A bonded poly (cationic phosphonate-amine) leaching resin

Abstract

The present invention provides a bonded poly (cationic phosphonate-amine) leaching resin and a preparation method thereof, which is prepared by copolymerization reaction between surface-bonded unsaturated quaternary ammonium cationic phosphonate resin and unsaturated cationic phosphonate and allyl ammonium salt and diunsaturated cationic phosphonate. The bonded poly (cationic phosphonate-amine) leaching resin not only has good hydrophilicity, can quickly extract rare earth metal ions in aqueous solution, but also has anion exchange function. In particular, the chemical stability of extraction in the solution is high, and the performance of extracting rare earth metal ions is long-lasting, which is particularly suitable for recycling in the extraction separation or enrichment recovery process 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 bonded leaching resin, in particular to a polystyrene-based leaching resin with surface-bonded poly(quaternary ammonium cationic phosphonate-organic amine), which has a capacity-variable rare earth salt dual extraction function and belongs to the field of functional polymer materials. Technical Background

[0002] It is well known to professionals that small molecule organic phosphoric acid / organic phosphonic acid and its esters and some organic amines have strong affinity and high coordination ability for uranyl or rare earth ions, and are the most widely used extractants in seawater uranium extraction or rare earth separation. However, the selectivity, loading capacity, stripping efficiency, water dispersibility, emulsification phenomenon, chemical stability, recycling and regeneration, and process loss of small molecule organic phosphonic acid esters or organic amines as solution extractants determine their use value in the extraction and separation industry. In addition, there is also a proton exchange reaction between metal ions and organic extractants in the solvent extraction process in hydrometallurgy. After multiple cycles of the extraction process, the acid concentration of the aqueous phase in the extraction system increases, and the organic extractant can be protonated and the extraction fails, so the saponification process of the organic extractant is indispensable. Based on this consideration, the organic amine unit is connected in the molecular structure of the organic phosphonic acid extractant. Compared with the traditional pure rare earth extractant, it presents the characteristics of synergistic extraction performance, extraction of rare earth metal cations and their accompanying antagonistic anions, and can maintain the material balance before and after the extraction of the rare earth salt solution.

[0003] The volatility, easy loss, emulsified third phase, flammability, and toxicity of traditional organic extractants are their major process defects. Therefore, scientists have immobilized organic phosphonates or organic amines on the surface of macroporous polystyrene, silica gel and other materials through bonding to form bonded leaching resins with the function of extracting rare earth ions from solutions. These resins have demonstrated high selective leaching performance in the fields of rare earth hydrometallurgy, enrichment and extraction and separation of precious metal ions in dilute solutions, simple operation, efficient solid-liquid separation, no loss in the process, and a clean environment.

[0004] There are usually several methods for immobilizing small molecule organic extractants: ①Use unsaturated small molecule organic phosphonates or organic amines as functional monomers, homopolymerize or copolymerize with other monomers to prepare polymer materials containing phosphine or amine. Unsaturated phosphonate monomers mainly include vinyl phosphonates or allyl phosphonates. Such organic phosphonate monomers have a single function and few varieties; and phosphonates or organic amines derived from acrylates or acrylamides as polymerizable monomers are also the research objects of phosphine-containing functional monomers. However, the chemical stability of such functional monomers is relatively low and the price is high, so they are limited in practical applications. ②Amino groups, acetyl groups, epoxy groups, etc. are grafted onto the surface of materials such as polystyrene and silica gel, and then organic phosphonates or organic amine extractants are bonded using Mannich reactions, phosphonylation reactions, substitution reactions, polyamine 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 groups grafted is small, so the number of solid support points of the bonded organic phosphonate or organic amine extractant is small, which limits the improvement of its saturated adsorption capacity and extraction capacity. Therefore, the organic phosphonate or organic amine bonded leaching resin prepared in this way has the disadvantage of small extraction capacity. ③ The functions of polymer materials are realized by grafting and polymerizing organic phosphine or organic amine monomers on the surface 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 or organic amine monomer raw materials during the grafting polymerization process, which not only causes the ineffective consumption of monomer raw materials, but also brings a necessary cleaning process to the re-functionalization process after grafting on the surface of the polymer material. Summary of the invention

[0005] In order to overcome the defects of the prior art, the present invention provides a bonded leaching resin in combination with the structural characteristics of organic phosphine and organic amine extractants, the synergistic effect of extraction performance, the technical requirements and application scope of polystyrene-based leaching resins. The bonded leaching resin specifically refers to a polystyrene-based leaching resin with poly (cationic phosphonate and organic amine) bonded on the surface, which can be used in industrial fields such as extraction and separation of rare earth ion solutions, uranium extraction from seawater, or enrichment and separation of precious metal ions in dilute solutions.

