JP2008127498A - Cyclocarbonate-containing (meth)acrylate compound, polymer, copolymer, film material, electrolyte and solid electrolyte film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a (meth)acrylate compound having a cyclocarbonate introduced thereinto which comes to a polymer or copolymer having flexibility, excellent solubility in an organic solvent, and film formability by polymerization and is suitably used in the formation of a solid electrolyte film. <P>SOLUTION: The cyclocarbonate-containing (meth)acrylate compound has a (meth)acryloyloxyethylcarbamic acid ester structure represented by formula (1) (wherein R<SP>1</SP>is hydrogen or a methyl group; R<SP>2</SP>is a cyclocarbonate group-containing monovalent organic group; and n is an integer of 1-6), and its polymer and copolymer are disclosed. A film material uses the same, and an electrolyte and the solid electrolyte film are disclosed. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a cyclocarbonate-containing (meth) acrylate compound which is a (meth) acrylate compound having a cyclocarbonate group, a polymer synthesized using this compound, a copolymer, a film material using these polymers or copolymers, an electrolyte, and The present invention relates to a solid electrolyte film.

As a method for producing a (meth) acrylate having a cyclocarbonate group, a method of synthesizing glycerin-1,2-carbonate from acrylic acid chloride or acrylic acid anhydride using a base (for example, see Non-Patent Document 1), Method utilizing transesterification of glycerin-1,2-carbonate and methyl methacrylate (for example, refer to Patent Document 1), organic amine or phosphine, alkali metal halide salt, alkali earth metal halide salt or alkali to glycidyl methacrylate Examples include a method in which carbon dioxide is allowed to act in the presence of an earth metal carbonate (see, for example, Patent Document 2). On the other hand, from the viewpoints of processability, miniaturization, and long-time driving of electronic devices, lithium ion batteries using an electrolytic solution are widely used for batteries used in these devices. However, from the viewpoint of safety, attention has been focused on the development of a solid electrolyte type lithium ion battery that does not use a safer electrolyte solution in place of the electrolyte lithium ion battery that remains in danger of ignition and explosion. Since cyclocarbonate compounds are already widely used as components of electrolytes, such as ethylene carbonate and propylene carbonate, polymer or copolymer materials having a cyclocarbonate structure in the side chain have high lithium ion conductivity. It is expected that As a study on a solid electrolyte film having a cyclocarbonate group, there are already reports on polymer materials derived from polymerizable monomers such as vinylene carbonate and propylene carbonate methacrylate (hereinafter abbreviated as PCMA) (see, for example, Non-Patent Document 2). . In particular, PCMA has high reactivity as a monomer, tends to give an insoluble polymer, has difficulty in handling, and has poor film forming ability.
U.S. Pat. No. 2,997,514 Japanese Patent No. 2565875 J. et al. Polymer Science., Polymer. Chem. Ed. (1976), 5 (2), 307-321. Macromolecules (1995), 28, 3468-3470.

  In the above prior art, there can be seen a method for easily synthesizing a (meth) acrylate having a cyclocarbonate in the side chain. For example, a polymer obtained for stability and high reactivity such as propylene carbonate (meth) acrylate. Were very hard and brittle and had low defects such as low solubility in organic solvents. In addition, the conventional method cannot simultaneously introduce a highly polar urethane bond and a cyclocarbonate group, which are considered advantageous for ion conduction, into the side chain.

  In the present invention, in order to solve the above-mentioned problems, the inventors have intensively studied. As a result, in order to improve film forming ability, (meth) acrylate having a highly reactive isocyanate group in the side chain is used, and urethane is reacted with alcohol. We have developed a method for easily synthesizing new (meth) acrylate compounds that introduce cyclic carbonate groups while forming bonds, and are also polymers or copolymers that are soft and have excellent solubility in organic solvents by polymerization using the compounds. Led to the development. Furthermore, the film made of the polymer and copolymer in which the lithium ion-containing electrolyte salt was dissolved became a solid electrolyte.

