Antibacterial hemodialysis membrane containing rare earth elements and preparation process of antibacterial hemodialysis membrane

Abstract

The invention discloses an antibacterial hemodialysis membrane containing rare earth elements and a preparation process of the antibacterial hemodialysis membrane, relates to the technical field of biological materials, and aims to improve human body affinity of the hemodialysis membrane and avoid adsorption of the hemodialysis membrane to human body protein in the dialysis process. In the preparation process of the dialysis membrane, a polyurethane system with a sulfonic acid group is introduced into the polyethersulfone resin for modification, the introduction of the sulfonic acid group can effectively improve the hydrophilicity of the membrane and inhibit the adsorption effect of protein, and the sulfonic acid group carries negative charges, so that the effect of thrombin in blood can be effectively inhibited to prevent blood coagulation, and the dialysis membrane has a good application prospect. The hemolysis and protein adsorption phenomena of blood in the dialysis process are avoided, the damage of dialysis to a human body is reduced, and nano-silver particles with an antibacterial function and samarium trichloride capable of promoting cell viability are also added in the process of preparing the dialysis membrane, so that the hemolysis and protein adsorption phenomena of the blood in the dialysis process are avoided; and the damage possibly caused by dialysis to the human body is further reduced.

Description

Technical Field

[0001] This invention relates to the field of biomaterials technology, specifically to an antibacterial hemodialysis membrane containing rare earth elements and its preparation process. Background Technology

[0002] Kidney failure is a clinical syndrome caused by the loss of kidney function, which leads to a series of symptoms and metabolic disorders. For patients with kidney failure, the kidneys are no longer able to handle the metabolic waste products such as urea produced by the body, so dialysis is often required to remove toxins from the body. Currently, hemodialysis mostly uses the principle of semi-permeable membranes, utilizing concentration gradients and osmotic gradients to purify human blood. In this process, blood is drawn from the body, purified through the dialysis membrane, and then returned to the body. However, due to material limitations, the composition of hemodialysis membranes differs from that of human blood vessels. During dialysis, various proteins in the blood are often adsorbed and remain on the surface of the dialysis membrane, causing a decrease in dialysis efficiency and hemolysis. This results in a loss of beneficial components in the human blood after dialysis. Samarium trichloride, as a rare earth element, can effectively improve cell activity and accelerate the body's recovery after dialysis. Therefore, it is necessary to develop a hemodialysis membrane with low protein adsorption and that can provide rare earth elements to the human body to meet the needs of kidney disease patients. Summary of the Invention

[0003] The purpose of this invention is to provide an antibacterial hemodialysis membrane containing rare earth elements and its preparation process, so as to solve the problems raised in the prior art.

[0004] To achieve the above objectives, the present invention provides the following technical solution: a preparation process for an antibacterial hemodialysis membrane containing rare earth elements, comprising the following steps: S1. Preparation of spinning solution; S11. Add polycaprolactone triol to N,N-dimethylformamide, heat to 105-125℃, stir for 25-30 min, cool to room temperature, add hexamethylene diisocyanate and dibutyltin dilaurate, heat to 75-78℃, stir and react for 12-24 h, remove excess solvent by rotary evaporation to obtain polyurethane prepolymer; S12. 6-Sulfonopyridine-2-carboxylic acid was dispersed in N,N-dimethylacetamide under a nitrogen atmosphere. p-Toluenesulfonic acid was added to the mixture and mixed thoroughly. Then, it was added dropwise to 1,5-hexadien-3,4-diol. The temperature was raised to 105-110℃ and the reaction was stirred for 8-12 hours. Excess solvent was removed by rotary evaporation to obtain the double bond sulfonic acid intermediate. S13. Under nitrogen atmosphere protection, the double bond sulfonic acid intermediate is mixed with butanediol, then diluted with N,N-dimethylformamide and mixed evenly. Polyurethane prepolymer and dibutyltin dilaurate are added to the mixture. Under nitrogen atmosphere protection, the temperature is raised to 80-85℃ and the reaction continues for 6-12 hours. Then, an initiator and vinyl sulfonic acid are added, the temperature is raised to 85-95℃, and the reaction continues for 8-16 hours. Excess solvent is removed by rotary evaporation, and the mixture is washed 2-3 times with deionized water and vacuum dried to constant weight to obtain the anti-coating polyurethane modifier. S14. Disperse the anti-coagulation polyurethane modifier into N-methylpyrrolidone, stir and mix evenly, then add nano samarium trichloride, nano silver, polyethersulfone resin and carboxymethyl cellulose, stir and mix evenly, and then defoam under vacuum to obtain the spinning solution. S2. Using a dry-wet spinning method, the spinning solution is extruded through a spinneret to form a hollow fiber membrane. The resulting membrane is washed with physiological saline and then dried with hot air at 105-120℃ to obtain an antibacterial hemodialysis membrane containing rare earth elements.

