Strong cation exchange chromatographic filler as well as preparation method and application thereof

Abstract

The invention relates to a strong cation exchange chromatographic filler as well as a preparation method and application thereof. The strong cation exchange chromatographic filler comprises sulfonated poly (glycidyl methacrylate)-divinyl benzene microspheres. The strong cation exchange chromatographic filler provided by the invention can simultaneously show excellent separation selectivity on rare earth elements, and also has long-term stability and excellent cycle performance, so that the economic cost is reduced, and the strong cation exchange chromatographic filler has relatively high economic benefits and is green and environment-friendly.

Description

Technical Field

[0001] The invention relates to the technical field of ion exchange chromatography, in particular to a strong cation exchange chromatography filler and a preparation method and application thereof. Background Art

[0002] Separation of rare earth elements can be difficult due to the similarities in their physical and chemical properties. Efforts have been made to develop technologies to efficiently extract these valuable metal ions from a variety of waste sources, including ores, wastewaters, and in particular from fluorescent lamp waste. Many strategies have been employed to pre-concentrate, separate, and recover rare earth elements, including precipitation, electrochemical extraction, ion exchange, and ionic liquid extraction. In general, however, these methods require large amounts of hazardous or expensive reagents, such as strong acids and extractant compounds. Large-scale solvent extraction involves large amounts of organic solvents, resulting in high material costs and the risk of water contamination with toxic chemicals.

[0003] As a classic separation technology, chromatography has broad application potential in the field of rare earth element separation due to its high separation efficiency and selectivity. However, traditional chromatographic separation materials, such as silica gel and alumina, are easily hydrolyzed under strong acid and alkali conditions due to the limitations of their inherent physical and chemical properties, and it is difficult to meet the needs of efficient and highly selective separation of rare earth elements. Against this background, the research on monodisperse porous polymer microspheres has gradually attracted the attention of scientific researchers. Compared with traditional chromatographic separation materials, monodisperse porous polymer microspheres have the following significant advantages: their ligands are highly flexible and can achieve maximum interaction between molecules and stationary phases. Using polymer microspheres as chromatographic fillers can not only reduce column pressure, but also significantly improve column efficiency. At present, polymer microspheres are mainly used as anion exchange chromatographic fillers and weak acid cation exchange stationary phases to separate and detect conventional cations (Li + 、Na + NH 4+ , K + Mg 2+ , Ca 2+ ) and restricted-access chromatographic packings for the separation of specific biomolecules.

[0004] Therefore, it is of great significance to design and develop a green and environmentally friendly strong cation exchange chromatography filler that can simultaneously show excellent separation selectivity for multiple rare earth elements. Summary of the invention

[0005] In order to solve the above technical problems, the present invention provides a strong cation exchange chromatography filler and its preparation method and application. The strong cation exchange chromatography filler has long-term stability and excellent circulation performance, can separate multiple rare earth elements at the same time, and has good separation effect.

[0006] To achieve this object, the present invention adopts the following technical solutions:

[0007] In a first aspect, the present invention provides a strong cation exchange chromatography filler, wherein the strong cation exchange chromatography filler comprises sulfonated poly(glycidyl methacrylate)-divinylbenzene microspheres.

[0008] The present invention obtains sulfonated poly(glycidyl methacrylate)-divinylbenzene) microspheres by subjecting poly(glycidyl methacrylate)-divinylbenzene) microspheres to sulfonic acid functionalization. Sulfonated poly(glycidyl methacrylate)-divinylbenzene microspheres can be used as strong cation exchange chromatography fillers to provide abundant interaction sites for efficient separation of rare earth elements, thereby showing excellent separation selectivity for a variety of rare earth elements, and also having long-term stability and excellent cycle performance, thereby reducing economic costs, having high economic benefits and being green and environmentally friendly.

[0009] Preferably, the average particle size of the sulfonated poly(glycidyl methacrylate)-divinylbenzene microspheres is 5-11 μm, for example, 5 μm, 5.5 μm, 6 μm, 6.5 μm, 7 μm, 7.5 μm, 8 μm, 8.5 μm, 9 μm, 9.5 μm, 10 μm, 10.5 μm or 11 μm, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0010] Preferably, the average pore size of the strong cation exchange chromatography filler is 2-20 nm, for example, it can be 2 nm, 4 nm, 6 nm, 8 nm, 10 nm, 12 nm, 14 nm, 16 nm, 18 nm or 20 nm, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0011] Preferably, the specific surface area of ​​the strong cation exchange chromatography filler is 50-500m 2 / g, for example, 50m 2 / g, 80m 2 / g、100m 2 / g, 200m 2 / g、300m 2 / g, 400m 2 / g or 500m 2 / g, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of brevity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0012] In a second aspect, the present invention provides a method for preparing the strong cation exchange chromatography filler as described in the first aspect, the preparation method comprising the following steps:

[0013] (1) Preparing polystyrene seed microspheres by dispersion polymerization;

[0014] (2) Preparation of poly(glycidyl methacrylate)-divinylbenzene microspheres by a two-step seed swelling method;

[0015] (3) Sulfonated poly(glycidyl methacrylate)-divinylbenzene microspheres were prepared using a sulfonation reagent.

[0016] Preferably, the method for preparing the polystyrene seed microspheres in step (1) comprises the following steps:

[0017] Styrene, initiator A and stabilizer are mixed and reacted to obtain the polystyrene seed microspheres.

[0018] Preferably, the reaction is carried out in a medium.

[0019] Preferably, the medium comprises an ethanol aqueous solution.

[0020] Preferably, the volume concentration of the ethanol aqueous solution is 85-100%, for example, it can be 85%, 85.5%, 86%, 88%, 90%, 92%, 94%, 96%, 98% or 100%, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0021] The volume concentration of the ethanol aqueous solution provided by the present invention is 85-100%, which means that anhydrous ethanol and water are calculated according to a specific volume ratio by formula (1):

[0022] V1 / (V1+V2) formula (1);

[0023] Wherein, V1 represents the volume of anhydrous ethanol added, and V2 represents the volume of water added.

