JP2013178152A - Radioactive substance adsorption/removal material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a selection removal material capable of easily performing treatment of a radioactive substance by selectively fastening the radioactive substance included in water and removing the radioactive substance from the water.SOLUTION: A radioactive substance removal material contains a polymer obtained by reacting water, polyalcohols, polyhydric aryl alcohols, or polycarboxylic acids with a cyclodextrin condensation polymer obtained by reacting cyclodextrins with organic dibasic acid or organic dibasic acid halides.

Description

  The present invention relates to a radioactive material adsorption removal material. The present invention relates to a material for removing radioactive substances from radioactive liquid containing radioactive substances generated from nuclear-related facilities such as nuclear power plants and establishments handling radioactive isotopes, and a method for producing the same. In particular, the present invention relates to a material capable of efficiently separating and removing radioactive substances from waste liquid containing radioactive substances generated in the event of a nuclear facility and minimizing the exposure of workers, and a method for manufacturing the same. .

  More specifically, the present invention relates to a selective fixing agent capable of collecting a radioactive substance when the radioactive substance flows into an aqueous system such as the sea, river, ground water, and reservoir water, and a radioactive material using the same. The present invention relates to a method for obtaining water substantially free of substances. In the present invention, cyclodextrin is condensed with an organic dibasic acid or an organic dibasic acid halide, and water, a polyhydric alcohol, a polyarylaryl alcohol, or a polycarboxylic acid is added to the terminal of the obtained condensation polymer. The present invention relates to a method for selectively fixing a radioactive substance contained in water using a cyclodextrin polymer having a novel structure, which can be obtained by esterification. Furthermore, this invention relates to the cyclodextrin polymer which has said novel structure, and its manufacturing method. The polymer according to the present invention can selectively and efficiently fix various radioactive substances contained in water.

Massive release radioactive cesium in the environment ^{(137 Cs),} because the behavior in vivo a water-soluble resembles a potassium or rubidium, human body, a compound that causes internal exposure when incorporated into animal and plant by radiation is there. Radioactive cesium has a half-life of about 30.2 years and the hazard persists for a relatively long time. For this reason, if radioactive cesium is released into the atmosphere, soil, seawater, groundwater, etc., it must be removed immediately and stored safely.

Similarly, since radioactive strontium ( ⁹⁰ Sr) has a similar electron arrangement and atomic radius to calcium, it replaces calcium in bone when taken into the body, accumulates in the body, and emits radiation over a long period of time. Radioactive strontium has a half-life of 28.8 years, and, like radioactive cesium, its toxicity persists for a relatively long period of time.

  Conventionally, as a contaminated water treatment technology containing radioactive cesium and radioactive strontium, methods using inorganic salts such as ferrocyanide, activated carbon, zeolite, ion exchange resin, etc. are common, but nonflammable inorganic substances are used. In the method, it is difficult to reduce the volume of the substance on which the contaminant is adsorbed, and in the method using zeolite, there is a problem that the adsorption performance of the radioactive substance is lowered in the presence of salt. On the other hand, a method using an organic material such as an ion exchange resin has a problem of deterioration of the material itself due to radiation, and a method using a reverse osmosis membrane has a problem that the amount that can be treated at one time is extremely small.

  Patent Document 1 (Japanese Patent Laid-Open No. 2001-133594) discloses an adsorbent that can selectively adsorb and remove at least one kind of cationic radionuclide such as cobalt, manganese, iron, chromium, zinc, strontium, cesium and the like. A method for removing radionuclides from reactor cooling water using a packed adsorbent packed tower is disclosed. In Patent Document 1, it is disclosed that a chelate resin in which a coordinating group capable of forming a chelate with a radionuclide is introduced into a matrix polymer as an adsorbent is used, and a coordination capable of forming a chelate with a radionuclide. It is disclosed that either one of titanate and ferrocyanide can be used as a group.

  Patent Document 2 (Japanese Patent Laid-Open No. 2007-271306) discloses a method of adsorbing and removing cesium by treating radioactive cesium and strontium contained in a waste liquid with denitrifying bacteria or cesium-accumulating bacteria. According to this method using microorganisms as a method for treating metal ions, radioactive substances can be selectively reduced reliably, but there are difficulties in treating radioactive substances widely released into the environment.

  Patent Document 3 (Japanese Patent Laid-Open No. 5-66295) discloses a method of removing radioactive substances mixed in a liquid by adsorbing radioactive substances to chitin or a complex of chitin and hydroxyapatite. Has been. According to this method, radioactive strontium can be effectively removed, but there remains a problem of how to treat hydroxyapatite that has adsorbed radioactive strontium.

  Patent Document 4 (Patent No. 3749941) discloses a cesium separation obtained by supporting a water-soluble hexacyanoiron (II) salt in the pores of a porous carrier and treating it with a solution in which a copper salt is dissolved. A material is disclosed. Although it is considered that radioactive cesium can be separated and removed using this separation material, as in the invention disclosed in other patent documents, there is a problem of how to treat a porous carrier adsorbed with radioactive cesium. Remain.

  There are not many documents disclosing techniques for adsorbing and removing radioactive cesium and strontium released into the environment, and development of materials that efficiently absorb and remove these radionuclides is further desired.

  From such a viewpoint, the present inventors have decided to search for an organic substance that can be easily reduced in volume without using an inorganic substance such as zeolite that is difficult to reduce in volume. And as an organic substance whose performance does not deteriorate even when used in radioactive material contaminated water with a strong radiation dose, a polymer obtained by condensing cyclodextrin and organic dibasic acid was found, and a selective radioactive substance containing this A remover is provided. A polymer containing a polymer obtained by condensing cyclodextrin with an organic dibasic acid can selectively remove cesium and / or strontium from radioactive material-contaminated water, and collects cesium and strontium-free water. This is clarified in the examples.

JP 2001-133594 A JP 2007-271306 A JP-A-5-66295 Japanese Patent No. 3749941

Mitsubishi Heavy Industries Technical Report, Vol. 35, no. 4, pages 282 to 285 Ebara Times, No. 218, 29-34

  The present invention is a selection that makes it easy to treat radioactive substances by selectively fixing radioactive substances contained in water, in particular radioactive cesium and / or strontium, and removing radioactive substances from water. An object is to provide a removal material. In addition, the present invention provides a method for selectively collecting radioactive substances contained in water using such a selective removal material, thereby obtaining water containing no radioactive substances at a high recovery rate.

  The inventors of the present invention reacted polyhydric alcohols, polyarylaryl alcohols and polycarboxylic acids with the end of a cyclodextrin condensation polymer obtained by condensing a water-soluble cyclodextrin with an organic dibasic acid. Using the new water-insoluble cyclodextrin polymer produced in this way as a component of the removal material, it is possible to collect radioactive substances contained in water and obtain water that does not contain radioactive substances at a high recovery rate. I found it. This radioactive material removal material can be directly collected into the water containing the radioactive substance, or the radioactive substance can be efficiently collected by such means as filling the column and allowing the water containing the radioactive substance to pass through. I found out that I can do it.

Aspects of the present invention are as follows:
1. A cyclodextrin condensation polymer obtained by reacting a cyclodextrin with an organic dibasic acid or an organic dibasic acid halide is reacted with water, a polyhydric alcohol, a polyarylaryl alcohol, or a polycarboxylic acid. A radioactive substance removing material containing the polymer obtained in the above.
2. Organic dibasic acid or organic dibasic acid halide is terephthalic acid, isophthalic acid, maleic acid, malic acid, malonic acid, succinic acid, fumaric acid, glutaric acid, adipic acid, phthalic acid, diglycolic acid or their halogens. 2. The material according to 1 above, selected from the group of compounds.
3. The polyhydric alcohol is selected from dihydric alcohols having 1 to 10 carbon atoms, trihydric alcohols, or tetrahydric alcohols, and the polyhydric aryl alcohols are hydroquinones, catechols, resorcinols, bisphenols or 3. The material according to 1 or 2 above, wherein the material is selected from substituted bisphenols, and the polyvalent carboxylic acids are selected from dicarboxylic acids, tricarboxylic acids, or tetracarboxylic acids.
4). 4. The material according to any one of 1 to 3 above, wherein the radioactive substance is radioactive cesium and / or strontium.
5. The end of the cyclodextrin condensation polymer obtained by reacting cyclodextrin with organic dibasic acid or organic dibasic acid halide is reacted with water, polyhydric alcohols, polyarylaryl alcohols or polycarboxylic acids. The radioactive substance-removing material containing the obtained polymer is brought into contact with water containing the radioactive substance, and the radioactive substance contained in the water is fixed to the radioactive substance-removing material, and water containing no radioactive substance is removed. A method characterized by obtaining.
6). Organic dibasic acid or organic dibasic acid halide is terephthalic acid, isophthalic acid, maleic acid, malic acid, malonic acid, succinic acid, fumaric acid, glutaric acid, adipic acid, phthalic acid, diglycolic acid or their halogens. 6. The method of claim 5, wherein the method is selected from
7). The polyhydric alcohol is selected from dihydric alcohols having 1 to 10 carbon atoms, trihydric alcohols, or tetrahydric alcohols, and the polyhydric aryl alcohols are hydroquinones, catechols, resorcinols, bisphenols or The method according to 5 or 6 above, wherein the method is selected from substituted bisphenols, and the polyvalent carboxylic acids are selected from dicarboxylic acids, tricarboxylic acids, or tetracarboxylic acids.
8). 8. The method according to any one of 5 to 7 above, wherein the radioactive substance is radioactive cesium and / or strontium.

