CN113529272B - Polyimide nanofiber membrane with carboxyl functional elements on surface and preparation method thereof - Google Patents
Polyimide nanofiber membrane with carboxyl functional elements on surface and preparation method thereof Download PDFInfo
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- D04H1/4334—Polyamides
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- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
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- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/74—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polycondensates of cyclic compounds, e.g. polyimides, polybenzimidazoles
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- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
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- D06M11/58—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides
- D06M11/59—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides with ammonia; with complexes of organic amines with inorganic substances
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Abstract
The polyimide nanofiber membrane with carboxyl functional motifs on the surface is synthesized into polyamide acid containing carboxyl functional motifs through condensation polymerization, then the polyamide acid nanofiber membrane is prepared through an electrostatic spinning method, polyamide acid nanofiber membranes with different cyclization degrees are obtained through pretreatment at different temperatures, then ammonia water induction, deionized water soaking and acidification treatment are sequentially carried out, the carboxyl functional motifs are induced to the surface, and finally the fiber membrane is completely cyclized through high-temperature heat treatment, so that the polyimide nanofiber membrane with the surface containing the carboxylic acid motifs is obtained. The preparation method can lead carboxyl functional elements in polyimide to be positioned on the surface of polyimide nanofiber in a large quantity, realizes surface carboxyl functionalization, has simple implementation process, is easy to flow and has wide application prospect.
Description
Technical Field
The invention belongs to the technical field of polyimide fiber membranes, and relates to a polyimide nanofiber membrane with carboxyl functional elements on the surface.
Background
The electrostatic spinning is a method for continuously preparing polymer nanofibers, and the nanofiber membrane prepared by the method has the advantages of high specific surface area, large porosity, good air permeability and the like. The main process of electrostatic spinning is to apply a certain voltage to the needle of spinning solution to form a taylor cone of polymer solution, gradually increase the voltage to destroy the surface tension of the polymer, and finally form stable jet flow to spray on the receiving substrate. In recent years, with the wide application of nano materials, the research on electrostatic spinning is continuously and deeply developed, and the application of the technology in various fields is promoted. At present, the composite material plays a very important role in energy application, reinforced composite materials, filter materials, electronic sensors and biological tissue engineering.
Polyimide is a novel high-performance polymer material, the molecular structure of polyimide can be designed, and a stable imide ring structure exists, so that the polyimide is endowed with outstanding thermal stability, chemical stability and excellent mechanical properties. The polyimide nanofiber membrane prepared by using the electrostatic spinning technology not only has extremely high specific surface area, but also has good chemical stability and thermal stability. In recent years, development of novel polyimide nanofibers with surface functionalization becomes a hot spot of current research, and preparation of polyimide nanofiber membranes containing functional groups becomes a common method by selecting dianhydride and diamine monomers with special functional groups through molecular structure design. However, in the high-temperature cyclization process, a large number of active functional groups are easily arranged in the polyimide nanofiber instead of on the surface of the fiber, and thus the surface functionalization of the polyimide fiber cannot be truly realized.
The method comprises the steps of preparing a polyamide acid solution by solution condensation polymerization of any polybasic acid anhydride and polybasic amine monomer containing carboxyl functional groups, preparing a nanofiber membrane by electrostatic spinning, properly heat-treating to obtain a partially cyclized polyamide acid nanofiber membrane, and finally inducing the carboxylic acid moieties to the surface of polyimide fiber successfully by alkali liquor induction and cyclizing again, thereby improving the carboxylic acid moiety content on the surface of the fiber.
Disclosure of Invention
The invention aims to provide a polyimide nanofiber membrane with carboxyl functional primitives on the surface, which successfully arranges carboxyl on the surface of a fiber by ammonia water induction on the fiber membrane, so that the number of the carboxyl functional primitives on the surface of the fiber is increased, and the surface functionalization is realized. Meanwhile, the nanofiber membrane still maintains higher thermal stability and chemical stability.
A polyimide nanofiber membrane with carboxyl functional elements on the surface is characterized in that the diameter of nanofibers is 50-700 nm, the thickness of the fiber membrane is 5-100 um, and carboxyl accounts for 0.5-10 wt% of the total content of the fiber membrane.
Further, the diameter of the nanofiber is 50-600 nm, the thickness of the fiber film is 15-80 um, the carboxyl content accounts for 0.5-8 wt% of the whole fiber film,
further, the polyimide nanofiber membrane with carboxyl functional units on the surface has the tensile strength of 10-50MPa, and the porosity of the fiber membrane is 50-95%.
Wherein at least one of the polybasic acid anhydride and the polybasic amine monomer contains carboxyl functional motifs; preferably a polybasic acid anhydride and a polyamine containing carboxyl functional moieties; the content of the polyamine containing carboxyl functional units in the polyamine monomer is 2-40 mol%.
