CN103061046A - Method for manufacturing PA6 porous nanofiber composite membrane - Google Patents
Method for manufacturing PA6 porous nanofiber composite membrane Download PDFInfo
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- CN103061046A CN103061046A CN2012105924026A CN201210592402A CN103061046A CN 103061046 A CN103061046 A CN 103061046A CN 2012105924026 A CN2012105924026 A CN 2012105924026A CN 201210592402 A CN201210592402 A CN 201210592402A CN 103061046 A CN103061046 A CN 103061046A
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Abstract
A method for manufacturing a PA6 porous nanofiber composite membrane comprises the following steps: (1) using formic acid and glacial acetic acid to prepare a mixed organic solvent, adding 10-20% by mass of PA6 into the mixed organic solvent, and performing stirring to obtain an even transparent electrospining solvent; (2) feeding the prepared electrospining solvent into an electrospining machine to perform spinning, respectively using propene polymer (PP), polyethylene glycol terephthalate (PET) and polyurethane non-woven fabrics with 30-100cm width as receiving base materials to perform continuous liquid supply and continuous spinning so as to obtain a volumed blank membrane; and (3) performing rolling hot-press molding of the blank membrane at the temperature of 100-120 DEG C, then performing vacuum drying at temperature of 60-80 DEG C for 10-15 hours to remove mixed organic solvent left on the blank membrane, and obtaining the porous nanofiber composite membrane. The method is high in production efficiency and has high specific surface area, porosity rate, mechanical strength, strong adsorptive property, good filter performance and barrier property.
Description
Technical field
The present invention relates to a kind of preparation method of nano-fiber composite film.
Background technology
Filtering material plays an important role in industrial production links such as feedstock purification, air cleaning, water purification and waste discharges.Demand for development filtering material biological, medical, electronic industry has higher filtering accuracy, particularly will less than 1 μ m particle good filter effect be arranged to diameter.The passage of filtering material must match with the size of particle mutually with gap structure, and less fibre diameter and aperture often have higher filter efficiency and filtering accuracy.The most direct method of preparation high-efficiency filtration media is exactly to use the fiber of nano-scale in the filtering material structure.Method of electrostatic spinning is the unique effective method of direct continuous production nanofiber.
The high-voltage electrostatic spinning method be exactly macromolecule polymer solution under the high voltage electrostatic field of several thousand to several ten thousand volts, the surface tension that overcomes solution forms charged jet, follows continuous acceleration, stretches, solvent evaporates finally obtains nano fibrous membrane receiving base material.Utilizing method of electrostatic spinning can access diameter is tens or the nanofiber of a few hundred nano-scale (conventional filter material fibre diameter 1/150), the nano fibrous membrane that forms has higher specific area and porosity, stronger absorption property and good filterability and barrier, be combined with nanometer particle easily, be suitable as very much high performance gas, liquid filtration material.
Summary of the invention
Lower for the preparation method's that overcomes existing tunica fibrosa production efficiency, specific area is less, porosity and mechanical strength is less, absorption property is relatively poor, filterability and barrier are relatively poor deficiency, the invention provides a kind of production efficiency higher, have a preparation method of the PA6 porous nano-fibre composite membrane of higher specific area, porosity and mechanical strength, stronger absorption property, good filterability and barrier.
The technical solution adopted for the present invention to solve the technical problems is:
A kind of preparation method of PA6 porous nano-fibre composite membrane, described preparation method may further comprise the steps:
1), the preparation of Electrospun solution: formic acid and glacial acetic acid form mixed organic solvents, wherein, the mass ratio of formic acid and glacial acetic acid is 3:1 ~ 1:3, the purity of formic acid and glacial acetic acid is all more than or equal to 99%, adding PA6 mixes, the mass percent of PA6 is to stir the Electrospun solution that obtains homogeneous transparent under 10 ~ 20%, 60 ℃ ~ 80 ℃ conditions, and the absolute viscosity of described Electrospun solution is between 600 ~ 2000mPa.S;
2), electrostatic spinning process: will prepare Electrospun solution and send into electrostatic spinning machine and carry out spinning, the process conditions of described spinning are: 20 ~ 30 ℃ of temperature, ambient humidity 20 ~ 40%, spinning cabinet air inlet and capacity 200 ~ 1000m
3/ h, spinning voltage 70 ~ 100KV receives base material hauling speed 0.4 ~ 2m/min;
Respectively with PP, the PET of 30cm ~ 100cm wide cut and polyurethane non-weave non-woven fabrics as receiving base material, carry out continuous liquid supply and continuous spinning, obtain the base film of rolling;
3), post processing: with described base film first by 100 ~ 120 ℃ of rollers hot-forming, again at 60 ℃ ~ 80 ℃ vacuumize 10 ~ 15h, remove mixed organic solvents residual on the described base film after, obtain the porous nano-fibre composite membrane.