  Hereinafter, the present invention will be described in detail.

  The present invention relates to a cyclodextrin condensation polymer obtained by reacting a cyclodextrin with an organic dibasic acid or an organic dibasic acid halide, water, a polyhydric alcohol, a polyarylaryl alcohol, or a polycarboxylic acid. The present invention relates to a radioactive substance removing material containing a polymer obtained by reacting acids. First, the polymer constituting the radioactive substance removing material of the present invention will be described.

  Cyclodextrins are a type of oligosaccharide in which several molecules of D-glucose are linked by α (1 → 4) glucoside bonds to form a cyclic structure. Generally, glucose in which 6, 7, or 8 glucoses are bonded is known, and they are called α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin, respectively. Cyclodextrins have pores that can enclose small molecules inside the ring structure. Since the hydroxy group of cyclodextrin is located outside the pores, the inside of the pores is hydrophobic and easily includes a hydrophobic substance.

Organic dibasic acids include, for example, aliphatic dicarboxylic acids, aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and fatty acids, and in the present invention, they react with the —CH ₂ OH group in the cyclodextrin molecule to sequentially condense. It is a compound that can form a polymer. Examples of such organic dibasic acids include terephthalic acid, isophthalic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, phthalic acid, diglycolic acid and the like. The organic dibasic acid halide refers to an acid halide of the above organic dibasic acid. In the present invention, it is particularly preferable to use terephthalic acid which is an organic dibasic acid or terephthalic acid dichloride (terephthaloyl dichloride) which is an organic dibasic acid halide. The reaction between the cyclodextrin and the organic dibasic acid can be performed, for example, at about 50 to 100 ° C, preferably about 60 to 90 ° C.

  Reacting water, polyhydric alcohols, polyarylaryl alcohols, or polycarboxylic acids means specifying the carboxyl group derived from the organic dibasic acid remaining at the end of the cyclodextrin condensation polymer obtained as described above. Means end-capping with a substituent. In order to endcap the carboxyl group, water, polyhydric alcohols, polyhydric aryl alcohols and polycarboxylic acids can be reacted and esterified. When the cyclodextrins and the organic dibasic acids are reacted, the ratio of the cyclodextrins to the organic dibasic acids is, for example, 1: 3 to 10, preferably 1: 3 to 5, etc., and the organic dibasic acids are excessive. Reaction under mild conditions. Then, organic dibasic acids react with a plurality of hydroxyl groups present in the molecule of cyclodextrins.

  As described above, cyclodextrins have the property that the outside of the pores is hydrophilic and the inside of the pores is hydrophobic. When excess organic dibasic acids are reacted with the cyclodextrins, a hydrophobic group is introduced outside the cyclodextrins. And cyclodextrin forms a crosslinked structure through the combined organic dibasic acids. Although the cyclodextrins themselves are basically water-soluble substances, the cyclodextrins can be rendered water-insoluble by introducing hydrophobic groups in this way. Furthermore, by devising the balance between hydrophilic groups and hydrophobic groups, it is possible to create substances with hydrophilic groups that are insoluble or sparingly soluble in water but can interact with substances contained in water. It becomes.

  To explain again in detail, the reaction of water, polyhydric alcohols, polyarylaryl alcohols, or polycarboxylic acids with the terminal of the condensation polymer of cyclodextrins and organic dibasic acids means, for example, having 1 to 1 carbon atoms Dihydric alcohols, trihydric alcohols or tetrahydric alcohols selected from 10 alcohols, polyvalent aryl alcohols having two or more hydroxyl groups in the aromatic ring, or two or more carboxyl groups in one molecule It means that a polyvalent carboxylic acid is reacted with a carboxyl end group derived from an organic dibasic acid to form an ester bond. That is, the end of the organic dibasic acid bonded to cyclodextrins is endcapped with water, polyhydric alcohols, polyarylaryl alcohols, or polycarboxylic acids. Polyhydric alcohols, polyarylaryl alcohols or polycarboxylic acids used for terminal end caps did not contribute to the end cap of organic dibasic acids because they had multiple hydroxyl groups A hydroxyl group will remain. The presence of the hydroxyl group at the end of the polymer in this way improves the affinity of the end group for water, and thus the chance of interaction with radioactive substances in water is also increased. The polymer produced in this way has a hydrophobic organic dibasic acid moiety and a hydrophilic end group, so that it is insoluble or hardly soluble in water, but can interact with radioactive substances contained in water. . That is, the polymer of the present invention has an ability to take in a radioactive substance contained in water into the pores of the cyclodextrin site.

  The chemical structural formula of the cyclodextrin polymer used in the present invention is considered to be represented by the following formula, for example:

  In this formula, the cyclodextrin portion is represented by a truncated cone, and terephthalic acid is used as the organic dibasic acid. Hydroxyl groups and organic dibasic acids in cyclodextrins are alternately bonded by ester bonds to form a network structure. The end of the polymer is capped with a trioxyethylene group having a hydroxy group as a result of the reaction with triethylene glycol, which is a polyhydric alcohol. The length of the terminal group can be changed depending on the compound used for the terminal end cap. Depending on the nature of the radioactive substance to be removed, the ratio of the number of bonds between the cyclodextrins and organic dibasic acids and the length of the end groups are changed as appropriate, so that the affinity of the cyclodextrin polymer with water and contained in water. It is possible to change the affinity with the radioactive material.

  Radioactive substances intended to be collected by the radioactive substance removing material of the present invention are generic names of substances having radioactivity, and radioactive elements (or nuclides) contained therein decay with time while emitting radiation, Ultimately, it is a stable isotope without radioactivity. Examples of radioactive substances intended to be collected with the material of the present invention include uranium 235, cesium 137, cobalt 60, strontium 90, iodine 129, iodine 131 and the like. The material of the present invention exhibits high performance particularly for collecting cesium 137 and strontium 90 contained in water.

  Next, a method for collecting a radioactive substance contained in water using the radioactive substance removing material of the present invention will be described. The present invention provides a terminal of a cyclodextrin condensation polymer obtained by reacting cyclodextrin with an organic dibasic acid or an organic dibasic acid halide, with water, polyhydric alcohols, polyarylaryl alcohols or polycarboxylic acids. The radioactive substance-removing material containing the polymer obtained by reacting with the water and the radioactive substance-containing water are brought into contact with each other, and the radioactive substance contained in the water is fixed to the radioactive substance-removing material to According to the method, characterized in that it contains uncontained water. The radioactive substance removing material of the present invention described above has a solid or semi-solid form. Therefore, the radioactive substance removing material of the present invention is dispersed in water containing the radioactive substance and stirred well to bring the radioactive substance removing material of the present invention into contact with the water containing the radioactive substance, and the water. The contained radioactive material can be fixed. More specifically, the radioactive substance removing material of the present invention containing 10 to 1000 times the cyclodextrin site with respect to the contained radioactive substance is added and stirred well. The polymer which is an active ingredient in the radioactive substance removing material of the present invention is dispersed in water and comes into contact with the radioactive substance contained in water. The radioactive substance is fixed to or near the interaction part by the interaction with the interaction part (cyclodextrin site) in the polymer that interacts with the radioactive substance. Depending on the amount of water to be treated, the concentration of the radioactive substance, and the amount of the radioactive substance removing material of the present invention, the contact can generally be made by a method such as stirring for 5 hours to several days. The fixing reaction can be suitably performed at room temperature, and can be heated as necessary. For example, it can be heated to a temperature of 20 to 150 ° C, preferably 50 to 120 ° C, more preferably 70 to 90 ° C. The polymer contained in the radioactive substance removing material of the present invention is advantageous in that the radioactive substance can be fixed particularly at low temperatures.