[0024] Preferably, the water includes any one of natural water, distilled water, purified water, deionized water or ultrapure water, or a combination of at least two of them.

[0025] Preferably, the styrene content is 10-20 vol% of the medium volume, for example, it can be 10 vol%, 11 vol%, 12 vol%, 13 vol%, 14 vol%, 15 vol%, 16 vol%, 17 vol%, 18 vol%, 19 vol% or 20 vol%, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0026] In the present invention, the particle size of the polystyrene seed microspheres is controlled by adjusting the concentration of the reaction medium ethanol water and the concentration of styrene, thereby obtaining polystyrene seed microspheres in a specific particle size range (with an average particle size of 1.21-6.1 μm). Furthermore, when the average particle size of the polystyrene seed microspheres is controlled to be 1-3 μm, they can be well used in the preparation of the strong ion exchange chromatography filler of the present invention.

[0027] Preferably, the initiator A is an oil-soluble initiator.

[0028] Preferably, the oil-soluble initiator comprises an oil-soluble peroxide and / or an oil-soluble azo compound.

[0029] Preferably, the oil-soluble peroxide includes any one of dibenzoyl peroxide, dicaprylyl peroxide or lauroyl peroxide, or a combination of at least two thereof.

[0030] Preferably, the oil-soluble azo compound comprises azobisisobutyronitrile and / or azobisisoheptanenitrile.

[0031] Preferably, the content of initiator A is 1-2wt% of the mass of styrene, for example, it can be 1wt%, 1.1wt%, 1.2wt%, 1.3wt%, 1.4wt%, 1.5wt%, 1.6wt%, 1.7wt%, 1.8wt%, 1.9wt% or 2wt%, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0032] Preferably, the stabilizer is a water-soluble polymer.

[0033] Preferably, the water-soluble polymer includes any one of polyvinyl pyrrolidone, polyvinyl alcohol or modified cellulose, or a combination of at least two thereof, and more preferably polyvinyl pyrrolidone.

[0034] Preferably, the average molecular weight of the polyvinyl pyrrolidone is 58,000.

[0035] In the present invention, too high or too low a stabilizer content will result in poor monodispersity of the polystyrene microspheres and even affect polymerization.

[0036] Preferably, the content of the stabilizer is 4-11wt% of the mass of styrene, for example, it can be 4wt%, 4.5wt%, 5wt%, 5.5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt% or 11wt%, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0037] Preferably, the reaction is carried out under stirring.

[0038] Preferably, the stirring speed is 100-200r / min, for example, it can be 100r / min, 110r / min, 120r / min, 130r / min, 140r / min, 150r / min, 160r / min, 170r / min, 180r / min, 190r / min or 200r / min, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0039] Preferably, the reaction temperature is 70-80°C, for example, it can be 70°C, 71°C, 72°C, 73°C, 74°C, 75°C, 76°C, 77°C, 78°C, 79°C or 80°C, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0040] Preferably, the reaction time is 18-24h, for example, it can be 18h, 19h, 20h, 21h, 22h, 23h or 24h, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0041] Preferably, the average particle size of the polystyrene seed microspheres is 1-3 μm, for example, it can be 1 μm, 1.2 μm, 1.4 μm, 1.6 μm, 1.8 μm, 2.0 μm, 2.2 μm, 2.4 μm, 2.6 μm, 2.8 μm or 3.0 μm, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the said range.

[0042] Preferably, the method for preparing poly(glycidyl methacrylate)-divinylbenzene microspheres in step (2) comprises the following steps:

[0043] The activator, emulsifier A and the polystyrene seed microspheres of step (1) are mixed to carry out the first swelling step; after the first swelling step, monomer glycidyl methacrylate, crosslinking agent, initiator B, emulsifier B and porogen are added to carry out the second swelling step; after the second swelling step, heating reaction is carried out to obtain the polyglycidyl methacrylate-divinylbenzene microspheres.

[0044] Preferably, the mass ratio of polystyrene seed microspheres, activator and emulsifier A in the first step swelling is (0.2-2): (0.5-5): (0.017-0.375), wherein (0.2-2) can be 0.2, 0.3, 0.4, 0.5, 0.8, 1, 1.2, 1.5, 1.8 or 2, (0.5-5) can be 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5 or 5, (0.017-0.375) can be 0.017, 0.02, 0.03, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35 or 0.375, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the said range.

[0045] Preferably, the activator comprises dibutyl phthalate.

[0046] Preferably, the emulsifier A comprises sodium dodecyl sulfonate and / or sodium dodecyl sulfate.

[0047] In the present invention, sodium dodecyl sulfate has a similar technical effect to sodium dodecyl sulfate, and subsequent experimental research is only conducted with sodium dodecyl sulfate.

[0048] Preferably, the sodium dodecyl sulfate comprises a sodium dodecyl sulfate aqueous solution with a mass fraction of 0.2-0.3% (eg, 0.2%, 0.22%, 0.24%, 0.26%, 0.28% or 0.3%).

[0049] In the present invention, the amount of sodium dodecyl sulfate added will affect the particle size monodispersity of the prepared poly(glycidyl methacrylate)-divinylbenzene microspheres. If the content is too high or too low, the monodispersity and uniformity of the prepared poly(glycidyl methacrylate)-divinylbenzene microspheres will be reduced, making them unsuitable for use as chromatographic fillers.

[0050] Preferably, the swelling temperature of the first swelling step is 25-35°C, for example, it can be 25°C, 26°C, 27°C, 28°C, 29°C, 30°C, 32°C, 34°C or 35°C, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0051] Preferably, the swelling time of the first swelling step is 4-24 h, for example, 4 h, 6 h, 8 h, 10 h, 12 h, 14 h, 16 h, 18 h or 20 h, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0052] Preferably, based on the total weight of the monomer glycidyl methacrylate, the crosslinker, the initiator B, the emulsifier B and the porogen as the mass of the total organic phase, the mass ratio of the polystyrene seed microspheres to the total organic phase is (0.02-0.2):3, wherein (0.02-0.2) can be 0.02, 0.03, 0.05, 0.08, 0.1, 0.13, 0.15, 0.18 or 0.2, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0053] In the present invention, the particle size of the obtained poly(glycidyl methacrylate)-divinylbenzene microspheres can be controlled by adjusting the latex ratio (i.e., the mass ratio of styrene seed microspheres to the total organic phase). When the latex ratio increases, the particle size of the microspheres decreases, and vice versa. When the latex ratio is lower than 0.02:3, the monodispersity of the microspheres decreases; similarly, when the latex ratio is higher than 0.2:3, the monodispersity of the microspheres decreases, and thus the microspheres are not suitable for use as chromatographic fillers.

