Polymer compound and composition

Abstract

The present disclosure relates to a polymer compound which can provide a solution having the lower critical solution temperature when dissolved in a solvent containing a compound having a carbonate ester structure in the molecule. The polymer compound preferably contains 10-500 units inclusive per molecule of a structural unit A represented by formula (1) in the molecule, wherein R1 is a hydrogen atom or a methyl group, Z1 is -COO- or -OCO-, Z2 is an alkylene group having 1-8 carbon atoms inclusive, and L1 is a cationic group and L2 is an anion, or L1 is an anionic group and L2 is a cation.

Description

Polymer compounds and compositions

[0001] The present invention relates to a polymer compound that, when dissolved in a solvent containing a compound having a carbonate ester structure in its molecule, yields a solution having a lower critical solution temperature, and to a composition containing the polymer compound and the solvent.

[0002] Certain compounds are known to possess a lower critical solution temperature (also known as "LCST"). Solutions of these compounds are homogeneous below the lower critical solution temperature, but separate into at least two phases above the lower critical solution temperature. In other words, the properties of the solution change with temperature, and actuators, filters, membranes, etc. that utilize this property are being investigated (Non-Patent Documents 1-3). Hydrophilic ionic liquids are known to be compounds that exhibit a lower critical solution temperature in solution (Patent Documents 1-3).

[0003] Japanese Patent Publication No. 2009-178617, Japanese Patent Publication No. 2009-203396, Japanese Patent Publication No. 2018-193429

[0004] Journal of the Japan Society for Precision Engineering, 2014, 80, 8, 709-712; Proceedings of the 62nd Spring Meeting of the Japan Society of Applied Physics, 11a-D4-10; ACS Appl. Mater. Interfaces 2023, 15, 31, 37837-37844

[0005] The prior art documents mentioned above primarily focused on substances exhibiting a lower critical solution temperature in aqueous solutions and examples of applications for such solutions, with insufficient investigation in organic solvent systems. For example, if a solution exhibiting a lower critical solution temperature can be realized using an organic solvent with a higher boiling point than water, it may be possible to realize actuators and other devices with higher operating temperatures than those previously studied. In particular, there is room for further investigation into examples using solvents containing compounds with a carbonate ester structure in their molecules.

[0006] Therefore, it is desirable to realize a composition that contains a solvent containing a compound having a carbonate ester structure in its molecule and has a lower critical solution temperature.

[0007] The polymer compound according to the present invention is characterized in that when dissolved in a solvent containing a compound having a carbonate structure in the molecule, a solution having a lower critical solution temperature is obtained.

[0008] The composition according to the present invention includes a polymer compound and a solvent containing a compound having a carbonate structure in the molecule, and is characterized by having a lower critical solution temperature.

[0009] The polymer compound according to the present invention, in one aspect, contains 10 to 500 units per molecule of the structural unit A represented by the formula (1) in the molecule, where R １ is a hydrogen atom or a methyl group, and Z １ is -COO- or -OCO-, and Z ２ is an alkylene group having 1 to 8 carbon atoms, and L １ is a cationic group and L ２ is an anion, or L １ is an anionic group and L ２ is a cation, which is preferable.

[0010] The polymer compound according to the present invention, in one aspect, as the structural unit A, all are the structural unit A represented by the formula (1) １ and the structural unit A ２ are included, and the structural unit A １ and the structural unit A ２ are preferably such that at least one of Z １ , Z ２ ... , L １ , and L ２ is different from each other.

[0011] The polymer compound according to the present invention, in one aspect, is preferably such that L １ is an onium group and L ２ is an anion.

[0012] The polymer compound according to the present invention, in one aspect, L １However, it is preferable that the onium group is selected from the group consisting of a substituted or unsubstituted heterocyclium group, a substituted or unsubstituted ammonium group, a substituted or unsubstituted phosphonium group, and a substituted or unsubstituted sulfonium group, which contains one to two heteroatoms, at least one of the heteroatoms being a nitrogen atom, and is a group containing at least one five-membered ring and a six-membered ring that include the heteroatoms.

[0013] In one embodiment, the polymer compound according to the present invention is L １ However, it is preferable that the onium group is selected from the group consisting of imidazolium, imidazolinium, imidazolidinium, pyrazolium, pyrazolinium, pyrazolidinium, oxazolium, oxazolinium, oxazolidinium, thiazolium, thiazolinium, thiazolidinium, pyrrolium, pyrrolidinium, pyridinium, piperidinium, pyrazinium, piperadinium, pyrimidinium, pyridazinium, morpholinium, thiomorpholinium, ammonium, phosphonium, and sulfonium groups, which are substituted with or unsubstituted by an alkyl group having 1 to 4 carbon atoms.

[0014] In one embodiment, the polymer compound according to the present invention is L ２ However, it is preferable that the anion is selected from the group consisting of chloride ions, bromide ions, iodide ions, carboxylate ions, tetrafluoroborate ions, hexafluorophosphate ions, hexafluoroantimonate ions, bis(fluorosulfonyl)imide ions, bis(trifluoromethanesulfonyl)imide ions, trifluoromethanesulfonate ions, difluorophosphate ions, difluoro(oxalate)borate ions, and thiocyanate ions.

[0015] In one embodiment, the polymer compound according to the present invention further contains, in the molecule, one to 500 units per molecule of the constituent unit B represented by formula (2), Z ３ However, -COOR ４ -, -OCOR ４ -, -OR ４- A group selected from the group consisting of substituted or unsubstituted aliphatic chain hydrocarbon groups, substituted or unsubstituted alicyclic hydrocarbon groups, substituted or unsubstituted aromatic hydrocarbon groups, substituted or unsubstituted phenylalkylene groups, and substituted or unsubstituted heterocyclylene groups, R ２ However, R is a group selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group, and a phenyl group. ３ However, R is a group selected from the group consisting of a hydrogen atom, a fluorine atom, a methyl group, a methoxy group, and a tert-butyl group. ４ However, it is preferable that the group is selected from the group consisting of a single bond, an alkylene group, and a cycloalkylene group.

[0016] In one embodiment, the polymer compound according to the present invention is Z ３ However, -COOR ４ -, -OCOR ４ -, -OR ４ - Preferably, the group is selected from the group consisting of a substituted or unsubstituted norborneylene group, a substituted or unsubstituted phenylene group, a substituted or unsubstituted phenylalkylene group, a substituted or unsubstituted imidazoylene group, and a substituted or unsubstituted pyridinylene group.

[0017] Further features and advantages of the present invention will become clearer through the following description of exemplary and non-limiting embodiments, with reference to the drawings.

[0018] According to the above configuration, a composition containing a solvent with a compound having a carbonate ester structure in its molecule and having a lower critical solution temperature can be realized. This allows for benefits such as increasing the operating temperature of actuators and other devices that use a solution with a lower critical solution temperature compared to conventional methods.

[0019] These are photographs showing the state of the solution from Synthesis Example 4B before and after heating. These are photographs showing the state of the solution from Synthesis Example 4C before and after heating.

[0020] Embodiments of polymer compounds and compositions according to the present invention will be described.

[0021] [Composition] The composition according to this embodiment comprises a polymer compound, which will be described later, and a solvent containing a compound having a carbonate ester structure in its molecule.

[0022] The solvent is not limited as long as it contains a compound having a carbonate ester structure in its molecule. Therefore, a compound having a carbonate ester structure in its molecule may be used as the solvent alone, or a mixture containing a compound having a carbonate ester structure in its molecule may be used. In the case of a mixture, it may be a mixture of multiple types of compounds having a carbonate ester structure in their molecules, or a mixture of one or more types of compounds having a carbonate ester structure in their molecules and one or more types of compounds not having a carbonate ester structure in their molecules. Any compound constituting the solvent may be one that is generally sold as a reagent, but it is preferable that it be of high purity, for example, battery grade is preferred.

[0023] Examples of compounds having a carbonate ester structure in their molecules include, but are not limited to, ethylene carbonate, propylene carbonate, vinylene carbonate, vinylethylene carbonate, fluoroethylene carbonate, dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate.

[0024] Compounds having a carbonate ester structure in their molecule preferably have a boiling point of 30°C or higher, more preferably 80°C or higher, and even more preferably 100°C or higher. In particular, using compounds with a boiling point of 100°C or higher can achieve a lower critical solution temperature higher than that of conventional aqueous solution compositions.

[0025] Compounds that do not have a carbonate ester structure in their molecule include, for example, 1,2-dimethoxyethane, 1,2-diethoxyethane, dibutyl ether, diglyme, diethylene glycol diethyl ether, triglyme, tetraglyme, methyl acetate, ethyl acetate, methyl difluoroacetate, ethyl trifluoroacetate, methyl propionate, ethyl propionate, vinyl acetate, n-n-butyl acetate, γ-butyrolactone, trimethyl phosphate, triethyl phosphate, trioctyl phosphate, tris(2,2,2-trifluoroethyl) phosphate, tris(trimethylsilyl) phosphate, N-methyl-2-pyrrolidone, N,N-dimethylformamide, 1,3-dimethyl-2-imidazolidinone, N,N-dimethylacetamide, ethylene sulfite, and Examples include, but are not limited to, ruphorane, 3-methylsulfolane, 1-propene-1,3-sultone, 1,5,2,4-dioxaditian-2,2,4,4-tetraoxide, dimethyl sulfoxide, acetonitrile, adiponitrile, valeronitrile, glutaronitrile, succinonitrile, isobutyronitrile, biphenyl, succinic anhydride, cyclohexylbenzene, thiophene, benzene, toluene, xylene, chlorobenzene, fluorobenzene, hexafluorobenzene, mesitylene, n-hexane, n-heptane, cyclohexane, 1,3-dioxolane, acetone, tetrahydrofuran, 1,4-dioxane, cyclopentyl methyl ether, diethyl ether, carbon tetrachloride, dichloromethane, 1,2-dichloroethane, and chloroform.

[0026] In cases where the solvent is a mixture of one or more compounds having a carbonate ester structure in their molecules and one or more compounds not having a carbonate ester structure in their molecules, the mixing ratio of compounds having a carbonate ester structure in their molecules to compounds not having a carbonate ester structure in their molecules is not particularly limited, but for example, the proportion of compounds having a carbonate ester structure in their molecules may be 0.05% by mass or more and 99.95% by mass or less.

[0027] The composition according to this embodiment may contain other substances, including polymer compounds and solvents. Examples of other substances include, but are not limited to, lithium hexafluoride phosphate, lithium tetrafluoroborate, lithium bis(trifluoromethanesulfonyl)imide, lithium trifluoromethanesulfonate, lithium bis(fluorosulfonyl)imide, lithium difluorophosphate, and lithium difluoro(oxalate)borate.

