JP2013140028A - Radioactive substance removal adsorption material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a selective removal material which selectively attaching to radioactive substances contained in water so as to remove radioactive substances from water, allowing for easy treatment of radioactive substances.SOLUTION: A radioactive substance removal adsorption material includes a polymer produced by a reaction of a cyclodextrin condensation polymer with water, polyalcohols, polyaryl alcohols, or polyvalent carboxylic acids. The cyclodextrin condensation polymer is produced by a reaction of cyclodextrins with organic dibasic acid or organic dibasic acid halide.

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 iodine into the environment (I ^129, I ^131), the human body is a compound that shows a strong toxicity to plants and animals, in particular radioactive iodine (I ¹³¹⁾ is a thyroid cancer when accumulate in human thyroid Trigger. Radioiodine (I ¹²⁹ ) is a β nuclide with a half-life of 1.571 × 10 ⁷ years, and its toxicity lasts for a long time. Therefore, if radioactive iodine (I ¹²⁹ , I ¹³¹ ) is released into the atmosphere, soil, seawater, groundwater, etc., it must be removed immediately and stored safely.

  Conventionally, as a treatment method for contaminated water containing radioactive iodine, methods using activated carbon, zeolite, ion exchange resin, reverse osmosis membrane, etc. are common, but methods using nonflammable inorganic substances adsorb contaminants. It is difficult to reduce the volume of the material, and the method using zeolite has a problem that the adsorption performance of the radioactive material 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.

  For example, Patent Document 1 discloses a method in which radioactive elements such as iodine are adsorbed in a zeolite window portion, the zeolite window portion is silica-coated with silicon alkoxide to close the window portion, and the elution of the contained iodine to the outside is suppressed. Is disclosed. The method disclosed in Patent Document 1 can effectively adsorb iodine, but does not disclose how to treat the zeolite after adsorption of iodine.

  Patent Document 2 discloses sodalite-type waste, in which radioactive iodine is collected by a zeolite carrying silver, and the zeolite from which iodine gas is collected is calcined in a firing furnace to obtain a sodalite-type waste solidified body. A method for producing a solidified body is disclosed. In the method disclosed in the cited document 2, the waste containing radioactive iodine can be made into a sodalite-type stable solid, but the volume of the sodalite-type solid itself is large and still difficult to store.

  Patent Document 3 discloses an iodine sampler. In Patent Document 3, the amount of radioactive iodine contained in the waste discharged from an incinerator or melting furnace of solid waste in a nuclear facility is measured using a filter cartridge filled with potassium zeolite. Even in the method disclosed in Patent Document 3, there is a problem of how to store the filter cartridge that collects radioactive iodine.

  Thus, none of the patent documents describes the treatment of zeolite after collecting radioactive iodine. At present, since a method for treating zeolite after collecting radioactive iodine has not been established, it can be said that it is difficult to use zeolite for treating contaminated water containing a large amount of radioactive iodine. The methods described in Patent Documents 1 to 3 are intended to collect radioactive iodine contained in the exhaust gas. However, zeolite is a method for treating radioactive iodine-contaminated water that may contain various salts. Is difficult to use.

  Furthermore, Patent Literature 4 and Patent Literature 5 disclose a method of removing radioactive iodine using a hydroxyl group ion exchange resin that is an organic material. However, since the methods described in Patent Document 4 and Patent Document 5 do not assume use in contaminated water with a long radiation dose, the bond in the ion exchange resin is broken at a location with a high radiation dose. There is a possibility that performance degradation will occur and the expected performance may not be shown.

  From such a viewpoint, it was decided to search for an organic substance that does not use zeolite, which is an inorganic substance that is difficult to reduce in volume. Then, as an organic substance whose performance does not deteriorate even when used in radioactive material contaminated water with a high radiation dose, a polymer obtained by condensing cyclodextrin and organic dibasic acid was found, and selective radioactive iodine containing this was found. A remover is provided. A polymer containing a polymer obtained by condensing a cyclodextrin and an organic dibasic acid can selectively remove iodine from radioactive material-contaminated water, and collects iodine-free water as an example. And revealed.

