A leaching resin with surface-bonded polycationic phosphonate

Abstract

The present invention provides a leaching resin with a surface-bonded polycationic phosphonate, and particularly relates to a polystyrene-based leaching resin with a surface-bonded polyquaternary ammonium cationic phosphonate for high-capacity adsorption and extraction of rare earth ions, which is prepared by copolymerization between a surface-bonded unsaturated cationic phosphonate resin and an unsaturated cationic phosphonate. The leaching resin with the surface-bonded polycationic phosphonate not only has good hydrophilicity and can quickly and highly extract rare earth metal ions in an aqueous solution, but also has an anion exchange function. In particular, the chemical stability of the extraction in the solution is high, and the performance of extracting rare earth metal ions is long-lasting, and it is particularly suitable for recycling in the process of extraction, separation or enrichment and recovery of precious metal ions or rare earth ions, or in the field of uranium extraction from seawater.

Description

Technical Field

[0001] The invention relates to a leaching resin with phosphonate bonded on the surface, in particular to a polystyrene-based leaching resin with polyquaternary ammonium cationic phosphonate bonded on the surface, belonging to the field of functional polymer materials. Technical Background

[0002] Professionals know that the separation of rare earth elements is the key to the development of the rare earth metallurgical industry. Small molecule organic phosphoric acid and its esters, or organic phosphonic acid and its esters have strong affinity and high coordination ability for rare earth ions. They are the most widely used solvent extractants in the rare earth hydrometallurgical industry, with many varieties and excellent performance. However, the selectivity, loading capacity, stripping efficiency, water dispersibility, emulsification phenomenon, extraction chemical stability, recycling and regeneration, and process loss of small molecule organic phosphonates as solution extractants determine their industrial use value for extracting and separating rare earths. In order to solve the defects of traditional organic phosphonate extractants such as volatility, easy loss, emulsified third phase, flammability, and toxicity, scientists have immobilized organic phosphonates on the surface of macroporous polystyrene, silica gel and other materials by covalent bonding to form bonded leaching resins with the function of extracting rare earth ions from solutions. They have demonstrated high selectivity leaching performance in the fields of rare earth hydrometallurgy, enrichment and extraction and separation of precious metal ions in dilute solutions, simple and efficient solid-liquid separation, no loss in the process, and clean environment.

[0003] There are usually several methods for the immobilization of organic phosphonates: ①Use unsaturated phosphonates as phosphine-containing functional monomers to homopolymerize or copolymerize with other monomers to prepare polyphosphonate-containing polymer materials. Unsaturated phosphonate monomers mainly include vinyl phosphonates or allyl phosphonates. Such organic phosphonate monomers have a single function and few varieties; and phosphonates derived from acrylates or acrylamides as polymerizable monomers are also the research objects of phosphine-containing functional monomers at present, but such phosphine-containing functional monomers have relatively low chemical stability for extraction and high prices, which are therefore limited in practical applications. ②Amino, acetyl, epoxy, etc. are grafted onto the surface of materials such as polystyrene and silica gel, and then organic phosphonate extractants are bonded using Mannich reactions, phosphonylation reactions, substitution reactions, etc. However, due to the influence of the surface area of ​​the material itself and the number of surface active functional groups, the number of amino, acetyl, and epoxy grafts is small, so the number of immobilization points for bonded organic phosphonate extractants is small, which limits the improvement space of its saturated adsorption capacity and extraction capacity. Therefore, the organic phosphonate bonded leaching resin prepared in this way has the disadvantage of small extraction capacity. ③ Use organic phosphine monomers to graft polymerize on the surface of polymer materials to achieve the phosphine function of polymer materials. The methods are diverse, the profiles are variable, and the performance and extraction capacity are adjustable. However, this method has an insurmountable defect, which is the homopolymerization problem of organic phosphine monomer raw materials during the graft polymerization process, which not only causes the ineffective consumption of organic phosphine monomer raw materials, but also brings a necessary cleaning process to the re-functionalization process after grafting on the surface of polymer materials. Summary of the invention

[0004] In order to overcome the defects of the prior art, the present invention provides a surface-bound polycationic phosphonate leaching resin in combination with the structural characteristics of the organic phosphine extractant and the technical requirements and application scope of the polystyrene-based leaching resin. The surface-bound polycationic phosphonate leaching resin is prepared by the following specific method: weighing the surface-bound unsaturated cationic phosphonate, and an aqueous initiator, dispersed in deionized water, stirred and swelled at room temperature for 1.5 hours under N2 protection, then added unsaturated cationic phosphonate and di-unsaturated cationic phosphonate, stirred evenly and poured into an organic solvent in a reactor, stirred and dispersed for 0.5 to 2 hours under N2 protection, raised the temperature of the material in the reactor to 50 to 90°C, carried out reverse suspension polymerization for 2 to 20 hours, lowered the temperature of the material in the reactor to room temperature, filtered, washed and dried to obtain the surface-bonded polycationic phosphonate type leaching resin.

[0005] The amount of the aqueous initiator is The amount of the unsaturated cationic phosphonate is 1.5-15% by mass. 5 to 500% by mass, the amount of the di-unsaturated cationic phosphonate is the surface-bound unsaturated cationic phosphonate The amount of water is 50-500% of the total mass of the unsaturated cationic phosphonate and the diunsaturated cationic phosphonate, and the amount of the organic solvent is 100~1000% of the quality.

[0006] The organic solvent is selected from one or more of toluene, xylene, chlorobenzene, decahydronaphthalene, carbon tetrachloride, 1,2-dichloroethane or petroleum ether (boiling range 60-90° C.).