  Thus, after the radioactive substance contained in water is fixed to the polymer that interacts with the radioactive substance, only the polymer (or the composition containing the polymer) to which the radioactive substance is fixed is separated. Separation may be performed using an existing solid-liquid separation technique, for example, a method using a centrifugal separator or a pressure filter. The filter for separation can be performed using a commercially available filter, glass filter, membrane, absorbent cotton, metal, resin or the like. Any filter or membrane may be used as long as it has a pore size capable of separating the polymer contained in the radioactive substance removing material of the present invention, but considering the particle size of a general polymer, the pore size is about 0.1. It is preferable to use one having a thickness of −100 μm.

  The polymer (polymer composition) to which the radioactive substance obtained by separation is fixed can be subjected to volume reduction treatment such as incineration. Careful attention should be paid to volume reduction and incineration so that radioactive substances fixed to the polymer are not released again into the environment. For example, the methods established in the above-mentioned conventional literature should be used. (See Non-Patent Document 1, Non-Patent Document 2, etc.)

  The water obtained after the separation of the polymer to which the radioactive material has been fixed is substantially completely free of the radioactive material. Therefore, water that could not be moved in the past due to the inclusion of radioactive substances can be reused if it can be reused, or discarded in a normal manner, such as the sea or river.

  This method can be applied to cope with the case where seawater or river water contains radioactive substances. That is, the radioactive substance removing material of the present invention can be introduced into seawater or river water containing the radioactive substance, and the radioactive substance removing material of the present invention can be recovered after a predetermined time has elapsed. As described above, the radioactive substance removing material of the present invention adheres a radioactive substance contained in seawater or river water, and if this is recovered using a collection network or a recovery device, the radioactive substance present in the environment is removed. It can be collected directly.

  The radioactive substance removing material of the present invention is packed into the column, and the radioactive substance removing material is radioactively disposed by passing the water containing the radioactive substance through the column and bringing the radioactive substance removing material into contact with the water containing the radioactive substance. It is also possible to fix the substance. In such a column processing method, a large amount of radioactive substance-containing water can be continuously processed at a time.

  In addition, the water containing the radioactive substance used in the method of the present invention contains at least one kind of the above-mentioned radioactive substance. The radioactive substance may be dissolved at any concentration in water, but usually radioactive substance-contaminated water that can be discharged from a nuclear facility or the like contains a very small amount (for example, 0.00017 ppm) of the radioactive substance. In this way, water containing a very small amount of radioactive material has a very large volume of water itself even though the amount of radioactive material to be treated is extremely small. Keeping such contaminated water is very difficult and increases the risk of spilling into the environment. Therefore, if the radioactive material dissolved in a very small amount can be concentrated and separated from the water and separated into the radioactive material to be treated and the water that can be reused, the processing efficiency of the radioactive material will increase, but such a large amount of The water problem can also be solved.

  As a radioactive substance removing material of the present invention, an active ingredient, a polymer that interacts with a radioactive substance, for example, silica gel, polymer beads, ion exchange resin, foam, film, membrane, various lattice structures and network structures, What is immobilized on a carrier such as a porous material can also be suitably used. For example, a solid carrier such as silica gel, polymer beads, or ion exchange resin, on which a polymer used in the present invention is supported, is laminated in a column, and water containing a radioactive substance is allowed to flow under atmospheric pressure or under pressure, By interacting with the polymer, radioactive substances contained in water can be effectively removed. Alternatively, the radioactive substance contained in the water or the membrane or the like is supported by filtering the water containing the radioactive substance at normal pressure or reduced pressure using a solid carrier such as a filter or membrane supported on the present invention. The radioactive substance can be removed by being fixed to the filter. Alternatively, a solid carrier such as a foam, a net-like structure, a lattice-like structure, or a porous material loaded with the polymer used in the present invention is poured into water containing radioactive material, seawater, or river water. Then, water is absorbed in the net part, lattice part, or pore part of the solid support, the radioactive substance contained in the water is fixed to the polymer of the present invention, and then the solid support is pressurized as necessary. (For example, by performing an operation such as squeezing), the water from which the radioactive material has been removed can be obtained.

  As described above, the composition in which the polymer used in the present invention is immobilized on a solid support can be used for a method of removing radioactive substances from water containing radioactive substances in a batch process, as well as a method of continuously treating them. Is also very suitably used.

  Thus, the radioactive substance removing material of the present invention can selectively fix the radioactive substance contained in water and remove it from the water. By using the radioactive substance removing material of the present invention, only the radioactive substance that requires strict and careful treatment is removed and concentrated from the water that could not be moved because a trace amount of radioactive substance was dissolved. Therefore, while the processing efficiency of the radioactive substance is dramatically increased, the safely recovered safe water can be processed or reused by a normal method. In the method for removing radioactive substances contained in water using the radioactive substance removing material of the present invention, the radioactive substance removing material is charged and dispersed in water, and the radioactive substance is fixed by stirring and separated. This is a relatively easy method and can be carried out at room temperature. Therefore, it is a safe method that does not cause the radioactive material to diffuse into the atmosphere. When a substance in which a polymer that interacts with a radioactive substance is immobilized on various solid carriers is used as the radioactive substance removing material of the present invention, it becomes possible to continuously remove the radioactive substance contained in water.

  In addition, when a polymer material is irradiated with radiation, structural damage such as tearing occurs in the polymer main chain or side chain, and a phenomenon such as brittleness is generally observed. The polymer used in the present invention needs to have sufficient strength to withstand radiation irradiation in consideration of the application of contacting with a radioactive substance. The polymer used in the present invention can be sufficiently used for a radioactive material removing material without damaging the strength and the fixing performance of the radioactive material even when irradiated with radiation.

It is drawing which illustrates typically the evaluation method of radioactive substance removal performance. It is drawing which demonstrates typically another evaluation method of radioactive substance removal performance. It is drawing which demonstrates typically another evaluation method of radioactive substance removal performance.

  A typical method for producing a polymer as an active ingredient of the radioactive substance removing material of the present invention is schematically shown:

A specific example of a method for producing a polymer used in the present invention from α-cyclodextrin will be described according to the above scheme.
α-Cyclodextrin (hereinafter referred to as “α-CD”) is dispersed in an organic solvent (for example, pyridine, dimethyl sulfoxide, dimethylformamide, etc., preferably dry pyridine). On the other hand, terephthaloyl dichloride is dissolved in an organic solvent (for example, tetrahydrofuran, dichloromethane, 1,4-dioxane, etc., preferably dry tetrahydrofuran), and this is added dropwise to the previously prepared α-CD dispersion. At this time, since heat is generated by the condensation reaction, it is desirable to drop the α-CD dispersion while cooling in an ice bath or the like. Thereafter, the reactor is attached to a hot water bath at 50 to 100 ° C., and the reaction solution is vigorously stirred. After completion of the reaction, remove the hot water bath, further cool as necessary to lower the temperature inside the reaction vessel to 0-10 ° C., water, polyhydric alcohols (triethylene glycol, polyethylene glycol, cyclohexanediol, glucose, etc.), Add polyvalent aryl alcohols (hydroquinone, phloroglucinol, benzenedimethanol, etc.) or polycarboxylic acids (iminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glutamic acid, etc.) and continue stirring. When the obtained solid is washed with a washing liquid such as alcohols, water or acetone and dried, the polymer used in the present invention can be obtained. At this time, from the viewpoint of preventing by-products such as pyridine used as a solvent and dimethyl phthalate methylated by phthaloyl dichloride as a raw material from remaining in the polymer, the obtained polymer is used for suction filtration. It is desirable to employ a washing method in which the mixture is collected on a funnel and sucked by adding an alcohol / water mixed solvent thereto, acetone is added and sucked on the funnel, and these steps are repeated at least twice.