[0005] Furthermore, in step S11, the Mw of the polycaprolactone triol is 500-1000; The mass ratio of polycaprolactone triol, hexamethylene diisocyanate, and dibutyltin dilaurate is 1:(0.48-1):(0.001-0.003).

[0006] Furthermore, in step S12, the mass ratio of 6-sulfonic acid pyridine-2-carboxylic acid, p-toluenesulfonic acid, and 1,5-hexadien-3,4-diol is 1:(0.003-0.006):(0.4-0.6).

[0007] Furthermore, in step S13, the mass ratio of the double bond sulfonic acid intermediate, butanediol, polyurethane prepolymer and dibutyltin dilaurate is (0.06-0.1):(0.115-0.124):1:(0.001-0.002).

[0008] Furthermore, in step S13, the mass ratio of the polyurethane prepolymer, initiator and vinyl sulfonic acid is 1:(0.0001-0.001):(0.02-0.04).

[0009] Furthermore, in step S13, the initiator is azobisisobutyronitrile.

[0010] Furthermore, in step S14, the spinning solution, by weight, is composed of 1-4 parts of anticoagulant polyurethane modifier, 0.1-0.8 parts of nano samarium trichloride, 0.3-1.5 parts of nano silver, 40-60 parts of polyethersulfone resin, 8-12 parts of carboxymethyl cellulose and 200-300 parts of N-methylpyrrolidone.

[0011] Furthermore, in step S14, the viscosity-average molecular weight of the polyethersulfone resin is 40,000-120,000.

[0012] Furthermore, an antibacterial hemodialysis membrane containing rare earth elements is prepared by the above method.

[0013] Compared with the prior art, the beneficial effects of the present invention are: In order to improve the biocompatibility of the hemodialysis membrane and avoid the adsorption of human proteins by the dialysis membrane during the dialysis process, the present invention modifies the dialysis membrane during its preparation. This invention first uses polycaprolactone triol and hexamethylene diisocyanate as raw materials to prepare an isocyanate-terminated polyurethane prepolymer. Then, it uses 6-sulfonic acid-containing pyridine-2-carboxylic acid as a raw material and reacts it with 1,5-hexadien-3,4-diol to prepare a double-bonded sulfonic acid intermediate containing sulfonic acid groups, alcohol hydroxyl groups, and olefin double bonds. This intermediate is then mixed with butanediol and reacted again with the polyurethane prepolymer, thereby introducing sulfonic acid groups into the polyurethane system. Furthermore, this invention also uses vinyl sulfonic acid and double-bonded... The polyurethane reaction further introduces sulfonic acid groups into the polyurethane system. The introduction of sulfonic acid groups can effectively improve the hydrophilicity of the membrane and inhibit the adsorption of proteins. In addition, the sulfonic acid groups have a negative charge, which can effectively inhibit the action of thrombin in the blood and prevent blood coagulation, thereby avoiding hemolysis and adsorption during the dialysis process and reducing the damage caused by dialysis to the human body. Furthermore, this invention also adds antibacterial silver nanoparticles and samarium trichloride, which can promote cell activity, during the preparation of the dialysis membrane, further reducing the potential damage of dialysis to the human body. Detailed Implementation

