A high-performance ion exchange resin material and preparation method thereof

Abstract

The present invention belongs to the technical field of resin materials, and specifically relates to a high-performance ion exchange resin material and a preparation method thereof. The method comprises the following steps: (1) modifying inorganic nanoparticles using an amino-containing silane coupling agent and a double-bond silane coupling agent to prepare a modified inorganic nanoparticle solution; (2) first adding graphene oxide to the modified inorganic nanoparticle solution, and then adding a reaction monomer and a reaction aid to obtain an ion exchange resin material dispersion after reaction; and (3) freeze-drying to obtain a high-performance ion exchange resin material. The amino groups on the surface of the inorganic nanoparticles can promote the dispersion between the graphene oxide sheets, while the alkenyl groups on the surface of the inorganic nanoparticles can participate in the cross-linking reaction of the acrylic acid monomer, so that the inorganic filler and the polymer form an organic cross-linked whole, which not only enhances the mechanical properties of the gel-type ion exchange resin material, but also further improves its adsorption performance.

Description

Technical Field

[0001] The invention belongs to the technical field of resin materials, and particularly relates to a high-performance ion exchange resin material and a preparation method thereof. Background Art

[0002] Dye wastewater is one of the most challenging industrial wastewaters to treat, characterized by complex composition, high chroma, high COD and BOD values, high levels of suspended solids, significant variability in water quality and volume, and a high concentration of recalcitrant substances. Dyes are primarily based on aromatic hydrocarbons and heterocyclic compounds, bearing chromogenic and polar groups. Their increasingly complex structures and increasingly stable properties, while offering ease of use, also present greater challenges in dye wastewater treatment. Currently, dye wastewater treatment methods primarily include oxidation (biooxidation, chemical oxidation, photocatalysis, and microwave-assisted methods), adsorption, coagulation, and electrochemical methods. Adsorption holds a special place in wastewater treatment due to its ability to selectively enrich specific compounds. Commonly used adsorbents include activated carbon, resins, and other adsorbent materials. Ion exchange resins, owing to their excellent pore structure and adsorption properties, are widely used in water treatment.

[0003] Ion exchange resins are typically prepared through organic synthesis. Common raw materials are styrene or acrylates, which are polymerized to form a three-dimensional network structure. Different types of chemically active groups (usually acidic or basic groups) are then introduced into the structure.

[0004] Ion exchange resins are typically manufactured as small, bead-like particles. Finer resin particles react faster, but they also offer greater resistance to liquid flow, requiring higher operating pressures. Resin particle size is typically determined by wet sieving, allowing the resin to fully swell and absorb water before sieving. The amount retained on different mesh screens is then counted, and the effective particle size is defined as the diameter at which 90% of the particles pass through the corresponding sieve openings. Ion exchange resins are hydrophilic and resilient, so they often contain a certain amount of bound water. The amount of bound water depends on the properties of the resin's functional groups and the degree of crosslinking, and varies with air humidity. To render ion exchange resins insoluble in water, they must be crosslinked with a crosslinking agent. The degree of crosslinking determines the width of the pores in the resin's network structure, but crosslinking must be moderate. Ion exchange resins exhibit a certain degree of stability and possess a high exchange capacity, which is their most important property.

[0005] Ion exchange resins have varying affinities for different ions in solution, meaning they selectively adsorb them. The strength of ion exchange and adsorption follows certain patterns, but can vary from resin to resin. Numerous varieties of ion exchange resins exist, each with distinct functions and properties due to its chemical composition and structure, suited to a variety of applications. The appropriate type and variety of resin should be selected based on the process requirements and material properties. Numerous new technologies based on ion exchange resins, such as chromatography, ion exclusion, and electrodialysis, each possess unique capabilities and can perform specialized tasks difficult to achieve with other methods.

[0006] A series of patents filed by Sinopec (CN109569717A and CN109575292A) describe the preparation of resin composites using nanocarbon materials, monomers, and comonomers through in-situ polymerization under the action of an initiator. The POSS structure imparts excellent heat resistance and significantly improves thermal stability to the ion exchange resin. A series of patents filed by Sichuan Hengda Environmental Technology Co., Ltd. (CN103990499A and CN103991924A) describe a method for pretreating and regenerating ion exchange resins used to treat wastewater from the electrolytic manganese production process. This method results in a larger specific surface area and porosity for the pretreated resin, improving adsorption capacity and desorption efficiency, and enabling operation in high-concentration acid conditions. The use of a single regeneration fluid reduces fluid usage, simplifies the regeneration process, and facilitates automated control. Patents filed in CN118772325A and CN119119391A also describe the preparation of various ion exchange resins and the study of their adsorption properties. However, the above patented technology has a complicated preparation process and uses expensive and hydrophobic long-chain molecular modifications, which results in limited improvement in adsorption performance and restricts the application of ion exchange resins. Summary of the Invention

[0007] In order to obtain an ion exchange resin with simple raw materials and preparation steps and strong adsorption capacity, the present application provides a gel-type high-performance ion exchange resin material and a preparation method thereof, which has wide application in the field of dye wastewater.

[0008] In a first aspect, the present application provides a method for preparing a high-performance ion exchange resin material, using the following technical solution:

[0009] A method for preparing a high-performance ion exchange resin material comprises the following steps:

[0010] (1) Modifying inorganic nanoparticles dispersed in a solvent using an amino-containing silane coupling agent and a double-bond silane coupling agent to prepare a modified inorganic nanoparticle solution;

[0011] (2) First, add graphene oxide to the modified inorganic nanoparticle solution, disperse it evenly, then add propylene monomer, crosslinking agent, and initiator in sequence, stir evenly, and obtain ion exchange resin material dispersion after sufficient reaction;

[0012] (3) Freeze-drying the ion exchange resin material dispersion to obtain a high-performance ion exchange resin material. The freeze-drying process can effectively prepare porous gel-type ion exchange resin materials.