[0006] The specific preparation method of the bonded poly (cationic phosphonate-amine) leaching resin is as follows: weigh the surface-bonded unsaturated cationic phosphonate Unsaturated cationic phosphonate, allylamine salt, di-unsaturated cationic phosphonate and aqueous initiator are put into deionized water together, stirred and swelled at room temperature for 2-24 hours under N2 protection, and then poured into an organic solvent into a reactor. After stirring and dispersing for 0.5-2.5 hours, the temperature of the materials in the reactor is increased to 50-90°C, reverse suspension polymerization is carried out for 2-20 hours, and then filtered, washed and dried to obtain the bonded poly (cationic phosphonate-amine) leaching resin.

[0007] The amount of the unsaturated cationic phosphonate is The weight of the allylamine salt is 1 to 6 times that of the surface-bound unsaturated cationic phosphonate. The weight of the diunsaturated cationic phosphonate is 1 to 6 times the weight of the surface-bound unsaturated cationic phosphonate. The amount of the aqueous initiator is 0 to 3 times the weight of the surface-bound unsaturated cationic phosphonate. The amount of deionized water is 0.2 to 2 times the total amount of unsaturated cationic phosphonate, allylamine salt and diunsaturated cationic phosphonate, and the amount of the organic solvent is 0.1 to 10% by weight. 2 to 20 times its weight.

[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, or cross-linked or non-cross-linked (olefin monomer-styrene) copolymer, R2 is selected from C1~C 18 Hydrocarbon, R3 is selected from C1~C 18 Hydrocarbon or C1~C 18 Alkoxy; 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 unsaturated cationic phosphonate has a structure shown in the general formula (III) or the general formula (IV):

[0012]

[0013] 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 Alkoxy, X - Select Cl - Br - or I - One of them.

[0014] The allylamine salt refers to one or more of N-allylamine hydrochloride, N-allylamine bromide, N-allylamine iodide, N-alkyl-N-allylamine hydrochloride, N-alkyl-N-allylamine bromide, N-alkyl-N-allylamine iodide, N,N-dialkyl-N-allylamine hydrochloride, N,N-dialkyl-N-allylamine bromide, N,N-dialkyl-N-allylamine iodide, N,N-diallylamine hydrochloride, N,N-diallylamine bromide, N,N-diallylamine iodide, N-alkyl-N,N-diallylamine hydrochloride, N-alkyl-N,N-diallylamine bromide or N-alkyl-N,N-diallylamine iodide; wherein the alkyl refers to C1~C 18 Hydrocarbon.

[0015] The di-unsaturated cationic phosphonate has a structure shown in the general formula (V) or the general formula (VI):

[0016]

[0017] 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 C1~C 18 Alkylene or X - Select Cl - Br - or I - One of the following; wherein n is a natural number between 0 and 200.

[0018] The aqueous initiator refers to one of azobisisobutylamidine hydrochloride, azobisisobutylimidazoline hydrochloride, azobiscyanovaleric acid, azobisisopropylimidazoline hydrochloride, potassium persulfate or ammonium persulfate;

[0019] The organic solvent is selected from one or more of chloroform, carbon tetrachloride, 1,2-dichloroethane, toluene, xylene, chlorobenzene, decahydronaphthalene, anisole, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, kerosene, diesel, paraffin oil, and petroleum ether (boiling range 60-90° C.).

[0020] Further, the surface-bound unsaturated cationic phosphonate In It is a substrate for immobilizing functional units such as unsaturated cationic phosphonate, poly (cationic phosphonate and organic amine). The substrate refers to a styrene-based polymer. The styrene-based polymer refers to a cross-linked or non-cross-linked styrene polymer, or a cross-linked or non-cross-linked (olefin monomer-styrene) copolymer. The specific morphology can be described by one of the concepts of resin microspheres, resin pellets, resin beads, resin particles, resin micropowder, resin powder, foam plastics, fibers, fabrics or polymer solutions.

[0021] Further, the surface-bound unsaturated cationic phosphonate The unsaturated cationic phosphonate in The surface is specifically prepared by quaternizing 2-hydroxy-3-(unsaturated tertiary amino)propylphosphonate with the chloromethylated styrene-based polymer to obtain a surface-bound unsaturated cationic phosphonate. The chloromethylated styrene-based polymer refers to chloromethylated cross-linked or non-cross-linked polystyrene, or chloromethylated cross-linked or non-cross-linked (olefin monomer-styrene) copolymer. After the unsaturated cationic phosphonate is connected to the surface, the unsaturated cationic structural unit has the characteristics of copolymerization with some olefin functional monomers, which can achieve The purpose of surface grafting modification of "graft-from" type. After the unsaturated cationic phosphonate is attached to the surface, the surface changes from hydrophobic to strongly hydrophilic.

[0022] 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 2 to 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 to 45°C, stir and react for 6 to 16 hours, then increase the reaction temperature to 60 to 90°C, continue to stir and react for 6 to 36 hours, and then filter, wash and dry to obtain a surface-bound unsaturated cationic phosphonate with a structure shown in general formula (I) or general formula (II).

