JP6472079B2 - Gel structure with pores, method for producing the same, and use thereof - Google Patents

Description

  The present invention relates to a gel structure having pores, a method for producing the same, and use thereof.

  In recent years, an increase in temperature and abnormal weather have occurred due to the influence of global warming, and the cause is the influence of greenhouse gases such as carbon dioxide. On the other hand, various efforts to reduce greenhouse gases have been made, but the amount of carbon dioxide emissions is still increasing, and a large amount of carbon dioxide emissions due to the development of emerging countries are expected in the future. Therefore, the importance of methods for reducing carbon dioxide emissions is increasing.

  As a carbon dioxide emission reduction method, a so-called Carbon Capture and Storage method in which carbon dioxide is fixed and stored in the ground or sequestered in the ocean is attracting attention worldwide (Non-Patent Documents 1 and 2). Carbon dioxide immobilization methods, which are important steps in this method, are roughly classified into three methods: biochemical methods, physicochemical methods, and chemical methods. Among them, the physicochemical method is suitable for carbon dioxide recovery in plants such as thermal power generation, steel, and cement because of its high carbon dioxide recovery efficiency, and is useful for future industrial development.

  The physicochemical methods include membrane separation using the difference in the permeation rate of the membrane depending on the type of gas, adsorption separation using an inorganic porous material such as zeolite, and chemical adsorption using an organic base solution such as amine. (Non-patent Document 3).

  Among these, zeolite is widely used as an adsorbent for exhaust gas from thermal power plants and the like. However, when using zeolite, there has been a problem that a dehumidification step is indispensable as a pretreatment because water vapor in the exhaust gas inhibits the adsorption of carbon dioxide.

  As a means for solving the problem, a method is disclosed in which carbon dioxide is selectively adsorbed without being affected by water vapor by using a substance obtained by chemically modifying the inner surface of pores of a mesoporous substance with an amine (non-patent document). References 4-6).

  On the other hand, as shown in the following reaction formula (1), the present inventors have obtained a ladder-type macrocyclic compound (hereinafter, referred to as “rigid” and heat-stabilized) by a condensation reaction of resorcinol and 1,5-pentane dial. (Referred to as "Noria") and have been researching it (Non-Patent Document 7).

It is disclosed that a hydrophobic hole of 3.05 mm exists in the center of Noria and that carbon dioxide can be selectively adsorbed in the hole (Non-patent Document 8). Further, it is known that Rb ⁺ ions can be selectively included since the size of hydrophobic vacancies in Noria and the diameter of Rb ⁺ ions are in good agreement (Non-patent Document 9). Furthermore, since Noria is a polyfunctional compound having 24 hydroxyl groups (OH groups), various functionalizations are possible.

Ding, S.-Y. et al., Chem. Soc. Rev. 2013, 42, 548. IPPC Special Report on Carbon Dioxide Capture and Storage, Working Group, Cambride University Press, New York (2006). Inui Chiyuki, CO2 fixation and sequestration technology, 11 (2006). H. de Sainte Claire Deville et al., Seances Acad. Sci. 1862, 54, 324. Development of energy-saving CO2 separation and recovery technology: Development of new CO2 adsorbent using mesopores, Global Environmental Industrial Technology Research Organization (RITE) (issued in 2011) Fiscal 2010 Carbon Dioxide Recovery Technology Advancement Report, Global Environmental Industrial Technology Research Organization, March 2012 Michael Rousseas, et al., ACS Nano, 2013, 7 (10), pp 8540-8546. J. Tian, et al., Angew. Chem. Int. Ed., 48, 5492 (2009). H. Kudo et al., Angew.Chem.Int.Ed., 45, 7948 (2006).

  The technologies disclosed in Non-Patent Documents 4 to 6 use mesoporous silica whose inner surface is chemically modified with amine. However, since silica is used, it is assumed that it is difficult to modify the inner surface of the pores with various functional groups, and it is difficult to adopt a structure other than mesoporous silica in which the inner surface of the pores is chemically modified with an amine. It is estimated that. Therefore, it is estimated that the inclusion object is specialized in carbon dioxide.

  Therefore, the techniques disclosed in Non-Patent Documents 4 to 6 are considered to have room for improvement from the viewpoint of efficiently including various inclusion objects.

  On the other hand, as described above, the Noria can include carbon dioxide or metal in the pores. However, since the hole is a hydrophobic hole, it does not have a functional group in the hole, and it is difficult to introduce the functional group into the hole.

  For this reason, there are problems that the amount of carbon dioxide uptake (adsorption amount) is small, and there are few types of metal ions that can be included, and it is difficult to efficiently include various inclusion objects. It was.

  Under such circumstances, if the present inventor can introduce a functional group into the pores of the above-mentioned Noria, the inventor will not only include the inclusion target such as carbon dioxide but also the inclusion target within the pore. A chemical reaction with a functional group can be generated, and the selective inclusion of the inclusion object having the advantages of the physicochemical method and the advantage of the chemical method is possible. I came up with the idea that it would be possible to provide compounds that enable efficient and efficient inclusion.

  Therefore, the present inventor diligently studied and provided with pores obtained by detaching Noria by hydrolysis or the like from a polymer obtained by crosslinking Noria esterified with an unsaturated compound. It has been found that the gel structure can introduce functional groups into the pores while retaining the pores derived from Noria, and has completed the present invention.

  That is, the present invention includes the following inventions.

[1] From a polymer obtained by polymerizing and crosslinking an ester obtained by esterifying one or more hydroxyl groups of a compound represented by the following chemical formula (1) with an unsaturated compound, the chemical formula (1) A gel structure having pores, wherein one or more of the compounds represented is desorbed,
The gel structure includes pores formed by desorption of the compound represented by the chemical formula (1),
The said pore is equipped with the functional group derived from the said unsaturated compound in the inner wall of the said hole, The gel structure characterized by the above-mentioned.

  [2] The unsaturated compound includes carboxylic acid halide, 2-chloro-4- (vinylphenyl) acetamide, isocyanate styrene, diisocyanate, 2- (vinyloxy) ethyl methacrylate, and 4- (2-vinyloxy). 1) The gel structure according to [1], which is one or more unsaturated compounds selected from the group consisting of ethoxystyrene.

  [3] The gel structure according to [2], wherein the carboxylic acid halide is methacryloyl chloride.

  [4] Any one of [1] to [3], wherein the ester is obtained by esterifying 24 hydroxyl groups of the compound represented by the chemical formula (1) with an unsaturated compound. The gel structure according to any one of the above.

  [5] The gel structure according to any one of [1] to [4], wherein the crosslinking is performed with a polyfunctional crosslinking agent.

  [6] The gel structure according to [5], wherein the polyfunctional crosslinking agent is a bifunctional to tetrafunctional crosslinking agent.

  [7] The cross-linking agent is a compound represented by the following chemical formula (2), a compound represented by the following chemical formula (3) having a weight average molecular weight (Mw) of 1,000 to 50,000, or divinylbenzene. The gel structure according to any one of [1] to [6], which is characterized in that it exists.

  [8] The gel structure according to [7], wherein the cross-linking agent is a compound represented by the chemical formula (2) and is a compound having n = 6 in the chemical formula (2).

  [9] The gel according to any one of [1] to [8], wherein the functional group is one or more functional groups selected from the group consisting of a carboxy group, an amino group, and a hydroxyl group. Structure.

  [10] In any one of [5] to [9], the molar ratio of the ester to the crosslinking agent is 1.0: 3.0 to 1.0: 96.0. The gel structure described.

  [11] The gel structure according to [10], wherein the molar ratio is 1.0: 12.0 to 1.0: 24.0.

  [12] The gel structure according to any one of [1] to [11], wherein the pore has an inner diameter of 3 to 10 mm.

  [13] A metal clathrate, comprising the gel structure according to any one of [1] to [12] as an active ingredient and capable of clathrating metal.

  [14] A carbon dioxide adsorbent comprising the gel structure according to any one of [1] to [12] as an active ingredient and capable of adsorbing carbon dioxide.

  [15] A carbon dioxide separation membrane comprising the carbon dioxide adsorbent according to [14] formed thereon.

  [16] (i) a step of obtaining an ester by forming an ester bond between one or more of the hydroxyl groups included in the compound represented by the following chemical formula (1) and the unsaturated compound;

(Ii) obtaining a polymer by polymerizing and crosslinking the ester in the presence of a crosslinking agent;
(Iii) A step of dehydrating one or more compounds represented by the chemical formula (1) from the polymer by hydrolyzing the polymer to obtain a gel structure having pores. And a method for producing a gel structure.

  [17] The unsaturated compound includes carboxylic acid halide, 2-chloro-4- (vinylphenyl) acetamide, isocyanate styrene, diisocyanate, 2- (vinyloxy) ethyl methacrylate, and 4- (2-vinyloxy). ) The method for producing a gel structure according to [16], wherein the gel structure is one or more unsaturated compounds selected from the group consisting of ethoxystyrene.

  [18] The crosslinking agent is a compound represented by the following chemical formula (2), a compound represented by the following chemical formula (3) having a weight average molecular weight (Mw) of 1,000 to 50,000, or divinylbenzene The method for producing a gel structure according to [16] or [17], wherein

  [19] In any one of [16] to [18], the molar ratio of the ester to the crosslinking agent is 1.0: 3.0 to 1.0: 96.0. The manufacturing method of the gel structure of description.

  [20] The method for producing a gel structure according to [19], wherein the molar ratio is 1.0: 12.0 to 1.0: 24.0.

  [21] The method for producing a gel structure according to any one of [16] to [20], wherein the polymerization is performed by a solution polymerization method or a solid layer polymerization method.

  [22] The method for producing a gel structure according to any one of [16] to [21], wherein the unsaturated compound and the crosslinking agent are both diisocyanates.

  The gel structure having pores according to the present invention includes pores formed by elimination of Noria, and has functional groups that react with carbon dioxide and / or metal ions in the pores. Compared with conventional materials, the amount of carbon dioxide adsorbed can be increased, the types of metal ions that can be included (adsorbed) can be increased, and the selectivity can be greatly improved. .