[0013] To improve the mechanical strength and adsorption properties of the ion exchange resin material, the present invention adds a certain amount of graphene oxide and silane-modified inorganic nanoparticles. Graphene oxide not only improves the mechanical properties of the acrylic ion exchange resin, but also contains a large number of surface-active functional groups (hydroxyl, carboxyl, etc.), which can react with dye molecules in wastewater, achieving excellent adsorption. However, strong hydrogen bonds exist between the oxygen-containing functional groups on the surface of graphene oxide and the acrylic monomers. Furthermore, the lamellar structure of graphene oxide and the strong van der Waals forces between the lamellar layers make it difficult to disperse during the in-situ polymerization of acrylic monomers. To improve its dispersibility, the present invention adds a certain amount of silane-modified inorganic nanoparticles. These silane-modified inorganic nanoparticles are mixed with graphene oxide before adding the reactive monomers. The inorganic nanoparticles are modified using two coupling agents: an amino-containing silane coupling agent and a double-bond silane coupling agent. This modification introduces two reactive functional groups, amino and alkenyl, onto the surface of the inorganic nanoparticles. During the pre-mixing process, the amino active groups on the surface of the inorganic nanoparticles easily combine with the numerous oxygen-containing functional groups on the surface of graphene oxide to form an inorganic nanoparticle-graphene oxide composite. The introduction of the inorganic nanoparticles promotes dispersion between the graphene oxide sheets and prevents agglomeration between the sheets. The alkenyl active groups on the surface of the inorganic nanoparticles can participate in the cross-linking reaction of the acrylic acid monomer, forming an organically cross-linked whole between the graphene oxide, inorganic nanoparticles, and acrylic acid polymer. This not only improves the mechanical properties of the gel-type ion exchange resin material, but also further introduces a porous structure, enhancing adsorption performance.

[0014] Optionally, the amino-containing silane coupling agent in step (1) is one of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-diethylenetriaminopropyltrimethoxysilane, 3-diethylenetriaminopropyltriethoxysilane, 3-diethylenetriaminopropylmethyldimethoxysilane, 3-diethylenetriaminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, and N-(2-aminoethyl)-3-aminopropyltrimethoxysilane.

[0015] Optionally, the double bond-containing silane coupling agent in step (1) is one of vinyltriethoxysilane, 3-(isomethacryloyloxy)propyltrimethoxysilane, vinyltrimethoxysilane, and vinyltri(β-methoxyethoxy)silane.

[0016] Optionally, the molar ratio of the amino-containing silane coupling agent to the double-bond silane coupling agent in step (1) is 1:(0.5-2). In particular, the molar ratio of the amino-containing silane coupling agent to the double-bond silane coupling agent is 1:(0.5-1), and further preferably, 1:(0.6-0.8). A larger amount of amino-silane coupling agent can better modify the graphene oxide while avoiding the introduction of excessive hydrophobic groups in the double-bond silane coupling agent, which may affect the adsorption performance of the gel-type ion exchange resin.

[0017] Optionally, the mass ratio of the sum of the mass of the amino-containing silane coupling agent and the double-bond-containing silane coupling agent to the inorganic nanoparticles in step (1) is (0.1-1):1.

[0018] Optionally, the inorganic nanoparticles in step (1) are selected from the group consisting of silicon dioxide, aluminum oxide, calcium carbonate, barium carbonate, titanium dioxide, zinc oxide, glass powder, montmorillonite, and calcium hydroxyphosphate; and the inorganic nanoparticles have a volume average particle size D50 of 10-100 nm. Specifically, the inorganic nanoparticles may be 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, or 100 nm.

[0019] Optionally, the specific preparation process of the modified inorganic nanoparticle solution in step (1) is as follows: the inorganic nanoparticles are uniformly dispersed in a mixed solution of ethanol and deionized water, an amino-containing silane coupling agent and a double-bond silane coupling agent are added to the mixed solution under magnetic stirring, and the mixture is heated in a water bath for a certain period of time to obtain the modified inorganic nanoparticle solution; the temperature of the heating reaction is 50-60°C, and the reaction time is 2-4h.

[0020] Optionally, the propylene monomer in step (2) is a mixture of acrylic acid and acrylamide in a mass ratio of 100:(10-50); the mass ratio of the propylene monomer, graphene oxide, inorganic nanoparticles, crosslinking agent, and initiator is 100:(1.5-3):(0.1-1.5):(0.3-1.5):(0.4-0.8). In particular, the mass ratio of the propylene monomer, graphene oxide, and inorganic nanoparticles is 100:(1.8-2.5):(0.4-1). An appropriate amount of inorganic nanoparticles can not only improve the dispersion properties of graphene oxide, but also prevent excessive inorganic nanoparticles from causing excessive loading of graphene oxide and affecting the porous structure of the gel-type ion exchange resin.

[0021] Optionally, the cross-linking agent in step (2) is N,N-methylenebisacrylamide; the initiator is one of ammonium persulfate, potassium persulfate and sodium persulfate; the reaction temperature is 50-70°C, and the reaction time is 3-5h; the dispersion adopts an ultrasonic process, the ultrasonic power is 100-200W, and the ultrasonic time is 0.5-1h.

