A medical film for a drainage bag and a method of manufacturing the same

Abstract

The application discloses a medical film for a drainage bag and a preparation method thereof, and relates to the field of medical films. In the preparation of the medical film for the drainage bag, modified bentonite is prepared by grafting 2-allyl-6-aminoaniline on bentonite coated by acrylate and acrylic acid; a grafting product is prepared by reacting 3-allyl-4-hydroxybenzaldehyde and biuret; modified polypropylene is prepared by sequentially reacting polypropylene powder, the grafting product and 3-(1H-imidazol-2-yl)-acrylic acid; and the medical film for the drainage bag is prepared by uniformly mixing the modified polypropylene, the modified bentonite and zinc chloride, casting the mixture into a film, and then treating the film with hydrogen-containing silicone oil and sodium hypochlorite. The medical film for the drainage bag prepared by the application has excellent antibacterial property, barrier property and mechanical property.

Description

Technical Field

[0001] This invention relates to the field of medical membranes, specifically to a drainage bag medical membrane and its preparation method. Background Technology

[0002] With the continuous development of medical technology, medical consumables are playing an increasingly important role in clinical treatment. Among them, drainage bags, as a common medical consumable, are widely used in various surgeries and postoperative recovery processes to collect and drain secretions such as blood and lymph from the patient's body. However, existing medical membranes for drainage bags still have certain shortcomings in terms of antibacterial and barrier properties, easily leading to infection and cross-infection, thus affecting treatment outcomes. Therefore, this invention prepares a medical membrane for drainage bags with excellent antibacterial and barrier properties. Summary of the Invention

[0003] The purpose of this invention is to provide a medical membrane for drainage bags and its preparation method, so as to solve the problems existing in the prior art.

[0004] To solve the above-mentioned technical problems, the present invention provides the following technical solution:

[0005] A drainage bag medical membrane is obtained by mixing and casting modified polypropylene, modified bentonite and zinc chloride into a film, and then treating it with hydrogen-containing silicone oil and sodium hypochlorite.

[0006] As an optimization, the hydrogen-containing silicone oil is model 1002 and comes from Shandong Luderui New Materials Co., Ltd.

[0007] As an optimization, the modified polypropylene is prepared by reacting polypropylene powder with graft material and 3-(1H-imidazol-2-yl)-acrylic acid in sequence.

[0008] As an optimization, the polypropylene powder is 50 mesh and comes from Dongguan Jiaqing Plastic Raw Materials Co., Ltd.

[0009] As an optimization, the graft is prepared by reacting 1,3-butadiene with 3-chloro-4-(1-imidazolyl)benzaldehyde.

[0010] As an optimization, the modified bentonite is prepared by grafting 2-allyl-6-aminoaniline onto calcium-based bentonite after coating with acrylate and acrylic acid.

[0011] As an optimization, the calcium-based bentonite is of 500 mesh and comes from Sishui Hengjian Bentonite Co., Ltd.

[0012] A method for preparing a medical membrane for a drainage bag includes the following preparation steps:

[0013] (1) Mix calcium-based bentonite, acrylate, acrylic acid, sodium hydroxide and deionized water in a mass ratio of 1:(0.6~0.8):(0.7~0.9):(0.2~0.4):(4~6), sonicate in a nitrogen atmosphere at 2~4℃ for 20~30 min, raise the temperature to 20~30℃ and sonicate for 1~3 h, add ammonium persulfate at 0.001~0.003 times the mass of calcium-based bentonite, raise the temperature to 55~65℃ and stir at 100~200 rpm for 5~7 h, cool naturally to room temperature and filter, wash with deionized water 3~5 times, dry at 100~110℃ for 11~13 h, grind and sieve through 100~300 mesh to obtain pre-modified bentonite;

[0014] (2) Pre-modified bentonite, hydrochloric acid, and deionized water are mixed at a mass ratio of 1:(0.1~0.2):(9~11), stirred at 40~50℃ and 100~200rpm for 4~6h, cooled naturally to room temperature, filtered, washed 3~5 times with deionized water, and dried at 65~75℃ for 8~10h to obtain carboxylated bentonite; carboxylated bentonite, 2-allyl-6-aminoaniline, phosphorus pentoxide, and polyphosphoric acid are mixed at a mass ratio of 1:(0.1~0.2):(9~11), stirred at 40~50℃ and 100~200rpm for 4~6h, filtered, washed 3~5 times with deionized water, and dried at 65~75℃ for 8~10h to obtain carboxylated bentonite; carboxylated bentonite, 2-allyl-6-aminoaniline, phosphorus pentoxide, and polyphosphoric acid are mixed at a mass ratio of 1:(0.1~0.2):(9~11), stirred at 40~50℃ and 100~200rpm for 4~6h, cooled naturally to room temperature ..., 2-allyl-6- Mix the ingredients in a mass ratio of 1:(1.9~2.1):(1.2~1.4):(37~39), stir at 85~95℃ and 100~200rpm for 20~30min in a nitrogen atmosphere, heat to 175~185℃ and continue stirring for 1~3h, cool naturally to room temperature and filter, wash 3~5 times with saturated sodium carbonate aqueous solution and deionized water respectively, and dry at 85~95℃ for 11~13h to obtain modified bentonite;

