CN120040855A - Antibacterial deodorizing polyethylene breathable film for medical and sanitary use and preparation method thereof - Google Patents
Antibacterial deodorizing polyethylene breathable film for medical and sanitary use and preparation method thereof Download PDFInfo
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Abstract
The application relates to the technical field of medical breathable films, in particular to an antibacterial deodorizing polyethylene breathable film for medical and sanitary use and a preparation method thereof. The antibacterial deodorizing polyethylene breathable film for medical and sanitary use is prepared from metal ion doped Mesoporous Silica (MSN) and Polyethylene (PE) breathable particles, wherein the particles comprise 1-5 parts of metal ion doped mesoporous silica nano antibacterial agent MSN and 100 parts of PE breathable particles, a resin matrix in the PE breathable particles is low-density polyethylene LDPE or linear low-density polyethylene LLDPE, and inorganic fillers used for forming a microporous structure in the PE breathable particles comprise at least one of stearic acid modified calcium carbonate, talcum powder, calcined shell powder, kaolin, silica fume, zeolite powder, titanium pigment, silicon dioxide and glass powder, wherein the average particle size of the stearic acid modified calcium carbonate is 50-2000 nm. The PE breathable film has deodorizing, antibacterial and antistatic effects, is used in the field of medical non-woven fabrics, and reduces the bacterial infection risk of medical staff.
Description
Technical Field
The application relates to the technical field of medical breathable films, in particular to an antibacterial deodorizing polyethylene breathable film for medical and sanitary use and a preparation method thereof.
Background
Polyethylene (PE) breathable films are applied to various fields due to the characteristics of good high temperature and low temperature resistance, corrosion resistance, high tensile strength, high water resistance, softness and the like. PE is suitable for use in various processing methods, such as blow molding and thermoforming. In addition, the product can be used for manufacturing various plastic products, food packages, disposable food containers, non-woven fabrics, industrial and household textiles due to the advantage of easy processing. It can be further processed into agricultural fabrics, medical textiles, cleaning cloths, sanitary products, outdoor ultraviolet-resistant fabrics, tent fabrics, carpet surfaces and the like, so that the novel ultraviolet-resistant fabric has a broad prospect.
The main components of the Polyethylene (PE) breathable film are PE particles and large-particle calcium carbonate, and the PE particles and the large-particle calcium carbonate are mixed according to a certain proportion, so that the corresponding PE breathable particles are prepared. After the PE breathable particles are used for preparing the film, the calcium carbonate in the PE breathable particles can cause micropores to be formed in the film, so that the breathable and moisture-permeable functions of the film are achieved. However, such breathable films attract viruses and mold, which raise safety and hygiene concerns. Therefore, the inventor provides an antibacterial deodorizing polyethylene breathable film for medical and sanitary use and a preparation method thereof.
Disclosure of Invention
The invention provides an antibacterial deodorizing polyethylene breathable film for medical and health and a preparation method thereof, and aims to solve the problem that the antibacterial property deviation of the conventional polyethylene breathable film causes concern of people on safety and sanitation.
The invention provides an antibacterial deodorizing polyethylene breathable film for medical and sanitary use, which is realized by the following technical scheme:
the antibacterial deodorizing polyethylene breathable film for medical and sanitary use is prepared from MSN-doped PE breathable particles, wherein the MSN-doped PE breathable particles comprise 1-5 parts by weight of copper ion-doped mesoporous silica nano antibacterial agent MSN and 100 parts by weight of PE breathable particles.
Preferably, the resin matrix in the PE breathable particles is low-density polyethylene LDPE or linear low-density polyethylene LLDPE, and the addition amount of the inorganic filler in the PE breathable particles is 5-50wt%.
Preferably, the inorganic filler used for forming the micropore structure in the PE breathable particles comprises at least one of stearic acid modified calcium carbonate, talcum powder, calcined shell powder, kaolin, silica fume, zeolite powder, titanium pigment, silicon dioxide and glass powder with the average particle size of 50-2000 nm.
The PE breathable film has deodorizing, antibacterial and antistatic effects, is used in the field of medical non-woven fabrics, and reduces the bacterial infection risk of medical staff.
Preferably, the metal ion doped mesoporous silica nano antibacterial agent MSN is at least one of Mn2+、Pb2+、Cu2+、Zn2+、Cu+、Zn2+、Fe3+、Fe2+、Ag+、Au+、Au3+, and the granularity distribution of mesoporous silica in the metal ion doped mesoporous silica nano antibacterial agent MSN is 20-200nm.
Further preferably, the metal ion doped mesoporous silica nano antimicrobial MSN is Cu 2+.
Preferably, the metal ion doped mesoporous silica nano antimicrobial MSN is prepared by taking metal salt, sodium hydroxide, cetyltrimethylammonium bromide and ethyl orthosilicate as raw materials through a sol-gel method in one step.
Further preferably, the preparation method of the metal ion doped mesoporous silica nano antimicrobial MSN comprises the following steps of firstly preparing a metal hydroxide seed solution by using metal salt, sodium hydroxide and cetyltrimethylammonium bromide, secondly adding tetraethyl orthosilicate into the metal hydroxide seed solution, reacting for 2-8 hours at 60-80 ℃, centrifuging the obtained solid, washing the obtained solid with pure water and ethanol for three times respectively, drying and crushing to obtain the finished MSN.
Preferably, the specific preparation method of the metal hydroxide seed solution in the first step comprises the steps of preparing a metal salt solution with the concentration of 0.06-320g/L, a cetyltrimethylammonium bromide solution with the concentration of 13g/L and a NaOH solution with the concentration of 0.5-1 mol/L for standby, then adding 1-7mL of the metal salt solution with the concentration of 0.06-320g/L and 1.0mL of the cetyltrimethylammonium bromide solution with the concentration of 13g/L into 100mL of ultrapure water with the temperature of 60-65 ℃ for mixing and stirring for at least half an hour, then adding 0.25mL of the NaOH solution with the concentration of 0.5-1 mol/L, heating to 60-80 ℃ and continuously stirring for at least half an hour to obtain the metal hydroxide seed solution.
Preferably, in the second step, 1-2mL of tetraethyl orthosilicate with the concentration of 15.0-20.0g/L is added into the metal hydroxide seed solution prepared in the first step, the reaction is carried out for 2-8 hours at the temperature of 60-80 ℃, and the solid obtained by centrifugation is washed three times with pure water and ethanol respectively, dried and crushed to obtain the finished product MSN.
Preferably, the metal salt in the metal salt solution is at least one of copper sulfate, copper chloride, copper nitrate, copper acetylacetonate, manganese sulfate, manganese chloride, manganese nitrate, manganese acetylacetonate, zinc sulfate, cuprous chloride, zinc nitrate, zinc acetylacetonate, ferrous sulfate, ferric chloride, ferric nitrate, ferric acetylacetonate, lead sulfate, lead chloride, lead nitrate, lead acetylacetonate, silver nitrate and chloroauric acid.
Preferably, the solvent in the metal salt solution is water or a mixed solvent formed by water and at least one of alcohols, heptane, benzene, toluene, xylene and acetone.
