High-performance ion exchange resin material and preparation method thereof

Abstract

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. Comprising the following steps: (1) modifying inorganic nanoparticles by adopting an amino-containing silane coupling agent and a double-bond-containing silane coupling agent to prepare a modified inorganic nanoparticle solution; (2) firstly adding graphene oxide into the modified inorganic nanoparticle solution, then adding a reaction monomer and a reaction aid, and reacting to obtain an ion exchange resin material dispersion liquid; and (3) freeze-drying to obtain the high-performance ion exchange resin material. Amino groups on the surfaces of the inorganic nanoparticles can promote dispersion between graphene oxide sheet layers, and alkenyl groups on the surfaces of the inorganic nanoparticles can participate in a cross-linking reaction of an acrylic monomer, so that an organic cross-linked whole is formed between the inorganic filler and a polymer; the mechanical property of the gel type ion exchange resin material is enhanced, and the adsorption performance of the gel type ion exchange resin material is further improved.

Description

Technical Field

[0001] The present 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 has the characteristics of complex components, high chroma, high COD and BOD values, a large amount of suspended solids, large variations in water quality and quantity, and a large number of refractory substances, and is one of the industrial wastewaters that are difficult to treat. Dyes mainly use aromatic hydrocarbons and heterocyclic compounds as the matrix, and are equipped with chromogenic groups and polar groups. The structure is becoming increasingly complex, the performance is becoming more and more stable, and while being convenient to use, it also brings greater difficulties to the treatment of printing and dyeing wastewater. At present, the treatment methods of dye wastewater mainly include oxidation methods (biological oxidation method, chemical oxidation, photocatalysis method, microwave synergistic method), adsorption method, coagulation method, and electrochemical method, etc. Among them, the adsorption method has a special position in the field of wastewater treatment due to its ability to selectively enrich certain compounds. Commonly used adsorbents include activated carbon, resin, and some other adsorption materials. Among them, ion exchange resin has been widely used in the field of water treatment due to its excellent pore structure and adsorption performance.

[0003] Ion exchange resins are usually prepared by organic synthesis methods. Commonly used raw materials are styrene or acrylate, and a three-dimensional spatial network structure skeleton is formed through a polymerization reaction, and then different types of chemically active groups (usually acidic or basic groups) are introduced onto the skeleton to make it.

[0004] Ion exchange resins are usually made into small bead-like particles. For those with finer resin particles, the reaction rate is larger, but the finer particles have a greater resistance to the passage of liquid and require a higher working pressure. The particle size of resin is usually measured by the wet screening method, that is, the resin is screened after being fully swollen by absorbing water, and the retention amount on different mesh sieves is counted. The sieve pore diameter corresponding to which 90% of the particles can pass through is called the effective particle size of the resin. Ion exchange resins have hydrophilicity and elasticity, so they often contain a certain amount of bound water. The content of bound water is related to the nature of the resin functional groups and the crosslinking degree, and changes with the air humidity. In order to make the ion exchange resin insoluble in water, it must be crosslinked with a crosslinking agent. The crosslinking degree determines the width of the mesh holes of the resin network structure, but it must be crosslinked moderately. Ion exchange resins have a certain stability and have a relatively high exchange capacity, which is also the most important performance of ion exchange resins.

[0005] Ion exchange resins have different affinities for different ions in solution, that is, they have selectivity in adsorbing them. There are certain rules for the strength of the ion resin exchange adsorption, but different resins will have differences. There are many varieties of ion exchange resins, which have different functions and characteristics due to different chemical compositions and structures, and are suitable for different uses. When applying resins, appropriate types and varieties should be selected according to process requirements and the properties of materials. A variety of new technologies based on ion exchange resins, such as chromatographic separation, ion exclusion, electrodialysis, etc., have unique functions and can perform various special tasks, which are difficult to achieve by other methods.

[0006] A series of patents (CN109569717A, CN109575292A) applied by Sinopec Corporation prepared resin composites by in-situ polymerization with nano-carbon materials, monomers, and comonomers as raw materials under the action of initiators. The POSS structure endows the ion exchange resin with good heat resistance and significantly improves the thermal stability. A series of patents (CN103990499A, CN103991924A) applied by Sichuan Hengda Environmental Technology Co., Ltd. studied a pretreatment and regeneration method for ion exchange resins used to treat the wastewater at the end of the electrolytic manganese production process. The pretreated resin has a larger specific surface area and porosity, improving the adsorption capacity and desorption efficiency, and can work under the condition of high-concentration acid during use; while using a single type of regeneration liquid reduces the amount of regeneration liquid used, and the regeneration operation process is simple and easy to realize automatic control. CN118772325A and CN119119391A also prepared various ion exchange resins and studied their adsorption properties. However, the preparation processes of the above patent technologies are complex, and they are modified with long-chain molecules with high prices and hydrophobic properties, and the improvement of adsorption properties is limited, which 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 its preparation method, which has a wide range of applications in the field of dye wastewater.