[0015] (3) Mix 3-allyl-4-hydroxybenzaldehyde, biuret and hydrochloric acid solution with a mass fraction of 36% to 38% at a mass ratio of 1:(0.6 to 0.7):(5 to 7), stir at 20 to 30°C and 100 to 200 rpm for 23 to 25 hours, add 30 to 32 times the mass of 3-allyl-4-hydroxybenzaldehyde in deionized water at a temperature of 2 to 4°C, let stand for 55 to 65 minutes, filter, wash with deionized water 3 to 5 times, and dry at 50 to 60°C for 11 to 13 hours to obtain the grafted material;

[0016] (4) Mix polypropylene powder and xylene at a mass ratio of 1:(8-9), stir at 120-130℃ and 100-200rpm for 1-3 hours in a nitrogen atmosphere, add 0.12-0.14 times the mass of the polypropylene powder graft, sonicate for 10-20 minutes, add 0.01-0.03 times the mass of the polypropylene powder benzoyl peroxide, heat to 125-135℃ and stir at 200-300rpm for 2-4 hours, cool to 65-75℃ and filter, wash 3-5 times with acetone, and then at 55℃. The pre-modified polypropylene was dried at 65℃ for 6-8 hours to obtain pre-modified polypropylene. The pre-modified polypropylene, 3-(1H-imidazol-2-yl)-acrylic acid, palladium acetate, potassium phosphate and dichloromethane were mixed in a mass ratio of 1:(0.6-0.8):(0.01-0.02):(0.01-0.03):(10-20), refluxed at 75-85℃ for 1-3 hours, cooled naturally to room temperature and filtered. The mixture was washed 3-5 times with dichloromethane and deionized water, respectively, and dried at 65-75℃ for 6-8 hours to obtain modified polypropylene.

[0017] (5) Mix hydrogen-containing silicone oil, chloroplatinic acid, and tetrahydrofuran at a mass ratio of 1:(0.01~0.03):(11~13), and sonicate at 20~30℃ for 5~15 min to obtain a hydrogen-containing silicone oil mixture; mix modified polypropylene, modified bentonite, dimethylimidazole, and zinc chloride at a mass ratio of 1:(0.04~0.06):(0.01~0.02):(0.03~0.05), heat to 165~175℃, and use an extrusion casting machine with zone 1 temperature of 155~165℃, zone 2 temperature of 185~195℃, zone 3 temperature of 200~210℃, and die temperature of 200~210℃. Under conditions of a rolling roller temperature of 85–95℃ and a draw ratio of 75–85, a cast film with a thickness of 20–40 μm is prepared. The cast film is then immersed in a mixture containing hydrogen-silicone oil, ultrasonicated at 20–30℃ for 20–30 min, removed and dried until no dripping occurs within 5–15 s, and allowed to stand at 70–80℃ for 8–10 h. It is then washed 3–5 times with deionized water and dried at 65–75℃ for 23–25 h. Finally, it is immersed in a 5%–15% sodium hypochlorite solution, ultrasonicated at 20–30℃ for 1–3 h, removed and washed 3–5 times with deionized water, and dried at 55–65℃ for 8–10 h to obtain a medical membrane for drainage bags.

[0018] As an optimization, the reaction equation for the modified bentonite in step (2) is:

[0019]

[0020] As an optimization, the reaction equation for the graft described in step (3) is:

[0021]

[0022] As an optimization, the reaction equation for the modified polypropylene in step (5) is:

[0023]

[0024] As an optimization, the reaction equation for the medical membrane of the drainage bag in step (5) is:

[0025]

[0026] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0027] In preparing the medical membrane for drainage bags, the present invention involves coating calcium-based bentonite with acrylate and acrylic acid, then grafting 2-allyl-6-aminoaniline to obtain modified bentonite; reacting 3-allyl-4-hydroxybenzaldehyde with biuret to obtain a graft; then reacting polypropylene powder sequentially with the graft and 3-(1H-imidazol-2-yl)-acrylic acid to obtain modified polypropylene; and finally mixing the modified polypropylene, modified bentonite, and zinc chloride, casting them into a film, and then treating it with hydrogen-containing silicone oil and sodium hypochlorite to obtain the medical membrane for drainage bags.

[0028] First, modified bentonite is prepared by grafting 2-allyl-6-aminoaniline onto calcium-based bentonite after coating it with acrylate and acrylic acid. A grafted compound is prepared by reacting 3-allyl-4-hydroxybenzaldehyde with biuret. Through electrostatic interaction between acrylic acid and calcium ions, calcium-based bentonite is intercalated, enhancing the dispersion between bentonite layers, increasing the path length of gas diffusion, and improving the barrier properties of the drainage bag membrane. The formation of carboxyl groups on the surface of calcium-based bentonite through acrylate hydrolysis, which react with o-phenylenediamine to form a benzimidazole structure, complexing zinc ions and forming a coordination crosslink. Simultaneously, when subjected to external force damage, the exposed benzimidazole can recombine with the released zinc ions, improving the mechanical properties and long-term barrier properties of the drainage bag membrane. A six-membered ring is prepared by reacting aldehyde groups with biuret, and then chlorinated with sodium hypochlorite to form a haloamine structure that can react with proteins within bacteria, inhibiting bacterial growth and reproduction, thus improving the antibacterial properties of the drainage bag membrane.