That is, the present invention relates to a cyclocarbonate-containing (meth) acrylate compound having a (meth) acryloyloxyethylcarbamate structure represented by the following general formula (1). (Wherein R ¹ is hydrogen or a methyl group, R ² is a monovalent organic group containing a cyclocarbonate group, and n is an integer of 1 to 6)

Furthermore, this invention relates to the polymer which has a repeating unit shown by following General formula (2) formed by superposing | polymerizing the cyclocarbonate containing (meth) acrylate compound which has a structure shown by the said General formula (1). (In the formula, R ¹ is hydrogen or a methyl group, R ² is a monovalent organic group containing a cyclocarbonate group, n is an integer of 1 to 6, and x is a natural number indicating the number of repeating units.)

Furthermore, the present invention provides a general formula (3) obtained by polymerizing a cyclocarbonate-containing (meth) acrylate compound having a structure represented by the general formula (1) and a polymerizable (meth) acrylic acid compound. Relates to a copolymer having a repeating unit represented by (Wherein R ¹ and R ³ are hydrogen or a methyl group, R ² is a monovalent organic group containing a cyclocarbonate group, R ⁴ is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms (for example, an alkyl group) ), A phenyl group, a benzyl group, a cyclohexyl group or — (CH ₂ CH ₂ O) _m CH ₃ oxyethylene group (m is an integer of 1 to 6), n is an integer of 1 to 6, x and y are (It is a natural number indicating the number of repeating units.)

  Furthermore, the present invention relates to a film material comprising a polymer having a structure represented by the general formula (2) or a copolymer having a structure represented by the general formula (3).

  Furthermore, this invention relates to the electrolyte containing the said film material and lithium ion containing electrolyte salt.

  Furthermore, this invention relates to the solid electrolyte film which consists of said electrolyte.

  As described above, according to the present invention, it is possible to produce a soft film-like polymer without giving an insoluble polymer like propylene carbonate (meth) acrylate (PCMA) as described above (meth). Acrylates can be obtained, and copolymerization with other polymerizable (meth) acrylic acid or (meth) acrylates is also possible, so that a film design tailored to the characteristics becomes possible. Furthermore, it is possible to obtain a solid electrolyte polymer having excellent ionic conductivity by dissolving the electrolyte salt.

In the general formula (1) showing the cyclocarbonate-containing (meth) acrylate compound of the present invention, a specific example of R ² showing a group containing a cyclocarbonate group is 2-oxo-1,3-dioxolan-4-yl. Groups and the like.

  Examples of the cyclocarbonate-containing (meth) acrylate compound represented by the general formula (1) of the present invention include 2- (meth) acryloyloxyethyl isocyanate represented by the following general formula (4) and the following general formula (5). It can manufacture by making the cyclocarbonate compound shown by react. The reaction is preferably performed by heating and stirring in an environment (water-free condition) from which water in the reaction system has been removed as much as possible. Moreover, when an alkyl tin compound is used for a catalyst, a yield can be improved and it is preferable.

（式中、Ｒ¹は、上記と同じ意味を有する。）

(In the formula, R ¹ has the same meaning as described above.)

（式中、Ｒ²及びｎは、上記と同じ意味を有する。）

(In the formula, R ² and n have the same meaning as described above.)

  For example, 2-methacryloyloxyethylcarbamic acid ester of 1- (2-oxo-1,3-dioxolan-4-yl) methanol (hereinafter abbreviated as MOI-G) is 2-methacryloyloxyethyl isocyanate and glycerol 1,2- It can be produced by heating and stirring carbonate (that is, 1- (2-oxo-1,3-dioxolan-4-yl) methanol) in an environment (water-free condition) from which water in the reaction system has been removed as much as possible. Moreover, when an alkyl tin compound is used for a catalyst, a yield can be improved.

  Specific examples of 2- (meth) acryloyloxyethyl isocyanate represented by the general formula (4) that can be used in the above-described method for producing a cyclocarbonate-containing (meth) acrylate compound include, for example, trade names manufactured by Showa Denko KK “Karenz AOI” (2-acryloyloxyethyl isocyanate), Showa Denko K.K., trade name “Karenz MOI” (2-methacryloyloxyethyl isocyanate) and the like can be used.

  Specific examples of the cyclocarbonate compound represented by the general formula (5) that can be used in the above-described method for producing a cyclocarbonate-containing (meth) acrylate compound include, for example, 1- (2-oxo-1,3-dioxolane-4- Yl) methanol, 2- (2-oxo-1,3-dioxolan-4-yl) ethanol, 3- (2-oxo-1,3-dioxolan-4-yl) propanol, 4- (2-oxo-1) , 3-Dioxolan-4-yl) butanol, 5- (2-oxo-1,3-dioxolan-4-yl) pentanol, 6- (2-oxo-1,3-dioxolan-4-yl) hexanol and the like Is mentioned.

