resin obtained by further polymerizing polycarbonate (meth) acrylate, and a polymer solid electrolyte using the same.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
Polycarbonate polyol
The polycarbonate polyol used in the present invention is a polymer having a carbonate bond in the polymer main chain and having 3 or more, preferably 3 to 50 hydroxyl groups in the terminal or side chain. A typical production method of this polycarbonate polyol is a method by a polycondensation reaction from a diol compound (A), a trihydric or higher polyhydric alcohol (B), and a compound (C) which becomes a carbonyl component.
[0011]
The diol compound (A) used as a raw material has the general formula HO-R_FourIt is represented by -OH. Where R_FourIs a divalent hydrocarbon group having 2 to 20 carbon atoms, and the group may contain an ether bond. For example, a linear or branched alkylene group, a cyclohexylene group, or a phenylene group.
[0012]
Specific examples of the diol compound include ethylene glycol, 1,2-propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, polyethylene glycol, neopentyl glycol, 1,3-propanediol, 1,4-butanediol, , 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, neopentyl glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and the like. These diols may be used alone or in admixture of two or more.
[0013]
  Examples of the trihydric or higher polyhydric alcohol (B) include trimethylol polypropylene.BExamples thereof include alcohols such as bread, trimethylolethane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, glycerin and sorbitol. Furthermore, alcohols having a hydroxyl group in which 1 to 5 equivalents of ethylene oxide, propylene oxide, or other alkylene oxide are added to the hydroxyl group of these polyhydric alcohols may be used. These polyhydric alcohols may be used alone or in combination of two or more.
[0014]
The compound (C) serving as the carbonyl component is any compound selected from carbonic acid diester, phosgene, and equivalents thereof. Specific examples thereof include carbonic acid diesters such as dimethyl carbonate, diethyl carbonate, diisopropyl carbonate, diphenyl carbonate, ethylene carbonate and propylene carbonate, phosgene, and halogenated formates such as methyl chloroformate, ethyl chloroformate and phenyl chloroformate. Etc. These may be used alone or in admixture of two or more.
[0015]
The polycarbonate polyol is synthesized by subjecting the above-described diol compound (A), a trihydric or higher polyhydric alcohol (B), and a compound (C) to be a carbonyl component to a polycondensation reaction under general conditions. . For example, the charged molar ratio of the diol compound (A) to the polyhydric alcohol (B) is preferably in the range of 50:50 to 99: 1, and the diol compound (C) as the carbonyl component ( The charged molar ratio of A) to the polyhydric alcohol (B) is preferably 0.2 to 2 equivalents with respect to the hydroxyl group of the diol compound and polyhydric alcohol.
[0016]
The number of equivalents (eq./mol) of hydroxyl groups present in the polycarbonate polyol after the polycondensation reaction at the charge ratio is 3 or more, preferably 3 to 50, more preferably 3 20. Within this range, a necessary amount of (meth) acrylate groups are formed by the esterification reaction described later, and moderate flexibility is imparted to the polycarbonate (meth) acrylate resin. The terminal functional group of this polycarbonate polyol is usually an OH group, but a part thereof may be a carbonate group.
[0017]
The molecular weight of the polycarbonate polyol after the polycondensation reaction is measured by GPC analysis, and the weight average molecular weight converted to standard polystyrene is in the range of 500 to 100,000, preferably 1000 to 50,000. It is convenient to obtain a polymer solid electrolyte having
[0018]
The method for producing the polycarbonate polyol described above is described in, for example, JP-A No. 64-1726. The polycarbonate polyol can also be produced by an ester exchange reaction between a polycarbonate diol and a trihydric or higher polyhydric alcohol as described in JP-A-3-181517.
[0019]
                Polycarbonate (meth) acrylate
  In the polycarbonate (meth) acrylate according to the present invention, a part of the hydroxyl groups of the polycarbonate polyol described above is an acrylate ester or a methacrylate.TheThis is a compound converted into a lauric acid ester, and in the present invention, both are referred to as polycarbonate (meth) acrylate.