[0029] Secondly, modified polypropylene was prepared by reacting polypropylene powder with grafted material and 3-(1H-imidazol-2-yl)-acrylic acid in sequence; modified polypropylene, modified bentonite, and zinc chloride were mixed and cast into a film, which was then treated with hydrogen-containing silicone oil and sodium hypochlorite to obtain a drainage bag medical film; using benzoyl peroxide as an initiator, a phenol-containing halogen amine precursor was grafted onto the long chain of polypropylene, and then 3-(1H-imidazol-2-yl)-acrylic acid was grafted through an esterification reaction, introducing imidazolium rings into the long chain of polypropylene, complexing zinc ions, enriching the crosslinking network, and simultaneously 3-( The carbon-carbon double bond on 1H-imidazol-2-yl)-acrylic acid can participate in hydrosilylation, further enhancing the crosslinking effect and improving the mechanical properties of the drainage bag medical membrane. Zinc chloride is used to form metal coordination crosslinks between modified polypropylene and modified bentonite. Simultaneously, zinc ions can interfere with bacterial metabolic pathways and inhibit bacterial growth, improving the mechanical properties and antibacterial properties of the drainage bag medical membrane. Hydrosilylation reaction using hydrogen-containing silicone oil enhances the degree of crosslinking and strengthens the membrane surface energy, further improving the mechanical properties and barrier properties of the drainage bag medical membrane. Detailed Implementation

[0030] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0031] The raw materials used in the following examples and comparative examples are all commercially available:

[0032] The hydrogen-containing silicone oil is model 1002 and comes from Shandong Luderui New Materials Co., Ltd.

[0033] The polypropylene powder is 50 mesh and comes from Dongguan Jiaqing Plastic Raw Materials Co., Ltd.

[0034] The calcium-based bentonite is of 500 mesh and comes from Sishui Hengjian Bentonite Co., Ltd.

[0035] Example 1:

[0036] A method for preparing a medical membrane for a drainage bag, the method comprising the following preparation steps:

[0037] (1) Calcium-based bentonite, acrylate, acrylic acid, sodium hydroxide and deionized water were mixed in a mass ratio of 1:0.6:0.7:0.2:4. The mixture was sonicated at 2°C for 30 min in a nitrogen atmosphere, then sonicated at 20°C for 3 h. Ammonium persulfate with a mass of 0.001 times that of calcium-based bentonite was added. The mixture was heated to 55°C and stirred at 100 rpm for 7 h. After naturally cooling to room temperature, the mixture was filtered, washed three times with deionized water, dried at 100°C for 13 h, ground and sieved through a 100-mesh sieve to obtain pre-modified bentonite.

[0038] (2) Premodified bentonite, hydrochloric acid and deionized water were mixed at a mass ratio of 1:0.1:9 and stirred at 40℃ and 100 rpm for 6 h. After naturally cooling to room temperature, the mixture was filtered, washed three times with deionized water, and dried at 65℃ for 10 h to obtain carboxylated bentonite. Carboxylated bentonite, 2-allyl-6-aminoaniline, phosphorus pentoxide and polyphosphoric acid were mixed at a mass ratio of 1:1.9:1.2:37 and stirred at 85℃ and 100 rpm for 30 min in a nitrogen atmosphere. The mixture was then heated to 175℃ and stirred for 3 h. After naturally cooling to room temperature, the mixture was filtered, washed three times with saturated sodium carbonate aqueous solution and deionized water, and dried at 85℃ for 13 h to obtain modified bentonite.

[0039] (3) Mix 3-allyl-4-hydroxybenzaldehyde, biuret and 36% hydrochloric acid solution at a mass ratio of 1:0.6:5, stir at 20℃ and 100rpm for 25h, add 30 times the mass of 3-allyl-4-hydroxybenzaldehyde in deionized water at 2℃, let stand for 55min, filter, wash 3 times with deionized water, and dry at 50℃ for 13h to obtain the grafted material.

[0040] (4) Mix polypropylene powder and xylene at a mass ratio of 1:8, stir at 120°C and 100 rpm for 3 h in a nitrogen atmosphere, add 0.12 times the mass of the graft material of polypropylene powder, sonicate for 10 min, add 0.01 times the mass of the polypropylene powder of benzoyl peroxide, heat to 125°C and stir at 200 rpm for 4 h, cool to 65°C and filter, wash 3 times with acetone, and dry at 55°C for 8 h to obtain pre-modified polypropylene; mix pre-modified polypropylene, 3-(1H-imidazol-2-yl)-acrylic acid, palladium acetate, potassium phosphate and dichloromethane at a mass ratio of 1:0.6:0.01:0.01:10, reflux at 75°C for 3 h, cool naturally to room temperature and filter, wash 3 times with dichloromethane and deionized water respectively, and dry at 65°C for 8 h to obtain modified polypropylene;