The polymer used in the present invention can form the same polymer by using β- and γ-cyclodextrin in addition to α-CD.
In this specification, the polymer thus obtained is referred to as “TC3-WA-αCD” (end-cap of the condensation polymer obtained by reacting α-CD and phthaloyl dichloride at a molar ratio of 1: 3 with water. Polymer ”,“ GC10-WA-βCD ”(a polymer in which the end of a condensation polymer obtained by reacting β-CD and diglycolyl chloride at a molar ratio of 1:10 was endcapped with water),“ TC10-IA -ΒCD "(a polymer obtained by reacting β-CD and phthaloyl dichloride in a molar ratio of 1:10 at a terminal end of the condensation polymer with iminodiacetic acid), or" TC10-TG-βCD "(β -A polymer obtained by reacting CD with phthaloyl dichloride at a molar ratio of 1:10 is a polymer in which the terminal of a condensation polymer is end-capped with triethylene glycol). These are all polymers which are active ingredients of the radioactive substance removing material of the present invention.

[Synthesis Example 1] Synthesis of a polymer obtained by end-capping a condensed cyclodextrin of α-cyclodextrin and terephthaloyl dichloride with water (hereinafter referred to as “TC3-WA-αCD”) A dropping funnel and a three-way cock with a balloon In a 200 mL three-necked flask with a stopcock, dry α-cyclodextrin (hereinafter referred to as “α-CD”, 0.97 g, 1.0 mmol, water content of 1% or less, Pure Chemical) and special grade pyridine (50 and was stirred at room temperature for 15 minutes. After placing the flask in an ice bath, terephthaloyl dichloride (0.61 g, 3.0 mmol, Tokyo Chemical Industry) dissolved in special grade tetrahydrofuran (40 mL, Wako Pure Chemical Industries) was added dropwise over 30 minutes. After the dropwise addition, the ice bath was removed, and the mixture was stirred in a hot water bath (80 ° C.) for 3 hours. After completion of the reaction, distilled water (0.11 g, 6.0 mmol) was added and stirred for 1 hour. After the crystals were filtered off with suction, the obtained crystals were washed with distilled water (50 mL × 3) and primary acetone (50 mL × 3, Junsei) in that order, and the resulting solid was vacuum dried at 70 ° C. overnight. did. 1.28 g of TC3-WA-αCD was obtained.
IR 3445, 2979, 1716, 1268, 1096, 1044, 1016, 730 cm ^-1

[Synthesis Example 2] Synthesis of a polymer obtained by end-capping a condensed cyclodextrin of α-cyclodextrin and terephthaloyl dichloride with water (hereinafter referred to as “TC5-WA-αCD”) A dropping funnel and a three-way cock with a balloon Put a dry α-CD (0.97 g, 1.0 mmol, water content 1% or less, Junsei Kagaku) and special grade pyridine (50 mL, Wako Pure Chemical Industries) into a 200 mL three-necked flask with a stopcock at room temperature. For 15 minutes. After placing the flask in an ice bath, terephthaloyl dichloride (1.02 g, 5.0 mmol, Tokyo Chemical Industry) dissolved in special grade tetrahydrofuran (40 mL, Wako Pure Chemical Industries) was added dropwise over 30 minutes. After the dropwise addition, the ice bath was removed, and the mixture was stirred in a hot water bath (80 ° C.) for 3 hours. After completion of the reaction, distilled water (0.18 g, 10 mmol) was added and stirred for 1 hour. After the crystals were filtered off with suction, the obtained crystals were washed with distilled water (50 mL × 3) and primary acetone (50 mL × 3, Junsei) in that order, and the resulting solid was vacuum dried at 70 ° C. overnight. did. 1.52 g of TC5-WA-αCD was obtained.
IR 3423, 2971, 1716, 1268, 1098, 1044, 1017, 729 cm ^-1

[Synthesis Example 3] Synthesis of a polymer (hereinafter referred to as “TC10-WA-αCD”) obtained by end-capping a condensed cyclodextrin of α-cyclodextrin and terephthaloyl dichloride with water A dropping funnel and a three-way cock with a balloon , Put dry α-CD (0.97 g, 1.0 mmol, water content 1% or less, Junsei Kagaku) and special grade pyridine (50 mL, Wako Pure Chemical Industries) into a 200 mL three-necked flask with a stopcock at room temperature For 15 minutes. After placing the flask in an ice bath, terephthaloyl dichloride (2.03 g, 10 mmol, Tokyo Chemical Industry) dissolved in special grade tetrahydrofuran (40 mL, Wako Pure Chemical Industries) was added dropwise over 30 minutes. After the dropwise addition, the ice bath was removed, and the mixture was stirred in a hot water bath (80 ° C.) for 3 hours. After completion of the reaction, distilled water (0.36 g, 20 mmol) was added and stirred for 1 hour. After the crystals were filtered off with suction, the obtained crystals were washed with distilled water (50 mL × 3) and primary acetone (50 mL × 3, Junsei) in that order, and the resulting solid was vacuum dried at 70 ° C. overnight. did. 2.14 g of TC10-WA-αCD was obtained.
IR 3480, 2985, 1717, 1268, 1097, 1045, 1017, 729 cm ^-1

[Synthesis Example 4] Synthesis of a polymer obtained by end-capping a condensed cyclodextrin of β-cyclodextrin and terephthaloyl dichloride with water (hereinafter referred to as “TC3-WA-βCD”) A dropping funnel and a three-way cock with a balloon In a 200 mL three-necked flask equipped with a stopcock, dry β-cyclodextrin (hereinafter abbreviated as `` β-CD '', 1.13 g, 1.0 mmol, water content 1% or less, pure chemical) and special grade pyridine (50 mL, Wako Pure Chemical Industries, Ltd.) was added and stirred at room temperature for 15 minutes. After placing the flask in an ice bath, terephthaloyl dichloride (0.61 g, 3.0 mmol, Tokyo Chemical Industry) dissolved in special grade tetrahydrofuran (40 mL, Wako Pure Chemical Industries) was added dropwise over 30 minutes. After the dropwise addition, the ice bath was removed, and the mixture was stirred in a hot water bath (80 ° C.) for 3 hours. After completion of the reaction, distilled water (0.11 g, 6.0 mmol) was added and stirred for 1 hour. After the crystals were filtered off with suction, the obtained crystals were washed with distilled water (50 mL × 3) and primary acetone (50 mL × 3, Junsei) in that order, and the resulting solid was vacuum dried at 70 ° C. overnight. did. 1.41 g of TC3-WA-βCD was obtained.
IR 3384, 2923, 1716, 1272, 1127, 1079, 1049, 731 cm ^-1

[Synthesis Example 5] Synthesis of a polymer obtained by end-capping a condensed cyclodextrin of β-cyclodextrin and terephthaloyl dichloride with water (hereinafter referred to as “TC5-WA-βCD”) A dropping funnel and a three-way cock with a balloon Put a dry β-CD (1.13 g, 1.0 mmol, water content 1% or less, Junsei Kagaku) and special grade pyridine (50 mL, Wako Pure Chemical Industries, Ltd.) into a 200 mL three-necked flask with a stopcock at room temperature. For 15 minutes. After placing the flask in an ice bath, terephthaloyl dichloride (1.02 g, 5.0 mmol, Tokyo Chemical Industry) dissolved in special grade tetrahydrofuran (40 mL, Wako Pure Chemical Industries) was added dropwise over 30 minutes. After the dropwise addition, the ice bath was removed, and the mixture was stirred in a hot water bath (80 ° C.) for 3 hours. After completion of the reaction, distilled water (0.18 g, 10 mmol) was added and stirred for 1 hour. After the crystals were filtered off with suction, the obtained crystals were washed with distilled water (50 mL × 3) and primary acetone (50 mL × 3, Junsei) in that order, and the resulting solid was vacuum dried at 70 ° C. overnight. did. 1.64 g of TC5-WA-βCD was obtained.
IR 3394, 2909, 1717, 1271, 1082, 1043, 1017, 730 cm ^-1

[Synthesis Example 6] Synthesis of a polymer obtained by end-capping a condensed cyclodextrin of β-cyclodextrin and terephthaloyl dichloride with water (hereinafter referred to as “TC10-WA-βCD”) A dropping funnel and a three-way cock with a balloon Put a dry β-CD (1.13 g, 1.0 mmol, water content 1% or less, Junsei Kagaku) and special grade pyridine (50 mL, Wako Pure Chemical Industries, Ltd.) into a 200 mL three-necked flask with a stopcock at room temperature. For 15 minutes. After placing the flask in an ice bath, terephthaloyl dichloride (2.03 g, 10 mmol, Tokyo Chemical Industry) dissolved in special grade tetrahydrofuran (40 mL, Wako Pure Chemical Industries) was added dropwise over 30 minutes. After the dropwise addition, the ice bath was removed, and the mixture was stirred in a hot water bath (80 ° C.) for 3 hours. After completion of the reaction, distilled water (0.36 g, 20 mmol) was added and stirred for 1 hour. After the crystals were filtered off with suction, the obtained crystals were washed with distilled water (50 mL × 3) and primary acetone (50 mL × 3, Junsei) in that order, and the resulting solid was vacuum dried at 70 ° C. overnight. did. 2.25 g of TC10-WA-βCD was obtained.
IR 3279, 2936, 1716, 1271, 1099, 1045, 1017, 729 cm ^-1

