Method for preparing aromatic polyamide porous membrane and aromatic polyamide porous membrane prepared thereby
The present invention provides a method for preparing an aromatic polyamide porous membrane and an aromatic polyamide porous membrane prepared by the above method. The method for preparing an aromatic polyamide porous membrane includes the following steps: mixing an ionic liquid with an aromatic polyamide into a solvent to form a mixed solution; the mixed solution forming a membrane in a coagulation bath; and extracting with an extractant to remove the solvent and the ionic liquid from the membrane to yield a porous membrane. In the method of the present invention, the application of the ionic liquid would greatly reduce the application of additives; further, the ionic liquid has a high stability and is easy to be separated from other solvents and be recycled, which assures the safety during the usage and recycle thereof.
1. A method for preparing an aromatic polyamide porous membrane, comprising the following steps:
mixing an ionic liquid with an aromatic polyamide into a solvent to form a mixed solution;
the mixed solution forming a membrane in a coagulation bath; and
extracting with an extractant to remove the solvent and the ionic liquid from the membrane to yield a porous membrane;
wherein the coagulation bath comprises a first component; and the first component is dichloromethane, the coagulation bath further comprises a second component that is at least one selected from the group consisting of N-methyl pyrrolidone, N,N-dimethyl acetamide, N,N-dimethyl formamide, dimethyl sulfoxide and triethyl phosphate, and a mass fraction of dichloromethane in the coagulation bath is 5-99.9%, 20-60%, or 30-50%; and a mass ratio of the ionic liquid to the aromatic polyamide is between 1:1 and 8:1, or between 1:1 and 6:1; or between 2:1 and 5:1; a temperature of the coagulation bath is 0-80° C. or 20-60° C., and a time for the mixed solution to form a membrane in the coagulation bath is 5-300 seconds or 10-200 seconds.
2. The method of claim 1 , wherein the ionic liquid is at least one selected from the group consisting of quaternary ammonium salt, quaternary phosphonium salt, imidazolium onium salt, pyridinium onium salt, piperidinium salt and pyrrolidine salt; and/or the aromatic polyamide is at least one selected from the group consisting of poly(p-phenylene terephthalamide), poly(m-phenylene isophthalamide), poly(p-benzamide) and polysulfone amide.
3. The method of claim 1 , wherein mixing an ionic liquid with aromatic polyamide into a solvent to form a mixed solution is implemented by one of the following methods:
1) mixing an ionic liquid with a first solvent to form an ionic liquid solution; mixing an aromatic polyamide with a second solvent to form an aromatic polyamide solution; and mixing the ionic liquid solution with the aromatic polyamide solution to obtain the mixed solution; or
2) mixing an ionic liquid with a first solvent to form an ionic liquid solution; forming an aromatic polyamide solution by polymerization, wherein a second solvent is applied in the polymerization; and mixing the ionic liquid solution with the aromatic polyamide solution to obtain the mixed solution; or
3) mixing an ionic liquid, an aromatic polyamide and a third solvent to obtain the mixed solution.
4. The method of claim 3 , wherein the aromatic polyamide is aromatic polyamide fiber.
5. The method of claim 3 , wherein the first solvent is at least one selected from the group consisting of water, ethanol, propanol, isopropanol, glycerol, tetrahydrofuran, pyridine, dichloromethane, trichloromethane, ethyl acetate, N,N-dimethyl formamide, N,N-dimethyl acetamide, N-methyl pyrrolidone and polyethylene glycol.
6. The method of claim 3 , wherein the second solvent is at least one selected from the following: N-methyl pyrrolidone, N,N-dimethyl acetamide, N,N-dimethyl formamide, dimethyl sulfoxide and tri-ethyl phosphate.
7. The method of claim 3 , wherein a mass ratio of the first solvent to the ionic liquid is between 0.05:1 and 0.8:1, or between 0.1:1 and 0.5:1.
8. The method of claim 3 , wherein a mass ratio of the second solvent to the aromatic polyamide is between 2:1 and 10:1, or between 3:1 and 8:1.
9. The method of claim 3 , wherein the third solvent is at least one selected from the following: N-methyl pyrrolidone, N,N-dimethyl acetamide, N,N-dimethyl formamide and dimethyl sulfoxide.
10. The method of claim 3 , wherein a mass fraction of the third solvent in the mixed solution is 20-80%, or 40-70%.
11. The method of claim 1 , wherein the extractant is at least one selected from water, dichloromethane, trichloromethane and ethanol; and/or a temperature of the extractant is 20-100° C. or 30-80° C.
12. The method of claim 1 , comprising: mixing an ionic liquid and an aromatic polyamide into a solvent to form a mixed solution; the mixed solution outflowing through a slit to form a membrane in a coagulation bath; extracting the membrane with an extractant to remove the ionic liquid and the solvent in the extraction tank and forming a porous membrane; and drying the porous membrane to yield an aromatic polyamide porous membrane.
13. The method of claim 12 , wherein the slit is formed by a scraper or an extrusion die-head.
14. The method of claim 12 , wherein the drying is infra-red drying and/or air-blow drying; and/or a drying temperature is 50-150° C. or 80-120° C.
15. An aromatic polyamide porous membrane prepared by a method as described in claim 1 .
16. A lithium ion secondary battery, comprising the aromatic polyamide porous membrane of claim 15 .