Phosphorus-containing resin as well as preparation method and application thereof

Abstract

The invention provides phosphorus-containing resin as well as a preparation method and application thereof. The phosphorus-containing resin has a structure as shown in a formula I, wherein S is a resin matrix; r1 is selected from hydrogen, phenyl and alkyl; r2 is selected from hydrogen and hydrocarbyl; r3 is selected from a hydroxyl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, a phenolic group and an amido group; r4 and R5 are respectively and independently selected from alkoxy and hydroxyl; and n is any integer from 0 to 10. The phosphorus-containing resin provided by the invention is simple to prepare, has high selectivity on metals such as iron, aluminum and copper, has good cycle performance, can be used in an actual extraction process, and realizes a more efficient separation effect. # imgabs0 # (formula I)

Description

Technical Field

[0001] The present invention relates to the technical field of organic synthesis, and particularly relates to a phosphorus-containing resin, a preparation method thereof, and an application thereof. Background Art

[0002] Resin solid-phase extraction is a developing metal separation and purification process, which has broad prospects in the field of metal extraction and has certain applications in the fields of chemical industry, electroplating, metallurgy, mining, and new energy.

[0003] By grafting specific functional groups onto the resin, it can obtain special selective ability for certain metals, so as to achieve the purpose of separating and purifying specific metals.

[0004] Compared with the traditional method, the resin solid-phase extraction method has the advantages of fast phase separation, low loss, simple operation, small pollution, low cost, and many cycle times.

[0005] However, the resins currently used for solid-phase extraction do not have high selectivity and cannot achieve the purpose of selective adsorption and purification; therefore, it is necessary to provide a new adsorbent to further improve the selectivity in the solid-phase extraction process, so as to improve the separation and purification effect of certain metal elements (especially iron, aluminum, and copper). Summary of the Invention

[0006] One object of the present invention is to provide a new adsorbent that has high selectivity for certain metals (especially iron, aluminum, and copper).

[0007] Therefore, according to the first aspect, the present invention provides a phosphorus-containing resin, which is characterized in that it has the structure shown in Formula I: (Formula I), Wherein: S is a resin matrix; R 1 is selected from hydrogen, phenyl, and alkyl; R 2 is selected from hydrogen and hydrocarbon group; R 3 is selected from hydroxyl, alkoxy, alkenyloxy, alkynyloxy, phenol group, and amine group; R 4 and R 5 each independently is selected from alkoxy and hydroxyl; n is any integer from 0 to 10.

[0008] According to the second aspect, the present invention provides a preparation method of the above phosphorus-containing resin, which is characterized in that it includes the following steps: S1. React the primary amine group of the primary amine resin with a halogenated carboxylic acid or its derivative of Formula II to obtain an intermediate resin, (Formula II), Wherein: R 2 As defined for Formula I; R 3 As defined for Formula I; X = Cl, Br or I; n is as defined for Formula I, and S2, in an acidic solution, in the presence of an aldehyde of the formula R 1 CHO, reacting the resulting intermediate resin with a phosphorus-containing substance of Formula III at a temperature of 40 - 120 °C to obtain the phosphorus-containing resin, wherein R 1 As defined for Formula I, (Formula III) Wherein: R 4 As defined for Formula I; R 5 As defined for Formula I.

[0009] According to a third aspect, the present invention provides the use of the above phosphorus-containing resin for adsorbing metals, wherein the metals are one or a combination of two or more of iron, aluminum, chromium, copper, nickel, manganese, zinc, and silver.

[0010] According to a fourth aspect, the present invention provides an extractant for solid-phase extraction of metal elements, characterized in that it contains the above phosphorus-containing resin.

[0011] According to a fifth aspect, the present invention provides a method for solid-phase extraction of metal elements, characterized in that an extractant containing the above phosphorus-containing resin is used, and the metals are one or a combination of two or more of iron, aluminum, chromium, copper, nickel, manganese, zinc, and silver.

[0012] The phosphorus-containing resin of the present invention has high selectivity for iron, aluminum, and copper, is simple to prepare, has good separation and purification effects when used, is green and environmentally friendly, and has low cost. Detailed Embodiments

[0013] Hereinafter, the aspects of the present invention, as well as further objects, features, and advantages, will be described in more detail.