  Furthermore, as a solvent that can be used in the above-described method for producing a cyclocarbonate-containing (meth) acrylate compound, 2- (meth) acryloyloxyethyl isocyanate represented by the general formula (4) that can be easily dehydrated other than alcohol and is a solute. As long as the organic solvent can dissolve the cyclocarbonate compound represented by the general formula (5), an aliphatic solvent, an aromatic solvent, a halogen solvent, an ether solvent, a ketone solvent, an aprotic solvent, or the like is used. For example, pentane, hexane, cyclohexane, toluene, xylene, nitrobenzene, chloroform, methylene chloride, diethyl ether, tetrahydrofuran, acetone, methyl ethyl ketone (2-butanone), methyl isobutyl ketone, cyclohexanone, N-methylpyrrolidinone, N, - dimethylformamide, dimethyl sulfoxide can be used. Of these, tetrahydrofuran and methylene chloride are preferable.

  Moreover, although the temperature range which can be used with the said manufacturing method is related also with the boiling point of the solvent to be used, it is preferable to carry out in the range of -40 degreeC-150 degreeC, and also it is carried out in the range of 0 degreeC-100 degreeC. More preferably, it is most preferable to carry out in a temperature range of 20 ° C to 60 ° C.

  Moreover, as an alkyltin compound which is a catalyst used suitably for the said reaction, di-n-butyltin dilaurate etc. are mentioned, for example. The amount of the alkyltin compound used is preferably 0.01 to 5 mol, more preferably 0.5 to 1 mol, per 100 mol of 2- (meth) acryloyloxyethyl isocyanate.

  The polymer having a repeating unit represented by the general formula (2) of the present invention (hereinafter sometimes referred to as a cyclocarbonate group-containing polymer) is a cyclocarbonate-containing (meth) acrylate represented by the general formula (1). It can be obtained by radical polymerization or cationic polymerization of a compound. In addition, the copolymer having a repeating unit represented by the general formula (3) of the present invention (hereinafter sometimes referred to as a cyclocarbonate group-containing copolymer) has a cyclocarbonate-containing (meta) group represented by the general formula (1). ) Acrylate compound and a compound polymerizable with this compound, that is, the following general formula (6)

（式中、Ｒ³及びＲ⁴は、上記と同じ意味を有する。）
で示される（メタ）アクリル酸化合物とのラジカル重合若しくはカチオン重合による共重合によって得ることができる。

(In the formula, R ³ and R ⁴ have the same meaning as described above.)
It can obtain by the copolymerization by radical polymerization or cationic polymerization with the (meth) acrylic acid compound shown by these.

  The cyclocarbonate group-containing polymer and the cyclocarbonate group-containing copolymer of the present invention preferably have a number average molecular weight (standard polystyrene conversion value by gel permeation chromatography) of 5,000 to 500,000, preferably 10,000 to 200,000. It is more preferable.

  In the ratio of the x value and the y value in the copolymer described in the general formula (3), y / (x + y) is preferably 0.2 or more, and more preferably 0.5 or more. Further, y / (x + y) is preferably 0.9 or less, and more preferably 0.7 or less. If y / (x + y) is less than 0.2, no film can be formed or an insoluble polymer tends to be formed. If it exceeds 0.9, tack tends to remain on the film that can be formed.

  As a polymerization method, in particular, radical polymerization has advantages such as a large reaction rate and no ionic impurities remain, and since it has advantages as a polymer material for use in electronic materials, a polymer or copolymer is obtained by radical polymerization. Is preferred.

  As a radical polymerization initiator used in the synthesis of the cyclocarbonate group-containing polymer described in the general formula (2) and the cyclocarbonate group-containing copolymer described in the general formula (3) of the present invention, a general radical initiator is used. Although usable, organic azo compounds such as 2,2'-azobis (2-methylpropionitrile) (AIBN), azobiscyclohexane-1-carbonitrile, azodibenzoyl, 1,1,3,3-tetramethyl Butylperoxy 2-ethylhexanoate, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclododecane, di-t-butylperoxyisophthalate, t -Butylperoxybenzoate, dicumyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl 2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) 3-hexyne, organic peroxides such as cumene hydroperoxide can be used.