[0008] In the first aspect, the present application provides a preparation method of a high-performance ion exchange resin material, adopting the following technical scheme: A preparation method of a high-performance ion exchange resin material includes the following steps: (1) Modify inorganic nanoparticles dispersed in a solvent with an amino silane coupling agent and a double-bond silane coupling agent to prepare a modified inorganic nanoparticle solution; (2) First, graphene oxide is added to the modified inorganic nanoparticle solution. After being uniformly dispersed, acrylic monomers, a crosslinking agent, and an initiator are sequentially added, and then stirred evenly. After sufficient reaction, a dispersion of the ion exchange resin material is obtained. (3) The dispersion of the ion exchange resin material is freeze-dried to obtain a high-performance ion exchange resin material. Through the freeze-drying process, a porous gel-type ion exchange resin material can be effectively prepared.

[0009] To improve the mechanical strength and adsorption performance of the ion exchange resin material, a certain amount of graphene oxide and silane-modified inorganic nanoparticles are added in the present invention. Graphene oxide can not only improve the mechanical properties of the acrylic-based ion exchange resin, but also contains many surface active functional groups (such as hydroxyl groups, carboxyl groups, etc.) itself. These functional groups can react with dye molecules in wastewater to achieve a good adsorption effect. However, there is a strong hydrogen bond between the oxygen-containing functional groups on the surface of graphene oxide and acrylic monomers, and the sheet structure of graphene oxide and the strong van der Waals force between the sheets lead to difficulties in its dispersion during the in-situ polymerization of acrylic monomers. To improve its dispersibility, a certain amount of silane-modified inorganic nanoparticles is added in the present invention. Before adding the reaction monomers, the silane-modified inorganic nanoparticles and graphene oxide are mixed in advance. The inorganic nanoparticles are modified with two coupling agents, namely an amino-silane coupling agent and a double-bond silane coupling agent. Through modification, two reactive functional groups, namely amino and alkenyl groups, are introduced onto the surface of the inorganic nanoparticles. In the pre-mixing process, the amino active groups on the surface of the inorganic nanoparticles are easily combined with a large number of 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 the 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 crosslinking reaction of acrylic monomers, so that an organic crosslinked whole is formed among graphene oxide-inorganic nanoparticles-acrylic polymers, which not only improves the mechanical properties of the gel-type ion exchange resin material, but also further introduces a porous structure to improve the adsorption performance.

[0010] Optionally, the amino-silane coupling agent described in step (1) is one of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-divinyltriaminopropyltrimethoxysilane, 3-divinyltriaminopropyltriethoxysilane, 3-divinyltriaminopropylmethyldimethoxysilane, 3-divinyltriaminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, and N-(2-aminoethyl)-3-aminopropyltrimethoxysilane.

[0011] Optionally, the silane coupling agent containing a double bond described in step (1) is one of vinyltriethoxysilane, 3-(methacryloyloxy)propyltrimethoxysilane, vinyltrimethoxysilane, and vinyltri(β-methoxyethoxy)silane.

[0012] Optionally, the molar ratio of the amino-functional silane coupling agent to the double-bond-containing silane coupling agent described in step (1) is 1:(0.5 - 2). Specifically, the molar ratio of the amino-functional silane coupling agent to the double-bond-containing silane coupling agent is 1:(0.5 - 1), and further preferably 1:(0.6 - 0.8). A larger amount of the amino-functional silane coupling agent can better modify graphene oxide, while avoiding excessive introduction of hydrophobic groups in the double-bond-containing silane coupling agent, which may affect the adsorption performance of the gel-type ion exchange resin.

[0013] Optionally, the mass ratio of the sum of the masses of the amino-functional silane coupling agent and the double-bond-containing silane coupling agent to the mass of the inorganic nanoparticles described in step (1) is (0.1 - 1):1.

[0014] Optionally, the inorganic nanoparticles described in step (1) are one of silica, aluminum oxide, calcium carbonate, barium carbonate, titanium dioxide, zinc oxide, glass powder, montmorillonite, or calcium hydroxyphosphate; the volume average particle size D50 of the inorganic nanoparticles is 10 - 100 nm. Specifically, it can be 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, or 100 nm.

[0015] 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, and under magnetic stirring, the amino-functional silane coupling agent and the double-bond-containing silane coupling agent are added to the mixed solution, and then 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 - 4 h.

[0016] Optionally, the acrylic monomer in step (2) is a mixture of acrylic acid and acrylamide with a mass ratio of 100:(10 - 50); the mass ratio of the acrylic 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). Specifically, the mass ratio of the acrylic 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 performance of graphene oxide but also avoid excessive loading of graphene oxide caused by too many inorganic nanoparticles, which may affect the porous structure of the gel-type ion exchange resin.

