CN115178105A - Long-acting filtering membrane with uniformly distributed biological electrets on polylactic acid nanofiber surface and preparation method thereof - Google Patents
Long-acting filtering membrane with uniformly distributed biological electrets on polylactic acid nanofiber surface and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a long-acting filtering membrane with a biological electret uniformly distributed on the surface of polylactic acid nano-fiber and a preparation method thereof, which is a technical scheme for efficiently synthesizing a biological electret material and uniformly distributing the biological electret material on the surface of the polylactic acid nano-fiber so as to comprehensively improve the mechanical property, the surface potential and the air filtering efficiency. The method can well control the microstructure of the biological electret, and inhibit self agglomeration or local agglomeration of the nano-scale electret in the forming process, thereby ensuring good processability of the electrostatic spinning polylactic acid fiber membrane and improving the surface potential, filtering performance and mechanical property of the fiber membrane.
Description
Technical Field
The invention relates to the technical field of functional materials, in particular to a long-acting filtering membrane with uniformly distributed biological electrets on the surface of polylactic acid nano fibers and a preparation method thereof.
Background
Air pollution is a long-term global problem, endangering atmospheric environment and human health, and air filtration is a key and effective method for improving air quality. The nanofiber-based filter medium has the advantages of small diameter, high specific surface area, high porosity and the like, improves the durability of filtration mainly through physical screening, and is widely applied to the field of air filtration. One of the most typical techniques for producing nanofibers is electrospinning, and large-scale industrial production has been achieved. However, the traditional electrospinning polymer materials are difficult to degrade in nature, and provide a great challenge for environmental protection. Polylactic acid as a novel bio-based degradable material has excellent properties such as high mechanical property, good biocompatibility and biodegradability, and shows good application prospect for replacing traditional high polymer materials in the field of air filter materials.
The common fiber filtering material mainly depends on the mechanical interception functions of Brown diffusion, interception, inertial collision, gravity sedimentation and the like to filter particles in air, but the filtering effect on submicron particles is not ideal. Therefore, electrets are often added into the fibers, which not only provides a general mechanical interception function, but also realizes the capture of particles by utilizing coulomb force generated by charges carried by the fibers, and the filtering efficiency is far higher than that of common fibers, and is more obvious particularly when filtering submicron-sized particles.
Commonly used electret materials fall into two broad categories, inorganic and organic: the inorganic electret materials comprise tourmaline, magnetizer, inorganic silicon and the like, and have the problems of poor application effect, high cost and the like; organic electret materials including organic glass, high molecular polymers and the like face the problems of difficult degradation, serious attenuation of stored charges and the like. As natural electret materials, materials such as bones and proteins can maintain a polarized or charged state for a long period of time, and thus there is a need for a high-charge storage type electret material having excellent biocompatibility and being friendly to the human body and the environment.
The hydroxyapatite is the main inorganic component of human body and animal skeleton, can realize chemical bond combination with organism tissue on the interface, has certain solubility in vivo, can release ions harmless to the organism and participate in vivo metabolism, and has excellent biocompatibility and bioactivity. Under different conditions, the crystal is granular, fibrous, needle-shaped or fibrous, the diameter can be as low as several nanometers, and the length can reach several millimeters. The high ionic activity endows the hydroxyapatite Dan Liang with good polarization potential, and is beneficial to implementing a rapid, simple and convenient electret effect, thereby obtaining high surface potential and a filtering effect.
Therefore, it is a problem worthy of research to provide a long-acting filtering membrane and a preparation method thereof, wherein the long-acting filtering membrane is formed by uniformly introducing a polylactic acid electrostatic spinning nanofiber membrane in an atomizing and depositing manner, so that high-performance and multifunctional biological electrets of a fully-degradable nanofiber membrane are uniformly distributed on the surface of polylactic acid nanofibers.
