CN111004493B - Antibacterial medical material and preparation method thereof - Google Patents
Antibacterial medical material and preparation method thereof Download PDFInfo
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- CN111004493B CN111004493B CN201911350393.8A CN201911350393A CN111004493B CN 111004493 B CN111004493 B CN 111004493B CN 201911350393 A CN201911350393 A CN 201911350393A CN 111004493 B CN111004493 B CN 111004493B
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Abstract
The invention discloses an antibacterial medical material and a preparation method thereof, wherein the antibacterial medical material comprises the following raw materials in parts by weight: 50-70 parts of polyurethane, 30-50 parts of polyvinyl chloride, 10-15 parts of carboxymethyl cyclodextrin-tourmaline composite material, 1-5 parts of magnesium borate whisker, 1-5 parts of plasticizer, 1-3 parts of lubricant, 1-3 parts of zinc oxide and 0.1-0.5 part of antioxidant. The antibacterial medical material obtained by the preparation method of the antibacterial medical material has good antibacterial performance and mechanical property, is nontoxic to human bodies, has good biocompatibility, and can be widely applied to various medical apparatus and instrument products such as medical catheters and the like.
Description
Technical Field
The invention relates to the technical field of sanitary materials, in particular to an antibacterial medical material and a preparation method thereof.
Background
The medical material has special performance and special function, is used for artificial organs, surgical repair, physical therapy rehabilitation, diagnosis and treatment of diseases, and does not have adverse effect on human tissues. The polymer material is widely used in medical use, and is especially used in making internal organs, external organs, medicine preparation and medical apparatus. The source of the biopolymer comprises natural biopolymer materials and synthetic biopolymer materials. The natural medical polymer material comes from nature and comprises cellulose, chitin, hyaluronic acid, collagen, gelatin, sodium alginate and the like; the synthetic medical polymer material is a polymer material artificially synthesized by a chemical method and used for medical use, and currently, polyurethane, silicon rubber, polyester fiber, polyvinylpyrrolidone, polyether ether ketone, polyethylene and the like are commonly used.
Hospital infection is a common problem in various hospitals at present, and is a difficult problem which always troubles the medical field, and seriously threatens the health and safety of human beings. Hospitals are the places where patients gather, various pathogenic microorganisms float in the environment, favorable external conditions are provided for the transmission of various infections or infectious diseases, and the occurrence of nosocomial infections is promoted.
There are many pathogenic bacteria causing nosocomial infection, such as Escherichia coli, Staphylococcus aureus, Escherichia coli, Pseudomonas aeruginosa, Staphylococcus epidermidis, Streptococcus, Serratia rubra, Klebsiella pneumoniae, Acinetobacter baumannii, Acinetobacter lofei, etc. The medical materials are difficult to be completely sterile, and if one material has medical functions in all aspects and certain bacteriostatic activity, the occurrence of nosocomial infection is hopefully reduced or relieved.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to solve the technical problem of providing an antibacterial medical material and a preparation method thereof, and the obtained antibacterial medical material has good antibacterial performance and mechanical property, is nontoxic to a human body, has good biocompatibility and can be widely applied to various medical apparatus and instrument products such as medical catheters and the like.
The purpose of the invention is realized by the following technical scheme:
an antibacterial medical material comprises the following raw materials in parts by weight: 50-70 parts of polyurethane, 30-50 parts of polyvinyl chloride, 10-15 parts of carboxymethyl cyclodextrin-tourmaline composite material, 1-5 parts of magnesium borate whisker, 1-5 parts of plasticizer, 1-3 parts of lubricant, 1-3 parts of zinc oxide and 0.1-0.5 part of antioxidant.
An antibacterial medical material comprises the following raw materials in parts by weight: 50-70 parts of polyurethane, 30-50 parts of polyvinyl chloride, 10-15 parts of modified carboxymethyl cyclodextrin-tourmaline composite material, 1-5 parts of magnesium borate whisker, 1-5 parts of plasticizer, 1-3 parts of lubricant, 1-3 parts of zinc oxide and 0.1-0.5 part of antioxidant.
The lubricant is one or a mixture of zinc stearate, ethylene bis-stearic acid amide and oleic acid amide.
The plasticizer is any one of acetyl tributyl citrate and dioctyl adipate.
The antioxidant is any one or a mixture of more of antioxidant 1010, antioxidant 168 and antioxidant 1076.
The carboxymethyl cyclodextrin-tourmaline composite material is prepared by the following method:
(1) tourmaline and 5-10 wt% of sodium hydroxide aqueous solution are mixed according to the solid-to-liquid ratio of 1 g: (8-12) mL, stirring for 30-50 minutes at 60-100 revolutions per minute at 40-60 ℃, filtering by adopting 800-mesh filter cloth, washing a filter cake by using water until a washing liquid is neutral, drying to constant weight, grinding, sieving by using a 300-mesh sieve to obtain alkalized tourmaline, mixing ethanol and water according to the volume ratio of (60-70) to (30-40) to obtain a hydroalcoholic mixed solution, mixing the hydroalcoholic mixed solution and a silane coupling agent according to the volume ratio of 100:5, stirring for 8-12 minutes at 65-75 ℃ at 200 revolutions per minute of 100-fold sand to obtain a coupling agent solution, adding 5-10g of the alkalized tourmaline into 150mL of 100-fold sand coupling agent solution, carrying out reflux reaction for 2-4 hours at 65-75 ℃, cooling to 20-30 ℃, filtering by adopting 800-mesh filter cloth, washing the filter cake for 3-5 times by using 150mL of 100-fold sand water-alcohol mixed solution, drying at 80-90 deg.C to constant weight, grinding, and sieving with 300 mesh sieve to obtain modified tourmaline;
(2) adding 8-12g beta-cyclodextrin into 35-45mL of 18-22 wt% sodium hydroxide solution, slowly dropwise adding 25-35mL of 14-16 wt% monochloroacetic acid aqueous solution at 55-65 ℃ while stirring at 200 revolutions per minute with 100-, stirring at 200 revolutions per minute for 100 plus materials until the precipitate is dissolved, then adding 600mL of methanol with 400 plus materials, stirring at 500 revolutions per minute for 200 plus materials for 10-20 minutes, standing for 20-40 minutes, separating out the white precipitate again, filtering by adopting 800-mesh filter cloth, washing the filter cake for 2-4 times by using 60-100mL of methanol, and drying at 40-60 ℃ for 40-60 minutes to obtain carboxymethyl cyclodextrin;
(3) adding 0.8-1.2g of modified tourmaline into 10-20mL of PBS (pH is 5.8), ultrasonically dispersing for 20-40 minutes at an ultrasonic frequency of 15-25kHz to obtain a modified tourmaline dispersion, dissolving 1-2g of carboxymethyl cyclodextrin and 0.1-0.2g N-hydroxysuccinimide in 40-50mL of PBS (pH is 5.8), stirring for 20-40 minutes at 100 revolutions per minute, adding 0.2-0.3g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, stirring for 20-40 minutes at 100 revolutions per minute, adding the modified tourmaline dispersion, stirring for 20-30 hours at 20-30 ℃ at 100 revolutions per minute, filtering with 800-mesh filter cloth, washing a filter cake with 60-100mL of water for 2-4 times, drying at 40-60 deg.C to constant weight, grinding, and sieving with 300 mesh sieve to obtain carboxymethyl cyclodextrin-tourmaline composite material.