[0028] The composition according to this embodiment has a lower critical solution temperature. That is, the composition according to this embodiment is a homogeneous solution below the lower critical solution temperature, but separates into at least two phases above the lower critical solution temperature. The lower critical solution temperature can be determined, for example, by heating the composition while visually observing it, and determining the temperature at which phase separation is observed as the lower critical solution temperature. Figure 1 shows the state of the solution of Synthesis Example 4B of the Examples described later at room temperature (Figure 1 left) and at around 128°C (Figure 1 right). At around room temperature it is a homogeneous solution, but at around 128°C it is a cloudy liquid, indicating that phase separation has occurred. Similarly, Figure 2 compares the state of the solution of Synthesis Example 4C of the Examples described later at room temperature and at around 60°C.

[0029] The lower critical solution temperature of the composition according to this embodiment is not particularly limited, but is preferably 30°C to 180°C, and more preferably 90°C to 130°C. The composition according to this embodiment is put into practical use by utilizing the change in properties at the lower critical solution temperature boundary, and when the lower critical solution temperature is within the above range, it is easy to achieve both a homogeneous solution at room temperature and phase separation at the temperature range where phase separation is necessary.

[0030] [Composition of Polymer Compound] The polymer compound according to this embodiment yields a solution (composition) having a lower critical solution temperature when dissolved in a solvent containing a compound having a carbonate ester structure in its molecule. The definition of "solvent" here follows the above explanation of solvents.

[0031] The polymer compound according to this embodiment may be a single compound or a mixture of multiple compounds. In the case of a mixture, it is preferable that at least one of the compounds constituting the mixture satisfies the following preferred requirements for a polymer compound, and it is more preferable that all of the compounds constituting the mixture satisfy the following preferred requirements for a polymer compound.

[0032] The polymer compound according to this embodiment is not particularly limited as long as a solution (composition) having a lower critical solution temperature can be obtained, but it may be a homopolymer or copolymer, or a derivative thereof, of a system selected from the group consisting of acrylamide, acrylate, methacrylate, vinyl ether, and vinyl. Furthermore, it is more preferable that the polymer compound according to this embodiment is a homopolymer or copolymer, or a derivative thereof, of a system selected from the group consisting of acrylate, methacrylate, and vinyl.

[0033] The number-average molecular weight of the polymer compound according to this embodiment is not particularly limited as long as it dissolves uniformly in the above solvent at room temperature, but it is preferably 500 or more and 500,000 or less. When the number-average molecular weight of the polymer compound is 500 or more, the solution containing the polymer compound is particularly likely to exhibit the lower critical solution temperature. When the number-average molecular weight of the polymer compound is 500,000 or less, the solubility of the polymer compound tends to be good. It is more preferable that the number-average molecular weight of the polymer compound is 1,000 or more.

[0034] In the polymer compound according to this embodiment, the ratio of the number-average molecular weight (Mn) to the weight-average molecular weight (Mw) (Mw / Mn) is not particularly limited and can be appropriately selected according to the temperature response characteristics required for the solution containing the polymer compound. For example, if the Mw / Mn of the polymer compound is 1.25 or less, when the solution containing the polymer compound is heated above the lower critical solution temperature, the phase separation proceeds quickly and is likely to cause a steep phase separation at the lower critical solution temperature, making it suitable when a steep change in properties at the lower critical solution temperature is desired. In this respect, the lower limit of the Mw / Mn of the polymer compound is not particularly limited, but it may be, for example, 1.01 or more.

[0035] On the other hand, if the Mw / Mn of the polymer compound is 2.0 or higher, when the solution containing the polymer compound is heated above the lower critical solution temperature, gradual phase separation occurs around the lower critical solution temperature. Therefore, this is suitable when a gradual change in properties near the lower critical solution temperature is desired. In this respect, there is no particular upper limit to the Mw / Mn of the polymer compound, but it may be, for example, 10 or less.

[0036] The polymer compound according to this embodiment preferably contains 10 to 500 units of the constituent unit A represented by formula (1) per molecule.

[0037] R １ This is a hydrogen atom or a methyl group. Z １ This is -COO- or -OCO-. ２ L is an alkylene group having 1 to 8 carbon atoms. １ and L ２ One of them is cationic and the other is anionic. That is, L １ It is a cationic group and L ２ A composition in which L is an anion, １ It is an anionic group and L ２ The configuration may be one in which L is a positive ion. １ It is an onium group and L ２ It is more preferable that Z is an anion. １ If it is -COO-, then constituent unit A is a constituent unit derived from an acrylate or methacrylate monomer, and Z １ If the result is -OCO-, then constituent unit A is a constituent unit derived from a vinyl monomer.

[0038] Z １ If it is -COO- or -OCO-, it will have a functional group (carbonyl group) in common with solvents containing compounds with a carbonate ester structure in the molecule, and will have a high affinity for that solvent. That is Z １ This contributes to the solubility of polymer compounds in solvents.

[0039] L １L ２ L is an ion pair and is temperature responsive. The inventors of this invention have found that L １ L ２ The relationship between the fact that it is temperature-responsive and the fact that the solution containing the polymer compound according to this embodiment has a lower critical solution temperature is estimated as follows: At relatively low temperatures, ionic bonding takes precedence over thermal motion. ２ is L １ Because it remains in the vicinity, the polarity of the side chain ends of constituent unit A is relatively low. Therefore, it is thought that polymer compounds become relatively soluble in solvents. On the other hand, at relatively high temperatures, thermal motion takes precedence over ionic bonding, L ２ is L １ It dissociates from the constituent unit A, and an ionic L is attached to the side chain end of the constituent unit A. １ Because of this remaining polarity, the polarity of the side chain ends of constituent unit A is relatively high. Therefore, the polymer compound becomes relatively difficult to dissolve in the solvent, which is thought to cause interactions between polymer side chains and lead to polymer aggregation. Thus, ion pairs L remain at the side chain ends of constituent unit A. １ L ２ The presence of this compound is thought to cause the polarity of the side chain ends to change with temperature, leading to the polymer compound exhibiting temperature responsiveness in its solubility to solvents.

[0040] L １ It is preferable that the onium group is selected from the group consisting of (i) a substituted or unsubstituted heterocyclium group comprising one or more heteroatoms, at least one of which is a nitrogen atom, and comprising at least one five-membered ring and a six-membered ring containing the heteroatoms, (ii) a substituted or unsubstituted ammonium group, (iii) a substituted or unsubstituted phosphonium group, and (iv) a substituted or unsubstituted sulfonium group. If these onium groups are substituted, it is more preferable that they are substituted with an alkyl group having 1 to 4 carbon atoms. １ Regarding "no substitution", Z ２ This means that it does not have any functional groups other than the hydrogen atom connected to it. １In the case where (i) above applies, the heteroatoms contained in the heterocyclium group are preferably one to five, and more preferably one to two.

[0041] L １ In the case where (i) above applies, examples of five-membered rings containing heteroatoms include, but are not limited to, imidazolium, imidazolinium, imidazolidinium, pyrazolium, pyrazolinium, pyrazolidinium, oxazolium, oxazolinium, oxazolidinium, thiazolium, thiazolinium, thiazolidinium, pyrrolium, and pyrrolidinium groups. １ In the case where (i) above applies, examples of six-membered rings containing heteroatoms include, but are not limited to, pyridinium, piperidinium, pyrazinium, piperadinium, pyrimidinium, pyridazinium, morpholinium, and thiomorpholinium groups.

[0042] L １ In the case where (i) above applies, L １ This may be a monocyclic heterocyclium group or a fused cyclic heterocyclium group. １ Examples of groups in which the group is a monocyclic heterocyclium group include, but are not limited to, imidazolium, imidazolinium, imidazolidinium, pyrazolium, pyrazolinium, pyrazolidinium, oxazolium, oxazolinium, oxazolidinium, thiazolium, thiazolinium, thiazolidinium, pyrrolium, pyrrolidinium, pyridinium, pyridinium, piperidinium, pyrazinium, piperadinium, pyrimidinium, pyridazinium, morpholinium, and thiomorpholinium groups. １Examples of cases where is a condensed cyclic heterocyclium group include, but are not limited to, indlium, indolinium, isoindolinium, isoindolinium, indazolium, azaindolinium, azaindolinium, quinolinium, isoquinolinium, quinoxalinium, quinazolinium, synnolinium, phthalazinium, benzimidazolium, benzoxazolium, benzoisoxazolium, benzothiazolium, phenanthrolinium, acridinium, phenazinium, carbazolium, phenoxazinium, and phenothiazinium. １ It is preferably a monocyclic heterocyclium group, and more preferably an onium group selected from the group consisting of imidazolium, imidazolinium, imidazolidinium, pyrazolium, pyrazolinium, pyrazolidinium, oxazolium, oxazolinium, oxazolidinium, thiazolium, thiazolinium, thiazolidinium, pyrrolium, pyrrolidinium, pyridinium, piperidinium, pyrazinium, piperadinium, pyrimidinium, pyridazinium, morpholinium, and thiomorpholinium.

[0043] L １ When the cyclic group is Z ２ The bonding position with the cyclic group L is not limited. １ In Z ２ The atom bonded to it can be any carbon atom or heteroatom that constitutes the cyclic group. However, L １ Structure and Z ２ The bonding position is L １ It can be selected insofar as it satisfies the requirement that it is an onium group. For example, L １ When is an imidazolium group, at least one nitrogen atom is Z ２ It is bonded to or has substituents.

[0044] L ２is preferably an anion selected from the group consisting of chloride ion, bromide ion, iodide ion, carboxylate ion, tetrafluoroborate ion, hexafluorophosphate ion, hexafluoroantimonate ion, bis(fluorosulfonyl)imide ion, bis(trifluoromethanesulfonyl)imide ion, trifluoromethanesulfonate ion, difluorophosphate ion, difluoro(oxalato)borate ion, and thiocyanate ion.

[0045] The polymer compound according to this embodiment may contain a plurality of types of structural units corresponding to structural unit A in the molecule. For example, the polymer compounds according to this embodiment are all structural units A represented by formula (1) １ and structural unit A ２ are included. Here, structural unit A １ and structural unit A ２ differ from each other in at least one of Z １ , Z ２ , L １ , and L ２ .

[0046] When the polymer compound according to this embodiment contains the structural unit A represented by formula (1) in the molecule, the polymer compound may preferably contain 1 unit or more and 500 units or less of the structural unit B represented by formula (2) per molecule. The abundance ratio of structural unit A and structural unit B is not particularly limited, but for example, it is preferable that structural unit A occupies 50 mol% or more.