Disclosure of Invention
The invention aims to provide a long-acting filtering membrane which uniformly introduces a polylactic acid electrostatic spinning nano-fiber membrane in an atomizing and depositing manner so as to realize high-performance and multifunctional distribution of a fully-degradable nano-fiber membrane on the surface of polylactic acid nano-fiber and a preparation method thereof.
The purpose of the invention is realized by the following steps:
the long-acting filtering membrane with the biological electret uniformly distributed on the surface of the polylactic acid nanofiber comprises a polylactic acid fiber membrane, wherein the biological electret is uniformly distributed on the surface of the polylactic acid nanofiber membrane, the content of the biological electret in the polylactic acid nanofiber is 0.05-30 wt%, and the biological electret is hydroxyapatite nanowhiskers synthesized by microwave-assisted biomimetic mineralization.
The diameter of the hydroxyapatite nano whisker is 1 to 20 nm, and the length-diameter ratio of the hydroxyapatite nano whisker is 5 to 200.
The thickness of the polylactic acid fiber membrane is 40-800 mu m, and the diameter of the nano-fiber in the polylactic acid fiber membrane is 5-100 nm.
A preparation method of a long-acting filtering membrane with uniformly distributed biological electrets on the surface of polylactic acid nano fibers comprises the following steps:
s1, preparing hydroxyapatite nano whisker: adding water-soluble calcium salt, water-soluble phosphate and a template agent into water, stirring and dissolving uniformly, then placing the mixture into a microwave reaction kettle, carrying out microwave-assisted biomimetic mineralization reaction under the stirring state, and cooling after the reaction is finished to obtain an aqueous solution deposited with hydroxyapatite nanowhiskers;
s2, preparing hydroxyapatite nano whisker dispersion liquid: directly treating the hydroxyapatite nanowhisker aqueous solution obtained in the step S1 by using plasma equipment to obtain a hydroxyapatite nanowhisker dispersion liquid;
s3, preparing the polylactic acid nanofiber membrane with uniformly distributed biological electrets: preparing a nanofiber membrane from polylactic acid dissolved in an organic solvent by an electrostatic spinning technology, and applying atomized hydroxyapatite nanowhisker dispersion liquid in the step S2 in the spinning process to obtain the polylactic acid nanofiber membrane with uniformly distributed biological electrets.
The water-soluble calcium salt in the step S1 is at least one of calcium chloride, calcium nitrate, calcium acetate and calcium hypochlorite, and the concentration of the water-soluble calcium salt is 0.01 to 2 mol/L; the water-soluble phosphate is at least one of ammonium dihydrogen phosphate, ammonium hydrogen phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, dipotassium hydrogen phosphate and potassium dihydrogen phosphate, and the molar ratio of calcium ions to phosphate ions is 2 to 1; the template agent is at least one of hexadecyl trimethyl ammonium bromide, stearic acid, oleic acid, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and octyl phenyl polyoxyethylene ether, the mass fraction of the template agent in the solution is 0.001 wt% -0.1 wt%, and the template agent can be used as a structure guiding agent to enable hydroxyapatite to grow into rod-shaped one-dimensional nano whiskers along a c axis.
The reaction temperature of the microwave-assisted synthesis in the step S1 is 100 to 250 ℃, and the reaction time is 1 to 30 minutes; the diameter of the hydroxyapatite nanowhisker obtained in the step S1 is 1 to 20 nm, and the length-diameter ratio is 5 to 200.
And in the step S2, the plasma processing equipment is at least one of a normal pressure jet type, a dielectric barrier discharge type and a rotary normal pressure type, the plasma discharge voltage is 1 to 80 kV, the plasma working gas is at least one of argon, helium, hydrogen, nitrogen and oxygen, the processing temperature is 10 to 50 ℃, and the processing temperature is 10 seconds to 30 minutes.