[0014] Phosphorus-containing resin According to a first aspect, the present invention provides a phosphorus-containing resin, characterized in that it has the structure shown in Formula I: (Formula I) Wherein: S is a resin matrix; R 1 Selected from hydrogen, phenyl, and alkyl; R 2 Selected from hydrogen and hydrocarbon groups; R 3 Selected from hydroxyl, alkoxy, alkenyloxy, alkynyloxy, phenol group and amine group; R 4 and R 5 Each independently selected from alkoxy and hydroxyl; n is any integer from 0 to 10.

[0015] There is no special limitation on the resin matrix S in the present invention. Preferably, it is selected from polystyrene resin, copolymer of styrene and divinylbenzene, phenolic resin, polyacrylic resin and silicone resin. More preferably, the resin matrix S is selected from polystyrene resin and copolymer of styrene and divinylbenzene.

[0016] Preferably, R 1 is selected from hydrogen, phenyl and C 1 -C 9 alkyl.

[0017] More preferably, R 1 is selected from hydrogen, phenyl, methyl and ethyl.

[0018] Preferably, R 2 is selected from hydrogen, optionally halogenated C 1 -C 10 alkyl, optionally halogenated C 1 -C 10 alkenyl, optionally halogenated C 1 -C 10 dienyl, optionally halogenated C 1 -C 10 alkynyl and optionally C 1 -C 4 alkyl or aryl substituted by halogen.

[0019] As an example of R 2 , hydrogen and the following groups can be cited: , , , , , , , , , , , , , , , , , , , , and , wherein is a linking site.

[0020] More preferably, R 2 is selected from hydrogen, C 1 -C 10 alkyl and optionally C 1 -C 4 alkyl or a phenyl group substituted with a halogen.

[0021] Even more preferably, R 2 is selected from hydrogen and the following groups: , , , , , , and , wherein is a linking site.

[0022] Preferably, R 3 is selected from a hydroxyl group, an optionally halogenated C 1 -C 10 alkoxy group, an optionally halogenated C 1 -C 10 alkenyloxy group, an optionally halogenated C 1 -C 10 alkynyloxy group, an optionally halogenated C 1 -C 10 phenoxy group and an amino group.

[0023] As examples of R 3 , there may be mentioned: , , , , , , , , , , , , , , , , , , , , , , and , wherein is a linking site.

[0024] More preferably, R 3 is selected from a hydroxyl group, an optionally halogenated C 1 -C 10 alkoxy group, and an amino group.

[0025] Even more preferably, the R 3 group is selected from the following groups: , , , , , , , and , wherein is a linking site.

[0026] Preferably, R 4 and R 5 are independently selected from C 1 -C 10 alkoxy groups and hydroxyl groups.

[0027] More preferably, R 4 and R 5 are selected from the following groups: , , , , and .

[0028] n is any integer from 0 to 10, i.e., it can be 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.

[0029] m, p, and q are each independently any integer from 0 to 9, i.e., they can be 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9.

[0030] Preferably, m, p, and q are each independently 1 or 2.

[0031] Preferably, the phosphorus-containing resin has a structure selected from the following: , , , , , , , , and , Wherein S is selected from polystyrene resin, copolymer of styrene and divinylbenzene, phenolic resin, polyacrylic resin and silicone-based resin.

[0032] Preferably, the phosphorus-containing resin has a structure selected from the following: , , , , , Wherein S is selected from polystyrene resin, copolymer of styrene and divinylbenzene.

[0033] The phosphorus-containing resin obtained according to the present invention has high selectivity for metal elements (especially iron, aluminum, copper), and can adsorb metal elements such as iron, aluminum, and copper in an acidic solution, providing a new extractant for the extraction and purification process.

[0034] Method for preparing the above phosphorus-containing resin According to a second aspect, the present invention provides a method for preparing the above phosphorus-containing resin, which is characterized by comprising the following steps: S1. React the primary amine group of the primary amine resin with a halogenated carboxylic acid or its derivative of formula II to obtain an intermediate resin, (Formula II), Wherein: R 2 As defined for formula I; R 3 As defined for formula I; X = Cl, Br or I; n is as defined for formula I, and S2. React the obtained intermediate resin with a phosphorus-containing substance of formula III in the presence of an aldehyde substance R 1 CHO, R 1 CHO at a temperature of 40 - 120 °C to obtain the phosphorus-containing resin, wherein R 1 As defined for formula I, (Formula III) Wherein R 4 As defined for formula I; R 5 As defined for formula I.