Technical conceive of the present invention is: by the macromolecule polymer solution of preparation PA6, with non-weave non-woven fabrics (thickness 20 ~ 150 μ m) as receiving base material, utilize Czech Elmarco NS4S1000U nano fiber electrostatic spinning machine to carry out continuous liquid supply and continuous spinning, obtain the composite membrane of traditional non-weaving cloth and electrostatic spinning nano fiber net, has higher mechanical strength and production efficiency, good uniformity and uniformity.
Nylon 6, namely PA6 is to contain amide group (macromolecular compound HNCO-) on the main chain.Nylon 6 has higher mechanical performance and spinning property, good anti-flammability and self-gravitation, wear-resisting, oil resistant, anti-general organic solvent.Nano fibrous membrane with the PA6 preparation has the functions such as infiltration, ultrafiltration and microfiltration, and there is higher using value in the fields such as its manufacturing at functional air filtering, ultra-pure water, the dirty water decontamination handles and automobile air cleaning systems.
Beneficial effect of the present invention is mainly manifested in: carry out electrostatic spinning under the normal temperature, technique is simple; Simulate countless side by side spinning of syringe needle, as spinning electrode and collecting electrode, realize continuous liquid supply and continuous spinning with steel wire, have than high efficiency and working ability; Prepared nano-fiber composite film has higher specific area, porosity and mechanical strength, stronger absorption property, good filterability and barrier.
The specific embodiment
Below the invention will be further described.
Embodiment 1
A kind of preparation method of PA6 porous nano-fibre composite membrane, described preparation method may further comprise the steps:
4), the preparation of Electrospun solution: formic acid and glacial acetic acid form mixed organic solvents, wherein, the mass ratio of formic acid and glacial acetic acid is 3:1, the purity of formic acid and glacial acetic acid is 99%, adding PA6 mixes, the mass percent of PA6 is to stir the Electrospun solution that obtains homogeneous transparent under 10%, 60 ℃ of condition, and the absolute viscosity of described Electrospun solution is between 600mPa.S;
5), electrostatic spinning process: will prepare Electrospun solution and send into electrostatic spinning machine and carry out spinning, the process conditions of described spinning are: 20 ℃ of temperature, ambient humidity 20%, spinning cabinet air inlet and capacity 200m
3/ h, spinning voltage 70KV receives base material hauling speed 0.4m/min;
Respectively with the PP non-weave non-woven fabrics of 30cm wide cut as receiving base material, carry out continuous liquid supply and continuous spinning, obtain the base film of rolling;
6), post processing: with described base film first by 100 ℃ of rollers hot-forming, again at 60 ℃ of vacuumize 10h, remove mixed organic solvents residual on the described base film after, obtain the porous nano-fibre composite membrane.
In the present embodiment, the electrical conductivity of polymer solution, viscosity characteristics and solvent evaporates performance, with formic acid and glacial acetic acid as mixed solvent, dispose certain density PA6 macromolecule Electrospun solution, as receiving base material, utilize method of electrostatic spinning to prepare the porous nano-fibre composite membrane with PP, PET and polyurethane non-weave non-woven fabrics.PA6 used in the present invention is the Ultramid B24N03 of BASF AG, molecular weight Nw=13000 g/mol.
PA6 macromolecule model Ultramid B24N03(BASF AG among the present invention), the concentration 10-20 wt% of Electrospun liquid, absolute viscosity is between 700 ~ 2000mPa.S, and whole Electrospun solution preparation process is finished in the Agitation Tank of the sealing of 30L.
The PA6 macromolecule is soluble in the formic acid organic solvent among the present invention, and is slightly soluble in the glacial acetic acid organic solvent.Both mixed solvents of the bright employing of we can effectively dissolve on the PA6 polymer basis, utilize the electrical conductivity of glacial acetic acid reduction spinning solution, improve the spinnability of polymer solution.The purity of described formic acid and glacial acetic acid is all more than or equal to 99%, and both mass ratioes are 3:1 ~ 1:3.