[0014] Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0015] The polycaprolactone triol used in this application has a molecular weight of MW=550; the nano silver used is commercially available AgPO1 type nano silver with a particle size of 80-90nm; and the polyethersulfone resin used has a viscosity-average molecular weight of 60000. Example 1. A preparation process for an antibacterial hemodialysis membrane containing rare earth elements, comprising the following steps: S1. Preparation of spinning solution; S11. By weight, add 1 part of polycaprolactone triol to N,N-dimethylformamide, heat to 115°C, stir for 30 min, cool to room temperature, add 0.48 parts of hexamethylene diisocyanate and 0.002 parts of dibutyltin dilaurate, heat to 75°C, stir and react for 18 h, remove excess solvent by rotary evaporation to obtain polyurethane prepolymer; S12. By weight, 1 part of 6-sulfonylpyridine-2-carboxylic acid was dispersed in N,N-dimethylacetamide under a nitrogen atmosphere. 0.005 parts of p-toluenesulfonic acid were added and mixed thoroughly. Then, the mixture was added dropwise to 0.4 parts of 1,5-hexadien-3,4-diol. The mixture was heated to 108°C and stirred for 10 hours. Excess solvent was removed by rotary evaporation to obtain the double-bonded sulfonic acid intermediate. S13. Under nitrogen atmosphere protection, 0.06 parts by weight of double bond sulfonic acid intermediate and 0.12 parts by weight of butanediol were mixed, diluted with N,N-dimethylformamide, and mixed evenly. Then, 1 part of polyurethane prepolymer and 0.002 parts of dibutyltin dilaurate were added. Under nitrogen atmosphere protection, the temperature was raised to 85°C and the reaction was continued for 8 hours. Then, 0.001 parts of azobisisobutyronitrile initiator and 0.02 parts of vinyl sulfonic acid were added. The temperature was raised to 95°C and the reaction was continued for 16 hours. After removing excess solvent by rotary evaporation, the mixture was washed twice with deionized water and vacuum dried to constant weight to obtain the anti-coating polyurethane modifier. S14. By weight, disperse 1 part of anti-coagulation polyurethane modifier into 200 parts of N-methylpyrrolidone, stir and mix evenly, then add 0.3 parts of nano samarium trichloride, 0.5 parts of nano silver, 50 parts of polyethersulfone resin and 10 parts of carboxymethyl cellulose, stir and mix evenly, and then defoam under vacuum to obtain spinning solution. S2. Using a dry-wet spinning method, the spinning solution is extruded through a spinneret to form a hollow fiber membrane. The resulting membrane is washed with physiological saline and then dried with hot air at 115°C to obtain an antibacterial hemodialysis membrane containing rare earth elements.

[0016] Example 2. A preparation process for an antibacterial hemodialysis membrane containing rare earth elements, comprising the following steps: Compared with Example 1, this example increases the amount of 1,5-hexadien-3,4-diol added in step S12; S1. Preparation of spinning solution; S11. By weight, add 1 part of polycaprolactone triol to N,N-dimethylformamide, heat to 115°C, stir for 30 min, cool to room temperature, add 0.48 parts of hexamethylene diisocyanate and 0.002 parts of dibutyltin dilaurate, heat to 75°C, stir and react for 18 h, remove excess solvent by rotary evaporation to obtain polyurethane prepolymer; S12. By weight, 1 part of 6-sulfonic acid pyridine-2-carboxylic acid was dispersed in N,N-dimethylacetamide under a nitrogen atmosphere. 0.005 parts of p-toluenesulfonic acid were added and mixed thoroughly. Then, the mixture was added dropwise to 0.6 parts of 1,5-hexadien-3,4-diol. The mixture was heated to 108°C and stirred for 10 hours. Excess solvent was removed by rotary evaporation to obtain the double bond sulfonic acid intermediate. S13. Under nitrogen atmosphere protection, 0.06 parts by weight of double bond sulfonic acid intermediate and 0.12 parts by weight of butanediol were mixed, diluted with N,N-dimethylformamide, and mixed evenly. Then, 1 part of polyurethane prepolymer and 0.002 parts of dibutyltin dilaurate were added. Under nitrogen atmosphere protection, the temperature was raised to 85°C and the reaction was continued for 8 hours. Then, 0.001 parts of azobisisobutyronitrile initiator and 0.02 parts of vinyl sulfonic acid were added. The temperature was raised to 95°C and the reaction was continued for 16 hours. After removing excess solvent by rotary evaporation, the mixture was washed twice with deionized water and vacuum dried to constant weight to obtain the anti-coating polyurethane modifier. S14. By weight, disperse 1 part of anti-coagulation polyurethane modifier into 200 parts of N-methylpyrrolidone, stir and mix evenly, then add 0.3 parts of nano samarium trichloride, 0.5 parts of nano silver, 50 parts of polyethersulfone resin and 10 parts of carboxymethyl cellulose, stir and mix evenly, and then defoam under vacuum to obtain spinning solution. S2. Using a dry-wet spinning method, the spinning solution is extruded through a spinneret to form a hollow fiber membrane. The resulting membrane is washed with physiological saline and then dried with hot air at 115°C to obtain an antibacterial hemodialysis membrane containing rare earth elements.