[0047] Z ３ is -COOR ４ -, -OCOR ４ -, -OR ４- is a group selected from the group consisting of substituted or unsubstituted aliphatic chain hydrocarbon groups, substituted or unsubstituted alicyclic hydrocarbon groups, substituted or unsubstituted aromatic hydrocarbon groups, substituted or unsubstituted phenylalkylene groups, and substituted or unsubstituted heterocyclylene groups. The alicyclic hydrocarbon group is preferably a norborneylene group. The aromatic hydrocarbon group is preferably a phenylene group. The heterocyclylene group is preferably an imidazoylene group or a pyridinylene group. ３ Regarding "unsubstituted," the term refers to carbon atoms and R ３ This means that it does not have any functional groups other than hydrogen atoms that are connected to it.

[0048] R ２ R is a group selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group, and a phenyl group. ３ R is a group selected from the group consisting of a hydrogen atom, a fluorine atom, a methyl group, a methoxy group, and a tert-butyl group. ４ This group is selected from the group consisting of single bonds, alkylene groups, and cycloalkylene groups.

[0049] [Examples of Industrial Use] Next, examples of how the composition according to this embodiment can be used for industrial purposes will be described.

[0050] The composition according to this embodiment can be used as an actuator. Since the composition undergoes phase separation in response to temperature changes, its shape and volume may change in response to temperature. This change can be used as a driving source or as an auxiliary agent for the actuator. Depending on the required dimensions of the actuator, the composition according to this embodiment may be used in combination with other substances. Conventional aqueous polymer gel actuators have the problem that their function may be impaired by the evaporation of water. However, since the composition according to this embodiment contains a solvent that includes a compound having a carbonate ester structure in its molecule, it is possible to use a solvent with a higher boiling point compared to conventional aqueous polymer gel actuators, making it easier to avoid problems associated with solvent evaporation.

[0051] The composition according to this embodiment can be used as a filter, a membrane, or the like having temperature responsiveness. For example, although an example in which a temperature-responsive polymer aqueous dispersion is imparted to graphene oxide nanosheets to realize a filter having temperature responsiveness has been conventionally reported, if the composition according to this embodiment is used instead of the aqueous dispersion of this system, a higher operating temperature range than before can be realized.

[0052] [Examples] The present invention will be further described below with reference to examples. However, the following examples do not limit the present invention.

[0053] (1) Evaluation apparatus and evaluation method Before showing specific synthesis examples, the evaluation apparatus and evaluation method applied when evaluating the synthesis examples and precursors will be described.

[0054] (Nuclear magnetic resonance) Using a nuclear magnetic resonance apparatus (JNM-ECZ500R / S1 manufactured by JEOL Ltd.), the １ H NMR of each synthesis example was measured. The resonance frequency was set to 500 MHz, and the measurement was performed at room temperature. The sample was prepared using a deuterated solvent such as deuterochloroform (CDCl ３ ), deuterated tetrahydrofuran (THF-d ８ ), deuterated acetone (acetone-d ６ ), and deuterated dimethyl sulfoxide (DMSO-d6) as the solvent. Tetramethylsilane (TMS) was used as an internal standard.

[0055] (Average molecular weight) Using an ultra-high performance liquid chromatograph (Nexera (registered trademark) X2 manufactured by Shimadzu Corporation), gel permeation chromatography (GPC) of each synthesis example was measured. The pump used was Nexera (registered trademark) X2 LC-30AD manufactured by Shimadzu Corporation. One organic solvent-based standard column (Shodex (registered trademark) GPC LF-804 manufactured by Resonac Co., Ltd.) was used as the column. A differential refractive index detector (RID-20A manufactured by Shimadzu Corporation) was used as the detector. The mobile phase was tetrahydrofuran, the measurement temperature was 35°C, and the flow rate was 0.5 mL per minute. The number average molecular weight (Mn) and weight average molecular weight (Mw) of the sample were determined using polystyrene as a standard substance.

[0056] (Anion Conversion Rate) Elemental analysis was performed on samples of the polymer compounds from each synthesis example before and after the ion exchange procedure using energy-dispersive X-ray spectroscopy (SEM-EDX) with a scanning electron microscope. The anion conversion rate due to the ion exchange procedure was determined by comparing the ions before and after the procedure.

[0057] (2) Synthesis of Precursors Precursors 1 to 6 were synthesized by the following procedure. Precursors 1 to 3 are polymer compounds represented by general formula (3), and precursors 4 to 6 are polymer compounds represented by formula (4). In precursor 1, R １ R is a methyl group, ３ R is a hydrogen atom, and m and n are each independent integers between 20 and 200. In precursor 2, R １ R is a methyl group, ３ is a methyl group, and m and n are each independently integers between 10 and 200. In precursor 3, R １ is a hydrogen atom, R ３ R is a hydrogen atom, and m and n are each independent integers between 10 and 200. In precursor 4, R １ R is a methyl group, X is a chlorine atom, and n is an integer between 10 and 200. In precursor 5, R １ R is a hydrogen atom, X is a chlorine atom, and n is an integer between 10 and 200. In precursor 6, R １ is a methyl group, X is an iodine atom, and n is an integer between 10 and 200.

[0058] (Precursor 1) In a nitrogen-filled three-necked flask, 12.5 g of 2-hydroxyethyl methacrylate, 10.0 g of styrene, and 15 mL of diethylene glycol ethyl methyl ether were added and heated with stirring until the internal temperature reached 85°C. Then, a solution of 0.1 g of dimethyl 2,2'-azobis(2-methylpropionate) dissolved in 15 mL of diethylene glycol ethyl methyl ether was added to the flask dropwise through a dropping funnel over 35 minutes. Subsequently, 4.5 mL of diethylene glycol ethyl methyl ether was added to the dropping funnel and added dropwise over 2 minutes. After that, stirring was continued for 5 hours while maintaining the temperature inside the flask at 85°C. To deactivate the dimethyl 2,2'-azobis(2-methylpropionate), the internal temperature was raised to 90°C, stirred for 30 minutes after heating, and then cooled until the temperature inside the flask dropped to room temperature. The reaction mixture was added dropwise to 200 mL of heptane to obtain a white precipitate. By repeatedly dissolving this precipitate in 100 mL of tetrahydrofuran and reprecipitation it in 300 mL of heptane, 14.7 g of a white solid was obtained.

[0059] １ The 1H NMR spectrum confirmed that the product was poly(2-hydroxyethyl methacrylate-co-styrene). １ H NMR (500MHz, THF-d ８ ): δ = 7.3 to 6.7 (br, 5H), 4.3 to 3.7 (br, 5H), 1.4 to 1.3 (br, 3H), 2.1 to 0.5 (br, 5H) (ppm)

[0060] The number-average molecular weight (Mn) of the product was 24346, and the Mw / Mn ratio was 1.61.

[0061] The product, which is precursor 1, has a distribution in m and n, but the average molecular weight and １ The m and n values ​​calculated from the 1H NMR spectrum are used as representative values. １ ​In the 1H NMR spectrum, the relative abundance of component A and component B is determined by focusing on the integral ratio of the peak derived from component A and the peak derived from component B of precursor 1. From this relative abundance and the average molecular weight, the values ​​of m and n, which represent the number of repeating units of component A and component B per molecule of precursor 1, can be calculated. For precursor 1, m is 112 and n is 93. The definition and method of determining m and n are the same for precursors 2 and 3.

[0062] (Precursor 2) Precursor 2 was synthesized in the same manner as Precursor 1, except that 4-methylstyrene was used instead of styrene, the internal temperature during the reaction was changed to 80°C, and the overall scale was set to approximately 27% of the synthesis of Precursor 1. After reprecipitation, 4.1 g of a white solid was obtained as the product.

[0063] １ From the 1H NMR spectrum, it was confirmed that the product was poly(2-hydroxyethyl methacrylate-co-p-methylstyrene). １ H NMR (500MHz, THF-d ８ ): δ = 7.3 to 6.5 (br, 4H), 4.3 to 3.0 (br, 5H), 2.4 to 2.1 (br, 3H), 2.1 to 0.2 (br, 8H) (ppm)

[0064] The number-average molecular weight Mn of the product was 45474, and the Mw / Mn ratio was 1.99. For this product, m was 191 and n was 174.

[0065] (Precursor 3) The precursor 3 was synthesized in the same manner as the precursor 1, except that 2-hydroxyethyl acrylate was used instead of 2-hydroxyethyl methacrylate, the internal temperature during the reaction was changed to 80°C, and the overall scale was set to approximately 40% of the synthesis of precursor 1. After reprecipitation, 6.0 g of a white solid was obtained as the product.

[0066] １ The 1H NMR spectrum confirmed that the product was poly(2-hydroxyethylacrylate-co-styrene). １ ¹H NMR (500 MHz, acetone-d ６ ​​): δ = 8.0 to 6.6 (br, 5H), 4.8 to 3.4 (br, 5H), 2.7 to 1.2 (br, 6H) (ppm)

[0067] The number-average molecular weight Mn of the product was 30986, and the Mw / Mn ratio was 2.05. For this product, m was 143 and n was 139.

[0068] (Precursor 4) In a nitrogen-purged three-necked flask, 4.0 g of 2-chloroethyl methacrylate and 27 mL of diethylene glycol ethyl methyl ether were added and heated with stirring until the internal temperature reached 80°C. Then, a solution of 0.04 g of dimethyl 2,2'-azobis(2-methylpropionate) dissolved in 1 mL of diethylene glycol ethyl methyl ether was added dropwise to the flask. The mixture was then stirred for 6 hours while maintaining the temperature at 80°C. To deactivate the dimethyl 2,2'-azobis(2-methylpropionate), the internal temperature was increased to 90°C, stirred for 30 minutes after heating, and then cooled until the temperature inside the flask dropped to room temperature. The reaction mixture was reprecipitated with water and methanol, and dried to obtain a white precipitate. The above procedure was repeated six times to obtain six lots of precursor 4. The yield, number average molecular weight Mn, Mw / Mn, and １ The 1H NMR spectra were as shown in the table below. Note that for all lots, １ The product was confirmed to be poly(2-chloroethyl methacrylate) from the 1H NMR spectrum.

[0069] Table 1: Synthesis of Prototype 4

[0070] (Precursor 5) Precursor 5 was synthesized in the same manner as precursor 4, except that 2-chloroethyl acrylate was used instead of 2-chloroethyl methacrylate. After reprecipitation, 3.4 g of a white solid was obtained as the product.

