CN113754853A - Antibacterial medical drainage polyurethane foam and preparation method thereof - Google Patents
Antibacterial medical drainage polyurethane foam and preparation method thereof Download PDFInfo
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- CN113754853A CN113754853A CN202111075517.3A CN202111075517A CN113754853A CN 113754853 A CN113754853 A CN 113754853A CN 202111075517 A CN202111075517 A CN 202111075517A CN 113754853 A CN113754853 A CN 113754853A
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/141—Hydrocarbons
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/143—Halogen containing compounds
- C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
- C08J9/145—Halogen containing compounds containing carbon, halogen and hydrogen only only chlorine as halogen atoms
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- C08G2101/00—Manufacture of cellular products
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
- C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
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Abstract
The invention discloses antibacterial medical drainage polyurethane foam and a preparation method thereof, and raw materials of the antibacterial medical drainage polyurethane foam comprise 100 parts of polyether polyol, 1.2-3.5 parts of organic silicon foam stabilizer, 1-15 parts of foaming agent, 0.1-1 part of tannic acid, 0.1-0.6 part of imidazolidinyl urea, 0.5-6 parts of silver sulfadiazine, 1-10 parts of chitosan, 35-65 parts of toluene diisocyanate, 0.1-0.5 part of amine catalyst, 0.10-0.70 part of zinc catalyst and 1-6 parts of water. The invention selects a plurality of antibacterial agents such as chitosan, tannic acid, silver sulfadiazine and the like to provide oxygen active sites for polyurethane foam, so that the polyurethane foam has antibacterial property, and meanwhile, the polyurethane foam has the advantages of excellent biocompatibility, no distortion, no anaphylactic reaction, excellent anticoagulation property, medical requirement compliance of toxicity test, excellent toughness and elasticity, good processing property, various processing modes and the like.
Description
Technical Field
The invention relates to the field of medical materials, in particular to antibacterial medical drainage polyurethane foam and a preparation method thereof.
Background
The negative pressure sealing drainage technology (VSD) is a brand new treatment method that a medical sponge dressing with a drainage tube is used for covering or filling the wound surface with skin and soft tissue defects, the wound surface is sealed by a semipermeable bio-membrane to form a sealed space, and finally the drainage tube is connected with a negative pressure source to promote the wound surface to heal through controllable negative pressure. In the traditional wound treatment method, necrotic tissues, abscesses, wound exudate, infectious toxins and metabolite resorption around the wound can form 'secondary hit' on a patient, so that the phenomena of inflammatory reaction, sepsis and multi-organ insufficiency or failure of the whole body of the patient occur. The VSD technology is similar to a cupping glass, a closed and negative pressure environment is formed on the wound surface of a human body, wound surface exudate, necrotic tissues and toxin are sucked out in time and drained out of the body, so that external infection is isolated, and the healing time is shortened. The VSD technology is simple and convenient to operate and easy to master in practical application, the curative effect is far better than that of conventional treatment, the treatment method is a pure physical method, side effects possibly caused by various chemical treatments can be completely avoided, and a flushing and drug delivery system is additionally arranged and can be used in combination with various drugs.
The negative pressure closed drainage technology is the most effective method for treating large-area burns and wounds, diabetic feet, fistulas (intestinal fistulas, osteomyelitis fistulas and the like) and various wounds which are difficult to heal at present, and can avoid serious consequences of wound infection, disability and even death of patients caused by adopting the traditional treatment method.
In addition, the VSD technology can also be used for treating large-area skin tissue defect avulsion, soft tissue infection, incision infection, application after skin grafting, burn and other diseases, and is widely applied to various clinical departments such as trauma surgery, orthopedics, general surgery, burn department and the like.
The common negative pressure drainage sponge at present mainly comprises polyvinyl alcohol sponge and polyurethane sponge, and both have a certain negative pressure drainage effect. However, because neither polyvinyl alcohol nor polyurethane is inherently antimicrobial, a large amount of antibiotic anti-inflammatory drugs are still required to treat the infection, which not only increases the physical burden on the patient during treatment, but also may lead to multiple drug resistant bacterial infections (MDR) in the patient due to antibiotic abuse, resulting in a greater risk of infection. Therefore, the negative pressure drainage sponge urgently needs to be added with an antibacterial agent in the preparation process, so that the sponge has antibacterial property, the abuse of antibiotics in the treatment process is reduced, the treatment process is accelerated, and the risk of drug-resistant bacteria is reduced.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides antibacterial medical drainage polyurethane foam and a preparation method thereof.