FIG. 1 is an image diagram showing that pores are formed by the elimination of Noria from a polymer obtained by polymerizing and crosslinking an ester in which the hydroxyl group of Noria is esterified. FIG. 2 is a diagram showing an IR spectrum of the compound obtained in Production Example 1. FIG. 3 is a diagram showing a ¹ HNMR spectrum of the compound obtained in Production Example 1. FIG. 4 is a diagram showing an IR spectrum of the white solid obtained in Production Example 2. FIG. 5 is a diagram showing the ¹ HNMR spectrum of the white solid obtained in Production Example 2. FIG. 6 is a diagram showing an IR spectrum of the white solid obtained in Production Example 3. FIG. 7 is a diagram showing a ¹ HNMR spectrum of a white solid obtained in Production Example 3. FIG. 8 is a diagram showing an IR spectrum of the white solid obtained in Production Example 4. FIG. 9 is a diagram showing a ¹ HNMR spectrum of a white solid obtained in Production Example 4. FIG. 10 is a diagram showing an IR spectrum of the gel structure obtained in Production Example 7. FIG. 11 is a diagram showing an IR spectrum of the gel structure obtained in Production Example 10. FIG. 12 is a diagram showing an IR spectrum of the gel structure obtained in Production Example 14. FIG. 13 is a diagram showing an IR spectrum of the gel structure obtained in Example 1. 14 is a diagram showing an IR spectrum of a solid obtained from the soluble part in Example 1. FIG. 15 is a diagram showing a ¹ HNMR spectrum of a solid obtained from the soluble portion in Example 1. FIG. FIG. 16 is a diagram showing an IR spectrum of the gel structure obtained in Example 2. FIG. 17 is a diagram showing an IR spectrum of a solid obtained from the soluble part in Example 2. 18 is a diagram showing a ¹ HNMR spectrum of a solid obtained from the soluble portion in Example 2. FIG. FIG. 19 is a diagram showing an IR spectrum of the gel structure obtained in Example 4. FIG. 20 is a diagram showing an IR spectrum of a solid obtained from the soluble part in Example 4. FIG. 21 shows the ¹ HNMR spectrum of the solid obtained from the soluble part in Example 4. FIG. 22 is a diagram showing an IR spectrum of a gel structure obtained by polymerizing and crosslinking MMA and DMA obtained in Comparative Example 1. FIG. 23 is a diagram showing an IR spectrum of the gel structure after hydrolysis obtained in Comparative Example 1.

  Hereinafter, the present invention will be described in detail. However, the scope of the present invention is not limited to these descriptions, and other than the following examples, modifications and implementations can be made as appropriate without departing from the spirit of the present invention. .

  Unless otherwise specified in this specification, “A to B” indicating a numerical range means “A or more and B or less”. Further, “mass” and “weight”, “mass%” and “weight%” are treated as synonyms, and “inclusion” and “adsorption” are treated as synonyms.

[Embodiment 1: Gel structure with pores]
The gel structure having pores according to the present invention is obtained by polymerizing and crosslinking an ester in which one or more hydroxyl groups of a compound (Noria) represented by the following chemical formula (1) are esterified with an unsaturated compound. A gel structure having pores obtained by detaching one or more compounds represented by the chemical formula (1) from the polymer obtained by the above chemical formula (1). ), And the pores are gel structures each having a functional group derived from the unsaturated compound on the inner wall of the pores.

  The gel structure having pores according to the present invention is a gel structure obtained by detaching Noria after forming the polymer. Therefore, the pores corresponding to the size, shape, number, and the like of Noria Is maintained, and the inner wall of the pore is provided with a functional group derived from the unsaturated compound. Therefore, not only the inclusion object is included in the pores, but also a chemical reaction between the functional group and the inclusion object can be performed. It is also easy to change the functional group as appropriate according to the inclusion target by appropriately selecting the unsaturated compound according to the inclusion target.

  Therefore, it is possible to provide a gel structure that enables efficient inclusion corresponding to various inclusion targets.

  As described above, Noria is a ladder-type macrocyclic compound that is rigid and has thermal stability, and can be synthesized by the above-described conventionally known method (Non-Patent Document 7).

  Noria has 24 hydroxyl groups as shown in chemical formula (1). In the gel structure having pores according to the present invention, one or more of Noria is desorbed from a polymer obtained by polymerizing and crosslinking an ester in which one or more of the hydroxyl groups are esterified with an unsaturated compound. First, the polymer will be described.

  The “one or more of hydroxyl groups” means that any hydroxyl group may be used as long as it is one or more of the hydroxyl groups represented by the chemical formula (1). For example, when there is one hydroxyl group to be esterified, any hydroxyl group among the hydroxyl groups represented by chemical formula (1) may be used, and when there are two or more hydroxyl groups to be esterified, it is represented by chemical formula (1). Among the hydroxyl groups, any two or more hydroxyl groups may be used.

  The unsaturated compound has an unsaturated bond for polymerization and crosslinking. In addition, the unsaturated compound includes a functional group that can react with a hydroxyl group of Noria and form an ester bond, such as —X (X: halogen), an isocyanate group, and a C═C bond. In addition, the unsaturated compound includes, for example, carbon dioxide and / or metal ions when an ester with a hydroxyl group of Noria such as a carbonyl group, an isocyanate group, a vinyloxy group, an epoxy group, or an oxetanyl group is hydrolyzed. A functional group capable of reacting with the functional group.

  For example, the unsaturated compound includes a carboxylic acid halide, 2-chloro-4- (vinylphenyl) acetamide, isocyanate styrene, diisocyanate, 2- (vinyloxy) ethyl methacrylate, 4- (2-vinyloxy) ethoxy. Examples thereof include styrene, bisepoxy compounds, bisoxetane compounds, and the like.

  By using these unsaturated compounds, it is possible to provide functional groups derived from these unsaturated compounds on the inner walls of the pores of the gel structure. For example, when a carboxylic acid halide is used, a carboxy group can be provided on the inner wall. In consideration of the chemical reaction with the inclusion object, the inclusion efficiency of each inclusion object can be improved by providing a preferable functional group according to the inclusion object.

  The carboxylic acid halide may be any of carboxylic acid fluoride, carboxylic acid chloride, carboxylic acid bromide, and carboxylic acid iodide. Moreover, the said carboxylic acid halide may be used 1 type, and may use 2 or more types.

  The carboxylic acid constituting the carboxylic acid halide may be an unsaturated carboxylic acid, such as acrylic acid, propiolic acid, methacrylic acid, crotonic acid, oleic acid, maleic acid, fumaric acid and the like.

  The carboxylic acid halide is not particularly limited, but is preferably a carboxylic acid chloride from the viewpoint that it has high reactivity and can easily form an ester bond with the hydroxyl group, and methacryloyl chloride. It is more preferable that

  When the unsaturated compound is a diisocyanate, one isocyanate group functions as a group that forms an ester bond with the hydroxyl group of Noria, and after hydrolysis with the other isocyanate group, an amino group is formed on the inner wall of the pore. A group is believed to be formed.

  In Noria, one or more hydroxyl groups out of 24 hydroxyl groups are esterified. The esterified hydroxyl group can be a site to be crosslinked in the subsequent crosslinking polymerization. Therefore, it is preferable that the number of hydroxyl groups to be esterified is large from the viewpoint of easily forming a gel structure that is a polymer by cross-linking polymerization. Specifically, 10 or more are preferable, 15 or more are more preferable, 20 or more are more preferable, and all 24 are most preferably esterified.

  The esterification, polymerization, and crosslinking can be performed by a conventionally known general method as described in the section “Method for producing gel structure having pores” described later. Polymerization is performed by chain polymerization of unsaturated bonds of the unsaturated compound. The degree of polymerization is not particularly limited, but the higher the degree of polymerization, the better. Since the degree of polymerization is high, a large number of crosslinking points can be taken, and thus the structure of the gel structure can be strengthened by crosslinking. And it is preferable to strengthen the structure of the gel structure because the shape of the pores can be easily maintained after the removal of Noria from the polymer.

  In order to polymerize and crosslink the esterified Noria to form a polymer (gel structure), it is preferable to react the esterified Noria with a crosslinking agent.

  The cross-linking agent is not particularly limited as long as it is a compound that can cross-link with an unsaturated bond of an esterified hydroxyl group to form a polymer, but has a gel structure with pores according to an embodiment of the present invention. In order to appropriately synthesize the body, it is important to adjust the type of the crosslinking agent and the amount charged.

  That is, in order to synthesize a gel structure having pores according to an embodiment of the present invention, the detachment of Noria from the polymer obtained by reacting the esterified Noria with a crosslinking agent is performed. However, depending on the type (structure) of the polymer, there is a possibility that the Noria cannot be eliminated. In addition, there is a possibility that the structure of the polymer collapses due to the elimination of the Noria. Therefore, in order to maintain the structure of the gel structure and retain the pores immobilized in the gel structure when the Noria is detached, the type of the crosslinking agent and the amount charged therein It is important to make appropriate adjustments.

  In view of the above matters, in order to synthesize a gel structure having pores according to an embodiment of the present invention, the cross-linking agent is preferably a polyfunctional cross-linking agent, and is bifunctional. A tetrafunctional crosslinking agent is more preferable, and a bifunctional crosslinking agent is more preferable. The “polyfunctional crosslinking agent” refers to a crosslinking agent having two or more functional groups, and bifunctional to tetrafunctional crosslinking agents are also included in the multifunctional crosslinking agent.

  Examples of the bifunctional crosslinking agent include compounds represented by the following chemical formula (2), a chemical formula (3) having a weight average molecular weight (Mw) of 1,000 to 50,000, or divinylbenzene. It is done.

  When the compound represented by the above chemical formula (2) is used as the cross-linking agent, the pores are easily retained after hydrolysis in the finally obtained gel structure. Is preferably used.

  The molar ratio of an ester obtained by esterifying one or more hydroxyl groups of Noria with an unsaturated compound (also simply referred to as “ester”) and a crosslinking agent is 1.0: 3.0 to 1.0: 96: 0 is preferable, and 1.0: 12.0 to 1.0: 24.0 is particularly preferable.

  By satisfying the molar ratio, a gel structure in which the shape, size and number of vacancies formed by the desorption of Noria (corresponding to the number of used Noria) are substantially maintained after desorption, Since it is easy to obtain a gel structure having fixed pores, inclusion of carbon dioxide, metal, or the like can be performed efficiently.

  When the molar ratio is less than 1.0: 3.0, that is, when the molar ratio of the crosslinking agent to the ester is less than 3.0, it becomes water-soluble after the elimination of Noria, and the gel structure Since it is highly possible that it cannot be maintained, it is not preferable. For example, in the comparative example described later, when the molar ratio is 1: 2.4, when the polymer is hydrolyzed, it becomes a water-soluble liquid, and the gel state cannot be maintained.

  On the other hand, when the molar ratio exceeds 1.0: 96.0, that is, when the molar ratio of the crosslinking agent to the ester exceeds 96.0, there is a possibility that Noria cannot be eliminated. When Noria cannot be removed, it is not preferable because holes cannot be obtained and desired inclusion cannot be performed.

  The gel structure having pores according to the present invention is a gel structure in which one or more Noria is desorbed from the polymer, and the gel structure is a void formed by the desorption of Noria. With holes.

