Polymer-based film, preparation method therefor, and use thereof
A polymer film has a loofah-like structure. It has a fibrous framework structure formed by three-dimensional interwoven and interconnected polymer fibers and a three-dimensional interconnected network pore structure distributed in the fibrous framework structure. The polymer is an organic polymer and the fibrous framework structure is integrally formed by the polymer. The film has a volume porosity of from 50% to 95%. The film is obtained by means of a combination method for atomization pretreatment and non-solvent phase separation. The film can be used in the fields of gas filtration, liquid filtration, oil-water separation, adsorption materials, catalysis, pharmaceutical sustained release materials, anti-adhesion coatings, oil delivery and oil spill interception.
1. A membrane comprising:
a fiber skeletal structure of three-dimensionally interwoven and interconnected polymer fibers, and nano-scale protrusions which are distributed on and integrally formed with the fiber skeletal structure,
wherein:
the fiber skeletal structure and the nano-scale protrusions comprise a first polymer and a second polymer,
the first polymer is at least one selected from the group consisting of polysulfone, polyethersulfone, sulfonated polyethersulfone, polyacrylonitrile, cellulose acetate, polyvinylidene fluoride, polyimide, acrylonitrile-styrene copolymers, polyvinylidene fluoride modified by acrylic acid grafting, sulfonated polysulfone, maleic anhydride-grafted polysulfone, sulfonated polyethersulfone, and acrylic acid-grafted polyacrylonitrile, and
the second polymer is at least one selected from the group consisting of chitosan, polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol, and polyoxyethylene polyoxypropylene ether block copolymer;
and
wherein:
a three-dimensionally interpenetrating network pore structure is distributed in the fiber skeletal structure, an average pore size of the pores is in a range of 0.1 μm to 10 μm,
a size of protrusions is in the range of from 20 to 400 nm, and
a volume porosity of the membrane is 50%-95%.
2. The membrane according to claim 1 , wherein the volume porosity of the membrane is 65% to 95%.
3. The membrane according to claim 1 , wherein the average pore size of the pores is from 0.1 to 5 μm.
4. The membrane according to claim 1 , wherein the average distance between two adjacent connection points in the thickness direction in the fiber skeletal structure of the membrane is smaller than the average distance between two adjacent connection points in the surface direction.
5. The membrane according to claim 1 , wherein a cross-section of the membrane has three-dimensionally interpenetrating network pores distributed along a thickness direction of the membrane and has substantially no other types of pores.
6. The membrane according to claim 1 , wherein
a cross-sectional diameter of a single polymer fiber between two connection points in the fiber skeletal structure of the membrane is less than or equal to 2 μm; and/or
a length of a single polymer fiber between two connection points in the fiber skeletal structure of the membrane is less than 10 μm.
7. The membrane according to claim 1 , wherein each of the polymer fibers has an inner cavity.
8. The membrane according to claim 1 , wherein the surface of the membrane has micro/sub-micron sized recess structures, with loofah sponge-like structures distributed on or around or among the recess structures.
9. The membrane according to claim 1 , wherein, in the membrane, a weight ratio of the first polymer to the second polymer is 1:(0.01 to 5).
10. The membrane according to claim 1 , wherein the membrane has a micro-nano composite network structure comprising at least two hydrophilic polymers, and the membrane is super-hydrophilic and super-lipophilic in air.
11. The membrane according to claim 1 , wherein the membrane has a micro-nano composite network structure comprising at least two hydrophobic polymers, and the membrane is super-hydrophobic in air.
12. The membrane according to claim 1 , wherein the membrane further comprises additives selected from inorganic nanoparticles and inorganic salt porogens.