In order to achieve the purpose, the invention designs an antibacterial medical drainage polyurethane foam, and the raw materials of the drainage polyurethane foam comprise, by weight, 100 parts of polyether polyol, 1.2-3.5 parts of an organic silicon foam stabilizer, 1-15 parts of a foaming agent, 0.1-1 part of tannic acid, 0.1-0.6 part of imidazolidinyl urea, 0.5-6 parts of silver sulfadiazine, 1-10 parts of chitosan, 35-65 parts of toluene diisocyanate, 0.1-0.5 part of an amine catalyst, 0.10-0.70 part of a zinc catalyst and 1-6 parts of water.
Further, the raw materials of the drainage polyurethane foam comprise, by weight, 100 parts of polyether polyol, 1.2-2.0 parts of an organosilicon foam stabilizer, 5-12 parts of a foaming agent, 0.4-1.0 part of tannic acid, 0.2-0.5 part of imidazolidinyl urea, 3-6 parts of silver sulfadiazine, 6-10 parts of chitosan, 35-45 parts of toluene diisocyanate, 0.1-0.3 part of an amine catalyst, 0.10-0.30 part of a zinc catalyst and 1-3 parts of water.
Further, the hydroxyl value of the polyether polyol is 50-165 mg KOH/g, and the molecular weight is 2800-4500.
Still further, the blowing agent is dichloromethane or cyclopentane.
Still further, the amine catalyst may be any one or more of triethylene diamine, ethylene diamine, triethylamine, triethanolamine and hexamethylene diamine.
Still further, the raw materials of the drainage polyurethane foam comprise, by weight, 55mg KOH/g of hydroxyl value, 30 parts of polyether polyol with molecular weight of 4300, 103mg KOH/g of hydroxyl value, 30 parts of polyether polyol with molecular weight of 3700, 164mg KOH/g of hydroxyl value, 40 parts of polyether polyol with molecular weight of 2800, 1.5 parts of silicone foam stabilizer, 10 parts of dichloromethane, 0.8 part of tannic acid, 0.3 part of imidazolidinyl urea, 4 parts of sulfadiazine silver, 8 parts of chitosan, 40 parts of toluene diisocyanate, 0.2 part of triethylene diamine, 0.15 part of zinc catalyst and 2 parts of water.
The invention also provides a preparation method of the antibacterial medical drainage polyurethane foam, which comprises the following steps:
1) weighing 100 parts of polyether polyol, 1.2-3.5 parts of organosilicon foam stabilizer, 1-15 parts of foaming agent, 0.1-1 part of tannic acid, 0.1-0.6 part of imidazolidinyl urea, 0.5-6 parts of silver sulfadiazine, 1-10 parts of chitosan, 35-65 parts of toluene diisocyanate, 0.1-0.5 part of amine catalyst, 0.1-0.7 part of zinc catalyst and 1-6 parts of water in parts by weight for later use;
2) mechanically stirring and uniformly mixing polyether polyol, an organic silicon foam stabilizer, a foaming agent, tannic acid, imidazolidinyl urea, silver sulfadiazine, chitosan and toluene diisocyanate to obtain a white material, namely a prepolymer;
3) and then pouring the amine catalyst, the zinc catalyst and water into the prepolymer, mechanically stirring and uniformly mixing, pouring into a mold for foaming, curing for 24 hours at 80 ℃, and demolding to obtain the drainage polyurethane foam.
The invention has the beneficial effects that:
1. the selection and the compounding of a plurality of polyether polyols ensure that the polyurethane foam has more proper aperture and aperture ratio
2. The gel catalyst used in the invention is safe and nontoxic
3. The drainage polyurethane foam has good antibacterial and bacteriostatic properties due to the addition of the antibacterial and bacteriostatic material, and the problem of anaerobic bacteria breeding in the negative pressure closed drainage technology is effectively solved due to the addition of the chitosan.
Detailed Description
The present invention is described in further detail below with reference to specific examples so as to be understood by those skilled in the art.