[0017] Optionally, the cross-linking agent described 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 3-5 h; the dispersion adopts an ultrasonic process, the ultrasonic power is 100-200 W, and the ultrasonic time is 0.5-1 h.

[0018] In a second aspect, the present application provides a high-performance ion exchange resin material prepared by the above preparation method. The three-dimensional porous network structure of this gel-type composite ion exchange resin material is conducive to the rapid entry of dye molecules. When adsorbing dyes, a certain concentration difference will be formed on its surface, prompting the dye molecules to quickly enter the hydrogel interior from the solution and adsorb the dyes through chemical action, electrostatic interaction, hydrogen bond, and hydrophobic interaction.

[0019] In summary, the present application has the following beneficial effects: 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 group and alkenyl group, are introduced onto the surface of the inorganic nanoparticles. In the pre-mixing process, the amino active groups on the surface of the inorganic nanoparticles are easily combined or react with a large number of oxygen-containing functional groups on the surface of graphene oxide in the form of hydrogen bonds to form an inorganic nanoparticle-graphene oxide composite. The introduction of inorganic nanoparticles promotes the 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 acrylic monomers, making an organic cross-linked whole among graphene oxide-inorganic nanoparticle-acrylic polymers, which not only improves the mechanical properties of the gel-type ion exchange resin material but also further introduces a porous structure to improve the adsorption performance. Specific Embodiments

[0020] The present invention is further illustrated by the following examples: According to the following examples, the present invention can be better understood. However, those skilled in the art can easily understand that the specific material ratios, process conditions, and their results described in the examples are only used to illustrate the present invention and should not and will not limit the present invention described in detail in the claims.

[0021] Unless otherwise specified, the types of raw materials and process conditions used in the following examples and comparative examples are the same.

[0022] Among them, the performance test methods for the high-performance ion exchange resin materials prepared in the following examples and comparative examples are as follows: (1) Use a tensile testing machine to test the tensile fracture performance (kPa) of the high-performance ion exchange resin material after water absorption and swelling; (2) Weigh a certain amount (m, g) of the high-performance ion exchange resin material and place it in a beaker. Add a certain volume (V, L) of methylene blue solution with a concentration of (ρ1, mg / L). Use an ultraviolet spectrophotometer to monitor the methylene blue concentration until the concentration no longer changes, and obtain the concentration ρ2. The adsorption capacity (mg / g) at equilibrium of the high-performance ion exchange resin material can be calculated using the formula (ρ1 - ρ2) * V / m.

[0023] Example 1 A preparation method of a high-performance ion exchange resin material, comprising the following steps: (1) Uniformly disperse inorganic nanoparticles in a mixed solution of ethanol and deionized water. Under magnetic stirring, add an amino-silane coupling agent and a double-bond silane coupling agent to the mixed solution, and react by water bath heating for a certain time to obtain a modified inorganic nanoparticle solution. The temperature of the heating reaction is 50 °C, and the reaction time is 4 h; The amino-silane coupling agent is 3-aminopropyltriethoxysilane; the double-bond silane coupling agent is vinyltriethoxysilane; the molar ratio of the amino-silane coupling agent to the double-bond silane coupling agent is 1:0.5; the mass ratio of the sum of the amino-silane coupling agent and the double-bond silane coupling agent to the mass of the inorganic nanoparticles is 0.5:1; the inorganic nanoparticles are silica with an average particle size of 50 nm; (2) First, add graphene oxide to the modified inorganic nanoparticle solution and ultrasonicate it at 200 W for 0.6 h. Then, add acrylic monomers, a crosslinking agent, and an initiator in sequence, stir evenly, and obtain an ion exchange resin material dispersion after full reaction. The acrylic monomers are a mixture of acrylic acid and acrylamide with a mass ratio of 100:25. The mass ratio of the acrylic monomers, 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 5 h; (3) Freeze-dry the ion exchange resin material dispersion to obtain the high-performance ion exchange resin material. After testing, the tensile fracture performance of this high-performance ion exchange resin material is 12.2 kPa, and the adsorption capacity at equilibrium is 1521 mg / g.

[0024] Example 2 A preparation method of a high-performance ion exchange resin material, comprising the following steps: (1) Uniformly disperse inorganic nanoparticles in a mixed solution of ethanol and deionized water. Under magnetic stirring, add an amino-silane coupling agent and a double-bond silane coupling agent to the mixed solution, and react by water bath heating for a certain time to obtain a modified inorganic nanoparticle solution. The temperature of the heating reaction is 60 °C, and the reaction time is 2 h; The amino group-containing silane coupling agent is 3-aminopropyltrimethoxysilane; the double bond-containing silane coupling agent is vinyltrimethoxysilane; the molar ratio of the amino group-containing silane coupling agent to the double bond-containing silane coupling agent is 1:1; the mass ratio of the sum of the masses of the amino group-containing silane coupling agent and the double bond-containing silane coupling agent to the mass of the inorganic nanoparticles is 0.8:1; the inorganic nanoparticles are silica with an average particle size of 50 nm; (2) First, graphene oxide is added to the modified inorganic nanoparticle solution, and ultrasonic treatment is carried out at 200 W for 0.6 h. Then, acrylic monomers, a crosslinking agent, and an initiator are added in sequence, and the mixture is stirred evenly. After sufficient reaction, a dispersion of the ion exchange resin material is obtained; the acrylic monomers are a mixture of acrylic acid and acrylamide with a mass ratio of 100:40; the mass ratio of the acrylic monomers, 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 3 h; (3) The dispersion of the ion exchange resin material is freeze-dried to obtain a high-performance ion exchange resin material. After testing, the tensile fracture property of the high-performance ion exchange resin material is 13.6 kPa, and the adsorption amount at equilibrium is 1588 mg / g.