The compounding amount of the radical initiator greatly affects the molecular weight of the polymer or copolymer to be obtained, but when synthesizing the above-mentioned cyclocarbonate group-containing polymer, the above-mentioned amount is 1 mol of the above-mentioned cyclocarbonate-containing (meth) acrylate compound. When the cyclocarbonate group-containing lake polymer is synthesized, it is preferable to add 0.01 to 10 mol with respect to a total of 1 mol of the cyclocarbonate-containing (meth) acrylate compound and the (meth) acrylic acid compound, It is more preferable to add 0.03 to 1 mol.
In some cases, a chain transfer agent such as dodecyl mercaptan, octyl mercaptan, thioglycol, or α-methylstyrene dimer may be used for the purpose of adjusting the molecular weight.

As the polymerization form, bulk polymerization is possible, but solution polymerization is preferable because the possibility of inadvertent gelation increases. As the solvent used for the solution polymerization, an ether solvent, a ketone solvent, an aprotic solvent, etc. having a solubility that does not interfere with the polymerization reaction can be used. For example, cyclohexane, diethyl ether, tetrahydrofuran, acetone, methyl ethyl ketone ( 2-butanone), methyl isobutyl ketone, cyclohexanone, N-methylpyrrolidinone, N, N-dimethylformamide, dimethyl sulfoxide and the like can be used. Of these, tetrahydrofuran, N-methylpyrrolidinone and dimethyl sulfoxide are preferable.
The polymerization temperature range that can be used is preferably -40 to 120 ° C, more preferably 0 to 100 ° C, and most preferably 20 to 80 ° C.

  In the synthesis of the copolymer represented by the general formula (3) of the present invention, the polymerizable monomers described below can be used. For example, methacrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, hexyl methacrylate and 2-ethylhexyl methacrylate, and methacrylic compounds such as cyclohexyl methacrylate. Methacrylic acid aromatic esters such as acid cycloalkyl ester, phenyl methacrylate, benzyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, etc. Acrylic acid alkyl esters, acrylic acid cycloalkyl esters such as cyclohexyl acrylate, and acrylic acid aromatic esters such as phenyl acrylate and benzyl acrylate, ethylene glycol monomethyl Methacrylic acid esters of ether, methacrylic acid esters of diethylene glycol monomethyl ether, acrylic acid esters of ethylene glycol monomethyl ether, there are glycol esters such as acrylic acid ester of diethylene glycol monomethyl ether.

    The cyclocarbonate group-containing polymer and the cyclocarbonate group-containing copolymer of the present invention are excellent in flexibility and excellent in solubility in an organic solvent, and thus can be suitably used as a film material.

  Further, by dissolving a lithium ion electrolyte salt or the like in the cyclocarbonate group-containing polymer or the cyclocarbonate group-containing copolymer of the present invention, a film-forming electrolyte can be obtained, and the electrolyte is dissolved in an organic solvent to form a film. By forming, a solid electrolyte film can be obtained.

  Any solvent can be used as a solvent for film production in the present invention as long as it dissolves the cyclocarbonate group-containing polymer or the cyclocarbonate group-containing copolymer of the present invention as long as it is not extremely low in volatility. Is possible. For example, tetrahydrofuran, N-methylpyrrolidinone, methyl isobutyl ketone, 2-butanone, acetone and the like can be used, and N-methylpyrrolidinone or tetrahydrofuran is preferred.

In the present invention, the Li ion-containing electrolyte salt dissolved in the film is selected from the group consisting of LiN (CF ₃ SO ₂ ) ₂ , LiN (C ₂ F ₅ SO ₂ ) ₂ , and LiC (CF ₃ SO ₂ ) _3. It is preferable to use at least one selected. In this case, the concentration of the lithium ion-containing electrolyte salt contained in the electrolyte is a molar ratio (lithium ion-containing electrolyte salt / cyclocarbonate group) with respect to the cyclocarbonate group in the cyclocarbonate group-containing polymer or copolymer forming the film. And preferably 0.2 or more, more preferably 0.7 or more, preferably 2.0 or less, more preferably 1.0 or less. The upper limit of the lithium ion-containing electrolyte salt that can be added is an amount that can be dissolved in the polymer or copolymer.