The organic solvent in the step S3 is at least one of dichloromethane, trichloromethane, dimethylformamide, N-methylpyrrolidone, hexafluoroisopropanol, methanol, ethanol, isopropanol and glycerol, and the concentration of the polylactic acid in the mixed solution is 0.5 to 22 wt%; the module voltage of electrostatic spinning is 15 to 60 kV, the receiving voltage is-15 to 0 kV, and the consumption rate of spinning stock solution is 1 to 60 mL/min.
The atomization speed of the biological electret in the step S3 is 0.5-50 mL/min, the diameter of the obtained biological electret modified polylactic acid nano fiber is 5-100 nm, the content of the biological electret in the polylactic acid nano fiber is 0.05-30 wt%, and the film thickness of the obtained polylactic acid fiber is 40-800 mu m.
The invention has the beneficial effects that: the invention provides a technical route for efficiently synthesizing the biological electret, and the biological electret has high surface activity, high dispersibility and uniform distribution on the surface of the fiber, provides a new way for improving the surface potential and the electrostatic adsorption effect of the polylactic acid nano fiber film, and is helpful for expanding the application and development of the degradable high polymer material in the field of long-acting air filtering materials.
Drawings
FIG. 1 is a flow chart of the present invention;
FIG. 2 is a transmission electron microscope observation of hydroxyapatite nanowhisker morphology of the plasma treatment solution in example 1 in accordance with the present invention;
FIG. 3 is a scanning electron microscope image of a commercially available conventional hydroxyapatite in comparative example 1 according to the present invention;
FIG. 4 is an image of the polylactic acid fiber film obtained in example 1 observed by a scanning electron microscope according to the present invention;
FIG. 5 is an image of the polylactic acid fiber membrane obtained in comparative example 1 observed by a scanning electron microscope according to the present invention.
Detailed Description
The invention is further illustrated by the following figures and examples.
Example 1:
as shown in figure 1, the long-acting filtering membrane with the biological electrets uniformly distributed on the surface of the polylactic acid nano fiber and the preparation method thereof comprise the following steps:
s1, preparing hydroxyapatite nano whisker: adding calcium chloride (0.01 mol/L), ammonium dihydrogen phosphate (0.01 mol/L) and stearic acid (0.001 wt%) into water, uniformly mixing, putting into a microwave reaction kettle, heating to 250 ℃ under a stirring state, reacting for 1 minute, and cooling after the reaction is finished to obtain an aqueous solution deposited with hydroxyapatite nanowhiskers;
s2, preparing hydroxyapatite nano whisker dispersion liquid: treating the aqueous solution obtained in the step S1 for 30 minutes by adopting dielectric barrier discharge type plasma equipment (working voltage is 1 kV, working gas is argon/nitrogen mixed gas, and temperature is 15-30 ℃) to obtain hydroxyapatite nano whisker dispersion liquid;
s3, preparing the polylactic acid nanofiber membrane with uniformly distributed biological electrets: polylactic acid is dissolved in dichloromethane/N-methyl pyrrolidone (the mass ratio is 7:3) to be used as spinning solution, nanofibers are prepared through an electrostatic spinning technology (the module voltage is 20 kV, the receiving voltage is-15 kV, the solution consumption rate is 0.5 mL/min), and meanwhile, dispersion liquid obtained through S2 is atomized (the speed is 0.5 mL/min) until the content of the biological electret reaches 0.05 wt%, and the thickness of a fiber film reaches 800 mu m.
