A composite adsorption material for uremia and a preparation method thereof

Abstract

The application belongs to the technical field of adsorbents, and provides a composite adsorbent material for uremia and a preparation method thereof, and the preparation steps are as follows: S1. Acrylamide, N,N'-methylenebisacrylamide, glycerol and deionized water are mixed, stirred, sodium alginate is added, stirred and dissolved, ammonium persulfate, calcium sulfate and tetramethylethylenediamine are sequentially added, stirred, ultrasonically treated, and heated and reacted to obtain a sodium alginate derivative; S2. The sodium alginate derivative and deionized water are mixed, modified high-density polyethylene is added, stirred, and soaked in a CaCl2 solution for crosslinking to obtain a sodium alginate composite material; S3. CeO2 / MoS2 functional material, sodium alginate and deionized water are mixed, the sodium alginate composite material is added and stirred, shaped, soaked in a CaCl2 solution for crosslinking, washed, and dried to obtain the composite adsorbent material. The composite adsorbent material has a high adsorption rate and high adsorption capacity for uremia toxins, and has good biocompatibility and hemocompatibility.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of adsorbents, and particularly relates to a composite adsorbent for uremia and a preparation method thereof. BACKGROUND

[0002] Uremia is the end-stage manifestation of renal failure, and has become a major disease that seriously threatens human health in recent years. At present, common uremia treatment methods include kidney transplantation, hemodialysis, hemoperfusion, and peritoneal dialysis. With the continuous development of dialysis technology, wearable artificial kidneys have brought new hope for the treatment of uremia patients. The wearable artificial kidney (WAK) greatly reduces the dialysate volume (<500 mL) through a "dialysis-adsorption" closed loop cycle, and the core bottleneck is the lack of an "high capacity, high selectivity, and regularly replaceable" adsorbent to achieve multiple regeneration of the dialysate, thereby improving the convenience and economy of treatment. However, traditional adsorbents such as activated carbon, zirconium phosphate, and zirconium oxide have poor adsorption selectivity for urea and creatinine small molecule toxins with large metabolic production, which cannot meet the clinical requirements.

[0003] Molybdenum disulfide (MoS2) is a kind of nanomaterial with special layered structure, which has shown wide application potential in many fields due to its unique physical and chemical properties. In the field of artificial kidney technology, the adsorption performance of molybdenum disulfide has attracted particular attention, which is mainly due to its large specific surface area and rich active sites on the edge, which can theoretically efficiently adsorb uremia toxins. However, there are still many challenges in directly applying molybdenum disulfide to artificial kidney technology, such as insufficient biological stability, poor biocompatibility, and selective adsorption bottleneck.

[0004] Chinese patent CN 118751214 A discloses a preparation method of an aminated bacterial cellulose / molybdenum disulfide composite adsorbent, an adsorbent and an application, which comprises the following steps: placing bacterial cellulose, sodium molybdate and thiourea into an aqueous solution, carrying out hydrothermal reaction, washing, and drying to obtain a bacterial cellulose / molybdenum disulfide nanocomposite material; adding PEI into the bacterial cellulose / molybdenum disulfide dispersed aqueous solution, stirring uniformly, washing, and drying to obtain a composite adsorbent. The composite adsorbent has excellent heavy metal ion adsorption performance, low preparation cost, and good stability. However, the adsorption effect of the composite adsorbent on uremia toxins is unknown, heavy metal ions belong to soft acids or borderline acids, which can form stable metal-sulfur coordination bonds with the exposed sulfur vacancies or edge sulfur atoms on the surface of MoS2, while uremia toxins (urea, creatinine, etc.) are mostly neutral or weakly polar molecules, which cannot be efficiently adsorbed through the same type of coordination, and the selective adsorption performance and applicability still need to be studied.

[0005] Therefore, it is urgent to develop a composite adsorbent for uremia, which has excellent adsorption performance and good adsorption stability for uremia toxins. SUMMARY

[0006] In order to solve the above technical problems, the present application aims to provide a composite adsorption material for uremia and a preparation method thereof.

