Rapidly degradable and antibacterial polyvinyl alcohol film cloth composite material and preparation method thereof

Abstract

The invention discloses a polyvinyl alcohol film cloth composite material capable of being quickly degraded and resisting bacteria and a preparation method of the polyvinyl alcohol film cloth composite material. The antibacterial solid material is prepared through a one-step method and specifically comprises the steps that a copper sulfate solution, a sodium hydroxide solution, a hexadecyl trimethyl ammonium bromide solution and ethyl orthosilicate are mixed and stirred, and finally the antibacterial solid material copper ion doped mesoporous silica nanospheres are obtained through centrifugal washing. Stirring the copper ion doped mesoporous silica nanospheres, a polyvinyl alcohol solution and glycerol at a high temperature, and preparing a single-layer or multi-layer antibacterial polyvinyl alcohol film from the obtained mixed solution through a coating method; the single-layer or multi-layer antibacterial polyvinyl alcohol film is compounded with polyvinyl alcohol spunlace cloth to obtain the rapidly degradable and antibacterial polyvinyl alcohol film cloth composite material. The antibacterial material copper ion doped mesoporous silica nanospheres and the polyvinyl alcohol solution are mixed at a high temperature, so that the antibacterial property of the polyvinyl alcohol film is enhanced, and the medical protection grade is reached.

Description

Technical Field

[0001] The present invention belongs to the field of antibacterial materials, and specifically relates to a polyvinyl alcohol film composite material that can be rapidly degraded and antibacterial, and a preparation method thereof. Background Art

[0002] Traditional disposable protective clothing often becomes medical waste that is difficult to degrade after use, imposing a burden on the environment. Therefore, biodegradable protective clothing has gradually become a research hotspot. Such protective clothing is made of biodegradable materials such as poly(lactic acid) (PLA), polyvinyl alcohol (PVA), etc. They are the most studied and adopted materials among all biodegradable materials. If their medical waste is landfilled, although it can be degraded within a certain period of time, it will still consume too much land resources; if it is incinerated, compared with other non-degradable materials, its advantages are not obvious. Therefore, improving the degradation rate of biodegradable protective clothing is also an important factor to be considered.

[0003] However, PVA has similar melting temperature and decomposition temperature, which is not conducive to being used in production by melting. To solve this problem, solution spinning is usually used to produce short fibers, and the fibers are made into cloth by a hydroentangling process; since the fiber gaps of hydroentangled cloth are relatively large and cannot meet the barrier requirements for harmful substances, the PVA film composite process is usually used to produce composite materials for making protective products.

[0004] Most of the composite materials produced by the existing PVA film composite process have poor antibacterial properties of the PVA film and cannot reach the medical protection level. Summary of the Invention

[0005] The technical problem to be solved by the present invention is to overcome the defects of the above-mentioned existing technologies, and provide a preparation method of a polyvinyl alcohol film composite material that can be rapidly degraded and antibacterial, aiming to mix the antibacterial solid material copper ion-doped mesoporous silica nanospheres with a polyvinyl alcohol solution at a high temperature to enhance the antibacterial properties of the polyvinyl alcohol film and reach the medical protection level.

[0006] To achieve the above object, the present invention is realized through the following technical solutions.

[0007] A preparation method of a polyvinyl alcohol film composite material that can be rapidly degraded and antibacterial, which includes:

[0008] Mix a copper sulfate solution, a sodium hydroxide solution, a cetyltrimethylammonium bromide solution (CTAB) and tetraethyl orthosilicate, and prepare the antibacterial solid material copper ion-doped mesoporous silica nanospheres (MSN) by a one-step method;

[0009] The antibacterial solid material, copper ion-doped mesoporous silica nanospheres, is mixed with polyvinyl alcohol and glycerol in pure water and stirred at high temperature. The resulting mixed solution is used to prepare monolayer or multilayer antibacterial polyvinyl alcohol films by a coating method;

[0010] The monolayer or multilayer antibacterial polyvinyl alcohol films are compounded with polyvinyl alcohol hydrospun cloth to obtain a polyvinyl alcohol film cloth composite material that can be rapidly degraded and has antibacterial properties.