[0054] Preferably, the cross-linking agent comprises divinylbenzene.

[0055] Preferably, based on the mass of the total organic phase as 100%, the mass of the cross-linking agent is 20-40%, for example, it can be 20%, 22%, 24%, 26%, 28%, 30%, 32%, 34%, 36%, 38% or 40%, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0056] Preferably, the mass ratio of the monomer glycidyl methacrylate to the cross-linking agent is (0.3-0.7):1, wherein (0.3-0.7) can be 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65 or 0.7, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0057] Preferably, the initiator B is an oil-soluble initiator.

[0058] Preferably, the oil-soluble initiator comprises an oil-soluble peroxide and / or an oil-soluble azo compound.

[0059] Preferably, the oil-soluble peroxide includes any one of dibenzoyl peroxide, dicaprylyl peroxide or lauroyl peroxide, or a combination of at least two thereof.

[0060] Preferably, the oil-soluble azo compound comprises azobisisobutyronitrile and / or azobisisoheptanenitrile.

[0061] Preferably, the mass ratio of the initiator B to the monomer glycidyl methacrylate is (0.04-0.1):1, wherein (0.04-0.1) can be 0.04, 0.05, 0.06, 0.07, 0.08, 0.09 or 0.1, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0062] Preferably, the emulsifier B includes sodium dodecyl sulfate and / or sodium dodecyl sulfonate, and more preferably sodium dodecyl sulfate.

[0063] Preferably, based on the mass of the total organic phase as 100%, the mass of the emulsifier B is 1-2.7%, for example, it can be 1%, 1.2%, 1.5%, 1.8%, 2%, 2.2%, 2.5% or 2.7%, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0064] Preferably, the porogen includes any one of toluene, dibutyl phthalate or cyclohexanol, or a combination of at least two thereof, and more preferably toluene.

[0065] Preferably, based on the mass of the total organic phase as 100%, the mass of the porogen is 45-55%, for example, it can be 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54% or 55%, and specific values ​​between the above points. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific points included in the range.

[0066] Preferably, the swelling temperature of the second swelling step is 25-35°C, for example, it can be 25°C, 26°C, 27°C, 28°C, 29°C, 30°C, 32°C, 34°C or 35°C, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0067] Preferably, the swelling time of the second swelling step is 6-48h, for example, it can be 6h, 10h, 15h, 20h, 25h, 30h, 35h, 40h, 45h or 48h, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0068] Preferably, the heating reaction is carried out under stirring.

[0069] Preferably, the stirring speed is 100-400r / min, for example, it can be 100r / min, 120r / min, 150r / min, 180r / min, 200r / min, 250r / min, 300r / min, 350r / min or 400r / min, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0070] Preferably, the temperature of the heating reaction is 70-80°C, for example, it can be 70°C, 71°C, 72°C, 73°C, 74°C, 75°C, 76°C, 77°C, 78°C, 79°C or 80°C, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0071] Preferably, the heating reaction time is 6-24h, for example, it can be 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h or 24h, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0072] Preferably, the average particle size of the poly(glycidyl methacrylate)-divinylbenzene microspheres is 5-11 μm, for example, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, or 11 μm, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0073] In the present invention, the particle size of the poly(glycidyl methacrylate)-divinylbenzene) microspheres can be controlled to be adjusted to 4-20 μm by regulating the particle size of the seed microspheres, the latex ratio or a combination of the two. Furthermore, when the average particle size is 5-11 μm, it can be well used as a strong cationic chromatographic seasoning.

[0074] At present, the chromatographic separation of rare earth elements in the prior art is only at the analytical level. In the present invention, in the preparation process of poly(glycidyl methacrylate)-divinylbenzene) microspheres, the particle size of polystyrene seed microspheres is regulated by step (1), and then the two swelling steps in step (2) work together to make the particle size of the prepared poly(glycidyl methacrylate)-divinylbenzene) microspheres controllable, and the microspheres can be enlarged to the preparative chromatography level, which is beneficial for the separation and purification of multiple rare earth elements at the same time, has good application prospects and potential, and thus expands its application scope.

[0075] Preferably, the preparation method of sulfonated poly(glycidyl methacrylate)-divinylbenzene microspheres in step (3) comprises the following steps:

[0076] a. hydrolyzing the poly(glycidyl methacrylate)-divinylbenzene microspheres in step (2) to obtain polymer microspheres with dihydroxy groups grafted on the surface;

[0077] b. Mixing the polymer microspheres grafted with dihydroxy groups on the surface described in a with a sulfonation reagent, and reacting them to obtain the sulfonated poly(glycidyl methacrylate)-divinylbenzene microspheres.

[0078] Preferably, the hydrolysis reaction in step a is carried out in a dilute aqueous sulfuric acid solution;

[0079] Preferably, the mass concentration of the poly(glycidyl methacrylate)-divinylbenzene microspheres in 0.1 M dilute sulfuric acid solution in step a is 0.02-0.1 g / mL, for example, 0.02 g / mL, 0.03 g / mL, 0.04 g / mL, 0.05 g / mL, 0.06 g / mL, 0.07 g / mL, 0.08 g / mL, 0.09 g / mL or 0.1 g / mL, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0080] Preferably, the hydrolysis reaction in step a is carried out under reflux.

[0081] Preferably, the temperature of the hydrolysis reaction in step a is 30-80°C, for example, it can be 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C or 80°C, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0082] Preferably, the hydrolysis reaction time in step a is 12-48 h, for example, it can be 12 h, 15 h, 18 h, 20 h, 25 h, 30 h, 35 h, 40 h, 45 h or 48 h, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0083] Preferably, the hydrolysis reaction in step a is followed by drying.

