Disposable antibacterial surgical membrane and preparation method thereof

Abstract

The invention relates to the technical field of surgical membranes, in particular to a disposable antibacterial surgical membrane and a preparation method thereof. The preparation method of the disposable antibacterial surgical membrane comprises the following steps: step 1, respectively drying low-density polyethylene, an ethylene-octylene copolymer, polyethylene grafted maleic anhydride, composite carrageenan, calcium carbonate, porous silicon dioxide and an auxiliary agent, mixing, and adding peroxide; carrying out melt extrusion and blow molding to form a film to obtain the antibacterial polyethylene film; 2, one face of the antibacterial polyethylene film is coated with a medical pressure-sensitive adhesive, curing is conducted, and a pressure-sensitive adhesive layer is obtained; covering a release film; the disposable antibacterial surgical membrane is obtained. The disposable antibacterial surgical membrane prepared in the invention has excellent antibacterial activity and mechanical properties.

Description

Technical Field

[0001] The invention relates to the technical field of surgical membranes, in particular to a disposable antibacterial surgical membrane and a preparation method thereof. Background Art

[0002] Antibacterial surgical membranes can prevent the surgical area from being contaminated by external microorganisms, ensure the smooth progress of the operation, and promote postoperative recovery. They play a vital role in surgical operations.

[0003] Although traditional surgical membranes can isolate the external environment and surgical wounds to a certain extent; however, as the requirements for surgical infection prevention and control increase, they have certain drawbacks: on the one hand, the surgical membranes in the prior art have insufficient antibacterial properties, and bacteria can easily invade through the cracks in the surgical membranes, causing infection, increasing patient pain and medical costs; and the antibacterial properties are generally directed against conventional bacteria such as Escherichia coli, but the antibacterial properties for Pseudomonas aeruginosa are relatively low, and still need to be further improved. On the other hand, the surgical membrane has poor water vapor permeability, which will cause water vapor condensation during surgery and increase surgical risks. In addition, there are problems with poor dispersibility and compatibility between materials such as antibacterial agents and polyethylene materials, resulting in poor mechanical properties and low toughness of the surgical membrane, and the antibacterial properties cannot be maximized.

[0004] In summary, it is of great significance to solve the above problems and prepare a disposable antibacterial surgical membrane. Summary of the invention

[0005] The object of the present invention is to provide a disposable antibacterial surgical membrane and a preparation method thereof, so as to solve the problems raised in the above background technology.

[0006] In order to solve the above technical problems, the present invention provides the following technical solutions:

[0007] A method for preparing a disposable antibacterial surgical membrane comprises the following steps:

[0008] Step 1: low-density polyethylene, ethylene-octene copolymer, polyethylene grafted maleic anhydride, composite carrageenan, calcium carbonate, porous silica, and additives are dried and mixed, and peroxide is added; melt extrusion and blow molding are performed to form a film to obtain an antibacterial polyethylene film;

[0009] Step 2: coating a medical pressure-sensitive adhesive on one side of the antibacterial polyethylene film, and ripening the film to obtain a pressure-sensitive adhesive layer; covering the film with a release film; and obtaining a disposable antibacterial surgical film.

[0010] More optimally, the raw materials of the antibacterial polyethylene film include the following components: by weight, 75-82 parts of low-density polyethylene, 10-15 parts of ethylene-octene copolymer, 8-10 parts of polyethylene grafted maleic anhydride, 12-15 parts of composite carrageenan, 20-23 parts of calcium carbonate, 7-10 parts of porous silica, 1-2 parts of additives, and 0.1-0.2 parts of peroxide.

[0011] More optimally, the process parameters of the melt extrusion are: the head temperature is 190-200°C, and the temperatures of the other five temperature zones are 165-175°C, 175-185°C, 185-195°C, 195-200°C, and 200-205°C respectively; the process parameters of the blow molding film are: the die temperature is 195-205°C, and the pulling speed is 320-380 mm / s.

[0012] More optimally, the preparation method of the composite carrageenan is:

[0013] S1-1: (1) Add carboxylated carbon nanotubes and N-(3-mercapto-2-methylpropanoyl)glycine to deionized water in sequence, stir evenly, filter and dry to obtain modified carbon nanotubes; (2) Grind and blend nano titanium dioxide and ammonium fluoride, heat treat at 450-500°C for 4-5 hours, cool to obtain fluorinated titanium dioxide; add fluorinated titanium dioxide and mercaptosilane coupling agent to anhydrous ethanol in sequence, add deionized water, heat to 70-80°C, stir for 4-6 hours, wash and dry to obtain modified titanium dioxide; (3) Compound the modified carbon nanotubes and modified titanium dioxide in proportion to obtain antibacterial particles;

[0014] S1-2: adding carrageenan to 80-85 vol% ethanol aqueous solution and stirring evenly, adding allyl succinic anhydride-anhydrous ethanol solution dropwise at 30-40° C. for 0.5-1 hour, adjusting the pH to 8±0.2; continuing stirring for 0.5-1 hour, washing and drying to obtain modified carrageenan;

[0015] S1-3: adding antibacterial particles and modified carrageenan to tetrahydrofuran in sequence, adding a photoinitiator, heating to 68-72° C., stirring for reaction for 4-5 hours, washing and drying to obtain composite carrageenan.

[0016] More optimally, the ratio of the antibacterial particles is: the mass ratio of the modified carbon nanotubes to the modified titanium dioxide is 1:(1.5-2); the mass ratio of the antibacterial particles to the modified carrageenan is (5-8):7.