13. The membrane according to claim 1 , wherein the membrane comprises a support layer.
14. A method for preparing a membrane, comprising:
1) dissolving at least a first polymer and a second polymer in a good solvent to form a membrane casting solution;
2) applying the membrane casting solution in the form of a film, exposing the film to a bath of atomized droplets for a period of time, wherein the atomized droplets are droplets of a first poor solvent for the first polymer; and
3) immersing the film obtained from step 2) in a solidification bath to obtain the membrane, wherein the solidification bath comprises a second poor solvent for the first polymer,
wherein the first polymer is at least one selected from the group consisting of polyvinyl chloride, polysulfone, polyethersulfone, sulfonated polyethersulfone, polyacrylonitrile, cellulose acetate, polyvinylidene fluoride, polyimide, acrylonitrile-styrene copolymers, polyvinylidene fluoride modified by acrylic acid grafting, sulfonated polysulfone, maleic anhydride-grafted polysulfone, sulfonated polyethersulfone, and acrylic acid-grafted polyacrylonitrile, and
the second polymer is at least one selected from the group consisting of chitosan, polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol, and polyoxyethylene polyoxypropylene ether block copolymer,
wherein the good solvent is selected from the group consisting of N,N-dimethylformamide, N-methylpyrrolidone, N,N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, dioxane, acetonitrile, acetone, chloroform, toluene, benzene, hexane, octane, tetramethyl sulfoxide, and mixtures thereof, and
the first and the second poor solvents for the first polymer are independently selected from the group consisting of water, ethanol, ethylene glycol, a mixed solvent containing water, and a solution containing a salt, an acid or a base; and
wherein the resulting membrane comprises:
a fiber skeletal structure of three-dimensionally interwoven and interconnected polymer fibers,
pores distributed in the fiber skeletal structure having an average pore size in a range of 0.1 μm to 10 μm, and
nano-scale protrusions distributed on the fiber skeletal structure having a size in the range of from 20 to 400 nm, and
a volume porosity of the membrane is 50%-95%.
15. The method according to claim 14 , wherein the bath of atomized droplets is generated by a method selected from the group consisting of pressure atomization, rotary disk atomization, high-pressure airflow atomization, sonic atomization, and ultrasonic wave atomization.
16. The method according to claim 14 , wherein:
in step 2), the size of the droplets in the droplet bath is 1 to 50 μm; and/or in step 2), the period of time is 1 s to 20 min.
17. The method according to claim 14 , wherein step 2) is carried out in an ambient humidity of greater than or equal to 40% at room temperature.
18. The method according to claim 14 , wherein step 2) is carried out in an ambient humidity of less than 40% at room temperature, and the membrane has micro/sub-micron sized recess structures.
19. The method according to claim 14 , wherein:
in step 1), a total concentration of the polymers in the membrane casting solution is 6 to 30 wt %.
20. The method according to claim 15 , wherein the membrane casting solution is uniformly coated on a support layer selected from a fabric.
21. A functional material comprising a membrane according to claim 1 , wherein the functional material is used for the fields of gas filtration, liquid filtration, oil-water separation, adsorption materials, catalysis, pharmaceutical sustained release materials, anti-adhesion coatings, oil delivery or oil spill interception.
22. The membrane according to claim 8 , wherein the recess structure has a size of 0.5 to 10 μm.
23. The membrane according to claim 10 , wherein the membrane has a contact angle to both water and oil in air of less than 10°, and a contact angle to oil under water of greater than 135°.
24. The membrane according to claim 11 , wherein the membrane has a contact angle to water in air of greater than 130°, and a contact angle to oil under water of smaller than 10°.
25. The membrane according to claim 12 , wherein the inorganic nanoparticles are selected from the group consisting of MnO 2 , SiO 2 , and ZnO; and the inorganic salt porogens are selected from the group consisting of LiCl, ZnCl 2 , MgCl 2 , and LiBr.
26. The method according to claim 14 , wherein in step 2), the thickness of the film as applied is in the range of from 50 to 500 μm.
27. The method according to claim 20 , wherein the support layer is a nonwoven fabric.
28. The method according to claim 20 , wherein the method is a roll-to-roll continuous process.
29. The functional material according to claim 21 , wherein the functional material is an oil-water separation membrane or a microfiltration membrane.