[0025] Example 3 A preparation method of a high-performance ion exchange resin material, comprising the following steps: (1) The inorganic nanoparticles are uniformly dispersed in a mixed solution of ethanol and deionized water. Under magnetic stirring, the amino group-containing silane coupling agent and the double bond-containing silane coupling agent are added to the mixed solution, and the reaction is carried out by water bath heating for a certain time to obtain a modified inorganic nanoparticle solution; the temperature of the heating reaction is 56 °C, and the reaction time is 3 h; The amino group-containing silane coupling agent is 3-aminopropyltrimethoxysilane; the double bond-containing silane coupling agent is 3-(methacryloyloxy)propyltrimethoxysilane; the molar ratio of the amino group-containing silane coupling agent to the double bond-containing silane coupling agent is 1:1.5; the mass ratio of the sum of the masses of the amino group-containing silane coupling agent and the double bond-containing silane coupling agent to the mass of the inorganic nanoparticles is 0.6:1; the inorganic nanoparticles are silica with an average particle size of 50 nm; (2) First, graphene oxide is added to the modified inorganic nanoparticle solution, and ultrasonic treatment is carried out at 200 W for 0.6 h. Then, acrylic monomers, a crosslinking agent, and an initiator are added in sequence, and stirred evenly. After sufficient reaction, an ion exchange resin material dispersion is obtained; the acrylic monomers are a mixture of acrylic acid and acrylamide with a mass ratio of 100:35; the mass ratio of the acrylic monomers, 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 h; (3) The ion exchange resin material dispersion is freeze-dried to obtain a high-performance ion exchange resin material. After testing, the tensile fracture property of the high-performance ion exchange resin material is 12.1 kPa, and the adsorption amount at equilibrium is 1607 mg / g.

[0026] Example 4 A preparation method of a high-performance ion exchange resin material, comprising the following steps: (1) The inorganic nanoparticles are uniformly dispersed in a mixed solution of ethanol and deionized water. Under magnetic stirring, an amino-silane coupling agent and a double-bond-containing silane coupling agent are added to the mixed solution, and a water bath is used for heating and reacting for a certain time to obtain a modified inorganic nanoparticle solution; the temperature of the heating reaction is 52 °C, and the reaction time is 2.5 h; The amino-silane coupling agent is N-(2-aminoethyl)-3-aminopropyltrimethoxysilane; the double-bond-containing silane coupling agent is 3-(methacryloyloxy)propyltrimethoxysilane; the molar ratio of the amino-silane coupling agent to the double-bond-containing silane coupling agent is 1:0.6; the mass sum of the amino-silane coupling agent and the double-bond-containing silane coupling agent and the mass ratio of the inorganic nanoparticles is 0.8:1; the inorganic nanoparticles are silica with an average particle size of 40 nm; (2) First, graphene oxide is added to the modified inorganic nanoparticle solution, and ultrasonic treatment is carried out at 200 W for 0.6 h. Then, acrylic monomers, a crosslinking agent, and an initiator are added in sequence, and stirred evenly. After sufficient reaction, an ion exchange resin material dispersion is obtained; the acrylic monomers are a mixture of acrylic acid and acrylamide with a mass ratio of 100:25; the mass ratio of the acrylic monomers, 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 5 h; (3) The ion exchange resin material dispersion is freeze-dried to obtain a high-performance ion exchange resin material. After testing, the tensile fracture property of the high-performance ion exchange resin material is 12.4 kPa, and the adsorption amount at equilibrium is 1556 mg / g.