By adopting the technical scheme, the metal ion doped mesoporous silica nano antibacterial agent MSN has lower synthesis difficulty and small synthesis pollution, is convenient for realizing the industrial production of the nano antibacterial agent MSN, and can further reduce the production cost of the nano antibacterial agent MSN and the production cost of the medical antibacterial deodorizing polyethylene breathable film.
The invention provides a preparation method of an antibacterial deodorizing polyethylene breathable film for medical and sanitary use, which is realized by the following technical scheme:
The preparation method of the antibacterial deodorizing polyethylene breathable film for medical and sanitary use comprises the following steps:
step one, preparing a metal ion doped mesoporous silica nano antibacterial agent MSN;
Uniformly mixing 1-5 parts of metal ion doped mesoporous silica nano-antibacterial agent MSN and 100 parts of PE breathable particles subjected to drying treatment at a high speed, and putting the mixture into a double-screw extruder for extrusion granulation, wherein the temperature of a feeding section is 160-180 ℃, the temperature of a plasticizing section is 160-180 ℃, the temperature of a homogenizing section is 160-180 ℃, the rotating speed of a double-screw is 60-72r/min, and the temperature of a die head is 160-180 ℃, so as to obtain MSN doped PE breathable particles;
putting MSN doped PE breathable particles into a double-screw extruder, feeding the particles at 160-180 ℃, plasticizing the particles at 160-180 ℃, homogenizing the particles at 160-180 ℃, setting the rotating speed of the double-screw extruder at 80-100r/min and the temperature of a die head at 160-180 ℃, putting the obtained molten extrusion materials into a casting machine, setting the rotating speed of the casting machine at 50-100r/min, and horizontally stretching the molten extrusion materials to obtain the medical antibacterial deodorizing polyethylene breathable film.
The preparation method of the invention is simpler, the synthesis difficulty of the metal ion doped mesoporous silica nano antimicrobial MSN is lower, the mass production is convenient to realize, the production cost of the medical antibacterial deodorizing polyethylene breathable film is reduced, and the market competitiveness of the medical antibacterial deodorizing polyethylene breathable film is further improved.
The antibacterial deodorizing polyethylene breathable film for medical and health use has the antibacterial performance on candida albicans of more than or equal to 99%, the antibacterial performance of escherichia coli of more than 99%, the antibacterial performance of staphylococcus aureus of more than 99%, the deodorizing grade of more than or equal to 2, the antistatic grade of 10 6-109 Ω & cm, the water vapor permeability of more than or equal to 1500g/m 2/24 h, and the hydrostatic pressure of more than or equal to 500mmH 2 0.
In summary, the application has the following advantages:
1. the PE breathable film has deodorizing, antibacterial and antistatic effects, is used in the field of medical non-woven fabrics, and reduces the bacterial infection risk of medical staff.
2. The preparation method is relatively simple, has low operation difficulty and is convenient for realizing batch manufacturing.
3. The antibacterial deodorizing polyethylene breathable film for medical and health use has the antibacterial performance on candida albicans of more than or equal to 99%, the antibacterial performance of escherichia coli of more than 99%, the antibacterial performance of staphylococcus aureus of more than 99%, the deodorizing grade of less than or equal to 2 grade, the antistatic grade of 10 6-109 Ω & cm, the water vapor permeability of more than or equal to 1500g/m 2/24 h, and the hydrostatic pressure of more than or equal to 500mmH 2 0.
Drawings
FIG. 1 is a transmission electron micrograph of mesoporous nano-silicon doped with no metal ions in preparation example 15, with dimensions of 20 and 200 nanometers, respectively.
FIG. 2 shows TEM images (100 nm in size) of Cu 2+ (a, b, c, d correspond to 0.01,0.1,1.0,10.0 mM) doped mesoporous MSN in preparation example 5 and preparation examples 12-14, respectively.
FIG. 3 is a graph of UV absorption spectra of MSN doped with different metal ions (Mn 2+、Pb2+、Cu2+、Zn2+、Cu2+、Zn2+、Fe3+).
FIG. 4 is a schematic representation of the preparation of Cu 2+ ion-doped MSN nanoparticles according to preparation example 5 of the present invention.
FIG. 5 is a graph showing the dynamic light scattering of Cu 2+ ion-doped MSN nanoparticles of preparation example 5 in accordance with the present invention.
Detailed Description
For a further understanding of the inventive and technical advances of the present invention, a detailed description of the preferred embodiments of the invention is provided below in conjunction with the examples and comparative examples. It should be noted that this specific embodiment is merely illustrative of the technical solution of the present invention, and not limiting, and those skilled in the art, after reading the present specification, may make modifications to this embodiment without creative contribution as needed, but are protected by patent laws within the scope of the claims of the present invention.
Examples
An antibacterial and deodorizing polyethylene ventilated membrane for medical and sanitary use is prepared by extruding and casting MSN doped PE ventilated particles. The MSN doped PE breathable particles are prepared from the following raw materials, by weight, 1-5 parts of metal ion doped mesoporous silica nano antibacterial agent MSN and 100 parts of PE breathable particles.
The resin matrix in the PE breathable particles is low-density polyethylene LDPE or linear low-density polyethylene LLDPE, and the addition amount of the inorganic filler in the PE breathable particles is 5-50wt%.
The inorganic filler used for forming the micropore structure in the PE breathable particles comprises at least one of stearic acid modified calcium carbonate, talcum powder, calcined shell powder, kaolin, silica fume, zeolite powder, titanium dioxide, silicon dioxide and glass powder with the average particle size of 50-500 nm. Preferably, the inorganic filler used to form the microporous structure in the PE breathable particles comprises stearic acid modified calcium carbonate having an average particle size of 50-2000 nm.
The metal ion doped mesoporous silica nano antibacterial agent MSN is at least one of Mn2+、Pb2+、Cu2 +、Zn2+、Cu+、Zn2+、Fe3+、Fe2+、Ag+、Au+. Preferably, the metal ion doped mesoporous silica nano antimicrobial MSN is Cu 2+.
The granularity distribution of the mesoporous silica in the metal ion doped mesoporous silica nano antibacterial agent MSN is 20-200nm.
The metal ion doped mesoporous silica nano antibacterial agent MSN is prepared by taking metal salt, sodium hydroxide, cetyltrimethylammonium bromide and ethyl orthosilicate as raw materials through a sol-gel method in one step.
The metal salt is at least one of copper sulfate, copper chloride, copper nitrate, copper acetylacetonate, manganese sulfate, manganese chloride, manganese nitrate, manganese acetylacetonate, zinc sulfate, cuprous chloride, zinc nitrate, zinc acetylacetonate, ferrous sulfate, ferric chloride, ferric nitrate, ferric acetylacetonate, lead sulfate, lead chloride, lead nitrate, lead acetylacetonate, silver nitrate, and chloroauric acid.