Example 2
A long-acting filtering membrane with biological electrets uniformly distributed on the surface of polylactic acid nano-fiber and a preparation method thereof comprise the following steps:
s1, preparing hydroxyapatite nano whisker: adding calcium nitrate (2 mol/L), disodium hydrogen phosphate (1 mol/L) and oleic acid (0.1 wt%) into water, uniformly mixing, putting into a microwave reaction kettle, heating to 100 ℃ under a stirring state, reacting for 30 minutes, and cooling after the reaction is finished to obtain an aqueous solution deposited with hydroxyapatite nanowhiskers;
s2, preparing hydroxyapatite nano whisker dispersion liquid: treating the aqueous solution obtained in the step S21 for 10 minutes by adopting rotary normal pressure plasma equipment (the working voltage is 80 kV, the working gas is argon, and the temperature is 25 to 35 ℃) to obtain hydroxyapatite nano whisker dispersion liquid;
s3, preparing the polylactic acid nanofiber membrane with uniformly distributed biological electrets: polylactic acid is dissolved in trichloromethane/dimethylformamide (the mass ratio is 6:4) to be used as spinning stock solution, nanofibers are prepared by an electrostatic spinning technology (module voltage is 60 kV, receiving voltage is 0 kV, stock solution consumption rate is 60 mL/min), and meanwhile, dispersion solution obtained in S22 is atomized (speed is 50 mL/min) until the content of the electret reaches 30 wt%, and the thickness of the fiber film reaches 40 mu m.
Example 3
As shown in fig. 1, a long-acting filtering membrane with biological electrets uniformly distributed on the surface of polylactic acid nano-fiber and a preparation method thereof, comprising the following steps:
s1, preparing hydroxyapatite nano whisker: adding calcium acetate (0.05 mol/L), potassium dihydrogen phosphate (0.04 mol/L) and hexadecyltrimethylammonium bromide (0.01 wt%) into water, uniformly mixing, putting into a microwave reaction kettle, heating to 150 ℃ under a stirring state, reacting for 15 minutes, and cooling after the reaction is finished to obtain an aqueous solution deposited with hydroxyapatite nanowhiskers;
s2, preparing hydroxyapatite nano whisker dispersion liquid: treating the aqueous solution obtained in the step S1 for 30 minutes by adopting normal-pressure jet plasma equipment (the working voltage is 20 kV, the working gas is argon, and the temperature is 25 to 50 ℃) to obtain hydroxyapatite nano whisker dispersion liquid;
s3, preparing the polylactic acid nanofiber membrane with uniformly distributed biological electrets: polylactic acid is dissolved in dimethylformamide/hexafluoroisopropanol (mass ratio 5:5) to be used as spinning stock solution, nanofibers are prepared by an electrostatic spinning technology (module voltage 40 kV, receiving voltage-10 kV, stock solution consumption rate 30 mL/min), and meanwhile, dispersion liquid obtained by S2 is atomized (speed 30 mL/min) until the content of the biological electret reaches 10 wt%, and the thickness of the fiber film reaches 80 μm.
Example 4
A long-acting filtering membrane with biological electrets uniformly distributed on the surface of polylactic acid nano-fiber and a preparation method thereof comprise the following steps:
s1, preparing hydroxyapatite nano whisker: adding calcium hypochlorite (0.2 mol/L), ammonium hydrogen phosphate (0.15 mol/L) and octyl phenyl polyoxyethylene ether (0.05 wt%) into water, uniformly mixing, putting into a microwave reaction kettle, heating to 200 ℃ under a stirring state, reacting for 5 minutes, and cooling after the reaction is finished to obtain an aqueous solution deposited with hydroxyapatite nanowhiskers;
s2, preparing hydroxyapatite nano whisker dispersion liquid: treating the aqueous solution obtained in the step S1 for 15 minutes by adopting dielectric barrier discharge type plasma equipment (the working voltage is 40 kV, the working gas is argon/nitrogen mixed gas, and the temperature is 20 to 40 ℃) to obtain hydroxyapatite nano whisker dispersion liquid;
s3, preparing the polylactic acid nanofiber membrane with uniformly distributed biological electrets: polylactic acid is dissolved in N-methyl pyrrolidone/dimethylformamide (the mass ratio is 7:3) to be used as spinning stock solution, nanofibers are prepared by an electrostatic spinning technology (module voltage is 35 kV, receiving voltage is 0 kV, stock solution consumption rate is 20 mL/min), and meanwhile, dispersion liquid obtained by S2 is atomized (speed is 10 mL/min) until the content of the biological electret reaches 15 wt%, and the thickness of the fiber film reaches 100 mu m.