  The gel structure has holes corresponding to the shape, size, number, and the like of the detached Noria. From the viewpoint of more stably maintaining the shape, size, and number of the pores, the molar ratio of the ester to the cross-linking agent is preferably the ratio described above.

  The number of Noria desorbed from the polymer may be one or more, and may be appropriately adjusted in accordance with how much the inclusion target needs to be included. From the viewpoint of improving the inclusion efficiency, it is preferable that the number of nolia to be desorbed is larger, and it is most preferable to desorb all of the noria used for forming the gel structure.

  The desorption can be performed by hydrolysis of the polymer, as will be described later.

  The said hole with which the gel structure provided with the hole based on this invention is equipped with the functional group derived from the said unsaturated compound in the inner wall of the said hole. Here, FIG. 1 is an image diagram showing that pores are formed by the elimination of Noria from a polymer obtained by polymerizing and crosslinking an ester in which the hydroxyl group of Noria is esterified.

  As shown in FIG. 1, the ester is reduced by hydrolysis of the polymer, and when Noria is removed with the original hydroxyl group, it corresponds to the shape, size and number of Noria (one in FIG. 1). Thus, a gel structure including the fixed voids (denoted as “Noria mold void” in the drawing) is generated. And the said void | hole equips the inner wall of a void | hole with the functional group (hydroxyl group in FIG. 1) derived from the said unsaturated compound which had formed the ester bond with the hydroxyl group of Noria. The “fixed vacancies” refer to vacancies in which the shape, size, number, and the like of the vacancies formed by the detachment of Noria are maintained (preferably all) after the detachment.

  The “inner wall of the hole” means a part forming the space of the hole. For example, in FIG. 1, the hydroxyl group derived from the unsaturated compound that has formed an ester bond with the hydroxyl group of Noria forms a hole along the outer periphery of Noria before desorption. In this case, when viewed from the inside of the pore, the one connecting the hydroxyl groups becomes the inner wall of the pore. These hydroxyl groups do not form a continuous wall, but are arranged toward the inside of the pores when viewed from the inside (space) of the pores. That is, “having a functional group derived from the unsaturated compound on the inner wall of the pore” means that the functional group forms at least a part of the inner surface of the pore when viewed from the inside of the pore. It means being.

  FIG. 1 shows a case where all the hydroxyl groups of Noria are esterified. For example, even when only one hydroxyl group of Noria is esterified, the unsaturated compound and the cross-linking agent are aligned along the outer periphery of Noria. It is thought that there is a case where holes are formed. In this case, the functional group derived from the unsaturated compound only needs to form at least a part of the inner surface of the pore when viewed from the inside of the pore.

  By providing the hole with a functional group derived from the unsaturated compound on the inner wall of the hole, the inclusion ability of carbon dioxide and / or metal can be remarkably improved. That is, the pores of Noria are not provided with a functional group as described above, and it is difficult to introduce the functional group into the pores. Therefore, Noria has a problem that the amount of carbon dioxide adsorbed and the types of metals that can be included are few.

  On the other hand, according to the above configuration, the shape, size, number, and the like of the vacancies formed by the elimination of Noria are substantially maintained, and the vacancies are provided with the functional groups. Can cause chemical reactions. That is, if the inclusion target is a metal ion, an ionic bond is formed between the functional group and the metal ion. If the inclusion target is carbon dioxide, carbon dioxide is adsorbed by the reaction between the functional group and carbon dioxide. can do.

  Therefore, in addition to simply including the inclusion object in the hole, it is possible to obtain an adsorption effect by a chemical reaction by the functional group. For example, in the case of only including the inclusion object in the hole of Noria As compared with, the types of inclusions and the amount of inclusion can be remarkably increased.

  Moreover, the gel structure provided with pores according to the present invention can efficiently include a desired inclusion object by selecting the type of the functional group corresponding to the inclusion object. For example, if it is desired to mainly adsorb carbon dioxide, efficient adsorption of carbon dioxide is performed by performing a reaction that generates a carbamate between the amino group and carbon dioxide, using the functional group as an amino group. It is possible.

  Thus, according to the inclusion target, various functional groups can be provided on the inner wall of the pore, so that a gel structure suitable for the inclusion target can be appropriately prepared. Moreover, since Noria can be produced by a one-step reaction, the gel structure having pores according to the present invention can be easily prepared. That is, it is possible to provide a gel structure having excellent inclusion ability that can be used for various kinds of inclusion objects by a very simple method.

  The functional group provided on the inner wall of the pore is not particularly limited as long as it is a functional group capable of reacting with carbon dioxide and / or metal ions. For example, the functional group is selected from the group consisting of a carboxy group, an amino group, and a hydroxyl group. The above functional groups can be mentioned. In addition, the functional group may vary depending on the type of unsaturated compound used for manufacturing the gel structure. Therefore, according to the object to adsorb | suck, the said functional group can be adjusted to a functional group with higher reactivity with the object to adsorb | suck.

  For example, when the functional group is an amino group, it is suitable for adsorption of carbon dioxide, and when a carboxy group is used, it is suitable for inclusion of an alkali metal as shown in Examples described later. When used, it is suitable for inclusion of general organic compounds such as polyethylene glycol, ethyl ether, alcohols, aldehyde compounds, polyamides, polyesters, polyurethanes and the like.

  By using, for example, a carboxylic acid halide as the unsaturated compound, the functional group provided on the inner wall of the pores can be a carboxy group. Among the carboxylic acid halides, methacryloyl chloride is more preferable.

  Further, for example, when one or more unsaturated compounds selected from the group consisting of 2-chloro-4- (vinylphenyl) acetamide, isocyanate styrene, and diisocyanate are used as the unsaturated compound, The functional group provided on the inner wall can be an amino group. Of these, diisocyanates are preferable in view of the simplicity of the reaction procedure of the gel structure such as post-treatment.

  Furthermore, for example, by using 2- (vinyloxy) ethyl methacrylate and / or 4- (2-vinyloxy) ethoxystyrene as the unsaturated compound, the functional group provided on the inner wall of the hole is a hydroxyl group. Can do.

  The inner diameter of the holes is 3 to 10 mm because Noria is used as a mold, and more preferably 4 to 6 mm. The “inner diameter” is a distance between two functional groups when attention is paid to any two functional groups among the functional groups forming the inner surface of the pores when viewed from the inside of the pores. Corresponds to the distance where is the maximum. For example, when the two-dimensional shape of the hole is substantially circular, the diameter of the circle is intended as the maximum distance. For example, when the two-dimensional shape of the hole is an ellipse, the major axis of the ellipse is intended as the maximum distance.

Since the pores are formed by desorbing Noria from the polymer, the pores are similar in size and shape to those of Noria that can include carbon dioxide and Rb ⁺ ions. . Further, as described above, the functional group is provided on the inner wall of the pore. Therefore, the synergistic improvement of the inclusion ability can be achieved by the physicochemical inclusion by the holes derived from the holes of the Noria and the chemical reaction between the functional group and the inclusion target.

[Embodiment 2: Metal Inclusion Agent]
The metal clathrating material according to the present invention contains the gel structure having pores according to the present invention as an active ingredient, and can clathrate the metal.

  As already described, the gel structure having pores according to the present invention can efficiently include metal ions such as alkali metal ions. Moreover, as shown in the Example mentioned later, it has also been demonstrated that the clathrate which was excellent with respect to rubidium and cesium is shown.

  Therefore, the metal clathrate according to the present invention can be used as a clathrate such as an alkali metal, or can be used as a rare metal recovery material or a radioactivity removal material.

  The metal enclosure according to the present invention may contain other components in addition to the gel structure having the pores according to the present invention. For example, you may have tetrahydrofuran (THF) as a solvent. Thereby, since the gel structure can be swollen, it can be expected that the metal can be more easily included. In addition, conventionally known diluents, excipients and the like may be contained as necessary. When other components are contained, the metal clad material according to the present invention can be produced by mixing and forming the gel structure and other components by a conventionally known method.

[Embodiment 3: Carbon dioxide adsorbent]
The carbon dioxide adsorbent according to the present invention contains the gel structure having pores according to the present invention as an active ingredient, and can adsorb carbon dioxide.

  As already explained, the gel structure having pores according to the present invention can adsorb carbon dioxide efficiently. For example, by using an amino group as a functional group provided on the inner wall of the pore in the gel structure, carbon dioxide can be efficiently adsorbed by a reaction between the amino group and carbon dioxide.

  The carbon dioxide adsorbent may contain other components such as conventionally known diluents and excipients, if necessary, in addition to the gel structure having pores according to the present invention. When other components are contained, the carbon dioxide adsorbent according to the present invention can be produced by mixing and molding the gel structure and other components by a conventionally known method.

[Embodiment 4: Carbon dioxide separation membrane]
The carbon dioxide separation membrane according to the present invention is formed by depositing the carbon dioxide adsorbent according to the present invention.

  Examples of the film forming method include a casting method and a spin coating method. Further, for example, by performing a pressure treatment using the obtained separation membrane, carbon dioxide can be separated by allowing carbon dioxide to pass through the inside of the separation membrane.

  In the separation membrane, for example, an amino group can be preferably used as the functional group provided on the inner wall of the pore of the gel structure provided with the pore according to the present invention.

  The separation membrane can be used to reduce carbon dioxide in the atmosphere by collecting carbon dioxide from carbon dioxide emission sources during production of electric power, steel, cement, etc., and storing it in the ground or isolating it into the ocean. .

[Embodiment 5: Method for producing gel structure with pores]
In another embodiment, the present invention is a method for producing a gel structure having pores formed by the above-described desorption of Noria.

The method for producing the gel structure includes the following steps:
(I) a step of obtaining an ester by forming an ester bond between one or more of the hydroxyl groups provided by Noria and the unsaturated compound;
(Ii) obtaining a polymer by polymerizing and crosslinking the ester in the presence of a crosslinking agent;
(Iii) A step of hydrolyzing the polymer to desorb one or more Noria from the polymer to obtain a gel structure having pores.

  Since the method for producing a gel structure having pores according to the present invention includes the above-described steps, the gel structure having substantially maintained the pores corresponding to the size, shape, number, etc. of Noria is fixed. A gel structure having pores can be obtained, and an inner wall of the pores is provided with a functional group derived from the unsaturated compound by the hydrolysis.

  Therefore, it is possible to provide a gel structure capable of enclosing the inclusion target in the pores and causing a chemical reaction between the inclusion target and the functional group in the pores.

  Moreover, the gel structure provided with the functional group suitable for performing a chemical reaction with an inclusion object can be easily prepared by selecting the said unsaturated compound suitably according to the inclusion object.

  Therefore, it is possible to provide a gel structure in which the inclusion ability of carbon dioxide or metal is remarkably improved.