The preparation method of the metal ion doped mesoporous silica nano antibacterial agent MSN comprises the following steps:
Step one, preparing a metal hydroxide seed solution by using metal salt, sodium hydroxide and cetyltrimethylammonium bromide;
The preparation method of the metal hydroxide seed solution in the first step comprises the steps of preparing 0.06-320g/L of metal salt solution and 13g/L of cetyltrimethylammonium bromide solution respectively, heating to 60-80 ℃ and continuously stirring for at least half an hour, wherein 1-7mL of 0.06-320g/L of metal salt solution and 1.0mL of 13g/L of cetyltrimethylammonium bromide solution are added into 100mL of ultrapure water with the temperature of 60-65 ℃, mixing and stirring for at least half an hour, and then adding 0.25mL of 0.5-1 mol/L of NaOH solution, heating to 60-80 ℃ and continuously stirring for at least half an hour;
The metal salt in the metal salt solution in the first step is at least one of copper sulfate, copper chloride, copper nitrate, copper acetylacetonate, manganese sulfate, manganese chloride, manganese nitrate, manganese acetylacetonate, zinc sulfate, zinc chloride, zinc nitrate, zinc acetylacetonate, ferric sulfate, ferric chloride, ferric nitrate, ferric acetylacetonate, lead sulfate, lead chloride, lead nitrate and lead acetylacetonate;
The solvent in the metal salt solution in the first step is water or a mixed solvent formed by water and at least one of alcohols, heptane, benzene, toluene, xylene, chloroform, diethyl ether and acetone;
Step two, adding tetraethyl orthosilicate into the metal hydroxide seed solution, reacting for 2-8 hours at 60-80 ℃, centrifuging to obtain a solid, washing the solid with pure water and ethanol for three times respectively, drying and crushing to obtain a finished product;
specifically, in the second step, 1-2mL of tetraethyl orthosilicate with the concentration of 15.0-20.0g/L is added into the metal hydroxide seed solution prepared in the first step, the reaction is carried out for 2-8 hours at the temperature of 60-80 ℃, the obtained solid is centrifuged, and the obtained solid is washed three times by pure water and ethanol respectively, dried and crushed to obtain the finished product MSN.
The preparation method of the antibacterial deodorizing polyethylene breathable film for medical and sanitary use comprises the following steps:
step one, preparing a metal ion doped mesoporous silica nano antibacterial agent MSN;
Uniformly mixing 1-5 parts of metal ion doped mesoporous silica nano-antibacterial agent MSN and 100 parts of PE breathable particles subjected to drying treatment at a high speed, and putting the mixture into a double-screw extruder for extrusion granulation, wherein the temperature of a feeding section is 100-120 ℃, the temperature of a plasticizing section is 120-140 ℃, the temperature of a homogenizing section is 160-180 ℃, the rotating speed of a double-screw is 60-72r/min, and the temperature of a die head is 160-180 ℃, so as to obtain MSN doped PE breathable particles;
putting the MSN doped PE breathable particles into a double-screw extruder, wherein the feeding section is 120-140 ℃, the plasticizing section is 140-160 ℃, the homogenizing section is 160-180 ℃, the rotating speed of the double-screw extruder is 80-100r/min, the die head temperature is 160-180 ℃, the obtained molten extrusion material is placed into a casting machine, the rotating speed of the casting machine is 50-100r/min, and the medical antibacterial deodorizing polyethylene breathable film is prepared by horizontal stretching.
The antibacterial deodorizing polyethylene breathable film for medical and sanitary use has the antibacterial performance of the escherichia coli to candida albicans more than or equal to 99%, the antibacterial performance of the escherichia coli more than 99%, the antibacterial performance of staphylococcus aureus more than 99%, the deodorizing grade more than or equal to 2, the antistatic grade 10 6-109 Ω & cm, the water vapor permeability more than or equal to 1500g/m 2/24 h, and the hydrostatic pressure more than or equal to 500mmH 2 0.
Preparation example 1. The preparation method of the lead ion doped mesoporous silica nano antimicrobial MSN comprises the following steps:
S1, preparing an industrial lead sulfate solution with the concentration of 50g/L, a cetyltrimethylammonium bromide solution with the concentration of 13g/L, a NaOH solution with the concentration of 27g/L and a tetraethyl orthosilicate solution with the concentration of 20.0g/L respectively;
S2, adding 1mL of industrial grade lead sulfate solution with the concentration of 50g/L and 1.0mL of cetyltrimethylammonium bromide solution with the concentration of 13g/L into 100mL of ultrapure water with the temperature of 60 ℃, mixing and stirring for half an hour, adding 0.25mL of sodium hydroxide solution with the concentration of 27g/L after fully mixing, heating to 60 ℃, and continuously stirring for half an hour to generate lead hydroxide seed solution;
S3, under the stirring condition, adding 1.0mL of tetraethyl orthosilicate with the concentration of 20.0g/L into a reaction kettle, continuously reacting for 4 hours at 60 ℃, and after the reaction is finished, cooling and centrifuging the reaction liquid in the reaction kettle to obtain a lead ion doped mesoporous silica nano antibacterial agent crude product precipitated at the lower layer;
S4, putting the crude product of the lead ion doped mesoporous silica nano antibacterial agent in the S3 into a reaction kettle filled with ethanol for cleaning, wherein the process is carried out at 90 ℃, because residual surfactant or pore-forming agent possibly exists in the nano antibacterial agent, stirring and cleaning are carried out for 4 hours by using ethanol, after the process is finished, the centrifugal operation is continued, filtrate is introduced into other reaction kettles for ethanol distillation and recycling, and the centrifuged massive solid is dried, crushed and sieved to obtain the lead ion doped mesoporous silica nano antibacterial agent MSN.
The preparation example 2 is different from the preparation example 1 in that the preparation method of the zinc ion doped mesoporous silica nano antimicrobial MSN is as follows:
S1, respectively preparing an industrial zinc sulfate solution with the concentration of 100g/L, a cetyltrimethylammonium bromide solution with the concentration of 13g/L, a NaOH solution with the concentration of 27g/L and a tetraethyl orthosilicate solution with the concentration of 20.0 g/L;
S2, adding 1mL of industrial zinc sulfate solution with the concentration of 100g/L and 1.0mL of cetyltrimethylammonium bromide solution with the concentration of 13g/L into 100mL of ultrapure water with the temperature of 60 ℃, mixing and stirring for half an hour, adding 0.25mL of sodium hydroxide solution with the concentration of 27g/L after fully mixing, heating to 60 ℃, and continuously stirring for half an hour to generate zinc hydroxide seed solution;
S3, under the stirring condition, adding 1.0mL of tetraethyl orthosilicate with the concentration of 20.0g/L into a reaction kettle, continuously reacting for 4 hours at 60 ℃, and after the reaction is finished, cooling and centrifuging the reaction liquid in the reaction kettle to obtain a zinc ion doped mesoporous silica nano antibacterial agent crude product deposited on the lower layer;
S4, putting the crude zinc ion doped mesoporous silica nano antibacterial agent in the S3 into a reaction kettle filled with ethanol for cleaning, wherein the process is carried out at 90 ℃, because residual surfactant or pore-forming agent possibly exists in the nano antibacterial agent, stirring and cleaning are carried out for 4 hours by using ethanol, after the process is finished, the centrifugal operation is continued, filtrate is introduced into other reaction kettles for ethanol distillation and recycling, and the centrifuged massive solid is dried, crushed and sieved to obtain the zinc ion doped mesoporous silica nano antibacterial agent MSN.