The modified carboxymethyl cyclodextrin-tourmaline composite material is prepared by the following method:
(1) tourmaline and 5-10 wt% of sodium hydroxide aqueous solution are mixed according to the solid-to-liquid ratio of 1 g: (8-12) mL, stirring at 40-60 ℃ for 30-50 minutes, filtering, washing a filter cake with water until a washing liquid is neutral, drying to constant weight, grinding to obtain alkalized tourmaline, mixing ethanol and water according to a volume ratio of (60-70) (30-40) to obtain a hydroalcoholic mixed solution, mixing the hydroalcoholic mixed solution and a silane coupling agent according to a volume ratio of 100:5, stirring at 65-75 ℃ for 8-12 minutes to obtain a coupling agent solution, adding 5-10g of alkalized tourmaline into 150mL of 100-fold-of-organic solvent solution, carrying out reflux reaction at 65-75 ℃ for 2-4 hours, cooling to 20-30 ℃, filtering, washing the filter cake with 150mL of 100-fold-of hydroalcoholic mixed solution for 3-5 times, drying at 80-90 ℃ to constant weight, and grinding to obtain modified tourmaline;
(2) adding 8-12g of beta-cyclodextrin into 35-45mL of 18-22 wt% sodium hydroxide solution, slowly dropwise adding 25-35mL of 14-16 wt% monochloroacetic acid aqueous solution at 55-65 ℃ while stirring, stirring for 4-6 hours at 55-65 ℃ to obtain a reaction solution, naturally cooling the reaction solution to 20-30 ℃, dropwise adding 36 wt% concentrated hydrochloric acid while stirring until the reaction solution is neutral, adding 400-600mL of methanol, stirring for 10-20 minutes, standing for 20-40 minutes, separating out a white precipitate, filtering, adding 8-12mL of water into a filter cake, stirring until the precipitate is dissolved, adding 400-600mL of methanol, stirring for 10-20 minutes, standing for 20-40 minutes, separating out the white precipitate again, filtering, washing the filter cake with 60-100mL of methanol for 2-4 times, and drying at 40-60 ℃ for 40-60 minutes to obtain carboxymethyl cyclodextrin;
(3) adding 0.8-1.2g of modified tourmaline into 10-20mL of PBS, performing ultrasonic dispersion for 20-40 minutes at an ultrasonic frequency of 15-25kHz to obtain a modified tourmaline dispersion solution, dissolving 1-2g of carboxymethyl cyclodextrin and 0.1-0.2g N-hydroxysuccinimide into 40-50mL of PBS, stirring for 20-40 minutes, adding 0.2-0.3g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, stirring for 20-40 minutes, adding the modified tourmaline dispersion solution, stirring for 20-30 hours at 20-30 ℃, filtering, washing a filter cake with 60-100mL of water for 2-4 times, drying at 40-60 ℃ to constant weight, and grinding to obtain a carboxymethyl cyclodextrin-tourmaline composite material;
(4) adding 80-120mg of modifier into 300mL of 200-mL water, stirring for 10-20 minutes at 50-70 ℃, adding 1.5-2.5g of carboxymethyl cyclodextrin-tourmaline composite material, stirring for 2-4 hours at 50-70 ℃, adding 80-120mg of silver nitrate, continuously stirring for 1-3 hours at 50-70 ℃, naturally cooling to 20-30 ℃, centrifuging for 10-20 minutes, drying the lower-layer precipitate at 40-60 ℃ to constant weight, and grinding to obtain the modified carboxymethyl cyclodextrin-tourmaline composite material.
The silane coupling agent is any one of gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropylmethyldiethoxysilane and gamma-aminopropylmethyldimethoxysilane.
The modifier is chlorogenic acid and/or matrine.
Preferably, the modifier is a mixture of chlorogenic acid and matrine, and the mass ratio of the chlorogenic acid to the matrine is 1: (2-4).
The preparation method of the antibacterial medical material comprises the following steps: weighing the raw materials according to the parts by weight, stirring for 8-12 minutes at the speed of 400 plus one minute and 600 revolutions per minute to obtain a mixture, and putting the mixture into a double-screw extruder for extrusion and granulation to obtain the composite material.
The antibacterial medical material obtained by the preparation method of the antibacterial medical material has good antibacterial performance and mechanical property, is nontoxic to human bodies, has good biocompatibility, and can be widely applied to various medical apparatus and instrument products such as medical catheters and the like.
Detailed Description
In the present invention, all the equipment and materials are commercially available or commonly used in the art, and the methods in the following examples are conventional in the art unless otherwise specified.
Polyurethane, thermoplastic polyurethane available from german bayer, type: DP 1485A.
The polyvinyl chloride was PVC-SG5 manufactured by Xinjiang Tianshi group (group) Co.
The magnesium borate whisker is purchased from Shanghai Kaiyofeng Kogyo, Inc., with the length-diameter ratio of 20 and the diameter of 1 μm.
Zinc stearate, purchased from Suzhou Chen aviation Fine chemical Co., Ltd, 325 mesh.
Acetyl tributyl citrate, purchased from Guangzhou Nuotan chemical Co.
Antioxidant 1010 produced by basf was used as antioxidant 1010.
Zinc oxide, purchased from Nanjing Baokett New Material Co., Ltd., primary particle size 30 nm.
Tourmaline is purchased from a manufacturer of Zhangteng mineral products in Lingshou county, 200 meshes.
Beta-cyclodextrin, purchased from Shanghai Michelin Biotech, Inc.
PBS (pH 5.8) purchased from xiamen haibiao technologies ltd.
N-hydroxysuccinimide, purchased from Shanghai Allandin Biotech, Inc.
1-Ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, purchased from Shanghai Allantin Biotechnology Ltd.
