CN109529642B - Preparation method of medical polyurethane porous membrane with chitosan sprayed on surface - Google Patents
Preparation method of medical polyurethane porous membrane with chitosan sprayed on surface Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0013—Casting processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/08—Polysaccharides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/24—Mechanical properties, e.g. strength
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Moulding By Coating Moulds (AREA)
- Materials For Medical Uses (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention relates to a preparation method of a medical polyurethane porous membrane with chitosan sprayed on the surface. The method comprises the steps of preparing a polyurethane membrane casting solution, scraping the membrane from the membrane casting solution, spraying a chitosan solution on the surface of a solution membrane, forming the solution membrane into a membrane in a coagulating bath, firstly, preparing the membrane casting solution containing polyurethane, an additive and an organic solvent according to a certain mass ratio, scraping the membrane casting solution into the solution membrane in a glass mold by using a scraper, then spraying a chitosan acetic acid aqueous solution or a chitosan powder aqueous solution on the surface of the solution membrane, finally placing the mold in the coagulating bath, and obtaining the polyurethane porous membrane through phase transformation of the solution membrane, wherein the surface and the section structure of the modified polyurethane porous membrane are not changed compared with the surface and the section structure before modification by adopting the chitosan spraying and modifying the surface of the polyurethane porous membrane, but the modified polyurethane porous membrane has better performance, the porosity of the polyurethane porous membrane is 1.20-1.40 times before modification, and the water absorption of the polyurethane porous membrane is 1.22-1.42 times before modification, the moisture permeability is 1.33-4.10 times of that before modification.
Description
Technical Field
The invention relates to a preparation method for modifying a polyurethane porous membrane, belonging to a modification method of a polymer microporous membrane.
Background
The polyurethane is prepared by the interaction of diisocyanate and dihydric alcohol, and can be prepared into polyurethane products with different performances and various expression forms by adjusting the proportion of soft segments and hard segments, selecting functional groups with different numbers and different types and adopting different synthesis processes. The medical polyurethane has good biocompatibility and biodegradability with organisms, so the medical polyurethane is widely applied to biomedical materials, is one of important polymers in the field of biomaterials, is widely applied to porous membranes or porous scaffold materials such as artificial skin, medical dressings and artificial blood vessels, and has wide application prospects which arouse people to be interested.
Common preparation methods of the medical polyurethane porous membrane include a particle pore-forming method, immersion precipitation phase conversion and a solution freeze-drying method. Various preparation methods and techniques have advantages and disadvantages, and a desired porous film is prepared by selecting an appropriate method or combining a plurality of methods according to actual requirements for the porous film. Currently, in order to further improve the moisture permeability, the air permeability, the hydrophilicity, the cell adhesion and other properties of the medical polyurethane porous membrane, research on modification of the polyurethane porous membrane is also receiving more and more attention.
The modification research of the polyurethane porous membrane mainly comprises physical modification and chemical modification, wherein the physical modification mainly comprises the preparation of a composite porous membrane by blending polyurethane, inorganic particles, organic particles and polymers, common particles comprise nano silicon dioxide, carbon nano tubes, chitosan powder, fibroin powder, wool powder and the like, common blended polymers comprise Cellulose Acetate (CA), Polysulfone (PS), Polyacrylonitrile (PAN), polyvinylidene fluoride (PVDF) and the like, and the chemical modification mainly comprises the modification of the chemical structure of the polyurethane, such as fluorine modification and silicon modification of acrylic polyurethane, silane coupling agent terminated polyurethane, polybutadiene-based polyurethane, methyl methacrylate copolymerization modified waterborne polyurethane membrane and the like. Compared with chemical modification, the physical modification process is simpler and more suitable for industrial production. For example, Xu et al, a polyurethane porous film is prepared by a blending solution of superfine down feather powder and polyurethane by adopting an immersion precipitation method, the moisture permeability of the film is obviously improved, the superfine down feather powder enables the pore size of the film to be increased, the connectivity among pores is better, and the hydrophilicity of the down feather powder enables more hydrophilic groups to be arranged in the porous film, thereby being beneficial to the transmission of water vapor molecules from one side with high humidity to one side with low humidity through the adsorption-diffusion-desorption process; the addition of the down powder leads the polyurethane molecules to be arranged loosely, the movement of the molecular chain is intensified, and the structural changes are beneficial to the increase of the moisture permeability of the polyurethane film. The chitosan micro powder/biomedical polyurethane blended porous membrane is prepared by a wet phase transition method by using a blending solution of biomedical polyurethane and superfine chitosan micro powder such as Chenyubo and the like. The water absorption swelling degree and the moisture vapor permeability of the film are greatly improved along with the increase of the chitosan micro powder. Dianhua et al modify polyurethane film with wool powder produced by chemical-mechanical process, and the experimental results show that the moisture permeability of the film increases with the increase of the filling amount of the wool powder, mainly because the wool particles are dispersed in the film gradually and continuously by interruption with the increase of the powder amount, the discontinuous channels become unblocked gradually, and the channels increase, thereby facilitating the transportation of water vapor.
