CN113957703A - Beaded nanofiber material and preparation method thereof - Google Patents
Beaded nanofiber material and preparation method thereof Download PDFInfo
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- CN113957703A CN113957703A CN202111213693.9A CN202111213693A CN113957703A CN 113957703 A CN113957703 A CN 113957703A CN 202111213693 A CN202111213693 A CN 202111213693A CN 113957703 A CN113957703 A CN 113957703A
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- 239000002121 nanofiber Substances 0.000 title claims abstract description 90
- 239000000463 material Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 229920000642 polymer Polymers 0.000 claims abstract description 62
- 239000002904 solvent Substances 0.000 claims abstract description 62
- 239000012528 membrane Substances 0.000 claims abstract description 37
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 32
- 239000000835 fiber Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000005191 phase separation Methods 0.000 claims abstract description 21
- 239000011324 bead Substances 0.000 claims abstract description 20
- 239000011148 porous material Substances 0.000 claims abstract description 17
- 238000005345 coagulation Methods 0.000 claims abstract description 16
- 230000015271 coagulation Effects 0.000 claims abstract description 16
- 238000007598 dipping method Methods 0.000 claims abstract description 7
- 239000007791 liquid phase Substances 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 29
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000000758 substrate Substances 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000004952 Polyamide Substances 0.000 claims description 10
- 229920002647 polyamide Polymers 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
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- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- 239000002033 PVDF binder Substances 0.000 claims description 7
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 7
- -1 polytetrafluoroethylene Polymers 0.000 claims description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 7
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- 230000005484 gravity Effects 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 239000004695 Polyether sulfone Substances 0.000 claims description 3
- 239000004697 Polyetherimide Substances 0.000 claims description 3
- 229920002492 poly(sulfone) Polymers 0.000 claims description 3
- 229920006393 polyether sulfone Polymers 0.000 claims description 3
- 229920001601 polyetherimide Polymers 0.000 claims description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 3
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 36
- 239000011259 mixed solution Substances 0.000 description 25
- 238000005470 impregnation Methods 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
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- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
- D06M10/08—Organic compounds
- D06M10/10—Macromolecular compounds
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/22—Polymers or copolymers of halogenated mono-olefins
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/26—Polymers or copolymers of unsaturated carboxylic acids or derivatives thereof
- D06M2101/28—Acrylonitrile; Methacrylonitrile
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/32—Polyesters
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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/34—Polyamides
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Nonwoven Fabrics (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Artificial Filaments (AREA)
Abstract
The invention relates to a beaded nano-fiber material and a preparation method thereof, which comprises the steps of firstly adding a non-solvent into a polymer solution to obtain a microgel polymer solution, then placing an electrostatic spinning fiber membrane into the microgel polymer solution for dipping, taking out the electrostatic spinning fiber membrane and placing the electrostatic spinning fiber membrane into an ultrasonic-assisted non-solvent coagulation bath, and increasing Rayleigh instability in the polymer dipping liquid phase separation process by utilizing ultrasonic waves, thereby preparing the beaded nano-fiber membrane. The average grain diameter of beads in the prepared beaded nanofiber material is 20-1000 nm, the average pore diameter of the material is 200-1000 nm, and the porosity is 80-95%. The method is simple and easy to implement, and the prepared beaded nanofiber has the advantages of multistage coarse structure, large specific surface area, small pore diameter, high porosity and the like, and can remarkably improve the filtering and separating precision and efficiency of the material.
Description
Technical Field
The invention belongs to the technical field of fiber materials, and relates to a beaded nanofiber material and a preparation method thereof.
Background
The beaded nanofiber material has the advantages of fine fiber diameter, multi-stage coarse structure, large specific surface area and the like, and shows wide application prospects in the fields of adsorption separation, bioengineering and the like. A technology for preparing beaded nano-fiber materials by utilizing an electrostatic spinning technology is respectively disclosed in the literature [ drug slow-release performance of electrostatic spinning polylactic acid beaded fibers [ J ]. International textile guide ] and the literature [ Superhydrophic and superoleophilic ceramic surface of pore coated electrospinless and polystylene-zeolite fiber for raw oil-water separation [ J ]. Physics and Chemistry of the Earth, part A/B/C,2016,92:7-13 ]. However, the bead grain size of the beaded nanofiber material prepared by the electrostatic spinning method is in the micron order, and beads with the nanometer grain size are difficult to obtain, so that the beaded nanofiber material has little effect on increasing the roughness of the material and the specific surface area of the material. Patent "a process for preparing beaded nanofibers" (CN103643337B) discloses a technique for preparing beaded nanofibers by electrospinning a solution of inorganic nanoparticles grafted with a polymer, by which a particle size range of < 1000nm can be obtained, but the technique is complicated and the interfacial bonding of the organic and inorganic phases is not controllable. Therefore, it is urgently needed to develop a new method for simply preparing the nanofiber material with the nanometer bead structure.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a beaded nanofiber material and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a preparation method of a beaded nanofiber material comprises the steps of firstly preparing a mixed solution of microgel by using a polymer, a solvent and a non-solvent, then placing a selected electrostatic spinning fiber substrate into the mixed solution for dipping, and then preparing a beaded nanofiber membrane by using an ultrasonic-assisted non-solvent induced phase separation method. The prepared beaded nanofiber takes the electrospun fiber as a base material, and a beaded structure is constructed on the surface of the electrospun fiber by an ultrasonic-assisted non-solvent induced phase separation method.