As the high-performance filtering material, there is the shortcoming that mechanical strength is low, service life is short in simple electrospun fibers film.The present invention obtains nano-fiber composite film with non-weave non-woven fabrics (thickness 20 ~ 150 μ m) as receiving base material, and nanofiber layer plays main filtering function, and non-woven fabrics base material provides film mechanical strength and structural intergrity.The nano-fiber composite film mechanical strength that the present invention obtains reaches 30 ~ 80MPa, and the thickness 10nm ~ 100nm of nanofiber layer is controlled.
Adopt NDJ-8S viscosimeter (Shanghai exact science instrument company) to measure the absolute viscosity of spinning solution among the present invention; Measure fibre diameter, aperture and the distribution situation thereof of nano-fiber composite film by VEGA 3 LMH type scanning electronic microscope (Czech Republic); Adopt XLW (PC)-500N type Intelligent electronic tensil testing machine (Labthink Instruments Co., Ltd.) to measure the mechanical performance (intensity and chain rupture elongation etc.) of nano fibrous membrane.
Embodiment 2
A kind of preparation method of PA6 porous nano-fibre composite membrane, described preparation method may further comprise the steps:
1) preparation of Electrospun solution: formic acid and glacial acetic acid form mixed organic solvents, wherein, the mass ratio of formic acid and glacial acetic acid is 2:1, the purity of formic acid and glacial acetic acid is 99.5%, adding PA6 mixes, the mass percent of PA6 is to stir the Electrospun solution that obtains homogeneous transparent under 15%, 70 ℃ of condition, and the absolute viscosity of described Electrospun solution is between 1000mPa.S;
2) electrostatic spinning process: will prepare Electrospun solution and send into electrostatic spinning machine and carry out spinning, the process conditions of described spinning are: 25 ℃ of temperature, ambient humidity 30%, spinning cabinet air inlet and capacity 500m
3/ h, spinning voltage 80KV receives base material hauling speed 1m/min;
Respectively with the PET non-weave non-woven fabrics of 50cm wide cut as receiving base material, carry out continuous liquid supply and continuous spinning, obtain the base film of rolling;
3) post processing: with described base film first by 110 ℃ of rollers hot-forming, again at 70 ℃ of vacuumize 12h, remove mixed organic solvents residual on the described base film after, obtain the porous nano-fibre composite membrane.
Other schemes of present embodiment are identical with embodiment 1.
Embodiment 3
A kind of preparation method of PA6 porous nano-fibre composite membrane, described preparation method may further comprise the steps:
1), the preparation of Electrospun solution: formic acid and glacial acetic acid form mixed organic solvents, wherein, the mass ratio of formic acid and glacial acetic acid is 1:3, the purity of formic acid and glacial acetic acid is 99.95%, adding PA6 mixes, the mass percent of PA6 is to stir the Electrospun solution that obtains homogeneous transparent under 20%, 80 ℃ of condition, and the absolute viscosity of described Electrospun solution is between 2000mPa.S;
2), electrostatic spinning process: will prepare Electrospun solution and send into electrostatic spinning machine and carry out spinning, the process conditions of described spinning are: 30 ℃ of temperature, ambient humidity 40%, spinning cabinet air inlet and capacity 1000m
3/ h, spinning voltage 100KV receives base material hauling speed 2m/min;
Respectively with the polyurethane non-weave non-woven fabrics of 100cm wide cut as receiving base material, carry out continuous liquid supply and continuous spinning, obtain the base film of rolling;
3), post processing: with described base film first by 120 ℃ of rollers hot-forming, again at 80 ℃ of vacuumize 15h, remove mixed organic solvents residual on the described base film after, obtain the porous nano-fibre composite membrane.
Other schemes of present embodiment are identical with embodiment 1.
Embodiment 4
In the present embodiment, in the Agitation Tank of 30L, with the 1.0 Ultramid B24N03 of kg PA6(BASF AG, down together) macromolecule directly is dissolved in the middle of formic acid and glacial acetic acid (mass ratio FA:AA=1:2) mixed solvent, be mixed with the solution of concentration 10wt%, 80 ℃ are stirred 5h, obtain the Electrospun solution of transparent and homogeneous.Measuring the solution absolute viscosity is 600 mPa.S.
