Hydroxamic acid type chelating resin, its preparation method and application

Abstract

The present application relates to chelating resin, it is characterized in linking phase end is N-phenyl-substituted benzoyl hydroxamic acid group, wherein R is mercapto or amino group.The present application also provides the preparation method of above-mentioned chelating resin.Firstly, by epoxy ring-opening reaction to the surface of polymer microspheres, introduce benzene acid group on the surface of polymer microspheres;Then, by the reaction of carboxyl and phenyl hydroxylamine, chelating resin containing hydroxamic acid structure is prepared.The chelating material provided by the present application is novel in structure, simple and reliable in preparation process, and the reaction conditions are mild, which is conducive to industrialization, and the chelating material prepared has high selectivity to metal ions such as zirconium, iron and titanium, and is very suitable as chelating resin for nuclide separation and purification and other fields.

Description

Technical Field

[0001] This invention relates to separation materials, specifically to an isohydroxamic acid chelating resin and its preparation method. Background Technology

[0002] With the rapid development of nuclear energy technology, radionuclides are increasingly widely used in nuclear medicine, nuclear materials, and scientific research. However, the separation and purification of radionuclides has always been a key technological bottleneck in these fields. Existing separation methods include solvent extraction, ion exchange, and chelate adsorption, among which chelate adsorption shows significant advantages in radionuclide purification due to its high selectivity and simple operation.

[0003] Hydroxamic acids are a class of typical chelating agents with highly efficient selectivity for metal ions. Their molecular structure contains oxygen and nitrogen atoms with lone pairs of electrons, positioned close to each other, enabling them to chelate with metal ions to form stable chelates. Therefore, hydroxamic acid chelating resins have significant application value in environmental remediation, resource recovery, and nuclear chemical separation. Currently, hydroxamic acid resins are mainly divided into two types: impregnated and bonded. Impregnated resins are simple to prepare, but during use, the bonded phase is prone to loss, resulting in a short service life. Bonded resins, because the bonded phase is covalently bonded to the resin surface, are less prone to loss and have a longer service life. However, currently reported bonded hydroxamic acid resins suffer from insufficient separation selectivity and strong attraction to target ions, leading to low radionuclide recovery rates. Therefore, there is an urgent need to develop novel bonded hydroxamic acid resins. Summary of the Invention

[0004] The purpose of this invention is to provide an isohydroxamic acid chelating resin and its preparation method. This is to address the aforementioned problems existing in the prior art.

[0005] The technical solution of this invention is: an isohydroxamic acid type chelating resin, wherein the bonding phase is terminated by an N-phenyl-substituted benzoyl isohydroxamic acid group, and its structural formula is:

[0006]

[0007] Where R is a thiol or amino group.

[0008] The present invention also provides a method for preparing the above-mentioned stationary phase, comprising the following steps:

[0009] a. Modification of polymer microspheres with benzoic acid structure: Add 0.2-2.0 g benzoic acid reagent, 0.1-2.0 g alkaline catalyst and 1.0 g divinylbenzene-glycidyl methacrylate copolymer microspheres to 10-40 mL of water, react at 30-100 °C for 3-24 h, filter, wash successively with water, 0.1-0.3 M dilute hydrochloric acid, water and methanol, and vacuum dry the obtained solid in a drying oven at 40-80 °C for 8-24 h to obtain polymer microspheres containing benzoic acid structure;

[0010] The benzoic acid reagent used in step a is one of 2-mercaptobenzoic acid, 4-mercaptobenzoic acid, 2-aminobenzoic acid, and 4-aminobenzoic acid; the alkaline catalyst is one or more of diisopropylethylamine, triethylamine, sodium hydroxide, sodium bicarbonate, potassium carbonate, and pyridine.

[0011] b. Hydroxime acidification of polymer microspheres: 1.0 g of polymer microspheres containing benzoic acid structure and 0.1-2.0 g of N,N-carbonyldiimidazole were added to 10-30 mL of organic solvent. The mixture was heated and stirred at 40-100 °C for 1-8 hours. 0.1 g-1.5 g of phenylhydroxylamine was added, and the mixture was heated and stirred at 40-100 °C for 1-48 hours. The mixture was filtered and washed successively with tetrahydrofuran, methanol, methanol-water, 0.5-1 M hydrochloric acid solution, water, and methanol. The resulting solid was vacuum dried in a drying oven at 40-80 °C for 8-24 hours to obtain the hydroxime acid polymer material.