The reason why the invention takes the electrostatic spinning fiber membrane as the base material is that: (1) the diameter of the electrostatic spinning fiber is in the nanometer level (less than 1000nm), which is beneficial to the low viscosity microgel polymer solution to form a nanometer bead structure on the surface, if the material with the fiber diameter in the micron level or even tens of microns, such as melt-blown or spun-bonded non-woven fabric, is taken as a base material, the bead structure can not be formed because the size of the material is not matched with the size of the microsphere formed on the surface of the microgel polymer solution. (2) The high porosity and the communicated pore structure of the electrostatic spinning fiber membrane are beneficial to mutual diffusion of a solvent and a non-solvent in the ultrasonic-assisted phase separation process.
The reason for using the microgel polymer solution of the present invention is that the microgel polymer solution contains a large amount of nucleated polymer crystallites, which contribute to the formation of a beaded structure during phase separation.
The ultrasonic-assisted non-solvent induced phase separation technology is adopted in the invention because the energy of ultrasonic waves can increase Rayleigh instability in the separation process of the polymer impregnation liquid phase, thereby promoting the polymer impregnation liquid of the microgel to form a bead structure on the surface of the electrospun fiber in the phase separation process.
The polymer is selected from polyacrylonitrile, polyvinylidene fluoride, polysulfone, polyethersulfone, polyamide, polyurethane and polyetherimide, the electrostatic spinning fiber base material is an electrostatic spinning nanofiber membrane, and the preparation of the electrostatic spinning nanofiber membrane is known technology.
The average particle size of beads in the beaded nanofiber material is 20-1000 nm.
As a preferred technical scheme:
in the preparation method of the beaded nano-fiber material, the weight average molecular weight of the polymer is 1 x 104～100×104g/mol, the concentration of the polymer in the microgel polymer solution is 1-5 wt%, and the viscosity of the microgel polymer solution is 200-2000 mPa.s.
In the preparation method of the beaded nano-fiber material, the solvent of the polymer solution is one or more of N, N-dimethylformamide, dimethyl sulfoxide, N-dimethylformamide, N-methylpyrrolidone and formic acid.
In the preparation method of the beaded nano-fiber material, the non-solvent used in the microgel polymer solution is one or more of water, methanol, ethanol, propanol, butanol, isopropanol and acetone, and the amount of the non-solvent used is 0.001 to 0.5 wt%.
In the preparation method of the beaded nano-fiber material, the electrostatic spinning fiber substrate is a polyamide electrostatic spinning nano-fiber membrane, a polytetrafluoroethylene electrostatic spinning nano-fiber membrane, a polyethylene terephthalate electrostatic spinning nano-fiber membrane, a polyvinylidene fluoride electrostatic spinning fiber membrane or a polyacrylonitrile electrostatic spinning nano-fiber membrane. The electrospun fiber substrate is required to be insoluble in the solvent used in the mixed solution.
The preparation method of the beaded nano-fiber material adopts the non-solvent impregnation amount of 5-30 ul cm-2。
According to the preparation method of the beaded nano-fiber material, ultrasonic frequency in ultrasonic-assisted non-solvent induced phase separation is 20-50 kHz, ultrasonic power is 50-200W, the non-solvent is one or more of water, methanol, ethanol, propanol, butanol, isopropanol and acetone or a mixture of the non-solvent and a solvent used by a polymer solution, and the solvent accounts for 0-30 wt% of the specific gravity of a coagulation bath.
The invention also provides the nanofiber material prepared by the method, the structure is a beaded nanofiber structure, the average pore diameter of the material is 200-1000 nm, and the porosity is 80-95%.