At present, the blending modification of the polyurethane porous membrane is mainly to modify the porous membrane body, although the moisture permeability, the air permeability and the swelling performance of the membrane are improved, the improvement of the hydrophilicity of the membrane surface is not obvious, and the elasticity and the toughness of the polyurethane membrane are reduced due to the addition of the blending material.
Disclosure of Invention
Aiming at the problems of the surface hydrophilicity of the polyurethane porous membrane, the invention aims to provide a modification method which can improve the surface hydrophilicity of the medical polyurethane porous membrane and can keep good elasticity and toughness of the medical polyurethane porous membrane, and in order to realize the aim, the technical scheme of the invention is as follows:
a preparation method of a medical polyurethane porous membrane with chitosan sprayed on the surface comprises the steps of preparing a polyurethane membrane casting solution, scraping the membrane from the membrane casting solution, spraying a chitosan solution on the surface of a solution membrane, and gelling the solution membrane in a coagulating bath to form a membrane, and is characterized in that the preparation method of the medical polyurethane porous membrane with chitosan sprayed on the surface comprises the following steps:
A. mixing, heating and stirring medical polyurethane, an organic solvent and an additive according to the proportion of 10-18 wt%, 74-87 wt% and 3-8 wt% until the medical polyurethane, the organic solvent and the additive are completely dissolved to prepare a casting solution;
the organic solvent is N, N-dimethylformamide or 1, 4-dioxane, and the additive is polyvinylpyrrolidone or polyethylene glycol;
B. scraping the casting solution into a solution film with the thickness of 150-300 microns in a glass plate mold by using a glass scraper;
C. uniformly spraying a certain amount of chitosan solution on the surface of a solution film in a sprayer under the pressure of 0.05-0.1 MPa;
the chitosan solution is a chitosan acetic acid aqueous solution or a chitosan powder aqueous solution, the concentration of chitosan is 0.5-2 wt%, and the volume of the chitosan solution sprayed can be changed, so that the weight proportion of chitosan in the porous membrane is 4-15 wt%;
D. and (3) placing the solution film with the surface sprayed with the chitosan solution for 1-2 min, then placing the glass plate into a deionized water bath, and carrying out gel film formation on the solution film in the water bath.
Due to the adoption of the technical scheme, the invention has the advantages that:
(1) the invention only modifies the surface of the medical polyurethane porous membrane, so that the hydrophilicity of the membrane surface is improved, and the good elasticity and toughness of the medical polyurethane porous membrane are maintained because chitosan or chitosan powder is not arranged inside the membrane.
(2) According to the invention, a chitosan solution is sprayed on the surface of the solution membrane in an atomizing spraying manner, so that the surface of the solution membrane is firstly gelled, phase separation occurs, a poor polymer phase forms a hole, the solution membrane with the surface gelled is immersed in coagulating bath water, the surface which is subjected to the phase separation can promote water to enter the solution membrane, the phase separation speed in the solution membrane is accelerated, the section structure of the membrane is further influenced, the porosity in the membrane is increased, the average pore size of the whole membrane is increased, and the improvement of the water absorption and moisture permeability of the membrane is facilitated.
(3) The solution is uniformly covered on the surface of the membrane by adopting an atomization spraying mode, and the method is simple and easy to implement and is easy to realize industrial production.