[0012] The organic solvent used in step b is one or more of dichloromethane, toluene, tetrahydrofuran, N,N-dimethylformamide, ethanol, and methanol.

[0013] The present invention has the following advantages:

[0014] 1. The structure of the hydroxamic acid bonded phase is novel. This invention is the first to prepare a chelating resin with N-phenyl-substituted benzoyl hydroxamic acid groups at the end of the bonded phase. The H atom on the hydroxamic acid group that is connected to the N atom is replaced by a phenyl group, which can reduce the electronegativity of the N atom and change the coplanarity of the molecule. This optimizes the material separation selectivity and improves the recovery rate of the target nuclide.

[0015] 2. The preparation method is simple and the reaction conditions are mild, making it easy to scale up. The chelating material provided by this invention is modified by the ring-opening reaction of epoxy groups with thiol or amino groups to form a carboxyl structure, and then further modified with isohydroxamic acid groups by activating the carboxyl groups. The preparation method is simple, the reaction efficiency is high, and it is conducive to industrialization. Detailed Implementation

[0016] The present invention will be further illustrated below with examples. These examples are merely illustrative and not intended to limit the scope of the invention.

[0017] Example 1

[0018] Weigh 600 mL of water, 6 g of polyvinyl alcohol, and 20 g of NaCl, and pour them into a 1 L reactor. Stir at 400 rpm for 3 hours until the solution is homogeneous. Weigh 0.9 g of azobisisobutyronitrile, 60 g of xylene, 50 g of glycidyl methacrylate, and 20 g of divinylbenzene, mix them thoroughly, and pour them into the 1 L reactor. Set the reactor temperature to 90 °C and stir at 300 rpm for 16 hours. Filter the mixture and wash it successively with tetrahydrofuran, water, and methanol. Dry the resulting solid under vacuum at 80 °C for 16 hours. After sieving, the particle size distribution (D90-D10) / D50 is 0.7, the particle size D50 is 65 μm, and the specific surface area is 300 m². 2 / g divinylbenzene-glycidyl methacrylate copolymer microspheres.

[0019] 2.0 g of 2-mercaptobenzoic acid, 2.0 g of sodium hydroxide, and 1.0 g of divinylbenzene-glycidyl methacrylate copolymer microspheres were added to 15 mL of water and reacted at 90 °C for 24 h. After filtration, the mixture was washed successively with water, 0.1 M dilute hydrochloric acid, water, and methanol. The resulting solid was vacuum dried at 80 °C for 8 h to obtain polymer microspheres containing benzoic acid structure. 1.0 g of polymer microspheres containing benzoic acid structure and 1.0 g of N,N-carbonyldiimidazole were added to 10 mL of tetrahydrofuran and heated and stirred at 40 °C for 1 h. Then, 1.0 g of phenylhydroxylamine was added, and the mixture was heated and stirred at 40 °C for another 48 h. After filtration, the mixture was washed successively with tetrahydrofuran, methanol, 50% methanol-water solution, 1 M hydrochloric acid solution, water, and methanol. The resulting solid was vacuum dried at 80 °C for 8 h to obtain isohydroxamic acid polymer material 1, whose structure is shown below. Infrared and elemental analysis showed that its Nwt% was 2.44%.

[0020]

[0021] Example 2

[0022] Weigh 600 mL of water, 6 g of polyvinyl alcohol, and 20 g of NaCl, and pour them into a 1 L reactor. Stir at 400 rpm for 3 hours until the solution is homogeneous. Weigh 0.9 g of azobisisobutyronitrile, 60 g of xylene, 50 g of glycidyl methacrylate, and 20 g of divinylbenzene, mix them thoroughly, and pour them into the 1 L reactor. Set the reactor temperature to 90 °C and stir at 300 rpm for 16 hours. Filter the mixture and wash it successively with tetrahydrofuran, water, and methanol. Dry the resulting solid under vacuum at 80 °C for 16 hours. After sieving, the particle size distribution (D90-D10) / D50 is 0.7, the particle size D50 is 65 μm, and the specific surface area is 300 m². 2 / g divinylbenzene-glycidyl methacrylate copolymer microspheres.