  The solid electrolyte film of the present invention can be peeled off, for example, from a Teflon (registered trademark) sheet after the cyclocarbonate group-containing polymer or cyclocarbonate group-containing copolymer of the present invention and a lithium ion-containing electrolyte salt are dissolved and mixed in an organic solvent. After casting on a transparent substrate, it can be formed preferably by drying in an inert atmosphere such as argon. The drying temperature is preferably 50 to 150 ° C.

  Specific examples according to the present invention will be described below, but the present invention is not limited thereto. In this example, sample preparation and ion conductivity measurement were performed in an argon atmosphere.

(Ion conductivity measurement)
The ion conductivity is measured by forming an electrochemical cell by sandwiching an electrolyte between stainless steel (SUS316) electrodes, and measuring the resistance component by applying an alternating current (0.1-100 kHz, 10-500 mV) between the electrodes. The AC impedance method was used to calculate from the real impedance intercept of the Cole-Cole plot.

Example 1 Synthesis of Methacrylate (MOI-G) A 50 ml three-necked eggplant flask equipped with a three-way cock and a dropping funnel was purged with nitrogen, and 20 ml of distilled dichloromethane, glycerol 1,2-carbonate ((5.905 g, 50.0 mmol), di-n-butyltin dilaurate (0.05 mmol), and then, from a dropping funnel, a solution of 2-methacryloyloxyethyl isocyanate [made by Showa Denko] (7.76 g, 50.0 mmol) in 5 ml of dichloromethane. Was added dropwise and stirred for 3 hours at 5 ° C. After completion of the reaction, dichloromethane was distilled off under reduced pressure, the resulting solid was recrystallized with a mixed solvent of hexane and dichloromethane, and the resulting white crystals were dried in vacuo and MOI was obtained. in -G (formula ^(1), R 1 = ^{methyl, n = 1, R 2 =} 2- oxo-1,3-di Kisoran 4-yl group) was obtained.
Yield: 11.52 g (84%), mp 69.1-69.8 ° C.
Elemental analysis: Theoretical value: C 48.35, H 5.53, N 5.13. Actual value: C 48.35, H 5.46, N 5.00.
¹ H-NMR (270 MHz, CDCl ₃ , room temperature, δ, ppm): 1.95 (s, 3 H, CH ₂ ═CC H ₃ —), 3.53 (dt, J = 5.13 (d), 5 .67 (t) Hz, 2H, -CH 2 C H 2 NH -), 4.25-4.33 (m, 4H, -NHCOOC H 2 CHC H 2 -), 4.55 (t, J = 8 _{.64Hz, 2H, -OC H 2 CH} 2 NH -), 4.92 (m, 1H, -NHCOOCH 2 C H -), 5.25 (m, 1H, -CH 2 N H COO -), 5. 62 (s, 1H, C H ₂ = CCH ₃ −), 6.14 (s, H, C H ₂ = CCH ₃ −).
¹³ C-NMR (270 MHz, d ₆ -dimethyl sulfoxide, room temperature, δ, ppm): 18.02 (CH ₂ ═C C H ₃ —), 40.58 (—CH ₂ C H ₂ NH—), 63. 33 (—NHCOOCH ₂ CH C H ₂ —), 63.50 ( —C H ₂ CH ₂ NH—), 66.03 (—NHCOO C H ₂ —), 74.98 (—NHCOOCH ₂ C HCH ₂ —) _{, 126.26 (C H 2 = CCH} 3 -), 136.13 (CH 2 C CH 3 -), 154.81 (-NHCOOCH 2 CHO C OO -), 156.19 (-NH C OO-), _{166.93 (CH 2 CCH 3 C OO-} ).
IR (KBr, cm- ¹ ): 1727 (C = Oin-NHCOO- and CCOO), 1805 (C = Oin-OCOO-), 3369 (NH).