[0035] Before step S1, the resin matrix can be pretreated.

[0036] Specifically, the pretreatment includes rinsing the resin matrix with a solvent, stirring and shaking the resin, and then removing the excess solvent.

[0037] Preferably, the solvent used in the pretreatment is water, ethanol, ether, toluene, dioxane, N,N-dimethylformamide, dichloromethane, ethyl acetate, or a mixture of one or more of these solvents.

[0038] Preferably, the reaction in step S1 is carried out in an alkaline solution at a temperature of 40 - 120 °C.

[0039] Preferably, the solute of the alkaline solution in step S1 is one or a combination of two or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, ammonia water, and calcium hydroxide.

[0040] Preferably, the solvent of the alkaline solution in step S1 is one or a combination of two or more of water, ethanol, methanol, and N,N-dimethylformamide.

[0041] Preferably, the concentration of the alkaline solution in step S1 is 0.1 - 5 mol / L.

[0042] Preferably, the molar ratio of the amount of the solute in the alkaline solution to the molar amount of the primary amine groups in the resin is 0.8 - 2.5:1.

[0043] Preferably, the molar ratio of the content of the primary amine groups in the resin to the molar amount of the halogenated carboxylic acid or its derivative of formula II is 1: 0.75 - 1.75, preferably 1: 0.8 - 1.5.

[0044] Preferably, the amount of the solvent used is 1 - 30 times the mass of the resin.

[0045] Preferably, the reaction time in step S1 is 4 - 48 hours.

[0046] Preferably, in step S2, the acid in the acidic solution is a mixture of one or more of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, and perchloric acid.

[0047] Preferably, in step S2, the aldehyde substance is any one or a mixture of formaldehyde, benzaldehyde, and C 1 -C 9 alkyl formaldehyde.

[0048] Preferably, in step S2, the aldehyde substance is any one or a mixture of formaldehyde, acetaldehyde, propionaldehyde, and benzaldehyde.

[0049] More preferably, in step S2, the aldehyde substance is selected from formaldehyde, acetaldehyde, and benzaldehyde.

[0050] Preferably, in step S2, the solvent in the acidic solution is one or a mixture of more of water, ethanol, methanol, and N,N-dimethylformamide.

[0051] Preferably, in step S2, the concentration of the acidic solution is 0.1 - 6 mol / L.

[0052] Preferably, the molar ratio of the amount of acid in the acidic solution to the molar amount of primary amine groups in the resin is 0.5 - 3:1.

[0053] Preferably, the molar ratio of the primary amine groups, aldehyde substances, and phosphorus-containing substances of formula III in the resin matrix is 1:1 - 1.5:0.75 - 1.75, preferably 1:1 - 1.25:0.8 - 1.5.

[0054] Preferably, the amount of the solvent in the acidic solution is 1 - 30 times the mass of the resin.

[0055] Preferably, in step S2, the reaction time is 4 - 48 hours.

[0056] The preparation method of the present invention can effectively prepare the phosphorus-containing resin of the present invention.

[0057] Application of the phosphorus-containing resin According to the third aspect, the present invention provides the use of the above phosphorus-containing resin for adsorbing metals, and the metals are one or a combination of more of iron, aluminum, chromium, copper, nickel, manganese, zinc, and silver.

[0058] The phosphorus-containing resin can be used to adsorb metals in the fields of hydrometallurgy and electroplating wastewater treatment. According to the fourth aspect, the present invention provides an extractant for solid-phase extraction of metal elements, which is characterized by containing the above phosphorus-containing resin.

[0059] According to the fifth aspect, the present invention provides a method for solid-phase extraction of metal elements, which is characterized by using an extractant containing the above phosphorus-containing resin, and the metals are one or a combination of two or more of iron, aluminum, chromium, copper, nickel, manganese, zinc, and silver.

[0060] The phosphorus-containing resin of the present invention can effectively adsorb iron, aluminum, chromium, copper, nickel, manganese, zinc, silver, etc., and has high selectivity for iron, aluminum, and copper in particular.