Drawings
FIG. 1 is a scanning electron micrograph of the upper and lower surfaces of a polyurethane porous film to which 4ml of a 0.5% aqueous chitosan acetic acid solution was spray-coated in example 1
FIG. 2 is a scanning electron micrograph of the upper and lower surfaces of a polyurethane porous film coated with 4ml of a 1% aqueous solution of chitosan acetic acid in example 2
FIG. 3 is a scanning electron micrograph of the upper and lower surfaces of the polyurethane porous film sprayed with 2ml of a 2% chitosan powder aqueous solution in example 4
The upper surface refers to the surface of the solution film that is in contact with the air, and the lower surface refers to the surface of the solution film that is in contact with the bottom of the glass mold.
Detailed Description
The invention adopts a physical method to carry out surface modification on the medical polyurethane porous membrane, improves the porosity, hydrophilicity and moisture permeability of the medical polyurethane porous membrane, and simultaneously reserves the elasticity and toughness of the polyurethane porous membrane.
A preparation method of a medical polyurethane porous membrane with chitosan sprayed on the surface comprises the following steps of preparing a polyurethane membrane casting solution, scraping the membrane by the membrane casting solution, spraying a chitosan solution on the surface of a solution membrane, and gelling the solution membrane in a coagulating bath to form a membrane, wherein the preparation method of the medical polyurethane porous membrane with chitosan sprayed on the surface comprises the following steps:
A. mixing, heating and stirring medical polyurethane, an organic solvent and an additive according to the proportion of 10-18 wt%, 74-87 wt% and 3-8 wt% for 6 hours to prepare a casting solution, and standing and defoaming for later use; the organic solvent is N, N-dimethylformamide or 1, 4-dioxane, and the additive is polyvinylpyrrolidone or polyethylene glycol;
B. scraping the casting solution into a solution film with the thickness of 150-300 microns in a glass plate mold by using a glass scraper;
C. uniformly spraying a certain amount of chitosan solution on the surface of a solution film in a sprayer under the pressure of 0.05-0.1 MPa; the chitosan solution is a chitosan acetic acid aqueous solution or a chitosan powder aqueous solution, the average grain diameter of the chitosan powder is 2-3 mu m, the chitosan concentration is 0.5-2 wt%, and the certain amount of the chitosan solution means that the volume of the sprayed chitosan solution can be changed, so that the proportion of chitosan in the porous membrane is 4-15 wt%;
the chitosan spraying liquid comprises a chitosan acetic acid aqueous solution and a chitosan powder aqueous solution, wherein the chitosan acetic acid aqueous solution is formed by dissolving chitosan in an acetic acid aqueous solution, the concentrations of the chitosan acetic acid aqueous solution are respectively 0.5wt%, 1 wt% and 2wt%, the chitosan powder solution is formed by dispersing chitosan powder in deionized water, and the chitosan contents are respectively 0.5wt%, 1 wt% and 2 wt%. The chitosan content in the porous membrane is changed by controlling the volume of the spraying liquid.
D. And (3) placing the solution film with the surface sprayed with the chitosan solution for 1-2 min, then placing the glass plate mold into a deionized water bath, and carrying out gel film formation on the solution film in the water bath. And completely soaking the gel polyurethane porous membrane in deionized water for 5-7 days, and then selecting a clean and ventilated place to hang the membrane to naturally dry the membrane.