[0017] Example 3. A preparation process for an antibacterial hemodialysis membrane containing rare earth elements, comprising the following steps: Compared with Example 2, this example increases the amount of double bond sulfonic acid intermediate added in step S13; S1. Preparation of spinning solution; S11. By weight, add 1 part of polycaprolactone triol to N,N-dimethylformamide, heat to 115°C, stir for 30 min, cool to room temperature, add 0.48 parts of hexamethylene diisocyanate and 0.002 parts of dibutyltin dilaurate, heat to 75°C, stir and react for 18 h, remove excess solvent by rotary evaporation to obtain polyurethane prepolymer; S12. By weight, 1 part of 6-sulfonic acid pyridine-2-carboxylic acid was dispersed in N,N-dimethylacetamide under a nitrogen atmosphere. 0.005 parts of p-toluenesulfonic acid were added and mixed thoroughly. Then, the mixture was added dropwise to 0.6 parts of 1,5-hexadien-3,4-diol. The mixture was heated to 108°C and stirred for 10 hours. Excess solvent was removed by rotary evaporation to obtain the double bond sulfonic acid intermediate. S13. Under nitrogen atmosphere protection, 0.1 parts by weight of double bond sulfonic acid intermediate and 0.12 parts by weight of butanediol were mixed, diluted with N,N-dimethylformamide, and mixed evenly. Then, 1 part of polyurethane prepolymer and 0.002 parts of dibutyltin dilaurate were added. Under nitrogen atmosphere protection, the mixture was heated to 85°C and reacted for 8 hours. Then, 0.001 parts of azobisisobutyronitrile initiator and 0.02 parts of vinyl sulfonic acid were added. The mixture was heated to 95°C and reacted for 16 hours. Excess solvent was removed by rotary evaporation. The mixture was washed twice with deionized water and vacuum dried to constant weight to obtain the anti-coating polyurethane modifier. S14. By weight, disperse 1 part of anti-coagulation polyurethane modifier into 200 parts of N-methylpyrrolidone, stir and mix evenly, then add 0.3 parts of nano samarium trichloride, 0.5 parts of nano silver, 50 parts of polyethersulfone resin and 10 parts of carboxymethyl cellulose, stir and mix evenly, and then defoam under vacuum to obtain spinning solution. S2. Using a dry-wet spinning method, the spinning solution is extruded through a spinneret to form a hollow fiber membrane. The resulting membrane is washed with physiological saline and then dried with hot air at 115°C to obtain an antibacterial hemodialysis membrane containing rare earth elements.

[0018] Example 4. A preparation process for an antibacterial hemodialysis membrane containing rare earth elements, comprising the following steps: Compared with Example 3, this example increases the amount of vinyl sulfonic acid added in step S13; S1. Preparation of spinning solution; S11. By weight, add 1 part of polycaprolactone triol to N,N-dimethylformamide, heat to 115°C, stir for 30 min, cool to room temperature, add 0.48 parts of hexamethylene diisocyanate and 0.002 parts of dibutyltin dilaurate, heat to 75°C, stir and react for 18 h, remove excess solvent by rotary evaporation to obtain polyurethane prepolymer; S12. By weight, 1 part of 6-sulfonic acid pyridine-2-carboxylic acid was dispersed in N,N-dimethylacetamide under a nitrogen atmosphere. 0.005 parts of p-toluenesulfonic acid were added and mixed thoroughly. Then, the mixture was added dropwise to 0.6 parts of 1,5-hexadien-3,4-diol. The mixture was heated to 108°C and stirred for 10 hours. Excess solvent was removed by rotary evaporation to obtain the double bond sulfonic acid intermediate. S13. Under nitrogen atmosphere protection, 0.1 parts by weight of double bond sulfonic acid intermediate and 0.12 parts by weight of butanediol were mixed, diluted with N,N-dimethylformamide, and mixed evenly. Then, 1 part of polyurethane prepolymer and 0.002 parts of dibutyltin dilaurate were added. Under nitrogen atmosphere protection, the mixture was heated to 85°C and reacted for 8 hours. Then, 0.001 parts of azobisisobutyronitrile initiator and 0.04 parts of vinyl sulfonic acid were added. The mixture was heated to 95°C and reacted for 16 hours. Excess solvent was removed by rotary evaporation. The mixture was washed twice with deionized water and vacuum dried to constant weight to obtain the anti-coating polyurethane modifier. S14. By weight, disperse 1 part of anti-coagulation polyurethane modifier into 200 parts of N-methylpyrrolidone, stir and mix evenly, then add 0.3 parts of nano samarium trichloride, 0.5 parts of nano silver, 50 parts of polyethersulfone resin and 10 parts of carboxymethyl cellulose, stir and mix evenly, and then defoam under vacuum to obtain spinning solution. S2. Using a dry-wet spinning method, the spinning solution is extruded through a spinneret to form a hollow fiber membrane. The resulting membrane is washed with physiological saline and then dried with hot air at 115°C to obtain an antibacterial hemodialysis membrane containing rare earth elements.