The preparation example 3 is different from the preparation example 1 in that the preparation method of the iron ion doped mesoporous silica nano antimicrobial MSN is as follows:
S1, respectively preparing an industrial grade ferric sulfate solution with the concentration of 150g/L, a cetyltrimethylammonium bromide solution with the concentration of 13g/L, a NaOH solution with the concentration of 27g/L and a tetraethyl orthosilicate solution with the concentration of 20.0 g/L;
S2, adding 1mL of industrial grade ferric sulfate solution with the concentration of 150g/L and 1.0mL of cetyltrimethylammonium bromide solution with the concentration of 13g/L into 100mL of ultrapure water with the temperature of 60 ℃, mixing and stirring for half an hour, adding 0.25mL of sodium hydroxide solution with the concentration of 27g/L after fully mixing, heating to 60 ℃, and continuously stirring for half an hour to generate ferric hydroxide seed solution;
S3, under the stirring condition, adding 1.0mL of tetraethyl orthosilicate with the concentration of 20.0g/L into a reaction kettle, continuously reacting for 4 hours at 60 ℃, and after the reaction is finished, cooling and centrifuging the reaction liquid in the reaction kettle to obtain a crude product of the iron ion doped mesoporous silica nano antibacterial agent deposited on the lower layer;
s4, putting the crude product of the iron ion doped mesoporous silica nano antibacterial agent in the S3 into a reaction kettle filled with ethanol for cleaning, wherein the process is carried out at 90 ℃, because residual surfactant or pore-forming agent possibly exists in the nano antibacterial agent, stirring and washing for 4 hours by using ethanol, continuing to carry out centrifugal operation after the process is finished, introducing filtrate into other reaction kettles for ethanol distillation and recycling, and drying, crushing and sieving the centrifuged massive solid to obtain the iron ion doped mesoporous silica nano antibacterial agent MSN.
The preparation example 4 is different from the preparation example 1 in that the preparation method of the manganese ion doped mesoporous silica nano antimicrobial MSN is as follows:
s1, respectively preparing an industrial manganese sulfate solution with the concentration of 100g/L, a cetyltrimethylammonium bromide solution with the concentration of 13g/L, a NaOH solution with the concentration of 27g/L and a tetraethyl orthosilicate solution with the concentration of 20.0 g/L;
S2, adding 1mL of industrial manganese sulfate solution with the concentration of 100g/L and 1.0mL of cetyltrimethylammonium bromide solution with the concentration of 13g/L into 100mL of ultrapure water with the temperature of 60 ℃, mixing and stirring for half an hour, adding 0.25mL of sodium hydroxide solution with the concentration of 27g/L after fully mixing, heating to 60 ℃, and continuously stirring for half an hour to generate manganese hydroxide seed solution;
s3, under the stirring condition, adding 1.0mL of tetraethyl orthosilicate with the concentration of 20.0g/L into a reaction kettle, continuously reacting for 4 hours at 60 ℃, and after the reaction is finished, cooling and centrifuging the reaction liquid in the reaction kettle to obtain a manganese ion doped mesoporous silica nano antibacterial agent crude product deposited on the lower layer;
S4, putting the manganese ion doped mesoporous silica nano antibacterial agent crude product in the S3 into a reaction kettle filled with ethanol for cleaning, wherein the process is carried out at 90 ℃, because residual surfactant or pore-forming agent possibly exists in the nano antibacterial agent, stirring and cleaning are carried out for 4 hours by using ethanol, after the process is finished, the centrifugal operation is continued, filtrate is introduced into other reaction kettles for ethanol distillation and recycling, and the centrifuged massive solid is dried, crushed and sieved to obtain the manganese ion doped mesoporous silica nano antibacterial agent MSN.
The preparation example 5 is different from the preparation example 1 in that the preparation method of the copper ion doped mesoporous silica nano antimicrobial MSN is as follows:
S1, respectively preparing an industrial-grade copper sulfate solution with the concentration of 160g/L, a cetyltrimethylammonium bromide solution with the concentration of 13g/L, a NaOH solution with the concentration of 27g/L and a tetraethyl orthosilicate solution with the concentration of 20.0 g/L;
S2, adding 1mL of 160g/L industrial grade copper sulfate solution and 1.0mL of 13g/L cetyltrimethylammonium bromide solution into 100mL of 60 ℃ ultrapure water, mixing and stirring for half an hour, adding 0.25mL of 27g/L sodium hydroxide solution after fully mixing, heating to 60 ℃ and continuously stirring for half an hour to generate copper hydroxide seed solution;
s3, under the stirring condition, adding 1.0mL of tetraethyl orthosilicate with the concentration of 20.0g/L into a reaction kettle, continuously reacting for 4 hours at 60 ℃, and after the reaction is finished, cooling and centrifuging the reaction liquid in the reaction kettle to obtain a copper ion doped mesoporous silica nano antibacterial agent crude product deposited on the lower layer;
S4, putting the crude product of the copper ion doped mesoporous silica nano antibacterial agent in the S3 into a reaction kettle filled with ethanol for cleaning, wherein the process is carried out at 90 ℃, because residual surfactant or pore-forming agent possibly exists in the nano antibacterial agent, stirring and washing for 4 hours by using ethanol, continuing to carry out centrifugal operation after the process is finished, introducing filtrate into other reaction kettles for ethanol distillation and recycling, and drying, crushing and sieving the centrifuged massive solid to obtain the copper ion doped mesoporous silica nano antibacterial agent MSN.
Preparation example 6 is different from preparation example 5 in that in the preparation method of the copper ion doped mesoporous silica nano-antimicrobial MSN, S2, adding 2mL of 160g/L industrial grade copper sulfate solution and 1.0mL of 13g/L cetyltrimethylammonium bromide solution into 100mL of 60 ℃ ultrapure water, mixing and stirring for half an hour, adding 0.25mL of 27g/L sodium hydroxide solution after full mixing, heating to 60 ℃ and continuously stirring for half an hour to generate copper hydroxide seed solution, S3, adding 1.0mL of 20.0g/L tetraethyl orthosilicate into a reaction kettle under the stirring condition, continuously reacting for 3.5 hours at 60 ℃, cooling and centrifuging the reaction solution in the reaction kettle after the reaction is finished to obtain a copper ion doped mesoporous silica nano-antimicrobial crude product precipitated at the lower layer, and the rest steps are the same.
Preparation example 7 is different from preparation example 5 in that S2, adding 3mL of 160g/L industrial grade copper sulfate solution and 1.0mL of 13g/L cetyltrimethylammonium bromide solution into 100mL of 60 ℃ ultrapure water, mixing and stirring for half an hour, adding 0.25mL of 27g/L sodium hydroxide solution after full mixing, heating to 60 ℃ and continuously stirring for half an hour to generate copper hydroxide seed solution, S3, adding 1.0mL of 20.0g/L tetraethyl orthosilicate into a reaction kettle under the stirring condition, continuously reacting for 3.5 hours at 60 ℃, cooling and centrifuging the reaction solution in the reaction kettle after the reaction is finished to obtain a copper ion doped mesoporous silica nano antibacterial agent crude product precipitated at the lower layer, and the rest steps are the same.