[0020]
  This esterification reaction can be performed by a normal esterification reaction. For example: 1) Polycarbonate polyol and acrylic acid halide or metaTheA method of condensing lauric acid halide in the presence of a base, 2) a method of condensing a polycarbonate polyol and acrylic acid anhydride or methacrylic acid anhydride in the presence of a catalyst, or 3) a polycarbonate polyol and acrylic acid or metaTheExamples include a method of condensing rilic acid in the presence of an acid catalyst.
[0021]
  Acrylic acid or metal used in these reactionsTheThe charging molar ratio of the raw material derived from rilic acid is 0.1 to 0.9, preferably 0.2 to 0.8 equivalents relative to the hydroxyl group of the polycarbonate polyol. Within this range, an appropriate molecular weight and degree of crosslinking are adjusted in the polymerization reaction of polycarbonate (meth) acrylate to be described later, so that a flexible polymer solid electrolyte is obtained.
[0022]
In the case of producing by the above method 1), examples of the acrylic acid halide or methacrylic acid halide used include acrylic acid chloride and methacrylic acid chloride, and the charged molar ratio is 0 with respect to the hydroxyl group of the polycarbonate polyol. 0.1 to 0.9, preferably 0.2 to 0.8 equivalent. As the base used in the reaction, organic bases such as triethylamine, pyridine, dimethylaminopyridine, diazabicycloundecene (DBU) or lithium carbonate, sodium carbonate, potassium carbonate, lithium hydroxide, sodium hydroxide, hydroxide Inorganic bases, such as potassium, can be mentioned, It is preferable that the preparation molar ratio with respect to the acid halide which is a raw material is 0.5-5 equivalent.
[0023]
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, dichloroethane, an aromatic hydrocarbon such as benzene, toluene, xylene, hexane, heptane, decane, Saturated hydrocarbons such as cyclohexane, ethers such as diethyl ether and tetrahydrofuran (THF) can also be used as a solvent. The reaction temperature is generally −20 to 100 ° C., preferably −5 to 50 ° C. Further, a polymerization inhibitor may be added during the reaction. After completion of the reaction, the desired esterified product can be isolated by processing according to a conventional method. Moreover, you may progress to the next stage reaction in the state of a reaction mixture.
[0024]
Next, the hydroxyl group in the polycarbonate (meth) acrylate remaining after the (meth) acrylated reaction is converted into a substituent having no polymerizability.
The substituent having no polymerizability is a group having no radical polymerizability and no photopolymerizability, and more specifically, a substituent that does not cause a polymerization reaction by irradiation with ultraviolet rays or radiation, or heat. The substituent having no polymerizability is preferably a substituent in which any group selected from the group consisting of an ester group, a carbonate group, and an ether group is bonded to the hydrocarbon skeleton. Moreover, it is preferable that this substituent does not contain an active proton.
[0025]
Among them, a substituent having no preferred polymerizability is a substituent having at least one group selected from an ester group, a carbonate group, or an ether group represented by the following formula.
(1) Ester group; -OCO-R₁
(Wherein R₁Is hydrogen, or an alkyl group or aryl group having 1 to 20 carbon atoms, and part or all of the hydrogen of the alkyl group or aryl group is substituted with an alkoxy group, a cyano group, an alkoxycarbonyl group, or a phenyl group. It may be. )
(2) carbonate group; -OCOO-R₂
(Wherein R₂Is an alkyl group having 1 to 5 carbon atoms or a phenyl group)
(3) Ether group; —O—R_Three
(Wherein R_ThreeIs an alkyl group having 1 to 10 carbon atoms or an aralkyl group)
These groups may be one kind or two or more kinds may be combined.
[0026]
(1) First, an OH group is converted to an ester group (-OCO-R₁ ) Will be described. Where R₁Is hydrogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group. A part or all of hydrogen of the alkyl group or aryl group may be substituted with an alkoxy group, a cyano group, an alkoxycarbonyl group, or a phenyl group. R₁Specific examples thereof include methyl group, ethyl group, propyl group, butyl group, pentyl group, 2-ethoxyethyl group, 2-cyanoethyl group, 2-methoxycarbonylethyl group, phenyl group and the like.