[Synthesis Example 7] Synthesis of a polymer obtained by end-capping a cyclodextrin of β-cyclodextrin and terephthaloyl dichloride with iminodiacetic acid (hereinafter referred to as “TC10-IA-βCD”) A dropping funnel with a balloon Put a dry β-CD (1.13 g, 1.0 mmol, water content 1% or less, Junsei Kagaku) and special grade pyridine (50 mL, Wako Pure Chemical Industries) into a 200 mL three-necked flask equipped with a three-way cock and stopcock. And stirred at room temperature for 15 minutes. After placing the flask in an ice bath, terephthaloyl dichloride (2.03 g, 10 mmol, Tokyo Chemical Industry) dissolved in special grade tetrahydrofuran (40 mL, Wako Pure Chemical Industries) was added dropwise over 30 minutes. After the dropwise addition, the ice bath was removed, and the mixture was stirred in a hot water bath (80 ° C.) for 3 hours. After completion of the reaction, iminodiacetic acid (2.66 g, 20 mmol, Tokyo Chemical Industry) was added and stirred for 1 hour. After the crystals were filtered off with suction, the obtained crystals were washed with distilled water (50 mL × 3) and primary acetone (50 mL × 3, Junsei) in that order, and the resulting solid was vacuum dried at 70 ° C. overnight. did. 4.14 g of TC10-IA-βCD was obtained.
IR 3381, 2936, 1716, 1270, 1097, 1044, 1017, 730 cm ^-1

Synthesis Example 8 Synthesis of β-cyclodextrin and isophthaloyl chloride condensed cyclodextrin with water endcapped (hereinafter referred to as “IC10-WA-βCD”) Dropping funnel, three-way with balloon Put a dry β-CD (1.13 g, 1.0 mmol, water content 1% or less, Junsei Kagaku) and special grade pyridine (50 mL, Wako Pure Chemical Industries) into a 200 mL three-necked flask with a cock and stopcock. Stir at room temperature for 15 minutes. After placing the flask in an ice bath, isophthaloyl chloride (2.03 g, 10 mmol, Tokyo Chemical Industry) dissolved in special grade tetrahydrofuran (40 mL, Wako Pure Chemical Industries) was added dropwise over 30 minutes. After the dropwise addition, the ice bath was removed, and the mixture was stirred in a hot water bath (80 ° C.) for 3 hours. After completion of the reaction, distilled water (0.36 g, 20 mmol) was added and stirred for 1 hour. After the crystals were filtered off with suction, the obtained crystals were washed with distilled water (50 mL × 3) and primary acetone (50 mL × 3, Junsei) in that order, and the resulting solid was vacuum dried at 70 ° C. overnight. did. 2.51 g of IC10-WA-βCD was obtained.
IR 3381, 2940, 1717, 1270, 1139, 1074, 1044, 728 cm ^-1

[Synthesis Example 9] Synthesis of a polymer obtained by end-capping a condensed cyclodextrin of β-cyclodextrin and diglycolyl chloride with water (hereinafter referred to as “GC10-WA-βCD”) A dropping funnel and a three-way cock with a balloon Put a dry β-CD (1.13 g, 1.0 mmol, water content 1% or less, Junsei Kagaku) and special grade pyridine (50 mL, Wako Pure Chemical Industries, Ltd.) into a 200 mL three-necked flask with a stopcock at room temperature. For 15 minutes. After placing the flask in an ice bath, diglycolyl chloride (1.71 g, 10 mmol, Tokyo Chemical Industry) dissolved in special grade tetrahydrofuran (40 mL, Wako Pure Chemical Industries) was added dropwise over 30 minutes. After the dropwise addition, the ice bath was removed, and the mixture was stirred in a hot water bath (80 ° C.) for 3 hours. After completion of the reaction, distilled water (0.36 g, 20 mmol) was added and stirred for 1 hour. After the crystals were filtered off with suction, the obtained crystals were washed with distilled water (50 mL × 3) and primary acetone (50 mL × 3, Junsei) in that order, and the resulting solid was vacuum dried at 70 ° C. overnight. did. 2.02 g of GC10-WA-βCD was obtained.
IR 3380, 2946, 1747, 1243, 1136, 1077, 998 cm ^-1

[Synthesis Example 10] Synthesis of a polymer obtained by end-capping a condensed cyclodextrin of β-cyclodextrin and terephthaloyl dichloride with triethylene glycol (hereinafter referred to as “TC10-TG-βCD”) A dropping funnel with a balloon Put a dry β-CD (1.13 g, 1.0 mmol, water content 1% or less, Junsei Kagaku) and special grade pyridine (50 mL, Wako Pure Chemical Industries) into a 200 mL three-necked flask equipped with a three-way cock and stopcock. And stirred at room temperature for 15 minutes. After placing the flask in an ice bath, terephthaloyl dichloride (2.03 g, 10 mmol, Tokyo Chemical Industry) dissolved in special grade tetrahydrofuran (40 mL, Wako Pure Chemical Industries) was added dropwise over 30 minutes. After the dropwise addition, the ice bath was removed, and the mixture was stirred in a hot water bath (80 ° C.) for 3 hours. After completion of the reaction, triethylene glycol (1.50 g, 10 mmol, ALDRICH) was added and stirred for 1 hour. After the crystals were filtered off with suction, the obtained crystals were washed with distilled water (50 mL × 3) and primary acetone (50 mL × 3, Junsei) in that order, and the resulting solid was vacuum dried at 70 ° C. overnight. did. 3.32 g of TC10-TG-βCD was obtained.
IR 3381, 2928, 1717, 1270, 1096, 1043, 1017, 729 cm ^-1

[Synthesis Example 11] Synthesis of a polymer obtained by end-capping a cyclodextrin of β-cyclodextrin and terephthaloyl dichloride with hexaethylene glycol (hereinafter referred to as “TC10-HG-βCD”) A dropping funnel with a balloon Put a dry β-CD (1.13 g, 1.0 mmol, water content 1% or less, Junsei Kagaku) and special grade pyridine (50 mL, Wako Pure Chemical Industries) into a 200 mL three-necked flask equipped with a three-way cock and stopcock. And stirred at room temperature for 15 minutes. After placing the flask in an ice bath, terephthaloyl dichloride (2.03 g, 10 mmol, Tokyo Chemical Industry) dissolved in special grade tetrahydrofuran (40 mL, Wako Pure Chemical Industries) was added dropwise over 30 minutes. After the dropwise addition, the ice bath was removed, and the mixture was stirred in a hot water bath (80 ° C.) for 3 hours. After completion of the reaction, hexaethylene glycol (2.82 g, 10 mmol, ALDRICH) was added and stirred for 1 hour. After the crystals were filtered off with suction, the obtained crystals were washed with distilled water (50 mL × 3) and primary acetone (50 mL × 3, Junsei) in that order, and the resulting solid was vacuum dried at 70 ° C. overnight. did. 4.26 g of TC10-HG-βCD was obtained.
IR 3610, 2941, 1717, 1270, 1098, 1045, 1017, 730 cm ^-1

[Synthesis Example 12] Synthesis of a polymer (hereinafter referred to as “TC10-BP-βCD”) obtained by end-capping a condensed cyclodextrin of β-cyclodextrin and terephthaloyl dichloride with 2,2′-bisphenol. , Three-way flask with balloon, 200 mL three-neck flask with stopcock, dry β-CD (1.13 g, 1.0 mmol, water content 1% or less, Junsei Kagaku) and special grade pyridine (50 mL, Wako Pure Chemical Industries, Ltd.) ) And stirred at room temperature for 15 minutes. After placing the flask in an ice bath, terephthaloyl dichloride (2.03 g, 10 mmol, Tokyo Chemical Industry) dissolved in special grade tetrahydrofuran (40 mL, Wako Pure Chemical Industries) was added dropwise over 30 minutes. After the dropwise addition, the ice bath was removed, and the mixture was stirred in a hot water bath (80 ° C.) for 3 hours. After completion of the reaction, 2,2′-biphenol (1.86 g, 10 mmol, ALDRICH) was added and stirred for 1 hour. After the crystals were filtered off with suction, the obtained crystals were washed with distilled water (50 mL × 3) and primary acetone (50 mL × 3, Junsei) in that order, and the resulting solid was vacuum dried at 70 ° C. overnight. did. 3.57 g of TC10-BP-βCD was obtained.
IR 3610, 2937, 1719, 1271, 1099, 1046, 1017, 729 cm ^-1