The calculation formula of the porosity and the water absorption related in the invention is as follows:
(1) porosity of the material
The porosity of the medical polyurethane porous membrane is measured by adopting a density method, and the calculation formula is as follows:
ε=（1-ρ film /ρ Fruit of Chinese wolfberry ）×100% （1）
Rho film: density of polyurethane porous film, ρ solid: the solid density of the polyurethane was 1.12g/cm3
(2) Water absorption rate
The liquid absorption rate of the medical polyurethane porous membrane is measured by a gravimetric method. Weighing (A) by weightW 1 ) Porous polyurethane membrane, subjecting to distillationSoaking in water for 24 hr, wiping off the surface water, and weighingW 2 ) The change in mass was compared. The calculation formula is as follows:
Q=（W 2 -W 1 ）×100%/W 1 （2）
the following examples describe the invention in more detail.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Example 1
Placing 400g of a mixed system of 14%, 81% and 5% by weight of medical polyurethane (BPU), N-Dimethylformamide (DMF) and polyvinylpyrrolidone 30 (PVP 30) in a water bath kettle at 40 ℃, stirring for 6 hours by using a mechanical stirring device, standing and defoaming after the medical polyurethane in the system is completely dissolved, and finishing the preparation of the casting solution. Pouring 0.25g of chitosan powder into a 50ml conical flask, adding 49.75ml of deionized water into the conical flask filled with the chitosan powder, adding 0.5ml of acetic acid solution into the conical flask, adding a clean magnet, stirring by using a magnetic stirrer until the acetic acid solution is completely dissolved, preparing 50ml of chitosan acetic acid aqueous solution with the concentration of 0.5%, and finishing the preparation of the chitosan acetic acid aqueous solution spraying liquid. Pouring a proper amount of the prepared casting membrane liquid into one end of a glass mold (120 mm multiplied by 180mm multiplied by 0.2 mm), scraping the casting membrane liquid from the top by using a glass scraper to form a liquid membrane with the thickness of 200 mu m, placing a 0.5% chitosan acetic acid aqueous solution into a sprayer, uniformly spraying 4ml of the chitosan acetic acid aqueous solution on the surface of the scraped liquid membrane under the pressure of 0.05MPa, placing for 2 minutes, then placing the glass mold into a deionized water bath, removing the membrane after two minutes, completely soaking in film soaking deionized water, changing water once a day, and selecting a clean and ventilated place to hang the membrane after 5 days to naturally dry the membrane. The content of chitosan in the polyurethane porous film after modification was 4.08%, the porosity was 1.20 times that of the unmodified film, the water absorption was 1.22 times that of the unmodified film, the moisture vapor permeability was 1.33 times that of the unmodified film, and the contact angle was decreased by 4 degrees with respect to the unmodified film. The front and back of the modified polyurethane porous membrane are shown in figure 1.
Example 2
Placing 400g of a mixed system of 10%, 87% and 3% by weight of medical polyurethane (BPU), N-Dimethylformamide (DMF) and polyethylene glycol 2000 (PEG 2000) in a water bath kettle at 40 ℃, stirring for 6 hours by using a mechanical stirring device, standing and defoaming after the medical polyurethane in the system is completely dissolved, and finishing the preparation of the casting solution. Pouring 0.5g of chitosan powder into a 50ml conical flask, adding 49.5ml of deionized water into the conical flask filled with the chitosan powder, adding 0.5ml of acetic acid solution into the conical flask, adding a clean magnet, stirring by using a magnetic stirrer until the acetic acid solution is completely dissolved, preparing 50ml of 1% chitosan acetic acid aqueous solution, and finishing the preparation of the chitosan acetic acid aqueous solution spraying liquid. Pouring a proper amount of prepared casting membrane liquid into one end of a glass mold (120 mm multiplied by 180mm multiplied by 0.3 mm), scraping the liquid membrane from the top by using a glass scraper to form a liquid membrane with the thickness of 300 mu m, placing a chitosan acetic acid aqueous solution with the concentration of 1% in a sprayer, uniformly spraying 4ml of chitosan acetic acid aqueous solution on the surface of the scraped liquid membrane under the pressure of 0.75MPa, placing for 1 minute, then placing the glass mold in a deionized water bath, removing the membrane after two minutes, completely soaking in membrane soaking deionized water, changing water once a day, and hanging the membrane in a clean and ventilated place after 5 days to naturally dry the membrane. The content of chitosan in the modified polyurethane porous film was 8.08%, the porosity was 1.23 times that of the unmodified film, the water absorption was 1.34 times that of the unmodified film, the moisture vapor permeability was 2.65 times that of the unmodified film, and the contact angle was decreased by 7 degrees relative to the unmodified film. The front and back of the modified polyurethane porous membrane are shown in figure 2.