Example 1
The preparation method of the antibacterial medical drainage polyurethane foam 1 comprises the following steps:
1) weighing 50 parts of polyether polyol with the hydroxyl value of 55mg KOH/g and the molecular weight of 4300, 50 parts of polyether polyol with the hydroxyl value of 103mg KOH/g and the molecular weight of 3700, 2.5 parts of organic silicon foam stabilizer, 10 parts of dichloromethane, 55 parts of toluene diisocyanate, 0.5 part of triethylene diamine, 0.5 part of zinc catalyst and 5 parts of water for later use;
2) mechanically stirring and uniformly mixing polyether polyol, an organic silicon foam stabilizer, dichloromethane, tannic acid, imidazolidinyl urea, silver sulfadiazine, chitosan and toluene diisocyanate to obtain a white material, namely a prepolymer;
3) and then pouring triethylene diamine, a zinc catalyst and water into the prepolymer, mechanically stirring and uniformly mixing, pouring into a mold for foaming, curing for 24 hours at 80 ℃, and demolding to obtain the drainage polyurethane foam 1.
Example 2
The preparation method of the antibacterial medical drainage polyurethane foam 2 comprises the following steps:
1) weighing 50 parts of polyether polyol with the hydroxyl value of 55mg KOH/g and the molecular weight of 4300, 50 parts of polyether polyol with the hydroxyl value of 103mg KOH/g and the molecular weight of 3700, 2 parts of organic silicon foam stabilizer, 8 parts of cyclopentane, 0.5 part of tannic acid, 0.5 part of imidazolidinyl urea, 1 part of silver sulfadiazine, 6 parts of chitosan, 55 parts of toluene diisocyanate, 0.2 part of ethylenediamine, 0.2 part of zinc catalyst and 4.5 parts of water according to the weight part ratio for later use;
2) mechanically stirring and uniformly mixing polyether polyol, an organic silicon foam stabilizer, cyclopentane, tannic acid, imidazolidinyl urea, silver sulfadiazine, chitosan and toluene diisocyanate to obtain a white material, namely a prepolymer;
3) and then, pouring ethylenediamine, a zinc catalyst and water into the prepolymer, mechanically stirring and uniformly mixing, pouring into a mold for foaming, curing for 24 hours at 80 ℃, and demolding to obtain the drainage polyurethane foam 2.
Example 3
The preparation method of the antibacterial medical drainage polyurethane foam 3 comprises the following steps:
1) weighing 30 parts of polyether polyol with the hydroxyl value of 55mg KOH/g and the molecular weight of 4300, 70 parts of polyether polyol with the hydroxyl value of 103mg KOH/g and the molecular weight of 3700, 1.5 parts of organic silicon foam stabilizer, 10 parts of cyclopentane, 0.1 part of tannic acid, 0.5 part of imidazolidinyl urea, 2 parts of silver sulfadiazine, 5 parts of chitosan, 45 parts of toluene diisocyanate, 0.3 part of triethylamine, 0.2 part of zinc catalyst and 5 parts of water according to the weight part ratio for later use;
2) mechanically stirring and uniformly mixing polyether polyol, an organic silicon foam stabilizer, cyclopentane, tannic acid, imidazolidinyl urea, silver sulfadiazine, chitosan and toluene diisocyanate to obtain a white material, namely a prepolymer;
3) and then triethylamine, a zinc catalyst and water are poured into the prepolymer, the mixture is mechanically stirred and uniformly mixed, the mixture is poured into a mould for foaming, the mixture is cured for 24 hours at the temperature of 80 ℃, and the mould is removed, so that the drainage polyurethane foam 3 is obtained.
Example 4
The preparation method of the antibacterial medical drainage polyurethane foam 4 comprises the following steps:
1) weighing 50 parts of polyether polyol with the hydroxyl value of 55mg KOH/g and the molecular weight of 4300, 50 parts of polyether polyol with the hydroxyl value of 164mg KOH/g and the molecular weight of 2800, 1.5 parts of organic silicon foam stabilizer, 10 parts of dichloromethane, 0.4 part of tannic acid, 0.5 part of imidazolidinyl urea, 3 parts of silver sulfadiazine, 5 parts of chitosan, 55 parts of toluene diisocyanate, 0.2 part of triethanolamine, 0.2 part of zinc catalyst and 3.5 parts of water for later use;
2) mechanically stirring and uniformly mixing polyether polyol, an organic silicon foam stabilizer, dichloromethane, tannic acid, imidazolidinyl urea, silver sulfadiazine, chitosan and toluene diisocyanate to obtain a white material, namely a prepolymer;
3) and then the triethanolamine, the zinc catalyst and the water are poured into the prepolymer, the mixture is mechanically stirred and uniformly mixed, the mixture is poured into a mould for foaming, the mixture is cured for 24 hours at the temperature of 80 ℃, and the drainage polyurethane foam 4 is obtained after demoulding.