Preparation example 8 is different from preparation example 5 in that S2 is that in the preparation method of copper ion doped mesoporous silica nano-antimicrobial MSN, 4mL of industrial grade copper sulfate solution with the concentration of 160g/L and 1.0mL of cetyltrimethylammonium bromide solution with the concentration of 13g/L are added into 100mL of ultrapure water with the temperature of 60 ℃ and mixed and stirred for half an hour, then 0.25mL of sodium hydroxide solution with the concentration of 27g/L is added after full mixing, the temperature is raised to 60 ℃ and stirred for half an hour continuously to generate copper hydroxide seed solution, S3 is that 1.0mL of tetraethyl orthosilicate with the concentration of 20.0g/L is added into a reaction kettle under the stirring condition and reacted continuously for 4 hours at 60 ℃, after the reaction is finished, the reaction liquid in the reaction kettle is cooled and centrifuged to obtain crude copper ion doped mesoporous silica nano-antimicrobial precipitated at the lower layer, and the rest steps are the same.
Preparation example 9 is different from preparation example 5 in that S2, 5mL of 160g/L industrial grade copper sulfate solution and 1.0mL of 13g/L cetyltrimethylammonium bromide solution are added into 100mL of 60 ℃ ultrapure water, mixed and stirred for half an hour, then 0.25mL of 27g/L sodium hydroxide solution is added after full mixing, the temperature is raised to 60 ℃ and stirring is continued for half an hour, copper hydroxide seed solution is generated, S3, 1.0mL of 20.0g/L tetraethyl orthosilicate is added into a reaction kettle under the stirring condition, the reaction is continued for 2.5 hours at 60 ℃, after the reaction is finished, the reaction solution in the reaction kettle is cooled and centrifuged, and the copper ion doped mesoporous silica nano antimicrobial crude product precipitated at the lower layer is obtained, and the rest steps are the same.
The preparation example 10 is different from the preparation example 5 in that S2, 6mL of 160g/L industrial grade copper sulfate solution and 1.0mL of 13g/L cetyltrimethylammonium bromide solution are added into 100mL of 60 ℃ ultrapure water, mixed and stirred for half an hour, then 0.25mL of 27g/L sodium hydroxide solution is added after full mixing, the temperature is raised to 60 ℃ and stirring is continued for half an hour, copper hydroxide seed solution is generated, S3, 1.0mL of 20.0g/L tetraethyl orthosilicate is added into a reaction kettle under the stirring condition, the reaction is continued for 3 hours at 60 ℃, after the reaction is finished, the reaction liquid in the reaction kettle is cooled and centrifuged, and the copper ion doped mesoporous silica nano antibacterial agent crude product deposited on the lower layer is obtained, and the rest steps are the same.
Preparation example 11 is different from preparation example 5 in that S2, 7mL of 160g/L industrial grade copper sulfate solution and 1.0mL of 13g/L cetyltrimethylammonium bromide solution are added into 100mL of 60 ℃ ultrapure water, mixed and stirred for half an hour, then 0.25mL of 27g/L sodium hydroxide solution is added after full mixing, the temperature is raised to 60 ℃ and stirring is continued for half an hour, copper hydroxide seed solution is generated, S3, 1.0mL of 20.0g/L tetraethyl orthosilicate is added into a reaction kettle under the stirring condition, the reaction is continued for 5 hours at 60 ℃, after the reaction is finished, the reaction liquid in the reaction kettle is cooled and centrifuged, and the copper ion doped mesoporous silica nano antibacterial agent crude product deposited on the lower layer is obtained, and the rest steps are the same.
The preparation example 12 is different from the preparation example 5 in that S1 is prepared into industrial grade cuprous chloride solution with the concentration of 0.06g/L and cetyltrimethylammonium bromide solution with the concentration of 13g/L respectively, naOH solution with the concentration of 27g/L and tetraethyl orthosilicate solution with the concentration of 20.0g/L, S2 is prepared into a reaction kettle by adding 1mL of industrial grade cuprous chloride solution with the concentration of 0.06g/L and 1.0mL of cetyltrimethylammonium bromide solution with the concentration of 13g/L into 100mL of ultrapure water with the temperature of 60 ℃, mixing and stirring for half an hour, adding 0.25mL of sodium hydroxide solution with the concentration of 27g/L after full mixing, heating to 60 ℃ and continuously stirring for half an hour, and then adding 1.0mL of tetraethyl orthosilicate with the concentration of 20.0g/L into the reaction kettle under the stirring condition, continuously reacting for 4 hours at 60 ℃, and centrifuging the reaction kettle after the reaction kettle is finished, carrying out centrifugation, and carrying out the same precipitation bacteria resisting on the mixed solution, and obtaining the crude product of mesoporous silica nano-doped with the same mesoporous silica.
The preparation example 13 is different from the preparation example 5 in that in the preparation method of the copper ion doped mesoporous silica nano-antimicrobial MSN, an industrial ferrous sulfate solution with the concentration of 150g/L and a cetyltrimethylammonium bromide solution with the concentration of 13g/L are respectively prepared, a NaOH solution with the concentration of 27g/L and a tetraethyl orthosilicate solution with the concentration of 20.0g/L are respectively prepared, S2, 1mL of industrial ferrous sulfate solution with the concentration of 150g/L and 1.0mL of cetyltrimethylammonium bromide solution with the concentration of 13g/L are added into 100mL of ultrapure water with the temperature of 60 ℃, mixed and stirred for half an hour, then 0.25mL of sodium hydroxide solution with the concentration of 27g/L is added, the mixture is heated to 60 ℃ and stirred continuously for half an hour, and then 1.0mL of tetraethyl orthosilicate with the concentration of 20.0g/L is put into a reaction kettle under the condition of stirring, the mixture is reacted continuously for 4 hours at the temperature of 60 ℃, and after the reaction is finished, the reaction kettle is cooled, the reaction liquid is subjected to centrifugation, and the rest of the mixed solution is subjected to the same precipitation step of preparing the mesoporous silica nano-antimicrobial.
Preparation example 14 is different from preparation example 5 in that in the preparation method of copper ion doped mesoporous silica nano-antimicrobial MSN, S1 is respectively prepared into an industrial silver nitrate solution with the concentration of 200g/L and a cetyltrimethylammonium bromide solution with the concentration of 13g/L, a NaOH solution with the concentration of 27g/L and a tetraethyl orthosilicate solution with the concentration of 20.0g/L, S2 is added into ultrapure water with the temperature of 60 ℃ for 1mL of the industrial silver nitrate solution with the concentration of 200g/L and 1.0mL of the cetyltrimethylammonium bromide solution with the concentration of 13g/L, the mixture is mixed and stirred for half an hour, then 0.25mL of a sodium hydroxide solution with the concentration of 27g/L is added, the mixture is heated to 60 ℃ and stirred continuously for half an hour, and then 1.0mL of tetraethyl orthosilicate with the concentration of 20.0g/L is put into a reaction kettle under the condition of stirring, the mixture is reacted continuously for 4 hours at 60 ℃, after the reaction is finished, the reaction kettle is cooled, and the rest of the mixture is subjected to centrifugation, and the crude product of the mesoporous silica nano-antimicrobial is obtained.