[0027]
  The esterification reaction can be carried out by the usual method as described above, 1) a method of condensing an acid halide in the presence of a base, 2) a method of condensing an acid anhydride in the presence of a catalyst, or 3). Examples thereof include a method of condensing a carboxylic acid in the presence of an acid catalyst. At this time, the charged molar ratio of the carboxylic acid-derived raw material used in the polycarbonate polyolofIt is 0.1-2.0 equivalent with respect to a hydroxyl group.
[0028]
  Specific examples of the acid halide include acetyl chloride, propionyl chloride, butyroyl chloride, hexanoyl chloride, 3-ethoxypropionyl chloride, 3-cyanopropionyl chloride, methylTheXinyl chloride, benzoyl chloride and the like can be mentioned.
[0029]
The base used in the reaction includes organic bases such as triethylamine, pyridine, dimethylaminopyridine and DBU, or inorganic bases such as lithium carbonate, sodium carbonate, potassium carbonate, lithium hydroxide, sodium hydroxide and potassium hydroxide. The charge molar ratio with respect to the acid halide as the raw material is preferably 0.5 to 5 equivalents.
[0030]
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, dichloroethane, an aromatic hydrocarbon such as benzene, toluene, xylene, hexane, heptane, decane, It is also possible to use saturated hydrocarbons such as cyclohexane, ethers such as diethyl ether and THF as the solvent. The reaction temperature is usually −20 to 100 ° C., preferably −5 to 50 ° C. Further, a polymerization inhibitor may be added during the reaction. After completion of the reaction, the desired product can be obtained by processing according to a conventional method.
[0031]
(2) Next, the OH group is converted to a carbonate group (-OCOO-R₂ ) Will be described. Where R₂Is preferably an alkyl group having 1 to 5 carbon atoms or a phenyl group, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a phenyl group.
[0032]
This carbonate esterification can be performed by a method of condensing alkyl chloroformate or allyl chloroformate in the presence of a base. Specific examples of alkyl chloroformate or allyl chloroformate include methyl chloroformate, ethyl chloroformate, propyl chloroformate, butyl chloroformate, phenyl chloroformate and the like. At this time, the charged molar ratio of alkyl chloroformate or allyl chloroformate used is preferably 0.1 to 2.0 equivalents relative to the hydroxyl group of the polycarbonate polyol.
[0033]
The base used in the reaction includes organic bases such as triethylamine, pyridine, dimethylaminopyridine and DBU, or inorganic bases such as lithium carbonate, sodium carbonate, potassium carbonate, lithium hydroxide, sodium hydroxide and potassium hydroxide. The charge molar ratio with respect to the alkyl chloroformate or allyl chloroformate as the raw material is preferably 0.5 to 5 equivalents.
[0034]
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, dichloroethane, an aromatic hydrocarbon such as benzene, toluene, xylene, hexane, heptane, decane, It is also possible to use saturated hydrocarbons such as cyclohexane, ethers such as diethyl ether and THF as the solvent. The reaction temperature is usually −20 to 100 ° C., preferably −5 to 50 ° C. Further, a polymerization inhibitor may be added during the reaction. After completion of the reaction, the desired product can be obtained by processing according to a conventional method.
[0035]
(3) An OH group is converted to an ether group (-O-R_Three ) Will be described. Where R_ThreeIs preferably an alkyl group having 1 to 10 carbon atoms or an aralkyl group. Specific examples thereof include groups such as methyl group, ethyl group, propyl group, butyl group and benzyl group.
[0036]
The etherification reaction can be performed by a method in which an alkyl halide or a halogenated aralkyl is reacted in the presence of a base. Specific examples thereof include methyl chloride, methyl bromide, methyl iodide, chloroethane, ethyl bromide, propyl chloride, butyl chloride, benzyl chloride and the like. At this time, the charged molar ratio of the alkyl halide or aralkyl halide used is preferably 0.1 to 2.0 equivalents relative to the hydroxyl group in the polycarbonate polyol.
[0037]
Examples of the base used in the reaction include organic bases such as dimethylaminopyridine and DBU, metal alkoxides such as potassium tert-butoxide, sodium tert-butoxide, sodium methoxide and sodium ethoxide, and lithium and sodium. Alkali metals or alkali metal hydrides such as sodium hydride and potassium hydride can be mentioned, and the charged molar ratio with respect to the raw material alkyl halide or halogenated aralkyl is preferably 0.5 to 5 equivalents.