Example 5
A long-acting filtering membrane with biological electrets uniformly distributed on the surface of polylactic acid nano fiber and a preparation method thereof comprise the following steps:
s1, preparing hydroxyapatite nano whisker: adding calcium acetate (0.8 mol/L), ammonium dihydrogen phosphate (0.5 mol/L) and sodium dodecyl benzene sulfonate (0.08 wt%) into water, uniformly mixing, placing into a microwave reaction kettle, heating to 140 ℃ under a stirring state, reacting for 20 minutes, and cooling after the reaction is finished to obtain an aqueous solution deposited with hydroxyapatite nanowhiskers;
s2, preparing hydroxyapatite nano whisker dispersion liquid: treating the aqueous solution obtained in the step S1 for 25 minutes by adopting dielectric barrier discharge type plasma equipment (working voltage is 10 kV, working gas is helium, and temperature is 20 to 30 ℃) to obtain hydroxyapatite nano whisker dispersion liquid;
s3, preparing the polylactic acid nanofiber membrane with uniformly distributed biological electrets: polylactic acid is dissolved in dichloromethane/hexafluoroisopropanol (mass ratio 9:1) to be used as spinning stock solution, nanofibers are prepared by an electrostatic spinning technology (module voltage 45 kV, receiving voltage 0 kV, stock solution consumption rate 20 mL/min), and meanwhile, dispersion solution obtained by S2 is atomized (speed 15 mL/min) until the content of the electret reaches 18 wt%, and the thickness of the fiber film reaches 500 mu m.
Comparative example 1 (addition of conventional hydroxyapatite Filler)
The hydroxyapatite dispersion and polylactic acid fiber film were prepared substantially by the method of example 1. In this example, instead of hydroxyapatite nanowhiskers synthesized by microwave-assisted biomimetic mineralization, commercially available hydroxyapatite powder (purity 99%, average diameter 2 nm, sienna, bio-technology limited) was added. Specifically, after directly stirring and dispersing hydroxyapatite powder in water, treating for 30 minutes by using a dielectric barrier discharge type plasma device (the working voltage is 1 kV, the working gas is argon/nitrogen mixed gas, and the temperature is 15 to 30 ℃) to obtain a stably dispersed aqueous solution; polylactic acid is dissolved in dichloromethane/N-methyl pyrrolidone (the mass ratio is 7:3) to be used as spinning stock solution, nanofibers are prepared through an electrostatic spinning technology (a module voltage is 20 kV, a receiving voltage is-15 kV, a stock solution consumption rate is 0.5 mL/min), and meanwhile, a hydroxyapatite dispersion liquid is atomized (a speed is 0.5 mL/min) until the content of hydroxyapatite reaches 0.05 wt%, and the thickness of a fiber film reaches 800 micrometers.
Comparative example 2 (dispersed biological electret without plasma treatment)
The method of example 2 was essentially used to prepare the bioelectrodes and polylactic acid nanofiber films. In contrast, the present example does not employ plasma treatment to disperse the hydroxyapatite nanowhiskers. Specifically, polylactic acid is dissolved in chloroform/dimethylformamide (mass ratio 6:4) to be used as spinning stock solution, nanofibers are prepared by an electrostatic spinning technology (module voltage 60 kV, receiving voltage 0 kV and stock solution consumption rate 60 mL/min), and simultaneously dispersion liquid obtained by S21 is atomized (speed 50 mL/min) until the content of the biological electret reaches 30 wt% and the thickness of the fiber film reaches 40 μm.