[0071] １ The 1H NMR spectrum confirmed that the product was poly(2-chloroethyl acrylate). １ H NMR (500MHz, CDCl ３ ​): δ = 4.4 to 4.2 (br, 2H), 3.8 to 3.6 (br, 2H), 2.6 to 2.3 (br, 1H), 2.2 to 1.4 (br, 2H) (ppm)

[0072] The number-average molecular weight (Mn) of the product was 5289, and the Mw / Mn ratio was 2.19.

[0073] (Precursor 6) The precursor 6 was synthesized in the same manner as the precursor 4, except that 2-iodoethyl methacrylate was used instead of 2-chloroethyl methacrylate. After reprecipitation, 2.2 g of a white solid was obtained as the product.

[0074] １ The 1H NMR spectrum confirmed that the product was poly(2-iodoethyl methacrylate). １ H NMR (500MHz, CDCl ３ ): δ = 4.8 to 4.0 (br, 2H), 3.6 to 3.0 (br, 2H), 2.8 to 0.3 (br, 5H) (ppm)

[0075] The number-average molecular weight (Mn) of the product was 18571, and the Mw / Mn ratio was 2.20.

[0076] (3) Synthesis of Polymer Compounds The synthesis methods for the polymer compounds in the following examples will be explained. In the explanation of the synthesis methods for each of the following examples, for synthesis methods where the main procedure is the same but the substrate compound used, the synthesis scale, and other details (such as the purification method) differ, the explanation will be omitted or simplified by referring to the synthesis method of the preceding example. The synthesis methods for each of the above examples modify the side chains using one of the precursors 1 to 6 as the starting material, but do not change the structure of the main chain. Therefore, the values ​​of m and n in each synthesis example are the same as the values ​​of m and n in the precursor used as the starting material in each example.

[0077] (3-1) Synthesis Examples 1A to 1C Synthesis Examples 1A to 1C are polymer compounds obtained using precursor 1 as a raw material. Synthesis Examples 1A to 1C are represented by general formula (5). m and n are each independent integers between 20 and 200. In Synthesis Example 1A, L ２ This is an iodide ion, and in synthesis example 1B, L ２ ​This is a benzoate ion, and in synthesis example 1C, L ２ This is the hexafluoroantimonate ion.

[0078] (Synthesis Example 1A) In a nitrogen-dried three-necked flask, 1.0 g of precursor 1 and 3 mL of tetrahydrofuran were added and stirred until precursor 1 dissolved in the tetrahydrofuran. Then, 1.26 g of 1,2-dimethylimidazole was added and stirred until dissolved, and the mixture was cooled to an internal temperature of 0°C. 1 g of p-toluenesulfonyl chloride was dissolved in 4 mL of tetrahydrofuran and added dropwise through a dropping funnel for 12 minutes. After the addition was complete, another 4 mL of tetrahydrofuran was added to the dropping funnel and added dropwise for 2 minutes. After the addition, the mixture was stirred for 14 hours (during which time the internal temperature rose from 0-15°C to around room temperature) to obtain a white solid. In this way, a polymer in which the hydroxyl groups of precursor 1 were tosylated was obtained.

[0079] 10 mL of anhydrous N,N-dimethylformamide was added to this three-necked flask, and the mixture was heated until the internal temperature reached 40°C, stirring until a white solid dissolved. Then, 1.43 g of sodium iodide was added, and the mixture was heated until the internal temperature reached 80°C, stirring for 5 hours. After adding a small amount of water, the solid in the flask was dissolved in 10 mL of dimethyl sulfoxide, and the solution was then placed into a cellulose tubing for dialysis. The cellulose tubing containing the solution was placed in a beaker filled with deionized water as a buffer, and dialysis was performed while gently stirring. The deionized water buffer was replaced as needed, and dialysis was performed for a total of 72 hours. After that, the contents of the cellulose tubing were placed into a flask, and the solvent and other substances were removed by vacuum distillation, followed by vacuum drying to obtain 0.8 g of a white solid.

[0080] １ ¹H NMR spectroscopy confirmed that the product was poly([dimethylimidazolium ethyl methacrylate][iodide]-co-styrene). １ H NMR (500MHz, DMSO-d ６ ​): δ = 7.8 to 7.3 (br, 2H), 7.3 to 6.5 (br, 5H), 4.9 to 3.9 (br, 4H), 3.7 (br, 3H), 2.7 to 2.4 (br, 3H), 2.0 to -0.2 (br, 8H) (ppm)

[0081] (Synthesis Example 1B) 0.2 g of Synthesis Example 1A and 10 mL of dimethyl sulfoxide were added to an Erlenmeyer flask and stirred until dissolved. 0.13 g of sodium benzoate was added to 10 mL of deionized water and stirred until dissolved. This aqueous solution was added dropwise to the flask containing the dimethyl sulfoxide solution for 5 minutes and stirred at room temperature for 18 hours. The liquid from the flask was placed into a cellulose tubing for dialysis. The cellulose tubing containing the solution was placed in a beaker filled with deionized water as a buffer, and dialysis was performed while gently stirring. The deionized water buffer was replaced as needed, and dialysis was performed for a total of 144 hours. After that, the contents of the cellulose tubing were placed into a flask, the solvent and other substances were removed by vacuum distillation, and then vacuum drying was performed to obtain 0.2 g of a white solid. The anion conversion rate was 90%.

[0082] １ ¹H NMR spectroscopy confirmed that the product was poly([dimethylimidazolium ethyl methacrylate][benzoate]-co-styrene). １ H NMR (500MHz, DMSO-d ６ ): δ = 8.0 ~ 7.3 (br, 2H), 7.8 (m, 2H), 7.3 ~ 6.5 (br, 5H), 7.2 (m, 1H), 7.2 (m, 2H) ), 4.7 to 3.8 (br, 4H), 3,7 (br, 3H), 2.8 to 2.1 (br, 3H), 2.0 to -0.3 (br, 8H) (ppm)

[0083] (Synthesis Example 1C) The synthesis was carried out in substantially the same manner as in Synthesis Example 1B, except that sodium hexafluoroantimonate was used instead of sodium benzoate, and 0.2 g of a white solid was obtained. The anion conversion rate was 91%.

[0084] １ ¹H NMR spectroscopy confirmed that the product was poly([dimethylimidazolium ethyl methacrylate][hexafluoroantimonate]-co-styrene).​​１ H NMR (500MHz, DMSO-d ６ ): δ = 7.7 to 7.3 (br, 2H), 7.2 to 6.4 (br, 5H), 4.9 to 4.0 (br, 4H), 3.7 (br, 3H), 2.5 to 2.3 (br, 3H), 1.9 to -0.3 (br, 8H) (ppm)

[0085] (3-2) Synthesis Examples 1D and 1E Synthesis Examples 1D and 1E are polymer compounds obtained using precursor 1 as a raw material. Synthesis Examples 1D and 1E are represented by general formula (6). m and n are each independent integers between 20 and 200. In Synthesis Example 1D, L ２ This is an iodide ion, and in synthesis example 1E, L ２ This is a benzoate ion.

[0086] (Synthesis Example 1D) The synthesis was carried out in substantially the same manner as in Synthesis Example 1A, except that 1-methylimidazole was used instead of 1,2-dimethylimidazole, and 0.26 g of a white solid was obtained.

[0087] １ ¹H NMR spectroscopy confirmed that the product was poly([methylimidazolium ethyl methacrylate][iodide]-co-styrene). １ H NMR (500MHz, DMSO-d ６ ): δ = 10.2 to 9.3 (br, 1H), 8.0 to 7.4 (br, 2H), 7.3 to 6.4 (br, 5H), 4.9 to 3.9 (br, 4H), 3.8 (br, 3H), 2.3 (br, 3H), 2.3 to -0.3 (br, 5H) (ppm)

[0088] (Synthesis Example 1E) The synthesis was carried out in substantially the same manner as the synthesis of Synthesis Example 1B, except that Synthesis Example 1D was used instead of Synthesis Example 1A, and 0.06 g of a white solid was obtained.

[0089] １ ¹H NMR spectroscopy confirmed that the product was poly([methylimidazolium ethyl methacrylate][benzoate]-co-styrene). １ H NMR (500MHz, DMSO-d ６ ​​): δ = 10.2 ~ 9.3 (br, 1H), 8.0 ~ 7.4 (br, 2H), 7.8 (m, 2H), 7.3 ~ 6.4 (br, 5H), 7.2 (m, 1H), 7.2 (m, 2H), 4.8 to 4.0 (br, 4H), 3.8 (br, 3H), 2.5 to -0.4 (br, 8H) (ppm)

[0090] (3-3) Synthesis Examples 1F and 1G Synthesis Examples 1F and 1G are polymer compounds obtained using precursor 1 as a raw material. Synthesis Examples 1F and 1G are represented by general formula (7). m and n are each independent integers between 20 and 200. In Synthesis Example 1F, L ２ This is an iodide ion, and in synthesis example 1G, L ２ This is a benzoate ion.

[0091] (Synthesis Example 1F) The synthesis was carried out in substantially the same manner as in Synthesis Example 1A, except that 1-butylimidazole was used instead of 1,2-dimethylimidazole, and 1.1 g of a white solid was obtained.

[0092] １ ¹H NMR spectroscopy confirmed that the product was poly([butylimidazolium ethyl methacrylate][iodide]-co-styrene). １ H NMR (500MHz, DMSO-d ６ ): δ = 10.2 ~ 9.4 (br, 1H), 8.4 ~ 7.3 (br, 2H), 7.4 ~ 6.2 (br, 5H), 5.2 ~ 3.7 (br, 6H), 2.0 (br, 3H), 2.7 ~ -0.4 (br, 12H) (ppm)

[0093] (Synthesis Example 1G) The synthesis was carried out in substantially the same manner as the synthesis of Synthesis Example 1B, except that Synthesis Example 1F was used instead of Synthesis Example 1A, and 0.2 g of a white solid was obtained.

[0094] １ ¹H NMR spectroscopy confirmed that the product was poly([butylimidazolium ethyl methacrylate][benzoate]-co-styrene). １ H NMR (500MHz, DMSO-d ６ ​​): δ = 10.2 to 9.4 (br, 1H), 8.1 to 7.5 (br, 2H), 7.8 (m, 2H), 7.4 to 6.4 (br, 5H), 7.2 (m, 1H), 7.2 (m, 2H), 4.9 to 3.2 (br, 6H), 1.7 (br, 3H), 2.7 to -0.3 (br, 12H) (ppm)

[0095] (3-4) Synthesis Examples 2A to 2C Synthesis Examples 2A to 2C are polymer compounds obtained using precursor 2 as a raw material. Synthesis Examples 2A to 2C are represented by general formula (8). m and n are each independent integers between 10 and 200. In Synthesis Example 2A, L ２ This is an iodide ion, and in synthesis example 2B, L ２ This is a benzoate ion, and in synthesis example 2C, L ２ This is the hexafluoroantimonate ion.