[0061] In some embodiments, the method includes the following steps: S1: Contact the above chelating resin composition with a solution containing iron, aluminum, and copper for extraction, and then perform solid-liquid separation to obtain a chelating resin composition loaded with iron, aluminum, and copper and a raffinate; S2: Use an acid solution to strip the chelating resin composition loaded with iron, aluminum, and copper, and then perform solid-liquid separation to obtain a stripped chelating resin composition and an iron, aluminum, and copper stripping solution.

[0062] The iron, aluminum, and copper-containing solution contains one or at least two combinations of iron, aluminum, and copper.

[0063] Advantageously, the extraction time is 1 min or more, such as 1 - 120 min, such as 5 - 100 min, such as 10 - 80 min, preferably 10 - 60 min.

[0064] Advantageously, the pH value of the iron, aluminum, and copper-containing solution is 0.2 - 3, such as 1 - 2.5, such as 1.5 - 2. When the solution does not contain iron and aluminum, the pH value is 0.2 - 5, such as 0.2 - 4.5. Advantageously, before stripping the chelating resin loaded with iron, aluminum, and copper, it is first washed with a dilute acid solution to wash down the impurity metals.

[0065] Advantageously, the acid solutions used for the washing and stripping are each independently selected from sulfuric acid solution and hydrochloric acid solution. Preferably, the concentration of the sulfuric acid solution used for the stripping is 0.5 - 6 mol / L, and the concentration of the hydrochloric acid solution is 1 - 8 mol / L; the pH value of the acid solution used for the washing is between 0.5 and 2.

[0066] The chelating resin composition of the present invention has improved selectivity for metal elements, especially iron, aluminum, and copper metal elements, and can effectively separate iron, aluminum, and copper from impurities such as chromium, nickel, manganese, zinc, and silver.

[0067] The "selectivity" described in this application is represented by the separation coefficient of metal elements β Furthermore, the separation coefficient is obtained from the following formula: β A / B =D A / D B =E A .(1 - E B ) / ((1 - E A ).E B ) In the formula, D A represents the ratio of the content of metal element A in the resin after one extraction to the content of metal element A in the raffinate aqueous phase; D B represents the ratio of the content of metal element B in the resin after one extraction to the content of metal element B in the raffinate aqueous phase; E A and E B respectively represent the extraction rates of metal element A and metal element B (extraction rate E = content of metal element in the resin after one extraction / content of metal element in the initial aqueous phase × 100%).

[0068] Among them, the metal extraction rate in the formula can be measured by the following method: Resin pretreatment: Mix the resin with 2 mol / L sulfuric acid and stir it at a rotation speed of 250 rpm / min for 30 min. Wash it with pure water until the supernatant is colorless, then wash it with 0.25 mol / L sodium hydroxide solution until the supernatant is alkaline, and then wash the resin with pure water to neutrality. Filter to obtain the pretreated resin for standby; Prepare 30 mL of a sulfate solution containing 0.05 g / L of each metal element as the initial aqueous phase. Adjust the pH value of the initial aqueous phase, and then mix it with 5 g of the pretreated resin and stir at room temperature for 60 min at a rotation speed of 250 rpm / min to achieve adsorption equilibrium. After stirring, perform solid-liquid separation to obtain the raffinate (equilibrium) aqueous phase. Determine the concentration of each metal element in the raffinate aqueous phase by inductively coupled plasma emission spectrometry (ICP), and calculate the content of the metal element in the resin by the difference method.

[0069] The "loading amount" described in this application can be measured by the following method: Prepare sulfate solutions of 0.5 mol / L of each metal element respectively, adjust the pH value of the initial aqueous phase, take 2 g of the pretreated resin in a beaker respectively, add 20 mL of the prepared solutions of each metal element to each, stir at room temperature for 60 min at a rotation speed of 250 rpm / min. After stirring, perform solid-liquid separation to obtain the raffinate aqueous phase, and repeat three times, each time contacting with a fresh initial aqueous phase. Determine the concentration of each metal element in the raffinate aqueous phase by inductively coupled plasma emission spectrometry (ICP), and calculate the content of the metal element in the resin by the difference method to obtain the loading amount of each metal element on the resin.

[0070] In this application, the terms "comprising" and "including" cover the cases where other elements not explicitly mentioned are also included or included, as well as the cases consisting of the mentioned elements.

[0071] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which this invention belongs. When the definition of a term in this specification conflicts with the meaning commonly understood by those skilled in the art to which this invention belongs, the definition in this article shall prevail.