[0041] (5) Hydrogen-containing silicone oil, chloroplatinic acid, and tetrahydrofuran were mixed at a mass ratio of 1:0.01:11 and ultrasonicated at 20°C for 15 minutes to obtain a hydrogen-containing silicone oil mixture; modified polypropylene, modified bentonite, dimethylimidazole, and zinc chloride were mixed at a mass ratio of 1:0.04:0.01:0.03 and heated to 165°C. The mixture was then extruded using a casting machine at temperatures of 155°C in zone one, 185°C in zone two, 200°C in zone three, 200°C in the die, and 80°C in the casting roll. A cast film with a thickness of 20 μm was prepared under conditions of 5℃ and a draw ratio of 75. The cast film was immersed in a mixture of hydrogen-silicone oil, sonicated at 20℃ for 30 min, removed and dried until no dripping occurred within 5 s, stood at 70℃ for 10 h, washed 3 times with deionized water, dried at 65℃ for 25 h, immersed in a 5% sodium hypochlorite solution, sonicated at 20℃ for 3 h, removed and washed 3 times with deionized water, and dried at 55℃ for 10 h to obtain a medical membrane for drainage bags.

[0042] Example 2:

[0043] A method for preparing a medical membrane for a drainage bag, the method comprising the following preparation steps:

[0044] (1) Calcium-based bentonite, acrylate, acrylic acid, sodium hydroxide and deionized water were mixed in a mass ratio of 1:0.7:0.8:0.3:5. The mixture was sonicated at 3°C ​​for 25 min in a nitrogen atmosphere, then sonicated at 25°C for 2 h. Ammonium persulfate with a mass of 0.002 times that of calcium-based bentonite was added. The mixture was heated to 60°C and stirred at 150 rpm for 6 h. After naturally cooling to room temperature, the mixture was filtered, washed 4 times with deionized water, dried at 105°C for 12 h, ground and sieved through a 200-mesh sieve to obtain pre-modified bentonite.

[0045] (2) Premodified bentonite, hydrochloric acid and deionized water were mixed at a mass ratio of 1:0.15:10 and stirred at 45℃ and 150rpm for 5h. After naturally cooling to room temperature, the mixture was filtered, washed 4 times with deionized water, and dried at 70℃ for 9h to obtain carboxylated bentonite. Carboxylated bentonite, 2-allyl-6-aminoaniline, phosphorus pentoxide and polyphosphoric acid were mixed at a mass ratio of 1:2:1.3:38 and stirred at 90℃ and 150rpm for 25min in a nitrogen atmosphere. The temperature was raised to 180℃ and stirred for 2h. After naturally cooling to room temperature, the mixture was filtered, washed 4 times with saturated sodium carbonate aqueous solution and deionized water respectively, and dried at 90℃ for 12h to obtain modified bentonite.

[0046] (3) Mix 3-allyl-4-hydroxybenzaldehyde, biuret and 37% hydrochloric acid solution at a mass ratio of 1:0.65:6, stir at 25℃ and 150 rpm for 24 h, add 31 times the mass of 3-allyl-4-hydroxybenzaldehyde in deionized water at 3℃, let stand for 60 min, filter, wash with deionized water 4 times, and dry at 55℃ for 12 h to obtain the grafted material;

[0047] (4) Mix polypropylene powder and xylene at a mass ratio of 1:8.5, stir at 125°C and 150 rpm for 2 h in a nitrogen atmosphere, add 0.13 times the mass of the grafting material of polypropylene powder, sonicate for 15 min, add 0.02 times the mass of the polypropylene powder of benzoyl peroxide, heat to 130°C and stir at 250 rpm for 3 h, cool to 70°C and filter, wash with acetone 4 times, and dry at 60°C for 7 h to obtain pre-modified polypropylene; mix pre-modified polypropylene, 3-(1H-imidazol-2-yl)-acrylic acid, palladium acetate, potassium phosphate and dichloromethane at a mass ratio of 1:0.7:0.015:0.02:15, reflux at 80°C for 2 h, cool naturally to room temperature and filter, wash with dichloromethane and deionized water 4 times respectively, and dry at 70°C for 7 h to obtain modified polypropylene;

[0048] (5) Hydrogen-containing silicone oil, chloroplatinic acid, and tetrahydrofuran were mixed at a mass ratio of 1:0.02:12 and ultrasonicated at 25°C for 10 min to obtain a hydrogen-containing silicone oil mixture; modified polypropylene, modified bentonite, dimethylimidazole, and zinc chloride were mixed at a mass ratio of 1:0.05:0.015:0.04 and heated to 170°C. The mixture was then extruded using a casting machine at temperatures of 160°C in zone one, 190°C in zone two, 205°C in zone three, 205°C in the die, and 90°C in the casting roll. A cast film with a thickness of 30 μm was prepared under conditions of 0℃ and a draw ratio of 80. The cast film was immersed in a mixture of hydrogen-silicone oil, sonicated at 25℃ for 25 min, removed and dried until no dripping occurred within 10 s, stood at 75℃ for 9 h, washed 4 times with deionized water, dried at 70℃ for 24 h, immersed in a 10% sodium hypochlorite solution, sonicated at 25℃ for 2 h, removed and washed 4 times with deionized water, and dried at 60℃ for 9 h to obtain a medical membrane for drainage bags.