[0007] In order to achieve the above-mentioned purpose, the technical scheme adopted by the present application is as follows:

[0008] In one aspect, the present application provides a preparation method of a composite adsorption material for uremia, comprising the following steps:

[0009] S1. Mix acrylamide, N,N'-methylenebisacrylamide, glycerol and deionized water, stir, add sodium alginate, stir to dissolve, then add ammonium persulfate, calcium sulfate and tetramethylethylenediamine in sequence, stir, ultrasonic, heat to 55-70℃ for 1-2h to obtain a sodium alginate derivative;

[0010] S2. Mix the sodium alginate derivative obtained in step S1 with deionized water, add modified high-density polyethylene, stir, then immerse it in a 2.5-4wt% CaCl2 solution for crosslinking for 1.5-2.5h to obtain a sodium alginate composite material;

[0011] S3. Mix CeO2 / MoS2 functional material, sodium alginate and deionized water, add the sodium alginate composite material obtained in step S2 and stir, then immerse it in a 2.5-4wt% CaCl2 solution for crosslinking for 1.5-2.5h after shaping, wash, freeze-dry to obtain a composite adsorption material.

[0012] The reaction mechanism and action of the present application are as follows:

[0013] Sodium alginate is a biopolymer extracted from natural brown algae, which has abundant hydroxyl and carboxyl groups, and can provide active sites for the adsorption of pollutants. However, sodium alginate as an adsorption material has the problems of high brittleness, poor fatigue resistance and poor creep resistance.

[0014] On the one hand, the applicant introduces acrylamide to prepare a sodium alginate derivative. After polymerization of acrylamide, a long chain of polyacrylamide is formed, and the amide group (-CONH2) of the long chain is combined with the carboxyl group (-COO -) by hydrogen bond / physical entanglement to form an interpenetrating network, linear sodium alginate is converted into a covalently cross-linked elastic network (sodium alginate-g-polyacrylamide); N,N'-methylene bisacrylamide as a cross-linking agent introduces covalent cross-linking points between polyacrylamide chains, significantly improves the gel elasticity, and solves the problem of brittleness and easy cracking of pure sodium alginate after cross-linking. 2+ After cross-linking, the problem of brittleness and easy cracking. At the same time, polyacrylamide not only can adsorb small molecule toxins such as urea and creatinine through hydrogen bond action, etc., but also its hydrophilic segment can absorb water, but the covalent cross-linked network will limit its unlimited expansion, and thus the material can not only adsorb toxins, but also not block the dialysis pipeline in uremia blood purification. More importantly, the surface of the composite adsorption material exists negatively charged groups, thereby reducing the adsorption of plasma proteins and platelets, which helps to improve the blood compatibility.

[0015] On the other hand, the applicant introduces high-density polyethylene to improve the mechanical stability of sodium alginate, but the high-density polyethylene is easy to agglomerate when directly added to water. Therefore, it is modified with furan sugar acid-γ-lactone to make it disperse uniformly. The modified high-density polyethylene provides a micron-sized rigid skeleton that can effectively disperse stress and reduce crack propagation, and is not easy to creep deformation under long-term stress, thereby improving the fatigue resistance and creep resistance of the sodium alginate composite material, and prolonging the service life of the composite adsorption material.

[0016] In addition, the applicant combines nano molybdenum disulfide and cerium nitrate hexahydrate to form a CeO2 / MoS2 nanomaterial by ultrasonic, and then modifies N-aminoethyl-3-aminopropyl triethoxysilane on the active site, which is more conducive to functional modification. Not only increases the total specific surface area and adsorption sites of molybdenum disulfide, improves the adsorption rate and adsorption capacity of the adsorption material to uremia toxins, but also reduces the cytotoxicity of molybdenum disulfide and improves the biocompatibility.

[0017] In some embodiments, the mass ratio of acrylamide to sodium alginate in step S1 is (5-8):1.

[0018] In some embodiments, the mass ratio of the sodium alginate derivative to the modified high-density polyethylene in step S2 is 1:(0.5-1.3).