[0027] Example 5 A preparation method of a high-performance ion exchange resin material, comprising the following steps: (1) Uniformly disperse inorganic nanoparticles in a mixed solution of ethanol and deionized water. Under magnetic stirring, add an amino group-containing silane coupling agent and a double bond-containing silane coupling agent to the mixed solution, and react by water bath heating for a certain time to obtain a modified inorganic nanoparticle solution; the temperature of the heating reaction is 56 °C, and the reaction time is 3 h; The amino group-containing silane coupling agent is 3-aminopropyltrimethoxysilane; the double bond-containing silane coupling agent is 3-(methacryloyloxy)propyltrimethoxysilane; the molar ratio of the amino group-containing silane coupling agent to the double bond-containing silane coupling agent is 1:0.7; the mass ratio of the sum of the masses of the amino group-containing silane coupling agent and the double bond-containing silane coupling agent to the mass of the inorganic nanoparticles is 0.6:1; the inorganic nanoparticles are silica with an average particle size of 50 nm; (2) First, add graphene oxide to the modified inorganic nanoparticle solution, and ultrasonicate at 200 W for 0.6 h. Then, sequentially add acrylic monomers, a crosslinking agent, and an initiator, stir evenly, and fully react to obtain an ion exchange resin material dispersion; the acrylic monomers are a mixture of acrylic acid and acrylamide with a mass ratio of 100:35; the mass ratio of the acrylic monomers, 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 4 h; (3) Lyophilize the ion exchange resin material dispersion to obtain a high-performance ion exchange resin material. After testing, the tensile fracture property of the high-performance ion exchange resin material is 11.9 kPa, and the adsorption amount at equilibrium is 1533 mg / g.

[0028] Example 6 A preparation method of a high-performance ion exchange resin material, comprising the following steps: (1) Uniformly disperse inorganic nanoparticles in a mixed solution of ethanol and deionized water. Under magnetic stirring, add an amino group-containing silane coupling agent and a double bond-containing silane coupling agent to the mixed solution, and react by water bath heating for a certain time to obtain a modified inorganic nanoparticle solution; the temperature of the heating reaction is 55 °C, and the reaction time is 3.5 h; The amino group-containing silane coupling agent is 3-aminopropyltriethoxysilane; the double bond-containing silane coupling agent is vinyltrimethoxysilane; the molar ratio of the amino group-containing silane coupling agent to the double bond-containing silane coupling agent is 1:0.6; the mass ratio of the sum of the masses of the amino group-containing silane coupling agent and the double bond-containing silane coupling agent to the mass of the inorganic nanoparticles is 0.6:1; the inorganic nanoparticles are silica with an average particle size of 80 nm; (2) First, graphene oxide is added to the modified inorganic nanoparticle solution, and ultrasonic treatment is carried out at 200 W for 0.6 h. Then, acrylic monomers, a crosslinking agent, and an initiator are added in sequence, and stirred evenly. After sufficient reaction, an ion exchange resin material dispersion is obtained; the acrylic monomers are a mixture of acrylic acid and acrylamide with a mass ratio of 100:28; the mass ratio of the acrylic monomers, 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 3.5 h. (3) The ion exchange resin material dispersion is freeze-dried to obtain a high-performance ion exchange resin material. After testing, the tensile fracture property of this high-performance ion exchange resin material is 12.6 kPa, and the adsorption amount at equilibrium is 1586 mg / g.

[0029] Example 7 A preparation method of a high-performance ion exchange resin material, comprising the following steps: (1) The inorganic nanoparticles are uniformly dispersed in a mixed solution of ethanol and deionized water. Under magnetic stirring, an amino-silane coupling agent and a double-bond silane coupling agent are added to the mixed solution, and a water bath heating reaction is carried out for a certain time to obtain a modified inorganic nanoparticle solution; the temperature of the heating reaction is 56 °C, and the reaction time is 3 h. The amino-silane coupling agent is 3-aminopropyltrimethoxysilane; the double-bond silane coupling agent is 3-(methacryloyloxy)propyltrimethoxysilane; the molar ratio of the amino-silane coupling agent to the double-bond silane coupling agent is 1:0.7; the mass sum of the amino-silane coupling agent and the double-bond silane coupling agent and the mass ratio of the inorganic nanoparticles is 0.6:1; the inorganic nanoparticles are silica with an average particle size of 50 nm. (2) First, graphene oxide is added to the modified inorganic nanoparticle solution, and ultrasonic treatment is carried out at 200 W for 0.6 h. Then, acrylic monomers, a crosslinking agent, and an initiator are added in sequence, and stirred evenly. After sufficient reaction, an ion exchange resin material dispersion is obtained; the acrylic monomers are a mixture of acrylic acid and acrylamide with a mass ratio of 100:35; the mass ratio of the acrylic monomers, 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 4 h. (3) The ion exchange resin material dispersion is freeze-dried to obtain a high-performance ion exchange resin material. After testing, the tensile fracture property of this high-performance ion exchange resin material is 12.3 kPa, and the adsorption amount at equilibrium is 1502 mg / g.