[0038]
The reaction can be carried out in the absence of a solvent, but a solvent inert to the reaction, for example, aromatic hydrocarbons such as benzene, toluene, xylene, saturated hydrocarbons such as hexane, heptane, decane, cyclohexane, diethyl ether, THF, etc. These ethers can also be used as a solvent. The reaction temperature is usually −20 to 100 ° C., preferably −5 to 50 ° C. Further, a polymerization inhibitor may be added during the reaction. After completion of the reaction, the desired product can be obtained by processing according to a conventional method.
[0039]
In addition, the order of the reaction for converting the OH group of the polycarbonate polyol into a (meth) acrylic acid ester and the reaction for converting it into a substituent having no polymerizability may be reversed from the above order. It is also possible to use a mixture of these reaction reagents. In particular, when the non-polymerizable substituent is a substituent having a carbonate group, a normal carbonyl component such as carbonic acid diester, phosgene, or chloroformate, which is one of the raw materials, in the stage of producing a polycarbonate polyol. By controlling the charging ratio of the compound to become, it is possible to make a part of the hydroxyl group a carbonate group. Then, a desired compound can be obtained by converting the remaining hydroxyl groups into (meth) acrylic acid esters.
[0040]
In the polycarbonate (meth) acrylate thus obtained, a hydroxyl group present in the polycarbonate polyol used as a raw material is partially converted into (meth) acrylate, and the rest is a substituent having no polymerizability. It has a structure converted to. Here, the ratio of the (meth) acrylate group and the non-polymerizable group is 0.1: 0.9 to 0.9: 0.1, preferably 0.2: 0.8 to 0.8: If it is 0.2 and is within this range, the polymer chain is flexible in the polymerization reaction of the polycarbonate (meth) acrylate, which will be described later, and the degree of crosslinking is adjusted. The product is flexible. Further, since there is substantially no free hydroxyl group, when a solid electrolyte is formed, no reaction with the metal occurs, and it becomes electrochemically stable, and the influence on the electrolyte is avoided.
[0041]
  This polycarbonate (meth) acrylate is(Meta)AkReThe double bond of the rate group can be used as a polymerizable monomer, and in particular, it can be effectively used as a raw material for solid electrolytes, adhesives, paints and the like.
[0042]
Polycarbonate (meth) acrylate resin
In the polycarbonate (meth) acrylate resin according to the present invention, a part of the hydroxyl group of the polycarbonate polyol described so far is converted into a (meth) acrylic acid ester, and the remaining hydroxyl group is converted into a non-polymerizable substituent. It is a polymer obtained by polymerizing polycarbonate (meth) acrylate as a raw material. Therefore, in the polymerization reaction, the double bond of the (meth) acrylic acid ester group is opened and the molecular chain of the polycarbonate (meth) acrylate is extended, or the crosslinking occurs between the molecules of the polycarbonate (meth) acrylate, and the molecular weight Will increase.
[0043]
  In advancing the polymerization reaction, polycarbonate (meth) acrylate can be used alone or in combination of two or more, and if necessary, other monomers are added,BothCan exist. Other monomers copolymerizable with polycarbonate (meth) acrylate include vinyl monomers, vinylidene monomers, vinylene monomers, and the like. Specifically, ethyl (meth) acrylate, ethoxyethyl (meth) acrylate, ethoxyethoxyethyl (meth) 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.
[0044]
The polymerization reaction may proceed in the presence of a solvent, and in that case, a carbonate ester is preferably used. Examples of the carbonate solvent include chain or cyclic carbonates such as ethylene carbonate, propylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, and dipropyl carbonate.
[0045]
Polymerization proceeds by radical polymerization, ionic polymerization, or the like, and is actually performed in the presence or absence of a radical catalyst or an ionic catalyst. Moreover, when using the produced | generated resin as a solid electrolyte, reaction can be easily advanced also by radiation irradiation polymerization methods, such as an ultraviolet-ray, and a thermal polymerization method.