[0019] In some embodiments, the preparation method of the modified high-density polyethylene in step S2 comprises the following steps:

[0020] Q1. Mix furan sugar acid-γ-lactone and deionized water, heat to 85-95℃, and stir for 1.5-3h to obtain a reaction solution;

[0021] Q2. The high-density polyethylene, a 3-7% potassium permanganate aqueous solution, is added to a closed high-pressure reaction kettle, stirred, heated to 65-80°C, reacted for 5-10 min, filtered, washed, and the reaction solution obtained in step Q1, p-toluenesulfonic acid, is added, stirred, heated to 140-150°C, reacted for 1-2 h, filtered, washed, and dried to obtain the modified high-density polyethylene.

[0022] In some embodiments, the mass ratio of the high-density polyethylene and the potassium permanganate aqueous solution is 1: (0.7-1.4).

[0023] In some embodiments, the mass ratio of the furan uronic acid-gamma-lactone and the high-density polyethylene is (0.35-0.6): 1.

[0024] In some embodiments, the particle size of the high-density polyethylene is 60-200 mesh.

[0025] In some embodiments, the mass ratio of the CeO2 / MoS2 functional material, sodium alginate, and sodium alginate composite in step S3 is (0.1-0.2): 1: (1-2.5).

[0026] In some embodiments, the preparation method of the CeO2 / MoS2 functional material in step S3 comprises the following steps:

[0027] R1. The nano-molybdenum disulfide is prepared by mixing ammonium molybdate tetrahydrate and thiourea and hydrothermal reaction;

[0028] R2. The nano-molybdenum disulfide obtained in step R1, cerium nitrate hexahydrate, and deionized water are mixed and ultrasonically dispersed, hydrochloric acid is added, heated to 90-95°C, stirred and reacted for 10-25 min, cooled, washed, and dried to obtain the CeO2 / MoS2 nanomaterial;

[0029] R3. The CeO2 / MoS2 nanomaterial obtained in step R2, N-aminoethyl-3-aminopropyl triethoxysilane, anhydrous ethanol, and nitric acid are mixed, heated and ultrasonically dispersed, washed, and dried to obtain the CeO2 / MoS2 functional material.

[0030] In some embodiments, the specific steps of step R1 are as follows:

[0031] The ammonium molybdate tetrahydrate, thiourea, and deionized water are added to a closed reaction kettle, ultrasonically treated at 100-200 W for 20-45 min, heated to 180-210°C, reacted for 16-24 h, cooled, centrifuged once, and the precipitate is washed with deionized water for 3-4 times, then dispersed with deionized water, centrifuged twice, and the upper liquid is taken and dried to obtain the nano-molybdenum disulfide.

[0032] In some embodiments, the ratio of CeO2 / MoS2 nanomaterial and N-aminoethyl-3-aminopropyltriethoxysilane in step R3 is 1 g: (6-10) mL.

[0033] In another aspect, the present invention provides a composite adsorbent material obtained by the above preparation method.

[0034] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0035] 1. The composite adsorbent material of the present invention has good mechanical stability, can withstand long-term hydraulic shock in the dialysis column, and has a fast adsorption rate and high adsorption capacity for uremic toxins. It also has good biocompatibility and blood compatibility, and has good market prospects in the field of hemodialysis.

[0036] 2. This invention solves the problems of brittleness, poor fatigue resistance and creep resistance of sodium alginate by introducing acrylamide and modified high-density polyethylene, thereby improving mechanical stability. At the same time, the functional modification of CeO2 / MoS2 nanomaterials improves adsorption performance and biocompatibility. Detailed Implementation

[0037] The present invention will be described below with reference to specific embodiments. It should be noted that the following embodiments are examples of the present invention and are used only to illustrate the invention, not to limit it. Other combinations and various modifications within the scope of the present invention can be made without departing from its spirit or scope.

[0038] Each composite adsorbent material was prepared according to the proportions and preparation methods of the raw materials specified in the following examples and comparative examples.

