CN115490891B - PVA/PDMS antibacterial hydrophobic membrane with three-level coarse structure and preparation method thereof - Google Patents
PVA/PDMS antibacterial hydrophobic membrane with three-level coarse structure and preparation method thereof Download PDFInfo
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- 239000004205 dimethyl polysiloxane Substances 0.000 title claims abstract description 20
- 235000013870 dimethyl polysiloxane Nutrition 0.000 title claims abstract description 20
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 title claims abstract description 20
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 title claims abstract description 20
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 19
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 17
- 239000012528 membrane Substances 0.000 title claims description 24
- 238000002360 preparation method Methods 0.000 title claims description 11
- 239000002131 composite material Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 24
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 8
- 238000007590 electrostatic spraying Methods 0.000 claims abstract description 5
- 238000005516 engineering process Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 12
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- 239000000843 powder Substances 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000013329 compounding Methods 0.000 claims description 7
- 239000003292 glue Substances 0.000 claims description 6
- 239000004005 microsphere Substances 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000000835 fiber Substances 0.000 claims description 5
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
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- 238000001523 electrospinning Methods 0.000 claims description 3
- 229920003023 plastic Polymers 0.000 claims description 3
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- 238000005303 weighing Methods 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
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- 239000000463 material Substances 0.000 abstract description 14
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- 239000003513 alkali Substances 0.000 abstract description 3
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- 238000002715 modification method Methods 0.000 abstract 1
- 238000005215 recombination Methods 0.000 abstract 1
- 230000006798 recombination Effects 0.000 abstract 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 33
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- 235000013305 food Nutrition 0.000 description 9
- 241000894006 Bacteria Species 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
- 208000035143 Bacterial infection Diseases 0.000 description 5
- 208000022362 bacterial infectious disease Diseases 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/103—Agents inhibiting growth of microorganisms
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/50—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyalcohols, polyacetals or polyketals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Abstract
The invention discloses a PVA/PDMS nano functional film which is prepared by an electrostatic spinning/electrostatic spraying composite technology and has multiple performances of hydrophobicity, antibiosis, corrosion resistance, degradability and the like. The three-level porous coarse structure is built through the composite recombination of the fiber-microsphere-porous structure, the hydrophobic modification is carried out on the alcohol hydrophilic material by taking structural modification as a main method, a simple hydrophobic modification method for the alcohol hydrophilic material is provided, the water contact angle of the PVA pure film is 33.8 degrees, the modified composite film is increased to 152.7 degrees, and good appearance and hydrophobicity are still shown in a strong acid and strong alkali environment. The antibacterial rate of the composite film reaches 98%, and the film after being observed to be modified still keeps antibacterial after 15 days.
Description
Technical Field
The invention relates to a nano composite functional packaging film and a preparation method thereof, and constructs a hydrophobic model with a three-level coarse structure, so that most alcohol hydrophilic materials are improved to absorb water, dissolve and lose efficacy and the like by the method. In particular to a simple and low-cost preparation method of a porous structure capable of loading nano particles to realize functions.
Technical Field
Bacterial infections continue to be a health hazard and threat to humans worldwide. According to World Health Organization (WHO) data, mortality from bacterial infection has been the leading cause in low-income countries for the last 15 years. Food-borne bacterial infections, which are diseases caused by the entry of toxic and harmful substances (including biological pathogens) into the human body through the food route, are particularly important in the classification of bacterial infections. Meanwhile, a great deal of spoilage waste is caused by bacterial infection of foods. For example, in summer, fruit and vegetable foods are easy to rot due to high-temperature bacteria breeding, fish protein foods containing more nutrients are easy to oxidize and deteriorate, and the quality guarantee period of the fruit can is prolonged only by adding a preservative. Not only does this weaken the flavor of the food itself, but also it is not possible to meet the ever-increasing quality standards and health requirements of people for the food. The common developed antibacterial or antioxidant packaging material has single function and poor effect, such as easy moisture absorption, acid and alkali resistance and the like. Therefore, the preparation of the nanometer packaging film which is applicable to the multistage environment and realizes the long-acting slow release effect is urgent. Most bacteria have the size of 2-6um, and the nanofiber spun by the invention can physically filter most bacteria due to the nanoscale diameter and pores, so that compared with a common membrane, the nanofiber effectively reduces the invasion of bacteria into the membrane and plays a primary barrier role. Secondly, nano-scale particles and low-surface energy substance PDMS are added in a compounding mode through a static spinning method to form a multistage rough surface with lower surface energy, and the contact angle of the material surface is improved to reach a hydrophobic film. Therefore, the hydrophilic material can be effectively subjected to hydrophobic modification by an electrostatic spinning/spraying method.