[0007] The basic raw materials required for preparing the surface-bonded polycationic phosphonate leaching resin of the present invention include: ① surface-bonded unsaturated cationic phosphonate It is the substrate of the leaching resin-immobilized polycationic phosphonate, and unsaturated cationic phosphonates are bonded to its surface, providing a basis for implementing graft-from grafting polymerization. ② Unsaturated cationic phosphonates are phosphonate monomers with high water solubility. ③ Di-unsaturated cationic phosphonates are phosphonates containing gemini quaternary ammonium cations, which are used as cross-linking agents in graft copolymerization and are crucial to improving grafting efficiency. The three basic raw materials are all derived from the same substance, namely 2-hydroxy-3-(unsaturated tertiary amino)propyl phosphonate. To this end, the present invention further provides the surface-bonded unsaturated cationic phosphonates The invention relates to a specific preparation method of unsaturated cationic phosphonate, diunsaturated cationic phosphonate and 2-hydroxy-3-(unsaturated tertiary amino)propyl phosphonate.

[0008] The surface-bound unsaturated cationic phosphonate It has the structure shown in general formula (I) or general formula (II):

[0009]

[0010] Wherein the general formula (I) or the general formula (II) Refers to cross-linked or non-cross-linked polystyrene resin, or cross-linked or non-cross-linked (olefin monomer-styrene) copolymer resin, R1 and R2 are selected from C1 to C 18 Hydrocarbon, R3 is selected from C1~C 18 Hydrocarbon or C1~C 18 Hydrocarbyloxy; wherein the olefin monomer refers to one or more of ethylene, propylene, vinyl chloride, vinyl acetate, methyl acrylate, ethyl acrylate, butyl acrylate, butadiene or acrylonitrile;

[0011] The surface-bound unsaturated cationic phosphonate The specific preparation method is as follows: weigh the solvent and chloromethyl In a reactor, swell at room temperature for 24 hours under N2 protection, then add 2-hydroxy-3-(unsaturated tertiary amino)propylphosphonate and a polymerization inhibitor, adjust the temperature of the material in the reactor to 25-45°C, stir and react for 6-16 hours, then increase the reaction temperature to 60-90°C, continue to stir and react for 6-12 hours, and then filter, wash and dry to obtain a surface-bound unsaturated cationic phosphonate having a schematic structure of the general formula (I) or the general formula (II).

[0012] The amount of solvent used is chloromethylated The amount of the 2-hydroxy-3-(unsaturated tertiary amino)propylphosphonate is 200-2000% by mass. The molar amount of the chloromethyl contained is 80-100%, and the amount of the polymerization inhibitor used is 0.1-10% of the weight of 2-hydroxy-3-(unsaturated tertiary amino)propyl phosphonate.

[0013] The solvent refers to one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, tetrahydrofuran, 1,4-dioxane, 2-methoxyethanol, 2-ethoxyethanol, N-methylpyrrolidone, dimethyl sulfoxide, N,N-dimethylformamide or N,N-dimethylacetamide.

[0014] The chloromethylation It refers to a chloromethylated cross-linked or non-cross-linked polystyrene resin, or a chloromethylated cross-linked or non-cross-linked (olefin monomer-styrene) copolymer resin, wherein the olefin monomer refers to one or more of vinyl chloride, vinyl acetate, methyl acrylate, ethyl acrylate, butyl acrylate, butadiene or acrylonitrile.

[0015] The unsaturated cationic phosphonate has a structure shown in the general formula (III) or the general formula (IV):

[0016]

[0017] Wherein R1 and R2 in the general formula (III) or the general formula (IV) are selected from C1 to C 18 Hydrocarbon, R3 is selected from C1~C 18 Hydrocarbon or C1~C 18 Hydroxyl, X - Select Cl - Br - or I - One of;

[0018] The specific preparation method of the unsaturated cationic phosphonate is as follows: weigh a solvent, 2-hydroxy-3-(unsaturated tertiary amino)propyl phosphonate, a monoalkylating agent and an inhibitor respectively into a reaction kettle, raise the temperature of the materials in the reaction kettle to 20-90° C. under N2 protection, stir and react for 6-12 hours, and then filter, wash and dry to obtain an unsaturated cationic phosphonate with a structure represented by general formula (III) or general formula (IV).

[0019] The amount of the solvent is 50-200% of the total mass of the monoalkylating agent and 2-hydroxy-3-(unsaturated tertiary amino) propyl phosphonate, the molar ratio of the monoalkylating agent to 2-hydroxy-3-(unsaturated tertiary amino) propyl phosphonate is 1.0-1.2:1, and the amount of the inhibitor is 0.1-10% of the weight of 2-hydroxy-3-(unsaturated tertiary amino) propyl phosphonate.

[0020] The monoalkylating agent has a structure shown in general formula (IX):

[0021] R1-X

[0022] General formula (IX)

[0023] Wherein R1 in the general formula (IX) is selected from C1 to C 18 Hydrocarbon group, X is selected from Cl, Br or I.

[0024] The solvent refers to one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, tetrahydrofuran, 1,4-dioxane, 2-methoxyethanol, 2-ethoxyethanol, N-methylpyrrolidone, dimethyl sulfoxide, N,N-dimethylformamide or N,N-dimethylacetamide;

[0025] The di-unsaturated cationic phosphonate has a structure shown in the general formula (V) or the general formula (VI):

[0026]

[0027] Wherein R1 and R2 in the general formula (V) or the general formula (VI) are selected from C1 to C 18 Hydrocarbon, R3 is selected from C1~C 18 Hydrocarbon or C1~C 18 Hydroxyl group, Refers to C2~C 18 Hydrocarbylene, X - Select Cl - Br - or I - One of them.