[0096] (Synthesis Example 2A) The synthesis was carried out in substantially the same manner as in Synthesis Example 1A, except that precursor 2 was used instead of precursor 1, and 2.1 g of a white solid was obtained.

[0097] １ ¹H NMR spectroscopy confirmed that the product was poly([dimethylimidazolium ethyl methacrylate][iodide]-co-p-methylstyrene). １ H NMR (500MHz, DMSO-d ６ ): δ = 7.9 to 7.3 (br, 2H), 7.3 to 6.2 (br, 4H), 5.1 to 3.1 (br, 7H), 2.8 to -0.4 (br, 14H) (ppm)

[0098] (Synthesis Example 2B) The synthesis was carried out in substantially the same manner as in Synthesis Example 1B, except that Synthesis Example 2A was used instead of Synthesis Example 1A, and N,N-dimethylformamide was used instead of dimethyl sulfoxide, yielding 0.33 g of solid. The anion conversion rate was 100%.

[0099] １ ¹H NMR spectroscopy confirmed that the product was poly([dimethylimidazolium ethyl methacrylate][benzoate]-co-p-methylstyrene). １ ​​H NMR (500MHz, DMSO-d ６ ): δ = 9.0 to 5.8 (br, 11H), 5.4 to 2.9 (br, 7H), 2.9 to -2.0 (br, 14H) (ppm)

[0100] (Synthesis Example 2C) The synthesis was carried out in substantially the same manner as in Synthesis Example 2B, except that sodium hexafluoroantimonate was used instead of sodium benzoate, and 0.70 g of solid was obtained. The anion conversion rate was 89%.

[0101] １ ¹H NMR spectroscopy confirmed that the product was poly([dimethylimidazolium ethyl methacrylate][hexafluoroantimonate]-co-p-methylstyrene). １ H NMR (500MHz, DMSO-d ６ ): δ = 7.9 to 7.2 (br, 2H), 7.2 to 6.0 (br, 4H), 5.0 to 2.9 (br, 7H), 2.8 to -0.4 (br, 14H) (ppm)

[0102] (3-5) Synthesis Examples 3A and 3B Synthesis Examples 3A and 3B are polymer compounds obtained using precursor 3 as a raw material. Synthesis Examples 3A and 3B are represented by general formula (9). m and n are each independent integers between 10 and 200. In Synthesis Example 3A, L ２ This is an iodide ion, and in synthesis example 3B, L ２ This is a benzoate ion.

[0103] (Synthesis Example 3A) The synthesis was carried out in substantially the same manner as in Synthesis Example 1A, except that precursor 3 was used instead of precursor 1, and 1.0 g of solid was obtained.

[0104] １ ¹H NMR spectroscopy confirmed that the product was poly([dimethylimidazolium ethyl acrylate][iodide]-co-styrene). １ H NMR (500MHz, DMSO-d ６ ): δ = 7.8 to 6.0 (br, 7H), 4.9 to 3.1 (br, 7H), 3.0 to 0.4 (br, 9H) (ppm)

[0105] ​​(Synthesis Example 3B) The synthesis was carried out in substantially the same manner as in Synthesis Example 2B, except that Synthesis Example 3A was used instead of Synthesis Example 2A, and 0.35 g of solid was obtained. The anion conversion rate was 100%.

[0106] １ ¹H NMR spectroscopy confirmed that the product was poly([dimethylimidazolium ethyl acrylate][benzoate]-co-styrene). １ H NMR (500MHz, DMSO-d ６ ): δ = 8.5 to 6.0 (br, 12H), 4.7 to 2.8 (br, 7H), 2.7 to 0.5 (br, 9H) (ppm)

[0107] (3-6) Synthesis Examples 3C and 3D Synthesis Examples 3C and 3D are polymer compounds obtained using precursor 3 as a raw material. Synthesis Examples 3C and 3D are represented by general formula (10). m and n are each independent integers between 10 and 200. In Synthesis Example 3C, L ２ This is an iodide ion, and in synthesis example 3D, L ２ This is a benzoate ion.

[0108] (Synthesis Example 3C) The synthesis was carried out in substantially the same manner as in Synthesis Example 3A, except that 1-butylimidazole was used instead of 1,2-dimethylimidazole, and 5.1 g of solid was obtained.

[0109] １ ¹H NMR spectroscopy confirmed that the product was poly([butylimidazolium ethyl acrylate][iodide]-co-styrene). １ H NMR (500MHz, DMSO-d ６ ): δ = 9.4 to 8.9 (br, 1H), 8.1 to 6.3 (br, 7H), 4.9 to 3.6 (br, 6H), 2.6 to 0.5 (br, 13H) (ppm)

[0110] (Synthesis Example 3D) The synthesis was carried out in substantially the same manner as the synthesis of Synthesis Example 2B, except that Synthesis Example 3C was used instead of Synthesis Example 2A, and 0.43 g of solid was obtained. The anion conversion rate was 95%.

[0111] １ ​​​¹H NMR spectroscopy confirmed that the product was poly([butylimidazolium ethyl acrylate][benzoate]-co-styrene). １ H NMR (500MHz, DMSO-d ６ ): δ = 10.5 to 9.3 (br, 1H), 8.9 to 6.3 (br, 12H), 5.0 to 3.0 (br, 6H), 2.5 to 0.6 (br, 13H) (ppm)

[0112] (3-7) Synthesis Examples 4A to 4D Synthesis Examples 4A to 4D are polymer compounds obtained using precursors as raw materials. Synthesis Examples 4A to 4D are represented by general formula (11). n is an integer between 10 and 200. In Synthesis Example 4A, L ２ This is an iodide ion, and in synthesis example 4B, L ２ This is a benzoate ion, and in synthesis example 4C, L ２ This is a hexafluorophosphate ion, and in synthesis example 4D, L ２ It is the tetrafluoroborate ion.

[0113] (Synthesis Example 4A) In a nitrogen-filled three-necked flask, 1.5 g of precursor 4 (Lot 1) synthesized above and 15 mL of anhydrous N,N-dimethylformamide were added, and the mixture was stirred until precursor 4 dissolved in the anhydrous N,N-dimethylformamide. Then, 4.9 g of 1,2-dimethylimidazole and 7.6 g of sodium iodide were added, and the mixture was heated to an internal temperature of 80°C and stirred for 8 hours while maintaining the temperature. After cooling to room temperature, a small amount of water was added and stirred, and the solution was placed in a cellulose tubing for dialysis, with both ends clipped. The cellulose tubing containing the solution was placed in a beaker filled with deionized water as a buffer, and dialysis was performed while gently stirring. The deionized water in the buffer was replaced as needed, and dialysis was performed for 96 hours. Then, the contents of the cellulose tubing were placed in a flask, the solvent and other substances were removed by vacuum distillation, and the mixture was dried to obtain 2.2 g of solid. The anion conversion rate was 98%.

[0114] １ ¹H NMR spectroscopy confirmed that the product is poly([dimethylimidazolium ethyl methacrylate][iodide]).​１ H NMR (500MHz, DMSO-d ６ ): δ = 8.2 ~ 7.5 (br, 2H), 5.4 ~ 3.6 (br, 7H), 3.1 ~ 2.5 (br, 3H), 2.3 ~ -0.4 (br, 5H) (ppm)

[0115] (Synthesis Example 4B) The synthesis was carried out in substantially the same manner as in Synthesis Example 2B, except that Synthesis Example 4A was used instead of Synthesis Example 2A, and 0.47 g of solid was obtained. The anion conversion rate was 88%.

[0116] １ ¹H NMR spectroscopy confirmed that the product is poly([dimethylimidazolium ethyl methacrylate][benzoate]). １ H NMR (500MHz, DMSO-d ６ ): δ = 8.3 to 7.7 (br, 4H), 7.4 to 7.0 (br, 3H), 5.1 to 3.6 (br, 7H), 2.9 to 2.3 (br, 3H), 2.2 to -0.4 (br, 5H) (ppm)

[0117] (Synthesis Example 4C) The synthesis was carried out in substantially the same manner as in Synthesis Example 4B, except that potassium hexafluorophosphate was used instead of sodium benzoate, and 0.51 g of solid was obtained. The anion conversion rate was 99%.

[0118] １ ¹H NMR spectroscopy confirmed that the product was poly([dimethylimidazolium ethyl methacrylate][hexafluorophosphate]). １ H NMR (500MHz, DMSO-d ６ ): δ = 7.9 to 7.2 (br, 2H), 5.4 to 3.5 (br, 7H), 2.9 to 2.2 (br, 3H), 2.1 to -1.0 (br, 5H) (ppm)

[0119] (Synthesis Example 4D) The synthesis was carried out in substantially the same manner as in Synthesis Example 4B, except that sodium tetrafluoroborate was used instead of sodium benzoate, and 0.24 g of solid was obtained. The anion conversion rate was 93%.

[0120] １ ​​​¹H NMR spectroscopy confirmed that the product is poly([dimethylimidazolium ethyl methacrylate][tetrafluoroborate]). １ H NMR (500MHz, DMSO-d ６ ): δ = 8.1 ~ 7.2 (br, 2H), 5.8 ~ 3.4 (br, 7H), 2.9 ~ 2.3 (br, 3H), 2.1 ~ -1.0 (br, 5H) (ppm)

[0121] (3-8) Synthesis Examples 4E to 4G Synthesis Examples 4E to 4G are polymer compounds obtained using precursor 4 as a raw material. Synthesis Examples 4E to 4G are represented by general formula (12). n is an integer between 10 and 200. In Synthesis Example 4E, L ２ This is an iodide ion, and in synthesis example 4F, L ２ This is a benzoate ion, and in synthesis example 4G, L ２ This is the hexafluoroantimonate ion.

[0122] (Synthesis Example 4E) The synthesis was carried out in substantially the same manner as in Synthesis Example 4A, except that 1-butylimidazole was used instead of 1,2-dimethylimidazole, and 4.0 g of a white solid was obtained. The anion conversion rate was 99%.