[0017] More optimally, in the raw materials of the modified carbon nanotubes, the mass ratio of carboxylated carbon nanotubes and N-(3-mercapto-2-methylpropanoyl)glycine is 1:(0.1-0.2); in the raw materials of the modified titanium dioxide, the mass ratio of nano titanium dioxide and ammonium fluoride is 1:(0.3-0.4); and the mass ratio of fluorinated titanium dioxide and mercaptosilane coupling agent is 1:(0.15-0.25).

[0018] More optimally, the preparation method of the porous silica is:

[0019] S2-1: Add allyl beta-cyclodextrin to DMF, add 1,1-carbonyldiimidazole, and stir at 20-25° C. for 1-2 hours; add 3-aminopropyltriethoxysilane, continue stirring for 20-24 hours, and evaporate the solvent to obtain cyclodextrin silane;

[0020] S2-2: Add hexadecyltrimethylammonium bromide to deionized water, add ammonia water and stir evenly; add tetraethyl orthosilicate and cyclodextrin silane, stir at 20-25°C for 2-3 hours; hydrothermally react at 95-100°C for 24 hours, wash and dry to obtain porous silica.

[0021] More optimally, in the raw materials of the cyclodextrin silane, the molar ratio of allyl beta-cyclodextrin, 1,1-carbonyldiimidazole, and 3-aminopropyltriethoxysilane is 1:(2-3):(2-3); the raw materials of the porous silica include the following components: by weight, 2.5-2.8 parts of hexadecyltrimethylammonium bromide, 0.8-1 part of ammonia water, 16-17 parts of tetraethyl orthosilicate, and 8-8.5 parts of cyclodextrin silane; the solubility of ammonia water is 20-25wt%.

[0022] More optimally, the medical pressure-sensitive adhesive comprises 95wt% to 97wt% of organic silicone adhesive and 3wt% to 5wt% of porous silica; the aging temperature is 140 to 180°C.

[0023] A disposable antibacterial surgical film prepared by a preparation method comprises an antibacterial polyethylene film, a pressure-sensitive adhesive layer and a release film. The thickness of the antibacterial polyethylene film is 40 to 60 μm; the thickness of the pressure-sensitive adhesive layer is 20 to 40 μm; and the thickness of the release film is 20 to 80 μm.

[0024] Compared with the prior art, the beneficial effects of the present application are as follows: the composite carrageenan is introduced in the present application as a reinforcing agent to effectively improve the antibacterial properties and tensile strength of the antibacterial polyethylene film; and porous silica is introduced as an auxiliary to further enhance the antibacterial properties, thereby effectively improving the water vapor permeability of the antibacterial surgical film and enhancing the practical applicability of the disposable antibacterial surgical film.

[0025] Among them, the composite carrageenan is based on carrageenan, which is first grafted and modified with allyl succinic anhydride; then grafted and loaded with antibacterial particles (a certain proportion of modified carbon nanotubes and modified titanium dioxide) to obtain a composite. Among them, carrageenan is a green material, and its introduction can effectively promote the crystallinity of low-density polyethylene, thereby improving the mechanical properties of antibacterial polyethylene film. However, its introduction amount should not be too much, as too much will hinder the adhesion and entanglement of low-molecular polyethylene molecular chains, reduce the regularity of the chain segments of low-density polyethylene, reduce the crystallinity, and be detrimental to mechanical properties. On the one hand, the scheme reduces its introduction amount; on the other hand, its graft modification, the grafting of allyl succinic anhydride to form an ester group, can promote grade similarity, and the allyl group contained can react and crosslink with low-density polyethylene. In addition, the use of allyl groups can promote the cross-linking loading of antibacterial particles, inhibit the aggregation of antibacterial particles, and improve their dispersibility in polyethylene films, thereby maximizing antibacterial properties. At the same time, by resisting the loading of particles and utilizing their own structural properties, the physical effect of the composite carrageenan in polyethylene can be increased and the interface properties can be improved; thereby promoting the dispersibility and compatibility of the composite carrageenan in polyolefin materials and effectively improving the mechanical properties of the antibacterial polyethylene film.

[0026] Among them, the antibacterial particles are obtained by compounding modified carbon nanotubes and modified titanium dioxide; the two have different structures, including tubular and particle, which can be staggered in the antibacterial polyethylene film to synergistically promote antibacterial properties. It is pre-grafted on carrageenan, which effectively promotes its dispersibility and compatibility, and can maximize the antibacterial performance. At the same time, the antibacterial particles have excellent antibacterial properties. They not only have an antibacterial rate of more than 99% for conventional bacteria such as Escherichia coli; at the same time, they also have high antibacterial properties for Pseudomonas aeruginosa. The reason is that the modification of carbon nanotubes with N-(3-mercapto-2-methylpropanoyl) glycine in the scheme can not only promote its cross-linking with carrageenan, but also improve the antibacterial properties; while titanium dioxide is modified with ammonium fluoride, which can promote the transformation of titanium dioxide lattice, and the doped fluorine effectively improves its antibacterial properties. At the same time, compared with single titanium dioxide, the antibacterial properties produced by the two compounds have a synergistic effect, so that the antibacterial property against Pseudomonas aeruginosa can reach about 99%. It has excellent performance.