[0023] The amount of solvent used is chloromethylated The weight of the 2-hydroxy-3-(unsaturated tertiary amino) propylphosphonate is 2 to 20 times that of the chloromethylated The molar amount of the chloromethyl contained is 1.0 to 1.2 times, and the amount of the polymerization inhibitor used is 0.3 to 3% of the weight of 2-hydroxy-3-(unsaturated tertiary amino)propyl phosphonate.

[0024] The chloromethylation It refers to chloromethylated cross-linked or non-cross-linked polystyrene, or chloromethylated cross-linked or non-cross-linked (olefin monomer-styrene) copolymer; 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.

[0025] The 2-hydroxy-3-(unsaturated tertiary amino)propylphosphonate has a structure shown in the general formula (VII) or the general formula (VIII):

[0026]

[0027] 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 Alkoxy;

[0028] The solvent is selected from one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, chloroform, dichloromethane, tetrahydrofuran, 1,4-dioxane, toluene, xylene, decahydronaphthalene, 2-methoxyethanol, 2-ethoxyethanol, N-methylpyrrolidone, dimethyl sulfoxide, N,N-dimethylformamide or N,N-dimethylacetamide.

[0029] 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.

[0030] Further, the unsaturated cationic phosphonate is the unsaturated cationic phosphonate bonded to the surface of the present invention. The functional monomers for realizing "graft-from" graft polymerization are the key to improving the extraction capacity of the bonded poly (cationic phosphonate-amine) leaching resin of the present invention. The specific preparation method of the unsaturated cationic phosphonate is as follows: respectively weigh the solvent, 2-hydroxy-3-(unsaturated tertiary amino) propylphosphonate, alkylating agent and inhibitor in a reaction kettle, raise the temperature of the materials in the reaction kettle to 20-90°C under N2 protection, continue stirring the reaction for 6-36 hours, and then filter, wash and dry to obtain the unsaturated cationic phosphonate of the structure shown in general formula (III) or general formula (IV).

[0031] The amount of the solvent is 50-200% of the total weight of the alkylating agent and 2-hydroxy-3-(unsaturated tertiary amino) propyl phosphonate, the molar ratio of the alkylating agent to 2-hydroxy-3-unsaturated tertiary amino propyl phosphonate is 1.0-1.2:1, and the amount of the inhibitor is 0.3-3% of the weight of 2-hydroxy-3-(unsaturated tertiary amino) propyl phosphonate.

[0032] The 2-hydroxy-3-(unsaturated tertiary amino)propylphosphonate has a structure shown in the general formula (VII) or the general formula (VIII):

[0033]

[0034] 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 Alkoxy; the alkylating agent has a structure shown in the general formula (IX):

[0035] R1-X

[0036] General formula (IX)

[0037] Wherein R1 in the general formula (IX) is selected from C1 to C 18 Hydrocarbyl, X is selected from one of Cl, Br or I;

[0038] The solvent refers to one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, chloroform, dichloromethane, tetrahydrofuran, 1,4-dioxane, toluene, xylene, decahydronaphthalene, 2-methoxyethanol, 2-ethoxyethanol, N-methylpyrrolidone, dimethyl sulfoxide, N,N-dimethylformamide or N,N-dimethylacetamide;

[0039] 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.

[0040] Further, the di-unsaturated cationic phosphonate is the unsaturated cationic phosphonate bonded to the surface of the present invention. The functional crosslinking agent for realizing the "graft-from" graft polymerization is to ensure that the surface is bonded with unsaturated cationic phosphonate The key to achieving high grafting efficiency of "graft-from" is as follows. The preparation method of the di-unsaturated cationic phosphonate is as follows: weigh the solvent, 2-hydroxy-3-(unsaturated tertiary amino)propyl phosphonate, dialkylating agent and 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 the di-unsaturated cationic phosphonate of the structure shown in general formula (V) or general formula (VI).

[0041] 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 0.50-0.55:1, and the amount of the inhibitor is 0.1-10% of the mass of 2-hydroxy-3-(unsaturated tertiary amino) propyl phosphonate.

[0042] The 2-hydroxy-3-(unsaturated tertiary amino)propylphosphonate has a structure shown in the general formula (VII) or the general formula (VIII):

[0043]

[0044] 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 Alkoxy;

[0045] The dialkylating agent has a structure shown in the general formula (X):

[0046]

[0047] In the general formula (X), Select C1~C 18 Alkylene or Wherein n is a natural number between 0 and 200, and X is one of Cl, Br or I.

[0048] 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.

[0049] 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.