[0072] Unless otherwise specified, all numerical values expressing amounts of ingredients, temperatures, times, etc. used in the specification and claims are understood to be modified by the term "about". Therefore, unless there is a contrary indication, the numerical parameters set forth herein are approximate values that can be varied according to the desired properties required.

[0073] Examples The concept of the present invention and the resulting technical effects will be further described below in conjunction with embodiments, so that those skilled in the art can fully understand the purpose, features, and effects of the present invention. It is not difficult for those skilled in the art to understand that the embodiments herein are only for illustrative purposes, and the scope of the present invention is not limited thereto.

[0074] Example 1: Preparation of Resin 1 The synthesis route of Resin 1 is as follows: Take 10 g of primary amino polystyrene resin (from Lanxiao Technology, model LX-D30), 3.3 g (35 mmol) of chloroacetic acid, and 3.7 g (35 mmol) of sodium carbonate in a 100 ml three-necked flask, add 50 mL of water, and under the condition of mechanical stirring, heat and react at 80 °C for 12 hours to obtain the intermediate resin 1.

[0075] Then, add 3 mL (30 mmol) of formaldehyde solution and 2.45 g (30 mmol) of phosphorous acid to the intermediate resin 1, add 70 mL of water, and under the condition of mechanical stirring, react at 100 °C for 24 hours to obtain Resin 1.

[0076] Example 2: Preparation of Resin 2 Take 10 g of primary amino polystyrene resin (from Lanxiao Technology, model LX-D30), 5.35 g (35 mmol) of 2-bromopropionamide, and 4.83 g (35 mmol) of potassium carbonate in a 100 mL three-necked flask, add 50 mL of water, and under the condition of mechanical stirring, heat and react at 80 °C for 24 hours to obtain the intermediate resin 2.

[0077] Then, add 5.3 mL (30 mmol) of acetaldehyde solution and 2.45 g (30 mmol) of phosphorous acid to the intermediate resin 2, add 70 mL of water, and under the condition of mechanical stirring, react at 100 °C for 24 hours to obtain Resin 2.

[0078] Example 3: Preparation of Resin 3 Take 10 g of primary amino polystyrene resin (from Lanxiao Technology, model LX-D30), 8.5 g (35 mmol) of ethyl 2-bromo-phenylacetate, and 1.4 g (35 mmol) of sodium hydroxide in a 100 mL three-necked flask, add 50 mL of ethanol, and under the condition of mechanical stirring, heat and react at 60 °C for 24 hours to obtain the intermediate resin 3.

[0079] Next, 3 mL (30 mmol) of formaldehyde solution and 4.15 g (30 mmol) of diethyl phosphite were added to the intermediate resin 3, 70 mL of water was added, and the reaction was carried out at 100 °C for 24 hours under mechanical stirring to obtain resin 3.

[0080] Example 4 Prepare 30 mL of a sulfate solution containing Fe 3+ , Al 3+ , Cr 3+ , Cu 2+ , Ni 2+ , Mn 2+ , Zn 2+ , Ag + each at 0.05 g / L as the initial aqueous phase, adjust the pH value of the initial aqueous phase to 1, and then mix and stir it with 5 g of the above resin at room temperature for 60 min at a rotation speed of 250 rpm / min. After extraction, the concentrations of various metal elements in the raffinate aqueous phase were measured by inductively coupled plasma emission spectrometry (ICP), and the metal element content in the resin was calculated by the subtraction method. The results are summarized in Table 1.

[0081] Table 1. Metal element content in the raffinate of each resin (g / l) Fe Al Cr Cu Ni Mn Zn Ag Resin 1 0.0011 0.0008 0.045 0.016 0.039 0.038 0.041 0.048 Resin 2 0.0002 0.0002 0.046 0.031 0.042 0.045 0.044 0.044 Resin 3 0.0001 0.0001 0.048 0.029 0.043 0.048 0.043 0.047 The extraction rates of various ions by each resin were calculated, and the results are summarized in Table 2.

[0082] Table 2. Extraction rates of metal elements by each resin Fe(%) Al(%) Cr(%) Cu(%) Ni(%) Mn(%) Zn(%) Ag(%) Resin 1 97.8 98.4 10 68 22 24 18 4 Resin 2 99.6 99.6 8 38 16 10 12 12 Resin 3 99.8 99.8 4 42 14 4 14 6 Furthermore, the separation factors of various metal elements for resins 1, 2, and 3 were calculated respectively, and the results are summarized in Tables 3, 4, and 5.