[0039] To facilitate implementation of this invention by those skilled in the art, the manufacturers of some raw materials for the embodiments and comparative examples are described below:

[0040] Sodium alginate: purchased from Shaanxi Panlong Yihai Pharmaceutical Co., Ltd.;

[0041] High-density polyethylene: purchased from Dongguan Nabaichuan Plastics Co., Ltd., particle size 100 mesh;

[0042] Unless otherwise specified, all other raw materials can be purchased from the market.

[0043] Preparation Example 1

[0044] The preparation method of modified high-density polyethylene A includes the following steps:

[0045] Q1. Mix 4.8g of furanuronic acid-γ-lactone with 200mL of deionized water, heat to 90℃, and stir for 2.5h to obtain the reaction solution;

[0046] Q2. 10 g of high-density polyethylene and 10.5 g of a 5% potassium permanganate aqueous solution were added into a sealed high-pressure reaction kettle, stirred uniformly, heated to 70°C, reacted for 8 min, filtered, washed with deionized water for 3 times, 10 g of the reaction solution obtained in step Q1, 0.08 g of p-toluenesulfonic acid were added, stirred uniformly, heated to 145°C, reacted for 1.5 h, filtered, washed with deionized water for 3 times first, and then washed with ethanol for 3 times, vacuum dried at 90°C and -0.05 MPa for 10 min to obtain modified high-density polyethylene A.

[0047] Preparation Example 2

[0048] The preparation method of modified high-density polyethylene B was the same as that in Preparation Example 1, except that the amount of the 5% potassium permanganate aqueous solution added was 6.5 g.

[0049] Preparation Example 3

[0050] The preparation method of modified high-density polyethylene C was the same as that in Preparation Example 1, except that the amount of furan carboxylic acid-γ-lactone added was 3.2 g.

[0051] Preparation Example 4

[0052] The preparation method of CeO2 / MoS2 functional material A comprises the following steps:

[0053] R1. 1.5 g of ammonium molybdate tetrahydrate, 3.15 g of thiourea and 50 mL of deionized water were added into a sealed reaction kettle, ultrasonicated at 150 W for 35 min, heated to 200°C, reacted for 20 h, cooled to room temperature, centrifuged at 12000 rpm for 30 min, the precipitate was washed with deionized water for 4 times, then dispersed with deionized water, centrifuged at 4500 rpm for 15 min, the upper liquid was taken, and dried at 60°C for 48 h to obtain nanometer molybdenum disulfide;

[0054] R2. 1 g of nanometer molybdenum disulfide, 0.37 g of cerium nitrate hexahydrate and 200 mL of deionized water obtained in step R1 were mixed, ultrasonically dispersed for 8 min, 5 mL of 0.12 mol / L hydrochloric acid was added, heated to 95°C, stirred and reacted for 15 min, cooled to room temperature, washed with anhydrous ethanol for 3 times, washed with deionized water for 3 times, and dried at 60°C for 16 h to obtain CeO2 / MoS2 nanomaterial;

[0055] R3. 1 g of CeO2 / MoS2 nanomaterial, 8 mL of N-aminoethyl-3-aminopropyl triethoxysilane, 60 mL of anhydrous ethanol and 0.5 mL of 30 wt% nitric acid solution obtained in step R2 were mixed, heated to 60°C, ultrasonicated at 150 W for 20 min, washed with deionized water for 2 times first, then washed with ethanol for 2 times, and dried at 75°C for 8 h to obtain CeO2 / MoS2 functional material A.