[0023] 1.5 g of 2-aminobenzoic acid, 2.0 g of triethylamine, and 1.0 g of divinylbenzene-glycidyl methacrylate copolymer microspheres were added to 20 mL of water and reacted at 60 °C for 24 h. After filtration, the mixture was washed successively with water, 0.1 M dilute hydrochloric acid, water, and methanol. The resulting solid was vacuum dried at 80 °C for 8 h to obtain polymer microspheres containing benzoic acid structure. 1.0 g of polymer microspheres containing benzoic acid structure and 2.0 g of N,N-carbonyldiimidazole were added to 30 mL of dichloromethane and heated and stirred at 80 °C for 4 h. Then, 1.5 g of phenylhydroxylamine was added, and the mixture was heated and stirred at 60 °C for another 24 h. After filtration, the mixture was washed successively with tetrahydrofuran, methanol, 50% methanol-water solution, 1 M hydrochloric acid solution, water, and methanol. The resulting solid was vacuum dried at 80 °C for 16 h to obtain isohydroxamic acid polymer material 2, whose structure is shown below. Infrared and elemental analysis showed that its Nwt% was 3.85%.

[0024]

[0025] Example 3

[0026] The isohydroxamic acid chelating resin obtained in Example 1 was used to pack a chromatographic column with an inner diameter * height of 4.6 * 50 mm for the separation of zirconium (Zr) in medical radionuclide yttrium (Y) target materials.

[0027] Sample solution (yttrium target simulation solution): 6M HCl solution containing 0.2 μg / mL Zr ions + 60 mg / mL LY ions;

[0028] Adsorption experiment apparatus: syringe pump (using a 10mL syringe), flow rate: 2.0mL / min;

[0029] Adsorption experiment procedure:

[0030] 1. Sample loading: Load 5 mL of sample solution and collect the outflow;

[0031] 2. Rinse: Rinse with 10 mL of 2M hydrochloric acid and collect the effluent;

[0032] 3. Washing: Rinse with 5 mL of pure water and collect the outflow;

[0033] 4. Elution: Rinse with 2 mL of 0.05 M oxalic acid and collect the eluent.

[0034] The fractions were analyzed by ICP-MS, and the results showed that the zirconium purity in the eluent of the isohydroxamic acid chelate material in Example 1 was 99%, and the recovery rate was 95%.

[0035] Example 4

[0036] The isohydroxamic acid chelating resin obtained in Example 1 was used to pack a chromatographic column with an inner diameter * height of 4.6 * 50 mm for the separation of gallium (Ga) from a medical radionuclide zinc (Zn) target.

[0037] Sample solution (zinc target simulation solution): 10M HCl solution containing 0.8μg / mL Ga ions + 80mg / mL Zn ions;

[0038] Adsorption experiment apparatus: syringe pump (using a 10mL syringe), flow rate: 1.0mL / min;

[0039] Adsorption experiment procedure:

[0040] 1. Sample loading: Load 10 mL of sample solution and collect the outflow;

[0041] 2. Rinse: Rinse with 20 mL of 10M hydrochloric acid and collect the effluent;

[0042] 3. Washing: Rinse with 5 mL of pure water and collect the outflow;

[0043] 4. Elution: Rinse with 2 mL of 1.5M hydrochloric acid and collect the eluent.

[0044] The fraction was analyzed by ICP-MS, and the results showed that the purity of Ga in the eluent of the isohydroxamic acid chelate material in Example 1 was 90%, and the recovery rate was 90%.

[0045] Example 5

[0046] The isohydroxamic acid chelating resin obtained in Example 2 was used to pack a chromatographic column with an inner diameter * height of 4.6 * 50 mm for the removal of titanium (Ti) from scandium (Sc) samples.