[0022] In a second aspect, the present application provides a high-performance ion exchange resin material prepared using the aforementioned preparation method. The three-dimensional porous network structure of this gel-type composite ion exchange resin material facilitates the rapid entry of dye molecules. During dye adsorption, a certain concentration gradient is formed on its surface, prompting the dye molecules to quickly enter the hydrogel from the solution. The dye is then adsorbed through chemical, electrostatic, hydrogen bonding, and hydrophobic interactions.

[0023] In summary, this application has the following beneficial effects:

[0024] The present invention uses graphene oxide and silane-modified inorganic nanoparticles as fillers to prepare an inorganic filler-modified gel-type ion exchange resin material. Through modification, two reactive functional groups, amino and alkenyl, are introduced onto the surfaces of the inorganic nanoparticles. During a pre-mixing process, the amino reactive groups on the surfaces of the inorganic nanoparticles readily hydrogen-bond or react with a large number of oxygen-containing functional groups on the graphene oxide surface to form an inorganic nanoparticle-graphene oxide composite. The introduction of the inorganic nanoparticles promotes dispersion between the graphene oxide lamellae and prevents agglomeration between the lamellae. The alkenyl reactive groups on the surfaces of the inorganic nanoparticles can participate in the cross-linking reaction of acrylic acid monomers, forming an organically cross-linked composite between the graphene oxide, the inorganic nanoparticles, and the acrylic acid polymer. This not only improves the mechanical properties of the gel-type ion exchange resin material, but also further introduces a porous structure to enhance adsorption performance. DETAILED DESCRIPTION

[0025] The present invention is further illustrated by the following examples. The present invention can be better understood according to the following examples. However, it will be readily understood by those skilled in the art that the specific material ratios, process conditions, and results described in the examples are merely illustrative of the present invention and should not, and do not, limit the present invention as described in detail in the claims.

[0026] Unless otherwise specified, the raw material types and process conditions used in the following examples and comparative examples are the same.

[0027] The performance test method of the high-performance ion exchange resin materials prepared in the following examples and comparative examples is as follows:

[0028] (1) Use a tensile testing machine to test the tensile fracture properties (kPa) of high-performance ion exchange resin materials after water absorption and swelling;

[0029] (2) Weigh a certain amount (m, g) of high-performance ion exchange resin material and place it in a beaker. Add a certain volume (V, L) and concentration (ρ1, mg / L) of methylene blue solution. Monitor the concentration of methylene blue with a UV spectrophotometer until the concentration does not change. The concentration ρ2 is obtained. The adsorption capacity (mg / g) of the high-performance ion exchange resin material when the adsorption reaches equilibrium can be calculated using the formula (ρ1-ρ2)*V / m.

[0030] Example 1

[0031] A method for preparing a high-performance ion exchange resin material comprises the following steps:

[0032] (1) Inorganic nanoparticles are uniformly dispersed in a mixed solution of ethanol and deionized water. Under magnetic stirring, an amino-containing silane coupling agent and a double-bond silane coupling agent are added to the mixed solution, and the mixed solution is heated in a water bath for a certain period of time to obtain a modified inorganic nanoparticle solution; the heating reaction temperature is 50°C and the reaction time is 4 hours;

[0033] The amino-containing silane coupling agent is 3-aminopropyltriethoxysilane; the double-bond silane coupling agent is vinyltriethoxysilane; the molar ratio of the amino-containing silane coupling agent to the double-bond silane coupling agent is 1:0.5; the mass ratio of the sum of the mass of the amino-containing silane coupling agent and the double-bond silane coupling agent to the inorganic nanoparticles is 0.5:1; the inorganic nanoparticles are silicon dioxide with an average particle size of 50 nm;

[0034] (2) First, graphene oxide is added to the modified inorganic nanoparticle solution, and ultrasonicated at 200W for 0.6h. Then, propylene monomer, crosslinking agent, and initiator are added in sequence, stirred evenly, and after sufficient reaction, an ion exchange resin material dispersion is obtained; the propylene monomer is a mixture of acrylic acid and acrylamide in a mass ratio of 100:25; the mass ratio of the propylene monomer, graphene oxide, inorganic nanoparticles, crosslinking agent, and initiator is 100:1.5:0.4:0.5:0.5; the crosslinking agent is N,N-methylenebisacrylamide; the initiator is ammonium persulfate; the reaction temperature is 55°C, and the reaction time is 5h;

[0035] (3) The ion exchange resin material dispersion is freeze-dried to obtain a high-performance ion exchange resin material. Testing has shown that the high-performance ion exchange resin material has a tensile strength of 12.2 kPa and an adsorption capacity of 1521 mg / g at equilibrium.

[0036] Example 2

[0037] A method for preparing a high-performance ion exchange resin material comprises the following steps:

[0038] (1) Inorganic nanoparticles are uniformly dispersed in a mixed solution of ethanol and deionized water. Under magnetic stirring, an amino-containing silane coupling agent and a double-bond silane coupling agent are added to the mixed solution, and the mixed solution is heated in a water bath for a certain period of time to obtain a modified inorganic nanoparticle solution; the heating reaction temperature is 60°C and the reaction time is 2 hours;

[0039] The amino-containing silane coupling agent is 3-aminopropyltrimethoxysilane; the double-bond silane coupling agent is vinyltrimethoxysilane; the molar ratio of the amino-containing silane coupling agent to the double-bond silane coupling agent is 1:1; the mass ratio of the sum of the mass of the amino-containing silane coupling agent and the double-bond silane coupling agent to the inorganic nanoparticles is 0.8:1; the inorganic nanoparticles are silicon dioxide with an average particle size of 50 nm;