[0123] １ ¹H NMR spectroscopy confirmed that the product is poly([butylimidazolium ethyl methacrylate][iodide]). １ H NMR (500MHz, DMSO-d ６ ): δ = 10.0 to 9.2 (br, 1H), 8.4 to 7.7 (br, 2H), 5.5 to 3.8 (br, 6H), 2.3 to -0.2 (br, 12H) (ppm)

[0124] (Synthesis Example 4F) The synthesis was carried out in substantially the same manner as the synthesis of Synthesis Example 2B, except that Synthesis Example 4E was used instead of Synthesis Example 2A, and 0.60 g of solid was obtained. The anion conversion rate was 93%.

[0125] １ ¹H NMR spectroscopy confirmed that the product is poly([butylimidazolium ethyl methacrylate][benzoate]).​​１ H NMR (500MHz, DMSO-d ６ ): δ = 10.8 ~ 9.8 (br, 1H), 9.2 ~ 6.4 (br, 7H), 5.3 ~ 3.8 (br, 6H), 2.2 ~ -0.1 (br, 12H) (ppm)

[0126] (Synthesis Example 4G) The synthesis was carried out in substantially the same manner as in Synthesis Example 4F, except that sodium hexafluoroantimonate was used instead of sodium benzoate, and 0.45 g of solid was obtained. The anion conversion rate was 84%.

[0127] １ ¹H NMR spectroscopy confirmed that the product was poly([butylimidazolium ethyl methacrylate][hexafluoroantimonate]). １ H NMR (500MHz, DMSO-d ６ ): δ = 10.0 to 9.0 (br, 1H), 8.2 to 7.5 (br, 2H), 6.2 to 3.7 (br, 6H), 2.3 to -0.4 (br, 12H) (ppm)

[0128] (3-9) Synthesis Examples 4H to 4K Synthesis Examples 4H to 4K are polymer compounds obtained using precursor 4 as a raw material. Synthesis Examples 4H to 4K are represented by general formula (13). In the formula, n is an integer from 10 to 200. In Synthesis Example 4H, L ２ This is an iodide ion, and in synthesis example 4I, L ２ This is a tetrafluoroborate ion, and in synthesis example 4J, L ２ This is a hexafluorophosphate ion, and in synthesis example 4K, L ２ This is the hexafluoroantimonate ion.

[0129] ​(Synthesis Example 4H) In a three-necked flask purged with nitrogen, 2.5 g of precursor 4 (Lot 2) synthesized above and 25 mL of anhydrous N,N-dimethylformamide were added and stirred until precursor 4 dissolved in the anhydrous N,N-dimethylformamide. Then, 7.0 g of pyridine and 12.6 g of sodium iodide were added and the mixture was heated to an internal temperature of 80°C, and stirred for 5 hours while maintaining the temperature. After cooling to room temperature, a small amount of water was added and stirred, and the solution was placed in a cellulose tubing for dialysis, with both ends clipped. The cellulose tubing containing the solution was placed in a beaker filled with deionized water as a buffer, and dialysis was performed while gently stirring. The deionized water buffer was replaced as needed, and dialysis was performed for 24 hours. Then, the contents of the cellulose tubing were placed in a flask, the solvent and other substances were removed by vacuum distillation, and the mixture was dried to obtain 4.1 g of solid. The anion conversion rate was 95%.

[0130] １ ¹H NMR spectroscopy confirmed that the product is poly([pyridinium ethyl methacrylate][iodide]). １ H NMR (500MHz, DMSO-d ６ ): δ = 9.7 to 9.1 (br, 2H), 9.0 to 8.6 (br, 1H), 8.6 to 8.1 (br, 2H), 6.0 to 3.6 (br, 4H), 2.3 to -0.8 (br, 5H) (ppm)

[0131] (Synthesis Example 4I) 0.75 g of Synthesis Example 4H and 7.5 mL of N,N-dimethylformamide were added to a beaker and stirred until dissolved. An aqueous solution of 1.3 g of sodium tetrafluoroborate with deionized water was gradually added to the beaker and stirred at room temperature for 90 minutes. The solution was placed in a cellulose tubing for dialysis, and both ends were secured with clips. The cellulose tubing containing the solution was then placed in a beaker filled with deionized water as a buffer, and dialysis was performed while gently stirring. The deionized water buffer was replaced as needed, and dialysis was performed for a total of 24 hours. The solid precipitated in the solution in the tubing was filtered, and the solid on the filter paper was dried to obtain 0.42 g of solid. The conversion rate of anions was 92%.

[0132] １ ​​¹H NMR spectroscopy confirmed that the product is poly([pyridinium ethyl methacrylate][tetrafluoroborate]). １ H NMR (500MHz, DMSO-d ６ ): δ = 9.4 to 8.9 (br, 2H), 8.8 to 8.5 (br, 1H), 8.5 to 8.0 (br, 2H), 5.6 to 3.5 (br, 4H), 2.3 to -0.7 (br, 5H) (ppm)

[0133] (Synthesis Example 4J) The synthesis was carried out in substantially the same manner as in Synthesis Example 4I, except that potassium hexafluorophosphate was used instead of sodium tetrafluoroborate, and 0.41 g of solid was obtained. The anion conversion rate was 100%.

[0134] １ ¹H NMR spectroscopy confirmed that the product is poly([pyridinium ethyl methacrylate][hexafluorophosphate]). １ H NMR (500MHz, DMSO-d ６ ): δ = 9.4 to 8.9 (br, 2H), 8.8 to 8.5 (br, 1H), 8.5 to 8.0 (br, 2H), 5.5 to 3.6 (br, 4H), 2.3 to -0.6 (br, 5H) (ppm)

[0135] (Synthesis Example 4K) The synthesis was carried out in substantially the same manner as in Synthesis Example 4I, except that sodium hexafluoroantimonate was used instead of sodium tetrafluoroborate, and 0.56 g of solid was obtained. The anion conversion rate was 87%.

[0136] １ ¹H NMR spectroscopy confirmed that the product was poly([pyridinium ethyl methacrylate][hexafluoroantimonate]). １ H NMR (500MHz, DMSO-d ６ ): δ = 9.6 to 8.9 (br, 2H), 8.8 to 8.5 (br, 1H), 8.5 to 8.0 (br, 2H), 5.5 to 3.5 (br, 4H), 2.3 to -0.7 (br, 5H) (ppm)

[0137] ​​(3-10) Synthesis Examples 4L to 4O Synthesis Examples 4L to 4O are polymer compounds obtained using precursor 4 as a raw material. Synthesis Examples 4L to 4O are represented by general formula (14). In the formula, n is an integer from 10 to 200. In Synthesis Example 4L, L ２ This is an iodide ion, and in synthesis example 4M, L ２ This is a tetrafluoroborate ion, and in synthesis example 4N, L ２ This is a benzoate ion, and in synthesis example 4O, L ２ This is a thiocyanate ion.

[0138] (Synthesis Example 4L) The synthesis was carried out in substantially the same manner as in Synthesis Example 4H, except that triethylamine was used instead of pyridine. However, lot 3 was used for precursor 4 instead of lot 2. 2.9 g of solid was obtained as the product. The anion conversion rate was 97%.

[0139] １ ¹H NMR spectroscopy confirmed that the product is poly([triethylammonium ethyl methacrylate][iodide]). １ H NMR (500MHz, DMSO-d ６ ): δ = 5.3 to 2.9 (br, 10H), 2.3 to 0.0 (br, 14H) (ppm)

[0140] (Synthesis Example 4M) The synthesis was carried out in substantially the same manner as the synthesis of Synthesis Example 4I, except that Synthesis Example 4L was used instead of Synthesis Example 4H, and 0.36 g of solid was obtained. The anion conversion rate was 93%.

[0141] １ ¹H NMR spectroscopy confirmed that the product is poly([triethylammonium ethyl methacrylate][tetrafluoroborate]). １ H NMR (500MHz, DMSO-d ６ ): δ = 5.1 to 2.9 (br, 10H), 2.4 to 0.5 (br, 14H) (ppm)

[0142] ​​(Synthesis Example 4N) The synthesis was carried out in substantially the same manner as in Synthesis Example 4M, except that sodium benzoate was used instead of sodium tetrafluoroborate, and 0.49 g of solid was obtained. The anion conversion rate was 87%.

[0143] １ ¹H NMR spectroscopy confirmed that the product is poly([triethylammonium ethyl methacrylate][benzoate]). １ H NMR (500MHz, DMSO-d ６ ): δ = 8.4 ~ 7.6 (br, 2H), 7.6 ~ 6.9 (br, 3H), 5.1 ~ 2.8 (br, 10H), 2.3 ~ -0.1 (br, 14H) (ppm)

[0144] (Synthesis Example 4O) The synthesis was carried out in substantially the same manner as in Synthesis Example 4M, except that potassium thiocyanate was used instead of sodium tetrafluoroborate, and 0.52 g of solid was obtained. The anion conversion rate was 92%.

[0145] １ ¹H NMR spectroscopy confirmed that the product is poly([triethylammonium ethyl methacrylate][thiocyanate]). １ H NMR (500MHz, DMSO-d ６ ): δ = 5.5 to 2.9 (br, 10H), 2.4 to -0.1 (br, 14H) (ppm)

[0146] (3-11) Synthesis Examples 4P and 4Q Synthesis Examples 4P and 4Q are polymer compounds obtained using precursor 4 as a raw material. Synthesis Examples 4P and 4Q are represented by general formula (15). In the formula, n is an integer from 10 to 200. In Synthesis Example 4P, L ２ This is an iodide ion, and in synthesis example 4Q, L ２ It is the tetrafluoroborate ion.

[0147] ​​(Synthesis Example 4P) The synthesis was carried out in substantially the same manner as in Synthesis Example 4H, except that 1-methylpyrrolidine was used instead of pyridine, and the reaction temperature was changed to 65°C. However, lot 4 was used instead of lot 2 for precursor 4. 1.5 g of solid was obtained as the product. The conversion rate of the anion was 95%.

[0148] １ ¹H NMR spectroscopy confirmed that the product is poly([1-methylpyrrolidinium ethyl methacrylate][iodide]). １ H NMR (500MHz, DMSO-d ６ ): δ = 5.8 ~ 2.9 (br, 11H), 2.5 ~ -0.4 (br, 9H) (ppm)

[0149] (Synthesis Example 4Q) The synthesis was carried out in substantially the same manner as the synthesis of Synthesis Example 4I, except that Synthesis Example 4P was used instead of Synthesis Example 4H, and 0.20 g of solid was obtained. The anion conversion rate was 82%.