[0047] Sample solution: 10M HCl solution containing 0.1 mg / mL Sc ions + 1 mg / mL Ti ions;

[0048] Adsorption experiment apparatus: syringe pump (using a 10mL syringe), flow rate: 1.0mL / min;

[0049] Adsorption experiment procedure:

[0050] 1. Sample loading: Load 10 mL of sample solution and collect the outflow;

[0051] 2. Rinse: Rinse with 2 mL of 10M hydrochloric acid and collect the effluent;

[0052] 3. Elution: Rinse with 2 mL of 0.2 M citric acid and collect the eluent.

[0053] ICP-MS analysis of the fractions showed that Sc was mainly present in the sample eluent with a purity of 99% and a recovery rate of 95%. Ti impurities appeared in the 0.2 M citric acid eluent. The isohydroxamic acid chelating material in Example 2 showed good removal efficiency of Ti impurities from the Sc sample.

Claims

1. A hydroxamic acid type chelating resin, characterized in that, The bonded phase is terminated by an N-phenyl-substituted benzoyl isohydroxamic acid group, and its structural formula is as follows: Where R is S or NH, and the sphere represents a schematic diagram of divinylbenzene-glycidyl methacrylate copolymer microspheres.

2. The isohydroxamic acid type chelating resin according to claim 1, characterized in that: The Nwt% in isohydroxamic acid chelating resins is 1-5%.

3. A method for preparing the chelating resin according to claim 1 or 2, comprising the following steps: a. Modification of polymer microspheres with benzoic acid structure: Add 0.2-2.0g (preferably 1.0-2.0g) of benzoic acid reagent, 0.1-2.0g (preferably 1.0-1.5g) of alkaline catalyst and 1.0g of divinylbenzene-glycidyl methacrylate copolymer microspheres to 10-40mL (preferably 20-30mL) of water, react at 30-100℃ (preferably 50-90℃) for 3-24h (preferably 16-24h), filter, wash successively with water, 0.1-0.3M dilute hydrochloric acid, water and methanol, and dry the resulting solid to obtain polymer microspheres containing benzoic acid structure; b. Hydroxime acidification of polymer microspheres: 1.0 g of polymer microspheres containing benzoic acid structure and 0.1-2.0 g (preferably 1.0-2.0 g) of N,N-carbonyldiimidazole are added to 10-30 mL (preferably 10-20 mL) of organic solvent. The mixture is heated and stirred at 40-100°C (preferably 60-100°C) for 1-8 hours (preferably 4-8 hours). Then, 0.1 g-1.5 g (preferably 1.0 g-1.5 g) of phenylhydroxylamine is added. The mixture is then heated and stirred at 40-100°C (preferably 60-80°C) for 1-48 hours (preferably 24-48 hours). The mixture is filtered and washed sequentially with tetrahydrofuran, methanol, 40-60% methanol-water solution, 0.5-1 M hydrochloric acid solution, water, and methanol. The resulting solid is dried to obtain the hydroxime acid polymer material.

4. The preparation method according to claim 3, characterized in that: The divinylbenzene-glycidyl methacrylate copolymer microspheres used in step a have a particle size of 10–500 μm and a specific surface area of ​​100–800 m². 2 / g.

5. The preparation method according to claim 3, characterized in that: The benzoic acid reagent used in step a is one or more of 2-mercaptobenzoic acid, 4-mercaptobenzoic acid, 2-aminobenzoic acid, and 4-aminobenzoic acid.

6. The preparation method according to claim 3, characterized in that: The alkaline catalyst used in step a is one or more of the following: diisopropylethylamine, triethylamine, sodium hydroxide, sodium bicarbonate, potassium carbonate, and pyridine.

7. The preparation method according to claim 3, characterized in that: The organic solvent used in step b is one or more of the following: dichloromethane, toluene, tetrahydrofuran, N,N-dimethylformamide, ethanol, and methanol.

8. The preparation method according to claim 3, characterized in that: The drying process involves vacuum drying at 40–80°C in a drying oven for 8–24 hours.

9. An application of the chelating resin according to claim 1 or 2, characterized in that: It can be used as a stationary phase or adsorbent material for the separation and purification of one or more metal ions such as zirconium, gallium, and titanium.

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