[0027] Among them, the introduction of porous silica can effectively promote the porosity and water vapor permeability of the surgical membrane. The reason is: compared with conventional porous silica or porous calcium carbonate; in the scheme, beta-cyclodextrin containing allyl is prepared to obtain cyclodextrin silane; then it is used with ethyl orthosilicate to prepare porous silica, so that it contains cyclodextrin structure. Due to its hygroscopicity, it can effectively improve the moisture absorption and air permeability of the surgical membrane, thereby promoting the permeation of water vapor, increasing the anti-fog property of the surgical membrane, inhibiting the condensation of water vapor, and improving the practical applicability of the surgical membrane. In addition, the allyl group contained can cross-link with polyolefin materials, effectively improving compatibility and ensuring mechanical properties. DETAILED DESCRIPTION

[0028] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0029] It should be noted that the following parts are calculated by weight, and the purchase manufacturers of all raw materials involved in the present invention are exemplary included without any special restrictions: in the following embodiments, allyl-beta-cyclodextrin is allyl-CD purchased from Xi'an Qiyue Biology; the CAS number of 1,1-carbonyldiimidazole is 530-62-1; the CAS number of tetraethyl orthosilicate is 78-10-4; the CAS number of N-(3-mercapto-2-methylpropanoyl)glycine is 89021-98-7; the CAS number of calcium stearate is 1592- 23-0; the CAS number of allyl succinic anhydride is 7539-12-0; the model of nano titanium dioxide is JD1227182412, and the brand is Jiadel; ammonium fluoride is industrial grade, and the brand is Runde; the particle size of carboxylated carbon nanotubes is 8-15nm, and the brand is Zhongke Leiming; the purity of carrageenan is 99%, and the brand is Shanghai Yuanye; the model of polyethylene grafted maleic anhydride is ZJ-800E; the model of low-density polyethylene is LEPD-2520D, and the model of ethylene octene copolymer is POE-8180. Calcium carbonate includes calcium carbonate with an average particle size of 2500 nanometers, 1500 nanometers, and 500 nanometers in a mass ratio of 1:1:1. The model of organic silicone adhesive is SILPURAN-2110; the thickness of the antibacterial polyethylene film is 50μm; the thickness of the pressure-sensitive adhesive layer is 30μm; the thickness of the release film is a PET film of 50μm.

[0030] Embodiment 1: A method for preparing a disposable antibacterial surgical membrane, comprising the following steps:

[0031] Pre-preparation: Preparation of porous silica: S2-1: Add 1 part of allyl beta-cyclodextrin to 50 parts of DMF, add 2.3 parts of 1,1-carbonyldiimidazole, and stir at 20°C for 1 hour; add 2 parts of 3-aminopropyltriethoxysilane, continue stirring for 20 hours, evaporate the solvent to obtain cyclodextrin silane; S2-2: Add 2.52 parts of hexadecyltrimethylammonium bromide to 13 parts of deionized water, add 0.84 parts of 25wt% ammonia water and stir evenly; add 16.3 parts of tetraethyl orthosilicate and 8.4 parts of cyclodextrin silane, stir at 20°C for 2 hours; hydrothermally react it at 100°C for 24 hours, wash and dry to obtain porous silica;

[0032] Preparation of composite carrageenan: S1-1: (1) 10 parts of carboxylated carbon nanotubes and 0.15 parts of N-(3-mercapto-2-methylpropanoyl) glycine were added to 50 parts of deionized water in sequence, ultrasonically dispersed for 15 minutes, stirred for 1 hour, filtered and dried to obtain modified carbon nanotubes; (2) 10 parts of nano titanium dioxide and 0.38 parts of ammonium fluoride were ground and blended, heat treated at 500°C for 5 hours, cooled to obtain fluorinated titanium dioxide; 10 parts of fluorinated titanium dioxide and 1.2 parts of 3-mercaptopropyltriethoxysilane were added to 85 parts of anhydrous ethanol in sequence, and 15 parts of deionized water were added; the temperature was raised to 75°C, stirred for 4 hours, washed and dried to obtain modified titanium dioxide; (3) the modified Carbon nanotubes and modified titanium dioxide are compounded in a mass ratio of 1:1.5 to obtain antibacterial particles; S1-2: 10 parts of carrageenan are added to 100 parts of 85 vol% ethanol aqueous solution and stirred evenly, and allyl succinic anhydride-anhydrous ethanol solution (8 parts of allyl succinic anhydride, 42 parts of anhydrous ethanol) is added dropwise at 30°C for 1 hour, and the pH is adjusted to 8.2; stirring is continued for 1 hour, washing and drying to obtain modified carrageenan; S1-3: antibacterial particles and modified carrageenan are added to tetrahydrofuran in sequence, photoinitiator AIBN is added, the temperature is raised to 70°C, stirred for reaction for 4 hours, washed and dried to obtain composite carrageenan, and the mass ratio of antibacterial particles to modified carrageenan is 7:7;

[0033] Step 1: 80 parts of low-density polyethylene, 12 parts of ethylene-octene copolymer, 8 parts of polyethylene grafted maleic anhydride, 14 parts of composite carrageenan, 21 parts of calcium carbonate, 8 parts of porous silica, and 2 parts of calcium stearate are dried and mixed, and 0.1 parts of dioctyl peroxydicarbonate are added; melt extrusion, during the process: the head temperature is 200°C, and the temperatures of the other 5 temperature zones are 170°C, 180°C, 190°C, 200°C, and 205°C respectively; blow molding film, during the process: the die temperature is 200°C, and the pulling speed is 3500mm / s; obtain an antibacterial polyethylene film;

[0034] Step 2: (1) Mix 96 wt% of organic silicone adhesive and 4 wt% of porous silica to obtain a medical pressure-sensitive adhesive; (2) Coat the medical pressure-sensitive adhesive on one side of the antibacterial polyethylene film and cure it at 160° C. to obtain a pressure-sensitive adhesive layer; cover with a release film to obtain a disposable antibacterial surgical film.