COMPARATIVE EXAMPLE 3 (without Bioelectret)
Polylactic acid nanofiber films were prepared essentially as in example 3, except that no electret was added. Specifically, polylactic acid was dissolved in dimethylformamide/hexafluoroisopropanol (mass ratio 5:5) to prepare nanofibers as a spinning dope by an electrospinning technique (block voltage 40 kV, reception voltage-10 kV, dope consumption rate 30 mL/min) until the thickness of the fiber film reached 80 μm.
Structural characterization and Performance testing
Observation by a transmission electron microscope: the microstructure and the dispersed morphology of the plasma-treated hydroxyapatite nanowhiskers were observed using a transmission electron microscope (model Hitachi HT7700, hitachi electron, japan) (fig. 2).
Observation by a scanning electron microscope: the microstructure of commercially available conventional hydroxyapatite nanoparticles (fig. 3), as well as the microstructure of polylactic acid fiber membrane (fig. 4 and 5), was observed by a field emission scanning electron microscope (model JSM-7900F, japan electronics).
And (3) testing tensile property: the resulting fiber film was cut to obtain tensile specimens, and the tensile properties of the composite material were measured using a universal tensile machine (model 4403, sensor 100N) from Instron, USA, according to the tensile properties test standards for plastics in ASTM D638-2003, american society for testing materials. At least 3 parallel test specimens were guaranteed per group and the results were averaged.
Surface potential test: the surface potential of the nanofiber membrane (area 100 mm 2) was measured using a non-contact electrostatic meter (VM 54XQS, quatek corp., usa) with a test height of 2 cm and constant temperature and humidity of 25 ℃ and 45%, and 20 data points were randomly collected and averaged for each sample.
And (3) testing the filtration performance: an LZC-K automatic filter material tester (Suzhou Huada instrument and equipment, inc.) is adopted to test the air filtering performance of the nanofiber membrane (the area is 100 cm < 2 >), the gas flow rate is set to be 85L/min, and the particle size range of NaCl atomized particles generated by an aerosol generator is 0.1 to 10 mu m. Each set of fibrous membranes was tested in at least 3 different positions and the results averaged.
TABLE 1 mechanical and filtration Property test results of polylactic acid nanofiber membranes
The experimental results are as follows: as shown in figure 2, the hydroxyapatite nano whisker synthesized by microwave-assisted biomimetic mineralization has good structural regularity and crystallinity, the diameter and the length-diameter ratio of the whisker are also well controlled, the structural foundation of the whisker serving as a biological electret is laid, and simultaneously, the good dispersion form can be obtained by combining plasma treatment. In sharp contrast, the commercially available hydroxyapatite nanoparticles had significant agglomeration and it was difficult to obtain a well dispersed morphology (fig. 3).
As shown in fig. 4, by atomizing the hydroxyapatite nanowhisker dispersion liquid treated by plasma and combining with an electrostatic spinning technology, the uniform distribution of the biological electrets on the surface of the polylactic acid nanofiber can be realized, the diameter of the polylactic acid fiber is in the nanometer level and the distribution is uniform (15 to 90 nm), the biological electrets are uniformly distributed on the surface of the nanofiber and have stronger interface binding force with the fiber, the high porosity and good three-dimensional communication structure of the fiber are ensured, and the mechanical property, the surface potential and the filtration efficiency of the nanofiber are improved. Figure 5 shows that the surface properties and the geometry of the hydroxyapatite also exhibit more important effects: after the conventional commercially available nano-hydroxyapatite is introduced, local agglomeration is easily formed, the diameter distribution of fibers is uneven, and a large number of micron-sized fiber structures appear.
Table 1 compares the tensile test, surface potential test and filterability test results of the polylactic acid nanofiber membranes obtained in the examples and comparative examples, and the polylactic acid nanofiber membrane obtained in example 1 ‒ has higher breaking strength (4.6 MPa ‒ 8.6.6 MPa) which is several times higher than that of a pure polylactic acid fiber membrane (2.6 MPa), embodies excellent mechanical properties, and completely meets the mechanical property requirements of the polylactic acid nanofiber membrane in the field of filter materials. However, the breaking strengths of comparative examples 1 and 2 were only 3.0 MPa and 4.2 MPa, mainly due to severe agglomeration caused by uncontrollable nanoparticle properties or unsuitable dispersion methods.