[0049] Example 3:

[0050] A method for preparing a medical membrane for a drainage bag, the method comprising the following preparation steps:

[0051] (1) Calcium-based bentonite, acrylate, acrylic acid, sodium hydroxide and deionized water were mixed in a mass ratio of 1:0.8:0.9:0.4:6. The mixture was sonicated at 4°C for 20 min in a nitrogen atmosphere, then sonicated at 30°C for 1 h. Ammonium persulfate was added at 0.003 times the mass of calcium-based bentonite. The mixture was then heated to 65°C and stirred at 200 rpm for 5 h. After naturally cooling to room temperature, the mixture was filtered, washed 5 times with deionized water, dried at 110°C for 11 h, ground and sieved through a 300-mesh sieve to obtain pre-modified bentonite.

[0052] (2) Premodified bentonite, hydrochloric acid and deionized water were mixed at a mass ratio of 1:0.2:11 and stirred at 50℃ and 200rpm for 4h. After naturally cooling to room temperature, the mixture was filtered, washed 5 times with deionized water, and dried at 75℃ for 8h to obtain carboxylated bentonite. Carboxylated bentonite, 2-allyl-6-aminoaniline, phosphorus pentoxide and polyphosphoric acid were mixed at a mass ratio of 1:2.1:1.4:39 and stirred at 95℃ and 200rpm for 20min in a nitrogen atmosphere. The temperature was raised to 185℃ and stirred for 1h. After naturally cooling to room temperature, the mixture was filtered, washed 5 times with saturated sodium carbonate aqueous solution and deionized water respectively, and dried at 95℃ for 11h to obtain modified bentonite.

[0053] (3) Mix 3-allyl-4-hydroxybenzaldehyde, biuret and 38% hydrochloric acid solution at a mass ratio of 1:0.7:7, stir at 30℃ and 200rpm for 23h, add 32 times the mass of 3-allyl-4-hydroxybenzaldehyde in deionized water at 4℃, let stand for 65min, filter, wash 5 times with deionized water, and dry at 60℃ for 11h to obtain the grafted material.

[0054] (4) Mix polypropylene powder and xylene at a mass ratio of 1:9, stir at 130°C and 200 rpm for 1 h in a nitrogen atmosphere, add graft material at 0.14 times the mass of polypropylene powder, sonicate for 20 min, add benzoyl peroxide at 0.03 times the mass of polypropylene powder, heat to 135°C and stir at 300 rpm for 2 h, cool to 75°C and filter, wash with acetone 5 times, and dry at 65°C for 6 h to obtain pre-modified polypropylene; mix pre-modified polypropylene, 3-(1H-imidazol-2-yl)-acrylic acid, palladium acetate, potassium phosphate and dichloromethane at a mass ratio of 1:0.8:0.02:0.03:20, reflux at 85°C for 1 h, cool naturally to room temperature and filter, wash with dichloromethane and deionized water 5 times each, and dry at 75°C for 6 h to obtain modified polypropylene;

[0055] (5) Hydrogen-containing silicone oil, chloroplatinic acid, and tetrahydrofuran were mixed at a mass ratio of 1:0.03:13 and ultrasonicated at 30°C for 5 minutes to obtain a hydrogen-containing silicone oil mixture; modified polypropylene, modified bentonite, dimethylimidazole, and zinc chloride were mixed at a mass ratio of 1:0.06:0.02:0.05 and heated to 175°C. The mixture was then extruded using a casting machine at temperatures of 165°C in zone one, 195°C in zone two, 210°C in zone three, 210°C in the die, and 95°C in the casting roll. Under the conditions of ℃ and a draw ratio of 85, a cast film with a thickness of 40 μm was prepared. The cast film was immersed in a mixture of hydrogen-silicone oil, sonicated at 30℃ for 20 min, removed and dried until no dripping occurred within 15 s, stood at 80℃ for 8 h, washed 5 times with deionized water, dried at 75℃ for 23 h, immersed in a 15% sodium hypochlorite solution, sonicated at 30℃ for 1 h, removed and washed 5 times with deionized water, and dried at 65℃ for 8 h to obtain a medical membrane for drainage bags.

[0056] Comparative Example 1:

[0057] The preparation method of the drainage bag medical membrane in Comparative Example 1 differs from that in Example 2 only in steps (2) and (5). Step (2) is omitted, and "modified bentonite" in step (5) is replaced with "pre-modified bentonite". The remaining steps are the same as in Example 2.

[0058] Comparative Example 2:

[0059] The preparation method of the drainage bag medical membrane in Comparative Example 2 differs from that in Example 2 only in steps (3) and (5). Step (3) is omitted, and step (4) is modified as follows: Polypropylene powder and xylene are mixed at a mass ratio of 1:8.5 and stirred at 125°C and 150 rpm for 2 hours in a nitrogen atmosphere. 0.13 times the mass of 3-allyl-4-hydroxybenzaldehyde of polypropylene powder is added, and the mixture is sonicated for 15 minutes. 0.02 times the mass of benzoyl peroxide of polypropylene powder is added, and the temperature is raised to 130°C. The mixture was stirred at 250 rpm for 3 hours, cooled to 70°C, filtered, washed four times with acetone, and dried at 60°C for 7 hours to obtain pre-modified polypropylene. The pre-modified polypropylene, 3-(1H-imidazol-2-yl)-acrylic acid, palladium acetate, potassium phosphate, and dichloromethane were mixed at a mass ratio of 1:0.7:0.015:0.02:15, refluxed at 80°C for 2 hours, naturally cooled to room temperature, filtered, washed four times each with dichloromethane and deionized water, and dried at 70°C for 7 hours to obtain modified polypropylene. The remaining steps were the same as in Example 2.