[0035] Embodiment 2: A method for preparing a disposable antibacterial surgical membrane, comprising the following steps:

[0036] Pre-preparation: Preparation of porous silica: S2-1: Add 1 part of allyl beta-cyclodextrin to 50 parts of DMF, add 2.3 parts of 1,1-carbonyldiimidazole, and stir at 20°C for 1 hour; add 2 parts of 3-aminopropyltriethoxysilane, continue stirring for 20 hours, evaporate the solvent to obtain cyclodextrin silane; S2-2: Add 2.52 parts of hexadecyltrimethylammonium bromide to 13 parts of deionized water, add 0.84 parts of 25wt% ammonia water and stir evenly; add 16.3 parts of tetraethyl orthosilicate and 8.4 parts of cyclodextrin silane, stir at 20°C for 2 hours; hydrothermally react it at 100°C for 24 hours, wash and dry to obtain porous silica;

[0037] Preparation of composite carrageenan: S1-1: (1) 10 parts of carboxylated carbon nanotubes and 0.15 parts of N-(3-mercapto-2-methylpropanoyl) glycine were added to 50 parts of deionized water in sequence, ultrasonically dispersed for 15 minutes, stirred for 1 hour, filtered and dried to obtain modified carbon nanotubes; (2) 10 parts of nano titanium dioxide and 0.38 parts of ammonium fluoride were ground and blended, heat treated at 500°C for 5 hours, cooled to obtain fluorinated titanium dioxide; 10 parts of fluorinated titanium dioxide and 1.2 parts of 3-mercaptopropyltriethoxysilane were added to 85 parts of anhydrous ethanol in sequence, and 15 parts of deionized water were added; the temperature was raised to 75°C, stirred for 4 hours, washed and dried to obtain modified titanium dioxide; (3) the modified Carbon nanotubes and modified titanium dioxide are compounded in a mass ratio of 1:1.5 to obtain antibacterial particles; S1-2: 10 parts of carrageenan are added to 100 parts of 85 vol% ethanol aqueous solution and stirred evenly, and allyl succinic anhydride-anhydrous ethanol solution (8 parts of allyl succinic anhydride, 42 parts of anhydrous ethanol) is added dropwise at 30°C for 1 hour, and the pH is adjusted to 8.2; stirring is continued for 1 hour, washing and drying to obtain modified carrageenan; S1-3: antibacterial particles and modified carrageenan are added to tetrahydrofuran in sequence, photoinitiator AIBN is added, the temperature is raised to 70°C, stirred for reaction for 4 hours, washed and dried to obtain composite carrageenan, and the mass ratio of antibacterial particles to modified carrageenan is 8:7;

[0038] Step 1: 82 parts of low-density polyethylene, 10 parts of ethylene-octene copolymer, 8 parts of polyethylene grafted maleic anhydride, 15 parts of composite carrageenan, 21 parts of calcium carbonate, 10 parts of porous silica, and 1 part of calcium stearate are dried and mixed, and 0.1 parts of dioctyl peroxydicarbonate are added; melt extrusion, during the process: the head temperature is 200°C, and the temperatures of the other 5 temperature zones are 170°C, 180°C, 190°C, 200°C, and 205°C respectively; blow molding film, during the process: the die temperature is 200°C, and the pulling speed is 3500mm / s; obtain an antibacterial polyethylene film;

[0039] Step 2: (1) 97 wt% of organic silicone adhesive and 3 wt% of porous silica are mixed and homogenized to obtain a medical pressure-sensitive adhesive; (2) the medical pressure-sensitive adhesive is coated on one side of an antibacterial polyethylene film and cured at 160° C. to obtain a pressure-sensitive adhesive layer; and a release film is covered to obtain a disposable antibacterial surgical film.

[0040] Embodiment 3: A method for preparing a disposable antibacterial surgical membrane, comprising the following steps:

[0041] Pre-preparation: Preparation of porous silica: S2-1: Add 1 part of allyl beta-cyclodextrin to 50 parts of DMF, add 2.3 parts of 1,1-carbonyldiimidazole, and stir at 20°C for 1 hour; add 2 parts of 3-aminopropyltriethoxysilane, continue stirring for 20 hours, evaporate the solvent to obtain cyclodextrin silane; S2-2: Add 2.52 parts of hexadecyltrimethylammonium bromide to 13 parts of deionized water, add 0.84 parts of 25wt% ammonia water and stir evenly; add 16.3 parts of tetraethyl orthosilicate and 8.4 parts of cyclodextrin silane, stir at 20°C for 2 hours; hydrothermally react it at 100°C for 24 hours, wash and dry to obtain porous silica;