[0040] (2) First, graphene oxide is added to the modified inorganic nanoparticle solution, and ultrasonicated at 200W for 0.6h. Then, propylene monomer, crosslinking agent, and initiator are added in sequence, stirred evenly, and after sufficient reaction, an ion exchange resin material dispersion is obtained; the propylene monomer is a mixture of acrylic acid and acrylamide in a mass ratio of 100:40; the mass ratio of the propylene monomer, graphene oxide, inorganic nanoparticles, crosslinking agent, and initiator is 100:3:1:1.5:0.8; the crosslinking agent is N,N-methylenebisacrylamide; the initiator is ammonium persulfate; the reaction temperature is 70°C, and the reaction time is 3h;

[0041] (3) The ion exchange resin material dispersion is freeze-dried to obtain a high-performance ion exchange resin material. Testing has shown that the high-performance ion exchange resin material has a tensile strength of 13.6 kPa and an adsorption capacity of 1588 mg / g at equilibrium.

[0042] Example 3

[0043] A method for preparing a high-performance ion exchange resin material comprises the following steps:

[0044] (1) Inorganic nanoparticles are uniformly dispersed in a mixed solution of ethanol and deionized water. Under magnetic stirring, an amino-containing silane coupling agent and a double-bond silane coupling agent are added to the mixed solution, and the mixed solution is heated in a water bath for a certain period of time to obtain a modified inorganic nanoparticle solution; the heating reaction temperature is 56°C and the reaction time is 3 hours;

[0045] The amino-containing silane coupling agent is 3-aminopropyltrimethoxysilane; the double-bond silane coupling agent is 3-(isomethylacryloyloxy)propyltrimethoxysilane; the molar ratio of the amino-containing silane coupling agent to the double-bond silane coupling agent is 1:1.5; the mass ratio of the sum of the mass of the amino-containing silane coupling agent and the double-bond silane coupling agent to the inorganic nanoparticles is 0.6:1; the inorganic nanoparticles are silicon dioxide with an average particle size of 50 nm;

[0046] (2) First, graphene oxide is added to the modified inorganic nanoparticle solution, and ultrasonicated at 200W for 0.6h. Then, propylene monomer, crosslinking agent, and initiator are added in sequence, stirred evenly, and after sufficient reaction, an ion exchange resin material dispersion is obtained; the propylene monomer is a mixture of acrylic acid and acrylamide in a mass ratio of 100:35; the mass ratio of the propylene monomer, graphene oxide, inorganic nanoparticles, crosslinking agent, and initiator is 100:2.2:0.7:1:0.6; the crosslinking agent is N,N-methylenebisacrylamide; the initiator is ammonium persulfate; the reaction temperature is 60°C, and the reaction time is 4h;

[0047] (3) The ion exchange resin material dispersion is freeze-dried to obtain a high-performance ion exchange resin material. Testing has shown that the high-performance ion exchange resin material has a tensile strength of 12.1 kPa and an adsorption capacity of 1607 mg / g at equilibrium.

[0048] Example 4

[0049] A method for preparing a high-performance ion exchange resin material comprises the following steps:

[0050] (1) Inorganic nanoparticles are uniformly dispersed in a mixed solution of ethanol and deionized water. Under magnetic stirring, an amino-containing silane coupling agent and a double-bond silane coupling agent are added to the mixed solution, and the mixed solution is heated in a water bath for a certain period of time to obtain a modified inorganic nanoparticle solution; the heating reaction temperature is 52°C and the reaction time is 2.5 hours;

[0051] The amino-containing silane coupling agent is N-(2-aminoethyl)-3-aminopropyltrimethoxysilane; the double-bond-containing silane coupling agent is 3-(isomethacryloyloxy)propyltrimethoxysilane; the molar ratio of the amino-containing silane coupling agent to the double-bond-containing silane coupling agent is 1:0.6; the mass ratio of the sum of the mass of the amino-containing silane coupling agent and the double-bond-containing silane coupling agent to the inorganic nanoparticles is 0.8:1; the inorganic nanoparticles are silicon dioxide with an average particle size of 40 nm;

[0052] (2) First, graphene oxide is added to the modified inorganic nanoparticle solution, and ultrasonicated at 200W for 0.6h. Then, propylene monomer, crosslinking agent, and initiator are added in sequence, stirred evenly, and after sufficient reaction, an ion exchange resin material dispersion is obtained; the propylene monomer is a mixture of acrylic acid and acrylamide in a mass ratio of 100:25; the mass ratio of the propylene monomer, graphene oxide, inorganic nanoparticles, crosslinking agent, and initiator is 100:1.5:1:0.5:0.8; the crosslinking agent is N,N-methylenebisacrylamide; the initiator is ammonium persulfate; the reaction temperature is 70°C, and the reaction time is 5h;

[0053] (3) The ion exchange resin material dispersion is freeze-dried to obtain a high-performance ion exchange resin material. Testing has shown that the high-performance ion exchange resin material has a tensile strength of 12.4 kPa and an adsorption capacity of 1556 mg / g at equilibrium.