[0083] Table 3. Separation factors of resin 1 1 Fe Al Cr Cu Ni Mn Zn Ag Fe 1.0 1.0 400.1 20.9 157.6 140.8 202.5 1066.9 Al 1.0 553.5 28.9 218.0 194.8 280.2 1476.0 Cr 1.5 0.1 0.4 0.4 0.5 2.7 Cu 1.0 7.5 6.7 9.7 51.0 Ni 1.0 0.9 1.3 6.8 Mn 1.0 1.4 7.6 Zn 1.0 5.3 Ag 1.0 Table 4. Separation factors of resin 2 2 Fe Al Cr Cu Ni Mn Zn Ag Fe 1.0 1.0 2863.5 406.3 1307.3 2241.0 1826.0 1826.0 Al 1.0 2863.5 406.3 1307.3 2241.0 1826.0 1826.0 Cr 1.0 0.1 0.5 0.8 0.6 0.6 Cu 1.0 3.2 5.5 4.5 4.5 Ni 1.0 1.7 1.4 1.4 Mn 1.0 0.8 0.8 Zn 1.0 1.0 Ag 1.0 Table 5. Separation factors of resin 3 3 Fe Al Cr Cu Ni Mn Zn Ag Fe 1.0 1.0 11976.0 689.1 3065.3 11976.0 3065.3 7817.7 Al 1.0 11976.0 689.1 3065.3 11976.0 3065.3 7817.7 Cr 1.0 0.1 0.3 1.0 0.3 0.7 Cu 1.0 4.4 17.4 4.4 11.3 Ni 1.0 3.9 1.0 2.6 Mn 1.0 0.3 0.7 Zn 1.0 2.6 Ag 1.0 It can be seen from Tables 3 - 5 that resins 1, 2, and 3 all have high selectivity for the two metal elements of iron and aluminum, and resin 1 has relatively high selectivity for copper.

[0084] Furthermore, the iron and aluminum loading amounts of resins 1, 2, and 3 were detected.

[0085] Prepare 0.5 mol / L ferric sulfate and aluminum sulfate solutions, adjust the initial pH value of the aqueous phase to 1.2. Take 2 g of the pretreated resin in a beaker respectively, add 20 mL of each prepared metal element solution to each, stir at room temperature for 60 min at a rotation speed of 250 rpm / min. After stirring is completed, perform solid-liquid separation to obtain the raffinate aqueous phase. Repeat three times, each time contacting a new initial aqueous phase. Use inductively coupled plasma emission spectrometry (ICP) to measure the concentration of each metal element in the raffinate aqueous phase, and calculate the content of metal elements in the resin by the difference method to obtain the loading amounts of iron and aluminum on Resins 1, 2, and 3. The results are summarized in Table 6.

[0086] Table 6. Loading amounts of iron and aluminum on Resins 1, 2, and 3 Example 5 Prepare 30 mL of a sulfate solution containing 0.05 g / L of each of Fe 3+ , Al 3+ , Cr 3+ , Cu 2+ , Ni 2+ , Mn 2+ , Zn 2+ , Ag + as the initial aqueous phase, adjust the initial pH value of the aqueous phase to 2.0, then mix and stir with 5 g of the above resin at room temperature for 60 min at a rotation speed of 250 rpm / min. After extraction is completed, use inductively coupled plasma emission spectrometry (ICP) to measure the concentration of each metal element in the raffinate aqueous phase, and calculate the content of metal elements in the resin by the difference method. The results are summarized in Table 7.

[0087] Table 7. Contents of metal elements in the raffinate of each resin (g / l) Fe Al Cr Cu Ni Mn Zn Ag Resin 1 0.0009 0.0008 0.042 0.009 0.041 0.045 0.042 0.049 Resin 2 0.0002 0.0003 0.040 0.013 0.044 0.048 0.039 0.045 Resin 3 0.0003 0.0004 0.041 0.014 0.045 0.044 0.040 0.046 Calculate the extraction rates of each resin for each ion, and the results are summarized in Table 8.

[0088] Table 8. Extraction rates of each resin for metal elements Furthermore, calculate the separation coefficients of each metal element for Resins 1, 2, and 3 respectively, and the results are summarized in Tables 9 - 11.