[Synthesis Example 13] Synthesis of a polymer obtained by end-capping a condensed cyclodextrin of γ-cyclodextrin and terephthaloyl dichloride with water (hereinafter referred to as “TC3-WA-γCD”) A dropping funnel and a three-way cock with a balloon In a 200 mL three-necked flask with a stopcock, dry γ-cyclodextrin (hereinafter referred to as “γ-CD”; 1.30 g, 1.0 mmol, water content of 1% or less, Junsei Kagaku) and special grade pyridine (50 mL, Wako Pure Chemical Industries, Ltd.) was added and stirred at room temperature for 15 minutes. After placing the flask in an ice bath, terephthaloyl dichloride (0.61 g, 3.0 mmol, Tokyo Chemical Industry) dissolved in special grade tetrahydrofuran (40 mL, Wako Pure Chemical Industries) was added dropwise over 30 minutes. After the dropwise addition, the ice bath was removed, and the mixture was stirred in a hot water bath (80 ° C.) for 3 hours. After completion of the reaction, distilled water (0.11 g, 6.0 mmol) was added and stirred for 1 hour. After the crystals were filtered off with suction, the obtained crystals were washed with distilled water (50 mL × 3) and primary acetone (50 mL × 3, Junsei) in that order, and the resulting solid was vacuum dried at 70 ° C. overnight. did. 1.55 g of TC3-WA-γCD was obtained.
IR 3385, 2922, 1715, 1271, 1149, 1080, 1018, 731 cm ^-1

[Synthesis Example 14] Synthesis of polymer obtained by end-capping condensed cyclodextrin of γ-cyclodextrin and terephthaloyl dichloride with water (hereinafter referred to as “TC5-WA-γCD”) Dropping funnel, three-way cock with balloon Put a dry γ-CD (1.30 g, 1.0 mmol, water content 1% or less, Junsei Kagaku) and special grade pyridine (50 mL, Wako Pure Chemical Industries) into a 200 mL three-necked flask with a stopcock at room temperature. For 15 minutes. After placing the flask in an ice bath, terephthaloyl dichloride (1.02 g, 5.0 mmol, Tokyo Chemical Industry) dissolved in special grade tetrahydrofuran (40 mL, Wako Pure Chemical Industries) was added dropwise over 30 minutes. After the dropwise addition, the ice bath was removed, and the mixture was stirred in a hot water bath (80 ° C.) for 3 hours. After completion of the reaction, distilled water (0.18 g, 10 mmol) was added and stirred for 1 hour. After the crystals were filtered off with suction, the obtained crystals were washed with distilled water (50 mL × 3) and primary acetone (50 mL × 3, Junsei) in that order, and the resulting solid was vacuum dried at 70 ° C. overnight. did. 1.77 g of TC5-WA-γCD was obtained.
IR 3386, 2923, 1712, 1269, 1149, 1081, 1017, 730 cm ^-1

[Synthesis Example 15] Synthesis of a polymer obtained by end-capping a condensed cyclodextrin of γ-cyclodextrin and terephthaloyl dichloride with water (hereinafter referred to as “TC10-WA-γCD”) A dropping funnel and a three-way cock with a balloon Put a dry γ-CD (1.30 g, 1.0 mmol, water content 1% or less, Junsei Kagaku) and special grade pyridine (50 mL, Wako Pure Chemical Industries) into a 200 mL three-necked flask with a stopcock at room temperature. For 15 minutes. After placing the flask in an ice bath, terephthaloyl dichloride (2.03 g, 10 mmol, Tokyo Chemical Industry) dissolved in special grade tetrahydrofuran (40 mL, Wako Pure Chemical Industries) was added dropwise over 30 minutes. After the dropwise addition, the ice bath was removed, and the mixture was stirred in a hot water bath (80 ° C.) for 3 hours. After completion of the reaction, distilled water (0.36 g, 20 mmol) was added and stirred for 1 hour. After the crystals were filtered off with suction, the obtained crystals were washed with distilled water (50 mL × 3) and primary acetone (50 mL × 3, Junsei) in that order, and the resulting solid was vacuum dried at 70 ° C. overnight. did. 2.37 g of TC10-WA-γCD was obtained.
IR 3386, 2941, 1716, 1269, 1097, 1043, 1017, 729 cm ^-1

[Comparative Synthesis Example 1] Synthesis of condensed cyclodextrin polymer of β-cyclodextrin and tert-butyldimethylsilyl chloride (hereinafter referred to as “TBDMS-β-CD”) A dropping funnel, a three-way cock with a balloon and a septum were attached. Β-cyclodextrin (5.0 g, 4.4 mmol, Wako Pure Chemical Industries) and dry pyridine (44 mL, Wako Pure Chemical Industries) were placed in a 200 ml three-necked flask. After placing the flask in an ice bath, tert-butyldimethylsilyl chloride (6.03 g, 40 mmol, Tokyo Chemical Industry) dissolved in dry pyridine (26 mL) was added dropwise over 2 hours. After completion of the dropwise addition, the ice bath was removed and the mixture was stirred at room temperature for 11 hours. After completion of the reaction, the reaction solution was poured into water (200 mL), and the precipitated white crystals were collected by filtration. The white crystals were dissolved in dichloromethane and washed with water. After the dichloromethane layer was dried over anhydrous sodium sulfate, the solvent was distilled off. TBDMS-β-CD (2.3 g, yield: 27%) was isolated from the obtained white crystals by silica gel column purification and recrystallization with acetone.

[Comparative Synthesis Example 2]
Synthesis of a polymer (hereinafter referred to as “TC10-MG-βCD”) obtained by end-capping a condensed cyclodextrin of β-cyclodextrin and terephthaloyl dichloride with diethylene glycol monomethyl ether. Place a dry β-CD (1.13 g, 1.0 mmol, water content 1% or less, Junsei Kagaku) and special grade pyridine (50 mL, Wako Pure Chemical Industries, Ltd.) in a 200 mL three-necked flask for 15 minutes at room temperature. Stir. After placing the flask in an ice bath, terephthaloyl dichloride (2.03 g, 10 mmol, Tokyo Chemical Industry) dissolved in special grade tetrahydrofuran (40 mL, Wako Pure Chemical Industries) was added dropwise over 30 minutes. After the dropwise addition, the ice bath was removed, and the mixture was stirred in a hot water bath (80 ° C.) for 3 hours. After completion of the reaction, diethylene glycol monomethyl ether (2.40 g, 20 mmol, ALDRICH) was added and stirred for 1 hour. After the crystals were filtered off with suction, the obtained crystals were washed with distilled water (50 mL × 3) and primary acetone (50 mL × 3, Junsei) in that order, and the resulting solid was vacuum dried at 70 ° C. overnight. did. 4.26 g of TC10-MG-βCD was obtained.
IR 3605, 2933, 1715, 1260, 1105, 1040, 1006, 730 cm ^-1

[Synthesis Example 16] Synthesis of polymer irradiated with γ-rays-irradiation dose: 0.61 kGy, amount of deionized water used: 5 mL)
In order to confirm whether the polymer used for the radioactive substance removing material of the present invention can withstand the irradiation of radiation, in the following synthesis example, a sample is prepared by irradiating the polymer used for the present invention with radiation. It was.
In a screw test tube, 350 mg of the polymer obtained in Synthesis Examples 1, 6, 7, 9, 10 and Comparative Synthesis Example 1, (TC3-WA-αCD, TC10-WA-βCD, TC10-IA-βCD, GC10) -WA-βCD, TC10-TG-βCD, TBDMS-aCD), and then 5 mL of deionized water. Six prepared screw test tubes were irradiated with 0.61 kGy of γ-rays. The polymer irradiated with γ-rays was subjected to suction filtration, washed with primary acetone (50 mL, Junsei Chemical), and vacuum dried at 70 ° C. overnight. Polymers irradiated with about 350 mg of γ rays (TC3-WA-αCD-SS, TC10-WA-βCD-SS, TC10-IA-βCD-SS, GC10-WA-βCD-SS, TC10-TG-βCD-SS , And TBDMS-βCD-SS).