[0046]
In polymerization by ultraviolet irradiation, a photosensitizer such as benzophenone, acetophenone, or 2,2-dimethoxy-2-phenylacetophenone can be used. In the polymerization by heat, a thermal polymerization initiator can be used. Depending on the reaction mechanism, a peroxide such as benzoyl peroxide or peroxydicarbonate, an azo such as 2,2′-azobisisobutyronitrile is used. Compounds, nucleophiles such as alkali metals, and electrophiles such as Lewis acids can be used alone or in combination.
[0047]
The polycarbonate (meth) acrylate resin thus obtained can be used as various molding materials used in a wide range of industrial fields. In particular, it is useful as a substrate for a solid electrolyte described later, an optical material such as a lens, and a film.
[0048]
Polymer solid electrolyte
The solid polymer electrolyte according to the present invention has a structure in which a metal salt of Group Ia of the periodic table is included in the above-described polycarbonate (meth) acrylate polymer resin. Here, the resin is obtained by performing polymerization reaction by adding polycarbonate (meth) acrylate to one or more kinds, and if necessary, adding another monomer copolymerizable with polycarbonate (meth) acrylate. Polymer.
[0049]
The metal salt of Group Ia of the periodic table is a salt of lithium, sodium, potassium, etc., and particularly LiClO._Four, LiBF_Four, LiPF₆, LiAsF₆, LiCF_ThreeSO_Three, LiN (CF_ThreeSO₂)₂, LiC (CF_ThreeSO₂)_ThreeOne or more lithium salts selected from are preferred. The concentration of the metal salt in the solid electrolyte is desirably 0.1 to 10 (mol / l).
[0050]
The solid electrolyte can be produced by mixing a pre-manufactured polycarbonate (meth) acrylate resin with a metal salt of Group Ia of the periodic table, or at least one of the polycarbonate (meth) acrylates as necessary. And the like, and a method in which the polymerization reaction is allowed to proceed after uniformly mixing the monomer and the group Ia metal salt of the periodic table. In particular, 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. As the polymerization method, the polymerization method of polycarbonate (meth) acrylate can be used similarly.
[0051]
For example, polycarbonate (meth) acrylate, metal salt of Group Ia of the Periodic Table, a solvent is added if necessary, and the uniform mixed solution is applied onto a flat substrate, and then irradiated with radiation such as ultraviolet rays and electron beams, Alternatively, polymerization is initiated by heat. In this way, a solid electrolyte thin film having a thickness of 0.1 to 1000 μm can be obtained.
[0052]
【Example】
EXAMPLES Next, although this invention is demonstrated through an Example, this invention is not limited to these Examples.
[0053]
Example 1
32.0 g of trimethylolpropane-ethylene oxide adduct (compound obtained by adding 3 mol of ethylene oxide to 1 mol of trimethylolpropane: Japanese emulsifier) in a glass reaction vessel equipped with a stirrer, a thermometer, a rectifying column, etc., diethylene glycol 114.6 g, dimethyl carbonate 124.3 g, and 28% sodium methoxide methanol solution 0.23 g as a catalyst were charged and mixed.
[0054]
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 methanol produced by the reaction was distilled off. Subsequently, it maintained at 150-155 degreeC under the reduced pressure of 5 mmHg, and diethylene glycol 10.3g produced | generated with a polymerization reaction was distilled off.
[0055]
After cooling to room temperature, 100 ml of chloroform and 2.3 g of activated clay were added and stirred again at 55 ° C. for 1 hour. Thereafter, the mixture was cooled to room temperature, the activated clay was filtered, and the filtrate was concentrated to obtain 145 g of a polycarbonate polyol as a viscous oil. By GPC analysis, the weight average molecular weight of this product was 4200.
[0056]
A glass reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and the like was charged with 42.0 g of polycarbonate polyol, 8.9 g of triethylamine, and 100 ml of dichloromethane, and cooled to 5 ° C. while mixing. From the dropping funnel, 3.6 g of acryloyl chloride was added dropwise over 10 minutes, and the mixture was further stirred at 5 ° C for 1 hour.
[0057]
Subsequently, 3.7 g of propionic acid chloride was dropped 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, and the filtrate was washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated to obtain 43.1 g of a viscous oil.