JP2001-091694 JP2003-255083 JP 2010-048765 JP2005-037133 JP2005-037147 Mitsubishi Heavy Industries Technical Report, Vol. 35, no. 4, pages 282 to 285 Ebara Times, No. 218, 29-34

  The present invention provides a selective removal material capable of facilitating the treatment of radioactive substances by selectively fixing radioactive substances contained in water, particularly radioactive iodine, and removing the radioactive substances from water. The purpose is to do. 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 iodine.
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 iodine.

  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 iodine 129 and iodine 131 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.

  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]
TBDMS-β-CD obtained in Comparative Synthesis Example 1 was dried (11.61 g, 6.0 mmol), and sodium hydroxide (6.72 g, 168 mmol) was refluxed in dry tetrahydrofuran (200 mL) for 2 hours. Benzyl bromide (29.62 g, 168 mmol) was added dropwise over 1 hour. After refluxing overnight, disappearance of the raw materials was confirmed by thin layer chromatography (TLC method), and the solvent was distilled off. The residue was desalted by extraction with hexane (300 mL) -water (200 mL × 2), the hexane phase was dried over anhydrous magnesium sulfate, and the solvent was distilled off. The obtained brown viscous liquid was dissolved in a small amount of dichloromethane, a large amount of methanol was added, and the precipitated solid was collected by filtration. This was purified by recrystallization from methanol / acetone to obtain TBDMS-Bn-β-CD (white, 15.49 g). Yield 81%.
Next, the obtained TBDMS-Bn-β-CD (13.75 g, 4.3 mmol) and tetrabutylammonium fluoride trihydrate (14.25 g, 45.15 mmol) were dissolved in tetrahydrofuran (150 mL) and refluxed overnight. I let you. The disappearance of the raw material was confirmed by TLC method, and the solvent was distilled off. The residue was dissolved in chloroform, washed with saturated brine, the chloroform phase was dried over anhydrous magnesium sulfate, and the solvent was distilled off. The obtained yellow viscous liquid was purified by silica gel column chromatography (CHCl ₃ / MeOH = 19/1) to obtain Bn-β-CD (white, 5.2 g). Yield 50%.

[Comparative Synthesis Example 3] Synthesis of condensed cyclodextrin polymer of α-cyclodextrin and tert-butyldimethylsilyl chloride (hereinafter referred to as “TBDMS-α-CD”) A dropping funnel, a three-way cock with a balloon and a septum were attached. In a 200 ml three-necked flask, α-cyclodextrin (4.28 g, 4.4 mmol, Wako Pure Chemical Industries) and dry pyridine (44 mL, Wako Pure Chemical Industries) were placed. 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-α-CD (1.26 g, yield: 26.4%) was isolated from the obtained white crystals by silica gel column purification and recrystallization with acetone.

[Comparative Synthesis Example 4] Synthesis of condensed cyclodextrin polymer of γ-cyclodextrin and tert-butyldimethylsilyl chloride (hereinafter referred to as “TBDMS-γ-CD”) A dropping funnel, a three-way cock with a balloon and a septum In a 200 ml three-necked flask, γ-cyclodextrin (5.71 g, 4.4 mmol, Wako Pure Chemical Industries) and dry pyridine (44 mL, Wako Pure Chemical Industries) were placed. 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-γ-CD (1.98 g, yield: 31.9%) was isolated from the obtained white crystals by silica gel column purification and recrystallization with acetone.