[Synthesis Example 17] (Synthesis of polymer irradiated with γ rays-irradiation dose: 0.61 kGy, amount of deionized water used: 15 mL)
350 mg of polymers obtained in Synthesis Examples 1, 6, 7, 9, 10 and Comparative Synthesis Example 1 (TC3-WA-αCD, TC10-WA-βCD, TC10-IA-βCD, GC10-WA) -ΒCD, TC10-TG-βCD, TBDMS-βCD), and then 15 mL of deionized water. Six prepared screw test tubes were irradiated with 0.61 kGy of γ-rays. The polymer irradiated with γ-rays was subjected to suction filtration, washed with primary acetone (50 mL, Junsei Chemical), and vacuum dried at 70 ° C. overnight. Polymers irradiated with about 350 mg of γ rays (TC3-WA-αCD-SL, TC10-WA-βCD-SL, TC10-IA-βCD-SL, GC10-WA-βCD-SL, TC10-TG-βCD-SL , And TMDMS-βCD-SL).

[Synthesis Example 18] (Synthesis of polymer irradiated with γ-rays-irradiation dose: 3.91 kGy, amount of deionized water used: 5 mL)
350 mg of polymers obtained in Synthesis Examples 1, 6, 7, 9, 10 and Comparative Synthesis Example 1 (TC3-WA-αCD, TC10-WA-βCD, TC10-IA-βCD, GC10-WA) -ΒCD, TC10-TG-βCD, TBDMS-βCD), and then 5 mL of deionized water. Six prepared screw-tubes were irradiated with 3.91 kGy of γ-rays. The polymer irradiated with γ-rays was subjected to suction filtration, washed with primary acetone (50 mL, Junsei Chemical), and vacuum dried at 70 ° C. overnight. Polymers irradiated with about 350 mg of γ rays (TC3-WA-αCD-LS, TC10-WA-βCD-LS, TC10-IA-βCD-LS, GC10-WA-βCD-LS, TC10-TG-βCD-LS , And TBDMS-βCD-LS).

[Synthesis Example 19] (Synthesis of polymer irradiated with γ-rays-irradiation dose: 3.91 kGy, amount of deionized water used: 15 mL)
350 mg of polymers obtained in Synthesis Examples 1, 6, 7, 9, 10 and Comparative Synthesis Example 1 (TC3-WA-αCD, TC10-WA-βCD, TC10-IA-βCD, GC10-WA- βCD, TC10-TG-βCD, TBDMS-βCD) were added, followed by 15 mL of deionized water. Six prepared screw-tubes were irradiated with 3.91 kGy of γ-rays. The polymer irradiated with γ-rays was subjected to suction filtration, washed with primary acetone (50 mL, Junsei Chemical), and vacuum dried at 70 ° C. overnight. Polymers irradiated with about 350 mg of γ rays (TC3-WA-αCD-LL, TC10-WA-βCD-LL, TC10-IA-βCD-LL, GC10-WA-βCD-LL, TC10-TG-βCD-LL , And TBDMS-βCD-LL).

[Example 1] (Evaluation of Radioactive Substance Removal Performance of Synthesized Polymer (1): Sample Tube Method)
The radioactive substance removing performance of the radioactive substance removing material of the present invention was evaluated according to the following method.
Cesium chloride (ALDRICH) was dissolved in deionized water to prepare an aqueous cesium solution (deionized water). After putting 25 g of cesium aqueous solution (deionized water) into a 50 mL sample tube, 5 g of cesium aqueous solution (deionized water) was collected. Each polymer (20 mg) prepared in the above synthesis example was placed in a sample tube and stirred at 500 rpm for 30 minutes. After stirring, filtration was performed to recover an aqueous solution. The concentration of cesium in the collected aqueous solution was measured with an ICP emission spectrometer, and the adsorption rate of cesium was calculated. FIG. 1 schematically illustrates the evaluation method. Table 1 shows the types of polymers used and the results of the cesium adsorption rate.

  By the method of Example 1, the cesium adsorption rate was measured for ferrocyanide (Daiichi Seika Kogyo Co., Ltd.) and A-type zeolite (Tosoh Corp.). The results are shown in Table 1 (comparison).

[Example 2] (Evaluation of Radioactive Substance Removal Performance of Synthesized Polymer (2): Syringe Method)
Example 5 was performed in order to confirm that the radioactive substance can be easily removed by filling the syringe used with the polymer in the present invention and circulating water containing the radioactive substance therein. In addition, a present Example becomes a model of the radioactive substance removal method by the method which circulates the water which contains the polymer used for this invention in a column, and contains a radioactive substance here.

    Cesium chloride (ALDRICH) was dissolved in deionized water to prepare an aqueous cesium solution (deionized water). A syringe was filled with each prepared polymer (200 mg), and then 20 g of a cesium aqueous solution (deionized water) was allowed to flow. After recovering the aqueous solution that passed through the syringe filled with the polymer, the iodine concentration in the aqueous solution was measured with an ICP emission spectrometer, and the adsorption rate of cesium was calculated. FIG. 2 schematically shows this evaluation method. Table 2 shows the types of polymers used and the results of iodine adsorption rate.

  By the method of Example 2, the cesium adsorption rate was measured for ferrocyanide (Daiichi Seika Kogyo Co., Ltd.), A-type zeolite (Tosoh Corp.) and absorbent cotton (Yamato Factory Co., Ltd.). The results are shown in Table 2 (comparison).

[Example 3] (Evaluation of Radioactive Substance Removal Performance of Synthesized Polymer (3): Syringe Method)
Cesium chloride (ALDROICH) was dissolved in deionized water to prepare an aqueous cesium solution (deionized water). A syringe was filled with a polymer irradiated with γ rays (200 mg, Synthesis Examples 16 to 19), and then 20 g of an aqueous cesium solution (deionized water) was allowed to flow. After recovering the aqueous solution that passed through the syringe filled with the polymer, the concentration of cesium in the aqueous solution was measured with an ICP emission spectrometer, and the adsorption rate of cesium was calculated. The types of polymers used and the results of iodine adsorption rates are shown in Tables 3 to 6, respectively.

    The same experiment was conducted for each polymer not irradiated with radiation. The results are shown in Table 7.

[Example 4] (Evaluation of Radioactive Substance Removal Performance of Synthesized Polymer (4): Sample Tube Method) The radioactive substance removal performance of the radioactive substance removal material of the present invention was evaluated according to the following method.
Strontium chloride (ALDRICH) was dissolved in deionized water to prepare an aqueous strontium solution (deionized water). 25 g of strontium aqueous solution (deionized water) was placed in a 50 mL sample tube, and then 5 g of strontium aqueous solution (deionized water) was collected. Each polymer (20 mg) prepared in the above synthesis example was placed in a sample tube and stirred at 500 rpm for 30 minutes. After stirring, filtration was performed to recover an aqueous solution. The concentration of strontium in the recovered aqueous solution was measured with an ICP emission spectrometer, and the adsorption rate of strontium was calculated. FIG. 3 schematically shows the evaluation method. Table 8 shows the results of polymer type and strontium adsorption rate.

    The strontium adsorption rate was measured for ferrocyanide (Daiichi Seika Kogyo Co., Ltd.) and A-type zeolite (Tosoh Corp.) by the method of Example 4. The results are shown in Table 8 (comparison).

[Example 5] (Evaluation of Radioactive Material Removal Performance of Synthesized Polymer (5): Sample Tube Method)
For the polymer that showed the best adsorption rate in Example 4 (Synthesis Example 6), it was measured whether the adsorption rate could be improved by extending the adsorption time.

  Strontium chloride (ALDRICH) was dissolved in deionized water to prepare an aqueous strontium solution (deionized water). 25 g of strontium aqueous solution (deionized water) was placed in a 50 mL sample tube, and then 5 g of strontium aqueous solution (deionized water) was collected. The polymer (20 mg) prepared in Synthesis Example 6 was placed in a sample tube and stirred at 500 rpm for 6 hours. After stirring, filtration was performed to recover an aqueous solution. The concentration of strontium in the recovered aqueous solution was measured with an ICP emission spectrometer, and the adsorption rate of strontium was calculated. Table 9 shows the polymer types and the results of the strontium adsorption rate.

    The strontium adsorption rate of the A-type zeolite (Tosoh Corporation) was measured by the method of Example 5. The results are shown in Table 9 (comparison).