[0056] Preparation Example 5

[0057] A preparation method of the CeO2 / MoS2 functional material B comprises the following steps:

[0058] R1. 1.5 g of ammonium molybdate tetrahydrate, 3.15 g of thiourea, and 50 mL of deionized water were added to a sealed reaction kettle, ultrasonic treatment was performed at 150 W for 35 min, heating was performed at 200℃, reaction was performed for 20 h, cooling was performed to room temperature, centrifugation was performed at 12000 rpm for 30 min, the precipitate was washed with deionized water for 4 times, and then dispersed with deionized water, centrifugation was performed at 4500 rpm for 15 min, the supernatant was taken, and drying was performed at 60℃ for 48 h to obtain nanometer molybdenum disulfide;

[0059] R2. 1 g of the nanometer molybdenum disulfide obtained in step R1, 0.37 g of cerium nitrate hexahydrate, and 200 mL of deionized water were mixed, ultrasonic dispersion was performed for 8 min, 5 mL of 0.12 mol / L hydrochloric acid was added, heating was performed to 95℃, stirring reaction was performed for 15 min, cooling was performed to room temperature, washing was performed with anhydrous ethanol for 3 times, washing was performed with deionized water for 3 times, and drying was performed at 60℃ for 16 h to obtain the CeO2 / MoS2 functional material B.

[0060] Preparation Example 6

[0061] A preparation method of the CeO2 / MoS2 functional material C is the same as that in the preparation example 4, except that the amount of N-aminoethyl-3-aminopropyl triethoxysilane added is 5.5 mL.

[0062] Example 1

[0063] A preparation method of a composite adsorption material for uremia comprises the following steps:

[0064] S1. 32.5 g of acrylamide, 0.15 g of N,N'-methylenebisacrylamide, 10 mL of glycerol, and 275 mL of deionized water were mixed and stirred uniformly, 5 g of sodium alginate was added and stirred to dissolve, 0.1 g of ammonium persulfate, 1 g of calcium sulfate, and 0.05 mL of tetramethyl ethylenediamine were sequentially added, stirring and ultrasonic treatment were performed for 5 min, heating was performed to 65℃, and reaction was performed for 1.5 h to obtain a sodium alginate derivative;

[0065] S2. 3 g of the sodium alginate derivative obtained in step S1 and 30 mL of deionized water were mixed, 2.7 g of modified high-density polyethylene A was added and stirred uniformly, and then the mixture was immersed in a 3 wt% CaCl2 solution for crosslinking for 2 h to obtain a sodium alginate composite material;

[0066] S3. 0.45 g of CeO2 / MoS2 functional material A, 3 g of sodium alginate, 100 mL of deionized water were mixed, 5.25 g of sodium alginate composite material obtained in step S2 was added and stirred for 10 min, a hydrophobic PTFE microporous plate (pore size 0.8 cm) mold was used for shaping, then it was immersed in a 3wt% CaCl2 solution for crosslinking for 2 h, washed with deionized water for 3 times, freeze-dried at -20℃ for 18 h to obtain a composite adsorption material.

[0067] Example 2

[0068] A preparation method of a composite adsorption material for uremia, comprising the following steps:

[0069] S1. 25 g of acrylamide, 0.15 g of N,N'-methylene bisacrylamide, 10 mL of glycerol and 220 mL of deionized water were mixed, stirred uniformly, 5 g of sodium alginate was added, stirred and dissolved, then 0.1 g of ammonium persulfate, 1 g of calcium sulfate, 0.05 mL of tetramethyl ethylenediamine were added in sequence, stirred uniformly and ultrasonically treated for 5 min, heated to 70℃ for reaction for 1 h to obtain a sodium alginate derivative;

[0070] S2. 3 g of the sodium alginate derivative obtained in step S1, 30 mL of deionized water were mixed, 1.5 g of modified high-density polyethylene A was added and stirred uniformly, then it was immersed in a 2.5wt% CaCl2 solution for crosslinking for 2.5 h to obtain a sodium alginate composite material;

[0071] S3. 0.3 g of CeO2 / MoS2 functional material A, 3 g of sodium alginate, 100 mL of deionized water were mixed, 3 g of the sodium alginate composite material obtained in step S2 was added and stirred for 10 min, a hydrophobic PTFE microporous plate (pore size 0.8 cm) mold was used for shaping, then it was immersed in a 2.5wt% CaCl2 solution for crosslinking for 2.5 h, washed with deionized water for 3 times, freeze-dried at -20℃ for 18 h to obtain a composite adsorption material.