[0150] １ ¹H NMR spectroscopy confirmed that the product is poly([1-methylpyrrolidinium ethyl methacrylate][tetrafluoroborate]). １ H NMR (500MHz, DMSO-d ６ ): δ = 5.7 to 2.8 (br, 11H), 2.4 to 0.0 (br, 9H) (ppm)

[0151] (3-12) Synthesis Examples 4R to 4V Synthesis Examples 4R to 4V are polymer compounds obtained using precursor 4 as a raw material. Synthesis Examples 4R to 4V are represented by general formula (16). In the formula, n is an integer from 10 to 200. In Synthesis Example 4R, L ２ This is an iodide ion, and in synthesis example 4S, L ２ This is a tetrafluoroborate ion, and in synthesis example 4T, L ２ This is a hexafluoroantimonate ion, and in synthesis example 4U, L ２ This is a benzoate ion, and in synthesis example 4V, L ２ This is a thiocyanate ion.

[0152] ​​(Synthesis Example 4R) The synthesis was carried out in substantially the same manner as in Synthesis Example 4H, except that 1-methylpiperidine was used instead of pyridine. However, lot 4 was used for precursor 4 instead of lot 2. 3.2 g of solid was obtained as the product. The anion conversion rate was 99%.

[0153] １ ¹H NMR spectroscopy confirmed that the product is poly([1-methylpiperidinium ethyl methacrylate][iodide]). １ H NMR (500MHz, DMSO-d ６ ): δ = 5.6 to 2.8 (br, 11H), 2.7 to -1.3 (br, 11H) (ppm)

[0154] (Synthesis Example 4S) The synthesis was carried out in substantially the same manner as the synthesis of Synthesis Example 4I, except that Synthesis Example 4R was used instead of Synthesis Example 4H, and 0.28 g of solid was obtained. The anion conversion rate was 89%.

[0155] １ ¹H NMR spectroscopy confirmed that the product is poly([1-methylpiperidinium ethyl methacrylate][tetrafluoroborate]). １ H NMR (500MHz, DMSO-d ６ ): δ = 5.4 ~ 2.7 (br, 11H), 2.4 ~ -0.8 (br, 11H) (ppm)

[0156] (Synthesis Example 4T) The synthesis was carried out in substantially the same manner as in Synthesis Example 4S, except that sodium hexafluoroantimonate was used instead of sodium tetrafluoroborate, and 0.21 g of solid was obtained. The anion conversion rate was 93%.

[0157] １ ¹H NMR spectroscopy confirmed that the product was poly([1-methylpiperidinium ethyl methacrylate][hexafluoroantimonate]). １ H NMR (500MHz, DMSO-d ６ ): δ = 5.1 to 2.9 (br, 11H), 2.4 to 0.1 (br, 11H) (ppm)

[0158] ​​​(Synthesis Example 4U) The synthesis was carried out in substantially the same manner as in Synthesis Example 4S, except that sodium benzoate was used instead of sodium tetrafluoroborate, and 0.23 g of solid was obtained. The anion conversion rate was 87%.

[0159] １ ¹H NMR spectroscopy confirmed that the product is poly([1-methylpiperidinium ethyl methacrylate][benzoate]). １ H NMR (500MHz, DMSO-d ６ ): δ = 8.3 to 7.7 (br, 2H), 7.6 to 7.1 (br, 3H), 5.8 to 2.9 (br, 11H), 2.6 to -0.1 (br, 11H) (ppm)

[0160] (Synthesis Example 4V) The synthesis was carried out in substantially the same manner as in Synthesis Example 4S, except that potassium thiocyanate was used instead of sodium tetrafluoroborate, and 0.36 g of solid was obtained. The anion conversion rate was 93%.

[0161] １ ¹H NMR spectroscopy confirmed that the product is poly([1-methylpiperidinium ethyl methacrylate][thiocyanate]). １ H NMR (500MHz, DMSO-d ６ ): δ = 5.1 to 2.9 (br, 11H), 2.4 to 0.1 (br, 11H) (ppm)

[0162] (3-13) Synthesis Examples 4W and 4X Synthesis Examples 4W and 4X are polymer compounds obtained using precursor 4 as a raw material. Synthesis Examples 4W and 4X are represented by general formula (17). In the formula, n is an integer from 10 to 200. In Synthesis Example 4W, L ２ This is an iodide ion, and in synthesis example 4X, L ２ It is the tetrafluoroborate ion.

[0163] ​​(Synthesis Example 4W) The synthesis was carried out in substantially the same manner as in Synthesis Example 4H, except that 4,5-dimethylthiazole was used instead of pyridine. However, lot 5 was used for precursor 4 instead of lot 2. 2.4 g of solid was obtained as the product. The anion conversion rate was 99%.

[0164] １ ¹H NMR spectroscopy confirmed that the product is poly([4,5-dimethylthiazolium ethyl methacrylate][iodide]). １ H NMR (500MHz, DMSO-d ６ ): δ = 11.0 ~ 9.8 (br, 1H), 6.0 ~ 3.7 (br, 4H), 3.7 ~ 2.3 (br, 6H), 2.0 ~ 0.0 (br, 5H) (ppm)

[0165] (Synthesis Example 4X) The synthesis was carried out in substantially the same manner as the synthesis of Synthesis Example 4I, except that Synthesis Example 4W was used instead of Synthesis Example 4H, and 0.48 g of solid was obtained. The anion conversion rate was 83%.

[0166] １ ¹H NMR spectroscopy confirmed that the product is poly([4,5-dimethylthiazolium ethyl methacrylate][tetrafluoroborate]). １ H NMR (500MHz, DMSO-d ６ ): δ = 10.5 ~ 9.8 (br, 1H), 5.8 ~ 3.7 (br, 4H), 3.7 ~ 2.3 (br, 6H), 2.2 ~ -0.3 (br, 5H) (ppm)

[0167] (3-14) Synthesis Examples 4Y and 4Z Synthesis Examples 4Y and 4Z are polymer compounds obtained using precursor 4 as a raw material. Synthesis Examples 4Y and 4Z are represented by general formula (18). In the formula, n is an integer from 10 to 200. In Synthesis Example 4Y, L ２ This is an iodide ion, and in synthesis example 4Z, L ２ It is the tetrafluoroborate ion.

[0168] ​​(Synthesis Example 4Y) The synthesis was carried out in substantially the same manner as in Synthesis Example 4H, except that 1-methylbenzimidazole was used instead of pyridine. However, lot 6 was used for precursor 4 instead of lot 2. 3.5 g of solid was obtained as the product. The anion conversion rate was 99%.

[0169] １ ¹H NMR spectroscopy confirmed that the product is poly([1-methylbenzimidazolium ethyl methacrylate][iodide]). １ H NMR (500MHz, DMSO-d ６ ): δ = 10.7 to 9.7 (br, 1H), 8.7 to 7.6 (br, 4H), 6.3 to 3.6 (br, 7H), 2.5 to -1.7 (br, 5H) (ppm)

[0170] (Synthesis Example 4Z) The synthesis was carried out in substantially the same manner as the synthesis of Synthesis Example 4I, except that Synthesis Example 4Y was used instead of Synthesis Example 4H, and 0.45 g of solid was obtained. The anion conversion rate was 92%.

[0171] １ ¹H NMR spectroscopy confirmed that the product is poly([1-methylbenzimidazolium ethyl methacrylate][tetrafluoroborate]). １ H NMR (500MHz, DMSO-d ６ ): δ = 10.2 ~ 9.3 (br, 1H), 9.1 ~ 7.4 (br, 4H), 6.4 ~ 3.6 (br, 7H), 2.4 ~ -2.0 (br, 5H) (ppm)

[0172] (3-15) Synthesis Examples 5A and 5B Synthesis Examples 5A and 5B are polymer compounds obtained using precursor 5 as a raw material. Synthesis Examples 5A and 5B are represented by general formula (19). n is an integer between 10 and 200. In Synthesis Example 5A, L ２ This is an iodide ion, and in synthesis example 5B, L ２ This is the hexafluorophosphate ion.

[0173] ​​(Synthesis Example 5A) The synthesis was carried out in substantially the same manner as in Synthesis Example 4A, except that precursor 5 was used instead of precursor 4, and 2.6 g of solid was obtained. The anion conversion rate was 98%.

[0174] １ ¹H NMR spectroscopy confirmed that the product is poly([dimethylimidazolium ethyl acrylate][iodide]). １ H NMR (500MHz, DMSO-d ６ ): δ = 8.3 to 7.6 (br, 2H), 4.9 to 3.3 (br, 7H), 3.0 to 0.8 (br, 6H) (ppm)

[0175] (Synthesis Example 5B) The synthesis was carried out in substantially the same manner as the synthesis of Synthesis Example 4C, except that Synthesis Example 5A was used instead of Synthesis Example 4A, and 0.53 g of solid was obtained. The anion conversion rate was 99%.

[0176] １ ¹H NMR spectroscopy confirmed that the product was poly([dimethylimidazolium ethyl acrylate][hexafluorophosphate]). １ H NMR (500MHz, DMSO-d ６ ): δ = 8.2 to 7.4 (br, 2H), 5.0 to 3.2 (br, 7H), 2.9 to 0.8 (br, 6H) (ppm)

[0177] (3-16) Synthesis Examples 6A and 6B Synthesis Examples 6A and 6B are polymer compounds obtained using precursor 6 as a raw material. Synthesis Examples 6A and 6B are represented by general formula (20). In the formula, n is an integer from 10 to 200. In Synthesis Example 6A, L ２ This is an iodide ion, and in synthesis example 6B, L ２ It is the tetrafluoroborate ion.

[0178] (Synthesis Example 6A) The synthesis was carried out in substantially the same manner as in Synthesis Example 4H, except that precursor 6 was used instead of precursor 4, trimethylamine (N,N-dimethylformamide solution) was used instead of pyridine, sodium iodide was omitted, and the reaction temperature was changed to room temperature, yielding 0.83 g of solid. The anion conversion rate was 94%.​​

[0179] １ ¹H NMR spectroscopy confirmed that the product is poly([trimethylammonium ethyl methacrylate][iodide]). １ H NMR (500MHz, DMSO-d ６ ): δ = 5.3 to 2.9 (br, 13H), 2.4 to -1.1 (br, 5H) (ppm)

[0180] (Synthesis Example 6B) The synthesis was carried out in substantially the same manner as the synthesis of Synthesis Example 4I, except that Synthesis Example 6A was used instead of Synthesis Example 4H, and dimethyl sulfoxide was used instead of N,N-dimethylformamide, and 0.53 g of solid was obtained. The anion conversion rate was 96%.