The alcohol substance taking polyvinyl alcohol as an example has better self-degradability and dispersibility, and the alcohol substance is prepared into nano fibers which are used as a base material of a packaging film, so that active nano particles can be uniformly loaded for compounding a functional film. However, PVA is extremely susceptible to deliquescence and failure due to the presence of a large number of hydroxyl groups in its molecular formula. Therefore, the three-level coarse structure is constructed on the surface of the fiber to effectively improve the water absorption. Based on the hydrophobic theory in the Cassie-Baxte model, if the roughness of the surface of such a material reaches a certain level, when a droplet is dropped on its surface, many air is accumulated in many rugged grooves on the surface of the material, thereby creating an "air cushion" that can prevent moisture from entering the surface of the material. The invention designs a multi-stage rugged air cushion on the surface of an alcohol material, which is characterized in that the fiber-microsphere-porous structure is recombined in a composite manner, and the structure modification is used as a main method for carrying out hydrophobic modification on a polyvinyl alcohol hydrophilic material. The three-level rough hydrophobic structure can not only prevent the water solution from being immersed, but also effectively prevent the adhesion and infiltration of pollutants such as bacteria, dust and the like.
With the development of the age, the safe green package with multiple performances is greatly paid attention to by researchers due to environmental pollution caused by waste generated by package failure, food quality safety problems and the like. The requirements of consumers on the quality safety of products are also higher, so that the requirements of packaging on the multi-performance compounding of barrier protection, material harmlessness, antibacterial freshness preservation, corrosion resistance, mechanical property and the like of the products are also stronger. Therefore, the development of the packaging material in the future should be advanced with time, the technical innovation brought by multi-process cross compounding, structure modification and the like is fully utilized, and the multi-performance cooperation of the packaging is realized; simultaneously, biological resources of China are fully utilized, the food safety problem is solved, meanwhile, sustainable development is advocated, and improvement of process technology is promoted.
Disclosure of Invention
In view of the above, the present invention aims to provide an alcohol hydrophilic material which is hydrophobically modified by constructing a tertiary coarse structure, and which reduces the hydroxyl content in the film and reduces the surface energy of the composite film by crosslinking a low surface energy substance PDMS on the surface of PVA; in addition, nanometer TiO is inserted into PDMS 2 The particles are structured with a convex porous structure on the microsphere surface, and the nano silver particles loaded in the PVA nanofiber are subjected to antibacterial slow release through the surface porous structure, so that the preparation of the hydrophobic-antibacterial-durable-degradable packaging material is realized.
A preparation method of a PVA/PDMS antibacterial hydrophobic membrane with a three-stage coarse structure comprises the following steps:
(1) Preparing an electrostatic spinning matrix fiber solution: weighing a proper amount of PVA powder by an electronic balance, placing the PVA powder into deionized water to prepare solutions with the concentration of 5%, 8%, 10% and 12%, respectively adding 3% of nano silver particles for mixing, placing the PVA powder into a magnetic stirrer which keeps the constant temperature of 80 ℃ for heating and stirring because the PVA is not easily dissolved in a normal-temperature aqueous solution, and standing the mixture for 10 hours to obtain a clear PVA/Ag spinning solution.
(2) Electrostatic spray PDMS/TiO 2 The preparation of the liquid comprises the steps of mixing n-hexane and absolute ethyl alcohol with the mass ratio of 1:2 as solvents, fully stirring the mixture by a magnetic stirrer, dissolving 10% PDMS liquid with the mass fraction of 10% in the solvents after 30 minutes, and respectively weighing TiO with the mass fractions of 0%, 3%, 5% and 8% 2 The powder is stirred for 10 hours at the constant temperature of 40 ℃ by a magnetic stirrer to finish 10 percent of PDMS/1 percent to 8 percent of TiO 2 And (3) preparing a composite liquid.