(Example 2) Radical polymerization of MOI-G MOI-G (0.201 g, 0.720 mmol) and AIBN (3 mol%: 3.54 mg, 0.021 mmol) were placed in a polymerization tube and purged with nitrogen. 0.72 ml of the dimethyl sulfoxide was added and sealed with a deaerated tube, and the reaction was stirred at 60 ° C. for 24 hours. After completion of the reaction, the reaction solution was dissolved in a small amount of dimethyl sulfoxide, purified by precipitation with chloroform, and the resulting solid was dried under vacuum to obtain polyMOI-G (in the general formula (2), R ¹ = methyl, n = 1, R ² = 2-oxo-1,3-dioxolan-4-yl group). Yield: 0.182 g (90%), Tg (glass transition point) = 72.3 ° C., number average molecular weight: 76,500
¹ H-NMR (270 MHz, d ₆ -dimethyl sulfoxide, 80 ° C., δ, ppm) 0.67-1.04 (3H, —CH ₂ CC H ₃ COO—), 1.66-1.97 (2H, -C H ₂ CCH ₃ COO-), 3.20-3.34 (2H, -COOCH ₂ C H ₂ NH-), 3.84-4.02 (2H, -NHCOOCH ₂ CHC H _2- ), 4 _{.15-4.34 (2H, -NHCOOC H 2 CHCH} 2 -), 4.53-4.63 (2H, -COOC H 2 CH 2 NH -), 4.93-5.06 (1H, -NHCOOCH ₂ C H CH _2- ), 6.95-7.21 (1H, -COOCH ₂ CH ₂ N H- )
¹³ C-NMR (270 MHz, d ₆ -dimethyl sulfoxide, room temperature, δ, ppm): 15.99-18.83 ( —C H ₂ C C H ₃ COO—), 44.03-44.91 (—CH _{2 C CH 3 COOCH 2 C H} 2 NH -), 51.03-57.41 (-NHCOOCH 2 CH C H 2 -), 62.77-64.07 (-COO C H 2 CH 2 NH-), _{65.83-66.48 (-NHCOO C H 2 CHCH 2} -), 74.71-75.27 (-NHCOOCH 2 C HCH 2 -), 155.00-156.36 (-NHCOOCH 2 CHO C OO- _{), 156.09-156.34 (-CH 2 NH C} OO -), 176.40-177.83 (-CH 2 CCH 3 C OOCH 2 -).
IR (KBr, cm ⁻¹ ) 1720 (C═O in —NHCOO— and CCOO), 1797 (C═O in —OCOO—), 3372 (NH).

(Example 3) Copolymerization of MOI-G and n-butyl acrylate MOI-G (0.273 g, 1.00 mmol) and AIBN (0.060 mmol) were added to the polymerization tube, followed by nitrogen substitution, and distillation. N-Butyl acrylate (0.128 g, 1.00 mmol) and 2.0 ml of dimethyl sulfoxide were added and sealed with a deaerated tube. After stirring at 60 ° C. for 24 hours, a small amount of dimethyl sulfoxide was added to the reaction solution, and precipitation purification was performed with a mixed solution of water and methanol (1: 2). The obtained solid was filtered and dried under vacuum, and a copolymer of MOI-G and n-butyl acrylate (in the general formula (3), R ¹ = methyl group, n = 1, R ² = 2-oxo- 1,3-dioxolan-4-yl group, R ³ = hydrogen, R ⁴ = n-butyl group, y / (x + y) = 0.5) was obtained. Yield: 0.258 g (69%), Tg (glass transition point) = 54.4 ° C., number average molecular weight: 122,300
¹ H-NMR (270 MHz, d ₆ -dimethyl sulfoxide, room temperature, δ, ppm): 0.57-0.92 (7H, —CH ₂ C (C H ₃ ) COO—, —C H ₂ CHCOOCH ₂ CH _{2 CH 2 C H 3), 1.17-1.33} (2H, -CH 2 CH 2 C H 2 CH 3), 1.37-1.54 (2H, -CH 2 C H 2 CH 2 CH 3) _{, 1.74-2.05 (3H, -C H 2} C (CH 3) COO -, - CH 2 C H COO -), 3.24-3.29 (2H, -CH 2 C H 2 NH- _{), 3.68-4.20 (2H, -NHCOOCH 2} CHC H 2 -), 4.07-4.26 (2H, -NHCOOC H 2 CH -, - COOC H 2 CH 2 CH 2 CH 3), _{4.45-4.57 (2H, -C H 2 CH} 2 NH -), 4.88-4.99 (1H, -NHCOOCH 2 C H CH 2 -), 7.39 (1H, -CH 2 CH ₂ N H −).