[0019] Example 5. A preparation process for an antibacterial hemodialysis membrane containing rare earth elements, comprising the following steps: Compared with Example 4, this example increases the amount of anti-condensation polyurethane modifier added in step S14; S1. Preparation of spinning solution; S11. By weight, add 1 part of polycaprolactone triol to N,N-dimethylformamide, heat to 115°C, stir for 30 min, cool to room temperature, add 0.48 parts of hexamethylene diisocyanate and 0.002 parts of dibutyltin dilaurate, heat to 75°C, stir and react for 18 h, remove excess solvent by rotary evaporation to obtain polyurethane prepolymer; S12. By weight, 1 part of 6-sulfonic acid pyridine-2-carboxylic acid was dispersed in N,N-dimethylacetamide under a nitrogen atmosphere. 0.005 parts of p-toluenesulfonic acid were added and mixed thoroughly. Then, the mixture was added dropwise to 0.6 parts of 1,5-hexadien-3,4-diol. The mixture was heated to 108°C and stirred for 10 hours. Excess solvent was removed by rotary evaporation to obtain the double bond sulfonic acid intermediate. S13. Under nitrogen atmosphere protection, 0.1 parts by weight of double bond sulfonic acid intermediate and 0.12 parts by weight of butanediol were mixed, diluted with N,N-dimethylformamide, and mixed evenly. Then, 1 part of polyurethane prepolymer and 0.002 parts of dibutyltin dilaurate were added. Under nitrogen atmosphere protection, the mixture was heated to 85°C and reacted for 8 hours. Then, 0.001 parts of azobisisobutyronitrile initiator and 0.04 parts of vinyl sulfonic acid were added. The mixture was heated to 95°C and reacted for 16 hours. Excess solvent was removed by rotary evaporation. The mixture was washed twice with deionized water and vacuum dried to constant weight to obtain the anti-coating polyurethane modifier. S14. By weight, 4 parts of anti-coagulation polyurethane modifier are dispersed into 200 parts of N-methylpyrrolidone. After stirring and mixing evenly, 0.3 parts of nano samarium trichloride, 0.5 parts of nano silver, 50 parts of polyethersulfone resin and 10 parts of carboxymethyl cellulose are added. After stirring and mixing evenly, vacuum defoaming is performed to obtain the spinning solution. S2. Using a dry-wet spinning method, the spinning solution is extruded through a spinneret to form a hollow fiber membrane. The resulting membrane is washed with physiological saline and then dried with hot air at 115°C to obtain an antibacterial hemodialysis membrane containing rare earth elements.

[0020] Comparative Example 1. A preparation process for an antibacterial hemodialysis membrane containing rare earth elements, comprising the following steps: Compared to Example 1, the spinning solution in this comparative example was prepared with the addition of an anti-coagulation polyurethane modifier. S1. Preparation of spinning solution; By weight, 0.3 parts of nano samarium trichloride, 0.5 parts of nano silver, 50 parts of polyethersulfone resin and 10 parts of carboxymethyl cellulose were added to 200 parts of N-methylpyrrolidone. After stirring and mixing evenly, the mixture was defoamed under vacuum to obtain the spinning solution. S2. Using a dry-wet spinning method, the spinning solution is extruded through a spinneret to form a hollow fiber membrane. The resulting membrane is washed with physiological saline and then dried with hot air at 115°C to obtain an antibacterial hemodialysis membrane containing rare earth elements.