[0060] Comparative Example 3:

[0061] The preparation method of the drainage bag medical membrane in Comparative Example 3 differs from that in Example 2 only in steps (4) and (5). Step (4) is omitted and modified as follows: Polypropylene powder and xylene are mixed at a mass ratio of 1:8.5, stirred at 125°C and 150 rpm for 2 hours in a nitrogen atmosphere, grafted material at 0.13 times the mass of polypropylene powder is added, ultrasonicated for 15 minutes, benzoyl peroxide at 0.02 times the mass of polypropylene powder is added, heated to 130°C and stirred at 250 rpm for 3 hours, cooled to 70°C and filtered, washed 4 times with acetone, and dried at 60°C for 7 hours to obtain pre-modified polypropylene. In step (5), "modified polypropylene" is replaced with "pre-modified polypropylene". The remaining steps are the same as in Example 2.

[0062] Comparative Example 4:

[0063] The preparation method of the drainage bag medical membrane in Comparative Example 4 differs from that in Example 2 only in step (5). Step (5) is modified as follows: Modified polypropylene, modified bentonite, dimethylimidazole, and zinc chloride are mixed in a mass ratio of 1:0.06:0.02:0.05, heated to 175°C, and then cast using an extrusion casting machine under the following conditions: zone 1 temperature 165°C, zone 2 temperature 195°C, zone 3 temperature 210°C, die temperature 210°C, casting roller temperature 95°C, and draw ratio 85, to obtain a cast film with a thickness of 40 μm. The cast film is then immersed in a 15% sodium hypochlorite solution, sonicated at 30°C for 1 hour, removed, washed 5 times with deionized water, and dried at 65°C for 8 hours to obtain the drainage bag medical membrane. The remaining steps are the same as in Example 2.

[0064] Test case

[0065] 1. Antibacterial properties

[0066] Test method: Take two identical square samples (2.5 cm on each side) of the drainage bag medical membrane obtained from each example and comparative example, and inoculate them with 25 μL of E. coli at a dose of 6.00 × 10⁻⁶. 6 A CFU suspension was dropped into the center of the sample. Another sample was then placed on top of the suspension and allowed to fully contact for 5 minutes. The sample was then transferred to a centrifuge tube containing sterilized Na2S2O3 solution and sonicated for 2 minutes. The solution was diluted in the same gradient. 25 μL of the diluted bacterial solution was dropped into an agar plate and incubated at 37°C for 24 hours. The viable count Q1 (Q0 for the blank group) was recorded, and the inhibition rate was calculated as (Q0-Q1) / Q0*100%.

[0067] 2. Barrier properties

[0068] Test Method: The medical membranes for drainage bags obtained in each embodiment and comparative example were tightly covered on a permeation cup containing dry silica gel. The cups were left to stand at 25°C and 75% RH for 8 hours. The water vapor permeation rate W0 was measured as: W0 = weight gain of the permeation cup / (effective permeation area · permeation time). The medical membranes for drainage bags obtained in each embodiment and comparative example were cut into samples with a diameter of 95 mm according to GB / T1038. A thin layer of vacuum silicone grease was applied to the convex edge of the permeable chamber. The samples were then adhered tightly to the vacuum silicone grease and tested at a relative humidity of 50%. Under the condition of oxygen flow rate and exhaust pressure of 0.5 MPa, the oxygen permeability P0 was measured using a VAC-VBS differential pressure gas permeation instrument. The drainage bag medical membranes obtained in each embodiment and comparative example were scratched with the same blade, immersed in deionized water, taken out and left to stand at 40°C for 12 hours, and the water vapor permeability W1 and permeability P1 were measured again. The water vapor barrier rate = (W0-W1) / W0*100% and the oxygen barrier rate = (P0-P1) / P0*100% were calculated.

[0069] 3. Mechanical properties

[0070] Test method: The drainage bag medical membranes obtained from each embodiment and comparative example were tested for tensile strength according to GB / T1040 under the condition of tensile rate of 50 mm / min.

[0071] Tables 1-2 below show the analysis results of the antibacterial properties, barrier properties, and mechanical properties of the drainage bag medical films of Examples 1-3 and Comparative Examples 1-4 of the present invention.

[0072] Table 1

[0073]

[0074]

[0075] Table 2

[0076] Antibacterial rate % Water vapor barrier rate % Oxygen barrier rate % Tensile strength (MPa) Example 1 99.95 86.7 89.6 39.2 Example 2 99.99 89.2 91.3 39.4 Example 3 99.98 85.8 90.5 38.9 Comparative Example 1 97.15 81.3 86.6 31.4 Comparative Example 2 75.23 85.4 89.1 38.8 Comparative Example 3 87.56 62.7 65.8 27.2 Comparative Example 4 99.93 85.6 87.2 24.5

[0077] A comparison of the experimental data from Examples 1-3 and Comparative Examples 1-4 in Tables 1-2 reveals that the medical membrane for the drainage bag prepared by this invention has good antibacterial properties, barrier properties, and mechanical properties.