[0050] Further, the 2-hydroxy-3-(unsaturated tertiary amino)propyl phosphonate is used to prepare the surface-bound unsaturated cationic phosphonate. The raw materials of unsaturated cationic phosphonates and di-unsaturated cationic phosphonates, from which it can be seen that the 2-hydroxy-3-(unsaturated tertiary amino) propyl phosphonate is the key raw material for implementing the bonded poly(cationic phosphonate-amine) leaching resin technology of the present invention. The 2-hydroxy-3-(unsaturated tertiary amino) propyl phosphonate is prepared by the following method: weigh the phosphite ester and put it into the reactor, add sodium alcohol under N2 protection and stirring, increase the temperature of the material in the reactor to 50-150°C, continuously add N-glycidyl-N,N-diallylamine or N-glycidyl-N-alkyl-N-allylamine to the reactor, stir and react for 8-12 hours, and separate and purify to obtain 2-hydroxy-3-(unsaturated tertiary amino) propyl phosphonic acid dialkyl ester with the structure shown in general formula (VII) or general formula (VIII).

[0051] The amount of phosphite used is 2 to 10 times the weight of N-glycidyl-N,N-diallylamine or N-glycidyl-N-alkyl-N-allylamine, and the amount of sodium alkoxide used is 0.3 to 3% of the weight of N-glycidyl-N,N-diallylamine or N-alkyl-N-glycidyl-N-allylamine.

[0052] The N-alkyl-N-glycidyl-N-allylamine has a structure shown in the general formula (XI):

[0053]

[0054] The hydrocarbon group refers to R2 in the general formula (XI), wherein R2 is selected from C1 to C 18 Hydrocarbon.

[0055] The phosphite has a structure shown in the general formula (XII):

[0056]

[0057] 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.

[0058] The sodium alkoxide refers to one of sodium methoxide, sodium ethoxide, sodium propoxide or sodium butoxide.

[0059] The present invention provides a bonded poly (cationic phosphonate-amine) leaching resin having the following beneficial effects:

[0060] ① The bonded poly (cationic phosphonate-amine) leaching resin of the present invention not only has good surface hydrophilicity and can quickly extract heavy metal ions or rare earth metal ions in aqueous solution, but also has the characteristics of anion exchange function and strong antibacterial property, and has a relatively high extraction capacity.

[0061] ② The bonded poly (cationic phosphonate-amine) 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.

[0062] ③ The raw materials required for preparing the bonded poly (cationic phosphonate-amine) leaching resin of the present invention are all industrial products, the raw materials are easily available, the preparation method is simple, and the process is safe and efficient.

[0063] ④ The bonded poly (cationic phosphonate-amine) leaching resin of the present invention has scientific structure and morphology design, comprehensive functions, optimized technology and superior performance.

[0064] ⑤ The bonded poly (cationic phosphonate-amine) leaching resin of the present invention has high extraction chemical stability, so that its performance of extracting heavy metal ions or rare earth metal ions is long-lasting and stable, and 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. DETAILED DESCRIPTION

[0065] The bonded poly (cationic phosphonate-amine) leaching resin and the preparation method thereof of the present invention are further described by the following examples, the purpose of which is to provide a better understanding of the content of the present invention.

[0066] Example 1 Preparation of bonded poly (cationic phosphonate-amine) leaching resin-1

[0067] Step 1: Preparation of diethyl 2-hydroxy-3-(N,N-diallylamino)propylphosphonate

[0068] Weigh 30 grams of diethyl phosphite and put it into a reactor. Under N2 protection, add 1.5 grams of sodium ethoxide while stirring, increase the temperature of the material in the reactor to 90-110°C, continuously add 7 grams of N-glycidyl-N,N-diallylamine to the reactor, stir and react for 8 hours, and recover the residue after excess diethyl phosphite by negative pressure rotary evaporation. After separation, 13.7 grams of 2-hydroxy-3-(N,N-diallylamino)propylphosphonic acid diethyl ester is obtained. The yield of 2-hydroxy-3-(N,N-diallylamino)propylphosphonic acid diethyl ester is 93.2% based on N-glycidyl-N,N-diallylamine.

[0069] Step 2: Preparation of diethyl 2-hydroxy-3-(N-benzyl-N,N-diallylammonium chloride)propylphosphonate

[0070] 13.7 g of 2-hydroxy-3-(N,N-diallylamino)propylphosphonic acid diethyl ester prepared in step 1 was dissolved in 50 g of tetrahydrofuran, and 8.2 g of benzyl chloride and 0.5 g of hydroquinone were added. Under N2 protection, the temperature of the reaction material liquid was adjusted to 60-70°C, and the reaction was carried out for 12 hours. The temperature of the reaction product system was then lowered to room temperature. After standing, the crude product was filtered and purified by recrystallization from isobutanol and vacuum dried to constant weight to obtain 17.3 g of white crystalline product with a yield of about 88%. Product FTIR (cm -1 , KBr tablet): 3442cm -1 The characteristic absorption peaks of hydroxyl group OH, 2937 and 2867 cm -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 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%, the P content is 7.37%, and the C 20 H 33 The theoretical chlorine content of ClNO4P was 8.48% and the theoretical phosphorus content was 7.41%, which was basically consistent, confirming that the product was 2-hydroxy-3-(N-benzyl-N,N-diallylammonium chloride)propylphosphonic acid diethyl ester.