[0084] Preferably, the drying treatment is carried out by vacuum drying, freeze drying or infrared drying, or a combination of at least two of them.

[0085] Preferably, the mass ratio of the surface-grafted dihydroxy polymer microspheres to the sulfonated reagent in step b is (1-5): (1.4-7), wherein (1-5) can be 1, 2, 3, 4 or 5, and (1.4-7) can be 1.4, 1.6, 1.8, 2, 2.5, 3, 4, 5, 6 or 7, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the said range.

[0086] Preferably, the reaction in step b is carried out in toluene.

[0087] Preferably, the mass ratio of the surface grafted dihydroxy polymer microspheres to toluene in step b is (1-5): (8.6-52), wherein (1-5) can be 1, 2, 3, 4 or 5, and (8.6-52) can be 8.6, 8.66, 8.7, 9, 10, 20, 30, 40, 50 or 52, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the said range.

[0088] Preferably, the mixing in step b comprises first mixing and stirring the polymer microspheres with dihydroxy groups grafted on the surface with toluene, and then adding the sulfonation reagent.

[0089] Preferably, the rotation speed of the mixing and stirring is 180-250r / min, for example, it can be 180r / min, 190r / min, 200r / min, 210r / min, 220r / min, 230r / min, 240r / min or 250r / min, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0090] Preferably, the mixing temperature is 40-100°C, for example, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C or 100°C, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0091] Preferably, the mixing and stirring time is 1-8h, for example, it can be 1h, 2h, 3h, 4h, 5h, 6h, 7h or 8h, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0092] Preferably, the sulfonating agent comprises 1,3-propane sultone or 1,4-butane sultone.

[0093] Preferably, the reaction temperature in step b is 80-120°C, for example, it can be 80°C, 85°C, 90°C, 95°C, 100°C, 110°C, 115°C or 120°C, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0094] Preferably, the reaction time in step b is 24-96 hours, for example, 24 hours, 30 hours, 40 hours, 50 hours, 60 hours, 70 hours, 80 hours, 90 hours or 96 hours, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0095] Preferably, after the reaction in step b is completed, the mixture is cooled to room temperature, filtered, washed and dried.

[0096] Preferably, the filtration comprises vacuum filtration.

[0097] Preferably, the washing comprises sequentially washing with excess ultrapure water and an alcohol solution for 3-5 times each to remove residual toluene.

[0098] Preferably, the alcohol solution comprises anhydrous ethanol and / or methanol.

[0099] Preferably, the drying comprises any one of vacuum drying, freeze drying or infrared drying, or a combination of at least two thereof.

[0100] Preferably, the vacuum drying temperature is 80-90°C, for example, it can be 80°C, 82°C, 84°C, 86°C, 88°C or 90°C, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0101] Preferably, the vacuum drying time is 6-24 h, for example, it can be 6 h, 8 h, 10 h, 12 h, 14 h, 16 h, 18 h, 20 h, 22 h or 24 h, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0102] Preferably, the preparation method of the strong cation exchange chromatography filler specifically comprises the following steps:

[0103] (1) Preparation of polystyrene seed microspheres by dispersion polymerization

[0104] Styrene is dissolved in an ethanol aqueous solution with a volume concentration of 85-100%, a stabilizer and an initiator A are added, and the mixture is reacted at 100-200 r / min and 70-80° C. for 18-24 hours to obtain polystyrene seed microspheres with a particle size of 1-3 μm.

[0105] (2) Preparation of poly(glycidyl methacrylate)-divinylbenzene microspheres by a two-step seed swelling method: The polystyrene seed microspheres, activator and emulsifier A described in step (1) are mixed in a mass ratio of (0.2-2):(0.5-5):(0.017-0.375), and the first swelling step is performed at 25-35°C for 4-24 hours; after the first swelling step, monomer glycidyl methacrylate, crosslinking agent, initiator B, emulsifier B and porogen are added, and the second swelling step is performed at 25-35°C for 6-48 hours; after the second swelling step, the system is heated to 70-80°C, and the reaction is carried out at a stirring speed of 100-400 r / min for 6-24 hours to obtain poly(glycidyl methacrylate)-divinylbenzene microspheres with a particle size of 5-11 μm.

[0106] (3) preparing sulfonated poly(glycidyl methacrylate)-divinylbenzene microspheres using a sulfonating agent, dissolving the poly(glycidyl methacrylate)-divinylbenzene microspheres described in step (2) in a 0.1 M dilute sulfuric acid solution, and reacting under reflux at 30-80° C. for 12-48 h, and obtaining poly(glycidyl methacrylate)-divinylbenzene microspheres grafted with dihydroxy groups on the surface after drying;

[0107] b. Take the dried surface-grafted dihydroxy polymer microspheres in a and add them to toluene, stir at 180-250r / min and 40-100°C for 1-8h, then add the sulfonation reagent, heat to 80-120°C, and react for 24-96h. After the reaction, cool to 20-30°C, filter, wash, and dry to obtain sulfonated poly(glycidyl methacrylate)-divinylbenzene microspheres, i.e., the strong cation exchange chromatography filler.

[0108] The present invention realizes the preparation of sulfonated poly(glycidyl methacrylate)-divinylbenzene microspheres with controllable particle size through the above-mentioned preparation method, and the average particle size thereof is 5-11 μm, and the microspheres have the characteristics of monodispersity and uniform particle size, and can be used as strong cation exchange chromatography fillers for separating and purifying multiple rare earth elements at the same time, with good selectivity, long-term stability and good circulation performance. Thus, a new idea can be provided for the development of liquid chromatography stationary phase materials, indicating that sulfonic acid functionalized polymer microspheres will have a wider range of applications in the future analytical chemistry and rare earth element separation fields. Future research directions may include improving the selectivity and stability of microspheres, as well as further reducing preparation costs and expanding the scope of application.