The principle of the invention is as follows:
according to the invention, a certain proportion of non-solvent is added into a polymer solution, the non-solvent is utilized to enable a homogeneous polymer solution to generate polymer nucleation growth to form a microgel mixed solution containing a large number of polymer microcrystals, and an ultrasonic technology is assisted in the non-solvent induced phase separation process to further increase Rayleigh instability in the phase separation process of the microgel solution, so that the formation of a bead structure is promoted.
Has the advantages that:
(1) different from the beaded nanofiber material prepared by conventional polymer solution electrostatic spinning, the beaded nanofiber prepared by the method has the average particle size of nanometer (20-1000 nm), and can effectively increase the surface roughness of the material and improve the specific surface area of the material while reducing the pore diameter of a fiber membrane.
(2) Different from the beaded nanofiber prepared by utilizing electrostatic spinning of inorganic nanoparticles grafted with polymers, the beaded nanofiber material prepared by the method disclosed by the invention is simple in preparation process and good in interface compatibility.
Drawings
Fig. 1 is an SEM picture of the beaded nanofiber material prepared in example 1.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
A preparation method of beaded nanofiber material comprises selecting weight average molecular weight of 5 × 104A polymer solution was prepared from g/mol of a polymer (polyacrylonitrile) and a solvent (dimethyl sulfoxide), and 0.001 wt% of a non-solvent (methanol) was added to the solution to obtain a microgel mixed solution having a concentration of 1 wt% and a viscosity of 200 mpa.s. Then, the selected polyamide electrostatic spinning nano-fiber base material is placed into the impregnation amount of 5ul cm-2The mixed solution of (a) was immersed, and after being taken out, it was placed in an ultrasonic-assisted nonsolvent (methanol) coagulation bath having a frequency of 20kHz and a power of 50W to undergo phase separation, thereby preparing a beaded nanofiber membrane, as shown in fig. 1.
The average grain diameter of the beads in the finally prepared beaded nano-fiber material is 50nm, the average pore diameter of the material is 200nm, and the porosity is 80%.
Example 2
A preparation method of beaded nanofiber material comprises selecting materials with weight average molecular weight of 57 × 104g/mol of polymer (polyvinylidene fluoride) and solvent (N, N-dimethylformamide) to prepare a polymer solution, and 0.01 wt% of non-solvent (water) is added to the solution to obtain a microgel mixed solution with the concentration of 2 wt% and the viscosity of 800 mPa.s. Then, the selected polytetrafluoroethylene electrostatic spinning nanofiber substrate is placed in an impregnation amount of 10ul cm-2Mixed solution of (2)Dipping in the solution, taking out, placing the solution in a non-solvent (mixture of water and N, N-dimethylformamide) coagulation bath assisted by ultrasonic waves with the frequency of 20kHz and the power of 100W for phase separation, wherein the N, N-dimethylformamide accounts for 2 wt% of the specific gravity of the coagulation bath, and preparing the beaded nano fiber membrane.
The average grain diameter of the beads in the finally prepared beaded nanofiber material is 50nm, the hydrophobic angle of the filter membrane is 150 degrees, the rolling angle is 3 degrees, the average pore diameter of the filter membrane material is 300nm, and the porosity is 85 percent.
Example 3
A preparation method of beaded nanofiber material comprises selecting weight average molecular weight of 20 × 104A polymer solution was prepared from g/mol of polymer (polysulfone) and solvent (N, N-dimethylformamide), and 0.15 wt% of non-solvent (ethanol) was added to the solution to obtain a microgel mixed solution having a concentration of 3 wt% and a viscosity of 800 mpa.s. Then, the selected polyethylene glycol terephthalate electrostatic spinning nano-fiber substrate is placed into an impregnation amount of 15ul cm-2The mixed solution is soaked, and after being taken out, the mixed solution is placed in a non-solvent (ethanol) coagulation bath with the frequency of 30kHz and the power of 120W for phase separation, and a beaded nano fiber membrane is prepared.
The average grain diameter of the beads in the finally prepared beaded nano-fiber material is 1000nm, the average pore diameter of the material is 600nm, and the porosity is 90%.
Example 4
A preparation method of beaded nanofiber material comprises selecting weight average molecular weight of 30 × 104A polymer solution was prepared from g/mol of a polymer (polyethersulfone) and a solvent (N-methylpyrrolidone), and 0.2 wt% of a non-solvent (water) was added to the solution to obtain a microgel mixed solution having a concentration of 2 wt% and a viscosity of 1000 mpa.s. Then the selected polyamide electrospun fiber substrate was placed in an impregnation amount of 25ul cm-2Is immersed in the mixed solution of (a) and is taken out and then is placed in an ultrasonic-assisted non-solvent (a mixture of water and propanol) coagulation bath with the frequency of 30kHz and the power of 200W for phase separation, wherein the amount of the propanol accounts for 20 wt% of the specific gravity of the coagulation bath, and a beaded nano-fiber membrane is prepared.