(Example 4) Copolymerization of MOI-G and n-butyl methacrylate MOI-G (0.273 g, 1.00 mmol) and AIBN (0.06 mmol) were added to the polymerization tube, followed by nitrogen substitution, and distillation. N-Butyl methacrylate (0.142 g, 1.00 mmol) and 2.0 ml of dimethyl sulfoxide were added and sealed with a deaerated tube. The mixture was stirred and reacted at 60 ° C. for 24 hours. After completion of the reaction, a small amount of dimethyl sulfoxide was added to the reaction solution, and precipitation purification was performed with water. The obtained solid was filtered and dried under vacuum, and a copolymer of MOI-G and n-butyl methacrylate (in the general formula (3), R ¹ = methyl group, n = 1, R ² = 2-oxo- 1,3-dioxolan-4-yl group, R ³ = methyl group, R ⁴ = n-butyl group, y / (x + y) = 0.5) was obtained. Yield: 0.337 g (81%), Tg (glass transition point) = 63.0 ° C., number average molecular weight: 58,300
¹ H-NMR (270 MHz, d ₆ -dimethyl sulfoxide, room temperature, δ, ppm): 0.59-1.01 (9H, —CH ₂ C (C H ₃ ) COO—, —CH ₂ C (C H _{3 ) COOCH 2 CH 2 CH 2 C} H 3), 1.25-1.45 (2H, -CH 2 CH 2 C H 2 CH 3), 1.47-1.64 (2H, -CH 2 C H 2 _{CH 2 CH 3), 1.66-1.95 (} 4H, -C H 2 C (CH 3) COO -, - C H 2 C (CH 3) COO -), 3.36-3.38 (2H _{, -CH 2 C H 2 NH -} ), 3.78-4.02 (2H, -NHCOOCH 2 CHC H 2 -), 4.14-4.35 (4H, -NHCOOC H 2 CHCH 2 -, - C _{H 2 CH 2 CH 2 CH 3} ), 4.52-4.55 (2H, -C H 2 CH 2 NH -), 4.96-5.08 (1H, -NHCOOCH 2 C H CH 2 -), _{7.40-7.54 (1H, -CH 2 CH 2} N H -).

(Example 5) Copolymerization of MOI-G and Methacrylate of Diethylene Glycol Monomethyl Ether (DEGMEM) MOI-G (0.273 g, 1.00 mmol) and AIBN (0.06 mmol) were added to a polymerization tube. After replacing with nitrogen, distilled DEGMEM (0.188 g, 1.00 mmol) and 2.0 ml of dimethyl sulfoxide were added, followed by deaeration and sealing. The mixture was stirred and reacted at 60 ° C. for 24 hours. After completion of the reaction, a small amount of dimethyl sulfoxide was added to the reaction solution, followed by precipitation purification with methanol. The obtained solid was filtered and dried under vacuum, and a copolymer of MOI-G and DEGMEM (in the general formula (3), R ¹ = methyl group, n = 1, R ² = 2-oxo-1,3 - to obtain a _{(CH 2 CH 2 O) m} CH 3, m = 2, y / (x + y) = 0.5) - dioxolan-4-yl group, R ³ = methyl, R ⁴ =. Yield: 0.304 g (66%), Tg (glass transition point = 31.0 ° C.), number average molecular weight: 65,700
¹ H-NMR (270 MHz, d ₆ -dimethyl sulfoxide, room temperature, δ, ppm): 0.61-1.08 (6H, —CH ₂ CC H ₃ ) COO—, —CH ₂ C (C H ₃ ) COO -), 1.61-2.04 (4H, -C H 2 C (CH 3) COO -, - C H 2 C (CH 3) COO -), 3.18-3.30 (3H, -OCH _{2 CH 2 OC H 3),} 3.42-3.73 (8H, -CH 2 C H 2 NH -, - COOCH 2 C H 2 OC H 2 C H 2 OCH 3), 3.80-4.13 _{(4H, -NHCOOCH 2 C H CH} 2 -, - COOC H 2 CH 2 O -), 4.15-4.36 (2H, -NHCOOC H 2 CHCH 2 -), 4.53-4.65 (2H _{, -C H 2 CH 2 NH -} ), 4.96-5.08 (1H, -NHCOOCH 2 C H CH 2 -), 7.38-7.50 (1H, -CH 2 CH 2 N H -) .