(3) Preparing nanofiber by electrostatic spinning: the prepared PVA solution was charged into a 10mL plastic syringe and placed in an electrospinning apparatus, ready for spinning. And (3) fixing the aluminum foil on a roller to serve as a collecting plate, adjusting technological parameters to start spinning, finishing spinning after 2 hours, and drying the PVA fiber film in a room temperature environment for 10 hours.
(4) Electrostatic spraying compounding technology: the same method uses PDMS/TiO 2 Placing the solution into a syringe, adjusting various parameters, spraying the solution on the surface of the spun PVA/Ag film for 2 hours in a crosslinking way, and removing the composite film after finishing the spraying, so as to carry out post-treatment. The composite membrane constructs a fiber-microsphere composite structure through a composite process, and nano TiO is added 2 The particles have a large number of rough porous structures on the surfaces of the microspheres, so that the hydrophobic membrane with a three-level rough structure is prepared.
(as in FIG. 1)
(5) And (3) drying: in order to volatilize the solvent completely in the film, the film is placed in a drying box for constant-temperature heating at 80 ℃, and deionized water, absolute ethyl alcohol and normal hexane which are not volatilized completely in the film are volatilized thoroughly, so that secondary structural change of the film due to hydroxyl after meeting water is prevented. An overall process diagram (see fig. 2).
(6) Preferably, the PVA is at an optimum concentration of 8% in step 1;
(7) Preferably, after the TiO in step 2 2 The optimal addition amount is 3%;
(8) Preferably, the process parameters for spinning PVA/Ag nanofibers in step 3 are as follows: the voltage is 18KV, the receiving distance is 15cm, the glue pushing speed is 0.3ml/h, and the rotating speed is 600r/min.
(9) Preferably, after the electrostatic spraying of PDMS/TiO in step 4 2 The process parameters of (a) are as follows: the voltage is 23KV, the receiving distance is 15cm,the glue pushing speed is 3.0ml/h, and the rotating speed is 500r/min.
(10) Preferably, the drying time in step 5 is 1.5 hours.
Compared with the prior art, the method is simple and feasible, has lower cost, and the three-level coarse structure prepared by the fiber-microsphere-porous structure can regulate the hydrophobicity and the nano particle leaching rate by the size of the microsphere, the porosity, the thickness of the film layer and the like (as shown in figure 3) so as to realize the self regulation of the antibacterial slow-release performance.
In the preparation method provided by the invention, because PVA (polyvinyl alcohol) has excellent dispersibility, the agglomeration phenomenon of nano particles can be prevented, and the uniformity of the antibacterial performance of nano silver can be realized (shown in figure 4). The hydrophobic stable composite membrane is prepared from the three-level coarse structure (shown in figure 5) and is separated out from the surface porous structure to achieve the characteristic of long-acting antibiosis (shown in figure 6). The PVA is good in degradability and non-toxic, is friendly to the environment, reduces the threat to the ecological environment, responds to the call for comprehensively enhancing the ecological environment protection, plays roles in pollution control and attack, improves ecological civilization, and has an irreducible development prospect in the field of multi-performance composite packaging of future foods and medicines.
Drawings
FIG. 1. Three-level coarse structure model;
FIG. 2. Process flow for preparing membranes by electrospinning/spray compounding;
FIG. 3. Composite membrane surface and cross-sectional SEM with "fiber-microsphere-porous" tertiary coarse structure;
FIG. 4 TEM characterization of loaded nano silver particles within PVA fibers;
FIG. 5. Hydrophobic stability of composite membranes;
FIG. 6. Composite membrane antimicrobial properties;
Detailed Description
The invention is further illustrated below in conjunction with the specific embodiments. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the teachings of the present invention, and equivalent changes and modifications are also within the scope of the present application as defined in the claims.