The average grain diameter of the beads in the finally prepared beaded nano-fiber material is 300nm, the average pore diameter of the material is 300nm, and the porosity is 93%.
Example 5
A preparation method of beaded nanofiber material comprises selecting weight average molecular weight of 100 × 104g/mol of polymer (polyetherimide) and solvent (N, N-dimethylformamide, dimethyl sulfoxide) to prepare a polymer solution, wherein the ratio of the N, N-dimethylformamide to the dimethyl sulfoxide is 3/7, and 0.005 wt% of non-solvent (water) is added to the solution to obtain a microgel mixed solution with the concentration of 1 wt% and the viscosity of 2000 mPa.s. Then, the selected polyamide electrostatic spinning nano-fiber substrate is placed into the impregnation amount of 20ul cm-2The mixed solution of (a) was immersed, and after being taken out, it was placed in a non-solvent (water) coagulation bath assisted by ultrasonic waves at a frequency of 50kHz and a power of 150W to undergo phase separation, thereby preparing a beaded nanofiber membrane.
The average grain diameter of the beads in the finally prepared beaded nano-fiber material is 500nm, the average pore diameter of the material is 350nm, and the porosity is 85%.
Example 6
A preparation method of beaded nanofiber material comprises selecting weight average molecular weight of 20 × 104g/mol of polymer (polyurethane) and solvent (N, N-dimethylacetamide and N-methylpyrrolidone) to prepare a polymer solution, wherein the ratio of N, N-dimethylacetamide to N-methylpyrrolidone is 5/5, 0.3 wt% of non-solvent (water) is added to the solution to obtain a microgel mixed solution having a concentration of 2 wt% and a viscosity of 1200 mPa.s. Then, the selected polytetrafluoroethylene electrostatic spinning nanofiber substrate is placed in an impregnation amount of 15ul cm-2The mixed solution of (a) was immersed, and after being taken out, it was placed in a non-solvent (water) coagulation bath assisted by ultrasonic waves having a frequency of 40kHz and a power of 125W to undergo phase separation, thereby preparing a beaded nanofiber membrane.
The average grain diameter of the beads in the finally prepared beaded nano-fiber material is 700nm, the average pore diameter of the material is 600nm, and the porosity is 89%.
Example 7
A preparation method of beaded nanofiber material comprises selecting weight average molecular weight of 9 × 104A polymer solution was prepared from g/mol of a polymer (polyacrylonitrile) and a solvent (dimethyl sulfoxide), and 0.003 wt% of a non-solvent (methanol) was added to the solution to obtain a microgel mixed solution having a concentration of 1.5 wt% and a viscosity of 800 mpa.s. Then, the selected polyethylene terephthalate electrospun nanofiber membrane substrate was placed in an impregnation amount of 30ul cm-2The mixed solution of (a) was immersed, and after being taken out, it was placed in a non-solvent (water) coagulation bath assisted by ultrasonic waves at a frequency of 50kHz and a power of 100W to undergo phase separation, thereby preparing a beaded nanofiber membrane.
The average grain diameter of the beads in the finally prepared beaded nano-fiber material is 600nm, the average pore diameter of the material is 1000nm, and the porosity is 95%.
Example 8
A preparation method of beaded nanofiber material comprises selecting weight average molecular weight of 1.8 × 104g/mol of a polymer (polyamide) and a solvent (formic acid) to prepare a polymer solution, and 0.002 wt% of a non-solvent (water) was added to the solution to obtain a microgel mixed solution having a concentration of 1.5 wt% and a viscosity of 300 mpa.s. Then placing the selected polyvinylidene fluoride electrostatic spinning nano-fiber substrate into the dipping quantity of 30ul cm-2The mixed solution of (a) was immersed, and after being taken out, it was placed in a non-solvent (water) coagulation bath assisted by ultrasonic waves at a frequency of 50kHz and a power of 100W to undergo phase separation, thereby preparing a beaded nanofiber membrane.
The average grain diameter of the beads in the finally prepared beaded nano-fiber material is 400nm, the average pore diameter of the material is 500nm, and the porosity is 90%.