[0028] The specific preparation method of the di-unsaturated cationic phosphonate is as follows: weigh a solvent, 2-hydroxy-3-(unsaturated tertiary amino)propyl phosphonate, a dialkylating agent and a polymerization inhibitor respectively in a reaction kettle, raise the temperature of the materials in the reaction kettle to 20-90° C. under N2 protection, stir and react for 6-12 hours, and then filter, wash and dry to obtain a di-unsaturated cationic phosphonate having a structure represented by general formula (V) or general formula (VI);

[0029] The amount of the solvent is 50-200% of the total mass of the dialkylating agent and 2-hydroxy-3-(unsaturated tertiary amino) propyl phosphonate, the molar ratio of the dialkylating agent to 2-hydroxy-3-(unsaturated tertiary amino) propyl phosphonate is 0.48-0.55:1, and the amount of the inhibitor is 0.1-10% of the mass of 2-hydroxy-3-(unsaturated tertiary amino) propyl phosphonate.

[0030] The dialkylating agent has a structure shown in the general formula (X):

[0031]

[0032] In the general formula (X), Select C1~C 18 Hydrocarbylene, X is selected from one of Cl, Br or I.

[0033] The solvent refers to one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, tetrahydrofuran, 1,4-dioxane, 2-methoxyethanol, 2-ethoxyethanol, N-methylpyrrolidone, dimethyl sulfoxide, N,N-dimethylformamide or N,N-dimethylacetamide;

[0034] wherein an unsaturated cationic phosphonate is bonded to the surface In the preparation methods of unsaturated cationic phosphonates and diunsaturated cationic phosphonates, a polymerization inhibitor is used, and the polymerization inhibitor refers to one or more of hydroquinone, p-methoxyphenol, tert-butylhydroquinone, 2,6-dibutylhydroquinone, 2,6-di-tert-butyl-p-cresol or 2,4,6-tri-tert-butylphenol.

[0035] The 2-hydroxy-3-(unsaturated tertiary amino)propylphosphonate has a structure shown in the general formula (VII) or the general formula (VIII):

[0036]

[0037] Wherein R2 in the general formula (VII) or the general formula (VIII) is selected from C1 to C 18 Hydrocarbon, R3 is selected from C1~C 18 Hydrocarbon or C1~C 18 Hydrocarbon oxygen.

[0038] The 2-hydroxy-3-(unsaturated tertiary amino) propyl phosphonate is prepared by the following method: weighing a phosphite ester and putting it into a reaction kettle, adding sodium alcoholate under N2 protection and stirring, raising the temperature of the material in the reaction kettle to 70-140°C, continuously adding N-glycidyl-N,N-diallylamine or N-glycidyl-N-alkyl-N-allylamine to the reaction kettle, stirring and reacting for 8-12 hours, and separating and purifying to obtain 2-hydroxy-3-(unsaturated tertiary amino) propyl phosphonic acid dialkyl ester.

[0039] The amount of phosphite used is 200-2000% of the weight of N-glycidyl-N,N-diallylamine or N-glycidyl-N-alkyl-N-allylamine, and the amount of sodium alkoxide used is 0.5-5% of the weight of N-glycidyl-N,N-diallylamine or N-alkyl-N-glycidyl-N-allylamine.

[0040] The N-alkyl-N-glycidyl-N-allylamine has a structure shown in the general formula (XI):

[0041]

[0042] The hydrocarbon group refers to R2 in the general formula (Ⅺ), and R2 is selected from C1 to C 18 Hydrocarbon.

[0043] The phosphite has a structure shown in the general formula (XII):

[0044]

[0045] Wherein R2 in the general formula (XII) is selected from C1 to C 18 Hydrocarbon, R3 is selected from C1~C 18 Hydrocarbon or C1~C 18 Hydroxyl group.

[0046] The sodium alkoxide refers to one of sodium methoxide, sodium ethoxide, sodium propoxide or sodium butoxide.

[0047] The present invention provides a surface-bonded polycationic phosphonate leaching resin having the following beneficial effects:

[0048] ① The surface of the leaching resin with surface-bonded polycationic phosphonate of the present invention not only bonds the phosphonate unit, but also has high surface hydrophilicity, and can be quickly dispersed in a metal salt aqueous solution, from which precious metal ions or rare earth ions can be quickly adsorbed and extracted.

[0049] ② The surface-bonded polycationic phosphonate leaching resin of the present invention has various chemical activities, such as the hydrolysis or partial hydrolysis of the phosphonate unit, the oxidizability of the hydroxyl group, etc., thereby achieving various changes in its functions and performances.

[0050] ③ The raw materials required for preparing the leaching resin with surface-bonded polycationic phosphonate of the present invention are few in variety, all of which are industrial products, and the preparation method is simple and comprehensive.

[0051] ④ The leaching resin with surface-bonded polycationic phosphonate of the present invention has high extraction chemical stability and is particularly suitable for recycling in the process of extraction, separation or enrichment and recovery of precious metal ions or rare earth ions. DETAILED DESCRIPTION

[0052] The following examples further illustrate the leaching resin with surface-bound polycationic phosphonate and the preparation method thereof in the present invention, the purpose of which is to provide a better understanding of the present invention.