[0042] Preparation of composite carrageenan: S1-1: (1) 10 parts of carboxylated carbon nanotubes and 0.15 parts of N-(3-mercapto-2-methylpropanoyl) glycine were added to 50 parts of deionized water in sequence, ultrasonically dispersed for 15 minutes, stirred for 1 hour, filtered and dried to obtain modified carbon nanotubes; (2) 10 parts of nano titanium dioxide and 0.38 parts of ammonium fluoride were ground and blended, heat treated at 500°C for 5 hours, cooled to obtain fluorinated titanium dioxide; 10 parts of fluorinated titanium dioxide and 1.2 parts of 3-mercaptopropyltriethoxysilane were added to 85 parts of anhydrous ethanol in sequence, and 15 parts of deionized water were added; the temperature was raised to 75°C, stirred for 4 hours, washed and dried to obtain modified titanium dioxide; (3) the modified Carbon nanotubes and modified titanium dioxide are compounded in a mass ratio of 1:1.5 to obtain antibacterial particles; S1-2: 10 parts of carrageenan are added to 100 parts of 85 vol% ethanol aqueous solution and stirred evenly, and allyl succinic anhydride-anhydrous ethanol solution (8 parts of allyl succinic anhydride, 42 parts of anhydrous ethanol) is added dropwise at 30°C for 1 hour, and the pH is adjusted to 8.2; stirring is continued for 1 hour, washing and drying to obtain modified carrageenan; S1-3: antibacterial particles and modified carrageenan are added to tetrahydrofuran in sequence, photoinitiator AIBN is added, the temperature is raised to 70°C, stirred for reaction for 4 hours, washed and dried to obtain composite carrageenan, and the mass ratio of antibacterial particles to modified carrageenan is 5:7;

[0043] Step 1: 75 parts of low-density polyethylene, 15 parts of ethylene-octene copolymer, 8 parts of polyethylene grafted maleic anhydride, 12 parts of composite carrageenan, 21 parts of calcium carbonate, 7 parts of porous silica, and 2 parts of calcium stearate are dried and mixed, and 0.1 parts of dioctyl peroxydicarbonate are added; melt extrusion, during the process: the head temperature is 200°C, and the temperatures of the other 5 temperature zones are 170°C, 180°C, 190°C, 200°C, and 205°C respectively; blow molding film, during the process: the die temperature is 200°C, and the pulling speed is 3500mm / s; obtain an antibacterial polyethylene film;

[0044] Step 2: (1) Mix 95 wt% of organic silicone adhesive and 5 wt% of porous silica to obtain a medical pressure-sensitive adhesive; (2) Coat the medical pressure-sensitive adhesive on one side of the antibacterial polyethylene film and cure it at 160° C. to obtain a pressure-sensitive adhesive layer; cover with a release film to obtain a disposable antibacterial surgical film.

[0045] Comparative Example 1: The porous silica was replaced with calcium carbonate having an average particle size of 2500 nanometers; the rest was the same as Example 1; specifically as follows:

[0046] Preparation of composite carrageenan: S1-1: (1) 10 parts of carboxylated carbon nanotubes and 0.15 parts of N-(3-mercapto-2-methylpropanoyl) glycine were added to 50 parts of deionized water in sequence, ultrasonically dispersed for 15 minutes, stirred for 1 hour, filtered and dried to obtain modified carbon nanotubes; (2) 10 parts of nano titanium dioxide and 0.38 parts of ammonium fluoride were ground and blended, heat treated at 500°C for 5 hours, cooled to obtain fluorinated titanium dioxide; 10 parts of fluorinated titanium dioxide and 1.2 parts of 3-mercaptopropyltriethoxysilane were added to 85 parts of anhydrous ethanol in sequence, and 15 parts of deionized water were added; the temperature was raised to 75°C, stirred for 4 hours, washed and dried to obtain modified titanium dioxide; (3) the modified Carbon nanotubes and modified titanium dioxide are compounded in a mass ratio of 1:1.5 to obtain antibacterial particles; S1-2: 10 parts of carrageenan are added to 100 parts of 85 vol% ethanol aqueous solution and stirred evenly, and allyl succinic anhydride-anhydrous ethanol solution (8 parts of allyl succinic anhydride, 42 parts of anhydrous ethanol) is added dropwise at 30°C for 1 hour, and the pH is adjusted to 8.2; stirring is continued for 1 hour, washing and drying to obtain modified carrageenan; S1-3: antibacterial particles and modified carrageenan are added to tetrahydrofuran in sequence, photoinitiator AIBN is added, the temperature is raised to 70°C, stirred for reaction for 4 hours, washed and dried to obtain composite carrageenan, and the mass ratio of antibacterial particles to modified carrageenan is 7:7;

[0047] Step 1: 80 parts of low-density polyethylene, 12 parts of ethylene-octene copolymer, 8 parts of polyethylene grafted maleic anhydride, 14 parts of composite carrageenan, 29 parts of calcium carbonate (15 parts of 2500 nanometers, 7 parts of 1500 nanometers, 7 parts of 500 nanometers), and 2 parts of calcium stearate are dried and mixed, and 0.1 parts of dioctyl peroxydicarbonate are added; melt extrusion, during the process: the head temperature is 200°C, and the temperatures of the other 5 temperature zones are 170°C, 180°C, 190°C, 200°C, and 205°C respectively; blow molding film, during the process: the die temperature is 200°C, and the pulling speed is 3500mm / s; obtain an antibacterial polyethylene film;

[0048] Step 2: (1) Mix 96 wt% of organic silicone adhesive and 4 wt% of 2500 nanometer calcium carbonate to obtain a medical pressure-sensitive adhesive; (2) Coat the medical pressure-sensitive adhesive on one side of the antibacterial polyethylene film and cure it at 160°C to obtain a pressure-sensitive adhesive layer; cover with a release film to obtain a disposable antibacterial surgical film.