Gamma-aminopropyltrimethoxysilane, purchased from Shanghai Allantin Biotechnology Ltd.
Silver nitrate, purchased from Shanghai Allan Biotechnology Ltd.
Chlorogenic acid, purchased from Shanxi pannier Biotech, Inc. with a purity of 98%.
Matrine, purchased from Shanxi pannier Biotech limited, with a purity of 98%.
Example 1
The antibacterial medical material comprises the following raw materials in parts by weight: 60 parts of polyurethane, 40 parts of polyvinyl chloride, 12 parts of carboxymethyl cyclodextrin-tourmaline composite material, 3 parts of magnesium borate whisker, 3 parts of plasticizer, 2 parts of lubricant, 2 parts of zinc oxide and 0.3 part of antioxidant.
The lubricant is zinc stearate.
The plasticizer is acetyl tributyl citrate.
The antioxidant is antioxidant 1010.
The carboxymethyl cyclodextrin-tourmaline composite material is prepared by the following method:
(1) tourmaline and 8 wt% sodium hydroxide aqueous solution are mixed according to the solid-to-liquid ratio of 1 g: 10mL of the mixture is mixed, stirred for 40 minutes at the temperature of 50 ℃ at the speed of 80 rpm, filtered by 800-mesh filter cloth, a filter cake is washed by water until the washing liquor is neutral, dried to constant weight, ground and sieved by a 300-mesh sieve to obtain the alkalized tourmaline, and ethanol and water are mixed according to the volume ratio of 65: 35 to obtain a hydroalcoholic mixed solution, mixing the hydroalcoholic mixed solution with a silane coupling agent according to a volume ratio of 100:5, stirring for 10 minutes at 70 ℃ at 200 revolutions per minute to obtain a coupling agent solution, adding 8g of alkalized tourmaline into 120mL of the coupling agent solution, performing reflux reaction for 3 hours at 70 ℃, cooling to 25 ℃, filtering by using 800-mesh filter cloth, washing a filter cake for 4 times by using 120mL of the hydroalcoholic mixed solution, drying to constant weight at 90 ℃, grinding, and sieving by using 300-mesh sieve to obtain modified tourmaline;
(2) adding 10g beta-cyclodextrin into 40mL20 wt% sodium hydroxide solution, slowly dropping 30mL15 wt% monochloroacetic acid aqueous solution at 60 ℃ while stirring at 200 r/min, dropping within 30 minutes, stirring at 60 ℃ at 200 r/min for 5 hours to obtain reaction solution, naturally cooling the reaction solution to 25 ℃, dropping 36 wt% concentrated hydrochloric acid while stirring at 200 r/min until the reaction solution is neutral, adding 500mL methanol, stirring at 400 r/min for 15 minutes, standing for 30 minutes to precipitate white precipitate, filtering with 800 mesh filter cloth, adding 10mL water into filter cake, stirring at 200 r/min until the precipitate is dissolved, adding 500mL methanol, stirring at 400 r/min for 15 minutes, standing for 30 minutes to precipitate white precipitate again, filtering with 800 mesh filter cloth, washing the filter cake with 80mL methanol for 3 times, drying at 50 deg.C for 60 min to obtain carboxymethyl cyclodextrin;
(3) adding 1g of modified tourmaline into 15mL of PBS (pH is 5.8), performing ultrasonic dispersion for 30 minutes at an ultrasonic frequency of 20kHz to obtain a modified tourmaline dispersion, dissolving 1.5g of carboxymethyl cyclodextrin and 0.15g N-hydroxysuccinimide in 45mL of PBS (pH is 5.8), stirring at 200 rpm for 30 minutes, adding 0.5g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, stirring at 200 rpm for 30 minutes, adding the modified tourmaline dispersion, stirring at 200 rpm for 24 hours at 25 ℃, filtering by adopting 800-mesh filter cloth, washing a filter cake with 80mL of water for 3 times, drying at 50 ℃ to constant weight, grinding, and sieving by using a 300-mesh sieve to obtain the carboxymethyl cyclodextrin-tourmaline composite material.
The silane coupling agent is gamma-aminopropyl trimethoxy silane.
The preparation method of the antibacterial medical material comprises the following steps: weighing the raw materials according to the parts by weight, stirring for 10 minutes at 500 revolutions per minute to obtain a mixture, putting the mixture into a double-screw extruder, and extruding and granulating, wherein the temperatures of all regions of the double-screw extruder are respectively as follows: 155 deg.C, 165 deg.C, 175 deg.C, 185 deg.C, 190 deg.C, 175 deg.C, 165 deg.C.
Comparative example 1
The antibacterial medical material comprises the following raw materials in parts by weight: 60 parts of polyurethane, 40 parts of polyvinyl chloride, 12 parts of carboxymethyl cyclodextrin, 3 parts of magnesium borate whisker, 3 parts of plasticizer, 2 parts of lubricant, 2 parts of zinc oxide and 0.3 part of antioxidant.
The lubricant is zinc stearate.
The plasticizer is acetyl tributyl citrate.
The antioxidant is antioxidant 1010.
The carboxymethyl cyclodextrin is prepared by the following method: adding 10g beta-cyclodextrin into 40mL20 wt% sodium hydroxide solution, slowly adding 30mL15 wt% monochloroacetic acid aqueous solution dropwise at 60 ℃ under 200 r/min stirring, stirring within 30 minutes, stirring for 5 hours at 60 ℃ under 200 r/min to obtain reaction liquid, naturally cooling the reaction liquid to 25 ℃, adding 36 wt% concentrated hydrochloric acid while stirring at 200 r/min until the reaction liquid is neutral, adding 500mL methanol, stirring at 400 r/min for 15 minutes, standing for 30 minutes to separate out white precipitate, filtering with 800-mesh filter cloth, adding 10mL water into filter cake, stirring at 200 r/min until the precipitate is dissolved, adding 500mL methanol, stirring at 400 r/min for 15 minutes, standing for 30 minutes to separate out white precipitate again, filtering with 800-mesh filter cloth, washing the filter cake with 80mL methanol for 3 times, drying at 50 ℃ for 60 minutes, grinding, and sieving with 300 mesh sieve to obtain carboxymethyl cyclodextrin.
Comparative example 2
The antibacterial medical material comprises the following raw materials in parts by weight: 60 parts of polyurethane, 40 parts of polyvinyl chloride, 12 parts of modified tourmaline, 3 parts of magnesium borate whisker, 3 parts of plasticizer, 2 parts of lubricant, 2 parts of zinc oxide and 0.3 part of antioxidant.