[0053] Example 1 Preparation of Surface-Bound Polycationic Phosphonate Extraction Resin-1

[0054] Step 1: Preparation of diethyl 2-hydroxy-3-(N,N-diallylamino)propylphosphonate

[0055] Weigh 130 g of diethyl phosphite into a reactor, add 9.5 g of sodium ethoxide slowly under N2 protection and stirring, raise the temperature of the material in the reactor to 100-110°C, slowly and continuously add 21 g of N-glycidyl-N,N-diallylamine to the reactor, stir and react for 8 hours, recover the excess diethyl phosphite by vacuum rotary evaporation, and separate the residue to obtain 37.5 g of viscous light yellow liquid product. The product IR (cm -1 , KBr membrane) include: 3404 is the characteristic absorption peak of hydroxyl OH, 3068cm -1 is the characteristic absorption peak of vinyl CH, 2925, 2867 is the characteristic absorption peak of methyl and methylene, 1645 is the characteristic peak of C=C, 1479, 1428 are the characteristic absorption peaks of CN, 1264 is the characteristic absorption peak of P=O double bond, and 1042 is the characteristic absorption peak of POC; 1H-NMR (CDCl3): 1.22 (t, 6H), 2.36 (m, 2H), 2.63 (m, 2H), 3.51 (m, 1H), 3.85 (d, 4H), 4.04 (m, 4H), 4.50 (m, 1H), 5.74 (m, 4H), 6.01 (m, 2H), it was determined that the product was 2-hydroxy-3-(N, N-diallylamino) propylphosphonic acid diethyl ester. Based on N-glycidyl-N, N-diallylamine, the yield of 2-hydroxy-3-(N, N-diallylamino) propylphosphonic acid diethyl ester was 93.7%. The following reaction formula-1 expresses the preparation process of 2-hydroxy-3-(N, N-diallylamino) propylphosphonic acid diethyl ester:

[0056]

[0057] Step 2: Surface bonding of unsaturated cationic phosphonates Preparation of Resin-1

[0058] Weigh 60 grams of isobutyl alcohol, 60 grams of 1,4-dioxane, 10 grams of chlorine balls (cross-linking degree 10%, chlorine content 18.86%, particle size 0.23-0.45 mm purchased from Nankai University Chemical Plant), 16 grams of 2-hydroxy-3-(N,N-diallylamino)propylphosphonic acid diethyl ester and 0.8 grams of hydroquinone in a reactor, swell at room temperature for 24 hours under N2 protection, adjust the temperature of the materials in the reactor to 30-40°C, stir and react for 12 hours, then increase the temperature of the materials in the reactor to 70-80°C, continue to stir and react for 8 hours, filter, wash with ethanol, Soxhlet extract for 24 hours, and vacuum dry to constant weight to obtain 23.6 grams of slightly brown spherical products. This product was analyzed by elution titration for free Cl - The content is 7.08%, and the effective grafting rate is calculated to be about 85%; the characteristic peaks in the infrared spectrum of the product after the chlorine ball grafting include: FTIR (cm -1 , KBr tablet): 3412cm -1 The characteristic absorption peak of hydroxyl group OH is 3031cm -1 Characteristic absorption peaks of vinyl, 2932, 2867cm -1 Characteristic absorption peaks of methyl and methylene, 1645 and 1478 cm -1 It is the characteristic absorption peak of benzene ring, 1256cm -1 Characteristic absorption peaks of P=O double bond, 1056, 1012 cm -1 The absorption peak of POC is shown at . The resin has been successfully grafted with unsaturated cationic phosphonates. The following reaction equation-2 schematically expresses the surface-bonded unsaturated cationic phosphonates. Preparation process of resin-1:

[0059]

[0060] Step 3: Preparation of diethyl 2-hydroxy-3-(N-benzyl-N,N-diallylammonium chloride)propylphosphonate

[0061] Dissolve 13.7 g of 2-hydroxy-3-(N,N-diallylamino)propylphosphonic acid diethyl ester in 50 g of tetrahydrofuran, add 6.2 g of benzyl chloride and 0.5 g of hydroquinone, and adjust the temperature of the reaction liquid to 60-70°C under N2 protection. React for 12 hours, then lower the temperature of the reaction product system to room temperature. After standing, filter to obtain the crude product, purify it by recrystallization from isobutanol, and vacuum dry to constant weight to obtain 17.3 g of product with a yield of about 88%. Product IR (cm -1 , KBr tablet): 3417cm -1 The characteristic absorption peaks of hydroxyl group OH, 2938 and 2868 cm -1 Characteristic absorption peaks of methyl and methylene, 1646 and 1478 cm -1 It is the characteristic absorption peak of benzene ring, 1256cm -1 Characteristic absorption peaks of P=O double bond, 1058, 1016cm -1 It is the characteristic absorption peak of POC; 1 H-NMR (δ, CD3OD): 1.26 (m, 6H), 2.22 (m, 1H), 3.27 (m, 2H), 3.51 (m, 2H), 3.81 (m, 1H), 3.91 (m, 4H), 4.05 (s, 2H), 4.17 (q, 4H), 4.91-5.10 (m, 6H), 7.02~7.22 (m, 5H); Chemical titration analysis of Cl in the product - The content is 8.37%, and C 20 H 33 The theoretical chlorine content of ClNO4P is 8.48%, which is basically consistent with the theoretical chlorine content of ClNO4P, confirming that the product is 2-hydroxy-3-(N-benzyl-N,N-diallylammonium chloride) propylphosphonic acid diethyl ester. The following reaction formula-3 expresses the preparation process of 2-hydroxy-3-(N-benzyl-N,N-diallylammonium chloride) propylphosphonic acid diethyl ester:

[0062]

[0063] Step 4: Preparation of 1,4-bis(N,N-diallyl-N-(2-hydroxy-3-(diethoxyphosphonyl)propyl)ammonium)butane