[0071] Step 3: Preparation of 1,4-bis(N,N-diallyl-N-(2-hydroxy-3-(diethoxyphosphonyl)propyl)ammonium)butane

[0072] 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 60The calculated Br content of Br2N2O8P2 is consistent with the theoretical value of 20.01%. Product spectrum analysis data: FTIR (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(bromide N,N-diallyl-N-(2-hydroxy-3-(diethoxyphosphino)propyl)ammonio)butane.

[0073] Step 4: Surface bonding of 2-hydroxy-3-(N,N-diallylammonium)propylphosphonic acid diethyl ester Preparation

[0074] The surface-bonded 2-hydroxy-3-(N,N-diallylammonium)propylphosphonic acid diethyl ester The preparation method is as follows: 60 g of tert-butyl alcohol, 60 g of 1,4-dioxane, 10 g of chlorine balls (cross-linking degree 7%, chlorine content 18.86%, particle size 0.23-0.45 mm purchased from the Chemical Plant of Nankai University), 13.7 g of 2-hydroxy-3-(N,N-diallylamino)propylphosphonic acid diethyl ester prepared in step 1 and 0.8 g of hydroquinone are weighed in a reactor, swelled at room temperature for 24 hours under N2 protection, the temperature of the material in the reactor is adjusted to 30-40°C, stirred for reaction for 12 hours, then the temperature of the material in the reactor is increased to 70-80°C, the stirring reaction is continued for 24 hours, filtered, washed with ethanol, extracted with Soxhlet for 24 hours, and vacuum dried to constant weight to obtain 20.8 g of surface-bound unsaturated cationic phosphonic acid diethyl ester. Analysis of surface-bound unsaturated cationic diethyl phosphonate by elution titration Free Cl in - The content is 8.66%; its FTIR (cm -1 , KBr tablet) The characteristic peaks in the spectrum include: 3426cm -1The characteristic absorption peak of hydroxyl group OH is 3037cm -1 Characteristic absorption peaks of vinyl, 2923, 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 characteristic absorption peak of POC is shown at It has the following schematic structure:

[0075]

[0076] Surface-bound unsaturated cationic diethyl phosphonate

[0077] Step 5: Bonding poly (cationic phosphonate-amine) leaching resin-1

[0078] Weigh 20.8 g of surface-bound unsaturated cationic diethyl phosphonate obtained in step 4 and 2.05 g of azobisisobutylamidine hydrochloride were dissolved in 35 g of deionized water, and swelled at room temperature for 24 hours under N2 protection to obtain a uniformly dispersed suspension; then 17.3 g of 2-hydroxy-3-(N-benzyl-N,N-diallylammonium chloride)propylphosphonic acid diethyl ester, 15 g of N-benzyl-N,N-diallylammonium hydrochloride, 5 g of 1,4-bis(bromide N,N-diallyl-N-(2-hydroxy-3-(diethoxyphosphine)) The acyl)propyl)ammonium)butane was dissolved in the above suspension, and then put into a reactor containing 250 g of toluene, stirred and dispersed for 1 hour, and then the temperature of the material in the reactor was raised to 50-55°C, and after reverse suspension polymerization for 2 hours, the temperature of the material in the reactor was raised to 70-80°C, and the polymerization reaction was continued for 4 hours, and the temperature of the material in the reactor was lowered to room temperature, filtered, washed with saturated sodium bicarbonate aqueous solution, and washed with deionizer until there was no free Cl in the washing water. - or Br - The resin was dried until it flowed out, and 83.9 grams of light yellow resin ball product was obtained. The water content of the resin ball product was about 36.3%, and the grafting efficiency was calculated to be 92.4%. The elemental analysis and spectral analysis showed that the The surface of the product has been successfully grafted with poly(cationic phosphonate-amine) leaching resin-1.

[0079] Comparative Example 1 Preparation of bonded poly (cationic phosphonate-amine) leaching resin-1'

[0080] According to the method and steps of Example 1, the "17.3 g of 2-hydroxy-3-(N-benzyl-N,N-diallylammonium chloride) propylphosphonic acid diethyl ester, 15 g of N-benzyl-N,N-diallylammonium hydrochloride, and 5 g of 1,4-bis(bromide N,N-diallyl-N-(2-hydroxy-3-(diethoxyphosphonyl)propyl)ammonium)butane" in Step 5 of Example 1 were replaced with "17.3 g of 2-hydroxy-3-(N-benzyl-N,N-diallylammonium chloride) propylphosphonic acid diethyl ester and 15 g of N-benzyl-N,N-diallylammonium hydrochloride" to obtain 58.6 g of light yellow resin ball product. The water content of the resin ball product was about 36.1% after analysis, and the grafting efficiency was calculated to be 70.2%. Elemental analysis and spectral analysis showed that the resin ball product had a water content of about 36.1%, and the grafting efficiency was calculated to be 70.2%. The product has been successfully grafted with poly(cationic phosphonate-amine).