[0030] Example 8 A preparation method of a high-performance ion exchange resin material, comprising the following steps: (1) Uniformly disperse inorganic nanoparticles in a mixed solution of ethanol and deionized water. Under magnetic stirring, add an amino-silane coupling agent and a double-bond silane coupling agent to the mixed solution, and react by water bath heating for a certain period of time to obtain a modified inorganic nanoparticle solution; the temperature of the heating reaction is 58 °C, and the reaction time is 2.8 h; The amino-silane coupling agent is 3-aminopropyltriethoxysilane; the double-bond silane coupling agent is vinyltrimethoxysilane; the molar ratio of the amino-silane coupling agent to the double-bond silane coupling agent is 1:0.8; the mass ratio of the sum of the masses of the amino-silane coupling agent and the double-bond silane coupling agent to the mass of the inorganic nanoparticles is 0.7:1; the inorganic nanoparticles are silica with an average particle size of 50 nm; (2) First, add graphene oxide to the modified inorganic nanoparticle solution, and ultrasonicate at 200 W for 0.6 h. Then, sequentially add acrylic monomers, a crosslinking agent, and an initiator, stir evenly, and fully react to obtain an ion exchange resin material dispersion; the acrylic monomers are a mixture of acrylic acid and acrylamide with a mass ratio of 100:35; the mass ratio of the acrylic monomers, 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 3.8 h; (3) Freeze-dry the ion exchange resin material dispersion to obtain a high-performance ion exchange resin material. After testing, the tensile fracture performance of this high-performance ion exchange resin material is 13.0 kPa, and the adsorption amount at equilibrium is 1623 mg / g.

[0031] Example 9 A preparation method of a high-performance ion exchange resin material, comprising the following steps: (1) Uniformly disperse inorganic nanoparticles in a mixed solution of ethanol and deionized water. Under magnetic stirring, add an amino-silane coupling agent and a double-bond silane coupling agent to the mixed solution, and react by water bath heating for a certain period of time to obtain a modified inorganic nanoparticle solution; the temperature of the heating reaction is 57 °C, and the reaction time is 3.2 h; The amino group-containing silane coupling agent is N-(2-aminoethyl)-3-aminopropyltrimethoxysilane; the double bond-containing silane coupling agent is 3-(methacryloyloxy)propyltrimethoxysilane; the molar ratio of the amino group-containing silane coupling agent to the double bond-containing silane coupling agent is 1:0.6; the mass ratio of the sum of the masses of the amino group-containing silane coupling agent and the double bond-containing silane coupling agent to the mass of the inorganic nanoparticles is 0.7:1; the inorganic nanoparticles are silica with an average particle size of 50 nm; (2) First, graphene oxide is added to the modified inorganic nanoparticle solution, and ultrasonic treatment is carried out at 200 W for 0.6 h. Then, acrylic monomers, a crosslinking agent, and an initiator are added in sequence, and after stirring evenly and fully reacting, an ion exchange resin material dispersion is obtained; the acrylic monomers are a mixture of acrylic acid and acrylamide with a mass ratio of 100:36; the mass ratio of the acrylic monomers, 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 4.3 h; (3) The ion exchange resin material dispersion is freeze-dried to obtain a high-performance ion exchange resin material. After testing, the tensile fracture performance of the high-performance ion exchange resin material is 12.9 kPa, and the adsorption amount at equilibrium is 1598 mg / g.

[0032] Example 10 A preparation method of a high-performance ion exchange resin material, comprising the following steps: (1) The inorganic nanoparticles are uniformly dispersed in a mixed solution of ethanol and deionized water. Under magnetic stirring, the amino group-containing silane coupling agent and the double bond-containing silane coupling agent are added to the mixed solution, and a water bath heating reaction is carried out for a certain time to obtain a modified inorganic nanoparticle solution; the temperature of the heating reaction is 56 °C, and the reaction time is 3 h; The amino group-containing silane coupling agent is 3-aminopropyltrimethoxysilane; the double bond-containing silane coupling agent is 3-(methacryloyloxy)propyltrimethoxysilane; the molar ratio of the amino group-containing silane coupling agent to the double bond-containing silane coupling agent is 1:0.7; the mass ratio of the sum of the masses of the amino group-containing silane coupling agent and the double bond-containing silane coupling agent to the mass of the inorganic nanoparticles is 0.6:1; the inorganic nanoparticles are silica with an average particle size of 50 nm; (2) First, graphene oxide is added to the modified inorganic nanoparticle solution, and ultrasonic treatment is carried out at 200 W for 0.6 h. Then, acrylic monomers, cross-linking agent, and initiator are added in sequence and stirred evenly. After sufficient reaction, an ion exchange resin material dispersion is obtained. The acrylic monomers are a mixture of acrylic acid and acrylamide with a mass ratio of 100:35. The mass ratio of the acrylic monomers, graphene oxide, inorganic nanoparticles, cross-linking agent, and initiator is 100:2.2:0.7:1:0.6. The cross-linking agent is N,N'-methylenebisacrylamide. The initiator is ammonium persulfate. The reaction temperature is 60 °C, and the reaction time is 4 h. (3) The ion exchange resin material dispersion is freeze-dried to obtain a high-performance ion exchange resin material. After testing, the tensile fracture property of the high-performance ion exchange resin material is 13.3 kPa, and the adsorption amount at equilibrium is 1653 mg / g.