Example 9
A preparation method of beaded nanofiber material comprises selecting weight average molecular weight of 1 × 104A polymer solution was prepared from g/mol of a polymer (polyamide) and a solvent (formic acid), and 0.003 wt% of a non-solvent (methanol) was added to the solution to obtain a microgel mixed solution having a concentration of 3 wt% and a viscosity of 700 mpa.s. Then, the selected polyacrylonitrile electrostatic spinning fiber substrate is placed in an impregnation amount of 25ul cm-2Soaking in the mixed solution of (1), and collectingAfter the filtration, the membrane was placed in a non-solvent (water) coagulation bath assisted by ultrasonic waves with a frequency of 30kHz and a power of 200W for phase separation to prepare a beaded nanofiber membrane.
The average grain diameter of the beads in the finally prepared beaded nano-fiber material is 500nm, the average pore diameter of the material is 600nm, and the porosity is 92%.
Example 10
A preparation method of beaded nanofiber material comprises selecting weight average molecular weight of 68 × 104Preparing a polymer solution from g/mol of polymer (polyvinylidene fluoride) and a solvent (N, N-dimethylformamide), and adding 0.1 wt% of a non-solvent (water) to the solution to obtain a microgel mixed solution with the concentration of 2 wt% and the viscosity of 1500 mPa.s. Then, the selected polyamide electrostatic spinning nano-fiber substrate is placed in an impregnation amount of 30ul cm-2The mixed solution of (a) was immersed, and after being taken out, it was placed in a non-solvent (water) coagulation bath assisted by ultrasonic waves at a frequency of 50kHz and a power of 200W to undergo phase separation, thereby preparing a beaded nanofiber membrane.
The average grain diameter of the beads in the finally prepared beaded nano-fiber material is 400nm, the average pore diameter of the material is 200nm, and the porosity is 93%.
Claims (10)
1. A preparation method of a beaded nanofiber material is characterized by comprising the following steps: firstly, selecting a polymer and a solvent, adding a non-solvent to obtain a microgel polymer solution, then placing the electrostatic spinning fiber membrane into the microgel polymer solution for dipping, taking out the microgel polymer solution, placing the microgel polymer solution into a non-solvent coagulation bath assisted by ultrasonic waves, and increasing Rayleigh instability in the separation process of a polymer dipping liquid phase by using the ultrasonic waves, thereby preparing the beaded nanofiber membrane.
2. The method for preparing the beaded nano fiber according to claim 1, wherein the polymer is selected from polyacrylonitrile, polyvinylidene fluoride, polysulfone, polyethersulfone, polyamide, polyetherimide; the electrostatic spinning fiber substrate is an electrostatic spinning nanofiber membrane.
3. The preparation method of the beaded nanofiber as claimed in claim 1, wherein the beaded nanofiber has a bead average particle size of 20-1000 nm.
4. The method of claim 1, wherein the polymer has a weight average molecular weight of 1 x 104～100×104g/mol, the concentration of the polymer in the microgel polymer solution is 1-5 wt%, and the viscosity of the microgel polymer solution is 200-2000 mPa.s.
5. The method as claimed in claim 2, wherein the solvent of the polymer solution is one or more selected from the group consisting of N, N-dimethylformamide, dimethylsulfoxide, N-dimethylformamide, N-methylpyrrolidone, and formic acid.
6. The method as claimed in claim 5, wherein the non-solvent used in the microgel polymer solution is one or more of water, methanol, ethanol, propanol, butanol, isopropanol, and acetone, and the amount of the non-solvent used is 0.001-0.5 wt%.
7. The method for preparing beaded nano-fiber material according to claim 6, wherein the electrospun fiber substrate is selected from the group consisting of polyamide electrospun nanofiber membrane, polytetrafluoroethylene electrospun nanofiber membrane, polyethylene terephthalate electrospun nanofiber membrane, polyvinylidene fluoride electrospun nanofiber membrane, and polyacrylonitrile electrospun nanofiber membrane.
8. The method as claimed in claim 7, wherein the microgel polymer solution is impregnated into the electrospun fiber substrate in an amount of 5 to 30ul cm-2。
9. The method for preparing beaded nano-fibers according to claim 1, wherein ultrasonic frequency for ultrasonic-assisted non-solvent induced phase separation is 20 to 50kHz, ultrasonic power is 50 to 200W, the non-solvent is one or more of water, methanol, ethanol, propanol, butanol, isopropanol and acetone or a mixture of the non-solvent and a solvent used in a polymer solution, and the amount of the solvent is 0 to 30 wt% of the specific gravity of the coagulation bath.
10. The beaded nano-fiber material produced by the method of any one of claims 1 to 9, characterized by: the average pore diameter of the material is 200-1000 nm, and the porosity is 80-95%.
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