The lubricant is zinc stearate.
The plasticizer is acetyl tributyl citrate.
The antioxidant is antioxidant 1010.
The modified tourmaline is prepared by the following method: tourmaline and 8 wt% sodium hydroxide aqueous solution are mixed according to the solid-to-liquid ratio of 1 g: 10mL of the mixture is mixed, stirred for 40 minutes at the temperature of 50 ℃ at the speed of 80 rpm, filtered by 800-mesh filter cloth, a filter cake is washed by water until the washing liquor is neutral, dried to constant weight, ground and sieved by a 300-mesh sieve to obtain the alkalized tourmaline, and ethanol and water are mixed according to the volume ratio of 65: 35 to obtain a hydroalcoholic mixed solution, mixing the hydroalcoholic mixed solution and a silane coupling agent according to a volume ratio of 100:5, stirring for 10 minutes at 70 ℃ at 200 rpm to obtain a coupling agent solution, adding 8g of alkalized tourmaline into 120mL of the coupling agent solution, performing reflux reaction for 3 hours at 70 ℃, cooling to 25 ℃, filtering by using 800-mesh filter cloth, washing a filter cake for 4 times by using 120mL of the hydroalcoholic mixed solution, drying to constant weight at 90 ℃, grinding, and sieving by using 300-mesh sieve to obtain the modified tourmaline.
The silane coupling agent is gamma-aminopropyl trimethoxy silane.
The preparation method of the antibacterial medical material comprises the following steps: weighing the raw materials according to the parts by weight, stirring for 10 minutes at 500 revolutions per minute to obtain a mixture, putting the mixture into a double-screw extruder, and extruding and granulating, wherein the temperatures of all regions of the double-screw extruder are respectively as follows: 155 deg.C, 165 deg.C, 175 deg.C, 185 deg.C, 190 deg.C, 175 deg.C, 165 deg.C.
Example 2
The antibacterial medical material comprises the following raw materials in parts by weight: 60 parts of polyurethane, 40 parts of polyvinyl chloride, 12 parts of modified carboxymethyl cyclodextrin-tourmaline composite material, 3 parts of magnesium borate whisker, 3 parts of plasticizer, 2 parts of lubricant, 2 parts of zinc oxide and 0.3 part of antioxidant.
The lubricant is zinc stearate.
The plasticizer is acetyl tributyl citrate.
The antioxidant is antioxidant 1010.
The modified carboxymethyl cyclodextrin-tourmaline composite material is prepared by the following method:
(1) tourmaline and 8 wt% sodium hydroxide aqueous solution are mixed according to the solid-to-liquid ratio of 1 g: 10mL of the mixture is mixed, stirred for 40 minutes at the temperature of 50 ℃ at the speed of 80 rpm, filtered by 800-mesh filter cloth, a filter cake is washed by water until the washing liquor is neutral, dried to constant weight, ground and sieved by a 300-mesh sieve to obtain the alkalized tourmaline, and ethanol and water are mixed according to the volume ratio of 65: 35 to obtain a hydroalcoholic mixed solution, mixing the hydroalcoholic mixed solution with a silane coupling agent according to a volume ratio of 100:5, stirring for 10 minutes at 70 ℃ at 200 revolutions per minute to obtain a coupling agent solution, adding 8g of alkalized tourmaline into 120mL of the coupling agent solution, performing reflux reaction for 3 hours at 70 ℃, cooling to 25 ℃, filtering by using 800-mesh filter cloth, washing a filter cake for 4 times by using 120mL of the hydroalcoholic mixed solution, drying to constant weight at 90 ℃, grinding, and sieving by using 300-mesh sieve to obtain modified tourmaline;
(2) adding 10g beta-cyclodextrin into 40mL20 wt% sodium hydroxide solution, slowly dropping 30mL15 wt% monochloroacetic acid aqueous solution at 60 ℃ while stirring at 200 r/min, dropping within 30 minutes, stirring at 60 ℃ at 200 r/min for 5 hours to obtain reaction solution, naturally cooling the reaction solution to 25 ℃, dropping 36 wt% concentrated hydrochloric acid while stirring at 200 r/min until the reaction solution is neutral, adding 500mL methanol, stirring at 400 r/min for 15 minutes, standing for 30 minutes to precipitate white precipitate, filtering with 800 mesh filter cloth, adding 10mL water into filter cake, stirring at 200 r/min until the precipitate is dissolved, adding 500mL methanol, stirring at 400 r/min for 15 minutes, standing for 30 minutes to precipitate white precipitate again, filtering with 800 mesh filter cloth, washing the filter cake with 80mL methanol for 3 times, drying at 50 deg.C for 60 min to obtain carboxymethyl cyclodextrin;
(3) adding 1g of modified tourmaline into 15mL of PBS (pH is 5.8), performing ultrasonic dispersion for 30 minutes at an ultrasonic frequency of 20kHz to obtain a modified tourmaline dispersion solution, dissolving 1.5g of carboxymethyl cyclodextrin and 0.15g N-hydroxysuccinimide in 45mL of PBS (pH is 5.8), stirring at 200 rpm for 30 minutes, adding 0.5g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, stirring at 200 rpm for 30 minutes, adding the modified tourmaline dispersion solution, stirring at 200 rpm for 24 hours at 25 ℃, filtering by adopting 800-mesh filter cloth, washing a filter cake with 80mL of water for 3 times, drying at 50 ℃ to constant weight, grinding, and sieving by using a 300-mesh sieve to obtain a carboxymethyl cyclodextrin-tourmaline composite material;
(4) adding 100mg of modifier into 250mL of water, stirring for 15 minutes at 60 ℃ at 200 rpm, adding 2g of carboxymethyl cyclodextrin-tourmaline composite material, stirring for 5 hours at 60 ℃ at 200 rpm, naturally cooling to 25 ℃, centrifuging for 15 minutes at 8000 rpm, drying the lower-layer precipitate at 50 ℃ to constant weight, grinding, and sieving with a 300-mesh sieve to obtain the modified carboxymethyl cyclodextrin-tourmaline composite material.
The modifier is chlorogenic acid.
The silane coupling agent is gamma-aminopropyl trimethoxy silane.
The preparation method of the antibacterial medical material comprises the following steps: weighing the raw materials according to the parts by weight, stirring for 10 minutes at 500 revolutions per minute to obtain a mixture, putting the mixture into a double-screw extruder, and extruding and granulating, wherein the temperatures of all regions of the double-screw extruder are respectively as follows: 155 deg.C, 165 deg.C, 175 deg.C, 185 deg.C, 190 deg.C, 175 deg.C, 165 deg.C.