[0081] Example 2 Preparation of bonded poly (cationic phosphonate-amine) leaching resin-2

[0082] According to the method and steps of Example 1, the "2.05 g of azobisisobutylamidine hydrochloride" in step 4 of Example 1 was replaced with "2.85 g of azobisisobutylamidine hydrochloride", and the "17.3 g of 2-hydroxy-3-(N-benzyl-N,N-diallylammonium chloride)propylphosphonic acid diethyl ester, 15 g of N-benzyl-N,N-diallylammonium hydrochloride, and 5 g of 1,4-bis(bromide N,N-diallyl-N-(2-hydroxy-3-(diethoxyphosphonyl)propyl)ammonium)butane" was replaced with "25 g of diethyl 2-hydroxy-3-(N-benzyl-N,N-diallylammonium chloride) propylphosphonate, 25 g of N-benzyl-N,N-diallylammonium hydrochloride, 5 g of 1,4-bis(N,N-diallyl-N-(2-hydroxy-3-(diethoxyphosphonyl)propyl)ammonium)butane", to obtain 108.5 g of light yellow resin ball product. The water content of the resin ball product was about 34.6%, and the grafting efficiency was calculated to be 93.6%. Elemental analysis and spectral analysis showed that the resin ball product had a water content of about 34.6%, and the grafting efficiency was calculated to be 93.6%. The resin bead product has been successfully grafted with poly(cationic phosphonate-amine).

[0083] Comparative Example 2 Preparation of bonded poly (cationic phosphonate-amine) leaching resin-2'

[0084] According to the method and steps of Example 1, the "2.05 g of azobisisobutylamidine hydrochloride" in Step 4 of Example 1 was replaced with "2.85 g of azobisisobutylamidine hydrochloride"; the "17.3 g of 2-hydroxy-3-(N-benzyl-N,N-diallylammonium chloride)propylphosphonic acid diethyl ester, 15 g of N-benzyl-N,N-diallylammonium hydrochloride, 5 g of 1,4-bis(bromide N,N-diallyl-N-( The "2-hydroxy-3-(diethoxyphosphonyl)propyl)ammonio)butane" was replaced with "25 g of 2-hydroxy-3-(N-benzyl-N,N-diallylammonium chloride)propylphosphonic acid diethyl ester, 25 g of N-benzyl-N,N-diallylammonium hydrochloride", and 68.6 g of light yellow resin ball product was obtained. The water content of the resin ball product was about 34.8% after analysis, and the grafting efficiency was calculated to be 63.2%. Elemental analysis and spectral analysis showed that the The resin bead product has been successfully grafted with poly(cationic phosphonate-amine).

[0085] Example 3 Preparation of bonded poly (cationic phosphonate-amine) leaching resin-3

[0086] According to the method and steps of Example 1, the "N-glycidyl-N,N-diallylamine" in step 1 of Example 1 is replaced with "N-glycidyl-N-benzyl-N-allylamine", the "2-hydroxy-3-(N,N-diallylamino)propylphosphonic acid diethyl ester" in step 2 is replaced with "2-hydroxy-3-(N-benzyl-N-allylamino)propylphosphonic acid diethyl ester", and the "2-hydroxy-3-(chlorinated N-benzyl-N,N-diallylamino)propylphosphonic acid diethyl ester" in step 5 is replaced with "2-hydroxy-3-(chlorinated N-benzyl-N,N-diallylamino)propylphosphonic acid diethyl ester". "(2-hydroxy-3-(diethoxyphosphonyl)propyl)ammoniomethyl)benzene" was replaced by "1,4-bis(diallyl-N-(2-hydroxy-3-(diethoxyphosphonyl)propyl)ammoniomethyl)benzene", "(2-hydroxy-3-(diethoxyphosphonyl)propyl)ammoniomethyl)benzene" was replaced by "(1,4-bis(diallyl-N-(2-hydroxy-3-(diethoxyphosphonyl)propyl)ammoniomethyl)benzene" and "(1,4-bis(diallyl-N-(2-hydroxy-3-(diethoxyphosphonyl)propyl)ammoniomethyl)benzene" was replaced by ... Resin-1" was replaced with "surface-bound unsaturated cationic diethyl phosphonate Resin - 2"

[0087]

[0088] Surface-bound unsaturated cationic phosphonates Resin-2

[0089] The obtained product was a light yellow resin ball with a similar appearance to that of Example 1. The water content of the resin ball product was about 35.7%, and the grafting efficiency was calculated to be 91.8%. The elemental analysis and spectral analysis showed that the resin ball product The resin bead product has been successfully grafted with poly(cationic phosphonate-amine).