Example 3
Placing 400g of a mixed system of 14%, 81% and 5% by weight of medical polyurethane (BPU), N-Dimethylformamide (DMF) and polyvinylpyrrolidone 30 (PVP 30) in a water bath kettle at 40 ℃, stirring for 6 hours by using a mechanical stirring device, standing and defoaming after the medical polyurethane in the system is completely dissolved, and finishing the preparation of the casting solution. Pouring 1g of chitosan powder into a 50ml conical flask, adding 49ml of deionized water into the conical flask filled with the chitosan powder, adding 0.5ml of acetic acid solution into the conical flask, adding a clean magnet, stirring by using a magnetic stirrer until the chitosan solution is completely dissolved, preparing 50ml of 2% chitosan acetic acid aqueous solution, and finishing the preparation of the spraying liquid. Pouring a proper amount of the prepared casting membrane liquid into one end of a glass mold (120 mm multiplied by 180mm multiplied by 0.15 mm), scraping the casting membrane liquid from the top by using a glass scraper to form a liquid membrane with the thickness of 150 mu m, placing a chitosan acetic acid aqueous solution with the concentration of 2% in a sprayer, uniformly spraying 4ml of the chitosan acetic acid aqueous solution on the surface of the scraped liquid membrane under the pressure of 0.1MPa, placing for 2 minutes, then placing the glass mold in a deionized water bath, removing the membrane after two minutes, completely soaking in membrane soaking deionized water, changing water once a day, and hanging the membrane in a clean and ventilated place after 5 days to naturally dry the membrane. The content of chitosan in the polyurethane porous film after modification was 14.49%, the porosity was 1.40 times that of the unmodified film, the water absorption was 1.42 times that of the unmodified film, the moisture vapor permeability was 4.10 times that of the unmodified film, and the contact angle was decreased by 24 degrees relative to the unmodified film. The front and back of the modified polyurethane porous membrane are shown in fig. 3.
Example 4
Placing 400g of a mixed system of 14%, 81% and 5% by weight of medical polyurethane (BPU), 1, 4-Dioxane (DO) and polyvinylpyrrolidone 30 (PVP 30) in a water bath kettle at 40 ℃, stirring for 6 hours by using a mechanical stirring device, standing and defoaming after the medical polyurethane in the system is completely dissolved, and finishing the preparation of the casting solution. Pouring 1.02g of chitosan powder into a 50ml conical flask, adding 50ml of deionized water, stirring until the chitosan powder is completely dispersed, and preparing 50ml of 2% chitosan powder aqueous solution to finish the preparation of the spraying liquid. Pouring a proper amount of the prepared casting membrane liquid into one end of a glass mold (120 mm multiplied by 180mm multiplied by 0.2 mm), scraping the casting membrane liquid from the top by using a glass scraper to form a liquid membrane with the thickness of 200 mu m, placing 2% chitosan powder aqueous solution into a sprayer, uniformly spraying 2ml of chitosan acetic acid aqueous solution on the surface of the scraped liquid membrane under 0.1MPa, placing for 2 minutes, then placing the glass mold into a deionized water bath, removing the membrane after two minutes, completely soaking in membrane soaking deionized water, changing water once a day, and hanging the membrane in a clean and ventilated place after 5 days to naturally dry the membrane. The content of chitosan in the polyurethane porous film after modification was 6.42%, the porosity was 1.14 times that of the unmodified film, the water absorption was 1.2 times that of the unmodified film, the moisture vapor permeability was 1.42 times that of the unmodified film, and the contact angle was decreased by 7 degrees with respect to the unmodified film.