Example 3
The antibacterial medical material comprises the following raw materials in parts by weight: 60 parts of polyurethane, 40 parts of polyvinyl chloride, 12 parts of modified carboxymethyl cyclodextrin-tourmaline composite material, 3 parts of magnesium borate whisker, 3 parts of plasticizer, 2 parts of lubricant, 2 parts of zinc oxide and 0.3 part of antioxidant.
The lubricant is zinc stearate.
The plasticizer is acetyl tributyl citrate.
The antioxidant is antioxidant 1010.
The modified carboxymethyl cyclodextrin-tourmaline composite material is prepared by the following method:
(1) tourmaline and 8 wt% sodium hydroxide aqueous solution are mixed according to the solid-to-liquid ratio of 1 g: 10mL of the mixture is mixed, stirred for 40 minutes at the temperature of 50 ℃ at the speed of 80 rpm, filtered by 800-mesh filter cloth, a filter cake is washed by water until the washing liquor is neutral, dried to constant weight, ground and sieved by a 300-mesh sieve to obtain the alkalized tourmaline, and ethanol and water are mixed according to the volume ratio of 65: 35 to obtain a hydroalcoholic mixed solution, mixing the hydroalcoholic mixed solution with a silane coupling agent according to a volume ratio of 100:5, stirring for 10 minutes at 70 ℃ at 200 revolutions per minute to obtain a coupling agent solution, adding 8g of alkalized tourmaline into 120mL of the coupling agent solution, performing reflux reaction for 3 hours at 70 ℃, cooling to 25 ℃, filtering by using 800-mesh filter cloth, washing a filter cake for 4 times by using 120mL of the hydroalcoholic mixed solution, drying to constant weight at 90 ℃, grinding, and sieving by using 300-mesh sieve to obtain modified tourmaline;
(2) adding 10g beta-cyclodextrin into 40mL20 wt% sodium hydroxide solution, slowly dropping 30mL15 wt% monochloroacetic acid aqueous solution at 60 ℃ while stirring at 200 r/min, dropping within 30 minutes, stirring at 60 ℃ at 200 r/min for 5 hours to obtain reaction solution, naturally cooling the reaction solution to 25 ℃, dropping 36 wt% concentrated hydrochloric acid while stirring at 200 r/min until the reaction solution is neutral, adding 500mL methanol, stirring at 400 r/min for 15 minutes, standing for 30 minutes to precipitate white precipitate, filtering with 800 mesh filter cloth, adding 10mL water into filter cake, stirring at 200 r/min until the precipitate is dissolved, adding 500mL methanol, stirring at 400 r/min for 15 minutes, standing for 30 minutes to precipitate white precipitate again, filtering with 800 mesh filter cloth, washing the filter cake with 80mL methanol for 3 times, drying at 50 deg.C for 60 min to obtain carboxymethyl cyclodextrin;
(3) adding 1g of modified tourmaline into 15mL of PBS (pH is 5.8), performing ultrasonic dispersion for 30 minutes at an ultrasonic frequency of 20kHz to obtain a modified tourmaline dispersion solution, dissolving 1.5g of carboxymethyl cyclodextrin and 0.15g N-hydroxysuccinimide in 45mL of PBS (pH is 5.8), stirring at 200 rpm for 30 minutes, adding 0.5g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, stirring at 200 rpm for 30 minutes, adding the modified tourmaline dispersion solution, stirring at 200 rpm for 24 hours at 25 ℃, filtering by adopting 800-mesh filter cloth, washing a filter cake with 80mL of water for 3 times, drying at 50 ℃ to constant weight, grinding, and sieving by using a 300-mesh sieve to obtain a carboxymethyl cyclodextrin-tourmaline composite material;
(4) adding 2g of carboxymethyl cyclodextrin-tourmaline composite material into 250mL of water, adding 100mg of silver nitrate, stirring at 60 ℃ for 5 hours at 200 rpm, naturally cooling to 25 ℃, centrifuging for 15 minutes at 8000 rpm, drying the lower-layer precipitate at 50 ℃ to constant weight, grinding, and sieving with a 300-mesh sieve to obtain the modified carboxymethyl cyclodextrin-tourmaline composite material.
The silane coupling agent is gamma-aminopropyl trimethoxy silane.
The preparation method of the antibacterial medical material comprises the following steps: weighing the raw materials according to the parts by weight, stirring for 10 minutes at 500 revolutions per minute to obtain a mixture, putting the mixture into a double-screw extruder, and extruding and granulating, wherein the temperatures of all regions of the double-screw extruder are respectively as follows: 155 deg.C, 165 deg.C, 175 deg.C, 185 deg.C, 190 deg.C, 175 deg.C, 165 deg.C.
Example 4
The antibacterial medical material comprises the following raw materials in parts by weight: 60 parts of polyurethane, 40 parts of polyvinyl chloride, 12 parts of modified carboxymethyl cyclodextrin-tourmaline composite material, 3 parts of magnesium borate whisker, 3 parts of plasticizer, 2 parts of lubricant, 2 parts of zinc oxide and 0.3 part of antioxidant.
The lubricant is zinc stearate.
The plasticizer is acetyl tributyl citrate.
The antioxidant is antioxidant 1010.