[0090] Example 4 Preparation of bonded poly (cationic phosphonate-amine) leaching resin-4

[0091] According to the method and steps of Example 1, the "N-glycidyl-N,N-diallylamine" in Step 1 of Example 1 is replaced with "N-glycidyl-N-benzyl-N-allylamine", the "2-hydroxy-3-(N-benzyl-N,N-diallylammonium chloride)propylphosphonic acid diethyl ester" in Step 5 is replaced with "2-hydroxy-3-(N,N-dibenzyl-N-allylammonium chloride)propylphosphonic acid diethyl ester", "1,4-bis(N,N-diallyl-N-(2-hydroxy-3-(diethoxyphosphonyl)propyl)ammonium)butane bromide" is replaced with "2,2'-bis(N,N-diallyl-N-(2-hydroxy-3-(diethoxyphosphonyl)propyl)ammonium)diethyl ether", "surface-bound unsaturated cationic phosphonic acid diethyl ester" is replaced with "2-hydroxy-3-(N,N-dibenzyl-N-allylammonium chloride)propylphosphonic acid diethyl ester". Resin-1" was replaced with "surface-bound unsaturated cationic diethyl phosphonate Resin-2”:

[0092]

[0093] Surface-bound unsaturated cationic phosphonates Resin-2

[0094] The obtained product was a light yellow resin ball with a similar appearance to that of Example 1. The water content of the resin ball product was about 33.8%, and the grafting efficiency was calculated to be 91.1%. The elemental analysis and spectral analysis showed that the resin ball product The resin bead product has been successfully grafted with poly(cationic phosphonate-amine).

[0095] From the comparison of the grafting efficiency of the bonded poly (cationic phosphonate-amine) leaching resins of Examples 1 to 4 and Comparative Examples 1 to 2, it can be seen that the grafting efficiency of the polystyrene-based resin balls after the surface suspension of unsaturated quaternary ammonium cationic phosphonate "graft-from" graft polymerization of "2-hydroxy-3-(N-benzyl-N,N-diallylammonium chloride)propylphosphonic acid diethyl ester" type cationic monomers is determined by the presence or absence of "1,4-bis(bromide N,N-diallyl-N-(2-hydroxy-3-(diethoxyphosphonyl)propyl)ammonium)butane" type cationic crosslinking agents.

Claims

1. A bonded poly (cationic phosphonate-amine) leaching resin, characterized in that: The following steps were used to prepare the product: Weigh the surface-bound unsaturated cationic phosphonate Unsaturated cationic phosphonate, allylamine salt, diunsaturated cationic phosphonate, and aqueous initiator are put into deionized water together, stirred and swollen at room temperature for 2 to 24 hours under N2 protection, and then poured into an organic solvent in a reactor, stirred and dispersed for 0.5 to 2.5 hours, and then the temperature of the materials in the reactor is increased to 50 to 90° C., and reverse phase suspension polymerization is carried out for 2 to 20 hours, and then filtered, washed, and dried to obtain the bonded poly (cationic phosphonate-amine) leaching resin; The amount of the unsaturated cationic phosphonate is The weight of the allylamine salt is 1 to 6 times that of the surface-bound unsaturated cationic phosphonate. The weight of the diunsaturated cationic phosphonate is 1 to 6 times the weight of the surface-bound unsaturated cationic phosphonate. 0 to 3 times the weight, excluding the 0 end point, the amount of the aqueous initiator is the surface-bonded unsaturated cationic phosphonate The amount of deionized water is 0.2 to 2 times the total mass of the unsaturated cationic phosphonate, allylamine salt and diunsaturated cationic phosphonate, and the amount of the organic solvent is 2 to 20 times the weight; 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, or cross-linked or non-cross-linked (olefin monomer-styrene) copolymer, R2 is selected from C1~C 18 Hydrocarbon, R3 is selected from C1~C 18 Hydrocarbon or C1~C 18 Alkoxy; 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 Alkoxy, X - Select Cl - Br - or I - One of; The allylamine salt refers to one or more of N-allylamine hydrochloride, N-allylamine bromide, N-allylamine iodide, N-alkyl-N-allylamine hydrochloride, N-alkyl-N-allylamine bromide, N-alkyl-N-allylamine iodide, N,N-dialkyl-N-allylamine hydrochloride, N,N-dialkyl-N-allylamine bromide, N,N-dialkyl-N-allylamine iodide, N,N-diallylamine hydrochloride, N,N-diallylamine bromide, N,N-diallylamine iodide, N-alkyl-N,N-diallylamine hydrochloride, N-alkyl-N,N-diallylamine bromide or N-alkyl-N,N-diallylamine iodide; wherein the alkyl refers to C1~C 18 Hydrocarbon; The di-unsaturated cationic phosphonate has a structure shown in general formula (V) or general formula (VI): Wherein R2 in the general formula (V) or the general formula (VI) is selected from C1 to C 18 Hydrocarbon, R3 is selected from C1~C 18 Hydrocarbon or C1~C 18 Hydroxyl group, Refers to C1~C 18 Alkylene or X - Select Cl - Br - or I - One of the following; wherein n is a natural number between 0 and 200; The aqueous initiator refers to one of azobisisobutylamidine hydrochloride, azobisisobutylimidazoline hydrochloride, azobiscyanovaleric acid, azobisisopropylimidazoline hydrochloride, potassium persulfate or ammonium persulfate; The organic solvent is selected from one or more of chloroform, carbon tetrachloride, 1,2-dichloroethane, toluene, xylene, chlorobenzene, decahydronaphthalene, anisole, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, kerosene, diesel, paraffin oil, and petroleum ether with a boiling range of 60 to 90°C.