[Example 6] (Evaluation of Radioactive Substance Removal Performance of Synthesized Polymer (6): Sample Tube Method)
For the polymer that showed the best adsorption rate in Example 4 (Synthesis Example 6), it was measured whether the adsorption rate could be improved by increasing the amount of polymer.

  Strontium chloride (ALDRICH) was dissolved in deionized water to prepare an aqueous strontium solution (deionized water). 25 g of strontium aqueous solution (deionized water) was placed in a 50 mL sample tube, and then 5 g of strontium aqueous solution (deionized water) was collected. The polymer (200 mg) prepared in Synthesis Example 6 was placed in a sample tube and stirred at 500 rpm for 30 minutes. After stirring, filtration was performed to recover an aqueous solution. The concentration of strontium in the recovered aqueous solution was measured with an ICP emission spectrometer, and the adsorption rate of strontium was calculated. Table 10 shows the results of polymer types and strontium adsorption rates.

    The strontium adsorption rate of the A-type zeolite (Tosoh Corporation) was measured by the method of Example 6. The results are shown in Table 10 (comparison).

[Example 7] (Evaluation of Radioactive Substance Removal Performance of Synthesized Polymer (7): Sample Tube Method)
About the polymer (Synthesis example 6) which showed the best adsorption rate in Example 4, it was measured whether the adsorption rate could be improved by increasing the amount of the polymer and extending the adsorption time.

  Strontium chloride (ALDRICH) was dissolved in deionized water to prepare an aqueous strontium solution (deionized water). 25 g of strontium aqueous solution (deionized water) was placed in a 50 mL sample tube, and then 5 g of strontium aqueous solution (deionized water) was collected. The polymer (200 mg) prepared in Synthesis Example 6 was placed in a sample tube and stirred at 500 rpm for 6 hours. After stirring, filtration was performed to recover an aqueous solution. The concentration of strontium in the recovered aqueous solution was measured with an ICP emission spectrometer, and the adsorption rate of strontium was calculated. Table 11 shows the results of polymer type and strontium adsorption rate.

    The strontium adsorption rate of the A-type zeolite (Tosoh Corporation) was measured by the method of Example 7. The results are shown in Table 11 (comparison).

[Example 8] (Evaluation of Radioactive Material Removal Performance of Synthesized Polymer (8))
In order to confirm whether or not the polymer (Synthesis Example 6) that showed the best adsorption rate in Example 4 was able to remove radioactive substances in the groundwater, Example 8 was performed.

  Strontium chloride (ALDRICH) was dissolved in groundwater collected from the campus of the National University Corporation Osaka University to prepare an aqueous solution of strontium (groundwater). After putting 25 g of strontium aqueous solution (groundwater) into a 50 mL sample tube, 5 g of strontium aqueous solution (groundwater) was collected. The polymer (200 mg) prepared in Synthesis Example 6 was placed in a sample tube and stirred at 500 rpm for 30 minutes. After stirring, filtration was performed to recover an aqueous solution. The concentration of strontium in the recovered aqueous solution was measured with an ICP emission spectrometer, and the adsorption rate of strontium was calculated. Table 12 shows the results of polymer type and strontium adsorption rate.

    The strontium adsorption rate of the A-type zeolite (Tosoh Corporation) was measured by the method of Example 8. The results are shown in Table 12 (comparison).

[Examples 9 and 10] (Evaluation of Radioactive Substance Removal Performance of Synthesized Polymer (9) and (10))
In the method of Example 8, the amount of the polymer was increased to 500 mg (Example 9) and 1 g (Example 10). Table 13 (Example 9) and Table 14 (Example 10) show the types of polymers and strontium adsorption rates.

    The strontium adsorption rate of the A-type zeolite (Tosoh Corporation) was measured by the methods of Examples 9 and 10. The results are shown in Table 13 (Comparative) (Comparative Example 9) and Table 14 (Comparative) (Comparative Example 10).

[Supplemental explanation]
In addition, the analysis method in each said Examples 1-10 is as follows:
The properties of each synthesized polymer were measured by infrared spectroscopy with a Spectrum 100 FT-IR Spectrometer (PerkinElmer) and identified. The concentration of cesium and strontium in the aqueous solution was determined by IPC (inductively coupled plasma) emission spectrometry using ICPS-7510 (SHIMADZU).

[Consideration of Examples and Comparative Examples]
Cesium could be adsorbed by a method (sample tube method) in which the polymer of the present invention was directly added to the cesium aqueous solution in the sample tube and stirred. However, the adsorption rate of inorganic substances such as ferrocyanide and A-type zeolite was not reached. On the other hand, according to a method (syringe method) in which the polymer of the present invention is filled in a syringe and a cesium aqueous solution is flowed, cesium at a level comparable to that of ferrocyanide or A-type zeolite can be adsorbed. The carboxyl group at the end of the polymer of the present invention and the cesium ion in the aqueous solution are considered to be repeatedly adsorbed and desorbed, and the cesium ion once adsorbed to the polymer of the present invention may be desorbed immediately. . It is speculated that using the polymer of the present invention, it may be difficult to adsorb and remove cesium ions at a level equivalent to that of inorganic substances by the sample tube method.

  On the other hand, in the syringe method, even if the cesium ions once adsorbed to the filled polymer are desorbed immediately, they are immediately re-adsorbed to the nearby polymer, so that it is considered that the holding ability of the polymer is high.

  Even when the polymer of the present invention was irradiated with γ-rays, no decrease in the amount of adsorbed cesium ions was observed. The polymer of the present invention can adsorb and remove radioactive substances without deterioration even in an environment where the polymer surface is irradiated with radiation.

  Unlike monovalent ion cesium, strontium, a divalent ion, could be effectively adsorbed by the sample tube method using the polymer of the present invention. This is presumably because strontium, a divalent ion, hardly desorbs once adsorbed to the polymer. And it was found that by adjusting the amount and adsorption time of the polymer of the present invention, an adsorption rate substantially equivalent to that of A-type zeolite can be obtained.

  The polymer of the present invention was able to adsorb strontium ions dissolved in groundwater. The polymer of the present invention can be used to adsorb and remove radioactive strontium released into the environment.

Claims (8)

A cyclodextrin condensation polymer obtained by reacting a cyclodextrin with an organic dibasic acid or an organic dibasic acid halide is reacted with water, a polyhydric alcohol, a polyarylaryl alcohol, or a polycarboxylic acid. A radioactive substance removing material containing the polymer obtained in the above. Organic dibasic acid or organic dibasic acid halide is terephthalic acid, isophthalic acid, maleic acid, malic acid, malonic acid, succinic acid, fumaric acid, glutaric acid, adipic acid, phthalic acid, diglycolic acid or these 2. A material according to claim 1 selected from halides. The polyhydric alcohol is selected from dihydric alcohols having 1 to 10 carbon atoms, trihydric alcohols, or tetrahydric alcohols, and the polyhydric aryl alcohols are hydroquinones, catechols, resorcinols, bisphenols or The material according to claim 1 or 2, selected from substituted bisphenols, wherein the polyvalent carboxylic acids are selected from dicarboxylic acids, tricarboxylic acids, or tetracarboxylic acids. The material according to any one of claims 1 to 3, wherein the radioactive substance is radioactive cesium and / or strontium. The end of the cyclodextrin condensation polymer obtained by reacting cyclodextrin with organic dibasic acid or organic dibasic acid halide is reacted with water, polyhydric alcohols, polyarylaryl alcohols or polycarboxylic acids. The radioactive substance-removing material containing the obtained polymer is brought into contact with water containing the radioactive substance, and the radioactive substance contained in the water is fixed to the radioactive substance-removing material, and water containing no radioactive substance is removed. A method characterized by obtaining. Organic dibasic acid or organic dibasic acid halide is terephthalic acid, isophthalic acid, maleic acid, malic acid, malonic acid, succinic acid, fumaric acid, glutaric acid, adipic acid, phthalic acid, diglycolic acid or their halides The method of claim 5, wherein the method is selected from: The polyhydric alcohol is selected from dialcohols having 1 to 10 carbon atoms, trialcohols or tetraalcohols, and the polyhydric aryl alcohols are hydroquinones, catechols, resorcinols, bisphenols or substituted bisphenols 7. The method according to claim 5 or 6, wherein the polyvalent carboxylic acids are selected from dicarboxylic acids, tricarboxylic acids, or tetracarboxylic acids. The method according to any one of claims 5 to 7, wherein the radioactive substance is radioactive cesium and / or strontium.