[0072] Example 3

[0073] A preparation method of a composite adsorption material for uremia, comprising the following steps:

[0074] S1. 40 g of acrylamide, 0.15 g of N,N'-methylene bisacrylamide, 10 mL of glycerol and 330 mL of deionized water were mixed, stirred uniformly, 5 g of sodium alginate was added, stirred and dissolved, then 0.1 g of ammonium persulfate, 1 g of calcium sulfate, 0.05 mL of tetramethyl ethylenediamine were added in sequence, stirred uniformly and ultrasonically treated for 5 min, heated to 55℃ for reaction for 2 h to obtain a sodium alginate derivative;

[0075] S2. 3 g of sodium alginate derivative obtained in step S1, 30 mL of deionized water, 3.9 g of modified high-density polyethylene A were mixed, stirred uniformly, and then immersed in a 4 wt% CaCl2 solution for crosslinking for 1.5 h to obtain a sodium alginate composite material;

[0076] S3. 0.6 g of CeO2 / MoS2 functional material A, 3 g of sodium alginate, and 100 mL of deionized water were mixed, 7.5 g of the sodium alginate composite material obtained in step S2 was added and stirred for 10 min, a hydrophobic PTFE microporous plate (pore size 0.8 cm) mold was used for shaping, and then the shaped product was immersed in a 4 wt% CaCl2 solution for crosslinking for 1.5 h, washed with deionized water for 3 times, and freeze-dried at -20℃ for 18 h to obtain a composite adsorption material.

[0077] Example 4

[0078] A preparation method of a composite adsorption material for uremia was the same as that in Example 1, except that an equal amount of modified high-density polyethylene B was used to replace modified high-density polyethylene A.

[0079] Example 5

[0080] A preparation method of a composite adsorption material for uremia was the same as that in Example 1, except that an equal amount of modified high-density polyethylene C was used to replace modified high-density polyethylene A.

[0081] Example 6

[0082] A preparation method of a composite adsorption material for uremia was the same as that in Example 1, except that an equal amount of CeO2 / MoS2 functional material B was used to replace CeO2 / MoS2 functional material A.

[0083] Example 7

[0084] A preparation method of a composite adsorption material for uremia was the same as that in Example 1, except that an equal amount of CeO2 / MoS2 functional material C was used to replace CeO2 / MoS2 functional material A.

[0085] Example 8

[0086] A preparation method of a composite adsorption material for uremia was the same as that in Example 1, except that the amount of acrylamide added was 22.5 g.

[0087] Example 9

[0088] A preparation method of a composite adsorption material for uremia was the same as that in Example 1, except that the amount of modified high-density polyethylene A added was 1.2 g.

[0089] Example 10

[0090] A preparation method of a composite adsorption material for uremia is the same as that in Example 1, except that the addition amount of the CeO2 / MoS2 functional material A is 0.15 g.

[0091] Comparative Example 1

[0092] A preparation method of a composite adsorption material for uremia is the same as that in Example 1, except that the modified high-density polyethylene A is replaced by an equal amount of commercially available high-density polyethylene.

[0093] Effect evaluation:

[0094] The composite adsorption materials prepared in Examples 1-10 and Comparative Example 1 are tested and analyzed, and the specific results are shown in Tables 1-2.

[0095] Performance test:

[0096] I. Adsorption performance

[0097] 10 ml of blood plasma solution containing urea and creatinine is taken respectively, 5 g of the composite adsorption material prepared in Examples 1-10 and Comparative Example 1 is added, sealed, and shaken for 2 h and 24 h respectively at 37°C and 150 rpm in a shaking bed. After the adsorption is completed, the changes of each toxin are measured, the adsorption rate and mechanical stability of the adsorbent to each toxin are calculated from the concentration difference before and after the adsorption, and the average value is taken after repeating three times.

[0098] Table 1

[0099]

[0100] From the results in Table 1, it can be seen that the composite adsorption materials prepared in Examples 1-3 have good adsorption performance and mechanical stability for urea and creatinine.