[0089] Table 9. Separation coefficients of Resin 1 1 Fe Al Cr Cu Ni Mn Zn Ag Fe 1.0 1.0 286.4 12.0 248.5 491.0 286.4 2673.2 Al 1.0 322.9 13.5 280.2 553.5 322.9 3013.5 Cr 0.9 0.0 0.9 1.7 1.0 9.3 Cu 1.0 20.8 41.0 23.9 223.2 Ni 1.0 2.0 1.2 10.8 Mn 1.0 0.6 5.4 Zn 1.0 9.3 Ag 1.0 Table 10. Separation coefficients of Resin 2 2 Fe Al Cr Cu Ni Mn Zn Ag Fe 1.0 1.5 996.0 87.5 1826.0 5976.0 882.8 2241.0 Al 1.0 662.7 58.2 1214.9 3976.0 587.4 1491.0 Cr 1.0 0.1 1.8 6.0 0.9 2.3 Cu 1.0 20.9 68.3 10.1 25.6 Ni 1.0 3.3 0.5 1.2 Mn 1.0 0.1 0.4 Zn 1.0 2.5 Ag 1.0 Table 11. Separation coefficients of Resin 3 3 Fe Al Cr Cu Ni Mn Zn Ag Fe 1.0 1.3 754.7 64.4 1491.0 1214.9 662.7 1905.2 Al 1.0 564.9 48.2 1116.0 909.3 496.0 1426.0 Cr 1.0 0.1 2.0 1.6 0.9 2.5 Cu 1.0 23.1 18.9 10.3 29.6 Ni 1.0 0.8 0.4 1.3 Mn 1.0 0.5 1.6 Zn 1.0 2.9 Ag 1.0 As can be seen from Table 9-11, at this time, Resins 1, 2, and 3 all have high selectivity for these two metal elements of iron, aluminum, and copper.

[0090] Further detect the loading amounts of Resins 1, 2, and 3 for iron, aluminum, and copper.

[0091] Prepare 0.5 mol / L ferric sulfate, aluminum sulfate, and copper sulfate solutions, adjust the initial pH value of the aqueous phase to 1.2. Respectively take 2 g of the pretreated resin in a beaker, add 20 mL of each prepared metal element solution to each, stir at room temperature for 60 min, at a rotation speed of 250 rpm / min. After stirring is completed, perform solid-liquid separation to obtain the raffinate aqueous phase. Repeat three times, each time contacting a new initial aqueous phase. Use inductively coupled plasma emission spectrometry (ICP) to measure the concentrations of each metal element in the raffinate aqueous phase. The content of the metal element in the resin is obtained by the subtraction method, and the loading amounts of Resins 1, 2, and 3 for iron, aluminum, and copper are obtained. The results are summarized in Table 12.

[0092] Table 12. Loading amounts of Resins 1, 2, and 3 for iron, aluminum, and copper The above-mentioned resin is repeatedly extracted and regenerated 10 times, and the metal loading amount hardly changes, proving that the above-mentioned resin has good repeated use performance.

[0093] The above only describes the exemplary embodiments or examples of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention can be subject to various changes and modifications. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention are included within the scope of the claims of this application.

Claims

1. A phosphorus-containing resin, characterized in that it has the structure of Formula I: (Formula Ⅰ) Wherein: S is a resin matrix; R 1 selected from hydrogen, phenyl and alkyl; R 2 selected from hydrogen and hydrocarbyl; R 3 selected from a hydroxyl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, a phenol group and an amine group; R 4 and R 5 each independently selected from an alkoxy group and a hydroxyl group; n is any integer from 0 to 10.

2. The phosphorus-containing resin according to claim 1, characterized in that the S is selected from any one or more of polystyrene resin, copolymer of styrene and divinylbenzene, phenolic resin, polyacrylic acid resin, and silicone-based resin.

3. The phosphorus-containing resin according to claim 1 or 2, characterized in that Said R 1 is selected from hydrogen, phenyl and C 1 -C 9 alkyl, preferably selected from hydrogen, phenyl, methyl and ethyl.

4. The phosphorus-containing resin according to any one of claims 1 to 3, characterized in that Said R 2 is selected from hydrogen, optionally halogenated C 1 -C 10 alkyl, optionally halogenated C 1 -C 10 alkenyl, optionally halogenated C 1 -C 10 dienyl, optionally halogenated C 1 -C 10 alkynyl and optionally C 1 -C 4 alkyl or aryl substituted by halogen, Preferably, R 2 is selected from hydrogen and the following groups: , , , , , , , , , , , , , , , , , , , , and , Among them is the connection site.