[0049] Comparative Example 2: The antibacterial particles used were modified titanium dioxide alone; the rest was the same as Example 1; the details are as follows:

[0050] Pre-preparation: Preparation of porous silica: S2-1: Add 1 part of allyl beta-cyclodextrin to 50 parts of DMF, add 2.3 parts of 1,1-carbonyldiimidazole, and stir at 20°C for 1 hour; add 2 parts of 3-aminopropyltriethoxysilane, continue stirring for 20 hours, evaporate the solvent to obtain cyclodextrin silane; S2-2: Add 2.52 parts of hexadecyltrimethylammonium bromide to 13 parts of deionized water, add 0.84 parts of 25wt% ammonia water and stir evenly; add 16.3 parts of tetraethyl orthosilicate and 8.4 parts of cyclodextrin silane, stir at 20°C for 2 hours; hydrothermally react it at 100°C for 24 hours, wash and dry to obtain porous silica;

[0051] Preparation of composite carrageenan: S1-1: Grind and blend 10 parts of nano titanium dioxide and 0.38 parts of ammonium fluoride, heat treat at 500°C for 5 hours, cool to obtain fluorinated titanium dioxide; add 10 parts of fluorinated titanium dioxide and 1.2 parts of 3-mercaptopropyltriethoxysilane to 85 parts of anhydrous ethanol in sequence, add 15 parts of deionized water; heat to 75°C, stir for 4 hours, wash and dry to obtain modified titanium dioxide; use it as antibacterial particles; S1-2: Add 10 parts of carrageenan to 100 parts of 85 vol% Stir evenly in an ethanol-water solution, add allyl succinic anhydride-anhydrous ethanol solution (8 parts of allyl succinic anhydride and 42 parts of anhydrous ethanol) dropwise at 30°C for 1 hour, and adjust the pH to 8.2; continue stirring for 1 hour, wash and dry to obtain modified carrageenan; S1-3: add antibacterial particles and modified carrageenan to tetrahydrofuran in sequence, add photoinitiator AIBN, heat to 70°C, stir and react for 4 hours, wash and dry to obtain composite carrageenan, and the mass ratio of antibacterial particles to modified carrageenan is 7:7;

[0052] Step 1: 80 parts of low-density polyethylene, 12 parts of ethylene-octene copolymer, 8 parts of polyethylene grafted maleic anhydride, 14 parts of composite carrageenan, 21 parts of calcium carbonate, 8 parts of porous silica, and 2 parts of calcium stearate are dried and mixed, and 0.1 parts of dioctyl peroxydicarbonate are added; melt extrusion, during the process: the head temperature is 200°C, and the temperatures of the other 5 temperature zones are 170°C, 180°C, 190°C, 200°C, and 205°C respectively; blow molding film, during the process: the die temperature is 200°C, and the pulling speed is 3500mm / s; obtain an antibacterial polyethylene film;

[0053] Step 2: (1) Mix 96 wt% of organic silicone adhesive and 4 wt% of porous silica to obtain a medical pressure-sensitive adhesive; (2) Coat the medical pressure-sensitive adhesive on one side of the antibacterial polyethylene film and cure it at 160° C. to obtain a pressure-sensitive adhesive layer; cover with a release film to obtain a disposable antibacterial surgical film.

[0054] Comparative Example 3: The modified titanium dioxide is replaced with directly purchased titanium dioxide; the rest is the same as Example 1; the details are as follows:

[0055] Pre-preparation: Preparation of porous silica: S2-1: Add 1 part of allyl beta-cyclodextrin to 50 parts of DMF, add 2.3 parts of 1,1-carbonyldiimidazole, and stir at 20°C for 1 hour; add 2 parts of 3-aminopropyltriethoxysilane, continue stirring for 20 hours, evaporate the solvent to obtain cyclodextrin silane; S2-2: Add 2.52 parts of hexadecyltrimethylammonium bromide to 13 parts of deionized water, add 0.84 parts of 25wt% ammonia water and stir evenly; add 16.3 parts of tetraethyl orthosilicate and 8.4 parts of cyclodextrin silane, stir at 20°C for 2 hours; hydrothermally react it at 100°C for 24 hours, wash and dry to obtain porous silica;

[0056] Preparation of composite carrageenan: S1-1: (1) 10 parts of carboxylated carbon nanotubes and 0.15 parts of N-(3-mercapto-2-methylpropanoyl) glycine were added to 50 parts of deionized water in sequence, ultrasonically dispersed for 15 minutes, stirred for 1 hour, filtered and dried to obtain modified carbon nanotubes; (3) The modified carbon nanotubes and titanium dioxide were compounded in a mass ratio of 1:1.5 to obtain antibacterial particles; S1-2: 10 parts of carrageenan were added to 100 parts of 85 vol% ethanol aqueous solution and stirred. At 30°C, add allyl succinic anhydride-anhydrous ethanol solution (8 parts allyl succinic anhydride, 42 parts anhydrous ethanol) dropwise for 1 hour, and adjust the pH to 8.2; continue stirring for 1 hour, wash and dry to obtain modified carrageenan; S1-3: add antibacterial particles and modified carrageenan to tetrahydrofuran in sequence, add photoinitiator AIBN, heat to 70°C, stir and react for 4 hours, wash and dry to obtain composite carrageenan, the mass ratio of antibacterial particles to modified carrageenan is 7:7;

[0057] Step 1: 80 parts of low-density polyethylene, 12 parts of ethylene-octene copolymer, 8 parts of polyethylene grafted maleic anhydride, 14 parts of composite carrageenan, 21 parts of calcium carbonate, 8 parts of porous silica, and 2 parts of calcium stearate are dried and mixed, and 0.1 parts of dioctyl peroxydicarbonate are added; melt extrusion, during the process: the head temperature is 200°C, and the temperatures of the other 5 temperature zones are 170°C, 180°C, 190°C, 200°C, and 205°C respectively; blow molding film, during the process: the die temperature is 200°C, and the pulling speed is 3500mm / s; obtain an antibacterial polyethylene film;

[0058] Step 2: (1) Mix 96 wt% of organic silicone adhesive and 4 wt% of porous silica to obtain a medical pressure-sensitive adhesive; (2) Coat the medical pressure-sensitive adhesive on one side of the antibacterial polyethylene film and cure it at 160° C. to obtain a pressure-sensitive adhesive layer; cover with a release film to obtain a disposable antibacterial surgical film.