Preparation example 15 differs from preparation example 1 in that the preparation method of the gold ion doped mesoporous silica nano antimicrobial MSN is as follows:
S1, respectively preparing an industrial grade chloroauric acid solution with the concentration of 170g/L, a cetyltrimethylammonium bromide solution with the concentration of 13g/L, a NaOH solution with the concentration of 27g/L and a tetraethyl orthosilicate solution with the concentration of 20.0 g/L;
S2, adding 1mL of industrial grade chloroauric acid solution with the concentration of 170g/L and 1.0mL of cetyltrimethylammonium bromide solution with the concentration of 13g/L into 100mL of ultrapure water with the temperature of 60 ℃, mixing and stirring for half an hour, adding 0.25mL of sodium hydroxide solution with the concentration of 27g/L after fully mixing, heating to 60 ℃, and continuously stirring for half an hour to generate gold hydroxide seed solution;
S3, under the stirring condition, adding 1.0mL of tetraethyl orthosilicate with the concentration of 20.0g/L into a reaction kettle, continuously reacting for 4 hours at 60 ℃, and after the reaction is finished, cooling and centrifuging the reaction liquid in the reaction kettle to obtain a gold ion doped mesoporous silica nano antibacterial agent crude product deposited on the lower layer;
S4, putting the gold ion doped mesoporous silica nano antibacterial agent crude product in the S3 into a reaction kettle filled with ethanol for cleaning, wherein the process is carried out at 90 ℃, because residual surfactant or pore-forming agent possibly exists in the nano antibacterial agent, stirring and cleaning are carried out for 4 hours by using ethanol, after the process is finished, the centrifugal operation is continued, filtrate is introduced into other reaction kettles for ethanol distillation and recycling, and the centrifuged massive solid is dried, crushed and sieved to obtain the gold ion doped mesoporous silica nano antibacterial agent MSN.
Preparation example 16A preparation method of metal ion-free doped mesoporous nano silicon comprises the steps of S1 preparing a cetyltrimethylammonium bromide solution with the concentration of 13g/L, a NaOH solution with the concentration of 27g/L and a tetraethyl orthosilicate solution with the concentration of 20.0g/L respectively, S2 adding 1.0mL of the cetyltrimethylammonium bromide solution with the concentration of 13g/L into 100mL of ultrapure water with the temperature of 60 ℃, stirring for half an hour, adding 0.25mL of the sodium hydroxide solution with the concentration of 27g/L, heating to 60 ℃ and continuously stirring for half an hour, adding 1.0mL of tetraethyl orthosilicate with the concentration of 20.0g/L into a reaction kettle under the stirring condition, continuously reacting for 4 hours at the temperature of 60 ℃, cooling and centrifuging the reaction solution in the reaction kettle after the reaction is finished to obtain a white precipitate crude metal ion-free doped mesoporous nano silicon at the lower layer, and the rest steps are the same.
Detailed description of the preferred embodiments
Example 1 an antibacterial deodorizing polyethylene breathable film for medical use is made from MSN-doped PE breathable particles. The MSN doped PE breathable particles are prepared from 2 parts of copper ion doped mesoporous silica nano antimicrobial MSN in preparation example 5 and 100 parts of PE breathable particles (source: changzhou double forming number BM 07).
The preparation method of the antibacterial deodorizing polyethylene breathable film for medical and sanitary use comprises the following steps:
Step one, preparing a copper ion doped mesoporous silica nano antimicrobial MSN, wherein the preparation method is described in preparation example 5;
Uniformly mixing 2 parts of copper ion doped mesoporous silica nano-antimicrobial MSN in preparation example 1 and 100 parts of PE breathable particles subjected to drying treatment at a high speed, putting the mixture into a double-screw extruder for extrusion granulation, wherein the feeding section is 170 ℃, the plasticizing section is 165 ℃, the homogenizing section is 175 ℃, the rotating speed of the double-screw is 72r/min, and the die head temperature is 175 ℃, so as to obtain MSN doped PE breathable particles;
Putting the MSN doped PE breathable particles into a double-screw extruder, feeding the particles at 180 ℃, plasticizing the particles at 180 ℃ and homogenizing the particles at 180 ℃ at 80r/min, and horizontally stretching the particles at 100r/min to obtain the medical antibacterial deodorizing polyethylene breathable film, wherein the rotating speed of the double-screw extruder is 80r/min, and the temperature of the die head is 180 ℃.
Example 2 differs from example 1 in that the medical antibacterial deodorizing polyethylene breathable film is made of MSN-doped PE breathable particles. The MSN doped PE breathable particles are prepared from 2 parts of zinc ion doped mesoporous silica nano antibacterial agent MSN in preparation example 2 and 100 parts of PE breathable particles.
Example 3 differs from example 1 in that the medical and sanitary antimicrobial deodorizing polyethylene breathable film is made of MSN-doped PE breathable particles. The MSN doped PE breathable particles are prepared from 2 parts of the iron ion doped mesoporous silica nano antibacterial agent MSN in preparation example 3 and 100 parts of PE breathable particles.
Example 4 differs from example 1 in that the medical and sanitary antimicrobial deodorizing polyethylene breathable film is made of MSN-doped PE breathable particles. The MSN doped PE breathable particles are prepared from 2 parts of the manganese ion doped mesoporous silica nano antibacterial agent MSN in preparation example 4 and 100 parts of PE breathable particles.
Example 5 differs from example 1 in that the medical and sanitary antimicrobial deodorizing polyethylene breathable film is made of MSN-doped PE breathable particles. The MSN doped PE breathable particles are prepared from 2 parts of lead ion doped mesoporous silica nano antibacterial agent MSN in preparation example 1 and 100 parts of PE breathable particles.
Example 6 differs from example 1 in that the medical and sanitary antimicrobial deodorizing polyethylene breathable film is made of MSN-doped PE breathable particles. The MSN doped PE breathable particles are prepared from 0.1 part of copper ion doped mesoporous silica nano antibacterial agent MSN in preparation example 5 and 100 parts of PE breathable particles.
Example 7 differs from example 1 in that the medical and sanitary antimicrobial deodorizing polyethylene breathable film is made of MSN-doped PE breathable particles. The MSN doped PE breathable particles are prepared from 0.5 part of copper ion doped mesoporous silica nano antibacterial agent MSN in preparation example 5 and 100 parts of PE breathable particles.
Example 8 differs from example 1 in that the medical and sanitary antimicrobial deodorizing polyethylene breathable film is made of MSN-doped PE breathable particles. The MSN doped PE breathable particles are prepared from 1.0 part of copper ion doped mesoporous silica nano antibacterial agent MSN in preparation example 5 and 100 parts of PE breathable particles.