Electrospun solution is mounted to Czech Elmarco NS4S1000U nano fiber electrostatic spinning machine by reservoir, with the PP non-weave non-woven fabrics (thickness 60 μ m) of 30cm ~ 100cm wide cut as receiving base material, base material hauling speed 0.4 m/min, carry out electrostatic spinning, obtain the nano-fiber composite film of rolling.
Present embodiment mesohigh electrostatic spinning condition satisfies: 25 ± 2 ℃ of environment temperatures, spinning cabinet air inlet and exhaust steam moisture＜40%RH, spinning electrode voltage 60KV, collecting electrode voltage-40KV, receiving range 20 cm, spinning cabinet air inflow 400 m
3/ h, capacity 600 m
3/ h.The post processing of nano-fiber composite film: hot-forming by 110 ℃ of rollers first, again at 75 ℃ of vacuumize 11h, after removing solvent residual on the described film, the mechanical strength of sampling and measuring nano-fiber composite film, and size and distribution situation thereof by scanning electron microscopic observation fibre diameter, aperture.
Other schemes of present embodiment are all identical with embodiment 1.
Embodiment 5
In the present embodiment, in the Agitation Tank of 30L, 1.2kg PA6 macromolecule directly is dissolved in the middle of formic acid and glacial acetic acid (mass ratio FA:AA=1:2) mixed solvent, is mixed with the solution of concentration 12wt%, 80 ℃ are stirred 5h, obtain the Electrospun solution of transparent and homogeneous.Measuring the solution absolute viscosity is 800mPa.S.
Electrospun solution is mounted to Czech Elmarco NS4S1000U nano fiber electrostatic spinning machine by reservoir, with the PP non-weave non-woven fabrics (thickness 60 μ m) of 30cm ~ 100cm wide cut as receiving base material, base material hauling speed 0.4m/min, carry out electrostatic spinning, obtain the nano-fiber composite film of rolling.
Other schemes of present embodiment are all identical with embodiment 1.
Embodiment 6
In the present embodiment, in the Agitation Tank of 30L, 1.4 kg PA6 macromolecules directly are dissolved in the middle of formic acid and glacial acetic acid (mass ratio FA:AA=1:2) mixed solvent, be mixed with the solution of concentration 14wt%, 80 ℃ are stirred 5h, obtain the Electrospun solution of transparent and homogeneous.Measuring the solution absolute viscosity is 1000mPa.S.
Electrospun solution is mounted to Czech Elmarco NS4S1000U nano fiber electrostatic spinning machine by reservoir, with the PP non-weave non-woven fabrics (thickness 60 μ m) of 30cm ~ 100cm wide cut as receiving base material, base material hauling speed 0.4m/min, carry out electrostatic spinning, obtain the nano-fiber composite film of rolling.
Other schemes of present embodiment are all identical with embodiment 1.
Embodiment 7
In the present embodiment, in the mixing agitator of 30L, 1.2 kg PA6 macromolecules directly are dissolved in the middle of formic acid and glacial acetic acid (mass ratio FA:AA=3:1) mixed solvent, be mixed with the solution of concentration 12wt%, 80 ℃ are stirred 5h, obtain the Electrospun solution of transparent and homogeneous.Measuring the solution absolute viscosity is 800mPa.S.
Electrospun solution is mounted to Czech Elmarco NS4S1000U nano fiber electrostatic spinning machine by reservoir, PP nonwoven fabric with 30cm ~ 100cm wide cut non-woven (thickness 60 μ m) is as receiving base material, base material hauling speed 0.4m/min, carry out electrostatic spinning, obtain the nano-fiber composite film of rolling.
Other schemes of present embodiment are all identical with embodiment 1.
Embodiment 8
In the present embodiment, in the Agitation Tank of 30L, 1.2kg PA6 macromolecule directly is dissolved in the middle of formic acid and glacial acetic acid (mass ratio FA:AA=2:1) mixed solvent, is mixed with the solution of concentration 12wt%, 80 ℃ are stirred 5h, obtain the Electrospun solution of transparent and homogeneous.Measuring the solution absolute viscosity is 800mPa.S.
Electrospun solution is mounted to Czech Elmarco NS4S1000U nano fiber electrostatic spinning machine by reservoir, with the PP non-weave non-woven fabrics (thickness 60 μ m) of 30cm ~ 100cm wide cut as receiving base material, base material hauling speed 0.4m/min, carry out electrostatic spinning, obtain the nano-fiber composite film of rolling.