[0064] Dissolve 13.7 g of 2-hydroxy-3-(N,N-diallylamino)propylphosphonic acid diethyl ester in 50 g of ethanol, add 5.5 g of 1,4-dibromobutane and 0.5 g of hydroquinone, and adjust the temperature of the reaction material liquid to 60-70°C under N2 protection. React for 18 hours, then lower the temperature of the reaction product system to room temperature. After standing, filter to obtain the crude product, purify it by recrystallization from ethanol, and vacuum dry it to constant weight to obtain 16.6 g of white crystalline product with a yield of about 87%. Chemical titration analysis of Br in the product - The content is 19.83%, which is consistent with the molecular formula C 30 H 60 The calculated Br content of Br2N2O8P2 is consistent with the theoretical value of 20.01%. Product spectrum analysis data: IR (cm -1 , KBr tablet): 3412cm -1 The characteristic absorption peaks of hydroxyl group OH are 2937 and 2868 cm -1 Characteristic absorption peaks of methyl and methylene, 1648 and 1437 cm -1 It is the characteristic absorption peak of CN, 1256cm -1 Characteristic absorption peaks of P=O double bond, 1138, 1016cm -1 It is the characteristic absorption peak of POC; 1 H-NMR (δ, CD3OD): 1.31 (t, 4H), 1.73 (t, 4H), 2.18 (m, 2H), 3.24 (t, 8H), 3.29 (m, 4H), 3.52 (m, 4H), 3.82 (m, 2H), 3.92 (m, 8H), 4.04 (s, 4H), 4.16 (q, 4H), 4.52 (s, 4H), 4.90-5.11 (m, 12H). Based on the above analytical data, it was confirmed that the product was 1,4-bis(N,N-diallyl-N-(2-hydroxy-3-(diethoxyphosphonyl)propyl)ammonio)butane bromide. The following reaction formula-3 expresses the preparation process of 1,4-bis(bromide N,N-diallyl-N-(2-hydroxy-3-(diethylphosphinoyl)propyl)ammonium)butane:

[0065]

[0066] Step 5: Surface-bonded polycationic phosphonate leaching resin-1

[0067] Weigh 20.8 g of surface-bound unsaturated cationic phosphonate Resin-1 and 0.65 g of azobisisobutylamidine hydrochloride were dissolved in 20 g of deionized water. After being dispersed evenly, 7.5 g of diethyl 2-hydroxy-3-(N-benzyl-N,N-diallylammonium chloride) propylphosphonate and 2.5 g of 1,4-bis(N,N-diallyl-N-(2-hydroxy-3-(diethylphosphinoyl)propyl)ammonium)butane were added. After stirring evenly, 150 g of toluene was poured into the reactor. Stirring and dispersing for 0.5 to 1.5 hours under N2 protection, the temperature of the material in the reactor was raised to 50 to 55 ° C. After 2 hours of polymerization reaction, the temperature of the material in the reactor was raised to 80 to 90 ° C. The polymerization reaction was continued for 2 hours. Then, the temperature of the material in the reactor was lowered to room temperature. After filtering, it was washed with deionized water until there was no Cl in the washing water. - or Br - The product was dried and weighed until it flowed out, and 45.2 grams of product was obtained. The product was analyzed to be leaching resin-1 (referred to as ER-1) with surface-bonded polycationic phosphonate, and the water content was about 28.5%. The grafting efficiency was calculated to be about 94%.

[0068] Comparative Example 1 Preparation of Surface-Bound Polycationic Phosphonate Extraction Resin-2

[0069] According to the method and steps of Example 1, the formula of step 5 is "weighing 20.8 grams of surface-bound unsaturated cationic phosphonate Resin-1 and 0.65 g of azobisisobutylamidine hydrochloride were dissolved in 20 g of deionized water, and after being evenly dispersed, 5 g of diethyl 2-hydroxy-3-(N-benzyl-N,N-diallylammonium)propylphosphonate and 5 g of 1,4-bis(bromide N,N-diallyl-N-(2-hydroxy-3-(diethoxyphosphonyl)propyl)ammonium)butane were added. The solution was changed to "weigh 20.8 g of surface-bound unsaturated cationic phosphonate" Resin-1 and 0.65 g of azobisisobutylamidine hydrochloride were dissolved in 20 g of deionized water, and after being evenly dispersed, 10 g of 2-hydroxy-3-(N-benzyl-N,N-diallylammonium chloride)propylphosphonic acid diethyl ester was added. The remaining preparation procedure was the same as in Example 1 to obtain 35.6 g of product. After analysis, the product was a surface-bound polycationic phosphonate leaching resin-2 (referred to as ER-2) with a water content of about 22.6%. The grafting efficiency was calculated to be about 67%.

[0070] Example 2 Preparation of Surface-Bound Polycationic Phosphonate Extraction Resin-3

[0071] Weigh the method and steps of Example 1, prepare 2-hydroxy-3-(N-benzyl-N-allylamino)propylphosphonic acid diethyl ester in step 1, and prepare surface-bound unsaturated cationic phosphonate in step 2 Resin-2, see the following formula:

[0072]

[0073] Step three prepares diethyl 2-hydroxy-3-(N-butyl-N-benzyl-N-allylammonium bromide)propylphosphonate, and step four prepares 1,4-bis(N-allyl-N-benzyl-N-(2-hydroxy-3-(diethylphosphinoyl)propyl)ammonium)butane.

[0074] Step 5: Weigh 20 grams of surface-bound unsaturated cationic phosphonate Resin-2 and 0.62 g of azobisisobutylamidine hydrochloride were dissolved in 20 g of deionized water. After being dispersed evenly, 7.5 g of 2-hydroxy-3-(N-butyl-N-benzyl-N-allylammonium bromide) propylphosphonic acid diethyl ester and 2.5 g of 1,4-bis(bromide N-allyl-N-benzyl-N-(2-hydroxy-3-(diethylphosphinoyl)propyl)ammonium)butane were added. After stirring evenly, 150 g of toluene was poured into the reactor. Stirring and dispersing for 0.5 to 1.5 hours under N2 protection, the temperature of the material in the reactor was raised to 50 to 55 ° C. After 2 hours of polymerization reaction, the temperature of the material in the reactor was raised to 70 to 80 ° C. The polymerization reaction was continued for another 2 hours. Then, the temperature of the material in the reactor was lowered to room temperature. After filtering, it was washed with deionized water until there was no Cl in the washing water. - or Br - After drying, 39.0 g of product was obtained. Analysis showed that the product was leaching resin-3 (referred to as ER-3) with surface-bonded polycationic phosphonate, and the water content was about 23.2%. The grafting efficiency was calculated to be about 94%.