[0011] The present invention provides a method for preparing doped MSN in a Cu 2+ solution and the process of its compounding with a PVA film. First, Cu 2+ doped MSN is prepared as a nano antibacterial agent by a sol-gel method. To ensure uniform mixing of MSN in the PVA film, the two are then stirred at high temperature to obtain an antibacterial PVA solution. Finally, the antibacterial PVA film is compounded with PVA hydrospun cloth to obtain an antibacterial polyvinyl alcohol film cloth composite material. The present invention prepares an antibacterial solid material by a one-step method (i.e., a one-pot method). Cu 2+ is embedded inside the silicon-oxygen chemical bond in a coordinated form and has good antibacterial properties.

[0012] The copper ion-doped mesoporous silica nanospheres prepared in the present invention belong to a mesoporous structure. The copper ions are embedded in the silicon-oxygen framework in a coordinated form. The hollow structure has many functions, such as deodorization, adsorption, antibacterial, environmental protection, and low cost, and is not a traditional solid material.

[0013] Furthermore, the specific preparation steps of the antibacterial solid material, copper ion-doped mesoporous silica nanospheres, are as follows:

[0014] First, ultrapure water is preheated to 60 - 65 °C and magnetically stirred. A copper sulfate solution and a cetyltrimethylammonium bromide solution are added, and the mixture is stirred for at least half an hour. Then, a sodium hydroxide solution is added, and the temperature is raised to 60 - 80 °C and stirred for at least half an hour to obtain a metal hydroxide seed solution. After that, tetraethyl orthosilicate is added to the metal hydroxide seed solution and stirred at 60 - 80 °C for 2 - 8 hours to obtain copper ion-doped mesoporous silica nanospheres as the antibacterial solid material.

[0015] Preferably, the concentration of the copper sulfate solution is 50 - 320 g / L, the concentration of the sodium hydroxide solution is 0.5 - 1.5 mol / L, the concentration of the cetyltrimethylammonium bromide solution is 10 - 15 g / L, and the concentration of tetraethyl orthosilicate is 15.0 - 20.0 g / L.

[0016] More preferably, the concentration of the copper sulfate solution is 50 - 320 g / L, the concentration of the sodium hydroxide solution is 1 mole per liter, the concentration of the cetyltrimethylammonium bromide solution is 13 g / L, and the concentration of the tetraethyl orthosilicate is 15.0 - 20.0 g / L.

[0017] Furthermore, before the antibacterial solid material, the copper ion-doped mesoporous silica nanospheres are subjected to high-temperature stirring with polyvinyl alcohol and glycerol, they are also subjected to centrifugation, washing, drying, and pulverization.

[0018] Preferably, the input amount of the copper ion-doped mesoporous silica nanospheres is 0.1% - 5.0% of the mass of the solute in the mixed solution.

[0019] More preferably, the input amount of the copper ion-doped mesoporous silica nanospheres is 2.0% - 5.0% of the mass of the solute in the mixed solution.

[0020] Furthermore, when the antibacterial solid material, the copper ion-doped mesoporous silica nanospheres are subjected to high-temperature stirring with polyvinyl alcohol and glycerol, a wetting agent is also added, and the wetting agent can be selected as SD-200.

[0021] Preferably, in the mixed solution, the input amount of polyvinyl alcohol is 82% - 87% of the mass of the solute in the mixed solution, and the input amount of glycerol is 10 - 13% of the mass of the solute in the mixed solution.

[0022] The present invention also provides a polyvinyl alcohol film cloth composite material that can be rapidly degraded and has antibacterial properties, which is prepared according to the above method.

[0023] The beneficial effects of the present invention are as follows: The present invention provides a method for preparing mesoporous MSN in a metal ion solution. This preparation method selects CTAB as the surfactant, and the doped MSN material prepared under alkaline conditions has controllable size, good dispersibility, low pollution, low cost, and a simple preparation process; after being mixed with the PVA solution at high temperature and then made into a film, it can be compounded with PVA spunlace cloth into single-layer and double-layer films.