[0054] Example 5

[0055] A method for preparing a high-performance ion exchange resin material comprises the following steps:

[0056] (1) Inorganic nanoparticles are uniformly dispersed in a mixed solution of ethanol and deionized water. Under magnetic stirring, an amino-containing silane coupling agent and a double-bond silane coupling agent are added to the mixed solution, and the mixed solution is heated in a water bath for a certain period of time to obtain a modified inorganic nanoparticle solution; the heating reaction temperature is 56°C and the reaction time is 3 hours;

[0057] The amino-containing silane coupling agent is 3-aminopropyltrimethoxysilane; the double-bond silane coupling agent is 3-(methacryloyloxy)propyltrimethoxysilane; the molar ratio of the amino-containing silane coupling agent to the double-bond silane coupling agent is 1:0.7; the mass ratio of the sum of the mass of the amino-containing silane coupling agent and the double-bond silane coupling agent to the inorganic nanoparticles is 0.6:1; the inorganic nanoparticles are silicon dioxide with an average particle size of 50 nm;

[0058] (2) First, graphene oxide is added to the modified inorganic nanoparticle solution, and ultrasonicated at 200W for 0.6h. Then, propylene monomer, crosslinking agent, and initiator are added in sequence, stirred evenly, and after sufficient reaction, an ion exchange resin material dispersion is obtained; the propylene monomer is a mixture of acrylic acid and acrylamide in a mass ratio of 100:35; the mass ratio of the propylene monomer, graphene oxide, inorganic nanoparticles, crosslinking agent, and initiator is 100:2.2:0.1:1:0.6; the crosslinking agent is N,N-methylenebisacrylamide; the initiator is ammonium persulfate; the reaction temperature is 60°C, and the reaction time is 4h;

[0059] (3) The ion exchange resin material dispersion is freeze-dried to obtain a high-performance ion exchange resin material. Testing has shown that the high-performance ion exchange resin material has a tensile strength of 11.9 kPa and an adsorption capacity of 1533 mg / g at equilibrium.

[0060] Example 6

[0061] A method for preparing a high-performance ion exchange resin material comprises the following steps:

[0062] (1) Inorganic nanoparticles are uniformly dispersed in a mixed solution of ethanol and deionized water. Under magnetic stirring, an amino-containing silane coupling agent and a double-bond silane coupling agent are added to the mixed solution, and the mixed solution is heated in a water bath for a certain time to obtain a modified inorganic nanoparticle solution; the heating reaction temperature is 55°C and the reaction time is 3.5 hours;

[0063] The amino-containing silane coupling agent is 3-aminopropyltriethoxysilane; the double-bond silane coupling agent is vinyltrimethoxysilane; the molar ratio of the amino-containing silane coupling agent to the double-bond silane coupling agent is 1:0.6; the mass ratio of the sum of the mass of the amino-containing silane coupling agent and the double-bond silane coupling agent to the inorganic nanoparticles is 0.6:1; the inorganic nanoparticles are silicon dioxide with an average particle size of 80 nm;

[0064] (2) First, graphene oxide is added to the modified inorganic nanoparticle solution, and ultrasonicated at 200W for 0.6h. Then, propylene monomer, crosslinking agent, and initiator are added in sequence, stirred evenly, and after sufficient reaction, an ion exchange resin material dispersion is obtained; the propylene monomer is a mixture of acrylic acid and acrylamide in a mass ratio of 100:28; the mass ratio of the propylene monomer, graphene oxide, inorganic nanoparticles, crosslinking agent, and initiator is 100:1.8:0.5:0.8:0.6; the crosslinking agent is N,N-methylenebisacrylamide; the initiator is ammonium persulfate; the reaction temperature is 60°C, and the reaction time is 3.5h;

[0065] (3) The ion exchange resin material dispersion is freeze-dried to obtain a high-performance ion exchange resin material. Testing has shown that the high-performance ion exchange resin material has a tensile strength of 12.6 kPa and an adsorption capacity of 1586 mg / g at equilibrium.

[0066] Example 7

[0067] A method for preparing a high-performance ion exchange resin material comprises the following steps:

[0068] (1) Inorganic nanoparticles are uniformly dispersed in a mixed solution of ethanol and deionized water. Under magnetic stirring, an amino-containing silane coupling agent and a double-bond silane coupling agent are added to the mixed solution, and the mixed solution is heated in a water bath for a certain period of time to obtain a modified inorganic nanoparticle solution; the heating reaction temperature is 56°C and the reaction time is 3 hours;

[0069] The amino-containing silane coupling agent is 3-aminopropyltrimethoxysilane; the double-bond silane coupling agent is 3-(methacryloyloxy)propyltrimethoxysilane; the molar ratio of the amino-containing silane coupling agent to the double-bond silane coupling agent is 1:0.7; the mass ratio of the sum of the mass of the amino-containing silane coupling agent and the double-bond silane coupling agent to the inorganic nanoparticles is 0.6:1; the inorganic nanoparticles are silicon dioxide with an average particle size of 50 nm;

[0070] (2) First, graphene oxide is added to the modified inorganic nanoparticle solution, and ultrasonicated at 200W for 0.6h. Then, propylene monomer, crosslinking agent, and initiator are added in sequence, stirred evenly, and after sufficient reaction, an ion exchange resin material dispersion is obtained; the propylene monomer is a mixture of acrylic acid and acrylamide in a mass ratio of 100:35; the mass ratio of the propylene monomer, graphene oxide, inorganic nanoparticles, crosslinking agent, and initiator is 100:2.2:1.5:1:0.6; the crosslinking agent is N,N-methylenebisacrylamide; the initiator is ammonium persulfate; the reaction temperature is 60°C, and the reaction time is 4h;

[0071] (3) The ion exchange resin material dispersion is freeze-dried to obtain a high-performance ion exchange resin material. Testing has shown that the high-performance ion exchange resin material has a tensile strength of 12.3 kPa and an adsorption capacity of 1502 mg / g at equilibrium.