[0075] Comparative Example 2 Preparation of Surface-Bound Polycationic Phosphonate Extraction Resin-4

[0076] According to the method and steps of Example 1, the formula of step 5 is "weighing 20 grams of surface-bound unsaturated quaternary ammonium cationic phosphonate Resin-2 and 0.62 g of azobisisobutylamidine hydrochloride were dissolved in 20 g of deionized water, and after being evenly dispersed, 5 g of 2-hydroxy-3-(N-butyl-N-benzyl-N-allylammonium)propylphosphonic acid diethyl ester and 5 g of 1,4-bis(bromide N-allyl-N-benzyl-N-(2-hydroxy-3-(diethylphosphinoyl)propyl)ammonium)butane were added. "Weigh 20 g of surface-bound unsaturated cationic phosphonate Resin-2 and 0.65 g of azobisisobutylamidine hydrochloride were dissolved in 20 g of deionized water, and after being evenly dispersed, 10 g of 2-hydroxy-3-(N-butyl-N-benzyl-N-allylammonium bromide)propylphosphonic acid diethyl ester was added. The remaining preparation procedure was the same as in Example 2 to obtain 34.7 g of product. After analysis, the product was a surface-bound polycationic phosphonate leaching resin-4 (denoted as ER-4), in which the water content was about 23.6%, and the grafting efficiency was calculated to be 67.4%.

[0077] Example 3 Preparation of Surface-Bound Polycationic Phosphonate Extraction Resin-5

[0078] The method and steps of Example 1 were weighed, with steps 1 to 3 remaining unchanged, and step 4 was used to prepare 1,4-bis(chlorinated N,N-diallyl-N-benzyl-N-(2-hydroxy-3-(O,O-diethylphosphinoyl)propyl)ammoniomethyl)benzene.

[0079] Step 5: Weigh 20 grams of surface-bound unsaturated quaternary ammonium cationic phosphonate Resin-1 and 0.65 g of azobisisobutylamidine hydrochloride were dissolved in 20 g of deionized water. After being dispersed evenly, 5.5 g of 2-hydroxy-3-(N-benzyl-N,N-diallylammonium chloride) propylphosphonic acid diethyl ester and 2.5 g of 1,4-bis(chlorinated N,N-diallyl-N-benzyl-N-(2-hydroxy-3-(diethylphosphinoyl)propyl)ammoniummethyl)benzene were added. After stirring evenly, 150 g of toluene was poured into the reactor. Stirring and dispersing for 0.5 to 1.5 hours under N2 protection, the temperature of the material in the reactor was raised to 50 to 55 ° C. After 2 hours of polymerization reaction, the temperature of the material in the reactor was raised to 70 to 80 ° C. The polymerization reaction was continued for 2 hours. Then, the temperature of the material in the reactor was lowered to room temperature. After filtering, it was washed with deionized water until there was no Cl in the washing water. - After drying, 39.9 g of product was obtained. Analysis showed that the product was leaching resin-5 (referred to as ER-5) with surface-bonded polycationic phosphonate, and the water content was about 25.6%. The grafting efficiency was calculated to be about 97%.

[0080] Comparative Example 3 Preparation of Surface-Bound Polycationic Phosphonate Extraction Resin-6

[0081] Weigh the method and steps of Example 3, and keep steps 1 to 4 unchanged. Step 5: weigh 20 g of surface-bound unsaturated cationic phosphonate. Resin-1 and 0.65 g of azobisisobutylamidine hydrochloride were dissolved in 20 g of deionized water, and after being dispersed evenly, 8 g of 2-hydroxy-3-(N-benzyl-N,N-diallylammonium chloride)propylphosphonic acid diethyl ester was added, stirred evenly, and 150 g of toluene was poured into the reactor. Stirring and dispersing for 0.5 to 1.5 hours under N2 protection, the temperature of the material in the reactor was raised to 50 to 55 ° C, and the polymerization reaction was continued for 2 hours. The temperature of the material in the reactor was raised to 70 to 80 ° C, and the polymerization reaction was continued for another 2 hours. Then, the temperature of the material in the reactor was lowered to room temperature, filtered, and washed with deionized water until there was no Cl in the washing water. - After drying, 33.6 g of product was obtained. Analysis showed that the product was leaching resin-6 (referred to as ER-6) with surface-bonded polycationic phosphonate, and the water content was about 24.2%. The grafting efficiency was calculated to be 68.3%.

[0082] Example 4 Preparation of Surface-Bound Polycationic Phosphonate Extraction Resin-7