Example 9 differs from example 1 in that the medical and sanitary antimicrobial deodorizing polyethylene breathable film is made of MSN-doped PE breathable particles. The MSN doped PE breathable particles are prepared from 5 parts of copper ion doped mesoporous silica nano antibacterial agent MSN in preparation example 5 and 100 parts of PE breathable particles.
Example 10 differs from example 1 in that the medical and sanitary antimicrobial deodorizing polyethylene breathable film is made of MSN-doped PE breathable particles. The MSN doped PE breathable particles are prepared from 6 parts of copper ion doped mesoporous silica nano antibacterial agent MSN in preparation example 5 and 100 parts of PE breathable particles.
Example 11 differs from example 1 in that the medical and sanitary antimicrobial deodorizing polyethylene breathable film is made of MSN-doped PE breathable particles. The MSN doped PE breathable particles are prepared from 2 parts of copper ion doped mesoporous silica nano antibacterial agent MSN in preparation example 6 and 100 parts of PE breathable particles.
Example 12 differs from example 1 in that the medical and sanitary antimicrobial deodorizing polyethylene breathable film is made of MSN-doped PE breathable particles. The MSN doped PE breathable particles are prepared from 2 parts of copper ion doped mesoporous silica nano antibacterial agent MSN in preparation example 7 and 100 parts of PE breathable particles.
Example 13 differs from example 1 in that the medical and sanitary antimicrobial deodorizing polyethylene breathable film is made of MSN-doped PE breathable particles. The MSN doped PE breathable particles are prepared from 2 parts of copper ion doped mesoporous silica nano antibacterial agent MSN in preparation example 8 and 100 parts of PE breathable particles.
Example 14 differs from example 1 in that the medical and sanitary antimicrobial deodorizing polyethylene breathable film is made of MSN-doped PE breathable particles. The MSN doped PE breathable particles are prepared from 2 parts of copper ion doped mesoporous silica nano antibacterial agent MSN in preparation example 9 and 100 parts of PE breathable particles.
Example 15 differs from example 1 in that the medical and sanitary antimicrobial deodorizing polyethylene breathable film is made of MSN-doped PE breathable particles. The MSN doped PE breathable particles are prepared from 2 parts of copper ion doped mesoporous silica nano antibacterial agent MSN in preparation example 10 and 100 parts of PE breathable particles.
Example 16 differs from example 1 in that the medical and sanitary antimicrobial deodorizing polyethylene breathable film is made of MSN-doped PE breathable particles. The MSN doped PE breathable particles are prepared from 2 parts of copper ion doped mesoporous silica nano antibacterial agent MSN in preparation example 11 and 100 parts of PE breathable particles.
Example 17 differs from example 1 in that the medical and sanitary antimicrobial deodorizing polyethylene breathable film is made of MSN-doped PE breathable particles. The MSN doped PE breathable particles are prepared from 2 parts of cuprous ion doped mesoporous silica nano antibacterial agent MSN in preparation example 12 and 100 parts of PE breathable particles
Example 18 differs from example 1 in that the medical and sanitary antimicrobial deodorizing polyethylene breathable film is made of MSN-doped PE breathable particles. The MSN doped PE breathable particles are prepared from 2 parts of ferrous ion doped mesoporous silica nano antimicrobial MSN in preparation example 13 and 100 parts of PE breathable particles
Example 19 differs from example 1 in that the medical and sanitary antimicrobial deodorizing polyethylene breathable film is made of MSN-doped PE breathable particles. The MSN doped PE breathable particles are prepared from 2 parts of silver ion doped mesoporous silica nano antibacterial agent MSN in preparation example 14 and 100 parts of PE breathable particles
Example 20 differs from example 1 in that the medical and sanitary antimicrobial deodorizing polyethylene breathable film is made of MSN-doped PE breathable particles. The MSN doped PE breathable particles are prepared from 2 parts of the gold ion doped mesoporous silica nano antibacterial agent MSN in preparation example 15 and 100 parts of PE breathable particles.
Control A differs from example 1 in that the polyethylene breathable film was made from PE breathable particles (Changzhou double forming number BM 07).
The control group B was different from example 1 in that the medical antibacterial deodorizing polyethylene breathable film was made of ion-free doped mesoporous silica doped PE breathable particles. The ion-free doped mesoporous silica doped PE breathable particles were prepared from 2 parts of ion-free doped mesoporous silica in preparation example 16 and 100 parts of PE breathable particles.
Comparative example 1 differs from example 1 in that the medical antibacterial deodorizing polyethylene breathable film is made of MSN-doped PE breathable particles. The MSN doped PE breathable particles are prepared from 2 parts of inorganic antibacterial agent and 100 parts of PE breathable particles. The inorganic antibacterial agent is nanometer copper powder with average grain diameter of 200 nm.
Comparative example 2 differs from example 1 in that the medical antibacterial deodorizing polyethylene breathable film is made of MSN-doped PE breathable particles. The MSN doped PE breathable particles are prepared from 2 parts of organic antibacterial agent and 100 parts of PE breathable particles. The organic antibacterial agent is benzethonium chloride (quaternary ammonium salt organic antibacterial agent).
Comparative example 3 differs from example 1 in that the medical antibacterial deodorizing polyethylene breathable film is made of MSN-doped PE breathable particles. The MSN doped PE breathable particles are prepared from 0.05 part of copper ion doped mesoporous silica nano antibacterial agent MSN in preparation example 5 and 100 parts of PE breathable particles.
Performance test:
1. the antibacterial activity value is measured according to ISO 18184.
2. The antibacterial rate test method comprises the steps of determining according to GB/T20944.2-2007, wherein the sample sterilization method is an autoclave sterilization method, the contact culture time of a sample and bacterial liquid is 18 hours, the control sample is a common PE breathable film, the colony concentrations of the control sample are respectively 105CFU/mL of staphylococcus aureus ATCC 6538:2.0, 105CFU/mL of escherichia coli 8099:1.9, 105CFU/mL of candida albicans ATCC 10231:1.6, and the antibacterial effect is proved when the antibacterial value is more than or equal to 2 or the antibacterial rate is more than or equal to 99 percent.
3. The deodorizing grade is measured according to GB/T33610.1-2019.
4. The antistatic grade test method is that the resistivity of the PE breathable film is less than 10 9 ohm-cm (omega-cm) according to GB/T12703-91, the antistatic performance is regarded as OK, the resistivity of the PE breathable film is more than 10 9 ohm-cm (omega-cm), and the PE breathable film is regarded as NG without the antistatic performance.
5. The water vapor transmission rate was measured in accordance with GB/T19082-2023.
6. The tensile breaking stress was measured according to GB/T19082-2023.
7. Hydrostatic pressure is measured according to GB/T19082-2023.
TABLE 1 Experimental results of copper ion doped mesoporous nanosilicons at different concentrations
TABLE 2 antibacterial and deodorant parameter tables for PE breathable films of examples 1-20, control groups, and comparative examples 1-4
TABLE 3 waterproof breathable parameter tables for PE breathable films of examples 1-20, control group, comparative examples 1-4
It can be seen from the combination of examples 1-14, control groups A-B and comparative examples 1-3 and the combination of tables 2-3 that the PE breathable film has deodorizing, antibacterial and antistatic effects, is used in the field of medical non-woven fabrics, and reduces the risk of bacterial infection of medical staff.