Example 1:
step 1: 9.5g,9.2g,9.0g and 8.8g of deionized water are weighed by an electronic balance as a solvent, 0.5g,0.8g,1.0g and 1.2g of PVA powder are weighed by the electronic balance as a solute and added into a small 20ml beaker filled with deionized water, 0.1g of nano silver particles are weighed and added, and finally the mixture is placed on a magnetic stirrer with a stirring speed of 500r/h and a constant temperature of 80 ℃ and stirred for 10 hours, thereby preparing a PVA/Ag solution with concentration of 5%, 8%, 10% and 12%.
Step 2: and (3) carrying out electrostatic spinning on the spinning solution in the step (1) under the process of voltage 18KV, receiving distance of 15cm, glue pushing speed of 0.3ml/h and rotating speed of 600r/h to obtain a PVA/Ag nanofiber membrane, and drying the PVA/Ag nanofiber membrane in a constant-temperature drying oven at 80 ℃ to obtain the nanofiber membrane with antibacterial property.
And 3, detecting the antibacterial property, namely taking 20 mu l of sterile water to be respectively placed in two bacterial groups of escherichia coli and staphylococcus aureus, vibrating the bacteria to a turbid state, respectively taking 5 mu l of sterile water to be dripped on the surface of solidified agar, performing flat coating to uniformly distribute the bacteria, respectively taking two sheared PVA/Ag film samples and blank filter paper to be placed in a coated culture dish, performing a comparison experiment in three parts, standing the three parts in a constant temperature box, and checking a bacteriostasis ring through a ZY-300IV multifunctional microorganism automatic measurement analyzer after 24 hours and 48 hours respectively, and analyzing the antibacterial property of the bacteriostasis ring. The addition of the obtained nano silver ensures that the antibacterial rate of the film to two bacteria reaches 95 percent.
Step 4: and (3) performing hydrophobicity test, wherein the water contact angle of the PVA nanofiber membrane with each concentration is smaller than 35 degrees.
Example 2:
step 1: 9.2g of deionized water is weighed by an electronic balance as a solvent, 0.8g of PVA powder is weighed by the electronic balance as a solute and added into a small 20ml beaker filled with deionized water, 0.1g of nano silver particles are weighed and added into the small beaker, and finally the small beaker is placed on a magnetic stirrer with the stirring speed of 500r/h and the constant temperature of 80 ℃ to be stirred for 10 hours, so that 8% of PVA solution is prepared.
Step 2: 4.5g of the n-ethane solution were weighed in a small beaker by means of an electronic balanceThen 9g of ethanol solution is weighed by the same method as solvent, 1.5g of PDMS colloid is weighed on an electronic balance, and a proper amount of TiO2 powder is weighed as solute to respectively finish 10 percent of PDMS/1 to 8 percent of TiO 2 And (3) preparing a composite liquid.
Step 3: the solution in step 1 was spun into 8% PVA nanomembrane in the same way as in example 1-step 2.
Step 4: and (3) placing the solution in the step (2) in a syringe, adjusting each parameter to be 23KV, wherein the receiving distance is 15cm, the glue pushing speed is 3.0ml/h, and the rotating speed is 500r/h. And (3) spraying the PVA/Ag film layer spun in the step (3) for 2 hours in a crosslinking way, removing the composite film after finishing, and placing the composite film in a constant-temperature drying oven at 80 ℃ for drying the solvent which is not completely volatilized.
Step 5: hydrophobic stability test for PVA/PDMS/Ag/TiO with tertiary coarse Structure 2 The composite film layer is used for detecting the comfort and corrosion resistance, and when TiO 2 When the addition amount is 3%, the structured porous structure is most ideal, the roughness reaches the maximum, the contact angle reaches 152.8 degrees, and the porous structure still maintains good stability and hydrophobicity in strong acid and alkali environments.
Step 6: antibacterial durability detection, the antibacterial performance of the composite membrane is detected by the same method as in the steps 2-3 of the example, the modified composite membrane keeps amplifying the antibacterial zone after 48 hours, the slow release effect of the nano silver is still maintained after 15 days, and the final antibacterial rate reaches 99%. Compared with the two membranes which are cultured under the flora, the pure PVA surface is soaked and weightless, the surface has no complete structure, the membrane cannot be reused, and compared with the lower modified composite membrane, the surface is complete, the original shape and performance are still maintained, the membrane can be recycled, and the waste and unrecyclability of materials are greatly reduced.