[Comparative Synthesis Example 5]
TBDMS-γ-CD obtained in Comparative Synthesis Example 4 was dried (8.46 g, 6.0 mmol), and sodium hydroxide (6.72 g, 168 mmol) was refluxed in dry tetrahydrofuran (200 mL) for 2 hours. Benzyl bromide (29.62 g, 168 mmol) was added dropwise over 1 hour. After refluxing overnight, disappearance of the raw materials was confirmed by thin layer chromatography (TLC method), and the solvent was distilled off. The residue was desalted by extraction with hexane (300 mL) -water (200 mL × 2), the hexane phase was dried over anhydrous magnesium sulfate, and the solvent was distilled off. The obtained brown viscous liquid was dissolved in a small amount of dichloromethane, a large amount of methanol was added, and the precipitated solid was collected by filtration. This was purified by recrystallization from methanol / acetone to obtain TBDMS-Bn-γ-CD (white, 7.16 g). Yield 79.5%.
Next, the obtained TBDMS-Bn-γ-CD (6.46 g, 4.3 mmol) and tetrabutylammonium fluoride trihydrate (14.25 g, 45.15 mmol) were dissolved in tetrahydrofuran (150 mL) and refluxed overnight. I let you. The disappearance of the raw material was confirmed by TLC method, and the solvent was distilled off. The residue was dissolved in chloroform, washed with saturated brine, the chloroform phase was dried over anhydrous magnesium sulfate, and the solvent was distilled off. The resulting yellow viscous liquid was purified by silica gel column chromatography (CHCl ₃ / MeOH = 19/1) to obtain Bn-γ-CD (white, 2.45 g). Yield 41.0%.

[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-A-CD) were added, followed by 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-β-CD-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-β-CD-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-β-CD) 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 Material Removal Performance of Synthesized Polymer (1))
The radioactive substance removing performance of the radioactive substance removing material of the present invention was evaluated according to the following method.
Iodine (Tokyo Chemical Industry) was dissolved in deionized water to prepare an iodine aqueous solution (deionized water). After putting 25 g of iodine aqueous solution (deionized water) into a 50 mL sample tube, 5 g of iodine 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 iodine concentration in the collected aqueous solution was measured with an ICP emission spectrometer, and the iodine removal rate was calculated. FIG. 1 schematically illustrates the evaluation method. The type of polymer used and the results of iodine removal rate are shown in Table 1.

  By the method of Example 1, the iodine removal rate was measured for the polymers synthesized in Comparative Synthesis Examples 1 to 5, activated carbon (Kishida Chemical Co., Ltd.) and amylose (Tokyo Chemical Industry Co., Ltd.). The results are shown in Table 1 (comparison).

[Example 2] (Evaluation of Radioactive Material Removal Performance of Synthesized Polymer (2))
Example 2 was performed to verify that the polymer used in the present invention functions effectively over a long period of time.
Iodine (Tokyo Chemical Industry) was dissolved in deionized water to prepare an iodine aqueous solution (deionized water). After putting 25 g of iodine aqueous solution (deionized water) into a 50 mL sample tube, 5 g of iodine aqueous solution (deionized water) was collected. Each polymer (20 mg) prepared in a sample tube was placed and stirred at 500 rpm for 24 hours. After stirring, filtration was performed to recover an aqueous solution. The iodine concentration in the collected aqueous solution was measured with an ICP emission spectrometer, and the iodine removal rate was calculated. The results are shown in Table 2.

  The iodine removal rate was measured for activated carbon (Kishida Chemical Co., Ltd.) and amylose (Tokyo Chemical Industry Co., Ltd.) by the method of Example 2. The results are shown in Table 2 (comparison).

[Example 3] (Evaluation of Radioactive Material Removal Performance of Synthesized Polymer (3))
Example 3 was performed to verify that the polymer used in the present invention can remove radioactive material in seawater.
Iodine (Tokyo Chemical Industry) was dissolved in 100% artificial seawater to prepare an iodine aqueous solution (100% artificial seawater). After putting 25 g of iodine aqueous solution (artificial seawater) into a 50 mL sample tube, 5 g of iodine aqueous solution (artificial seawater) was collected. Each polymer (20 mg) prepared in a sample tube was placed and stirred at 500 rpm for 24 hours. After stirring, filtration was performed to recover an aqueous solution. The iodine concentration in the collected aqueous solution was measured with an ICP emission spectrometer, and the iodine removal rate was calculated. The type of polymer used and the results of iodine removal rate are shown in Table 3.