[0021] Comparative Example 2. A preparation process for an antibacterial hemodialysis membrane containing rare earth elements, comprising the following steps: Compared with Example 1, no nano-silver was added when preparing the spinning solution in this comparative example; S1. Preparation of spinning solution; S11. By weight, add 1 part of polycaprolactone triol to N,N-dimethylformamide, heat to 115°C, stir for 30 min, cool to room temperature, add 0.48 parts of hexamethylene diisocyanate and 0.002 parts of dibutyltin dilaurate, heat to 75°C, stir and react for 18 h, remove excess solvent by rotary evaporation to obtain polyurethane prepolymer; S12. By weight, 1 part of 6-sulfonylpyridine-2-carboxylic acid was dispersed in N,N-dimethylacetamide under a nitrogen atmosphere. 0.005 parts of p-toluenesulfonic acid were added and mixed thoroughly. Then, the mixture was added dropwise to 0.4 parts of 1,5-hexadien-3,4-diol. The mixture was heated to 108°C and stirred for 10 hours. Excess solvent was removed by rotary evaporation to obtain the double-bonded sulfonic acid intermediate. S13. Under nitrogen atmosphere protection, 0.06 parts by weight of double bond sulfonic acid intermediate and 0.12 parts by weight of butanediol were mixed, diluted with N,N-dimethylformamide, and mixed evenly. Then, 1 part of polyurethane prepolymer and 0.002 parts of dibutyltin dilaurate were added. Under nitrogen atmosphere protection, the temperature was raised to 85°C and the reaction was continued for 8 hours. Then, 0.001 parts of azobisisobutyronitrile initiator and 0.02 parts of vinyl sulfonic acid were added. The temperature was raised to 95°C and the reaction was continued for 16 hours. After removing excess solvent by rotary evaporation, the mixture was washed twice with deionized water and vacuum dried to constant weight to obtain the anti-coating polyurethane modifier. S14. By weight, 1 part of anti-coagulation polyurethane modifier is dispersed into 200 parts of N-methylpyrrolidone. After stirring and mixing evenly, 0.3 parts of nano samarium trichloride, 50 parts of polyethersulfone resin and 10 parts of carboxymethyl cellulose are added. After stirring and mixing evenly, vacuum defoaming is performed to obtain the spinning solution. S2. Using a dry-wet spinning method, the spinning solution is extruded through a spinneret to form a hollow fiber membrane. The resulting membrane is washed with physiological saline and then dried with hot air at 115°C to obtain an antibacterial hemodialysis membrane containing rare earth elements.

[0022] Testing: Hollow fiber membranes prepared in Examples 1-5 and Comparative Examples 1-2 with an inner diameter of 350 micrometers and a wall thickness of 95 micrometers were washed with physiological saline and dried with hot air at 115°C to obtain antibacterial hemodialysis membrane samples for testing. The water flux (0.1 MPa) of the dialysis membranes of the test samples prepared in Examples 1-5 and Comparative Examples 1-2 was tested. The dialysis membranes of the test samples prepared in Examples 1-5 and Comparative Examples 1-2 were loaded into an ultrafiltration device. After preloading with deionized water for 15 min at 0.2 MPa, the clearance rate was tested at 0.1 MPa using urea phosphate buffer (1 g / L). Protein adhesion experiment: The dialysis membranes of the test samples prepared in Examples 1-5 and Comparative Examples 1-2 were cut into small pieces of 2×2cm, and immersed in 10mL of bovine serum albumin phosphate buffer (1g / L). After continuous shaking for 6h in the dark at 25℃, the membranes were taken out and the absorbance of the bovine serum albumin phosphate buffer solution before and after membrane adsorption was tested with 280nm UV. The protein content adsorbed by the membrane was calculated from the formula. Protein adsorption capacity = (C 未吸附 ×V 未吸附 -C 吸附后 ×V 吸附后 ) / membrane area; In the formula, C 未吸附 V represents the concentration of phosphate buffer without adsorbed bovine serum albumin. 未吸附 This represents the volume of phosphate buffer solution without adsorbed bovine serum albumin; C 吸附后 V represents the concentration of bovine serum albumin phosphate buffer after adsorption. 吸附后 This represents the volume of bovine serum albumin phosphate buffer after adsorption. The antibacterial properties of the dialysis membranes prepared in Examples 1-5 and Comparative Examples 1-2 were tested according to GB / T 20944.3-2008. The test results are shown in Table 1 below; Table 1.