[0024] The antibacterial solid material of the present invention, the copper ion-doped mesoporous silica nanospheres, has good antibacterial properties and can reach the medical protection level; at the same time, the prepared polyvinyl alcohol film cloth composite material can be completely degraded by the Fenton reaction in hot water, reducing the difficulty of waste treatment, and thus can be applied to fields such as medical and health. Specific Embodiments

[0025] In order to further clarify the present invention, a series of embodiments are given below. These embodiments are completely illustrative and are only used to specifically describe the present invention and should not be construed as a limitation of the present invention.

[0026] The present invention provides a method for preparing a polyvinyl alcohol film cloth composite material that can be rapidly degraded and has antibacterial properties. The steps are as follows: Mix a copper sulfate solution, a sodium hydroxide solution, a cetyltrimethylammonium bromide solution, and tetraethyl orthosilicate, and prepare an antibacterial solid material, copper ion-doped mesoporous silica nanospheres, by a one-step method; Mix the antibacterial solid material, copper ion-doped mesoporous silica nanospheres, with polyvinyl alcohol and glycerol in pure water and stir at a high temperature. The obtained mixed solution is used to prepare a single-layer or multi-layer antibacterial polyvinyl alcohol film by a coating method; The single-layer or multi-layer antibacterial polyvinyl alcohol film is compounded with a polyvinyl alcohol spunlace cloth to obtain a polyvinyl alcohol film cloth composite material that can be rapidly degraded and has antibacterial properties.

[0027] The specific preparation steps of the antibacterial solid material, copper ion-doped mesoporous silica nanospheres, are as follows:

[0028] Prepare solutions of anhydrous copper sulfate (Cu 2 SO 4 ) with a concentration of 160 g / L, cetyltrimethylammonium bromide (CTAB) solution with a concentration of 13.0 g / L, and sodium hydroxide (NaOH) solution with a concentration of 1.0 mol / L respectively;

[0029] Prepare the antibacterial solid material by a one-pot method. First, preheat 100 mL of ultrapure water to 60 °C and carry out magnetic stirring. Add 1.0 mL of the copper sulfate solution and the cetyltrimethylammonium bromide solution respectively, and mix and stir for at least half an hour to obtain a diluted Cu 2+ warm solution; Then add 0.25 mL of the NaOH solution, raise the temperature to 60 - 80 °C and continue stirring for at least half an hour to obtain a metal hydroxide seed solution; Then add 1.0 mL of 15 g / L tetraethyl orthosilicate (TEOS) to the metal hydroxide seed solution, raise the temperature to around 80 °C, and stir for 2 - 4 hours to obtain doped MSN, that is, copper ion-doped mesoporous silica nanospheres. The finally obtained doped MSN is washed three times with centrifugation, pure water, and ethanol respectively, and then dried and pulverized.

[0030] The dried doped MSN is mixed with PVA, glycerol, and a wetting agent in pure water at a high temperature according to mass ratios of 0.1%, 0.2%, 0.5%, 1.0%, 2.0%, and 5.0% respectively, and then the mixed solution is compounded with the PVA spunlace cloth by a coating method respectively. The specific content is as follows:

[0031] 1) Weigh 0.035 grams of MSN and mix it with PVA - 2499 (28.0625 grams, 86.65%), glycerol (4.08 grams, 12.60%), and wetting agent (0.21 grams, 0.65%) at high temperature for 2 - 4 hours. Then, prepare single - layer and double - layer antibacterial PVA films with a grammage of 20 gsm from the mixed solution through the coating method. Finally, wet - compound them with PVA spunlace fabric to obtain a PVA film - fabric composite material that can be rapidly degraded and has antibacterial properties, named 0.1% single - layer antibacterial PVA (abbreviated as 0.1 single - layer) and 0.1% double - layer antibacterial PVA (abbreviated as 0.1 double - layer) respectively.