[0059] Comparative Example 4: Carrageenan was not introduced, and the rest was the same as Example 1; the details are as follows:

[0060] Pre-preparation: Preparation of porous silica: S2-1: Add 1 part of allyl beta-cyclodextrin to 50 parts of DMF, add 2.3 parts of 1,1-carbonyldiimidazole, and stir at 20°C for 1 hour; add 2 parts of 3-aminopropyltriethoxysilane, continue stirring for 20 hours, evaporate the solvent to obtain cyclodextrin silane; S2-2: Add 2.52 parts of hexadecyltrimethylammonium bromide to 13 parts of deionized water, add 0.84 parts of 25wt% ammonia water and stir evenly; add 16.3 parts of tetraethyl orthosilicate and 8.4 parts of cyclodextrin silane, stir at 20°C for 2 hours; hydrothermally react it at 100°C for 24 hours, wash and dry to obtain porous silica;

[0061] Preparation of antibacterial particles: S1-1: (1) 10 parts of carboxylated carbon nanotubes and 0.15 parts of N-(3-mercapto-2-methylpropanoyl) glycine were added to 50 parts of deionized water in sequence, ultrasonically dispersed for 15 minutes, stirred for 1 hour, filtered and dried to obtain modified carbon nanotubes; (2) 10 parts of nano titanium dioxide and 0.38 parts of ammonium fluoride were ground and blended, heat treated at 500°C for 5 hours, cooled to obtain fluorinated titanium dioxide; 10 parts of fluorinated titanium dioxide and 1.2 parts of 3-mercaptopropyltriethoxysilane were added to 85 parts of anhydrous ethanol in sequence, and 15 parts of deionized water were added; the temperature was raised to 75°C, stirred for 4 hours, washed and dried to obtain modified titanium dioxide; (3) The modified carbon nanotubes and modified titanium dioxide were compounded in a mass ratio of 1:1.5 to obtain antibacterial particles;

[0062] Step 1: 87 parts of low-density polyethylene, 12 parts of ethylene-octene copolymer, 8 parts of polyethylene grafted maleic anhydride, 7 parts of antibacterial particles, 21 parts of calcium carbonate, 8 parts of porous silica, and 2 parts of calcium stearate are dried and mixed, and 0.1 parts of dioctyl peroxydicarbonate are added; melt extrusion, during the process: the head temperature is 200°C, and the temperatures of the other 5 temperature zones are 170°C, 180°C, 190°C, 200°C, and 205°C respectively; blow molding film, during the process: the die temperature is 200°C, and the pulling speed is 3500mm / s; obtain an antibacterial polyethylene film;

[0063] Step 2: (1) Mix 96 wt% of organic silicone adhesive and 4 wt% of porous silica to obtain a medical pressure-sensitive adhesive; (2) Coat the medical pressure-sensitive adhesive on one side of the antibacterial polyethylene film and cure it at 160° C. to obtain a pressure-sensitive adhesive layer; cover with a release film to obtain a disposable antibacterial surgical film.

[0064] Performance test: The disposable antibacterial surgical membranes prepared in the examples and comparative examples were subjected to relevant performance tests; (1) at room temperature, the longitudinal tensile strength was tested using an electronic tensile machine; (2) according to the water vapor permeability test content in Appendix D of YY0852, the water vapor permeability of the membrane was tested for 24 hours; (3) according to the test content of the fifth part of the antibacterial property in YY / T0471.5, the antibacterial rate of the membrane against Pseudomonas aeruginosa was tested; the obtained data are shown in the following table:

[0065]

[0066] Conclusion: From the data in the above table, it can be seen that the present application has prepared a disposable antibacterial surgical membrane with excellent tensile strength, water vapor permeability, and high Pseudomonas aeruginosa antibacterial rate; the antibacterial effect is better than that of conventional surgical membranes. At the same time, from the data of the comparative examples, it can be seen that in comparative example 1, the water vapor permeability is further reduced due to the lack of introduction of porous silica prepared by a specific method; in comparative example 2, due to the introduction of a single modified titanium dioxide, the antibacterial synergy is reduced, resulting in a decrease in related performance; in comparative example 3, due to the unmodified titanium dioxide, the antibacterial property and compatibility are reduced, resulting in a decrease in related performance; in comparative example 4, due to the lack of introduction of carrageenan, the related processing performance is reduced, resulting in a significant decrease in tensile strength.

[0067] Finally, it should be noted that the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art can still modify the technical solutions described in the aforementioned embodiments or replace some of the technical features therein by equivalents. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for preparing a disposable antibacterial surgical membrane, characterized in that: The following steps are involved: Step 1: low-density polyethylene, ethylene-octene copolymer, polyethylene grafted maleic anhydride, composite carrageenan, calcium carbonate, porous silica, and additives are dried and mixed, and peroxide is added; melt extrusion and blow molding are performed to form a film to obtain an antibacterial polyethylene film; Step 2: coating a medical pressure-sensitive adhesive on one side of the antibacterial polyethylene film, and ripening the film to obtain a pressure-sensitive adhesive layer; covering the film with a release film; and obtaining a disposable antibacterial surgical film.