[0072] Example 8

[0073] A method for preparing a high-performance ion exchange resin material comprises the following steps:

[0074] (1) Inorganic nanoparticles are uniformly dispersed in a mixed solution of ethanol and deionized water. Under magnetic stirring, an amino-containing silane coupling agent and a double-bond silane coupling agent are added to the mixed solution, and the mixed solution is heated in a water bath for a certain period of time to obtain a modified inorganic nanoparticle solution; the heating reaction temperature is 58°C and the reaction time is 2.8 hours;

[0075] The amino-containing silane coupling agent is 3-aminopropyltriethoxysilane; the double-bond silane coupling agent is vinyltrimethoxysilane; the molar ratio of the amino-containing silane coupling agent to the double-bond silane coupling agent is 1:0.8; the mass ratio of the sum of the mass of the amino-containing silane coupling agent and the double-bond silane coupling agent to the inorganic nanoparticles is 0.7:1; the inorganic nanoparticles are silicon dioxide with an average particle size of 50 nm;

[0076] (2) First, graphene oxide is added to the modified inorganic nanoparticle solution, and ultrasonicated at 200W for 0.6h. Then, propylene monomer, crosslinking agent, and initiator are added in sequence, stirred evenly, and after sufficient reaction, an ion exchange resin material dispersion is obtained; the propylene monomer is a mixture of acrylic acid and acrylamide in a mass ratio of 100:35; the mass ratio of the propylene monomer, graphene oxide, inorganic nanoparticles, crosslinking agent, and initiator is 100:2.5:0.8:1.2:0.7; the crosslinking agent is N,N-methylenebisacrylamide; the initiator is ammonium persulfate; the reaction temperature is 65°C, and the reaction time is 3.8h;

[0077] (3) The ion exchange resin material dispersion is freeze-dried to obtain a high-performance ion exchange resin material. Testing has shown that the high-performance ion exchange resin material has a tensile strength of 13.0 kPa and an adsorption capacity of 1623 mg / g at equilibrium.

[0078] Example 9

[0079] A method for preparing a high-performance ion exchange resin material comprises the following steps:

[0080] (1) Inorganic nanoparticles are uniformly dispersed in a mixed solution of ethanol and deionized water. Under magnetic stirring, an amino-containing silane coupling agent and a double-bond silane coupling agent are added to the mixed solution, and the mixed solution is heated in a water bath for a certain time to obtain a modified inorganic nanoparticle solution; the heating reaction temperature is 57°C and the reaction time is 3.2 hours;

[0081] The amino-containing silane coupling agent is N-(2-aminoethyl)-3-aminopropyltrimethoxysilane; the double-bond-containing silane coupling agent is 3-(isomethacryloyloxy)propyltrimethoxysilane; the molar ratio of the amino-containing silane coupling agent to the double-bond-containing silane coupling agent is 1:0.6; the mass ratio of the sum of the mass of the amino-containing silane coupling agent and the double-bond-containing silane coupling agent to the inorganic nanoparticles is 0.7:1; the inorganic nanoparticles are silicon dioxide with an average particle size of 50 nm;

[0082] (2) First, graphene oxide is added to the modified inorganic nanoparticle solution, and ultrasonicated at 200W for 0.6h. Then, propylene monomer, crosslinking agent, and initiator are added in sequence, stirred evenly, and after sufficient reaction, an ion exchange resin material dispersion is obtained; the propylene monomer is a mixture of acrylic acid and acrylamide in a mass ratio of 100:36; the mass ratio of the propylene monomer, graphene oxide, inorganic nanoparticles, crosslinking agent, and initiator is 100:2.4:0.7:1.3:0.6; the crosslinking agent is N,N-methylenebisacrylamide; the initiator is ammonium persulfate; the reaction temperature is 66°C, and the reaction time is 4.3h;

[0083] (3) The ion exchange resin material dispersion is freeze-dried to obtain a high-performance ion exchange resin material. Testing has shown that the high-performance ion exchange resin material has a tensile strength of 12.9 kPa and an adsorption capacity of 1598 mg / g at equilibrium.

[0084] Example 10

[0085] A method for preparing a high-performance ion exchange resin material comprises the following steps:

[0086] (1) Inorganic nanoparticles are uniformly dispersed in a mixed solution of ethanol and deionized water. Under magnetic stirring, an amino-containing silane coupling agent and a double-bond silane coupling agent are added to the mixed solution, and the mixed solution is heated in a water bath for a certain period of time to obtain a modified inorganic nanoparticle solution; the heating reaction temperature is 56°C and the reaction time is 3 hours;

[0087] The amino-containing silane coupling agent is 3-aminopropyltrimethoxysilane; the double-bond silane coupling agent is 3-(methacryloyloxy)propyltrimethoxysilane; the molar ratio of the amino-containing silane coupling agent to the double-bond silane coupling agent is 1:0.7; the mass ratio of the sum of the mass of the amino-containing silane coupling agent and the double-bond silane coupling agent to the inorganic nanoparticles is 0.6:1; the inorganic nanoparticles are silicon dioxide with an average particle size of 50 nm;

[0088] (2) First, graphene oxide is added to the modified inorganic nanoparticle solution, and ultrasonicated at 200W for 0.6h. Then, propylene monomer, crosslinking agent, and initiator are added in sequence, stirred evenly, and after sufficient reaction, an ion exchange resin material dispersion is obtained; the propylene monomer is a mixture of acrylic acid and acrylamide in a mass ratio of 100:35; the mass ratio of the propylene monomer, graphene oxide, inorganic nanoparticles, crosslinking agent, and initiator is 100:2.2:0.7:1:0.6; the crosslinking agent is N,N-methylenebisacrylamide; the initiator is ammonium persulfate; the reaction temperature is 60°C, and the reaction time is 4h;

[0089] (3) The ion exchange resin material dispersion is freeze-dried to obtain a high-performance ion exchange resin material. Testing has shown that the high-performance ion exchange resin material has a tensile strength of 13.3 kPa and an adsorption capacity of 1653 mg / g at equilibrium.