Other schemes of present embodiment are all identical with embodiment 1.
Embodiment 9
In the present embodiment, in the Agitation Tank of 30L, 1.2kg PA6 macromolecule directly is dissolved in the middle of formic acid and glacial acetic acid (mass ratio FA:AA=1:1) mixed solvent, is mixed with the solution of concentration 12wt%, 80 ℃ are stirred 5h, obtain the Electrospun solution of transparent and homogeneous.Measuring the solution absolute viscosity is 800mPa.S.
Electrospun solution is mounted to Czech Elmarco NS4S1000U nano fiber electrostatic spinning machine by reservoir, with the PP non-weave non-woven fabrics (thickness 60 μ m) of 30cm ~ 100cm wide cut as receiving base material, base material hauling speed 0.4m/min, carry out electrostatic spinning, obtain the nano-fiber composite film of rolling.
Other schemes of present embodiment are all identical with embodiment 1.
Embodiment 10
In the present embodiment, in the Agitation Tank of 30L, 1.2kg PA6 macromolecule directly is dissolved in the middle of formic acid and glacial acetic acid (mass ratio FA:AA=1:3) mixed solvent, be mixed with the solution of concentration 12wt%, 80 ℃ are stirred 5h, and the PA6 macromolecule fails fully to be dissolved, and can't carry out spinning.
Other schemes of present embodiment are all identical with embodiment 1.
Embodiment 11
In the present embodiment, in the Agitation Tank of 30L, 1.2kg PA6 macromolecule directly is dissolved in the middle of formic acid and glacial acetic acid (mass ratio FA:AA=1:2) mixed solvent, is mixed with the solution of concentration 12wt%, 80 ℃ are stirred 5h, obtain the Electrospun solution of transparent and homogeneous.Measuring the solution absolute viscosity is 800mPa.S.
Electrospun solution is mounted to Czech Elmarco NS4S1000U nano fiber electrostatic spinning machine by reservoir, PP nonwoven fabric with 30cm ~ 100cm wide cut non-woven (thickness 60 μ m) is as receiving base material, base material hauling speed 1.0m/min, carry out electrostatic spinning, obtain the nano-fiber composite film of rolling.
Other schemes of present embodiment are all identical with embodiment 1.
Embodiment 12
In the present embodiment, in the Agitation Tank of 30L, 1.2kg PA6 macromolecule directly is dissolved in the middle of formic acid and glacial acetic acid (mass ratio FA:AA=1:2) mixed solvent, is mixed with the solution of concentration 12wt%, 80 ℃ are stirred 5h, obtain the Electrospun solution of transparent and homogeneous.Measuring the solution absolute viscosity is 800mPa.S.
Electrospun solution is mounted to Czech Elmarco NS4S1000U nano fiber electrostatic spinning machine by reservoir, with the PP non-weave non-woven fabrics (thickness 60 μ m) of 30cm ~ 100cm wide cut as receiving base material, base material hauling speed 1.6m/min, carry out electrostatic spinning, obtain the nano-fiber composite film of rolling.
Other schemes of present embodiment are all identical with embodiment 1.
Embodiment 13
In the present embodiment, in the Agitation Tank of 30L, 1.2kg PA6 macromolecule directly is dissolved in the middle of formic acid and glacial acetic acid (mass ratio FA:AA=1:2) mixed solvent, is mixed with the solution of concentration 12wt%, 80 ℃ are stirred 5h, obtain the Electrospun solution of transparent and homogeneous.Measuring the solution absolute viscosity is 800mPa.S.
Electrospun solution is mounted to Czech Elmarco NS4S1000U nano fiber electrostatic spinning machine by reservoir, with the PET non-weave non-woven fabrics (thickness 30 μ m) of 30cm ~ 100cm wide cut as receiving base material, base material hauling speed 0.4m/min, carry out electrostatic spinning, obtain the nano-fiber composite film of rolling.
Other schemes of present embodiment are all identical with embodiment 1.
Embodiment 14
In the present embodiment, in the Agitation Tank of 30L, 1.2kg PA6 macromolecule directly is dissolved in the middle of formic acid and glacial acetic acid (mass ratio FA:AA=1:2) mixed solvent, is mixed with the solution of concentration 12wt%, 80 ℃ are stirred 5h, obtain the Electrospun solution of transparent and homogeneous.Measuring the solution absolute viscosity is 800mPa.S.