[0109] In a third aspect, the present invention provides a use of the strong cation exchange chromatography filler as described in the first aspect in the separation of rare earth elements.

[0110] Preferably, the rare earth elements include scandium Sc, lutetium Lu, ytterbium Yb, thulium Tm, erbium Er, holmium Ho, dysprosium Dy, terbium Tb, gadolinium Gd, europium Eu, samarium Sm, neodymium Nd, praseodymium Pr, cerium Ce and lanthanum La.

[0111] Preferably, in the process of separating rare earth elements using the ion exchange chromatography filler, the chromatographic conditions include: column temperature 25°C, detection wavelength 658nm, flow rate 1.0mL / min; the post-column derivatization liquid is arsenazo III, and the post-column derivatization pump flow rate is 0.6mL / min; the mobile phase for gradient elution is 800mM α-hydroxyisobutyric acid, and its pH is 2.5-3.5.

[0112] Compared with the prior art, the present invention has at least the following beneficial effects:

[0113] The present invention obtains sulfonated poly(glycidyl methacrylate)-divinylbenzene) microspheres by subjecting poly(glycidyl methacrylate)-divinylbenzene) microspheres to sulfonic acid functionalization. Sulfonated poly(glycidyl methacrylate)-divinylbenzene microspheres can be used as strong cation exchange chromatography fillers to provide abundant interaction sites for efficient separation of rare earth elements, thereby showing excellent separation selectivity for 15 kinds of rare earth elements, and also having long-term stability and excellent cycle performance, thereby reducing economic costs, having high economic benefits and being green and environmentally friendly.

[0114] Furthermore, the present invention optimizes the preparation method of strong cation exchange chromatography filler, prepares polystyrene seed microspheres of different particle sizes, and controls the particle size of poly(glycidyl methacrylate)-divinylbenzene microspheres by regulating the particle size of the seed microspheres, the latex ratio or a combination of the two, thereby obtaining a strong cation exchange chromatography filler with controllable particle size, thereby improving its separation and purification effect on multiple rare earth elements. BRIEF DESCRIPTION OF THE DRAWINGS

[0115] Figure 1 A preparation route map of the strong cation exchange chromatography filler provided by the present invention;

[0116] Figure 2 The SEM image and particle size distribution characterization diagram of the polystyrene seed microspheres described in Example 1 of the present invention;

[0117] Figure 3 The SEM image of the sulfonic acid functionalized polymer microsphere chromatographic filler described in Example 1 of the present invention and its corresponding EDS elemental map;

[0118] Figure 4 This is an infrared spectrum of the sulfonic acid functionalized polymer microsphere chromatographic filler described in Example 1 of the present invention;

[0119] Figure 5 The SEM image and particle size distribution characterization diagram of the polystyrene seed microspheres described in Example 2 of the present invention;

[0120] Figure 6 The separation chromatogram of 15 rare earth elements by the strong cation exchange chromatography column A described in Application Example 1 of the present invention;

[0121] Figure 7 The separation chromatogram of 15 rare earth elements by the strong cation exchange chromatography column B described in Application Example 2 of the present invention;

[0122] Figure 8 The separation chromatogram of 15 rare earth elements by the strong cation exchange chromatography column C described in Application Example 3 of the present invention;

[0123] Fig. 9 The separation chromatogram of 15 rare earth elements by the strong cation exchange chromatography column D described in Application Example 4 of the present invention;

[0124] Fig.10 This is a chromatogram of separation of 15 rare earth elements by the strong cation exchange chromatography column E described in comparative application example 1 of the present invention;

[0125] Fig.11 This is a chromatogram of the separation of 15 rare earth elements by the weak cation exchange chromatography column F described in Comparative Application Example 2 of the present invention. DETAILED DESCRIPTION

[0126] The technical solution of the present invention is further described below in conjunction with the accompanying drawings and through specific implementation methods. However, the following examples are only simplified examples of the present invention and do not represent or limit the scope of protection of the present invention. The scope of protection of the present invention shall be subject to the claims.

[0127] Unless otherwise specified, the raw materials and reagents used in the following examples are commercially available. Information on some of the raw materials is as follows:

[0128] Polyvinyl pyrrolidone, molecular weight 58000 (K29-32), was purchased from Shanghai MacLean Biochemical Technology Co., Ltd. P816205.

[0129] The preparation process of the strong cation exchange chromatography filler provided by the present invention is as follows Figure 1 shown.

[0130] Example 1

[0131] This embodiment provides a strong cation exchange chromatographic filler, and the preparation method of the strong cation exchange chromatographic filler comprises the following steps:

[0132] (1) Preparation of polystyrene seed microspheres by dispersion polymerization

[0133] 1.0 g of polyvinyl pyrrolidone was dissolved in 85.5 mL of anhydrous ethanol and 15.5 mL of ultrapure water, and 15 mL of styrene and 0.1 g of azobisisobutyronitrile were added. The mixture was reacted at 200 r / min and 80° C. for 18 h to obtain polystyrene seed microspheres with an average particle size of 1.21 μm.

[0134] (2) Preparation of poly(glycidyl methacrylate)-divinylbenzene microspheres (PGMA-DVB) by a two-step seed swelling method

[0135] 3 mL of dibutyl phthalate, 30 mL of sodium dodecyl sulfate (0.3%) and 1 g of the polystyrene seed microspheres described in step (1) were mixed, and the first swelling step was carried out at 25°C for 24 h. After the first swelling step, 4.65 mL of monomer glycidyl methacrylate, 10.88 mL of divinylbenzene, 0.2 g of azobisisobutyronitrile, 0.8 g of sodium dodecyl sulfate and 16.05 mL of toluene were added, and the second swelling step was carried out at 25°C for 24 h. After the second swelling step, the system was heated to 75°C and reacted for 12 h at a stirring speed of 200 r / min to obtain PGMA-DVB with an average particle size of about 5 μm.