[0090] Comparative Example 1

[0091] A method for preparing a high-performance ion exchange resin material comprises the following steps:

[0092] (1) Inorganic nanoparticles are uniformly dispersed in a mixed solution of ethanol and deionized water. An aminosilane coupling agent is added to the mixed solution under magnetic stirring, and the mixed solution is heated in a water bath for a certain period of time to obtain a modified inorganic nanoparticle solution; the heating reaction temperature is 56°C and the reaction time is 3 hours;

[0093] The amino-containing silane coupling agent is 3-aminopropyltrimethoxysilane; the mass ratio of the amino-containing silane coupling agent to the inorganic nanoparticles is 0.6:1; the inorganic nanoparticles are silicon dioxide with an average particle size of 50 nm;

[0094] (2) First, graphene oxide is added to the modified inorganic nanoparticle solution, and ultrasonicated at 200W for 0.6h. Then, propylene monomer, crosslinking agent, and initiator are added in sequence, stirred evenly, and after sufficient reaction, an ion exchange resin material dispersion is obtained; the propylene monomer is a mixture of acrylic acid and acrylamide in a mass ratio of 100:35; the mass ratio of the propylene monomer, graphene oxide, inorganic nanoparticles, crosslinking agent, and initiator is 100:2.2:0.7:1:0.6; the crosslinking agent is N,N-methylenebisacrylamide; the initiator is ammonium persulfate; the reaction temperature is 60°C, and the reaction time is 4h;

[0095] (3) The ion exchange resin material dispersion is freeze-dried to obtain a high-performance ion exchange resin material. Testing has shown that the high-performance ion exchange resin material has a tensile strength of 7.2 kPa and an adsorption capacity of 1124 mg / g at equilibrium.

[0096] Comparative Example 2

[0097] A method for preparing a high-performance ion exchange resin material comprises the following steps:

[0098] (1) Inorganic nanoparticles are uniformly dispersed in a mixed solution of ethanol and deionized water. A double-bond silane coupling agent is added to the mixed solution under magnetic stirring, and the mixed solution is heated in a water bath for a certain period of time to obtain a modified inorganic nanoparticle solution; the heating reaction temperature is 56°C and the reaction time is 3 hours;

[0099] The double-bond silane coupling agent is 3-(isomethacryloyloxy)propyltrimethoxysilane; the mass ratio of the double-bond silane coupling agent to the inorganic nanoparticles is 0.6:1; the inorganic nanoparticles are silicon dioxide with an average particle size of 50 nm;

[0100] (2) First, graphene oxide is added to the modified inorganic nanoparticle solution, and ultrasonicated at 200W for 0.6h. Then, propylene monomer, crosslinking agent, and initiator are added in sequence, stirred evenly, and after sufficient reaction, an ion exchange resin material dispersion is obtained; the propylene monomer is a mixture of acrylic acid and acrylamide in a mass ratio of 100:35; the mass ratio of the propylene monomer, graphene oxide, inorganic nanoparticles, crosslinking agent, and initiator is 100:2.2:0.7:1:0.6; the crosslinking agent is N,N-methylenebisacrylamide; the initiator is ammonium persulfate; the reaction temperature is 60°C, and the reaction time is 4h;

[0101] (3) The ion exchange resin material dispersion is freeze-dried to obtain a high-performance ion exchange resin material. Testing has shown that the high-performance ion exchange resin material has a tensile strength of 8.3 kPa and an adsorption capacity of 1041 mg / g at equilibrium.

[0102] Comparative Example 3

[0103] A method for preparing a high-performance ion exchange resin material comprises the following steps:

[0104] (1) Inorganic nanoparticles are uniformly dispersed in a mixed solution of ethanol and deionized water. Under magnetic stirring, an amino-containing silane coupling agent and a double-bond silane coupling agent are added to the mixed solution, and the mixed solution is heated in a water bath for a certain period of time to obtain a modified inorganic nanoparticle solution; the heating reaction temperature is 56°C and the reaction time is 3 hours;

[0105] The amino-containing silane coupling agent is 3-aminopropyltrimethoxysilane; the double-bond silane coupling agent is 3-(methacryloyloxy)propyltrimethoxysilane; the molar ratio of the amino-containing silane coupling agent to the double-bond silane coupling agent is 1:0.7; the mass ratio of the sum of the mass of the amino-containing silane coupling agent and the double-bond silane coupling agent to the inorganic nanoparticles is 0.6:1; the inorganic nanoparticles are silicon dioxide with an average particle size of 50 nm;

[0106] (2) Adding propylene monomer, crosslinking agent, initiator and graphene oxide to the modified inorganic nanoparticle solution in sequence, stirring evenly, and obtaining an ion exchange resin material dispersion after sufficient reaction; the propylene monomer is a mixture of acrylic acid and acrylamide in a mass ratio of 100:35; the mass ratio of the propylene monomer, graphene oxide, inorganic nanoparticles, crosslinking agent and initiator is 100:2.2:0.7:1:0.6; the crosslinking agent is N,N-methylenebisacrylamide; the initiator is ammonium persulfate; the reaction temperature is 60°C and the reaction time is 4 hours;

[0107] (3) The ion exchange resin material dispersion is freeze-dried to obtain a high-performance ion exchange resin material. Testing has shown that the high-performance ion exchange resin material has a tensile strength of 8.9 kPa and an adsorption capacity of 1215 mg / g at equilibrium.