[0181] １ ¹H NMR spectroscopy confirmed that the product is poly([trimethylammonium ethyl methacrylate][tetrafluoroborate]). １ H NMR (500MHz, DMSO-d ６ ): δ = 5.1 to 2.7 (br, 13H), 2.3 to 0.0 (br, 5H) (ppm)

[0182] (3-17) Comparative Synthesis Examples The comparative synthesis examples are polymer compounds represented by formula (21).

[0183] ​​In a nitrogen-purged three-necked flask, 34 mL of anhydrous toluene, 3.8 g of purified 2-chloroethyl vinyl ether, 4.8 g of anisaldehyde, and 4.7 g of 1,4-dioxane were added. The resulting solution was cooled to 5°C, 1 mL of 0.20 mol / L hexane solution of ethanesulfonic acid was added, and the mixture was stirred under ice for 5 minutes. Then, the mixture was cooled to -70°C, 1 mL of 0.20 mol / L gallium chloride solution was added, and the polymerization reaction was carried out by uniform stirring while maintaining the temperature at -70°C. After 7 hours, the reaction was stopped by adding 25 mL of methanol with a small amount of ammonia water added. The stopped solution was returned to room temperature, 100 mL of dichloromethane was added, and the mixture was washed with deionized water until neutral. After dehydration, the solvent and other substances were removed by vacuum distillation to obtain 8.9 g of a pale yellow oily component. The obtained crude product was repeatedly purified by reprecipitation to obtain 4.4 g of a white solid.

[0184] １ ¹H NMR spectroscopy confirmed that the obtained product was poly(2-chloroethyl vinyl ether-alt-p-methoxybenzaldehyde). The number-average molecular weight Mn of this compound was 9883, and the Mw / Mn ratio was 1.63.

[0185] In a nitrogen-purged three-necked flask, 4.4 g of the poly(2-chloroethyl vinyl ether-alt-p-methoxybenzaldehyde) synthesized above, 100 mL of anhydrous N,N-dimethylformamide, 9.9 g of 1,2-dimethylimidazole, and 15.4 g of sodium iodide were added, and the internal temperature was raised to 80°C. The mixture was then stirred while maintaining an internal temperature of around 80°C for 72 hours, after which it was cooled to room temperature. A small amount of water was added to the resulting reaction solution to dissolve all the solids, and the solution was then placed into a cellulose tubing for dialysis. The cellulose tubing containing the solution was placed in a beaker filled with deionized water as a buffer, and dialysis was performed while gently stirring. The deionized water buffer was replaced as needed, and dialysis was performed for a total of 24 hours. In this way, an aqueous solution of poly([2-dimethylimidazolium vinyl ether][iodide]-alt-p-methoxybenzaldehyde) with an iodine anion as a counterion was obtained.

[0186] ​To the aqueous solution of poly([2-dimethylimidazolium vinyl ether][iodide]-alt-p-methoxybenzaldehyde) obtained above, an aqueous solution of sodium tetrafluoroborate (an aqueous solution prepared by dissolving 4.5 g of sodium tetrafluoroborate in 30 mL of deionized water) was added dropwise. When a brown mass formed at the bottom, the dropwise addition was stopped, and the solution was placed in a cellulose tube. The cellulose tube containing the solution was placed in a beaker filled with deionized water, and dialysis was performed for a total of 24 hours while gently stirring. After that, the contents of the cellulose tube were placed in a flask, and the solvent and other substances were removed by vacuum distillation. The resulting light brown solid was vacuum dried at 50°C for 6 hours to obtain 1.9 g of light brown solid.

[0187] １ ¹H NMR spectroscopy confirmed that the product is poly([2-dimethylimidazolium vinyl ether][tetrafluoroborate]-alt-p-methoxybenzaldehyde). １ H NMR (500MHz, DMSO-d ６ ): δ = 7.7 to 7.4 (br, 2H), 7.4 to 6.5 (br, 4H), 4.4 to 2.6 (br, 6H), 3.7 (br, 3H), 3.4 (br, 6H), 2.7 to 1.4 (br, 2H) (ppm)

[0188] (4) Evaluation of the lower critical solution temperature Each polymer compound in the synthesis examples and comparative synthesis examples shown in Table 2 was dissolved in propylene carbonate to obtain a homogeneous solution with a concentration of 1% by mass. The temperature of each solution was increased while visually observing it, and if at least one of the phenomena of clouding of the solution and generation of particles in the solution was observed, the temperature at which the phenomenon was observed was identified as the lower critical solution temperature. The same tests were also performed when the solvent was a mixed solution of ethylene carbonate and diethyl carbonate (weight ratio 1:1), and when the solvent was a mixed solution of ethylene carbonate, diethyl carbonate, and ethyl methyl carbonate (weight ratio 1:1:1).

[0189] ​Figure 1 shows the propylene carbonate solution of Synthesis Example 4B at room temperature (Figure 1 left) and at around 128°C (Figure 1 right). At around room temperature, it was a homogeneous solution, while at around 128°C, it was a cloudy liquid due to phase separation. Since the temperature at which cloudiness occurred was 120°C, the lower critical solution temperature was determined to be 120°C.

[0190] Figure 2 shows the state of a solution obtained by dissolving Synthesis Example 4C in a mixed solution of ethylene carbonate, diethyl carbonate, and ethyl methyl carbonate (weight ratio 1:1:1) at room temperature (Figure 2 left) and at around 60°C (Figure 2 right). At around room temperature, it was a homogeneous solution, while at around 60°C, it was a cloudy liquid due to phase separation. Since the temperature at which cloudiness occurred was 40°C, the lower critical solution temperature was determined to be 40°C.

[0191] Other synthesis examples and comparative synthesis examples shown in Table 2 were also tested in the same manner as the examples in Figures 1 and 2. The test results for each combination of polymer compound and solvent are shown in Table 2. For combinations where a temperature value is indicated, that temperature is the lower critical solution temperature. "Soluble" indicates that a homogeneous solution was obtained but did not reach the lower critical solution temperature. "Insoluble" indicates that a homogeneous solution was not obtained, in which case heating was not performed. "PC" indicates propylene carbonate, "EC / DEC" indicates a mixed solution of ethylene carbonate and diethyl carbonate (weight ratio 1:1), and "EC / DEC / EMC" indicates a mixed solution of ethylene carbonate, diethyl carbonate, and ethyl methyl carbonate (weight ratio 1:1:1).

[0192] Table 2: Evaluation of lower critical solution temperature

[0193] [Other Embodiments] With regard to other configurations, the embodiments disclosed herein are illustrative in all respects, and it should be understood that the scope of the present invention is not limited thereto. Those skilled in the art will readily understand that modifications can be made as appropriate without departing from the spirit of the invention. Therefore, other embodiments modified without departing from the spirit of the invention are naturally included within the scope of the present invention.

Claims

1. A polymer compound that, when dissolved in a solvent containing a compound having a carbonate ester structure in its molecule, yields a solution with a lower critical solution temperature.

2. The molecule contains 10 to 500 units of the constituent unit A represented by formula (1) per molecule, R １ However, it is a hydrogen atom or a methyl group, Z １ However, it is -COO- or -OCO-, Z ２ However, it is an alkylene group having 1 to 8 carbon atoms, and L １ It is a cationic group and L ２ L is an anion, or １ It is an anionic group and L ２ The polymer compound according to claim 1, wherein is a cation.

3. As the constitutional unit A, all are constitutional units A represented by the formula (1) １ and constitutional unit A ２ are included, and the constitutional unit A １ and the constitutional unit A ２ differ from each other in that at least one of Z １ , Z ２ , L １ , and L ２ is different from each other. The polymer compound according to claim 2.

4. L １ It is an onium group and L ２ The polymer compound according to claim 2, wherein is an anion.

5. L １ The polymer compound according to claim 4, wherein the onium group is selected from the group consisting of a substituted or unsubstituted heterocyclium group, a substituted or unsubstituted ammonium group, a substituted or unsubstituted phosphonium group, and a substituted or unsubstituted sulfonium group, and the onium group is a group that includes one or more heteroatoms, at least one of the heteroatoms being a nitrogen atom, and at least one of a five-membered ring and a six-membered ring containing the heteroatoms.

6. L １ The polymer compound according to claim 5, wherein the onium group is selected from the group consisting of an imidazolium group, an imidazolinium group, an imidazolidinium group, a pyrazolium group, a pyrazolinium group, a pyrazolidinium group, an oxazolium group, an oxazolinium group, an oxazolidinium group, a thiazolium group, a thiazolinium group, a thiazolidinium group, a pyrrolium group, a pyrrolidinium group, a pyridinium group, a piperidinium group, a pyrazinium group, a piperadinium group, a pyrimidinium group, a pyridazinium group, a morpholinium group, a thiomorpholinium group, an ammonium group, a phosphonium group, and a sulfonium group, and is either substituted with an alkyl group having 1 to 4 carbon atoms or is unsubstituted.

7. L ２ The polymer compound according to claim 4, wherein the anion is selected from the group consisting of chloride ions, bromide ions, iodide ions, carboxylate ions, tetrafluoroborate ions, hexafluorophosphate ions, hexafluoroantimonate ions, bis(fluorosulfonyl)imide ions, bis(trifluoromethanesulfonyl)imide ions, trifluoromethanesulfonate ions, difluorophosphate ions, difluoro(oxalate)borate ions, and thiocyanate ions.

8. The molecule further contains 1 to 500 units of the constituent unit B represented by formula (2) per molecule, Z ３ However, -COOR ４ -, -OCOR ４ -, -OR ４ - A group selected from the group consisting of substituted or unsubstituted aliphatic chain hydrocarbon groups, substituted or unsubstituted alicyclic hydrocarbon groups, substituted or unsubstituted aromatic hydrocarbon groups, substituted or unsubstituted phenylalkylene groups, and substituted or unsubstituted heterocyclylene groups, R ２ However, R is a group selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group, and a phenyl group. ３ However, the group is selected from the group consisting of a hydrogen atom, a fluorine atom, a methyl group, a methoxy group, and a tert-butyl group, R ４ The polymer compound according to claim 2, wherein the group is selected from the group consisting of a single bond, an alkylene group, and a cycloalkylene group.

9. Z ３ However, -COOR ４ -, -OCOR ４ -, -OR ４ - A polymer compound according to claim 8, wherein the group is selected from the group consisting of a substituted or unsubstituted norborneylene group, a substituted or unsubstituted phenylene group, a substituted or unsubstituted phenylalkylene group, a substituted or unsubstituted imidazoylene group, and a substituted or unsubstituted pyridinylene group.

10. A composition comprising a polymer compound according to any one of claims 1 to 9, and a solvent containing a compound having a carbonate ester structure in its molecule, wherein the composition has a lower critical solution temperature.

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