  As the unsaturated compound and the crosslinking agent used in the method for producing the gel structure having the pores, the same unsaturated compound and crosslinking agent as described in Embodiment 1 can be used.

  The method of step (i) is performed by a general method for performing an esterification reaction. Examples of the method include a method of stirring Noria and an unsaturated compound in a solvent.

  The solvent is not particularly limited as long as it can dissolve Noria and an unsaturated compound. For example, triethylamine, dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), and the like can be used. The said solvent may use 1 type and may mix and use 2 or more types.

  In the step (i), the amount of the unsaturated compound used may be 1 mol or more with respect to 1 mol of Norway.

  Moreover, in order to esterify all 24 hydroxyl groups of Noria, the amount of the unsaturated compound used is preferably 24 mol to 1000 mol, more preferably 48 mol to 100 mol, relative to 1 mol of Noria. preferable.

  The temperature and reaction time in the esterification reaction in step (i) are appropriately determined depending on the type of unsaturated compound used. For example, when methacryloyl chloride is used as the unsaturated compound, it is preferable to stir at room temperature for about 24 hours or more. In addition, "room temperature" means 20-25 degreeC.

  The molar ratio of the esterified Noria used in step (ii) to the cross-linking agent is preferably Noria: cross-linking agent = 1.0: 3.0 to 1.0: 96: 0. The ratio is more preferably 0: 4.0 to 1.0: 10.0, and particularly preferably 1.0: 12.0 to 1.0: 24.0.

  By satisfying the molar ratio, a gel structure in which the shape, size, number, and the like of vacancies formed by the elimination of Noria are substantially maintained, that is, a gel structure having fixed vacancies is obtained. Since it is easy, it is preferable when providing the gel structure which can perform inclusion of carbon dioxide, a metal, etc. efficiently.

  As the polymerization method in step (ii), a general polymerization method can be used, but a solution polymerization method or a solid phase polymerization method is preferable.

  The solid phase polymerization method can be performed, for example, by the following steps: (a) preparing a solution of a Noria derivative (esterified Noria) containing a photopolymerization initiator; (b) the solution A cast film is prepared from the film, and the film is irradiated with ultraviolet rays and heated to form a crosslinkable film; (c) after that, the crosslinkable film is treated with an acidic aqueous solution or an alkaline aqueous solution, Noria is desorbed from the crosslinkable film.

  The solution polymerization method can be performed, for example, by stirring esterified Noria in a suitable solvent in the presence of a polymerization initiator and a crosslinking agent.

  In step (ii), the solvent that can be used in the case of polymerizing by a solution polymerization method is not particularly limited, and examples thereof include dimethylformamide (DMF), triethylamine, N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), Dimethylacetamide (DMAc) or the like can be used. The said solvent may use 1 type and may mix and use 2 or more types.

  As the polymerization initiator, those generally used can be used. For example, azobisisobutyl nitrile (AIBN), benzoyl peroxide (BPO), etc. can be mentioned. Moreover, the usage-amount of a polymerization initiator is suitably determined by the kind.

  Although the reaction conditions in the said polymerization reaction are suitably determined by the kind of crosslinking agent and polymerization initiator to be used, for example, the reaction is allowed to proceed for 20 to 24 hours under the condition of 60 ° C.

  In the above method, an unsaturated compound is added in step (i) and a crosslinking agent is added in step (ii). However, the unsaturated compound and the crosslinking agent are the same compound. In some cases, for example, in the case of a diisocyanate, the diisocyanate remaining without being used in the esterification reaction in step (i) and the esterified Noria are polymerized and crosslinked to form a heavy polymer. A coalescence (gel structure) can be formed.

  That is, the method for producing a gel structure having pores according to the present invention includes a case where both the unsaturated compound and the crosslinking agent are diisocyanates.

  That is, when using a diisocyanate that acts as both the unsaturated compound and the cross-linking agent, by adding an excess of diisocyanate in step (i), the system after completion of esterification of Noria is completed. Since the diisocyanate remains and the residual diisocyanate acts as a crosslinking agent, the polymerization and crosslinking reaction can proceed without adding another compound as a crosslinking agent in step (ii). Of course, after adding an appropriate amount of diisocyanate in step (i) to complete the esterification reaction, a new diisocyanate is added in step (ii) to advance the polymerization / crosslinking reaction. Also good.

  In step (iii), as shown in FIG. 1, Noria is desorbed by hydrolysis, and holes are formed using the desorbed Noria as a template.

The method of hydrolysis in step (iii) can be carried out using methods common to those skilled in the art, and is not particularly limited. For example, the polymer obtained in step (ii) is added with an aqueous NaOH solution (for example, , 6M NaOH aqueous solution, etc.) followed by heating / stirring under reflux conditions, and sulfuric acid (eg, 70% H ₂ SO ₄ etc.) added, followed by heating / stirring under refluxing conditions After adding hydrochloric acid, it can be carried out by heating and stirring.

  The reaction conditions are appropriately determined depending on the hydrolysis method. For example, when a 6M NaOH aqueous solution is added, the reaction is allowed to proceed at 120 ° C. for 6 hours under reflux conditions.

  For example, after hydrolysis using an aqueous NaOH solution, a part soluble in the aqueous NaOH solution and an insoluble part are generated as the reaction product. The unnecessary portion is separated by filtration, and treated with concentrated hydrochloric acid, sulfuric acid, acetic acid, citric acid, etc. (acid precipitation) to obtain a gel structure having pores formed by elimination of Noria. Can do. Note that the soluble portion includes the desorbed Noria.

  The pores are provided with functional groups derived from the unsaturated compound on the inner wall. For example, in the example shown in FIG. 1, a hydroxyl group is provided as the functional group. Therefore, it is possible to perform a chemical reaction using the hydroxyl group in the pores.

  The present invention will be described more specifically based on production examples, examples and comparative examples, and FIGS. 2 to 23, but the present invention is not limited thereto.

[Chemicals used]
Based on the above reaction formula (1), Noria is a condensation reaction between resorcinol and 1,5-pentane dial in an ethanol solution at 80 ° C. in the presence of hydrochloric acid (manufactured by Tokyo Chemical Industry). What was synthesized by performing over 48 hours was used.

  As methyl methacrylate, ethyl acetate, sodium hydrogen carbonate, anhydrous magnesium sulfate, hydrochloric acid, hexane, azoisobutyl nitrile (AIBN), and sodium hydroxide, commercially available products (all manufactured by Tokyo Chemical Industry) were used as they were.

Triethylamine and N, N-dimethylformamide (DMF) were obtained by drying a commercially available product (manufactured by Tokyo Kasei Co., Ltd.) with CaH ₂ (manufactured by Tokyo Kasei Co., Ltd.) and then purifying it by distillation under reduced pressure.

Chloroform (CHCl ₃ ) and dichloromethane (CH ₂ Cl ₂ ) were obtained by drying commercially available products (manufactured by Tokyo Chemical Industry) with CaCl ₂ (manufactured by Tokyo Chemical Industry) and then purifying them by atmospheric distillation.

  Commercial products (all manufactured by Tokyo Chemical Industry Co., Ltd.) were used for methacryloyl chloride, 1,3-diaminopropane, 1.6-diaminohexane, 1.12-diaminododecane, and methyl methacrylate.

[Structural analysis]
About the compound obtained in the present Example, the structural analysis of the compound obtained using the apparatus shown below was conducted.

(I) Nuclear magnetic resonance (NMR) spectrum In this example, a 400 MHz-NMR spectrum was measured using a ¹ H nuclear magnetic resonance apparatus (JOEL ECS-400K manufactured by JEOL Ltd.).

(Ii) IR spectrum In this example, using a Fourier transform near infrared / middle infrared / far infrared spectroscopy (FT-IR) apparatus (Spectraum 100 (R) manufactured by PerkinElmer Japan Co., Ltd.), IR spectrum was measured.

(Iii) Thermogravimetry (TGA)
In this example, thermogravimetric loss temperature measurement was performed using TGA-50 manufactured by Shimadzu Corporation. The measurement was performed under the measurement conditions of heating to 200 ° C. at a temperature rising rate of 30 ° C./min and heating to 450 ° C. at a temperature rising rate of 10 ° C./min using an aluminum pan in a nitrogen atmosphere. I went.

[Production Example 1]
[Synthesis of Noria-MA]

  Hereinafter, the compound in which the hydroxyl group of Noria is esterified with a methacryloyl group is referred to as “Noria-MA” and the synthesis thereof will be described. The reaction formula (2) represents a synthesis method of Noria-MA.

  After weighing 6.84 g (4 mmol: functional group equivalent 96 mmol) of Noria into a 300 ml eggplant flask containing a stir bar, 140 ml of triethylamine was added and stirred for 30 minutes in a nitrogen atmosphere. Thereafter, methacryloyl chloride (18.4 ml, that is, 192 mmol (2 equivalents to the functional group of Noria)) was added under ice-cooling, followed by stirring at room temperature for 24 hours to complete the esterification reaction shown in the reaction formula (2). I let you.

  After completion of the esterification reaction, the solvent was concentrated by an evaporator and then diluted by adding ethyl acetate. The resulting solution was filtered through a membrane and the salts were filtered off.

  The resulting filtrate was then washed once with 150 ml of aqueous sodium bicarbonate and once with 150 ml of 1N hydrochloric acid and three times with 100 ml of deionized water. In addition, the said washing | cleaning adds a filtrate and washing | cleaning liquid (sodium hydrogencarbonate aqueous solution, hydrochloric acid, or deionized water) to a separatory funnel, and after stirring, isolate | separates an organic layer and an aqueous layer, and discharges | emits the said aqueous layer Was done by.

Next, the obtained organic layer was dried over anhydrous magnesium sulfate, filtered off anhydrous magnesium sulfate, concentrated using an evaporator, and diluted with ethyl acetate. Then, Noria-MA was isolated using column chromatography (developing solvent: ethyl acetate) (Rf = 0.94). The isolated Noria-MA was distilled off under reduced pressure, dissolved in chloroform as a good solvent, and hexane as a poor solvent was added to the resulting solution for precipitation purification. The obtained solid was dried at room temperature for 24 hours to obtain 2.54 g (yield 20%) of a white solid as a product. The structural analysis of the obtained white solid was performed by measuring an IR spectrum and a ¹ HNMR spectrum at 400 MHz. The measurement results are shown in FIGS. 2 and 3, and the main peak positions are shown below.
IR (KBr, cm ⁻¹ ): 1739 (vC═O: ester), 1494 (vC═C: methacryloyl group)
¹ NMR (DMSO-d ₆ , TMS) δ (ppm): 0.57 to 2.20 (m, 60H, H ^a , H ^b , H ^f ), 3.74 to 4.41 (m, 12H, H ^{c), 5.55~6.18 (m, 48H} , Hg, Hg), 6.43~7.50 (m, 24H, H c, H d)
Incidentally, shown in the upper ^{H X (X = a, b} , c, d, f or g), the position of ^{H X (X = a, b} , c, d, f or g) in the structural formula of FIG. 3 Corresponds to the protons.