[0033] Comparative Example 1 A preparation method of a high-performance ion exchange resin material includes the following steps: (1) Inorganic nanoparticles are uniformly dispersed in a mixed solution of ethanol and deionized water. Under magnetic stirring, an amino-silane coupling agent is added to the mixed solution, and a water bath heating reaction is carried out for a certain time to obtain a modified inorganic nanoparticle solution. The temperature of the heating reaction is 56 °C, and the reaction time is 3 h. The amino-silane coupling agent is 3-aminopropyltrimethoxysilane. The mass ratio of the amino-silane coupling agent to the inorganic nanoparticles is 0.6:1. The inorganic nanoparticles are silica with an average particle size of 50 nm. (2) First, graphene oxide is added to the modified inorganic nanoparticle solution, and ultrasonic treatment is carried out at 200 W for 0.6 h. Then, acrylic monomers, cross-linking agent, and initiator are added in sequence and stirred evenly. After sufficient reaction, an ion exchange resin material dispersion is obtained. The acrylic monomers are a mixture of acrylic acid and acrylamide with a mass ratio of 100:35. The mass ratio of the acrylic monomers, graphene oxide, inorganic nanoparticles, cross-linking agent, and initiator is 100:2.2:0.7:1:0.6. The cross-linking agent is N,N'-methylenebisacrylamide. The initiator is ammonium persulfate. The reaction temperature is 60 °C, and the reaction time is 4 h. (3) The ion exchange resin material dispersion is freeze-dried to obtain a high-performance ion exchange resin material. After testing, the tensile fracture property of the high-performance ion exchange resin material is 7.2 kPa, and the adsorption amount at equilibrium is 1124 mg / g.

[0034] Comparative Example 2 A preparation method of a high-performance ion exchange resin material includes the following steps: (1) Uniformly disperse inorganic nanoparticles in a mixed solution of ethanol and deionized water. Under magnetic stirring, add a double-bond silane coupling agent to the mixed solution, and react by water bath heating for a certain period of time to obtain a modified inorganic nanoparticle solution. The temperature of the heating reaction is 56 °C, and the reaction time is 3 h. The double-bond silane coupling agent is 3-(methacryloyloxy)propyltrimethoxysilane. The mass ratio of the double-bond silane coupling agent to the inorganic nanoparticles is 0.6:1. The inorganic nanoparticles are silica with an average particle size of 50 nm. (2) First, add graphene oxide to the modified inorganic nanoparticle solution and ultrasonicate it at 200 W for 0.6 h. Then, sequentially add acrylic monomers, a crosslinking agent, and an initiator, stir evenly, and obtain an ion exchange resin material dispersion after sufficient reaction. The acrylic monomers are a mixture of acrylic acid and acrylamide with a mass ratio of 100:35. The mass ratio of the acrylic monomers, 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 h. (3) Freeze-dry the ion exchange resin material dispersion to obtain a high-performance ion exchange resin material. After testing, the tensile fracture property of the high-performance ion exchange resin material is 8.3 kPa, and the adsorption amount at equilibrium is 1041 mg / g.

[0035] Comparative Example 3 A preparation method of a high-performance ion exchange resin material, comprising the following steps: (1) Uniformly disperse inorganic nanoparticles in a mixed solution of ethanol and deionized water. Under magnetic stirring, add an amino silane coupling agent and a double-bond silane coupling agent to the mixed solution, and react by water bath heating for a certain period of time to obtain a modified inorganic nanoparticle solution. The temperature of the heating reaction is 56 °C, and the reaction time is 3 h. The amino silane coupling agent is 3-aminopropyltrimethoxysilane. The double-bond silane coupling agent is 3-(methacryloyloxy)propyltrimethoxysilane. The molar ratio of the amino silane coupling agent to the double-bond silane coupling agent is 1:0.7. The mass sum of the amino silane coupling agent and the double-bond silane coupling agent to the mass of the inorganic nanoparticles is 0.6:1. The inorganic nanoparticles are silica with an average particle size of 50 nm. (2) Acrylate monomers, a crosslinking agent, an initiator, and graphene oxide are successively added to the modified inorganic nanoparticle solution and stirred evenly. After sufficient reaction, an ion exchange resin material dispersion is obtained. The acrylate monomers are a mixture of acrylic acid and acrylamide with a mass ratio of 100:35. The mass ratio of the acrylate monomers, 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 h. (3) The ion exchange resin material dispersion is freeze-dried to obtain a high-performance ion exchange resin material. After testing, the tensile fracture performance of the high-performance ion exchange resin material is 8.9 kPa, and the adsorption capacity at equilibrium is 1215 mg / g.