[0136] (3) Preparation of sulfonated poly(glycidyl methacrylate)-divinylbenzene microspheres (PGMA-DVB-1,3-PS) using sulfonation reagent

[0137] a. Dissolve 2.5 g of the poly(glycidyl methacrylate)-divinylbenzene microspheres prepared in step (2) in 50 mL of a 0.1 M dilute sulfuric acid solution, reflux for 24 h at 50° C., and vacuum dry to obtain poly(glycidyl methacrylate)-divinylbenzene microspheres with dihydroxy groups grafted on the surface;

[0138] b. Take 2.5 g of the surface-grafted dihydroxy polymer microspheres in a after drying, add them to a three-necked flask containing 40 mL of toluene, stir at 200 r / min and 70°C for 5 hours, and then slowly add 2.5 mL of 1,3-propane sultone within 10 minutes. After the addition is complete, heat to 100°C and react for 48 hours. After the reaction is completed, cool to 25°C and filter with a sand core funnel. After washing with ultrapure water and methanol 3 times each, place it in a vacuum drying oven at 80°C and dry it for 12 hours to obtain PGMA-DVB-1,3-PS, which is the strong cation exchange chromatography filler.

[0139] The characterization and analysis of the above-mentioned strong cation exchange chromatography filler PGMA-DVB-1,3-PS are as follows:

[0140] (1) Micromorphology analysis

[0141] The microstructure and particle size distribution of polystyrene seed microspheres were characterized by field emission scanning electron microscopy (FE-SEM). Figure 2 shown.

[0142] The morphology of sulfonated poly(glycidyl methacrylate)-divinylbenzene microspheres (PGMA-DVB-1,3-PS) was characterized by field emission scanning electron microscopy (FE-SEM). Figure 3 shown. Figure 3 (af) show the SEM images (ae) of the microspheres and their corresponding energy dispersive X-ray spectroscopy (EDS) element distribution maps (f), where (a) represents the SEM image of full element scanning, (b) represents the SEM image of oxygen element scanning, (c) represents the SEM image of carbon element scanning, (d) represents the SEM image of sulfur element scanning, and (e) represents the SEM image of non-element scanning.

[0143] pass Figure 3 (a)-(d) show that the sulfonated poly(glycidyl methacrylate)-divinylbenzene microspheres provided by the present invention have uniform particle size and smooth surface. And they all show good monodispersity, and their average particle size is about 5μm. The distribution of carbon, oxygen and sulfur elements in PGMA-DVB-1,3-PS microspheres is revealed by energy dispersive X-ray (EDX). As shown in (f), the weight percentages of carbon, oxygen and sulfur in PGMA-DVB-1,3-PS microspheres are 90.70%, 7.74% and 1.56%, respectively. This result confirms that the sulfonic acid group has been successfully introduced into poly(glycidyl methacrylate)-divinylbenzene microspheres (PGMA-DVB).

[0144] (2) Infrared spectroscopy analysis

[0145] like Figure 4 As shown, poly(glycidyl methacrylate)-divinylbenzene microspheres are -1 、1486.9cm -1 、1510.9cm -1 and 1602.8cm -1 The characteristic peak at 1731.1cm is attributed to the benzene ring absorption peak in poly(glycidyl methacrylate)-divinylbenzene. -1 It is the vibration absorption peak of C=O in the ester bond at 1074.3cm -1 It is the stretching vibration absorption peak of OCO in the ester bond, 1340.3cm -1 、1170.1cm -1 、1043.3cm -1 , and 669.1cm -1 The new peak corresponds to the sulfonic acid group

[0146] Example 2

[0147] This embodiment provides a strong cation exchange chromatographic filler, and the preparation method of the strong cation exchange chromatographic filler comprises the following steps:

[0148] (1) Preparation of polystyrene seed microspheres by dispersion polymerization

[0149] 1.0 g of polyvinyl pyrrolidone was dissolved in 100 mL of anhydrous ethanol, and 20 mL of styrene and 0.2 g of azobisisobutyronitrile were added. The mixture was reacted at 100 r / min and 70° C. for 24 h to obtain polystyrene seed microspheres with an average particle size of 3 μm.

[0150] (2) Preparation of poly(glycidyl methacrylate)-divinylbenzene microspheres (PGMA-DVB) by a two-step seed swelling method

[0151] 1 mL of dibutyl phthalate, 15 mL of sodium dodecyl sulfate (0.2%) and 1 g of the polystyrene seed microspheres described in step (1) were mixed, and the first swelling step was carried out at 30°C for 4 h. After the first swelling step, 4.65 mL of monomer glycidyl methacrylate, 10.88 mL of divinylbenzene, 0.2 g of azobisisobutyronitrile, 0.8 g of sodium dodecyl sulfate and 16.05 mL of toluene were added, and the second swelling step was carried out at 35°C for 24 h. After the second swelling step, the system was heated to 70°C and reacted at a stirring speed of 100 r / min for 24 h to obtain PGMA-DVB with an average particle size of about 7.45 μm.

[0152] (3) Preparation of sulfonated poly(glycidyl methacrylate)-divinylbenzene microspheres (PGMA-DVB-1,3-PS) using sulfonation reagent

[0153] a. Dissolve 1 g of the poly(glycidyl methacrylate)-divinylbenzene microspheres prepared in step (2) in 50 mL of 0.1 M dilute sulfuric acid solution, reflux for 48 h at 30° C., and vacuum dry to obtain poly(glycidyl methacrylate)-divinylbenzene microspheres with dihydroxy groups grafted on the surface;

[0154] b. Take 1g of the surface-grafted dihydroxy polymer microspheres in a after drying, add it to a three-necked flask containing 10mL of toluene, stir at 180r / min and 40°C for 8h, and then slowly add 1mL of 1,3-propane sultone within 10min. After the addition is complete, heat to 80°C and react for 96h. After the reaction is completed, cool to 25°C and filter with a sand core funnel. After washing with ultrapure water and anhydrous ethanol 3 times each, place it in a vacuum drying oven at 90°C and dry it for 24h to obtain the strong cation exchange chromatography filler PGMA-DVB-1,3-PS.

[0155] like Figure 5 As shown, the microscopic morphology and particle size distribution of the polystyrene seed microspheres obtained in step (1) of this example were characterized using a field emission scanning electron microscope (FE-SEM).