Also significant is that example 1 ‒ all exhibited very high surface potentials (6.2 kV to 14.5 kV) and hardly decayed with time, demonstrating very high long-term stability. In particular, the initial value of the surface potential of example 2 is as high as 14.5 kV, which is 2.23 times that of comparative example 2 and nearly 4.53 times that of comparative example 3; and after 90 days, the surface potential of example 2 remained at 13.9 kV, while comparative examples 2 and 3 attenuated significantly to 0.5 kV and 0.2 kV. The dispersion degree of the biological electret and the surface potential of the polylactic acid nanofiber membrane are closely related to the filtering performance, the embodiment 2 with the highest surface potential is most excellent in the filtering test, and the filtering efficiencies of PM0.3 and PM2.5 reach 99.7% and 99.9% respectively; much higher than comparative examples 1-3, which have lower surface potentials (both PM0.3 and PM2.5 filtration efficiencies < 90%).
Therefore, the technical scheme provided by the invention enables the biological electret to have good surface property and structural regularity, and obviously improves the dispersion degree and the efficiency in the polylactic acid nano fiber, and the biological electret has the advantages that: (1) The structural regularity and the uniformity of the hydroxyapatite nanowhiskers synthesized by microwave-assisted biomimetic mineralization enable the hydroxyapatite nanowhiskers to be easily stripped and dispersed in polylactic acid, and further the efficacy of the biological electret is better exerted; (2) The plasma treatment technology promotes the surface activation of the nano crystal whiskers and the uniform dispersion capability in the solution, so that the nano crystal whiskers are uniformly distributed on the surface of the polylactic acid nano fiber and are the basis for exerting the function of the biological electret; (3) The electrostatic spinning technology can realize extremely high and long-acting surface potential in the polylactic acid nano fiber containing the uniformly distributed biological electret, is beneficial to improving the filtering efficiency of a fiber membrane, and has good application prospect.
Claims (9)
1. A long-acting filtering membrane with uniformly distributed biological electrets on the surface of polylactic acid nano fibers is characterized in that: the composite material comprises a polylactic acid fiber film, wherein biological electrets are uniformly distributed on the surface of the polylactic acid nanofiber film, the content of the biological electrets in the polylactic acid nanofiber is 0.05-30 wt%, and the biological electrets are hydroxyapatite nanowhiskers synthesized by microwave-assisted biomimetic mineralization.
2. The long-acting filtering membrane with the biological electrets distributed on the surfaces of the polylactic acid nanofibers according to claim 1, wherein the long-acting filtering membrane comprises: the diameter of the hydroxyapatite nano whisker is 1 to 20 nm, and the length-diameter ratio of the hydroxyapatite nano whisker is 5 to 200.
3. The long-acting filtering membrane with the biological electrets distributed on the surfaces of the polylactic acid nanofibers according to claim 1, wherein the long-acting filtering membrane comprises: the thickness of the polylactic acid fiber membrane is 40-800 mu m, and the diameter of the nano-fiber in the polylactic acid fiber membrane is 5-100 nm.