[0083] Weigh 20 g of surface-bound unsaturated cationic phosphonate Resin-1 and 0.65 g of azobisisobutylamidine hydrochloride were dissolved in 20 g of deionized water, and after being dispersed uniformly, 6.0 g of diethyl 2-hydroxy-3-(N-benzyl-N,N-diallylammonium chloride)propylphosphonate, 6.0 g of diethyl 2-hydroxy-3-(N-butyl-N-benzyl-N-allylammonium bromide)propylphosphonate, 2.0 g of 1,4-bis(bromide N-allyl-N-benzyl-N-(2-hydroxy-3-(diethylphosphinoyl)propyl)ammonium)butane, and 2.0 g of 1,4-bis(bromide N-allyl-N-benzyl-N-(2-hydroxy-3-(diethylphosphinoyl)propyl)ammonium)butane were added. 0 g 1,4-bis(chlorinated N,N-diallyl-N-benzyl-N-(2-hydroxy-3-(diethylphosphinoyl)propyl)ammoniummethyl)benzene, stir evenly, pour 150 g toluene into the reactor, stir and disperse for 0.5-1.5 hours under N2 protection, raise the temperature of the material in the reactor to 50-55°C, and after 2 hours of polymerization, raise the temperature of the material in the reactor to 70-90°C, stir and polymerize for 2 hours, then cool down, filter, and wash with deionized water until there is no Cl in the washing water - or Br - After drying, 47.5 g of product was obtained. Analysis showed that the product was leaching resin-7 (referred to as ER-7) with surface-bonded polycationic phosphonate, and the water content was about 26.8%. The grafting efficiency was calculated to be about 92%.

[0084] The analytical data of Examples 1 to 4 and Comparative Examples 1 to 3 show that the surface-bound unsaturated cationic phosphonate provided by the present invention The resin is a solid-supported resin with pendant double bonds. The suspension polymerization method is used. One of the key factors that determine its "graft-from" grafting efficiency is the cross-linking agent; the second is the increase in the amount of unsaturated cationic monomers, and its grafting efficiency is slightly reduced, indicating that the "graft-from" method is The amount of grafting on the resin surface cannot be too high.

Claims

1. A leaching resin having a surface-bonded polycationic phosphonate, characterized in that: The preparation was carried out by the following steps: weighing the surface-bound unsaturated cationic phosphonate and an aqueous initiator, dispersed in deionized water, stirred and swelled at room temperature for 0.5 hour under N2 protection; then unsaturated cationic phosphonate and diunsaturated cationic phosphonate were added, stirred evenly and poured into an organic solvent in a reactor, stirred and dispersed for 0.5 to 2 hours under N2 protection, the temperature of the material in the reactor was increased to 50 to 90° C., reverse phase suspension polymerization was performed for 2 to 20 hours, the temperature of the material in the reactor was reduced to room temperature, and then separated, filtered, washed and dried to obtain the leaching resin of the surface-bonded polycationic phosphonate; The amount of aqueous initiator is surface-bound unsaturated cationic phosphonate The amount of the unsaturated cationic phosphonate is 1.5-15% by mass. 5 to 500% by mass, the amount of the diunsaturated cationic phosphonate is the surface-bound unsaturated cationic phosphonate The amount of deionized water is 50-500% of the total mass of the unsaturated cationic phosphonate and the diunsaturated cationic phosphonate, and the amount of organic solvent is 100-1000% of mass; The surface-bound unsaturated cationic phosphonate It has the structure shown in general formula (I) or general formula (II): Wherein the general formula (I) or the general formula (II) Refers to cross-linked or non-cross-linked polystyrene resin, or cross-linked or non-cross-linked (olefin monomer-styrene) copolymer resin, R1 and R2 are selected from C1 to C 18 Hydrocarbon, R3 is selected from C1~C 18 Hydrocarbon or C1~C 18 Hydrocarbyloxy; wherein the olefin monomer refers to one or more of ethylene, propylene, vinyl chloride, vinyl acetate, methyl acrylate, ethyl acrylate, butyl acrylate, butadiene or acrylonitrile; The unsaturated cationic phosphonate has a structure shown in the general formula (III) or the general formula (IV): Wherein R1 and R2 in the general formula (III) or the general formula (IV) are selected from C1 to C 18 Hydrocarbon, R3 is selected from C1~C 18 Hydrocarbon or C1~C 18 Hydroxyl, X - Select Cl - Br - or I - One of; The di-unsaturated cationic phosphonate has a structure shown in the general formula (V) or the general formula (VI): Wherein R1 and R2 in the general formula (V) or the general formula (VI) are selected from C1 to C 18 Hydrocarbon, R3 is selected from C1~C 18 Hydrocarbon or C1~C 18 Hydroxyl group, Refers to C2~C 18 Hydrocarbylene, X - Select Cl - Br - or I - One of; The aqueous initiator refers to one of azobisisobutylamidine hydrochloride, azobisisobutylimidazoline hydrochloride, azobiscyanovaleric acid, azobisisopropylimidazoline hydrochloride, potassium persulfate or ammonium persulfate.

2. The leaching resin of the surface-bonded polycationic phosphonate according to claim 1, characterized in that The surface-bound unsaturated cationic phosphonate The preparation method is as follows: weigh the solvent and chloromethyl In a reactor, swell at room temperature for 24 hours under N2 protection, then add 2-hydroxy-3-(unsaturated tertiary amino)propylphosphonate and a polymerization inhibitor, adjust the temperature of the material in the reactor to 25-45°C, stir and react for 6-16 hours, then increase the reaction temperature to 60-90°C, continue to stir and react for 6-12 hours, and then filter, wash and dry to obtain a surface-bound unsaturated cationic phosphonate having a schematic structure of the general formula (I) or the general formula (II). The amount of solvent used is chloromethylated The amount of the 2-hydroxy-3-(unsaturated tertiary amino)propylphosphonate is 200-2000% by mass. The molar amount of chloromethyl contained is 80-100%, and the amount of the polymerization inhibitor used is 0.1-10% of the weight of 2-hydroxy-3-(unsaturated tertiary amino)propyl phosphonate; Chloromethylation Refers to chloromethylated cross-linked or non-cross-linked polystyrene resin, or chloromethylated cross-linked or non-cross-linked (olefin monomer-styrene) copolymer resin, wherein the olefin monomer refers to one or more of ethylene, propylene, vinyl chloride, vinyl acetate, methyl acrylate, ethyl acrylate, butyl acrylate, butadiene or acrylonitrile; The 2-hydroxy-3-(unsaturated tertiary amino)propylphosphonate has a structure shown in the general formula (VII) or the general formula (VIII): Wherein R1 and R2 in the general formula (VII) or the general formula (VIII) are selected from C1 to C 18 Hydrocarbon, R3 is selected from C1~C 18 Hydrocarbon or C1~C 18 Hydroxyl group.