[0078] The difference between Comparative Example 1 and Example 2 is that 2-allyl-6-aminoaniline was not grafted onto the pre-modified bentonite. Through data comparison, Examples 1, 2, and 3 showed higher water vapor barrier rate, oxygen barrier rate, and tensile strength compared to Comparative Example 1. This indicates that the formation of carboxyl groups on the surface of calcium-based bentonite by acrylate hydrolysis, which react with o-phenylenediamine to form a benzimidazole structure, complexes zinc ions, and forms a coordination crosslink. At the same time, when subjected to external force damage, the exposed benzimidazole can re-complex with the released zinc ions, improving the mechanical properties and long-term barrier properties of the drainage bag medical membrane.

[0079] The difference between Comparative Example 2 and Example 2 is that 3-allyl-4-hydroxybenzaldehyde and biuret were not reacted to obtain the graft compound. Through data comparison, Examples 1, 2, and 3 showed higher antibacterial rates than Comparative Example 2, indicating that the six-membered ring prepared by reacting the aldehyde group with biuret and then chlorinating it with sodium hypochlorite forms a halogen amine structure that can react with proteins in bacteria and inhibit bacterial growth and reproduction, thereby improving the antibacterial properties of the medical membrane of the drainage bag.

[0080] The difference between Comparative Example 3 and Example 2 is that 3-(1H-imidazol-2-yl)-acrylic acid was not grafted onto the pre-modified polypropylene. Data comparison showed that Examples 1, 2, and 3 had higher antibacterial rates, water vapor barrier rates, oxygen barrier rates, and tensile strength compared to Comparative Example 3. This indicates that grafting 3-(1H-imidazol-2-yl)-acrylic acid via esterification introduces imidazolium rings onto the long polypropylene chain, complexing zinc ions and enriching the crosslinking network. Simultaneously, the carbon-carbon double bonds on 3-(1H-imidazol-2-yl)-acrylic acid can participate in hydrosilylation, further enhancing the crosslinking effect and improving the mechanical properties of the drainage bag medical membrane. Furthermore, the metal coordination crosslinking formed between modified polypropylene and modified bentonite using zinc chloride allows the imidazolium rings to re-complex with zinc ions when subjected to external force damage. Simultaneously, the zinc ions can interfere with bacterial metabolic pathways and inhibit bacterial growth, improving the mechanical properties, barrier properties, and antibacterial activity of the drainage bag medical membrane.

[0081] The difference between Comparative Example 4 and Example 2 is that the cast film was not treated with hydrogen-containing silicone oil. Through data comparison, Examples 1, 2, and 3 showed lower water vapor permeability and oxygen permeability and higher tensile strength compared with Comparative Example 4. This indicates that the use of hydrogen-containing silicone oil to carry out hydrosilylation reaction can enhance the degree of crosslinking and strengthen the surface energy of the film, thereby further improving the mechanical properties and barrier properties of the medical membrane for drainage bags.

[0082] The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of the present invention. It should be understood that the above description is only a specific embodiment of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for preparing a medical membrane for a drainage bag, characterized in that, The preparation steps include the following: (1) Mix calcium-based bentonite, acrylate, acrylic acid, sodium hydroxide and deionized water, disperse by ultrasonication, heat up, add ammonium persulfate, heat up again, filter, wash and dry, grind and sieve to obtain pre-modified bentonite; (2) Mix pre-modified bentonite, hydrochloric acid and deionized water, filter after reaction, wash and dry to obtain carboxylated bentonite; mix carboxylated bentonite, 2-allyl-6-aminoaniline, phosphorus pentoxide and polyphosphoric acid, stir and react, filter after cooling, wash and dry to obtain modified bentonite. (3) Mix 3-allyl-4-hydroxybenzaldehyde, biuret and hydrochloric acid solution, stir, add ice water, let stand, filter, wash and dry to obtain graft material; (4) Mix polypropylene powder and xylene, add grafting material, disperse ultrasonically, add benzoyl peroxide, heat and stir, cool and filter, wash and dry to obtain pre-modified polypropylene; mix pre-modified polypropylene, 3-(1H-imidazol-2-yl)-acrylic acid, palladium acetate, potassium phosphate and dichloromethane, reflux reaction, cool and filter, wash and dry to obtain modified polypropylene; (5) Mix hydrogen-containing silicone oil, chloroplatinic acid and tetrahydrofuran, disperse by ultrasonication to obtain a hydrogen-containing silicone oil mixture; mix modified polypropylene, modified bentonite, dimethylimidazole and zinc chloride, heat, and obtain a cast film by extrusion casting mechanism; immerse the cast film in the hydrogen-containing silicone oil mixture, sonicate, allow to stand for reaction, wash and dry, immerse in sodium hypochlorite solution, sonicate, wash and dry to obtain a drainage bag medical film.

2. The method for preparing a medical membrane for a drainage bag according to claim 1, characterized in that, The preparation process of the pre-modified bentonite in step (1) is as follows: calcium-based bentonite, acrylate, acrylic acid, sodium hydroxide and deionized water are mixed in a mass ratio of 1:(0.6~0.8):(0.7~0.9):(0.2~0.4):(4~6), and ultrasonicated at 2~4℃ for 20~30 min in a nitrogen atmosphere. The mixture is then heated to 20~30℃ and ultrasonicated for 1~3 h. Ammonium persulfate is added at 0.001~0.003 times the mass of calcium-based bentonite. The mixture is heated to 55~65℃ and stirred at 100~200 rpm for 5~7 h. After naturally cooling to room temperature, the mixture is filtered, washed 3~5 times with deionized water, dried at 100~110℃ for 11~13 h, ground and sieved through a 100~300 mesh to obtain the pre-modified bentonite.