Electrospun solution is mounted to Czech Elmarco NS4S1000U nano fiber electrostatic spinning machine by fluid reservoir, with the polyurethane PA66 non-weave non-woven fabrics (thickness 90 μ m) of 30cm ~ 100cm wide cut as receiving base material, base material hauling speed 0.4m/min, carry out electrostatic spinning, obtain the nano-fiber composite film of rolling.
Other schemes of present embodiment are all identical with embodiment 1.
Claims (1)
1. the preparation method of a PA6 porous nano-fibre composite membrane, it is characterized in that: described preparation method may further comprise the steps:
1), the preparation of Electrospun solution: formic acid and glacial acetic acid form mixed organic solvents, wherein, the mass ratio of formic acid and glacial acetic acid is 3:1 ~ 1:3, the purity of formic acid and glacial acetic acid is all more than or equal to 99%, adding PA6 mixes, the mass percent of PA6 is to stir the Electrospun solution that obtains homogeneous transparent under 10 ~ 20%, 60 ℃ ~ 80 ℃ conditions, and the absolute viscosity of described Electrospun solution is between 600 ~ 2000mPa.S;
2), electrostatic spinning process: will prepare Electrospun solution and send into electrostatic spinning machine and carry out spinning, the process conditions of described spinning are: 20 ~ 30 ℃ of temperature, ambient humidity 20 ~ 40%, spinning cabinet air inlet and capacity 200 ~ 1000m
3/ h, spinning voltage 70 ~ 100KV receives base material hauling speed 0.4 ~ 2m/min;
Respectively with PP, the PET of 30cm ~ 100cm wide cut and polyurethane non-weave non-woven fabrics as receiving base material, carry out continuous liquid supply and continuous spinning, obtain the base film of rolling;
3), post processing: with described base film first by 100 ~ 120 ℃ of rollers hot-forming, again at 60 ℃ ~ 80 ℃ vacuumize 10 ~ 15h, remove mixed organic solvents residual on the described base film after, obtain the porous nano-fibre composite membrane.
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| CN105903271A (en) * | 2016-03-30 | 2016-08-31 | 南通醋酸纤维有限公司 | Regulable mixed nanostructured fiber composite filtering material and preparation method thereof |
| CN106391127A (en) * | 2016-09-21 | 2017-02-15 | 天津工业大学 | Ag/PA6 (Polyamide 6) dendritic nano-fiber catalyst |
| CN106492767A (en) * | 2016-09-14 | 2017-03-15 | 中国科学院城市环境研究所 | A kind of for Passive sampler in sorbing material and preparation method thereof |
| CN111748909A (en) * | 2020-06-30 | 2020-10-09 | 军事科学院系统工程研究院军需工程技术研究所 | Preparation method and application of bio-based nylon 56 nanofiber membrane |
| CN112226911A (en) * | 2020-09-22 | 2021-01-15 | 上海世龙科技有限公司 | Hydrophilic composite membrane and preparation method thereof |
| CN113875770A (en) * | 2021-09-18 | 2022-01-04 | 美埃(南京)纳米材料有限公司 | Preparation method of nano antibacterial mixed liquor and nano antibacterial filter material |
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| CN105903271A (en) * | 2016-03-30 | 2016-08-31 | 南通醋酸纤维有限公司 | Regulable mixed nanostructured fiber composite filtering material and preparation method thereof |
| CN105903271B (en) * | 2016-03-30 | 2018-07-13 | 南通醋酸纤维有限公司 | Controllable mixing nanostructured fibers composite filter material and preparation method thereof |
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| CN106391127A (en) * | 2016-09-21 | 2017-02-15 | 天津工业大学 | Ag/PA6 (Polyamide 6) dendritic nano-fiber catalyst |
| CN111748909A (en) * | 2020-06-30 | 2020-10-09 | 军事科学院系统工程研究院军需工程技术研究所 | Preparation method and application of bio-based nylon 56 nanofiber membrane |
| CN112226911A (en) * | 2020-09-22 | 2021-01-15 | 上海世龙科技有限公司 | Hydrophilic composite membrane and preparation method thereof |
| CN113875770A (en) * | 2021-09-18 | 2022-01-04 | 美埃(南京)纳米材料有限公司 | Preparation method of nano antibacterial mixed liquor and nano antibacterial filter material |
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Application publication date: 20130424 |