2. The method for preparing a disposable antibacterial surgical membrane according to claim 1, characterized in that: The raw materials of the antibacterial polyethylene film include the following components: by weight, 75-82 parts of low-density polyethylene, 10-15 parts of ethylene-octene copolymer, 8-10 parts of polyethylene grafted maleic anhydride, 12-15 parts of composite carrageenan, 20-23 parts of calcium carbonate, 7-10 parts of porous silica, 1-2 parts of additives, and 0.1-0.2 parts of peroxide.

3. The method for preparing a disposable antibacterial surgical membrane according to claim 1, characterized in that: The process parameters of the melt extrusion are: the head temperature is 190-200°C, and the temperatures of the other five temperature zones are 165-175°C, 175-185°C, 185-195°C, 195-200°C, and 200-205°C respectively; the process parameters of the blow molding film are: the die temperature is 195-205°C, and the pulling speed is 320-380 mm / s.

4. The method for preparing a disposable antibacterial surgical membrane according to claim 1, characterized in that: The preparation method of the composite carrageenan is as follows: S1-1: (1) adding carboxylated carbon nanotubes and N-(3-mercapto-2-methylpropanoyl)glycine to deionized water in sequence, stirring evenly, filtering, and drying to obtain modified carbon nanotubes; (2) grinding and blending nano titanium dioxide and ammonium fluoride, heat treating at 450-500° C. for 4-5 hours, cooling to obtain fluorinated titanium dioxide; sequentially adding fluorinated titanium dioxide and mercaptosilane coupling agent to anhydrous ethanol, adding deionized water, heating to 70-80° C., stirring for 4-6 hours, washing, and drying to obtain modified titanium dioxide; (3) compounding modified carbon nanotubes and modified titanium dioxide in proportion to obtain antibacterial particles; S1-2: adding carrageenan to 80-85 vol% ethanol aqueous solution and stirring evenly, adding allyl succinic anhydride-anhydrous ethanol solution dropwise at 30-40° C. for 0.5-1 hour, adjusting the pH to 8±0.2; continuing stirring for 0.5-1 hour, washing and drying to obtain modified carrageenan; S1-3: adding antibacterial particles and modified carrageenan to tetrahydrofuran in sequence, adding a photoinitiator, heating to 68-72° C., stirring for reaction for 4-5 hours, washing and drying to obtain composite carrageenan.

5. The method for preparing a disposable antibacterial surgical membrane according to claim 4, characterized in that: The ratio of the antibacterial particles is: the mass ratio of the modified carbon nanotubes to the modified titanium dioxide is 1:(1.5-2); the mass ratio of the antibacterial particles to the modified carrageenan is (5-8):

7.

6. The method for preparing a disposable antibacterial surgical membrane according to claim 4, characterized in that: In the raw materials of the modified carbon nanotubes, the mass ratio of carboxylated carbon nanotubes and N-(3-mercapto-2-methylpropanoyl)glycine is 1:(0.1-0.2); in the raw materials of the modified titanium dioxide, the mass ratio of nano titanium dioxide and ammonium fluoride is 1:(0.3-0.4); and the mass ratio of fluorinated titanium dioxide and mercaptosilane coupling agent is 1:(0.15-0.25).

7. The method for preparing a disposable antibacterial surgical membrane according to claim 1, characterized in that: The preparation method of the porous silica is: S2-1: Add allyl beta-cyclodextrin to DMF, add 1,1-carbonyldiimidazole, and stir at 20-25° C. for 1-2 hours; add 3-aminopropyltriethoxysilane, continue stirring for 20-24 hours, and evaporate the solvent to obtain cyclodextrin silane; S2-2: Add hexadecyltrimethylammonium bromide to deionized water, add ammonia water and stir evenly; add tetraethyl orthosilicate and cyclodextrin silane, stir at 20-25°C for 2-3 hours; hydrothermally react at 95-100°C for 24 hours, wash and dry to obtain porous silica.

8. The method for preparing a disposable antibacterial surgical membrane according to claim 7, characterized in that: In the raw materials of the cyclodextrin silane, the molar ratio of allyl beta-cyclodextrin, 1,1-carbonyldiimidazole and 3-aminopropyltriethoxysilane is 1:(2-3):(2-3); the raw materials of the porous silica include the following components: by weight, 2.5-2.8 parts of hexadecyltrimethylammonium bromide, 0.8-1 part of ammonia water, 16-17 parts of tetraethyl orthosilicate, and 8-8.5 parts of cyclodextrin silane; the solubility of ammonia water is 20-25wt%.

9. The method for preparing a disposable antibacterial surgical membrane according to claim 1, characterized in that: The medical pressure-sensitive adhesive comprises 95wt% to 97wt% of organic silicone adhesive and 3wt% to 5wt% of porous silicon dioxide; the curing temperature is 140 to 180°C.

10. The disposable antibacterial surgical membrane prepared by the method for preparing a disposable antibacterial surgical membrane according to any one of claims 1 to 9, characterized in that: The disposable antibacterial surgical film comprises an antibacterial polyethylene film, a pressure-sensitive adhesive layer and a release film. The thickness of the antibacterial polyethylene film is 40 to 60 μm; the thickness of the pressure-sensitive adhesive layer is 20 to 40 μm; and the thickness of the release film is 20 to 80 μm.

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