(Analysis result)
The measured IR spectrum as described above, the peak of 1739cm ^-1 due to C = O stretching vibration of ester bonds that are not observed in Noria, a peak of 1497cm ^-1 due to C = C stretching vibration of methacryloyl group Was newly confirmed. From this, it was suggested that the esterification reaction proceeded between Noria and methacryloyl chloride, and the esterification of Noria proceeded.

Subsequently, in the ¹ NMR spectrum, the peak near 9 ppm attributed to the hydroxyl group of Noria disappeared, the peak near 7 ppm attributed to the proton of the benzene ring of Noria, and 5.5 attributed to the proton of the methacryloyl group. From the integration ratio with the peak around ˜6.5 ppm, it was confirmed that the introduction ratio (D.I) indicating the ratio of the esterified group in the hydroxyl group of Noria was 99% or more. From this, it was confirmed that almost all hydroxyl groups of Noria were esterified and Noria-MA was synthesized.

[Production Example 2]
[Synthesis of 1,3-bis (methacrylamide) propane (hereinafter referred to as “DMA3”)]

  2.1 g (10 mmol) of 1,3-diaminopropane was weighed into a 50 ml eggplant flask, 16.5 ml (110 mmol) of triethylamine was added, and the mixture was stirred for 1 hour. Thereafter, 2.0 ml (22 mmol) of methacryloyl chloride was added and stirred for 12 hours to complete the reaction represented by the reaction formula (3).

  After the reaction was completed, the resulting reaction solution was diluted with chloroform, washed 3 times with 1N hydrochloric acid and once with deionized water, and the organic layer was recovered. The cleaning was performed in the same manner as in Production Example 1.

  The recovered organic layer was dehydrated by adding anhydrous magnesium sulfate. After anhydrous magnesium sulfate was filtered off, it was concentrated with an evaporator, and the resulting solid was recrystallized using a mixed solvent of chloroform and hexane. Specifically, crystals were deposited by cooling the mixed solution. As a result of the recrystallization operation, 0.62 g (yield 30%) of a white solid was obtained.

The structural analysis was performed by measuring the IR spectrum of the obtained white solid and the ¹ HNMR spectrum at 400 MHz. The measurement results are shown in FIGS. 4 and 5, and the main peak positions are shown below.
IR (KBr, cm ⁻¹ ): 1651 (vC═O: amide), 1532 (vC═C: methacryloyl group)
¹ NMR (DMSO-d ₆ , TMS) δ (ppm): 1.48 to 1.62 (t, 2H, H ^f ), 1.76 to 1.84 (s, 6H, H ^d ), 2.96 To 3.14 (t, 4H, H ^e ), 5.24 (s, 4H, H ^b ), 5.61 (s, 2H, H ^c ), 7.78 to 7.96 (t, 2H, H) ^a )
Note that H ^X (any of X = a to f) shown above corresponds to the proton at the position of H ^X (any of X = a to f) in the structural formula in FIG.

(Analysis result)
The measured IR spectrum as described above, the peak of 1532cm ^-1 due to and methacryloyl group peak of 1651 cm ^-1 due to the amide bond was confirmed. This suggested that DMA3 was synthesized.

Subsequently, in the ¹ NMR spectrum, an 8 ppm peak attributed to the amide group bond and a peak in the vicinity of 5 to 6 ppm attributed to the proton of the methacryloyl group were confirmed, and their integration ratio is shown in the above reaction formula. It was confirmed that it almost coincided with the theoretical value calculated from the structural formula of DMA3. From this result, it was confirmed that DMA3 was synthesized.

[Production Example 3]
[Synthesis of 1,6-bis (methacrylamide) hexane (hereinafter referred to as “DMA6”)]

By performing the same operation as in Production Example 2 except that 1.16 g (10 mmol) of 1.6-diaminohexane was used instead of 2.1 g (10 mmol) of 1,3-diaminopropane, 0.99 g ( Yield 40%) was obtained as a white solid. Moreover, the structural analysis of the obtained white solid was performed by measuring an IR spectrum and a ¹ HNMR spectrum at 400 MHz in the same manner as in Production Example 2. The measurement results are shown in FIGS. 6 and 7, and the main peak positions are shown below.
IR (KBr, cm ⁻¹ ): 1654 (vC═O: amide), 1541 (vC═C: methacryloyl group)
¹ NMR (DMSO-d ₆ , TMS) δ (ppm): 1.12 to 1.46 (m, 8H, H ^f ), 1.70 to 1.88 (s, 6H, H ^d ), 2.91 To 3.13 (t, 4H, H ^e ), 5.10 (s, 2H, H ^b ), 5.64 (s, 2H, H ^c ), 7.66 to 7.93 (t, 2H, H) ^a )
Note that H ^X (any of X = a to f) shown above corresponds to the proton at the position of H ^X (any of X = a to f) in the structural formula in FIG.

(Analysis result)
The measured IR spectrum as described above, the peak of 1541cm ^-1 due to and methacryloyl group peak of 1654 cm ^-1 due to the amide bond was confirmed. This suggested that DMA6 was synthesized.

Subsequently, in the ¹ NMR spectrum, an 8 ppm peak attributed to the amide group bond and a peak in the vicinity of 5 to 6 ppm attributed to the proton of the methacryloyl group were confirmed, and their integration ratio is shown in the above reaction formula. It was confirmed that it almost coincided with the theoretical value calculated from the structural formula of DMA6. From this result, it was confirmed that DMA6 was synthesized.

[Production Example 4]
[Synthesis of 1,12-bis (methacrylamide) dodecane (hereinafter referred to as “DMA12”)]

  5.0 g (25 mmol) of 1,12-diaminododecane was introduced into a 300 ml eggplant flask, 150 ml (234 mmol) of dichloromethane and 8.25 ml (55 mmol) of triethylamine were added and stirred for 1 hour. Thereafter, 5.3 ml (55 mmol) of methacryloyl chloride was added and stirred for 12 hours to complete the reaction represented by the reaction formula (5).

After finishing the reaction, the reaction solution obtained was washed, dehydrated with a desiccant, filtered with a desiccant, concentrated, and recrystallized in the same manner as in Production Example 2. 4.6 g ( A white solid with a yield of 55% was obtained. Moreover, the structural analysis was performed by measuring the IR spectrum of the obtained white solid and the ¹ HNMR spectrum at 400 MHz in the same manner as in Production Example 2. The measurement results are shown in FIGS. 8 and 9, and the main peak positions are shown below.
IR (KBr, cm ⁻¹ ): 1651 (vC═O: amide), 1532 (vC═C: methacryloyl group)
¹ NMR (DMSO-d ₆ , TMS) δ (ppm): 1.12 to 1.46 (quin, 10H, H ^g ), 1.79 (s, 6H, H ^d ), 3.01 to 3.09 ^{(q, 4H, H f)} , 5.25 (s, 2H, H b), 5.57 (s, 2H, H c), 7.83 (s, 2H, H a)
Incidentally, shown in the upper ^{H X (X = a, b} , c, d, f or g), the position of ^{H X (X = a, b} , c, d, f or g) in the structural formula of FIG. 9 Corresponds to the protons.

(Analysis result)
The measured IR spectrum as described above, the peak of 1532cm ^-1 due to and methacryloyl group peak of 1654 cm ^-1 due to the amide bond was confirmed. This suggested that 1,12-bis (methacrylamide) dodecane (hereinafter referred to as DMA12) was synthesized.

Subsequently, in the ¹ NMR spectrum, an 8 ppm peak attributed to the amide group bond and a peak in the vicinity of 5 to 6 ppm attributed to the proton of the methacryloyl group were confirmed, and their integration ratio is shown in the above reaction formula. It was confirmed that it almost coincided with the theoretical value calculated from the structural formula of DMA12. From this result, it was confirmed that DMA12 was synthesized.

[Production Examples 5 to 8]
[Production of Noria-Gel (3)]
In Production Examples 5 to 8, a gel structure having a Noria skeleton (hereinafter referred to as “Noria-Gel (3)”) was produced by reacting Noria-MA and DMA3 at various charging ratios.

  0.1 g (0.03 mmol) of Noria-MA obtained in Production Example 1, 0.0033 g (0.02 mmol) of azobisbutylnitrile (AIBN), that is, 3.0 mol% with respect to the functional group of Noria-MA, and Various charge ratios of DMA3 obtained in Production Example 2 (Noria-MA: DMA3 = 1.0 / 0 (Production Example 5), 1.0 / 2.4 (Production Example 6), 1.0 / 12 (Production Example 7) and 1.0 / 24.0 (Production Example 8)) were introduced into the polymerization tube, and then 3 ml of DMF was added and dissolved.

  The obtained solution is frozen using liquid oxygen and then degassed by degassing using an oil rotary vacuum pump, sealed, and stirred at 60 ° C. for 20 hours. The reaction shown in the reaction formula (6) was terminated. After the completion of the reaction, a gel structure (Noria-Gel (3)) was obtained.

The obtained Noria-Gel (3) was washed with diethyl ether, dried for 24 hours, and then subjected to structural analysis by measuring an IR spectrum. Noria-MA: DMA3 = 1.0 / 0, 1.0 / 2.4, 1.0 / 12.0, 1.0 / 24.0, each obtained by changing the charging ratio. The IR spectrum of (3) showed similar results. Here, as one of them, the IR spectrum of Noria-Gel (3) obtained at a charging ratio of Noria-MA: DMA3 = 1.0 / 12.0 is shown in FIG. Is shown below.
IR (KBr, cm ⁻¹ ): 1741, 1126 (vC═O: ester), 1660 (vC═O: amide)
Further, the yield of the obtained Noria-Gel (3) was 87% in Production Example 5, and> 99% in Production Examples 6 to 8.

(Analysis result)
In each IR spectrum of Noria-Gel (3) measured as described above, the disappearance of the 1532 cm ⁻¹ peak due to the methacryloyl group was observed, and a new 1741 cm ⁻¹ peak due to the ester bond, amide A peak at 1660 cm ⁻¹ due to binding was observed. From the observation results, it was confirmed that Noria-Gel (3) is a crosslinking compound having a Noria skeleton.

  Hereinafter, the gel structure obtained at a charging ratio: Noria-MA: DMA3 = 1.0 / 0 is referred to as Noria-Gel (3) (A). Similarly, the charging ratio: Noria-MA: DMA3. = The gel structure obtained at 1.0 / 2.4 is the gel structure obtained at Noria-Gel (3) (B), charging ratio: Noria-MA: DMA3 = 1.0 / 12.0 The gel structure obtained with Noria-Gel (3) (C) and charging ratio: Noria-MA: DMA3 = 1.0 / 24.0 is referred to as Noria-Gel (3) (D).