Example 6 Evaluation of Ionic Conductivity of MOI-G / DEGMEM Copolymer 10% by mass acetonitrile solution of MOI-G: DEGMEM (50:50) copolymer obtained in Example 5 and LiN (SO ₂ SF ₃ ) ₂ 10% by mass acetonitrile solution was mixed in an equal amount, cast on a Teflon (registered trademark) sheet, and vacuum-dried in argon at room temperature for 12 hours, at 80 ° C. and normal pressure for 12 hours, and at 80 ° C. under reduced pressure for 12 hours. An electrolyte was obtained. The electrolyte sample was sandwiched between two SUS316 plates, and the ionic conductivity at 20 ° C. was measured by the aforementioned AC impedance method. As a result, it was 0.9 × 10 ⁻⁵ (S / cm) (20 ° C.).

(Comparative Example 1) PCMA polymerization PCMA (5.03 g, 0.027 mol), AIBN (0.16 g, 0.97 mmol) and 2-butanone (12.05 g) in a 500 ml round bottom separable flask. ), And a Dimroth type cooler, a stir bar, and a thermometer were attached. Polymerization was performed at 80 ° C. with stirring in a nitrogen stream. After 10 minutes, the formation of a white precipitate was confirmed, and after 60 minutes, a white rock-like solid was deposited around the stirring blade. The solid was separated from the stirring blade and pulverized with a mortar to obtain a white powder unnecessary for the organic solvent and water. The yield was 4.59g. The spectrum data of the obtained PCMA polymer are shown below. No film system performance due to poor solubility. After the powder was heated and melted, an attempt was made to form a film, but no film was formed.
IR (KBr, cm ⁻¹ ): 1798 (O ₂ C═O , CycloCarbonate), 1734 (CH ₂ ═C (CH ₃ ) ( C═O ) O)

(Comparative Example 2) Ionic conductivity evaluation Since PCMA did not form a film as it was, PCMA monomer was used in place of MOI-G: DEGMEM (50:50) of Example 6, and PCMA, polymerization initiator AIBN and PCMA were used. A solution in which 0.2 mmol equivalent of LiN (SO ₂ SF ₃ ) ₂ was dissolved was prepared, sandwiched between two stainless plates, and heated and dried in argon at 100 ° C. and normal pressure for 15 hours to be transparent. A film-like electrolyte was obtained. As a result of measuring the ionic conductivity at 120 ° C. by the AC impedance method, it was 1.8 × 10 ⁻⁸ (S / cm) (120 ° C.).

Claims (6)

A cyclocarbonate-containing (meth) acrylate compound having a (meth) acryloyloxyethylcarbamate structure represented by the following general formula (1). (Wherein R ¹ is hydrogen or a methyl group, R ² is a monovalent organic group containing a cyclocarbonate group, and n is an integer of 1 to 6)

The polymer which has a repeating unit shown by following General formula (2) formed by superposing | polymerizing the cyclocarbonate containing (meth) acrylate compound of Claim 1. (In the formula, R ¹ is hydrogen or a methyl group, R ² is a monovalent organic group containing a cyclocarbonate group, n is an integer of 1 to 6, and x is a natural number indicating the number of repeating units.)

The copolymer which has a repeating unit shown by General formula (3) formed by superposing | polymerizing the cyclocarbonate containing (meth) acrylate compound of Claim 1, and the said compound and the (meth) acrylic acid compound which can superpose | polymerize. Wherein R ¹ and R ³ are hydrogen or a methyl group, R ² is a monovalent organic group containing a cyclocarbonate group, R ⁴ is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, a phenyl group, benzyl Group, cyclohexyl group or oxyethylene group represented by — (CH ₂ CH ₂ O) _m CH ₃ (m is an integer of 1 to 6), n is an integer of 1 to 6, x and y are natural numbers indicating the number of repeating units. .)

  A film material comprising the polymer or copolymer according to claim 2.   An electrolyte comprising the film material according to claim 4 and a lithium ion electrolyte salt.   A solid electrolyte film comprising the electrolyte according to claim 5.