[0032] 2) Weigh 0.070 grams of MSN and mix it with PVA - 2499 (28.0625 grams, 86.57%), glycerol (4.08 grams, 12.58%), and wetting agent (0.21 grams, 0.65%) at high temperature for 2 - 4 hours. Then, prepare single - layer and double - layer antibacterial PVA films with a grammage of 20 gsm from the mixed solution through the coating method. Finally, wet - compound them with PVA spunlace fabric to obtain a PVA film - fabric composite material that can be rapidly degraded and has antibacterial properties, named 0.2% single - layer antibacterial PVA (abbreviated as 0.2 single - layer) and 0.2% double - layer antibacterial PVA (abbreviated as 0.2 double - layer) respectively.

[0033] 3) Weigh 0.160 grams of MSN and mix it with PVA - 2499 (28.0625 grams, 86.30%), glycerol (4.08 grams, 12.55%), and wetting agent (0.21 grams, 0.65%) at high temperature for 2 - 4 hours. Then, prepare single - layer and double - layer antibacterial PVA films with a grammage of 20 gsm from the mixed solution through the coating method. Finally, wet - compound them with PVA spunlace fabric to obtain a PVA film - fabric composite material that can be rapidly degraded and has antibacterial properties, named 0.5% single - layer antibacterial PVA (abbreviated as 0.5 single - layer) and 0.5% double - layer antibacterial PVA (abbreviated as 0.5 double - layer) respectively.

[0034] 4) Weigh 0.328 grams of MSN and mix it with PVA - 2499 (28.0625 grams, 85.88%), glycerol (4.08 grams, 12.48%), and wetting agent (0.21 grams, 0.64%) at high temperature for 2 - 4 hours. Then, prepare single - layer and double - layer antibacterial PVA films with a grammage of 20 gsm from the mixed solution through the coating method. Finally, wet - compound them with PVA spunlace fabric to obtain a PVA film - fabric composite material that can be rapidly degraded and has antibacterial properties, named 1.0% single - layer antibacterial PVA (abbreviated as 1.0 single - layer) and 1.0% double - layer antibacterial PVA (abbreviated as 1.0 double - layer) respectively.

[0035] 5) Weigh 0.660 g of MSN and mix it with PVA-2499 (28.0625 g, 85.00%), glycerol (4.08 g, 12.36%), and wetting agent (0.21 g, 0.64%) at high temperature for 2 - 4 hours according to a ratio of 2.0%. Then, prepare single-layer and double-layer antibacterial PVA films with a grammage of 20 gsm from the mixed solution by the coating method. Finally, wet-compound them with PVA spunlace fabric to obtain a PVA film-fabric composite material that can be rapidly degraded and antibacterial, which are respectively named 2.0% single-layer antibacterial PVA (abbreviated as 2.0 single-layer) and 2.0% double-layer antibacterial PVA (abbreviated as 2.0 double-layer).

[0036] 6) Weigh 1.700 g of MSN and mix it with PVA-2499 (28.0625 g, 82.40%), glycerol (4.08 g, 11.98%), and wetting agent (0.21 g, 0.62%) at high temperature for 2 - 4 hours according to a ratio of 5.0%. Then, prepare single-layer and double-layer antibacterial PVA films with a grammage of 20 gsm from the mixed solution by the coating method. Finally, wet-compound them with PVA spunlace fabric to obtain a PVA film-fabric composite material that can be rapidly degraded and antibacterial, which are respectively named 5.0% single-layer antibacterial PVA (abbreviated as 5.0 single-layer) and 5.0% double-layer antibacterial PVA (abbreviated as 5.0 double-layer).