[0058]
This viscous oil was subjected to NMR analysis, and its proton NMR chart is shown in FIG. From the NMR chart, both the characteristic signal of the acrylate ester and the characteristic signal of the propionate ester were recognized, and it was confirmed that a part of the OH group of the polyol became the acrylate ester and the rest became the propionate ester. It was found to be the target polycarbonate acrylate.
[0059]
(Example 2)
26.6 g of trimethylolpropane-ethylene oxide adduct (compound in which 3 mol of ethylene oxide is added to 1 mol of trimethylolpropane: Japanese emulsifier product) in a glass reaction vessel equipped with a stirrer, a thermometer, a rectifying column and the like, dipropylene 120.8 g of glycol, 103.6 g of dimethyl carbonate and 0.19 g of 28% sodium methoxide methanol solution as a catalyst were charged and mixed.
[0060]
Subsequently, it hold | maintained at 95 degreeC under normal pressure for 2 hours, Then, it heated up to 150 degreeC in 5 hours, and also heated at 150 degreeC for 4 hours, and the methanol produced | generated by reaction was distilled off. Then, under reduced pressure of 5 mmHg, the temperature was maintained at 150 to 155 ° C., and 14.7 g of diethylene glycol produced along with the polymerization reaction was distilled off.
[0061]
After cooling to room temperature, 100 ml of chloroform and 1.9 g of activated clay were added and stirred at 55 ° C. for 1 hour. After cooling to room temperature again, the activated clay was filtered, and the filtrate was concentrated to obtain 147 g of a polycarbonate polyol as a viscous oil. According to GPC analysis, this polycarbonate polyol had a weight average molecular weight of 4,800.
[0062]
Next, 48.0 g of polycarbonate polyol, 8.9 g of triethylamine, and 100 ml of dichloromethane were charged into a glass reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and the like, mixed and cooled to 5 ° C. From the dropping funnel, 3.6 g of acryloyl chloride was added dropwise over 10 minutes, and the mixture was further stirred at 5 ° C for 1 hour. Thereafter, 3.1 g of acetyl chloride 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 stirring was continued for another 2 hours at room temperature. The reaction solution was filtered, and the filtrate was washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated to obtain 49.1 g of a viscous oil.
[0063]
The NMR analysis of this viscous oil was performed, and from the proton NMR chart shown in FIG. 2, both the characteristic signal of the acrylate ester and the characteristic signal of the acetate ester were recognized, and a part of the OH group of the polyol was converted to the acrylate ester. Moreover, it was confirmed that the remainder was converted into acetate ester, and it was found to be the target polycarbonate acrylate.
[0064]
(Example 3)
In a glass reaction vessel equipped with a stirrer, a thermometer, a rectifying column, etc., 26.6 g of trimethylolpropane-ethylene oxide adduct (compound in which 3 mol of ethylene oxide is added to 1 mol of trimethylolpropane: Japanese emulsifier product), 1, 4-Butanediol 81.1 g, dimethyl carbonate 103.6 g and 28% sodium methoxide methanol solution 0.19 g as a catalyst were charged and mixed.
[0065]
By maintaining at 95 ° C. for 2 hours under normal pressure, the temperature was raised to 150 ° C. in 5 hours, and further heating at 150 ° C. for 4 hours to distill off the methanol produced in the reaction. Subsequently, 9.6 g of 1,4-butanediol produced by the polymerization reaction was distilled off while maintaining the pressure at 150 to 155 ° C. under a reduced pressure of 5 mmHg.
[0066]
After cooling to room temperature, 100 ml of chloroform and 1.9 g of activated clay were added and stirred at 55 ° C. for 1 hour. After cooling to room temperature again, the activated clay was filtered, and the filtrate was concentrated to obtain 106 g of a polycarbonate polyol as a viscous oil. The weight average molecular weight of this polycarbonate polyol was 5500 by GPC analysis.
[0067]
Next, 55.0 g of polycarbonate polyol, 8.9 g of triethylamine, and 100 ml of dichloromethane were charged into a glass reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and the like, mixed and cooled to 5 ° C. From the dropping funnel, 3.1 g of methacryloyl chloride was added dropwise over 10 minutes, and the mixture was further stirred at 5 ° C. for 1 hour. Thereafter, 4.6 g of propionic acid chloride was dropped 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, and the filtrate was washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated to obtain 57.1 g of a viscous oil.