[0023] Finally, it should be noted that the above descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A process for preparing an antibacterial hemodialysis membrane containing rare earth elements, characterized in that: The following steps are involved: S1. Preparing a spinning solution; S11. Add polycaprolactone triol to N,N-dimethylformamide, heat to 105-125°C, stir for 25-30 minutes, cool to room temperature, add hexamethylene diisocyanate and dibutyltin dilaurate, heat to 75-78°C, stir for 12-24 hours, and remove excess solvent by rotary evaporation to obtain a polyurethane prepolymer; S12. 6-sulfonic acid pyridine-2-carboxylic acid is dispersed in N,N-dimethylacetamide under nitrogen atmosphere, p-toluenesulfonic acid is added thereto, mixed evenly, and then added dropwise to 1,5-hexadiene-3,4-diol, heated to 105-110° C., stirred for reaction for 8-12 hours, and then the excess solvent is removed by rotary evaporation to obtain a double bond sulfonic acid intermediate; S13. Under nitrogen atmosphere protection, the double-bond sulfonic acid intermediate is mixed with butanediol, and N,N-dimethylformamide is added to dilute. After mixing evenly, a polyurethane prepolymer and dibutyltin dilaurate are added thereto. Under nitrogen atmosphere protection, the temperature is raised to 80-85°C, and the reaction is continued for 6-12 hours. An initiator and vinyl sulfonic acid are added thereto, and the temperature is raised to 85-95°C. After the reaction is continued for 8-16 hours, the excess solvent is removed by rotary evaporation, and the mixture is washed with deionized water for 2-3 times, and then vacuum dried to a constant weight to obtain an anti-coagulation polyurethane modifier. S14. The anticoagulant polyurethane modifier is dispersed in N-methylpyrrolidone, stirred and mixed, and then nano-samarium chloride, nano-silver, polyethersulfone resin and carboxymethyl cellulose are added thereto, stirred and mixed, and then vacuum-defoamed to obtain a spinning solution; S2. The spinning solution is extruded through a spinneret using a dry-wet spinning method to prepare a hollow fiber membrane. The obtained membrane layer is washed with physiological saline and then dried with hot air at 105-120° C. to obtain an antibacterial hemodialysis membrane containing rare earth elements.

2. The process for preparing an antibacterial hemodialysis membrane containing rare earth elements according to claim 1, characterized in that: In step S11, the Mw of the polycaprolactone triol is 500-1000; The mass ratio of the polycaprolactone triol, hexamethylene diisocyanate and dibutyltin dilaurate is 1:(0.48-1):(0.001-0.003).

3. The process for preparing an antibacterial hemodialysis membrane containing rare earth elements according to claim 1, characterized in that: In step S12, the mass ratio of the 6-sulfonic acid pyridine-2-carboxylic acid, p-toluenesulfonic acid, and 1,5-hexadiene-3,4-diol is 1:(0.003-0.006):(0.4-0.6).

4. The process for preparing an antibacterial hemodialysis membrane containing rare earth elements according to claim 1, characterized in that: In step S13, the mass ratio of the double-bond sulfonic acid intermediate, butanediol, polyurethane prepolymer and dibutyltin dilaurate is (0.06-0.1):(0.115-0.124):1:(0.001-0.002).

5. The process for preparing an antibacterial hemodialysis membrane containing rare earth elements according to claim 1, characterized in that: In step S13, the mass ratio of the polyurethane prepolymer, the initiator and the vinyl sulfonic acid is 1: (0.0001-0.001): (0.02-0.04).

6. The process for preparing an antibacterial hemodialysis membrane containing rare earth elements according to claim 1, characterized in that: In step S13, the initiator is azobisisobutyronitrile.

7. The process for preparing an antibacterial hemodialysis membrane containing rare earth elements according to claim 1, characterized in that: In step S14, the spinning solution is composed of 1-4 parts of anticoagulant polyurethane modifier, 0.1-0.8 parts of nano samarium trichloride, 0.3-1.5 parts of nano silver, 40-60 parts of polyether sulfone resin, 8-12 parts of carboxymethyl cellulose and 200-300 parts of N-methyl pyrrolidone in parts by weight.

8. The process for preparing an antibacterial hemodialysis membrane containing rare earth elements according to claim 1, characterized in that: In step S14, the viscosity average molecular weight of the polyethersulfone resin is 40,000-120,000.

9. An antibacterial hemodialysis membrane containing rare earth elements prepared by the preparation process according to any one of claims 1 to 8.

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