[Production Examples 9 to 11]
[Production of Noria-Gel (6)]
In Production Examples 9 to 11, a gel structure having a Noria skeleton (hereinafter referred to as “Noria-Gel (6)”) was produced by reacting Noria-MA and DMA6 at various charging ratios.

Instead of DMA3, DMA6 obtained in Production Example 3 was prepared by using various charging ratios (Noria-MA: DMA6 = 1.0 / 2.4 (Production Example 9), 1.0 / 12.0 (Production Example). 10) and 1.0 / 24.0 (Production Example 11)), except that it was used in the same manner as in Production Examples 5 to 8 to obtain Nolia-Gel (6). Moreover, the structural analysis of the above-mentioned Noria-Gel (6) was performed by measuring the IR spectrum in the same manner as in Production Examples 5-8. Similar to Production Examples 5 to 8, the IR spectra of each Noria-Gel (6) obtained using various amounts of DMA6 showed similar results. Here, as one of them, the IR spectrum of Noria-Gel (6) obtained in Production Example 10 is shown in FIG. 11, and the main peak positions are shown below.
IR (KBr, cm ⁻¹ ): 1741, 1126 (vC═O: ester), 1660 (vC═O: amide)
Moreover, the yield of the obtained Noria-Gel (6) was a preparation ratio of> 99% in all of Production Examples 9 to 11.

(Analysis result)
In each IR spectrum of each Noria-Gel (6) measured as described above, it was confirmed that an IR spectrum peak was present at the same position as in Production Examples 5-8. Therefore, it was confirmed that Noria-Gel (6) is a cross-linking compound having a Noria skeleton, similarly to Noria-Gel (3).

  In the following, the gel structure obtained with a charging ratio: Noria-MA: DMA6 = 1.0 / 2.4 is referred to as Noria-Gel (6) (A), and similarly, the charging ratio: Noria-MA. : The gel structure obtained with DMA6 = 1.0 / 12.0 was obtained with Noria-Gel (6) (B), charging ratio: Noria-MA: DMA6 = 1.0 / 24.0. The gel structure is referred to as Noria-Gel (6) (C).

[Production Examples 12 to 16]
[Production of Noria-Gel (12)]
In Production Examples 12 to 16, a gel structure having a Noria skeleton (hereinafter referred to as “Noria-Gel (12)”) was produced by reacting Noria-MA and DMA12 at various charging ratios.

  Instead of DMA3, DMA12 obtained in Production Example 4 was prepared by using various preparation ratios (Noria-MA: DMA12 = 1.0 / 2.4 (Production Example 12), 1.0 / 4.8 (Production Example). 13), 1.0 / 7.2 (Production Example 14), 1.0 / 12.0 (Production Example 15), and 1.0 / 24.0 (Production Example 16)). In the same manner as in Examples 5 to 8, Noria-Gel (12) was obtained.

Moreover, the structure analysis of Noria-Gel (12) was performed by measuring IR spectrum similarly to the manufacture examples 5-8. As in Production Examples 5 to 8, the IR spectra of each Noria-Gel (12) obtained using various amounts of DMA12 showed similar results. Here, as one of them, the IR spectrum of Noria-Gel (12) obtained in Production Example 15 is shown in FIG. 12, and the main peak positions are shown below.
IR (KBr, cm ⁻¹ ): 1741, 1126 (vC═O: ester), 1660 (vC═O: amide)
In addition, the yield of Noria-Gel (12) was> 99% in all the production examples 12 to 16 in the charging ratio.

(Analysis result)
In each IR spectrum of Noria-Gel (12) measured as described above, it was confirmed that an IR spectrum peak was present at the same position as in Production Examples 5 to 11. Therefore, it was confirmed that Noria-Gel (12) is a cross-linking compound having a Noria skeleton, like Noria-Gel (3) and Noria-Gel (6).

  In the following, the gel structure obtained with the charging ratio: Noria-MA: DMA12 = 1.0 / 2.4 is referred to as Noria-Gel (12) (A). Similarly, the charging ratio: Noria-MA. : The gel structure obtained with DMA12 = 1.0 / 4.8 was obtained with Noria-Gel (12) (B), charging ratio: Noria-MA: DMA12 = 1.0 / 7.2 The gel structure was prepared using Noria-Gel (12) (C) charging ratio: Noria-MA: DMA12 = 1.0 / 12.0. The gel structure obtained was prepared using Noria-Gel (12) (D), charging ratio. : Noria-MA: The gel structure obtained with DMA12 = 1.0 / 24.0 is referred to as Noria-Gel (12) (E).

[Desorption of Noria from Noria-Gel]
[Reference Example 1]
(Decore by hydrolysis of Noria-Gel (3) (A))
0.05 g of Noria-Gel (3) (A) was weighed into a 30 ml eggplant flask, and 10 ml of NaOH aqueous solution (6M) was added. Thereafter, the mixture was stirred at 120 ° C. for 6 hours under reflux (reflux) conditions, and a hydrolysis reaction with respect to Noria-Gel (3) (A) was performed. After completion of the reaction, the reaction product was subjected to acid precipitation using concentrated hydrochloric acid and filtered through a membrane (manufactured by Advantech). As a result, only a polymer soluble in water was obtained.

[Reference Example 2]
(Decore by hydrolysis of Noria-Gel (3) (B))
The same operation as in Reference Example 1 was performed except that Noria-Gel (3) (B) was used instead of Noria-Gel (3) (A). As a result, only a polymer soluble in water was obtained.

[Reference Example 3]
(Decore by hydrolysis of Noria-Gel (3) (C))
The same operation as in Reference Example 1 was performed, except that Noria-Gel (3) (C) was used instead of Noria-Gel (3) (A). As a result, only a polymer soluble in water was obtained.

  [Example 1]

  The hydrolysis shown in Reaction Formula (9) was performed under the same conditions as in Reference Example 1 except that Noria-Gel (3) (D) was used instead of Noria-Gel (3) (A). As a result, a part soluble in the NaOH aqueous solution and an insoluble part were obtained.

After separating the soluble part and the insoluble part by filtration using a membrane, the insoluble part was subjected to acid precipitation using concentrated hydrochloric acid. As a result, a brown gel structure was obtained. Obtained. After the gel structure was washed with a large amount of tap water, it was vacuum-dried at 60 ° C., dried for 24 hours, and IR spectrum was measured for structural analysis. The yield of the gel structure was 0.03 g (yield 60%). The measurement results of the IR spectrum are shown in FIG. 13, and the main peak positions are shown below.
IR (KBr, cm ⁻¹ ): 1711, 1192 (vC═O: carboxyl group), 1630 (vC═O: amide)
On the other hand, as a result of acidifying the soluble part with concentrated hydrochloric acid, a brown solid was obtained. The solid was washed with a large amount of tap water, then vacuum dried at 60 ° C., and the structure was analyzed by measuring the IR spectrum and ¹ NMR spectrum of the dried product over 24 hours. went. The measurement results are shown in FIGS.

(Analysis result)
The IR spectrum of the gel structure of the brown, when compared with the IR spectrum of Noria-Gel (3) (D ), the peak in the vicinity of 1126cm ^-1 due to the peak and ester bond at around 1400 cm ^-1 due to benzene ring And a new peak at 1711 cm ⁻¹ due to carboxylic acid appeared.

In addition, the brown solid in the IR spectrum was confirmed a peak of 1440cm ^-1 due to benzene ring of peaks and Noria of 3392cm ^-1 due to a hydroxyl group of ^Noria, 1 in the HNMR spectrum, protons of hydroxyl groups of Noria A peak in the vicinity of 9 ppm attributed to 6 and a peak in the vicinity of 6 to 7.5 ppm attributed to the proton of the benzene ring of Noria was confirmed.

  From the above matters, in Example 1, the portion soluble in the NaOH aqueous solution is Noria, and the pores in which the Noria site has been removed as a soluble portion from Noria-Gel (3) (D) It was suggested that a gel structure provided with (hereinafter referred to as Gel-MA (Noria) (3) (D)) was obtained.

[Reference Example 4]
(Decore by hydrolysis of Noria-Gel (6) (A))
The same operation as in Reference Example 1 was performed except that Noria-Gel (6) (A) was used instead of Noria-Gel (3) (A). As a result, only a polymer soluble in water was obtained.

[Example 2]
(Decore by hydrolysis of Noria-Gel (6) (B))

  Hydrolysis shown in Reaction Formula (10) was performed under the same conditions as in Reference Example 1 except that Noria-Gel (6) (B) was used instead of Noria-Gel (3) (A). As a result, a part soluble in the NaOH aqueous solution and an insoluble part were obtained.

As a result of performing the same process as Example 1 with respect to the said insoluble part, the brown gel structure was obtained. The gel structure was dried by the same method as in Example 1, and the IR spectrum was measured for structural analysis. The yield of the gel structure was 0.09 g (yield 18%). The measurement results of the IR spectrum are shown in FIG. 16, and the main peak positions are shown below.
IR (KBr, cm ⁻¹ ): 1718, 1182 (vC═O: carboxyl group), 1624 (vC═O: amide)
On the other hand, as a result of acidifying the soluble part with concentrated hydrochloric acid, a brown solid was obtained. The solid was also subjected to structural analysis by measuring the IR spectrum and ¹ NMR spectrum in the same manner as in Example 1. The measurement results are shown in FIGS.

(Analysis result)
Regarding the IR spectrum of the brown gel structure, when compared with the IR spectrum of Noria-Gel (6) (D), the peak and ester bond in the vicinity of 1400 cm ⁻¹ due to the benzene ring are the same as in Example 1. reduction in peak near 1126cm ^-1 due to, as well, it was confirmed that the peak of 1718 cm ^-1 due to carboxylic acid was emerging.

In addition, the brown solid in the IR spectrum was confirmed a peak of 1436cm ^-1 due to benzene ring of peaks and Noria of 3407cm ^-1 due to a hydroxyl group of ^Noria, 1 in the HNMR spectrum, protons of hydroxyl groups of Noria A peak in the vicinity of 9 ppm attributed to 6 and a peak in the vicinity of 6 to 7.5 ppm attributed to the proton of the benzene ring of Noria was confirmed.

  From the above-mentioned matters, in Example 2, the portion soluble in the NaOH aqueous solution is Noria, and the pores in which the Noria site has been eliminated as the soluble portion from the Noria-Gel (6) (B). It was suggested that a gel structure provided with (hereinafter referred to as Gel-MA (Noria) (6) (B)) was obtained.