The above description of the embodiments is only for aiding in the understanding of the method of the present invention and its core ideas. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims.
Claims (5)
1. The preparation method of the PVA/PDMS antibacterial hydrophobic membrane with the three-stage coarse structure is characterized by comprising the following steps of:
(1) Preparing an electrostatic spinning matrix fiber solution: weighing a proper amount of PVA powder by an electronic balance, placing the PVA powder into deionized water to prepare solutions with the concentration of 5%, 8%, 10% and 12%, respectively adding 3% of nano silver particles for mixing, placing the PVA powder into a magnetic stirrer which keeps the constant temperature of 80 ℃ for heating and stirring as the PVA is not easily dissolved in normal-temperature aqueous solution, and standing for 10 hours to obtain a clear PVA/Ag spinning solution;
(2) Electrostatically spraying PDMS/TiO 2 The preparation of the solution comprises the steps of mixing n-hexane and absolute ethyl alcohol with the mass ratio of 1:2 as solvents, fully stirring the mixture by a magnetic stirrer, dissolving 10% PDMS colloid with the mass fraction of 3%, 5% and 8% of TiO respectively in the solvents after 30 minutes 2 The powder is stirred for 10 hours at the constant temperature of 40 ℃ by a magnetic stirrer to finish PDMS/TiO 2 Preparing a solution;
(3) Preparing nanofiber by electrostatic spinning: filling the prepared PVA/Ag spinning solution into a 10mL plastic injector, and placing the plastic injector into an electrostatic spinning device to prepare for spinning; fixing an aluminum foil on a roller as a collecting plate, adjusting technological parameters to start spinning, finishing spinning after 2 hours, and drying a PVA/Ag film in a room temperature environment for 10 hours;
(4) Electrostatic spraying compounding technology: PDMS/TiO 2 Placing the solution in a syringe, adjusting various parameters, spraying the solution on the surface of the spun PVA/Ag film for 2 hours in a crosslinking way, and removing the composite film for post-treatment after finishing; the composite membrane constructs a fiber-microsphere composite structure through a composite process, and nano TiO is added 2 Particles, so that a large number of rough porous structures are arranged on the surfaces of the microspheres to prepare a hydrophobic film with a three-level rough structure;
(5) And (3) drying: in order to volatilize the solvent completely in the film, the film is placed in a drying box for constant-temperature heating at 80 ℃, and deionized water, absolute ethyl alcohol and normal hexane which are not volatilized completely in the film are volatilized thoroughly, so that secondary structural change of the film due to hydroxyl after meeting water is prevented.
2. The method according to claim 1, wherein the PVA concentration in step 1 is 8%; tiO in step 2 2 The optimum addition amount is 3%.
3. The method according to claim 1, wherein the process parameters of the electrospinning in step 3 are: the voltage is 18KV, the receiving distance is 15cm, the glue pushing speed is 0.3ml/h, and the rotating speed is 600r/min.
4. The method according to claim 1, wherein the electrostatic spraying process parameters in step 4 are: the voltage is 23KV, the receiving distance is 15cm, the glue pushing speed is 3.0ml/h, and the rotating speed is 500r/min.
5. The method of claim 1, wherein the drying time in step 5 is 1.5 hours.
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CN101165083A (en) * | 2006-10-16 | 2008-04-23 | 中国科学院化学研究所 | Ultra-hydrophobic polystyrene thin film enhanced by nano silicon dioxide particles and preparation method thereof |
CN106048892A (en) * | 2016-07-15 | 2016-10-26 | 东华大学 | Preparation method of GO/SA/PVA composite nanofiber membrane carrying nano silver particles |
CN107737529A (en) * | 2017-10-13 | 2018-02-27 | 中国科学院生态环境研究中心 | A kind of preparation method of super-hydrophobic oleophobic composite membrane |
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