[0068]
  When this viscous oil was analyzed by NMR, the proton NMR chart shown in FIG.TheBoth the characteristic signal of the lyric acid ester and the characteristic signal of the propionic acid ester were recognized, and it was confirmed that a part of the OH group of the polyol was converted to methacrylic acid ester and the rest was converted to propionic acid ester. Polycarbonate metaTheIt was found that the relation was obtained.
[0069]
Example 4
LiPF was added to a solvent prepared by mixing 1.0 g of the polycarbonate acrylate prepared in Example 1 with ethylene carbonate and propylene carbonate at a weight ratio of 1: 1.₆Was added to 3.0 g of an electrolyte solution dissolved at a concentration of 1 (mol / l), mixed, and heated to 40 ° C. to prepare a uniform solution.
[0070]
A silicon rubber mold with an inner diameter of 20 mm was stuck on the glass substrate, and 150 μl of the previously prepared solution was dropped into the mold. While this substrate was placed on a hot plate installed in a nitrogen box and heated to 70 ° C., an irradiation intensity of 300 (mW / cm) was used using Spot Cure UIS-2502 manufactured by USHIO.²) For 30 minutes.
[0071]
A cured polymer electrolyte thin film having a thickness of 423 μm was obtained. This thin film was punched out to a diameter of 10 mm, sandwiched between SUS electrodes, measured for complex impedance with Solartron 1255B, and analyzed. As a result, the ionic conductivity was 2.88 (mS / cm).
[0072]
(Example 5)
LiPF was added to a solvent obtained by mixing 1.0 g of the polycarbonate acrylate prepared in Example 2 with ethylene carbonate and propylene carbonate at a weight ratio of 1: 1.₆Was added to 4.0 g of an electrolytic solution dissolved at a concentration of 1 (mol / l), mixed, and heated to 40 ° C. to prepare a uniform solution.
[0073]
Thereafter, a polymer electrolyte thin film having a thickness of 465 μm was produced in the same manner as in Example 4. The ionic conductivity of the obtained polymer electrolyte was determined to be 2.95 (mS / cm).
[0074]
(Example 6)
  Polycarbonate meta produced in Example 3TheLiPF in a solvent in which 1.0 g of relate was mixed with ethylene carbonate and propylene carbonate at a weight ratio of 1: 1.₆Was added to 4.0 g of an electrolytic solution dissolved at a concentration of 1 (mol / l), mixed, and heated to 40 ° C. to prepare a uniform solution.
[0075]
Then, it carried out similarly to Example 4 and produced the polymer electrolyte thin film with a thickness of 465 micrometers. The ionic conductivity of the obtained polymer electrolyte was determined to be 2.62 (mS / cm).
[0076]
(Comparative Example 1)
In the esterification reaction of the polycarbonate polyol of Example 1, the reaction was carried out in the same manner as in Example 1 except that the amount of acryloyl chloride used was 7.2 g and the amount of propionic acid chloride was 0 g. .8 g was obtained as a viscous oil.
[0077]
A proton NMR chart of this viscous oil is shown in FIG. From the NMR chart, a characteristic signal of the acrylate ester was observed, and it was confirmed that the OH group of the polyol was converted to the acrylate ester.
[0078]
LiPF was added to a solvent in which 1.0 g of this polycarbonate acrylate was mixed with ethylene carbonate and propylene carbonate at a weight ratio of 1: 1.₆Was added to 4.0 g of an electrolytic solution dissolved at a concentration of 1 (mol / l), mixed, and heated to 40 ° C. to prepare a uniform solution. Then, it carried out similarly to Example 4 and produced the polymer electrolyte thin film with a thickness of 465 micrometers. When the ionic conductivity of the obtained polymer electrolyte was determined, it was 2.12 (mS / cm).
[0079]
Table 1 summarizes the ionic conductivity of the polymer electrolytes obtained in Examples 4 to 6 and Comparative Example 1.
[Table 1]

[0080]
【The invention's effect】
In the polycarbonate (meth) acrylate according to the present invention, the OH group contained in the polycarbonate polyol used as a raw material is partly esterified to (meth) acrylate, and the remaining OH group is an ester group, carbonate. Group and ether group, and substantially no unreacted OH group remains.