[0156] Example 3

[0157] This embodiment provides a strong cation exchange chromatography filler, which differs from Embodiment 1 in that 1 g of polystyrene seed microspheres in step (2) is replaced with 0.6 g of polystyrene seed microspheres to obtain PGMA-DVB with an average particle size of 5.55 μm, and other raw materials, amounts and preparation methods are the same as those in Embodiment 1.

[0158] Example 4

[0159] This embodiment provides a strong cation exchange chromatography filler, which differs from Embodiment 1 in that 1 g of polystyrene seed microspheres in step (2) is replaced with 0.2 g of polystyrene seed microspheres to obtain PGMA-DVB with an average particle size of about 6 μm, and other raw materials, amounts and preparation methods are the same as those in Embodiment 1.

[0160] Example 5

[0161] This embodiment provides a strong cation exchange chromatography filler, which differs from Example 2 in that 1 g of polystyrene seed microspheres in step (2) is replaced by 0.6 g of polystyrene seed microspheres to obtain PGMA-DVB with an average particle size of about 8.55 μm, and other raw materials, amounts and preparation methods are the same as those in Example 2.

[0162] Example 6

[0163] This embodiment provides a strong cation exchange chromatography filler, which differs from Example 2 in that 1 g of polystyrene seed microspheres in step (2) is replaced with 0.2 g of polystyrene seed microspheres to obtain PGMA-DVB with an average particle size of about 10.62 μm, and other raw materials, amounts and preparation methods are the same as those in Example 2.

[0164] Example 7

[0165] This embodiment provides a strong cation exchange chromatography filler, which differs from embodiment 1 in that ultrapure water is not added in step (1), the amount of anhydrous ethanol is adjusted from 85.5 mL to 100 mL, and other raw materials, amounts and preparation methods are the same as those in embodiment 1. The average particle size of the prepared polystyrene seed microspheres is 1.59 μm; the average particle size of PGMA-DVB is about 6 μm.

[0166] Comparative Example 1

[0167] This comparative example provides a commercially available strong cation exchange chromatography filler (purchased from Qingdao Shenghan Chromatography Technology Co., Ltd., PS-DVB microspheres, 7.3 μm, 55% cross-linking degree).

[0168] Comparative Example 2

[0169] This comparative example provides a weak cation exchange chromatography filler, which differs from Example 1 only in that the sulfonated reagent 1,3-propane sultone in step (3) is replaced by an equal mass of lysine anhydride to prepare carboxyl functionalized polymer microspheres, and the other raw materials, contents and preparation methods are the same as those in Example 1 to obtain the weak cation exchange chromatography filler.

[0170] Application Example 1

[0171] This application example provides a strong cation exchange chromatographic column, the preparation method of which comprises the following steps:

[0172] The strong cation exchange chromatography filler PGMA-DVB-1,3-PS obtained in Example 1 was loaded into a 4.6×150 mm stainless steel chromatography column to obtain a strong cation exchange chromatography column A.

[0173] Application Example 2

[0174] This application example provides a strong cation exchange chromatographic column, the preparation method of which comprises the following steps:

[0175] The strong cation exchange chromatography filler PGMA-DVB-1,3-PS obtained in Example 4 was loaded into a 4.6×150 mm stainless steel chromatography column to obtain a strong cation exchange chromatography column B.

[0176] Application Example 3

[0177] This application example provides a strong cation exchange chromatographic column, the preparation method of which comprises the following steps:

[0178] The strong cation exchange chromatography filler PGMA-DVB-1,3-PS obtained in Example 2 was loaded into a 4.6×150 mm stainless steel chromatography column to obtain a strong cation exchange chromatography column C.

[0179] Application Example 4

[0180] This application example provides a strong cation exchange chromatographic column, the preparation method of which comprises the following steps:

[0181] The strong cation exchange chromatography filler PGMA-DVB-1,4-PS obtained in Example 6 was loaded into a 4.6×150 mm stainless steel chromatography column to obtain a strong cation exchange chromatography column D.

[0182] Application Comparative Example 1

[0183] This application example provides a strong cation exchange chromatographic column, the preparation method of which comprises the following steps:

[0184] The strong cation exchange chromatography filler described in Comparative Example 1 was loaded into a 4.6×150 mm stainless steel chromatography column to obtain a strong cation exchange chromatography column E.

[0185] Application Comparative Example 2

[0186] This application example provides a weak cation exchange chromatography column, the preparation method of which comprises the following steps:

[0187] The weak cation exchange chromatography filler obtained in Comparative Example 2 was loaded into a 4.6×150 mm stainless steel chromatography column to obtain a weak cation exchange chromatography column F.

[0188] The cation exchange chromatography columns obtained in the above Application Examples 1-4 and Comparative Application Examples 1-2 were used to test the chromatographic performance of 15 rare earth elements. The test conditions were as follows:

[0189] EasySep-3030 liquid chromatograph was used, and the chromatographic conditions were as follows: column temperature (25°C), ultraviolet detector (UV) 658nm, flow rate 1.0mL / min; post-column derivatization liquid: arsenazo III, post-column derivatization pump flow rate 0.6mL / min, pH 3.37, 800mM α-hydroxyisobutyric acid (α-HIBA) was used as the mobile phase for gradient elution. The gradient elution program is shown in Table 1.

[0190] Table 1

[0191] Time / min A%(water) B% (α-HIBA, 800 mM, pH = 3.37) 0 85 15 50 85 15 70 75 25 130 60 40 160 60 40 210 30 70 240 30 70

[0192] The feasibility of using 1,3-propane sultone functionalized poly(glycidyl methacrylate)-divinylbenzene microspheres (i.e., sulfonated poly(glycidyl methacrylate)-divinylbenzene microspheres, PGMA-DVB-1,3-PS) for chromatographic separation of rare earth elements was studied for different sample concentrations, elution modes, eluent concentrations, eluent flow rates, and column temperatures. The separation effects of the cation exchange chromatographic columns obtained in Application Examples 1-4 and Comparative Application Examples 1-2 are shown in Figure 2. Figure 6-11 As shown, through Figure 6-9 and Fig.10 and Fig.11 It can be seen from the comparison that using α-HIBA as the eluent and a linear concentration gradient from 0 to 800 mM for 240 min, the strong cation exchange chromatographic filler provided by the present invention can achieve good separation of 15 rare earth ions (scandium Sc, lutetium Lu, ytterbium Yb, thulium Tm, erbium Er, holmium Ho, dysprosium Dy, terbium Tb, gadolinium Gd, europium Eu, samarium Sm, neodymium Nd, praseodymium Pr, cerium Ce and lanthanum La ions).