The modified carboxymethyl cyclodextrin-tourmaline composite material is prepared by the following method:
(1) tourmaline and 8 wt% sodium hydroxide aqueous solution are mixed according to the solid-to-liquid ratio of 1 g: 10mL of the mixture is mixed, stirred for 40 minutes at the temperature of 50 ℃ at the speed of 80 rpm, filtered by 800-mesh filter cloth, a filter cake is washed by water until the washing liquor is neutral, dried to constant weight, ground and sieved by a 300-mesh sieve to obtain the alkalized tourmaline, and ethanol and water are mixed according to the volume ratio of 65: 35 to obtain a hydroalcoholic mixed solution, mixing the hydroalcoholic mixed solution with a silane coupling agent according to a volume ratio of 100:5, stirring for 10 minutes at 70 ℃ at 200 revolutions per minute to obtain a coupling agent solution, adding 8g of alkalized tourmaline into 120mL of the coupling agent solution, performing reflux reaction for 3 hours at 70 ℃, cooling to 25 ℃, filtering by using 800-mesh filter cloth, washing a filter cake for 4 times by using 120mL of the hydroalcoholic mixed solution, drying to constant weight at 90 ℃, grinding, and sieving by using 300-mesh sieve to obtain modified tourmaline;
(2) adding 10g beta-cyclodextrin into 40mL20 wt% sodium hydroxide solution, slowly dropping 30mL15 wt% monochloroacetic acid aqueous solution at 60 ℃ while stirring at 200 r/min, dropping within 30 minutes, stirring at 60 ℃ at 200 r/min for 5 hours to obtain reaction solution, naturally cooling the reaction solution to 25 ℃, dropping 36 wt% concentrated hydrochloric acid while stirring at 200 r/min until the reaction solution is neutral, adding 500mL methanol, stirring at 400 r/min for 15 minutes, standing for 30 minutes to precipitate white precipitate, filtering with 800 mesh filter cloth, adding 10mL water into filter cake, stirring at 200 r/min until the precipitate is dissolved, adding 500mL methanol, stirring at 400 r/min for 15 minutes, standing for 30 minutes to precipitate white precipitate again, filtering with 800 mesh filter cloth, washing the filter cake with 80mL methanol for 3 times, drying at 50 deg.C for 60 min to obtain carboxymethyl cyclodextrin;
(3) adding 1g of modified tourmaline into 15mL of PBS (pH is 5.8), performing ultrasonic dispersion for 30 minutes at an ultrasonic frequency of 20kHz to obtain a modified tourmaline dispersion solution, dissolving 1.5g of carboxymethyl cyclodextrin and 0.15g N-hydroxysuccinimide in 45mL of PBS (pH is 5.8), stirring at 200 rpm for 30 minutes, adding 0.5g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, stirring at 200 rpm for 30 minutes, adding the modified tourmaline dispersion solution, stirring at 200 rpm for 24 hours at 25 ℃, filtering by adopting 800-mesh filter cloth, washing a filter cake with 80mL of water for 3 times, drying at 50 ℃ to constant weight, grinding, and sieving by using a 300-mesh sieve to obtain a carboxymethyl cyclodextrin-tourmaline composite material;
(4) adding 100mg of modifier into 250mL of water, stirring for 15 minutes at 60 ℃ at 200 rpm, adding 2g of carboxymethyl cyclodextrin-tourmaline composite material, stirring for 3 hours at 60 ℃ at 200 rpm, adding 100mg of silver nitrate, continuously stirring for 2 hours at 60 ℃ at 200 rpm, naturally cooling to 25 ℃, separating for 15 minutes at 8000 rpm, drying the lower-layer precipitate at 50 ℃ to constant weight, grinding, and sieving with a 300-mesh sieve to obtain the modified carboxymethyl cyclodextrin-tourmaline composite material.
The silane coupling agent is gamma-aminopropyl trimethoxy silane.
The modifier is chlorogenic acid.
The preparation method of the antibacterial medical material comprises the following steps: weighing the raw materials according to the parts by weight, stirring for 10 minutes at 500 revolutions per minute to obtain a mixture, putting the mixture into a double-screw extruder, and extruding and granulating, wherein the temperatures of all regions of the double-screw extruder are respectively as follows: 155 deg.C, 165 deg.C, 175 deg.C, 185 deg.C, 190 deg.C, 175 deg.C, 165 deg.C.
Example 5
The antibacterial medical material comprises the following raw materials in parts by weight: 60 parts of polyurethane, 40 parts of polyvinyl chloride, 12 parts of modified carboxymethyl cyclodextrin-tourmaline composite material, 3 parts of magnesium borate whisker, 3 parts of plasticizer, 2 parts of lubricant, 2 parts of zinc oxide and 0.3 part of antioxidant.
The lubricant is zinc stearate.
The plasticizer is acetyl tributyl citrate.
The antioxidant is antioxidant 1010.
The modified carboxymethyl cyclodextrin-tourmaline composite material is prepared by the following method:
(1) tourmaline and 8 wt% sodium hydroxide aqueous solution are mixed according to the solid-to-liquid ratio of 1 g: 10mL of the mixture is mixed, stirred for 40 minutes at the temperature of 50 ℃ at the speed of 80 rpm, filtered by 800-mesh filter cloth, a filter cake is washed by water until the washing liquor is neutral, dried to constant weight, ground and sieved by a 300-mesh sieve to obtain the alkalized tourmaline, and ethanol and water are mixed according to the volume ratio of 65: 35 to obtain a hydroalcoholic mixed solution, mixing the hydroalcoholic mixed solution with a silane coupling agent according to a volume ratio of 100:5, stirring for 10 minutes at 70 ℃ at 200 revolutions per minute to obtain a coupling agent solution, adding 8g of alkalized tourmaline into 120mL of the coupling agent solution, performing reflux reaction for 3 hours at 70 ℃, cooling to 25 ℃, filtering by using 800-mesh filter cloth, washing a filter cake for 4 times by using 120mL of the hydroalcoholic mixed solution, drying to constant weight at 90 ℃, grinding, and sieving by using 300-mesh sieve to obtain modified tourmaline;
(2) adding 10g beta-cyclodextrin into 40mL20 wt% sodium hydroxide solution, slowly dropping 30mL15 wt% monochloroacetic acid aqueous solution at 60 ℃ while stirring at 200 r/min, dropping within 30 minutes, stirring at 60 ℃ at 200 r/min for 5 hours to obtain reaction solution, naturally cooling the reaction solution to 25 ℃, dropping 36 wt% concentrated hydrochloric acid while stirring at 200 r/min until the reaction solution is neutral, adding 500mL methanol, stirring at 400 r/min for 15 minutes, standing for 30 minutes to precipitate white precipitate, filtering with 800 mesh filter cloth, adding 10mL water into filter cake, stirring at 200 r/min until the precipitate is dissolved, adding 500mL methanol, stirring at 400 r/min for 15 minutes, standing for 30 minutes to precipitate white precipitate again, filtering with 800 mesh filter cloth, washing the filter cake with 80mL methanol for 3 times, drying at 50 deg.C for 60 min to obtain carboxymethyl cyclodextrin;
(3) adding 1g of modified tourmaline into 15mL of PBS (pH is 5.8), performing ultrasonic dispersion for 30 minutes at an ultrasonic frequency of 20kHz to obtain a modified tourmaline dispersion solution, dissolving 1.5g of carboxymethyl cyclodextrin and 0.15g N-hydroxysuccinimide in 45mL of PBS (pH is 5.8), stirring at 200 rpm for 30 minutes, adding 0.5g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, stirring at 200 rpm for 30 minutes, adding the modified tourmaline dispersion solution, stirring at 200 rpm for 24 hours at 25 ℃, filtering by adopting 800-mesh filter cloth, washing a filter cake with 80mL of water for 3 times, drying at 50 ℃ to constant weight, grinding, and sieving by using a 300-mesh sieve to obtain a carboxymethyl cyclodextrin-tourmaline composite material;
(4) adding 100mg of modifier into 250mL of water, stirring for 15 minutes at 60 ℃ at 200 rpm, adding 2g of carboxymethyl cyclodextrin-tourmaline composite material, stirring for 3 hours at 60 ℃ at 200 rpm, adding 100mg of silver nitrate, continuously stirring for 2 hours at 60 ℃ at 200 rpm, naturally cooling to 25 ℃, separating for 15 minutes at 8000 rpm, drying the lower-layer precipitate at 50 ℃ to constant weight, grinding, and sieving with a 300-mesh sieve to obtain the modified carboxymethyl cyclodextrin-tourmaline composite material.