[0081]
Therefore, the resin obtained by polymerizing this polycarbonate (meth) acrylate is adjusted to an appropriate degree of polymerization and degree of cross-linking, ensuring flexibility of the polymer chain and being also possible as a resin molded product. There is flexibility.
[0082]
Therefore, this polycarbonate (meth) acrylate resin in which the metal salt of Group Ia of the periodic table is uniformly dispersed has flexibility in the polymer chain, so that metal ions can move easily and high ionic conductivity can be obtained. Moreover, since this polycarbonate (meth) acrylate resin has substantially no free hydroxyl group, it does not react with metal and is excellent in electrochemical stability. Furthermore, since this polycarbonate (meth) acrylate resin is adjusted to an appropriate molecular weight and degree of crosslinking, it becomes a flexible polymer solid electrolyte. Therefore, it can be used as an electrolyte for electrochemical elements such as primary batteries, secondary batteries, and capacitors.
[Brief description of the drawings]
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 polycarbonate meta obtained in Example 3. FIG.TheIt is a proton NMR chart of a relation.
4 is a proton NMR chart of the polycarbonate acrylate obtained in Comparative Example 1. FIG.

Claims (13)

In polycarbonate polyol having 3 or more hydroxyl groups in the molecule, a part of the hydroxyl groups are converted to (meth) acrylic acid ester groups, and the remaining hydroxyl groups are converted to non-polymerizable substituents. Polycarbonate (meth) acrylate characterized by The polycarbonate (meth) acrylate according to claim 1, wherein the number of equivalents of hydroxyl groups in the polycarbonate polyol is 3 to 50 (eq./mol). The polycarbonate (meth) acrylate according to claim 1 or 2, wherein the polycarbonate polyol has a weight average molecular weight of 500 to 100,000. 4. The polymer according to claim 1, wherein the polycarbonate polyol is a polymer obtained by a polycondensation reaction with a diol compound, a trihydric or higher polyhydric alcohol, and a compound that becomes a carbonyl component. The polycarbonate (meth) acrylate described. 5. The polycarbonate (meth) acrylate according to claim 4, wherein the compound to be the carbonyl component is any one of carbonic acid diester, phosgene, and halogenated formic acid ester. 2. The polycarbonate (meth) acrylate according to claim 1, wherein the group having no polymerizability is a group having no radical polymerizability and no photopolymerizability. 2. The substituent having no polymerizability is a substituent in which any group selected from the group consisting of an ester group, a carbonate group, and an ether group is bonded to a hydrocarbon skeleton. Or the polycarbonate (meth) acrylate of 6. The substituent having no polymerizability is a substituent having at least one group selected from an ester group, a carbonate group, and an ether group represented by the following formula: Any of the polycarbonate (meth) acrylates.
(1) -OCO-R ₁
(In the formula, R ₁ is hydrogen, or an alkyl group or aryl group having 1 to 20 carbon atoms, and a part or all of hydrogen of the alkyl group or aryl group is an alkoxy group, a cyano group, an alkoxycarbonyl group, Or may be substituted with a phenyl group)
(2) -OCOO-R ₂
(Wherein R ₂ is an alkyl group having 1 to 5 carbon atoms or a phenyl group)
(3) -O-R ₃
(Wherein R ₃ is an alkyl group having 1 to 10 carbon atoms or an aralkyl group) The polycarbonate (meth) acrylate according to any one of claims 1, 6 , 7 and 8, wherein the substituent having no polymerizability is an ester group derived from a saturated aliphatic carboxylic acid. The ratio of the (meth) acrylic acid ester group and the non-polymerizable substituent is 0.1: 0.9 to 0.9: 0.1 (equivalent ratio). The polycarbonate (meth) acrylate in any one of 1-9. A polycarbonate (meth) acrylate resin, which is a polymer of the polycarbonate (meth) acrylate according to any one of claims 1 to 10. A polymer solid electrolyte, wherein the polycarbonate (meth) acrylate resin according to claim 11 contains a group Ia metal salt of the periodic table. The polymer solid electrolyte according to claim 12, wherein the Group Ia metal of the periodic table is lithium.

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