[0101] Compared with Example 1, Example 4 changes the mass ratio of high-density polyethylene to potassium permanganate aqueous solution in the preparation of modified high-density polyethylene, which is insufficient in oxidation sites and may leave unoxidized crystal regions, which is not conducive to the subsequent modification of furan sugar acid-γ-lactone. In Example 5, the mass ratio of furan sugar acid-γ-lactone to high-density polyethylene is changed in the preparation of modified high-density polyethylene, which is insufficient in surface grafting of high-density polyethylene. In Comparative Example 1, an equal amount of commercially available high-density polyethylene is used to replace the modified high-density polyethylene A, which further makes the modification degree of high-density polyethylene low and the dispersity poor in Examples 4-5 and Comparative Example 1, and finally makes the mechanical stability of the composite material poor, cracks may occur during long-term dialysis, and thus the adsorption rate of the composite adsorption material during long-term dialysis is affected.

[0102] Compared with Example 1, Example 6 does not graft N-aminoethyl-3-aminopropyl triethoxysilane when preparing CeO2 / MoS2 functional material, and Example 7 changes the ratio of CeO2 / MoS2 composite nanomaterial and N-aminoethyl-3-aminopropyl triethoxysilane when preparing CeO2 / MoS2 functional material. Both of them reduce the amino active groups, which not only reduces the adsorption of uremia toxins, but also reduces the biocompatibility, thereby affecting the stability during long-term dialysis.

[0103] Compared with Example 1, Example 8 changes the mass ratio of acrylamide and sodium alginate, which reduces the effective sites, reduces the adsorption rate, and makes the gel elasticity poor and easy to break, thereby affecting the adsorption rate of the composite adsorption material during long-term dialysis.

[0104] Compared with Example 1, Example 9 changes the mass ratio of sodium alginate derivative and modified high-density polyethylene, which makes the skeleton of the composite adsorption material sparse and easy to creep and break, thereby reducing the urea / cratin clearance rate during long-term dialysis.

[0105] Compared with Example 1, Example 10 changes the mass ratio of CeO2 / MoS2 functional material, sodium alginate and sodium alginate composite material, which significantly reduces the adsorption capacity and clearance rate.

[0106] II. Blood compatibility

[0107] The composite adsorption materials prepared in Examples 1-3, 6-8 were soaked in normal saline for 30 min, the surface water was filtered and dried by a sand core funnel, 1 g of adsorbent was added to 5 ml of freshly provided human blood, and then the mixture was placed in a 37℃ water bath for constant temperature, and then taken out after 2 h to measure the blood cell change on a blood cell analyzer, and the average value was obtained by repeating three times.

[0108] Table 2

[0109]

[0110] As shown in Table 2, the composite adsorption materials prepared in Examples 1-3 have good blood compatibility.

[0111] Compared with Example 1, Example 6 does not graft N-aminoethyl-3-aminopropyl triethoxysilane when preparing CeO2 / MoS2 functional material, and Example 7 changes the ratio of CeO2 / MoS2 composite nanomaterial and N-aminoethyl-3-aminopropyl triethoxysilane when preparing CeO2 / MoS2 functional material. Both of them reduce the amino active groups, which reduces the negative charge shielding effect and reduces the blood compatibility.

[0112] Example 8 changed the mass ratio of acrylamide and sodium alginate compared to Example 1, the gel elasticity is poor, the particles are easily broken under the shear of blood flow or extracorporeal circulation, generating micron-sized debris, which in turn exhibits a decrease in blood compatibility.

[0113] The above is only the preferred embodiment of the present application, and does not limit the present application in any form. Although the present application is disclosed as above with the preferred embodiment, it is not intended to limit the present application. Any person skilled in the art, without departing from the scope of the technical solution of the present application, can make some changes or modifications to the above disclosed technical content, which are equivalent to equivalent embodiments. Any simple modification, equivalent change and modification of the above embodiments made according to the technical essence of the present application, without departing from the technical solution content of the present application, still belong to the scope of the technical solution.