[Example 3]
(Decore by hydrolysis of Noria-Gel (6) (C))
The reaction formula (8) described in Example 2 is shown in the same manner as in Reference Example 1 except that Noria-Gel (6) (C) is used instead of Noria-Gel (3) (A). Hydrolysis was performed. As a result, a part soluble in the NaOH aqueous solution and an insoluble part were obtained.

As a result of performing the same treatment as in Example 1 on the soluble part and the insoluble part, a brown solid was obtained from the soluble part, and a brown gel structure was obtained from the insoluble part. was gotten. The brown solid and the gel structure were dried by the same method as in Example 1 and structural analysis was performed. The yield of the gel structure was 0.25 g (yield 50%). As a result of the structural analysis, a result similar to the spectrum of the brown solid obtained in Example 2 was obtained from the measurement by IR spectrum and ¹ HNMR spectrum of the brown solid. Moreover, the result similar to the spectrum in the gel structure obtained in Example 2 was also obtained from the measurement by IR spectrum of the gel structure.

(Analysis result)
The IR spectrum and ¹ NMR spectrum of the brown solid and the gel structure were similar to the spectrum obtained in Example 2, and a peak was observed at the same position. From the above, in Example 3, as in Example 2, the part soluble in the NaOH aqueous solution is Noria, and the Noria site is desorbed as a soluble part from Noria-Gel (6) (C). It was suggested that a gel structure with pores (hereinafter referred to as Gel-MA (Noria) (6) (C)) was obtained.

[Reference Example 5]
(Decore by hydrolysis of Noria-Gel (12) (A))
Reference Example except that Noria-Gel (12) (A) was used instead of Noria-Gel (3) (A), and 1 N hydrochloric acid was used instead of concentrated hydrochloric acid for the reaction. The same operation as 1 was performed. As a result, only a polymer soluble in water was obtained.

[Reference Example 6]
(Decore by hydrolysis of Noria-Gel (12) (B))
The same operation as in Reference Example 5 was performed except that Noria-Gel (12) (B) was used instead of Noria-Gel (12) (A). As a result, only a polymer soluble in water was obtained.

[Example 4]
(Decore by hydrolysis of Noria-Gel (12) (D))

  Hydrolysis shown in Reaction Formula (11) was performed under the same conditions as in Reference Example 1 except that Noria-Gel (12) (D) was used instead of Noria-Gel (3) (A). As a result, a part soluble in the NaOH aqueous solution and an insoluble part were obtained.

The soluble part and the insoluble part were separated by filtration using a membrane, and then the insoluble part was subjected to acid precipitation using 1N hydrochloric acid. As a result, a brown gel structure was obtained. Got. After the gel structure was washed with a large amount of tap water, it was vacuum-dried at 60 ° C., dried for 24 hours, and IR spectrum was measured for structural analysis. The yield of the gel structure was 0.32 g (64% yield). The measurement results of the IR spectrum are shown in FIG. 19, and the main peak positions are shown below.
IR (KBr, cm ⁻¹ ): 1741, 1126 (vC═O: carboxyl group), 1660 (vC═O: amide)
On the other hand, as a result of acidifying the soluble part with 1N hydrochloric acid, a brown solid was obtained. The solid was washed with a large amount of tap water, then vacuum dried at 60 ° C., and IR spectrum and ¹ NMR spectrum were measured on the dried product over 24 hours. The measurement results are shown in FIGS.

(Analysis result)
Respect IR spectrum of the gel structure of the brown, when compared with the IR spectrum of Noria-Gel (12) (D ), the peak in the vicinity of 1126cm ^-1 due to the peak and ester bond at around 1400 cm ^-1 due to benzene ring As well as a new peak at 1718 cm ⁻¹ due to carboxylic acid.

In addition, the brown solid in the IR spectrum was confirmed a peak of 1436cm ^-1 due to benzene ring of peaks and Noria of 3407cm ^-1 due to a hydroxyl group of ^Noria, 1 in the HNMR spectrum, protons of hydroxyl groups of Noria A peak in the vicinity of 9 ppm attributed to 6 and a peak in the vicinity of 6 to 7.5 ppm attributed to the proton of the benzene ring of Noria was confirmed.

  From the above, in Example 4, the portion soluble in the NaOH aqueous solution is Noria, and the pores in which the Noria site has been removed as a soluble portion from Noria-Gel (12) (D). It was suggested that the provided gel structure (hereinafter referred to as Gel-MA (Noria) (12) (D)) was obtained.

[Example 5]
(Decore by hydrolysis of Noria-Gel (12) (C))
The reaction formula (9) described in Example 4 is shown under the same conditions as in Reference Example 1 except that Noria-Gel (12) (C) is used instead of Noria-Gel (12) (A). Hydrolysis was performed. As a result, a part soluble in NaOH aqueous solution and an insoluble part were obtained.

As a result of performing the same processing as in Example 4 on the soluble part and the insoluble part, a brown solid was obtained from the soluble part, and a brown gel structure was obtained from the insoluble part. was gotten. The brown solid and the gel structure were dried in the same manner as in Example 4, and then structural analysis was performed. The yield of the gel structure was 0.185 g (yield 37%). As a result of the structural analysis, a result similar to the spectrum of the brown solid obtained in Example 4 was obtained from the measurement by IR spectrum and ¹ HNMR spectrum of the brown solid. Moreover, the result similar to the spectrum in the gel structure obtained in Example 4 was obtained from the IR spectroscopic measurement of the gel structure.

(Analysis result)
The IR spectrum and ¹ NMR spectrum of the brown solid and the gel structure were similar to the spectrum obtained in Example 4, and a peak was observed at the same position. From the above, in Example 5, as in Example 4, the part that is soluble in the NaOH aqueous solution is Noria, and the Noria site is removed as a soluble part from Noria-Gel (12) (C). It was suggested that a separated gel structure with pores (hereinafter referred to as Gel-MA (Noria) (12) (C)) was obtained.

[Example 6]
(Decore by hydrolysis of Noria-Gel (12) (E))
The reaction formula (9) shown in Example 4 is shown under the same conditions as in Reference Example 1 except that Noria-Gel (12) (E) was used instead of Noria-Gel (12) (A). Hydrolysis was performed. As a result, a part soluble in NaOH aqueous solution and an insoluble part were obtained.

As a result of performing the same processing as in Example 4 on the soluble part and the insoluble part, a brown solid was obtained from the soluble part, and a brown gel structure was obtained from the insoluble part. was gotten. The brown solid and the gel structure were dried in the same manner as in Example 4, and then structural analysis was performed. The yield of the gel structure was 0.48 g (96% yield). As a result of the structural analysis, a result similar to the spectrum of the brown solid obtained in Example 4 was obtained from the measurement by IR spectrum and ¹ HNMR spectrum of the brown solid. Moreover, the result similar to the spectrum in the gel structure obtained in Example 4 was obtained from the IR spectroscopic measurement of the gel structure.

(Analysis result)
The IR spectrum and ¹ NMR spectrum of the brown solid and the gel structure were similar to the spectrum obtained in Example 4, and a peak was observed at the same position. From the above, in Example 5, as in Example 4, the part soluble in the NaOH aqueous solution is Noria, and from Noria-Gel (12) (E), the Noria site is removed as the soluble part. It was suggested that a separated gel structure with pores (hereinafter referred to as Gel-MA (Noria) (12) (E)) was obtained.

[Thermogravimetric loss temperature measurement]
Nolia-Gel (X) (X = 3, 6 or 12) obtained in the above Production Examples 5 to 16 and Gel-MA (Noria) (X) (X = TGA measurement was performed on 3, 6 or 12). The results are shown in Table 1 below.

  In Table 1, “Feed ratio” indicates the molar ratio of Noria and MMA (X) (X = 3, 6 or 12). Further, “-” indicates that Gel-MA (Noria) was not obtained.

  When a gel structure (part insoluble in NaOH aqueous solution) is generated after hydrolysis, the gel structure (Gel-MA (Noria) (X) (X = 3, 6 or 12)) after hydrolysis, Compared with the gel structure before decomposition (Noria-Gel (X) (X = 3, 6 or 12)), the thermal decomposition start temperature is lower in the gel structure after hydrolysis. Was observed. This is presumably because the heat resistance of the gel structure was lowered due to the elimination of Noria by hydrolysis.

[Comparative Example 1]
In order to confirm the effect of using Noria in the Examples, the gel structure (hereinafter referred to as “Noria”) was obtained by hydrolyzing a polymer obtained by polymerizing and crosslinking methyl methacrylate and DMA6 without using Noria. Gel (MA) (referred to as (6)).
(Synthesis of Gel (MMA) (6))

  A gel structure (hereinafter referred to as Gel (MMA) (6)) was produced by reacting methyl methacrylate with DMA6.

  0.1 g (1 mmol) of methyl methacrylate (MMA), 0.0049 g of AIBN (0.03 mmol: 3.0 mol% with respect to the vinyl group of MMA), and 0.252 g (1 mmol) of DMA6 were introduced into the polymerization tube. Then, 3 ml of DMF was added and dissolved. The resulting solution was frozen using liquid oxygen, then degassed using an oil rotary vacuum pump, freeze degassed, sealed, and then sealed at 60 ° C. for 20 hours. Stirring was performed to complete the reaction represented by the reaction formula (12).

After the reaction, a gel structure was obtained. The obtained gel structure was washed with diethyl ether, dried for 24 hours, and then subjected to structural analysis by measuring an IR spectrum. FIG. 22 shows the IR spectrum of the obtained Gel (MMA) (6), and the main peak positions are shown below.
IR (KBr, cm ⁻¹ ): 3421, 1668 (vC═O: amide), 1733, 1244 (vC═O: ester)
Moreover, the yield of the obtained Gel (MMA) (6) was 1.32 g (yield> 99%).

(Analysis result)
In IR spectra of were measured as previously described Gel (MMA) (6), a peak of 3421cm ^-1 and 1668 cm ^-1 due to the amide bond DMA6, and the peak of 1733 cm ^-1 due to an ester bond of MMA And 1244 cm ⁻¹ peaks were observed. From the observation result, it was confirmed that the obtained gel structure (Gel (MMA) (6)) was a crosslinkable polymer composed of MMA and DMA6.

  (Hydrolysis of Gel (MMA) (6))

  Gel structure (Gel (MA) (6)) was produced by hydrolyzing Gel (MMA) (6).