4. A preparation method of a long-acting filtering membrane with uniformly distributed biological electrets on the surface of polylactic acid nano fibers is characterized by comprising the following steps: the method comprises the following steps:
s1, preparing hydroxyapatite nano whisker: adding water-soluble calcium salt, water-soluble phosphate and a template agent into water, stirring and dissolving uniformly, then placing the mixture into a microwave reaction kettle, carrying out microwave-assisted biomimetic mineralization reaction under the stirring state, and cooling after the reaction is finished to obtain an aqueous solution deposited with hydroxyapatite nanowhiskers;
s2, preparing hydroxyapatite nano whisker dispersion liquid: directly treating the hydroxyapatite nanowhisker aqueous solution obtained in the step S1 by using plasma equipment to obtain a hydroxyapatite nanowhisker dispersion liquid;
s3, preparing the polylactic acid nanofiber membrane with uniformly distributed biological electrets: preparing a nanofiber membrane from polylactic acid dissolved in an organic solvent by an electrostatic spinning technology, and applying atomized hydroxyapatite nanowhisker dispersion liquid in the step S2 in the spinning process to obtain the polylactic acid nanofiber membrane with uniformly distributed biological electrets.
5. The method for preparing the long-acting filtering membrane with the biological electret distributed on the surface of the polylactic acid nanofiber according to claim 4, is characterized in that: the water-soluble calcium salt in the step S1 is at least one of calcium chloride, calcium nitrate, calcium acetate and calcium hypochlorite, and the concentration of the water-soluble calcium salt is 0.01 to 2 mol/L; the water-soluble phosphate is at least one of ammonium dihydrogen phosphate, ammonium hydrogen phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, dipotassium hydrogen phosphate and potassium dihydrogen phosphate, and the molar ratio of calcium ions to phosphate ions is 2 to 1; the template agent is at least one of hexadecyl trimethyl ammonium bromide, stearic acid, oleic acid, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and octyl phenyl polyoxyethylene ether, the mass fraction of the template agent in the solution is 0.001 wt% -0.1 wt%, and the template agent can be used as a structure guiding agent to enable hydroxyapatite to grow into rod-shaped one-dimensional nano whiskers along a c axis.
6. The method for preparing the long-acting filtering membrane with the biological electret distributed on the surface of the polylactic acid nanofiber according to claim 4, is characterized in that: the reaction temperature of the microwave-assisted synthesis in the step S1 is 100 to 250 ℃, and the reaction time is 1 to 30 minutes; the diameter of the hydroxyapatite nanowhisker obtained in the step S1 is 1 to 20 nm, and the length-diameter ratio is 5 to 200.
7. The method for preparing the long-acting filtering membrane with the biological electret distributed on the surface of the polylactic acid nanofiber according to claim 4, is characterized in that: and in the step S2, the plasma processing equipment is at least one of a normal pressure jet type, a dielectric barrier discharge type and a rotary normal pressure type, the plasma discharge voltage is 1 to 80 kV, the plasma working gas is at least one of argon, helium, hydrogen, nitrogen and oxygen, the processing temperature is 10 to 50 ℃, and the processing temperature is 10 seconds to 30 minutes.
8. The method for preparing the long-acting filtering membrane with the biological electret distributed on the surface of the polylactic acid nanofiber according to claim 4, is characterized in that: the organic solvent in the step S3 is at least one of dichloromethane, trichloromethane, dimethylformamide, N-methylpyrrolidone, hexafluoroisopropanol, methanol, ethanol, isopropanol and glycerol, and the concentration of polylactic acid in the mixed solution is 0.5-22 wt%; the module voltage of electrostatic spinning is 15 to 60 kV, the receiving voltage is-15 to 0 kV, and the consumption rate of spinning stock solution is 1 to 60 mL/min.
9. The method for preparing the long-acting filtering membrane with the biological electret distributed on the surface of the polylactic acid nanofiber according to claim 4, is characterized in that: the atomization speed of the biological electret in the step S3 is 0.5-50 mL/min, the diameter of the obtained biological electret modified polylactic acid nano fiber is 5-100 nm, the content of the biological electret in the polylactic acid nano fiber is 0.05-30 wt%, and the film thickness of the obtained polylactic acid fiber is 40-800 mu m.
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| CN117535881A (en) * | 2023-11-20 | 2024-02-09 | 北华航天工业学院 | Bio-based nanowire modified nanofiber membrane and preparation method and application thereof |
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