[0108] As can be seen from the above-described Examples 1-10 and Comparative Examples 1-3, the present invention uses graphene oxide and silane-modified inorganic nanoparticles as fillers to prepare inorganic filler-modified gel-type ion exchange resin materials. Through modification, two reactive functional groups, amino and alkenyl, are introduced onto the surfaces of the inorganic nanoparticles. In the pre-mixing process, the amino active groups on the surfaces of the inorganic nanoparticles easily combine with a large amount of oxygen-containing functional groups on the surfaces of the graphene oxide to form an inorganic nanoparticle-graphene oxide composite. The introduction of the inorganic nanoparticles promotes dispersion between the graphene oxide lamellae and prevents agglomeration between the lamellae. The alkenyl active groups on the surfaces of the inorganic nanoparticles can participate in the cross-linking reaction of the acrylic acid monomer, forming an organically cross-linked integral body between the graphene oxide-inorganic nanoparticles-acrylic acid polymer, thereby not only improving the mechanical properties of the gel-type ion exchange resin material, but also further introducing a porous structure to improve adsorption performance. Compared with Example 10, Comparative Examples 1 and 2 lacked both an amino-containing silane coupling agent and a double-bond silane coupling agent, respectively. Consequently, they failed to achieve the technical effects of both dispersing graphene and connecting the polymer, lacking a synergistic effect. The inorganic filler could not be evenly dispersed, resulting in reduced mechanical properties and adsorption performance of the gel-type ion exchange resin. Furthermore, Comparative Example 3 did not pre-mix the inorganic nanoparticles with graphene oxide. The addition of polar monomers such as acrylic acid caused flocculation of the graphene oxide, impairing the dispersion of the inorganic nanoparticles on the graphene oxide and hindering product performance.

[0109] Finally, it should be noted that the above embodiments of the present invention are merely examples for illustrating the present invention and are not intended to limit the embodiments of the present invention. Those skilled in the art will appreciate that other variations and modifications can be made based on the above description. It is not possible to enumerate all embodiments here. Any obvious variations or modifications arising from the technical solution of the present invention remain within the scope of protection of the present invention.

Claims

1. A method for preparing a high-performance ion exchange resin material, characterized in that: The following steps are involved: (1) Modifying inorganic nanoparticles dispersed in a solvent using an amino-containing silane coupling agent and a double-bond silane coupling agent to prepare a modified inorganic nanoparticle solution; (2) First, add graphene oxide to the modified inorganic nanoparticle solution, disperse it evenly, then add propylene monomer, crosslinking agent, and initiator in sequence, stir evenly, and obtain ion exchange resin material dispersion after sufficient reaction; (3) freeze-drying the ion exchange resin material dispersion to obtain a high-performance ion exchange resin material; The propylene monomer in step (2) is a mixture of acrylic acid and acrylamide in a mass ratio of 100:(10-50); the mass ratio of the propylene monomer, graphene oxide, inorganic nanoparticles, crosslinking agent, and initiator is 100:(1.8-2.5):(0.4-1):(0.3-1.5):(0.4-0.8); The molar ratio of the amino-containing silane coupling agent to the double-bond silane coupling agent in step (1) is 1:(0.5-2); The mass ratio of the sum of the mass of the amino-containing silane coupling agent and the double-bond-containing silane coupling agent to the inorganic nanoparticles in step (1) is (0.1-1):

1.

2. The method for preparing a high-performance ion exchange resin material according to claim 1, wherein: The amino-containing silane coupling agent in step (1) is one of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-diethylenetriaminopropyltrimethoxysilane, 3-diethylenetriaminopropyltriethoxysilane, 3-diethylenetriaminopropylmethyldimethoxysilane, 3-diethylenetriaminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, and N-(2-aminoethyl)-3-aminopropyltrimethoxysilane.

3. The method for preparing a high-performance ion exchange resin material according to claim 1, wherein: The double bond-containing silane coupling agent in step (1) is one of vinyltriethoxysilane, 3-(isomethacryloyloxy)propyltrimethoxysilane, vinyltrimethoxysilane, and vinyltri(β-methoxyethoxy)silane.

4. The method for preparing a high-performance ion exchange resin material according to claim 1, wherein: The inorganic nanoparticles in step (1) are one of silicon dioxide, aluminum oxide, calcium carbonate, barium carbonate, titanium dioxide, zinc oxide, glass powder, montmorillonite or calcium hydroxyphosphate; the average particle size of the inorganic nanoparticles is 10-100 nm.

5. The method for preparing a high-performance ion exchange resin material according to claim 1, wherein: The specific preparation process of the modified inorganic nanoparticle solution in step (1) is as follows: the inorganic nanoparticles are uniformly dispersed in a mixed solution of ethanol and deionized water, an amino-containing silane coupling agent and a double-bond silane coupling agent are added to the mixed solution under magnetic stirring, and the mixture is heated in a water bath for a certain time to obtain the modified inorganic nanoparticle solution; the temperature of the heating reaction is 50-60°C, and the reaction time is 2-4h.

6. The method for preparing a high-performance ion exchange resin material according to claim 1, wherein: In step (2), the cross-linking agent is N,N-methylenebisacrylamide; the initiator is one of ammonium persulfate, potassium persulfate and sodium persulfate; the reaction temperature is 50-70° C., and the reaction time is 3-5 h.

7. A high performance ion exchange resin material, characterized in that: The high-performance ion exchange resin material is prepared by the preparation method of any one of claims 1 to 6.