  0.1 g of Gel (MMA) (6) obtained by the reaction shown in the reaction formula (12) was weighed into a 30 ml eggplant flask, and 10 ml of 6M NaOH aqueous solution was added. Thereafter, the mixture was stirred at 120 ° C. for 6 hours under reflux (reflux) conditions, and the hydrolysis reaction shown in the reaction formula (13) was terminated. After completion of the reaction, the reaction solution was filtered through a membrane to obtain a reddish brown solid. The solid was subjected to acid precipitation using concentrated hydrochloric acid. As a result, a reddish brown gel structure was obtained. The gel structure was dried in a vacuum dryer under conditions of 60 ° C. for 24 hours, and an IR spectrum was measured for structural analysis. Further, the yield of the obtained Gel (MA) (6) was 0.082 g (yield 80%). FIG. 23 shows the IR spectrum result of the obtained Gel (MA) (6).

(Analysis result)
In the IR spectrum, it was observed that the peak intensity in the vicinity of 3400 cm ⁻¹ due to the carboxylic acid (carboxyl group) was increased as compared with that before hydrolysis (that is, Gel (MMA) (6)). From the above, it was shown that the hydrolysis reaction shown in the reaction formula (13) proceeded to form a carboxylic acid. That is, as the hydrolysis progressed, it was shown that the bond between MMA and DMA6 was dissociated, and carboxylic acid was formed.

[Examples 7 to 11]
[Evaluation of inclusion capacity of alkali metals]
(Generation of alkali metal picrate)

  The alkali metal picrate used for evaluation of the alkali metal inclusion ability shown below was produced by the reaction shown in the above reaction formula (14).

  To a 100 ml Erlenmeyer flask into which 25 ml of deionized water was introduced, 0.3 g (1.3 mmol) of picric acid was added to prepare a saturated solution of picric acid, followed by filtration using a Kiriyama funnel to obtain a saturated aqueous picric acid solution. CsOH (1.3 mmol / 1.5 ml) was added to the saturated aqueous picric acid solution while confirming with pH test paper until the solution showed neutrality.

  The obtained neutral solution was allowed to stand at room temperature to precipitate a salt. The precipitated salt was filtered, washed with ethanol, washed with ether, and then recrystallized using deionized water.

  As a result, yellow acicular crystals Cs picric acid was produced. Moreover, the same operation was performed using another alkali metal (Na, K, Rb) instead of Cs to produce an alkali metal picrate.

(Evaluation of inclusion ability)
The deionized aqueous solution of guest (picrate) was 2.4 × 10 ⁻⁴ wt% with respect to the host polymer: Gel-MA (Noria) obtained in Examples 1-3, 5 and 6. After adding to a concentration, the guest solution was extracted from the liquid containing the host and the guest into a 5 ml sample tube and stirred at room temperature (25 ° C.) for 24 hours. Moreover, the guest solution adjusted to the density ^| concentration of 2.4 * 10 < ^-4 > weight% was used as an object sample in absence of a host. After completion of the stirring, the obtained aqueous layer is transferred to a quartz cell, and the absorbance at the absorption maximum wavelength (355 nm) of picric acid anion is measured. The absorbance is compared with the absorbance of the target sample. (Ex (%)) was determined.

Calculation method of inclusion rate Ex (%) = [Abs (Bi) −Abs (Ex)] / [Abs (Bi)] × 100
Abs (Bi): Absorbance after extraction in the absence of host (wavelength = 355 nm)
Abs (Ex): Absorbance after extraction operation in the presence of host (wavelength = 355 nm)
The evaluation results of the inclusion ability are shown in Table 2 below.

  In Table 2, “Feed ratio” indicates the molar ratio of Noria and MMA (X) (X = 3, 6 or 12).

[Comparative Examples 2 and 3]
About the gel structure obtained in Comparative Example 1: Gel (MMA) (6), the alkali metal inclusion ability was evaluated in the same manner as the evaluation of the alkali metal inclusion ability in Examples 7 to 11. Evaluation (Comparative Example 2).

  In addition, the gel structure obtained in Production Example 11: Noria-Gel (6) (C) was also subjected to alkali metal inclusion in the same manner as the alkali metal inclusion ability was evaluated in the examples. The ability was evaluated (Comparative Example 3).

  Evaluation results of alkali metal inclusion ability in Comparative Examples 2 and 3, and gel structure obtained by hydrolyzing Noria-Gel (6) (C) in Example 3: Gel-MA (Noria) (6) The alkali metal inclusion capacity of (C) was compared. The results are shown in Table 3 below.

  In Table 3, “Feed ratio” indicates the molar ratio of Noria to MMA (X) (X = 3, 6 or 12). Further, “-” indicates that Noria is not used.

(Analysis result)
From Table 2, gel structures using the same DMA (Gel-MA (Noria) (6) (B) and Gel-MA (Noria) (6) (C), and Gel-MA (Noria) ( 12) When comparing (D) and Gel-MA (Noria) (12) (E)), the charge ratio of Noria-MA and DMA is 1.0: It was found that the one with 24.0 shows a higher inclusion rate regardless of the type of alkali metal. Therefore, regardless of the length of the methylene chain of DMA, a larger amount of DMA with respect to Noria-MA is preferable in order to retain vacancies derived from the detached Noria site in the resulting gel structure. I understood that.

  Also, from Table 2, when the charging ratio of Noria-MA and DMA is 1.0: 24.0, the number of methylene groups in the methylene chain of DMA is 6> 3> 12 in the order of all alkali metals. It was found that when the charging ratio was 1.0: 12.0, the metal inclusion rate was higher when the number of methylene groups was 6 than when the charging ratio was 1.0: 12.0.

In the gel structure using DMA12, even when the charging ratio is Noria-MA: DMA = 1.0: 24.0, it shows inclusion ability against alkali metals other than Rb ⁺ and Cs ⁺ ions. There wasn't. Furthermore, regarding the gel structure using DMA12, Gel-MA (Noria) (12) (D) (preparation ratio: Noria-MA: DMA = 1.0: 12.0) has an inclusion ability in all metals. Not shown.

  From the above, if the length of the methylene chain is too long, the pores of the gel structure are difficult to be retained (fixed), and those using DMA having 6 methylene groups may retain the pores. Was suggested to be high.

  Furthermore, from Table 3, it was found that the gel structure obtained without using Noria showed almost no inclusion ability with respect to alkali metals, unlike the gel structure obtained with Noria. From this, it has been found that by using Noria, it is possible to form pores capable of including an alkali metal in the resulting gel structure.

  Since this invention is excellent in the clathrate ability of metal ions, such as an alkali metal, it can be utilized for a metal clathrate. Moreover, since this invention is excellent in the adsorption property of a carbon dioxide, it can be utilized as a carbon dioxide separation membrane formed by forming a carbon dioxide adsorbent and the adsorbent.

Claims (22)

The polymer represented by the following chemical formula (1) is represented by the above chemical formula (1) from a polymer obtained by polymerizing and crosslinking an ester obtained by esterifying one or more of the hydroxyl groups provided in the compound represented by the following chemical formula (1). A gel structure having pores formed by detaching one or more compounds,
The gel structure includes pores formed by desorption of the compound represented by the chemical formula (1),
The said pore is equipped with the functional group derived from the said unsaturated compound in the inner wall of the said hole, The gel structure characterized by the above-mentioned.

  The unsaturated compounds include carboxylic acid halides, 2-chloro-4- (vinylphenyl) acetamide, isocyanate styrene, diisocyanate, 2- (vinyloxy) ethyl methacrylate, and 4- (2-vinyloxy) ethoxystyrene. The gel structure according to claim 1, wherein the gel structure is one or more unsaturated compounds selected from the group consisting of:   The gel structure according to claim 2, wherein the carboxylic acid halide is methacryloyl chloride.   4. The ester according to claim 1, wherein 24 esters of the compound represented by the chemical formula (1) are esterified with an unsaturated compound. 5. Gel structure.   The gel structure according to any one of claims 1 to 4, wherein the crosslinking is performed by a polyfunctional crosslinking agent.   The gel structure according to claim 5, wherein the polyfunctional crosslinking agent is a bifunctional to tetrafunctional crosslinking agent. The crosslinking agent is a compound represented by the following chemical formula (2), a compound represented by the following chemical formula (3) having a weight average molecular weight (Mw) of 1,000 to 50,000, or divinylbenzene. The gel structure according to claim 5 or 6, characterized by the above.

  The gel structure according to claim 7, wherein the cross-linking agent is a compound represented by the chemical formula (2), and is a compound of n = 6 in the chemical formula (2).   The gel structure according to claim 1, wherein the functional group is one or more functional groups selected from the group consisting of a carboxy group, an amino group, and a hydroxyl group.   The gel structure according to any one of claims 5 to 9, wherein a molar ratio of the ester to the crosslinking agent is 1.0: 3.0 to 1.0: 96.0. .   The gel structure according to claim 10, wherein the molar ratio is 1.0: 12.0 to 1.0: 24.0.   The gel structure according to any one of claims 1 to 11, wherein the hole has an inner diameter of 3 to 10 mm.   A metal clad material comprising the gel structure according to any one of claims 1 to 12 as an active ingredient and capable of clathrating metal.   A carbon dioxide adsorbent comprising the gel structure according to any one of claims 1 to 12 as an active ingredient and capable of adsorbing carbon dioxide.   A carbon dioxide separation membrane comprising the carbon dioxide adsorbent according to claim 14 formed thereon. (I) a step of obtaining an ester by forming an ester bond between one or more hydroxyl groups provided in the compound represented by the following chemical formula (1) and the unsaturated compound;

(Ii) obtaining a polymer by polymerizing and crosslinking the ester in the presence of a crosslinking agent;
(Iii) A step of dehydrating one or more compounds represented by the chemical formula (1) from the polymer by hydrolyzing the polymer to obtain a gel structure having pores. And a method for producing a gel structure having pores.   The unsaturated compounds include carboxylic acid halides, 2-chloro-4- (vinylphenyl) acetamide, isocyanate styrene, diisocyanate, 2- (vinyloxy) ethyl methacrylate, and 4- (2-vinyloxy) ethoxystyrene. The method for producing a gel structure according to claim 16, which is one or more unsaturated compounds selected from the group consisting of: The crosslinking agent is a compound represented by the following chemical formula (2), a compound represented by the following chemical formula (3) having a weight average molecular weight (Mw) of 1,000 to 50,000, or divinylbenzene. The method for producing a gel structure according to claim 16 or 17, wherein:

  The gel structure according to any one of claims 16 to 18, wherein a molar ratio of the ester to the crosslinking agent is 1.0: 3.0 to 1.0: 96.0. Manufacturing method.   The said molar ratio is 1.0: 12.0-1.0: 24.0, The manufacturing method of the gel structure of Claim 19 characterized by the above-mentioned.   The method for producing a gel structure according to any one of claims 16 to 20, wherein the polymerization is performed by a solution polymerization method or a solid layer polymerization method.   The method for producing a gel structure according to any one of claims 16 to 21, wherein the unsaturated compound and the crosslinking agent are both diisocyanates.

Images