[0036] It can be seen from the above Examples 1-10 and Comparative Examples 1-3 that 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 surface of the inorganic nanoparticles. In the pre-mixing process, the amino active groups on the surface of the inorganic nanoparticles are easily combined with a large number of oxygen-containing functional groups on the surface of graphene oxide to form an inorganic nanoparticle-graphene oxide composite. The introduction of inorganic nanoparticles promotes the 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 crosslinking reaction of acrylic acid monomers, forming an organic crosslinked whole among graphene oxide-inorganic nanoparticles-acrylic polymers, which not only improves the mechanical properties of the gel-type ion exchange resin material but also further introduces a porous structure to improve the adsorption performance. Compared with Example 10, in Comparative Examples 1-2, the amino-silane coupling agent and the double bond-containing silane coupling agent are respectively missing, and the technical effects of dispersing graphene and connecting polymers cannot be achieved simultaneously, and no synergistic effect can be presented. The inorganic filler cannot be evenly dispersed, resulting in a decrease in the mechanical properties of the gel-type ion exchange resin and a deterioration in the adsorption performance. In Comparative Example 3, the inorganic nanoparticles and graphene oxide are not pre-mixed, and the addition of polar monomers such as acrylic acid causes a flocculation effect of graphene oxide, affecting the dispersion of graphene oxide by the inorganic nanoparticles and being unfavorable for improving the product performance.

[0037] Finally, it should be noted that the above embodiments of the present invention are only examples for explaining the present invention and are not intended to limit the embodiments of the present invention. For those of ordinary skill in the art, other different forms of changes and modifications can be made based on the above description. It is impossible to list all the embodiments here. Any obvious changes or modifications derived from the technical solutions of the present invention still fall within the protection scope of the present invention.

Claims

1. A preparation method of a high-performance ion exchange resin material, characterized in that, It includes the following steps: (1) Modify inorganic nanoparticles dispersed in a solvent with an amino-silane coupling agent and a double-bond-containing silane coupling agent to prepare a modified inorganic nanoparticle solution; (2) First, add graphene oxide to the modified inorganic nanoparticle solution. After uniform dispersion, successively add acrylic monomers, a crosslinking agent, and an initiator, stir evenly, and obtain an ion exchange resin material dispersion after sufficient reaction; (3) Freeze-dry the ion exchange resin material dispersion to obtain a high-performance ion exchange resin material.

2. The preparation method of the high-performance ion exchange resin material according to claim 1, characterized in that, The amino-silane coupling agent described in step (1) is one of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-divinyltriaminopropyltrimethoxysilane, 3-divinyltriaminopropyltriethoxysilane, 3-divinyltriaminopropylmethyldimethoxysilane, 3-divinyltriaminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane.

3. The preparation method of the high-performance ion exchange resin material according to claim 1, characterized in that, The double-bond-containing silane coupling agent described in step (1) is one of vinyltriethoxysilane, 3-(methacryloyloxy)propyltrimethoxysilane, vinyltrimethoxysilane, vinyltris(β-methoxyethoxy)silane.

4. The preparation method of the high-performance ion exchange resin material according to claim 1, characterized in that, The molar ratio of the amino-silane coupling agent to the double-bond-containing silane coupling agent described in step (1) is 1:(0.5 - 2).

5. The preparation method of the high-performance ion exchange resin material according to claim 1, characterized in that, The mass ratio of the sum of the masses of the amino-silane coupling agent and the double-bond-containing silane coupling agent to the mass of the inorganic nanoparticles in step (1) is (0.1 - 1):

1.

6. The preparation method of the high-performance ion exchange resin material according to claim 1, characterized in that, The inorganic nanoparticles described in step (1) are one of silica, aluminum oxide, calcium carbonate, barium carbonate, titanium dioxide, zinc oxide, glass powder, montmorillonite, or hydroxyapatite; the average particle size of the inorganic nanoparticles is 10 - 100 nm.

7. The preparation method of the high-performance ion exchange resin material according to claim 1, characterized in that, The specific preparation process of the modified inorganic nanoparticle solution in step (1) is: uniformly disperse the inorganic nanoparticles in a mixed solution of ethanol and deionized water. Under magnetic stirring, add the amino-silane coupling agent and the double-bond-containing silane coupling agent to the mixed solution, and react by water bath heating for a certain time to obtain a modified inorganic nanoparticle solution; the temperature of the heating reaction is 50 - 60°C, and the reaction time is 2 - 4 h.

8. The preparation method of the high-performance ion exchange resin material according to claim 1, characterized in that, The acrylic monomers described in step (2) are a mixture of acrylic acid and acrylamide with a mass ratio of 100:(10 - 50); the mass ratio of the acrylic monomers, 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).

9. The preparation method of the high-performance ion exchange resin material according to claim 1, characterized in that, The crosslinking agent described 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 - 5 h.

10. A high-performance ion exchange resin material, characterized in that, Prepared by the preparation method of a high-performance ion exchange resin material according to any one of claims 1 - 9.