[0193] Furthermore, through Figure 6-9 The analysis shows that Figure 6 and Figure 7 The separation effect is stronger than Figure 8 and Fig. 9 , which further indicates that by adjusting the particle size of the polymer microspheres in the preparation process of the strong cation exchange chromatographic filler, the separation effect of the obtained strong cation exchange chromatographic filler on rare earth elements can be further optimized. In addition, in more than 100 chromatographic separation experiments of rare earth ions, it was recorded that the separation effect of the sulfonic acid functionalized polymer chromatographic column degraded very little, indicating that the strong cation exchange chromatographic filler provided by the present invention has good long-term stability and excellent cycle performance.

[0194] In summary, the strong cation exchange chromatography filler (sulfonated poly(glycidyl methacrylate)-divinylbenzene microspheres) provided by the present invention has high potential in the separation and purification of rare earth elements, and can be used as a green and environmentally friendly alternative to traditional solvent extraction methods.

[0195] The applicant declares that the above is only a specific implementation mode of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention shall fall within the protection scope and disclosure scope of the present invention.

Claims

1. A strong cation exchange chromatography filler, characterized in that: The strong cation exchange chromatography filler comprises sulfonated poly(glycidyl methacrylate)-divinylbenzene microspheres.

2. The strong cation exchange chromatography filler according to claim 1, characterized in that The average particle size of the sulfonated poly(glycidyl methacrylate)-divinylbenzene microspheres is 5-11 μm; Preferably, the average pore size of the strong cation exchange chromatography filler is 2-20 nm; Preferably, the specific surface area of ​​the strong cation exchange chromatography filler is 50-500m 2 / g.

3. A method for preparing a strong cation exchange chromatography filler as claimed in claim 1 or 2, characterized in that: The preparation method comprises the following steps: (1) Preparing polystyrene seed microspheres by dispersion polymerization; (2) Preparation of poly(glycidyl methacrylate)-divinylbenzene microspheres by a two-step seed swelling method; (3) Sulfonated poly(glycidyl methacrylate)-divinylbenzene microspheres were prepared using a sulfonation reagent.

4. The method for preparing a strong cation exchange chromatography filler according to claim 3, characterized in that: The method for preparing the polystyrene seed microspheres in step (1) comprises the following steps: Styrene, initiator A and stabilizer are mixed and reacted to obtain the polystyrene seed microspheres.

5. The method for preparing a strong cation exchange chromatography filler according to claim 4, characterized in that: The reaction is carried out in a medium; Preferably, the medium comprises an ethanol aqueous solution; Preferably, the volume concentration of the ethanol aqueous solution is 85-100%; Preferably, the content of styrene is 10-20 vol% of the volume of the medium; Preferably, the average particle size of the polystyrene seed microspheres is 1-3 μm.

6. The method for preparing a strong cation exchange chromatography filler according to any one of claims 3 to 5, characterized in that: The preparation method of poly(glycidyl methacrylate)-divinylbenzene microspheres in step (2) comprises the following steps: The activator, emulsifier A and the polystyrene seed microspheres of step (1) are mixed to carry out the first swelling step; after the first swelling step, monomer glycidyl methacrylate, crosslinking agent, initiator B, emulsifier B and porogen are added to carry out the second swelling step; after the second swelling step, heating reaction is carried out to obtain the polyglycidyl methacrylate-divinylbenzene microspheres.

7. The method for preparing a strong cation exchange chromatography filler according to claim 6, characterized in that: The mass ratio of the polystyrene seed microspheres, the activator and the emulsifier A in the first step of swelling is (0.2-2):(0.5-5):(0.017-0.375); Preferably, based on the total weight of the monomer glycidyl methacrylate, the crosslinking agent, the initiator B, the emulsifier B and the porogen as the mass of the total organic phase, the mass ratio of the polystyrene seed microspheres to the total organic phase is (0.02-0.2):3; Preferably, the average particle size of the poly(glycidyl methacrylate)-divinylbenzene microspheres is 5-11 μm.

8. The method for preparing a strong cation exchange chromatography filler according to any one of claims 3 to 7, characterized in that: The preparation method of the sulfonated poly(glycidyl methacrylate)-divinylbenzene microspheres in step (3) comprises the following steps: a. hydrolyzing the poly(glycidyl methacrylate)-divinylbenzene microspheres in step (2) to obtain polymer microspheres with dihydroxy groups grafted on the surface; b. Mixing the polymer microspheres grafted with dihydroxy groups on the surface described in a with a sulfonation reagent, and reacting them to obtain the sulfonated poly(glycidyl methacrylate)-divinylbenzene microspheres.

9. The method for preparing a strong cation exchange chromatography filler according to claim 8, characterized in that: The hydrolysis reaction in step a is carried out in a dilute sulfuric acid solution; Preferably, the mass concentration of the poly(glycidyl methacrylate)-divinylbenzene microspheres in the 0.1M dilute sulfuric acid solution in step a is 0.02-0.1 g / mL; Preferably, the mass ratio of the surface-grafted dihydroxy polymer microspheres to the sulfonated reagent in step b is (1-5):(1.4-7); Preferably, the reaction in step b is carried out in toluene; Preferably, the mixing in step b comprises first mixing and stirring the polymer microspheres grafted with dihydroxy groups on the surface with toluene, and then adding the sulfonation reagent; Preferably, the sulfonating agent comprises 1,3-propane sultone or 1,4-butane sultone.

10. Use of the strong cation exchange chromatography filler as claimed in claim 1 or 2 in the separation of rare earth elements.

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