The modifier is matrine.
The silane coupling agent is gamma-aminopropyl trimethoxy silane.
The preparation method of the antibacterial medical material comprises the following steps: weighing the raw materials according to the parts by weight, stirring for 10 minutes at 500 revolutions per minute to obtain a mixture, putting the mixture into a double-screw extruder, and extruding and granulating, wherein the temperatures of all regions of the double-screw extruder are respectively as follows: 155 deg.C, 165 deg.C, 175 deg.C, 185 deg.C, 190 deg.C, 175 deg.C, 165 deg.C.
Example 6
The antibacterial medical material comprises the following raw materials in parts by weight: 60 parts of polyurethane, 40 parts of polyvinyl chloride, 12 parts of modified carboxymethyl cyclodextrin-tourmaline composite material, 3 parts of magnesium borate whisker, 3 parts of plasticizer, 2 parts of lubricant, 2 parts of zinc oxide and 0.3 part of antioxidant.
The lubricant is zinc stearate.
The plasticizer is acetyl tributyl citrate.
The antioxidant is antioxidant 1010.
The modified carboxymethyl cyclodextrin-tourmaline composite material is prepared by the following method:
(1) tourmaline and 8 wt% sodium hydroxide aqueous solution are mixed according to the solid-to-liquid ratio of 1 g: 10mL of the mixture is mixed, stirred for 40 minutes at the temperature of 50 ℃ at the speed of 80 rpm, filtered by 800-mesh filter cloth, a filter cake is washed by water until the washing liquor is neutral, dried to constant weight, ground and sieved by a 300-mesh sieve to obtain the alkalized tourmaline, and ethanol and water are mixed according to the volume ratio of 65: 35 to obtain a hydroalcoholic mixed solution, mixing the hydroalcoholic mixed solution with a silane coupling agent according to a volume ratio of 100:5, stirring for 10 minutes at 70 ℃ at 200 revolutions per minute to obtain a coupling agent solution, adding 8g of alkalized tourmaline into 120mL of the coupling agent solution, performing reflux reaction for 3 hours at 70 ℃, cooling to 25 ℃, filtering by using 800-mesh filter cloth, washing a filter cake for 4 times by using 120mL of the hydroalcoholic mixed solution, drying to constant weight at 90 ℃, grinding, and sieving by using 300-mesh sieve to obtain modified tourmaline;
(2) adding 10g beta-cyclodextrin into 40mL20 wt% sodium hydroxide solution, slowly dropping 30mL15 wt% monochloroacetic acid aqueous solution at 60 ℃ while stirring at 200 r/min, dropping within 30 minutes, stirring at 60 ℃ at 200 r/min for 5 hours to obtain reaction solution, naturally cooling the reaction solution to 25 ℃, dropping 36 wt% concentrated hydrochloric acid while stirring at 200 r/min until the reaction solution is neutral, adding 500mL methanol, stirring at 400 r/min for 15 minutes, standing for 30 minutes to precipitate white precipitate, filtering with 800 mesh filter cloth, adding 10mL water into filter cake, stirring at 200 r/min until the precipitate is dissolved, adding 500mL methanol, stirring at 400 r/min for 15 minutes, standing for 30 minutes to precipitate white precipitate again, filtering with 800 mesh filter cloth, washing the filter cake with 80mL methanol for 3 times, drying at 50 deg.C for 60 min to obtain carboxymethyl cyclodextrin;
(3) adding 1g of modified tourmaline into 15mL of PBS (pH is 5.8), performing ultrasonic dispersion for 30 minutes at an ultrasonic frequency of 20kHz to obtain a modified tourmaline dispersion solution, dissolving 1.5g of carboxymethyl cyclodextrin and 0.15g N-hydroxysuccinimide in 45mL of PBS (pH is 5.8), stirring at 200 rpm for 30 minutes, adding 0.5g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, stirring at 200 rpm for 30 minutes, adding the modified tourmaline dispersion solution, stirring at 200 rpm for 24 hours at 25 ℃, filtering by adopting 800-mesh filter cloth, washing a filter cake with 80mL of water for 3 times, drying at 50 ℃ to constant weight, grinding, and sieving by using a 300-mesh sieve to obtain a carboxymethyl cyclodextrin-tourmaline composite material;
(4) adding 100mg of modifier into 250mL of water, stirring for 15 minutes at 60 ℃ at 200 rpm, adding 2g of carboxymethyl cyclodextrin-tourmaline composite material, stirring for 3 hours at 60 ℃ at 200 rpm, adding 100mg of silver nitrate, continuously stirring for 2 hours at 60 ℃ at 200 rpm, naturally cooling to 25 ℃, separating for 15 minutes at 8000 rpm, drying the lower-layer precipitate at 50 ℃ to constant weight, grinding, and sieving with a 300-mesh sieve to obtain the modified carboxymethyl cyclodextrin-tourmaline composite material.
The modifier is a mixture of chlorogenic acid and matrine, and the mass ratio of the chlorogenic acid to the matrine is 1: 3.
the silane coupling agent is gamma-aminopropyl trimethoxy silane.
The preparation method of the antibacterial medical material comprises the following steps: weighing the raw materials according to the parts by weight, stirring for 10 minutes at 500 revolutions per minute to obtain a mixture, putting the mixture into a double-screw extruder, and extruding and granulating, wherein the temperatures of all regions of the double-screw extruder are respectively as follows: 155 deg.C, 165 deg.C, 175 deg.C, 185 deg.C, 190 deg.C, 175 deg.C, 165 deg.C.
Test example 1
The mechanical properties and hardness of the antibacterial medical materials prepared in the examples and comparative examples were tested, and the specific test results are shown in table 1.