3. The method for preparing a medical membrane for a drainage bag according to claim 1, characterized in that, The preparation process of carboxylated bentonite in step (2) is as follows: pre-modified bentonite, hydrochloric acid and deionized water are mixed at a mass ratio of 1:(0.1~0.2):(9~11), stirred at 40~50℃ and 100~200rpm for 4~6h, cooled naturally to room temperature and filtered, washed with deionized water 3~5 times, and dried at 65~75℃ for 8~10h to obtain carboxylated bentonite.

4. The method for preparing a medical membrane for a drainage bag according to claim 1, characterized in that, The preparation process of the modified bentonite in step (2) is as follows: carboxylated bentonite, 2-allyl-6-aminoaniline, phosphorus pentoxide and polyphosphoric acid are mixed in a mass ratio of 1:(1.9~2.1):(1.2~1.4):(37~39), stirred for 20~30 min at 85~95℃ and 100~200 rpm in a nitrogen atmosphere, heated to 175~185℃ and stirred for 1~3 h, cooled naturally to room temperature and filtered, washed 3~5 times with saturated sodium carbonate aqueous solution and deionized water respectively, and dried at 85~95℃ for 11~13 h to obtain modified bentonite.

5. The method for preparing a medical membrane for a drainage bag according to claim 1, characterized in that, The preparation process of the graft in step (3) is as follows: 3-allyl-4-hydroxybenzaldehyde, biuret and hydrochloric acid solution with a mass fraction of 36%~38% are mixed at a mass ratio of 1:(0.6~0.7):(5~7), stirred at 20~30℃ and 100~200rpm for 23~25h, 30~32 times the mass of 3-allyl-4-hydroxybenzaldehyde in deionized water at a temperature of 2~4℃ are added, the mixture is allowed to stand for 55~65min and then filtered, washed with deionized water 3~5 times, and dried at 50~60℃ for 11~13h to obtain the graft.

6. The method for preparing a medical membrane for a drainage bag according to claim 1, characterized in that, The preparation process of the pre-modified polypropylene in step (4) is as follows: Polypropylene powder and xylene are mixed at a mass ratio of 1:(8~9), stirred for 1~3 hours at 120~130℃ and 100~200rpm in a nitrogen atmosphere, grafted material of 4~5 times the mass of polypropylene powder is added, ultrasonicated for 10~20 minutes, benzoyl peroxide of 0.01~0.03 times the mass of polypropylene powder is added, heated to 125~135℃ and stirred at 200~300rpm for 2~4 hours, cooled to 65~75℃ and filtered, washed 3~5 times with acetone, and dried at 55~65℃ for 6~8 hours to obtain pre-modified polypropylene.

7. The method for preparing a medical membrane for a drainage bag according to claim 1, characterized in that, The preparation process of the modified polypropylene in step (4) is as follows: pre-modified polypropylene, 3-(1H-imidazol-2-yl)-acrylic acid, palladium acetate, potassium phosphate and dichloromethane are mixed in a mass ratio of 1:(0.6~0.8):(0.01~0.02):(0.01~0.03):(10~20), refluxed at 75~85℃ for 1~3h, naturally cooled to room temperature and filtered, washed 3~5 times with dichloromethane and deionized water respectively, and dried at 65~75℃ for 6~8h to obtain modified polypropylene.

8. The method for preparing a medical membrane for a drainage bag according to claim 1, characterized in that, The preparation process of the drainage bag medical membrane in step (5) is as follows: Hydrogen-containing silicone oil, chloroplatinic acid, and tetrahydrofuran are mixed in a mass ratio of 1:(0.01~0.03):(11~13), and ultrasonicated at 20~30℃ for 5~15 minutes to obtain a hydrogen-containing silicone oil mixture; modified polypropylene, modified bentonite, dimethylimidazole, and zinc chloride are mixed in a mass ratio of 1:(0.04~0.06):(0.01~0.02):(0.03~0.05), heated to 165~175℃, and extruded using a casting machine at a zone temperature of 155~165℃ in zone one, 185~195℃ in zone two, 200~210℃ in zone three, and a die temperature of 2... Under conditions of 00~210℃, casting roller temperature 85~95℃, and draw ratio 75~85, a casting film with a thickness of 20~40μm is prepared. The casting film is immersed in a mixture of hydrogen-silicone oil, ultrasonicated at 20~30℃ for 20~30min, removed and dried until no dripping occurs within 5~15s, and then allowed to stand at 70~80℃ for 8~10h. It is then washed 3~5 times with deionized water and dried at 65~75℃ for 23~25h. Finally, it is immersed in a 5%~15% sodium hypochlorite solution, ultrasonicated at 20~30℃ for 1~3h, removed and washed 3~5 times with deionized water, and dried at 55~65℃ for 8~10h to obtain a medical membrane for drainage bags.

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