Claims

1. A method for preparing a composite adsorbent material for uremia, characterized by, The method comprises the following steps: S1. Mix acrylamide, N,N'-methylenebisacrylamide, glycerol and deionized water, stir, add sodium alginate, stir to dissolve, then add ammonium persulfate, calcium sulfate, tetramethyl ethylenediamine in sequence, stir, ultrasonic, heat to 55-70 DEG C reaction 1-2h, to obtain sodium alginate derivative; S2. Mix the sodium alginate derivative obtained in step S1 with deionized water, add modified high-density polyethylene, stir, then immerse it in a 2.5-4wt% CaCl2 solution for crosslinking for 1.5-2.5h to obtain a sodium alginate composite material; S3. Mix CeO2 / MoS2 functional material, sodium alginate and deionized water, add the sodium alginate composite material obtained in step S2 and stir, then immerse it in a 2.5-4wt% CaCl2 solution for crosslinking for 1.5-2.5h after shaping, wash, freeze-dry to obtain a composite adsorption material; The preparation method of the modified high-density polyethylene in step S2 comprises the following steps: Q1. Mix furan sugar acid-gamma-lactone and deionized water, heat to 85-95 DEG C, stir for 1.5-3h to obtain a reaction solution; Q2. Add high-density polyethylene and 3-7% potassium permanganate aqueous solution to a closed high-pressure reaction kettle, stir, heat to 65-80 DEG C, react for 5-10min, filter, wash, add the reaction solution obtained in step Q1 and p-toluenesulfonic acid, stir, heat to 140-150 DEG C and react for 1-2h, filter, wash, dry to obtain modified high-density polyethylene; The preparation method of the CeO2 / MoS2 functional material in step S3 comprises the following steps: R1. Mix ammonium molybdate tetrahydrate and thiourea, and hydrothermally react to obtain nanometer molybdenum disulfide; R2. Mix the nanometer molybdenum disulfide obtained in step R1, cerium nitrate hexahydrate and deionized water, ultrasonic dispersion, add hydrochloric acid, heat to 90-95 DEG C, stir and react for 10-25min, cool, wash, dry to obtain CeO2 / MoS2 nanomaterial; R3. Mix the CeO2 / MoS2 nanomaterial obtained in step R2, N-aminoethyl-3-aminopropyl triethoxysilane, anhydrous ethanol and nitric acid, heat and ultrasonic, wash, dry to obtain CeO2 / MoS2 functional material.

2. The method for preparing a composite adsorbent material for uremia according to claim 1, characterized in that, The mass ratio of acrylamide to sodium alginate in step S1 is (5-8):

1.

3. The method of claim 1, wherein the composite adsorbent material is prepared by the steps of: mixing a base material with a binder; and heating the mixture to a temperature of 500-800°C for 1-3 hours. The mass ratio of sodium alginate derivative to modified high-density polyethylene in step S2 is 1:(0.5-1.3).

4. The method for preparing a composite adsorbent material for uremia according to claim 1, characterized in that, The mass ratio of high-density polyethylene to potassium permanganate aqueous solution is 1:(0.7-1.4).

5. The method for preparing a composite adsorbent material for uremia according to claim 1, characterized in that, The mass ratio of furan sugar acid-gamma-lactone to high-density polyethylene is (0.35-0.6):

1.

6. The method of claim 1, wherein the composite adsorbent material is prepared by the steps of: mixing a base material with a binder; and heating the mixture to a temperature of 500-800°C for 1-3 hours. The mass ratio of CeO2 / MoS2 functional material, sodium alginate and sodium alginate composite material in step S3 is (0.1-0.2):1:(1-2.5).

7. The method for preparing a composite adsorbent material for uremia according to claim 1, characterized in that, The amount ratio of CeO2 / MoS2 nanomaterial to N-aminoethyl-3-aminopropyl triethoxysilane in step R3 is 1g:(6-10)mL.

8. The composite adsorbent material produced by the method of any one of claims 1-7.

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