TABLE 1 anti-inflammatory effect test results of antibacterial medical materials
| Tensile strength, MPa | Elongation at break,% | Shore hardness, A | |
| Test method | ASTMD412 | ASTMD412 | ASTMD2240 |
| Example 1 | 18.2 | 351 | 85 |
| Comparative example 1 | 14.1 | 302 | 80 |
| Comparative example 2 | 16.4 | 326 | 83 |
| Example 2 | 20.3 | 387 | 88 |
| Example 3 | 20.8 | 403 | 89 |
| Example 4 | 22.1 | 420 | 91 |
| Example 5 | 22.4 | 428 | 91 |
| Example 6 | 24.2 | 451 | 93 |
Test example 2
The antibacterial medical materials prepared in the examples and comparative examples were soaked in water at 25 ℃ for 30 days, and the antibacterial properties against escherichia coli (ATCC 25922) and staphylococcus aureus (ATCC25293) after 30 days of soaking were tested, with reference to test standard ASTM E2149-01, and the specific test results are shown in table 2.
TABLE 2 antibacterial Effect test results Table
Test example 3
The cytotoxicity of the antibacterial medical materials of examples 1 to 6 was evaluated by the MTT method. The cytotoxicity test results showed that the cytotoxicity of examples 1 to 6 was rated as grade 1. This shows that the antibacterial medical material of the invention has good biocompatibility and meets the requirements of biological safety.
Claims (8)
1. An antibacterial medical material is characterized by comprising the following raw materials in parts by weight: 50-70 parts of polyurethane, 30-50 parts of polyvinyl chloride, 10-15 parts of modified carboxymethyl cyclodextrin-tourmaline composite material, 1-5 parts of magnesium borate whisker, 1-5 parts of plasticizer, 1-3 parts of lubricant, 1-3 parts of zinc oxide and 0.1-0.5 part of antioxidant;
the modified carboxymethyl cyclodextrin-tourmaline composite material is prepared by the following method:
(1) tourmaline and 5-10 wt% of sodium hydroxide aqueous solution are mixed according to the solid-to-liquid ratio of 1 g: (8-12) mL, stirring at 40-60 ℃ for 30-50 minutes, filtering, washing a filter cake with water until a washing liquid is neutral, drying to constant weight, grinding to obtain alkalized tourmaline, mixing ethanol and water according to a volume ratio of (60-70) (30-40) to obtain a hydroalcoholic mixed solution, mixing the hydroalcoholic mixed solution and a silane coupling agent according to a volume ratio of 100:5, stirring at 65-75 ℃ for 8-12 minutes to obtain a coupling agent solution, adding 5-10g of alkalized tourmaline into 150mL of 100-fold-of-organic solvent solution, carrying out reflux reaction at 65-75 ℃ for 2-4 hours, cooling to 20-30 ℃, filtering, washing the filter cake with 150mL of 100-fold-of hydroalcoholic mixed solution for 3-5 times, drying at 80-90 ℃ to constant weight, and grinding to obtain modified tourmaline;
(2) adding 8-12g of beta-cyclodextrin into 35-45mL of 18-22 wt% sodium hydroxide solution, slowly dropwise adding 25-35mL of 14-16 wt% monochloroacetic acid aqueous solution at 55-65 ℃ while stirring, stirring for 4-6 hours at 55-65 ℃ to obtain a reaction solution, naturally cooling the reaction solution to 20-30 ℃, dropwise adding 36 wt% concentrated hydrochloric acid while stirring until the reaction solution is neutral, adding 400-600mL of methanol, stirring for 10-20 minutes, standing for 20-40 minutes, separating out a white precipitate, filtering, adding 8-12mL of water into a filter cake, stirring until the precipitate is dissolved, adding 400-600mL of methanol, stirring for 10-20 minutes, standing for 20-40 minutes, separating out the white precipitate again, filtering, washing the filter cake with 60-100mL of methanol for 2-4 times, and drying at 40-60 ℃ for 40-60 minutes to obtain carboxymethyl cyclodextrin;
(3) adding 0.8-1.2g of modified tourmaline into 10-20mL of PBS, performing ultrasonic dispersion for 20-40 minutes at an ultrasonic frequency of 15-25kHz to obtain a modified tourmaline dispersion solution, dissolving 1-2g of carboxymethyl cyclodextrin and 0.1-0.2g N-hydroxysuccinimide into 40-50mL of PBS, stirring for 20-40 minutes, adding 0.2-0.3g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, stirring for 20-40 minutes, adding the modified tourmaline dispersion solution, stirring for 20-30 hours at 20-30 ℃, filtering, washing a filter cake with 60-100mL of water for 2-4 times, drying at 40-60 ℃ to constant weight, and grinding to obtain a carboxymethyl cyclodextrin-tourmaline composite material;
(4) adding 80-120mg of modifier into 300mL of 200-mL water, stirring for 10-20 minutes at 50-70 ℃, adding 1.5-2.5g of carboxymethyl cyclodextrin-tourmaline composite material, stirring for 2-4 hours at 50-70 ℃, adding 80-120mg of silver nitrate, continuously stirring for 1-3 hours at 50-70 ℃, naturally cooling to 20-30 ℃, centrifuging for 10-20 minutes, drying the lower-layer precipitate at 40-60 ℃ to constant weight, and grinding to obtain the modified carboxymethyl cyclodextrin-tourmaline composite material.
2. The antimicrobial medical material of claim 1, wherein the lubricant is one or more of zinc stearate, ethylene bis stearamide, oleamide.
3. The antibacterial medical material according to claim 1, wherein the plasticizer is any one of acetyl tributyl citrate and dioctyl adipate.
4. The antimicrobial medical material of claim 1, wherein the antioxidant is any one or a mixture of antioxidants 1010, 168, 1076.
5. The antibacterial medical material according to claim 1, wherein the silane coupling agent is any one of γ -aminopropyltriethoxysilane, γ -aminopropyltrimethoxysilane, γ -aminopropylmethyldiethoxysilane and γ -aminopropylmethyldimethoxysilane.
6. The antibacterial medical material according to claim 1, wherein the modifier is chlorogenic acid and/or matrine.
7. The antibacterial medical material of claim 1, wherein the modifier is a mixture of chlorogenic acid and matrine, and the mass ratio of the chlorogenic acid to the matrine is 1: (2-4).
8. The method for preparing an antibacterial medical material according to any one of claims 1 to 7, comprising the steps of: weighing the raw materials according to the parts by weight, stirring for 8-12 minutes at the speed of 400 plus one minute and 600 revolutions per minute to obtain a mixture, and putting the mixture into a double-screw extruder for extrusion and granulation to obtain the composite material.
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