5. The phosphorus-containing resin according to any one of claims 1 - 4, characterized in that The R 3 is selected from hydroxy, optionally halogenated C 1 -C 10 alkoxy, optionally halogenated C 1 -C 10 alkenyloxy, optionally halogenated C 1 -C 10 alkynyloxy, optionally halogenated phenol group and amine group, Preferably, R 3 is selected from the following groups: , , , , , , , , , , , , , , , , , , , , , , and , Among them is the connection site.

6. The phosphorus-containing resin according to claim 1, characterized in that Said R 4 and R 5 are independently selected from hydroxy and C 1 -C 10 alkoxy groups, Preferably, R 4 and R 5 are selected from the following groups: , , , , and .

7. The phosphorus-containing resin according to any one of claims 1 - 6, characterized in that n is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10; m in claim 4, p in claim 5, and q in claim 6 are each independently 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9.

8. The phosphorus-containing resin according to any one of claims 1 - 7, characterized in that it has a structure selected from the following: , , , , , , , , and , Wherein S is selected from polystyrene resin, copolymer of styrene and divinylbenzene, phenolic resin, polyacrylic acid resin, and silicone-based resin.

9. A method for preparing the phosphorus-containing resin according to any one of claims 1 - 8, characterized in that it includes the following steps: S1. React the primary amine groups of the primary amine resin with a halogenated carboxylic acid or its derivative of Formula II to obtain an intermediate resin, (Formula II), Wherein: R 2 as defined in any one of claims 1, 4 or 8; R 3 as defined in any one of claims 1, 5 or 8; X = Cl, Br or I, n is as defined in any one of claims 1, 6 or 8, and S2. In an acidic solution, in the presence of an aldehyde of the formula R 1 CHO, react the resulting intermediate resin with a phosphorus-containing substance of formula III at a temperature of 40 - 120 °C to obtain the phosphorus-containing resin, where R 1 is as defined for formula I in any one of claims 1, 3 or 8, (Formula III) Wherein R 4 as defined for formula I in any one of claims 1, 6 or 8; R 5 as defined for formula I in any one of claims 1, 6 or 8.

10. The preparation method according to claim 9, characterized in that the reaction in step S1 is carried out in an alkaline solution at a temperature of 40 - 120 °C. Preferably, the solute of the alkaline solution is one or a combination of two or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, ammonia water, and calcium hydroxide; the solvent of the alkaline solution is one or a combination of two or more of water, ethanol, methanol, and N,N-dimethylformamide; the concentration of the alkaline solution is 0.1 - 5 mol / L.

11. The preparation method according to claim 9 or 10, characterized in that the molar ratio of the content of the primary amine groups of the resin in step S1 to the molar amount of the halogenated carboxylic acid or its derivative of Formula II is 1: 0.75 - 1.75, preferably 1:0.8 - 1.

5.

12. The preparation method according to claim 9, characterized in that the solute of the acidic solution is a mixture of one or more of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, and perchloric acid; the solvent of the acidic solution is a mixture of one or more of water, ethanol, methanol, and N,N-dimethylformamide; the concentration of the acidic solution is 0.1 - 6 mol / L.

13. The preparation method according to any one of claims 9 - 12, characterized in that The molar ratio of the primary amine group content of the resin in step S1, the aldehyde substance in step S2 and the phosphorus-containing substance of formula III is 1:1 - 1.5:0.75 - 1.75, preferably 1:1 - 1.25:0.8 - 1.

5.

14. Use of the phosphorus-containing resin according to any one of claims 1 - 8 for adsorbing metals, wherein the metals are one or more combinations of iron, aluminum, chromium, copper, nickel, manganese, zinc, and silver.

15. An extractant for solid-phase extraction of metal elements Characterized in that it contains the phosphorus-containing resin according to any one of claims 1 - 8.

16. A method for solid-phase extraction of metal elements Characterized in that an extractant containing the phosphorus-containing resin according to any one of claims 1 - 8 is used, and the metals are one or more combinations of iron, aluminum, chromium, copper, nickel, manganese, zinc, and silver.

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