3. The leaching resin of the surface-bonded polycationic phosphonate according to claim 1, characterized in that The preparation method of the unsaturated cationic phosphonate is as follows: weigh a solvent, 2-hydroxy-3-(unsaturated tertiary amino)propyl phosphonate, a monoalkylating agent and a polymerization inhibitor respectively in a reaction kettle, raise the temperature of the materials in the reaction kettle to 20-90° C. under N2 protection, stir and react for 6-12 hours, and then filter, wash and dry to obtain an unsaturated cationic phosphonate with a structure represented by general formula (III) or general formula (IV); The amount of the solvent is 50-200% of the total mass of the monoalkylating agent and 2-hydroxy-3-(unsaturated tertiary amino) propyl phosphonate, the molar ratio of the monoalkylating agent to 2-hydroxy-3-(unsaturated tertiary amino) propyl phosphonate is 1.0-1.2:1, and the amount of the polymerization inhibitor is 0.1-10% of the weight of 2-hydroxy-3-(unsaturated tertiary amino) propyl phosphonate; 2-Hydroxy-3-(unsaturated tertiary amino)propylphosphonate has the structure shown in the general formula (VII) or the general formula (VIII): Wherein R1 and R2 in the general formula (VII) or the general formula (VIII) are selected from C1 to C 18 Hydrocarbon, R3 is selected from C1~C 18 Hydrocarbon or C1~C 18 Alkyloxy; The monoalkylating agent has a structure shown in general formula (IX): R1-X General formula (IX) Wherein R1 in the general formula (IX) is selected from C1 to C 18 Hydrocarbon group, X is selected from Cl, Br or I.

4. A leaching resin having a surface-bound polycationic phosphonate according to claim 1 or 3, characterized in that The preparation method of the di-unsaturated cationic phosphonate is as follows: respectively weigh a solvent, 2-hydroxy-3-(unsaturated tertiary amino)propyl phosphonate, a dialkylating agent and a polymerization inhibitor into a reaction kettle, raise the temperature of the materials in the reaction kettle to 20-90° C. under N2 protection, stir and react for 6-12 hours, and then filter, wash and dry to obtain a di-unsaturated cationic phosphonate having a structure represented by general formula (V) or general formula (VI); The amount of the solvent is 50-200% of the total mass of the dialkylating agent and 2-hydroxy-3-(unsaturated tertiary amino) propyl phosphonate, the molar ratio of the dialkylating agent to 2-hydroxy-3-(unsaturated tertiary amino) propyl phosphonate is 0.48-0.55:1, and the amount of the inhibitor is 0.1-10% of the mass of 2-hydroxy-3-(unsaturated tertiary amino) propyl phosphonate; The dialkylating agent has a structure shown in the general formula (X): In the general formula (X), Select C1~C 18 Hydrocarbylene, X is selected from one of Cl, Br or I.

5. The leaching resin of the surface-bonded polycationic phosphonate according to claim 2, characterized in that The 2-hydroxy-3-(unsaturated tertiary amino) propyl phosphonate is prepared by the following method: weighing phosphite and putting it into a reaction kettle, adding sodium alcoholate under N2 protection and stirring, then raising the temperature of the material in the reaction kettle to 70-140° C., continuously adding N-glycidyl-N,N-diallylamine or N-glycidyl-N-alkyl-N-allylamine to the reaction kettle, stirring and reacting for 8-12 hours, and separating and purifying to obtain 2-hydroxy-3-(unsaturated tertiary amino) propyl phosphonate; The N-glycidyl-N-alkyl-N-allylamine has a structure shown in the general formula (XI): The hydrocarbon group refers to R1 in the general formula (Ⅺ), and R1 is selected from C1 to C 18 Hydrocarbon; The phosphite has a structure shown in the general formula (XII): Wherein R2 in the general formula (XII) is selected from C1 to C 18 Hydrocarbon, R3 is selected from C1~C 18 Hydrocarbon or C1~C 18 Alkyloxy; The sodium alcoholate refers to one of sodium methoxide, sodium ethoxide, sodium propoxide or sodium butoxide; The amount of the phosphite is 2 to 10 times the weight of N-glycidyl-N,N-diallylamine or N-glycidyl-N-alkyl-N-allylamine, and the amount of the sodium alkoxide is 0.5 to 5% of the weight of N-glycidyl-N,N-diallylamine or N-glycidyl-N-alkyl-N-allylamine.

6. The leaching resin of the surface-bonded polycationic phosphonate according to claim 1, characterized in that The organic solvent is selected from one or more of toluene, xylene, chlorobenzene, decahydronaphthalene, anisole, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether and petroleum ether.

7. The leaching resin of the surface-bonded polycationic phosphonate according to claim 4, characterized in that The solvent is selected from one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, tetrahydrofuran, 1,4-dioxane, 2-methoxyethanol, 2-ethoxyethanol, N-methylpyrrolidone, dimethyl sulfoxide, N,N-dimethylformamide or N,N-dimethylacetamide.

8. The leaching resin of the surface-bonded polycationic phosphonate according to claim 4, characterized in that The polymerization inhibitor refers to one or more of hydroquinone, p-methoxyphenol, tert-butylhydroquinone, 2,6-dibutylhydroquinone, 2,6-di-tert-butyl-p-cresol or 2,4,6-tri-tert-butylphenol.

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