[0037] Table 1 Evaluation of experimental results of PVA film-fabric composites doped with different proportions of antibacterial agent MSN

[0038]

[0039]

[0040] Note: The test method is by absorption method, and the test objects are Staphylococcus aureus, Escherichia coli, and Candida albicans. The test standard is GB / T 20944.2 - 2007. The sample sterilization method is autoclaving. The contact culture time between the sample and the bacterial solution is 18 h. The control sample is 100% cotton fabric, and the colony concentrations are Staphylococcus aureus ATCC 6538: 2.0×10 5 CFU / mL; Escherichia coli 8099: 1.9×10 5 CFU / mL; Candida albicans ATCC 10231: 1.6×10 5 CFU / mL; The judgment criterion is that when the antibacterial value ≥ 2 or the antibacterial rate ≥ 99%, it is proved to have antibacterial effect.

[0041] The above are only the preferred embodiments of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and refinements can be made, and these improvements and refinements should also be regarded as the protection scope of the present invention.

Claims

1. A method for preparing a rapidly degradable and antibacterial polyvinyl alcohol film cloth composite material, characterized in that: include: The copper sulfate solution, sodium hydroxide solution, hexadecyltrimethylammonium bromide solution and ethyl orthosilicate are mixed to prepare the antibacterial solid material copper ion doped mesoporous silica nanospheres through a one-step method; The antibacterial solid material copper ion doped mesoporous silica nanospheres are mixed with polyvinyl alcohol and glycerol in pure water and stirred at high temperature, and the obtained mixed solution is used to prepare a single-layer or multi-layer antibacterial polyvinyl alcohol film by a coating method; The single-layer or multi-layer antibacterial polyvinyl alcohol film is compounded with the polyvinyl alcohol spunlace cloth to obtain a polyvinyl alcohol film-cloth composite material that is rapidly degradable and antibacterial.

2. The preparation method according to claim 1, characterized in that: The specific preparation steps of the antibacterial solid material copper ion doped mesoporous silica nanospheres are as follows: First, preheat ultrapure water to 60-65°C and perform magnetic stirring, add copper sulfate solution and hexadecyltrimethylammonium bromide solution, and mix and stir for at least half an hour; then add sodium hydroxide solution, raise the temperature to 60-80°C and continue to stir for at least half an hour to obtain a metal hydroxide seed solution; then add ethyl orthosilicate to the metal hydroxide seed solution, stir at 60-80°C for 2-8 hours to obtain antibacterial solid material copper ion doped mesoporous silica nanospheres.

3. The preparation method according to claim 2, characterized in that: The concentration of the copper sulfate solution is 50-320 g / L, the concentration of the sodium hydroxide solution is 0.5-1.5 mol / L, the concentration of the hexadecyltrimethylammonium bromide solution is 10-15 g / L, and the concentration of tetraethyl orthosilicate is 15.0-20.0 g / L.

4. The preparation method according to claim 2, characterized in that: The concentration of the copper sulfate solution is 50-320 g / L, the concentration of the sodium hydroxide solution is 1 mol / L, the concentration of the hexadecyltrimethylammonium bromide solution is 13 g / L, and the concentration of tetraethyl orthosilicate is 15.0-20.0 g / L.

5. The preparation method according to claim 1, characterized in that: The antibacterial solid material copper ion doped mesoporous silica nanospheres are further centrifuged, washed, dried and crushed before being stirred with polyvinyl alcohol and glycerol at high temperature.

6. The preparation method according to claim 1, characterized in that: The input amount of the copper ion doped mesoporous silica nanospheres is 0.1%-5.0% of the mass of the solute in the mixed solution.

7. The preparation method according to claim 6, characterized in that: The input amount of the copper ion doped mesoporous silica nanospheres is 2.0%-5.0% of the mass of the solute in the mixed solution.

8. The preparation method according to claim 1, characterized in that: When the antibacterial solid material copper ion-doped mesoporous silica nanospheres are stirred with polyvinyl alcohol and glycerol at high temperature, a wetting agent is also added.

9. The preparation method according to claim 8, characterized in that: In the mixed solution, the input amount of polyvinyl alcohol is 82%-87% of the solute mass of the mixed solution, and the input amount of glycerol is 10%-13% of the solute mass of the mixed solution.

10. A rapidly degradable and antibacterial polyvinyl alcohol film cloth composite material, characterized in that: Prepared according to the method according to any one of claims 1 to 9.

Images