In conclusion, the antibacterial performance of the medical and sanitary antibacterial deodorizing polyethylene breathable film escherichia coli is more than or equal to 99%, the antibacterial performance of staphylococcus aureus is more than or equal to 99%, the deodorizing grade is more than or equal to 2, the antistatic grade is 10 6-109 Ω & cm, the water vapor permeability is more than or equal to 1500g/m 2/24 h, and the hydrostatic pressure is more than or equal to 500mmH 2 0.
Claims (10)
1. The medical antibacterial deodorizing polyethylene breathable film is characterized by being prepared from MSN doped PE breathable particles, wherein the MSN doped PE breathable particles comprise 1-5 parts by weight of metal ion doped mesoporous silica nano antibacterial agent MSN and 100 parts by weight of PE breathable particles, a resin matrix in the PE breathable particles is low-density polyethylene LDPE or linear low-density polyethylene LLDPE, the addition amount of inorganic filler in the PE breathable particles is 5-50wt%, and the inorganic filler used for forming a microporous structure in the PE breathable particles comprises at least one of stearic acid modified calcium carbonate, talcum powder, calcined shell powder, kaolin, silica fume, zeolite powder, silica and glass powder, wherein the average particle size of the stearic acid modified calcium carbonate, talcum powder, calcined shell powder, kaolin, silica fume, zeolite powder, silica and glass powder.
2. The medical antibacterial deodorizing polyethylene breathable film according to claim 1, wherein at least one of Mn2+、Pb2+、Cu2+、Zn2+、Cu+、Cu2+、Zn2+、Fe3+、Fe2+、Ag+、Au+ metal ions doped in the metal ion doped mesoporous silica nano antibacterial agent MSN is adopted, and the granularity distribution of mesoporous silica in the metal ion doped mesoporous silica nano antibacterial agent MSN is 20-200nm.
3. The medical antibacterial deodorizing polyethylene breathable film according to claim 2, characterized in that the metal ion doped mesoporous silica nano antibacterial agent MSN is Cu 2+.
4. The medical antibacterial deodorizing polyethylene breathable film according to claim 1, characterized in that the metal ion doped mesoporous silica nano antibacterial agent MSN is prepared by a sol-gel method by taking metal salt, sodium hydroxide, cetyltrimethylammonium bromide and ethyl orthosilicate as raw materials in one step.
5. The medical antibacterial deodorizing polyethylene breathable film according to claim 4, characterized in that the preparation method of the metal ion doped mesoporous silica nano antibacterial agent MSN comprises the following steps of preparing a metal hydroxide seed solution from metal salt, sodium hydroxide and cetyltrimethylammonium bromide, adding tetraethyl orthosilicate into the metal hydroxide seed solution, reacting for 2-8 hours at 60-80 ℃, centrifuging the obtained solid, washing the obtained solid with pure water and ethanol three times respectively, drying and crushing to obtain the finished MSN.
6. The antibacterial deodorizing polyethylene breathable film for medical use according to claim 5, characterized in that the specific preparation method of the metal hydroxide seed solution in the first step comprises the steps of preparing a concentrated metal salt solution with the concentration of 0.06-320g/L, a cetyltrimethylammonium bromide solution with the concentration of 13g/L and a NaOH solution with the concentration of 0.5-1 mol/L for standby, adding 1-7mL of the metal salt solution with the concentration of 0.06-320g/L and 1.0mL of the cetyltrimethylammonium bromide solution with the concentration of 13g/L into 100mL of ultrapure water with the temperature of 60-65 ℃ for mixing and stirring for at least half an hour, adding 0.25mL of the NaOH solution with the concentration of 0.5-1 mol/L, heating to 60-80 ℃ and continuously stirring for at least half an hour to obtain the metal hydroxide seed solution.
7. The antibacterial deodorizing polyethylene breathable film for medical and sanitary use according to claim 6, characterized in that the second step is characterized in that 1-2mL of tetraethyl orthosilicate with the concentration of 15.0-20.0g/L is added into the metal hydroxide seed solution prepared in the first step, the mixture is reacted for 2-8 hours at the temperature of 60-80 ℃, and the solid obtained by centrifugation is washed three times with pure water and ethanol respectively, dried and crushed to obtain the finished MSN.
8. The medical antibacterial deodorizing polyethylene breathable film according to claim 6, wherein the metal salt in the metal salt solution is at least one of copper sulfate, copper chloride, copper nitrate, copper acetylacetonate, manganese sulfate, manganese chloride, manganese nitrate, manganese acetylacetonate, zinc sulfate, cuprous chloride, zinc nitrate, zinc acetylacetonate, ferrous sulfate, ferric chloride, ferric nitrate, ferric acetylacetonate, lead sulfate, lead chloride, lead nitrate, lead acetylacetonate, silver nitrate and chloroauric acid, and the solvent in the metal salt solution is water or a mixed solvent of water and at least one of alcohols, heptane, benzene, toluene, xylene and acetone.
9. A method for preparing the medical antibacterial deodorizing polyethylene breathable film according to any one of claims 1-8, which is characterized by comprising the following steps:
step one, preparing a metal ion doped mesoporous silica nano antibacterial agent MSN;
Uniformly mixing 1-5 parts of metal ion doped mesoporous silica nano-antibacterial agent MSN and 100 parts of PE breathable particles subjected to drying treatment at a high speed, and putting the mixture into a double-screw extruder for extrusion granulation, wherein the temperature of a feeding section is 160-180 ℃, the temperature of a plasticizing section is 160-180 ℃, the temperature of a homogenizing section is 160-180 ℃, the rotating speed of a double-screw is 60-72r/min, and the temperature of a die head is 160-180 ℃, so as to obtain MSN doped PE breathable particles;
putting MSN doped PE breathable particles into a double-screw extruder, feeding the particles at 160-180 ℃, plasticizing the particles at 160-180 ℃, homogenizing the particles at 160-180 ℃, setting the rotating speed of the double-screw extruder at 80-100r/min and the temperature of a die head at 160-180 ℃, putting the obtained molten extrusion materials into a casting machine, setting the rotating speed of the casting machine at 50-100r/min, and horizontally stretching the molten extrusion materials to obtain the medical antibacterial deodorizing polyethylene breathable film.
10. The method for preparing the medical antibacterial deodorizing polyethylene breathable film according to claim 6, wherein the medical antibacterial deodorizing polyethylene breathable film in the third step has an antibacterial property of more than or equal to 99% on candida albicans, an antibacterial property of more than 99% on escherichia coli, an antibacterial property of more than 99% on staphylococcus aureus, a deodorizing grade of more than or equal to 2, an antistatic grade of 10 6-109 Ω & cm, a water vapor transmission capacity of more than or equal to 1500g/m 2/24 h, and a hydrostatic pressure of more than or equal to 500mmH 2 0.
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