Example 5
The preparation method of the antibacterial medical drainage polyurethane foam 5 comprises the following steps:
1) weighing 30 parts of polyether polyol with the hydroxyl value of 55mg KOH/g and the molecular weight of 4300, 70 parts of polyether polyol with the hydroxyl value of 164mg KOH/g and the molecular weight of 2800, 1.5 parts of an organic silicon foam stabilizer, 15 parts of cyclopentane, 0.2 part of tannic acid, 0.4 part of imidazolidinyl urea, 3 parts of silver sulfadiazine, 6 parts of chitosan, 40 parts of toluene diisocyanate, 0.3 part of hexamethylene diamine, 0.2 part of a zinc catalyst and 1.5 parts of water for later use;
2) mechanically stirring and uniformly mixing polyether polyol, an organic silicon foam stabilizer, cyclopentane, tannic acid, imidazolidinyl urea, silver sulfadiazine, chitosan and toluene diisocyanate to obtain a white material, namely a prepolymer;
3) and then pouring hexamethylene diamine, a zinc catalyst and water into the prepolymer, mechanically stirring and uniformly mixing, pouring into a mold for foaming, curing for 24 hours at 80 ℃, and demolding to obtain the drainage polyurethane foam 5.
Example 6
The preparation method of the antibacterial medical drainage polyurethane foam 6 comprises the following steps:
1) weighing 30 parts of polyether polyol with the hydroxyl value of 55mg KOH/g and the molecular weight of 4300, 30 parts of polyether polyol with the hydroxyl value of 103mg KOH/g, 30 parts of polyether polyol with the molecular weight of 3700, 40 parts of polyether polyol with the hydroxyl value of 164mg KOH/g and the molecular weight of 2800, 1.5 parts of organic silicon foam stabilizer, 10 parts of dichloromethane, 0.8 part of tannic acid, 0.3 part of imidazolidinyl urea, 4 parts of sulfadiazine silver, 8 parts of chitosan, 40 parts of toluene diisocyanate, 0.2 part of triethylene diamine, 0.15 part of zinc catalyst and 2 parts of water according to the weight part ratio for later use;
2) mechanically stirring and uniformly mixing polyether polyol, an organic silicon foam stabilizer, dichloromethane, tannic acid, imidazolidinyl urea, silver sulfadiazine, chitosan and toluene diisocyanate to obtain a white material, namely a prepolymer;
3) and then pouring triethylene diamine, a zinc catalyst and water into the prepolymer, mechanically stirring and uniformly mixing, pouring into a mold for foaming, curing for 24 hours at 80 ℃, and demolding to obtain the drainage polyurethane foam 6.
The drainage polyurethane foams 1 to 6 prepared in examples 1 to 6 were tested for antibacterial property, cytotoxicity and open cell content:
1. test for antibacterial Properties
2. Cytotoxicity test
3. Open cell content test
Compared with the existing products sold in the market, the drainage polyurethane foams 1-6 prepared in the embodiments 1-6 have obviously better performances than the products sold in the market, wherein the drainage polyurethane foam 6 has the best effect.
Other parts not described in detail are prior art. Although the present invention has been described in detail with reference to the above embodiments, it is only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and the embodiments are within the scope of the present invention.
Claims (7)
1. An antibacterial medical drainage polyurethane foam is characterized in that: the raw materials of the drainage polyurethane foam comprise, by weight, 100 parts of polyether polyol, 1.2-3.5 parts of an organic silicon foam stabilizer, 1-15 parts of a foaming agent, 0.1-1 part of tannic acid, 0.1-0.6 part of imidazolidinyl urea, 0.5-6 parts of silver sulfadiazine, 1-10 parts of chitosan, 35-65 parts of toluene diisocyanate, 0.1-0.5 part of an amine catalyst, 0.10-0.70 part of a zinc catalyst and 1-6 parts of water.