2. A bonded poly (cationic phosphonate-amine) leaching resin 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 2 to 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 to 45°C, stir and react for 6 to 16 hours, then increase the reaction temperature to 60 to 90°C, continue to stir and react for 6 to 36 hours, and then filter, wash and dry to obtain a surface-bound unsaturated cationic phosphonate with a structure shown in general formula (I) or general formula (II). The amount of solvent used is chloromethylated The weight of the 2-hydroxy-3-(unsaturated tertiary amino) propylphosphonate is 2 to 20 times that of the chloromethylated The amount of the polymerization inhibitor is 1.0 to 1.2 times the molar amount of the chloromethyl group contained, and the amount of the polymerization inhibitor is 0.3 to 3% by weight of 2-hydroxy-3-(unsaturated tertiary amino)propyl phosphonate; The chloromethylation Refers to chloromethylated cross-linked or non-cross-linked polystyrene, or chloromethylated cross-linked or non-cross-linked (olefin monomer-styrene) copolymer, 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 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 Alkoxy; The solvent is selected from one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, chloroform, dichloromethane, tetrahydrofuran, 1,4-dioxane, toluene, xylene, decahydronaphthalene, 2-methoxyethanol, 2-ethoxyethanol, N-methylpyrrolidone, dimethyl sulfoxide, N,N-dimethylformamide or N,N-dimethylacetamide; 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.

3. A bonded poly (cationic phosphonate-amine) leaching resin 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, an alkylating 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, continue stirring and reacting for 6-36 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 weight of the alkylating agent and 2-hydroxy-3-(unsaturated tertiary amino) propyl phosphonate, the molar ratio of the alkylating agent to 2-hydroxy-3-unsaturated tertiary amino propyl phosphonate is 1.0-1.2:1, and the amount of the inhibitor is 0.3-3% of the weight of 2-hydroxy-3-(unsaturated tertiary amino) propyl phosphonate; The 2-hydroxy-3-(unsaturated tertiary amino)propylphosphonate has a structure shown in the general formula (VII) or the general formula (VIII): 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 Alkoxy; The alkylating 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 Hydrocarbyl, X is selected from one of Cl, Br or I; The solvent refers to one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, chloroform, dichloromethane, tetrahydrofuran, 1,4-dioxane, toluene, xylene, decahydronaphthalene, 2-methoxyethanol, 2-ethoxyethanol, N-methylpyrrolidone, dimethyl sulfoxide, N,N-dimethylformamide or N,N-dimethylacetamide; 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.

4. A bonded poly (cationic phosphonate-amine) leaching resin according to claim 1, 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 0.50-0.55:1, and the amount of the inhibitor is 0.1-10% of the mass of 2-hydroxy-3-(unsaturated tertiary amino) propyl phosphonate; The 2-hydroxy-3-(unsaturated tertiary amino)propylphosphonate has a structure shown in the general formula (VII) or the general formula (VIII): 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 Alkoxy; The dialkylating agent has a structure shown in the general formula (X): In the general formula (X), Select C1~C 18 Alkylene or wherein n is a natural number between 0 and 200, and X is one of Cl, Br or I; 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; 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.

5. A bonded poly (cationic phosphonate-amine) leaching resin according to claim 2, 3 or 4, characterized in that 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 50-150°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, separating and purifying to obtain 2-hydroxy-3-(unsaturated tertiary amino) propyl phosphonate having a structure represented by general formula (VII) or general formula (VIII); 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 0.3 to 3% of the weight of N-glycidyl-N,N-diallylamine or N-alkyl-N-glycidyl-N-allylamine; The N-alkyl-N-glycidyl-N-allylamine has a structure shown in the general formula (XI): The hydrocarbon group refers to R2 in the general formula (Ⅺ), wherein R2 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 alkoxide refers to one of sodium methoxide, sodium ethoxide, sodium propoxide or sodium butoxide.

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