Example 5
Placing 400g of a mixed system of 12%, 83% and 5% by weight of medical polyurethane (BPU), 1, 4-Dioxane (DO) and polyethylene glycol 2000 (PEG 2000) in a water bath kettle at 40 ℃, stirring for 6 hours by using a mechanical stirring device, standing and defoaming after the medical polyurethane in the system is completely dissolved, and finishing the preparation of the casting solution. Pouring 1.02g of chitosan powder into a 50ml conical flask, adding 50ml of deionized water, stirring until the chitosan powder is completely dispersed, and preparing 50ml of 2% chitosan powder aqueous solution to finish the preparation of the spraying liquid. Pouring a proper amount of the prepared casting membrane liquid into one end of a glass mold (120 mm multiplied by 180mm multiplied by 0.2 mm), scraping the casting membrane liquid from the top by using a glass scraper to form a liquid membrane with the thickness of 200 mu m, placing chitosan powder aqueous solution with the concentration of 2% in a sprayer, uniformly spraying 4ml of chitosan acetic acid aqueous solution on the surface of the scraped liquid membrane under the pressure of 0.1MPa, placing for 1.5 minutes, then placing the glass mold in a deionized water bath, removing the membrane after two minutes, completely soaking in film soaking deionized water, changing water once a day, and hanging the membrane in a clean and ventilated place after 5 days to naturally dry the membrane. The content of chitosan in the polyurethane porous film after modification was 10.38%, the porosity was 1.22 times that of the unmodified film, the water absorption was 1.35 times that of the unmodified film, the moisture vapor permeability was 3.17 times that of the unmodified film, and the contact angle was decreased by 10 degrees with respect to the unmodified film.
Example 6
Placing 400g of a mixed system of 18%, 74% and 8% by weight of medical polyurethane (BPU), N-Dimethylformamide (DMF) and polyethylene glycol 2000 (PEG 2000) in a water bath kettle at 40 ℃, stirring for 6 hours by using a mechanical stirring device, standing and defoaming after the medical polyurethane in the system is completely dissolved, and finishing the preparation of the casting solution. Pouring 1.02g of chitosan powder into a 50ml conical flask, adding 50ml of deionized water, stirring until the chitosan powder is completely dispersed, and preparing 50ml of 2% chitosan powder aqueous solution to finish the preparation of the spraying liquid. Pouring a proper amount of the prepared casting membrane liquid into one end of a glass mold (120 mm multiplied by 180mm multiplied by 0.15 mm), scraping the casting membrane liquid from the top by using a glass scraper to form a liquid membrane with the thickness of 150 mu m, placing chitosan powder aqueous solution with the concentration of 2% in a sprayer, uniformly spraying 6ml of chitosan acetic acid aqueous solution on the surface of the scraped liquid membrane under the pressure of 0.1MPa, placing for 1 minute, then placing the glass mold in a deionized water bath, removing the membrane after two minutes, completely soaking in membrane soaking deionized water, changing water once a day, and hanging the membrane in a clean and ventilated place after 5 days to naturally dry the membrane. The content of chitosan in the polyurethane porous film after modification was 13.81%, the porosity was 1.33 times that of the unmodified film, the water absorption was 1.39 times that of the unmodified film, the moisture vapor permeability was 3.86 times that of the unmodified film, and the contact angle was decreased by 15 degrees with respect to the unmodified film.
Claims (1)
1. A preparation method of a medical polyurethane porous membrane with chitosan sprayed on the surface comprises the steps of preparing a polyurethane membrane casting solution, scraping the membrane from the membrane casting solution, spraying a chitosan solution on the surface of a solution membrane, and gelling the solution membrane in a coagulating bath to form a membrane, and is characterized in that the preparation method of the medical polyurethane porous membrane with chitosan sprayed on the surface comprises the following steps:
A. mixing, heating and stirring medical polyurethane, an organic solvent and an additive according to the proportion of 10-18 wt%, 74-87 wt% and 3-8 wt% until the medical polyurethane, the organic solvent and the additive are completely dissolved to prepare a casting solution;
the organic solvent is N, N-dimethylformamide or 1, 4-dioxane, and the additive is polyvinylpyrrolidone or polyethylene glycol;
B. scraping the casting solution into a solution film with the thickness of 150-300 microns in a glass plate mold by using a glass scraper;
C. putting the chitosan solution into a sprayer, and uniformly spraying a certain amount of chitosan solution on the surface of the solution film under the pressure of 0.05-0.1 MPa;
the chitosan solution is a chitosan acetic acid aqueous solution or a chitosan powder aqueous solution, the concentration of chitosan is 0.5-2 wt%, and the volume of the chitosan solution sprayed can be changed, so that the weight proportion of chitosan in the porous membrane is 4-15 wt%;
D. and (3) placing the solution film with the surface sprayed with the chitosan solution for 1-2 min, then placing the glass plate into a deionized water bath, and carrying out gel film formation on the solution film in the water bath.
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