2. The antibacterial medical drainage polyurethane foam according to claim 1, wherein: the raw materials of the drainage polyurethane foam comprise, by weight, 100 parts of polyether polyol, 1.2-2.0 parts of an organic silicon foam stabilizer, 5-12 parts of a foaming agent, 0.4-1.0 part of tannic acid, 0.2-0.5 part of imidazolidinyl urea, 3-6 parts of silver sulfadiazine, 6-10 parts of chitosan, 35-45 parts of toluene diisocyanate, 0.1-0.3 part of an amine catalyst, 0.10-0.30 part of a zinc catalyst and 1-3 parts of water.
3. The antibacterial medical drainage polyurethane foam according to claim 1 or 2, wherein: the hydroxyl value of the polyether polyol is 50-165 mg KOH/g, and the molecular weight is 2800-4500.
4. The antibacterial medical drainage polyurethane foam according to claim 1 or 2, wherein: the foaming agent is dichloromethane or cyclopentane.
5. The antibacterial medical drainage polyurethane foam according to claim 1 or 2, wherein: the amine catalyst is one or more of triethylene diamine, ethylene diamine, triethylamine, triethanolamine and hexamethylene diamine.
6. The antibacterial medical drainage polyurethane foam according to claim 1, wherein: the drainage polyurethane foam comprises, by weight, 55mg KOH/g of hydroxyl value, 30 parts of polyether polyol with the molecular weight of 4300, 103mg KOH/g of hydroxyl value, 30 parts of polyether polyol with the molecular weight of 3700, 164mg KOH/g of hydroxyl value, 40 parts of polyether polyol with the molecular weight of 2800, 1.5 parts of an organic silicon foam stabilizer, 10 parts of dichloromethane, 0.8 part of tannic acid, 0.3 part of imidazolidinyl urea, 4 parts of sulfadiazine silver, 8 parts of chitosan, 40 parts of toluene diisocyanate, 0.2 part of triethylene diamine, 0.15 part of a zinc catalyst and 2 parts of water.
7. A method for preparing the antibacterial medical drainage polyurethane foam of claim 1, which is characterized in that: the method comprises the following steps:
1) weighing 100 parts of polyether polyol, 1.2-3.5 parts of organosilicon foam stabilizer, 1-15 parts of foaming agent, 0.1-1 part of tannic acid, 0.1-0.6 part of imidazolidinyl urea, 0.5-6 parts of silver sulfadiazine, 1-10 parts of chitosan, 35-65 parts of toluene diisocyanate, 0.1-0.5 part of amine catalyst, 0.1-0.7 part of zinc catalyst and 1-6 parts of water in parts by weight for later use;
2) mechanically stirring and uniformly mixing polyether polyol, an organic silicon foam stabilizer, a foaming agent, tannic acid, imidazolidinyl urea, silver sulfadiazine, chitosan and toluene diisocyanate to obtain a white material, namely a prepolymer;
3) and then pouring the amine catalyst, the zinc catalyst and water into the prepolymer, mechanically stirring and uniformly mixing, pouring into a mold for foaming, curing for 24 hours at 80 ℃, and demolding to obtain the drainage polyurethane foam.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114452434A (en) * | 2022-01-26 | 2022-05-10 | 武汉理工大学 | Broad-spectrum antibacterial polyurethane foam dressing and preparation method and application thereof |
| CN117567790A (en) * | 2024-01-15 | 2024-02-20 | 四川大学 | Medical polyurethane foam with procoagulant inner surface and anticoagulant outer surface and preparation method thereof |
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| CN114452434A (en) * | 2022-01-26 | 2022-05-10 | 武汉理工大学 | Broad-spectrum antibacterial polyurethane foam dressing and preparation method and application thereof |
| CN117567790A (en) * | 2024-01-15 | 2024-02-20 | 四川大学 | Medical polyurethane foam with procoagulant inner surface and anticoagulant outer surface and preparation method thereof |
| CN117567790B (en) * | 2024-01-15 | 2024-03-26 | 四川大学 | Medical polyurethane foam with procoagulant inner surface and anticoagulant outer surface and preparation method thereof |
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