  By the method of Example 3, the iodine removal rate was measured for the polymers synthesized in Comparative Synthesis Examples 1 and 2, activated carbon (Kishida Chemical Co., Ltd.), and amylose (Tokyo Chemical Industry Co., Ltd.). The results are shown in Table 3 (comparison).

[Example 4] (Evaluation of Radioactive Substance Removal Performance of Synthesized Polymer (4))
In order to confirm that the polymer used in the present invention functions for a long time even in seawater, Example 4 was performed.
Iodine (Tokyo Kasei Kogyo) is dissolved in artificial seawater (mixture of artificial seawater and deionized water. Artificial seawater concentrations of 10%, 50%, and 100%, respectively) are used to produce an iodine aqueous solution. did. After putting 25 g of iodine aqueous solution (artificial seawater) into a 50 mL sample tube, 5 g of iodine aqueous solution (artificial seawater) was collected. Each polymer (20 mg) prepared in a sample tube was placed and stirred at 500 rpm for 24 hours. After stirring, filtration was performed to recover an aqueous solution. The iodine concentration in the collected aqueous solution was measured with an ICP emission spectrometer, and the iodine removal rate was calculated. Table 4 shows the types of polymers used and the results of iodine removal rate.

    The iodine removal rate was measured for activated carbon (Kishida Chemical Co., Ltd.) by the method of Example 4. The results are shown in Table 4 (comparison).

[Example 5] (Evaluation of Radioactive Substance Removal Performance of Synthesized Polymer (5))
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.
Iodine (Tokyo Chemical Industry) was dissolved in deionized water to prepare an iodine aqueous solution (deionized water). The syringe was filled with each prepared polymer (200 mg), and then 20 g of an iodine 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 removal rate of iodine was calculated. FIG. 2 schematically shows this evaluation method. Table 5 shows the types of polymers used and the results of the iodine removal rate.

    By the method of Example 5, the iodine removal rate was measured for the polymers synthesized in Comparative Synthesis Examples 1 and 2, activated carbon (Kishida Chemical Co., Ltd.), and amylose (Tokyo Chemical Industry Co., Ltd.). The results are shown in Table 5 (comparison).

[Example 6] (Evaluation of Radioactive Material Removal Performance of Synthesized Polymer (6))
Example 6 was carried out in order to confirm that the polymer used in the present invention can remove radioactive substances in seawater by a simple method using a syringe.
Iodine (Tokyo Chemical Industry) was dissolved in 100% artificial seawater to prepare an iodine aqueous solution (100% artificial seawater). The syringe was filled with each prepared polymer (200 mg), and then 20 g of an iodine aqueous solution (artificial seawater) was poured. 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 removal rate of iodine was calculated. The types of polymers used and the results of iodine removal rate are shown in Table 6.

[Examples 7 to 10] (Evaluation of Radioactive Material Removal Performance of Synthesized Polymer (7))
Iodine (Tokyo Chemical Industry) was dissolved in deionized water to prepare an iodine aqueous 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 iodine 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 removal rate of iodine was calculated. The kind of polymer used and the result of the iodine removal rate are shown in Tables 7 to 10, respectively.

    The same experiment was conducted for each polymer not irradiated with radiation. The results are shown in Table 11.

[Supplemental explanation]
In addition, the analysis method in each said Examples 1-7 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 iodine concentration in the aqueous solution was measured by IPC (inductively coupled plasma) emission spectrometry using ICPS-7510 (SHIMADZU).

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 claim 1, wherein the radioactive substance is radioactive iodine. 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 iodine.