A preparation method of a polyimide nanofiber membrane with carboxyl functional motifs on the surface comprises the following steps:
a: synthesizing a polyamic acid solution containing carboxyl functional motifs by a solution polycondensation method, and preparing a polyamic acid nanofiber membrane containing the carboxyl functional motifs by electrostatic spinning;
b: performing heat treatment on the polyamic acid nanofiber membrane obtained in the step A to obtain a partially cyclized polyamic acid nanofiber membrane;
c: placing the partially cyclized polyamide acid nanofiber membrane obtained in the step B into a dilute ammonia water solution with the concentration of 0.005-0.025 wt% for treatment for 6 s-5 min;
d: immersing the polyamide acid nanofiber membrane treated in the step C into deionized water for standing for 0.5-12 h;
e: placing the polyamide acid nanofiber membrane treated in the step D into an acid solution with the concentration of 0.3-1 wt% to acidify for 10 min-5 h;
f: and E, performing heat treatment on the polyamide acid nanofiber membrane treated in the step E to obtain the polyimide nanofiber membrane with carboxyl functional elements on the surface of the polyimide nanofiber.
Wherein, the polyamide acid solution containing carboxyl functional units in the step A is prepared by solution condensation polymerization of any polybasic acid anhydride or polyamine monomer containing carboxyl functional units, wherein at least one monomer of the polybasic acid anhydride and the polyamine monomer contains carboxyl functional units; preferably a polybasic acid anhydride and a polyamine containing carboxyl functional moieties; the content of the polyamine containing carboxyl functional units in the polyamine monomer is 2-40 mol%.
Wherein the heat treatment temperature in the step B is 120-350 ℃ and the heat preservation time is 0.5-4h.
Wherein the concentration of the dilute ammonia water in the step C is 0.006-0.023 wt% and the treatment time is 8 s-3 min; the complex quaternization of carboxyl and ammonia occurs by treatment in dilute ammonia solution, and further, deionized water can be used for washing to neutrality after treatment.
Wherein the deionized water temperature in the step D is 20-55 ℃, and the standing time is 0.6-10 h; the movement of the molecular chain segments and the induction arrangement of the functional primitives to the surface occur in the standing process.
Wherein the concentration of the acid solution in the step E is 0.4-0.9 wt% and the acidification time is 15 min-4 h; the acid is preferably acetic acid; further, after acidification, deionized water is used for cleaning to be neutral, and the mixture is naturally dried.
Wherein the dilute aqueous ammonia solution, water and acid solution in steps C-E are used in excess.
Wherein, the heat treatment conditions in the step F are as follows: heating to 250-350 deg.c, preferably 280-320 deg.c, maintaining for 0.5-4 hr and maintaining for 1-2 hr.
Compared with the prior art, the method has the following excellent effects:
1. the method provided by the invention is simple and convenient to operate, easy to repeat and controllable in conditions, improves the content of carboxylic acid elements on the surface of the fiber membrane by an induction method, and realizes carboxyl functionalization on the surface of the polyimide nanofiber.
2. The method provided by the invention can enable the carboxyl in the polyimide to be arranged on the surface of the fiber in a large amount, greatly improves the possibility and efficiency of further reaction of carboxyl functional groups, and the polyimide nanofiber membrane prepared by the reaction of the carboxyl and containing other functional elements on the surface can be used as a novel functional polyimide material.
3. The polyimide nanofiber membrane with the surface containing functional primitives prepared by the invention has the advantages of enhanced hydrophilicity, micro-crosslinking structure after being treated by ammonia water, high porosity, excellent chemical stability and thermal dimensional stability of the polyimide nanofiber membrane are maintained, and meanwhile, the mechanical property of the fiber membrane is greatly improved.
Drawings
FIG. 1a is a scanning electron microscope image of a polyimide nanofiber membrane prepared according to example 1, with a surface carboxyl group containing polyimide, magnification of 50000 times
FIG. 1b is a total reflection infrared spectrum of a polyimide nanofiber membrane prepared according to example 1 and having carboxyl groups on the surface
FIG. 2a is a scanning electron microscope image of a polyimide nanofiber membrane prepared according to example 2, with a surface carboxyl group containing polyimide, magnification of 50000 times
FIG. 2b is a total reflection infrared spectrum of a polyimide nanofiber membrane prepared according to example 2 and having carboxyl groups on the surface
FIG. 3a is a scanning electron microscope image of a polyimide nanofiber membrane prepared according to example 3, with a surface carboxyl group containing polyimide, magnification of 50000 times
FIG. 3b is a total reflection infrared spectrum of a polyimide nanofiber membrane prepared according to example 3 and having carboxyl groups on the surface
FIG. 4a is a scanning electron microscope image of a polyimide nanofiber membrane prepared according to example 4, with a surface carboxyl group containing polyimide, magnification of 50000 times
FIG. 4b is a total reflection infrared spectrum of a polyimide nanofiber membrane prepared according to example 4 and having carboxyl groups on the surface
FIG. 5a is a scanning electron microscope image of a polyimide nanofiber membrane prepared according to example 5, with a surface carboxyl group containing polyimide, magnification of 50000 times
FIG. 5b is a total reflection infrared spectrum of a polyimide nanofiber membrane prepared according to example 5 and having carboxyl groups on the surface
Detailed Description
The invention is further illustrated below in conjunction with specific embodiments. It should be noted that: the following examples are only for illustrating the invention and are not intended to limit the technical solutions described in the invention. Thus, although the present invention has been described in detail with reference to the following examples, it will be understood by those skilled in the art that the present invention may be modified or equivalents; all technical solutions and modifications thereof that do not depart from the spirit and scope of the present invention are intended to be included in the scope of the appended claims.
Comparative example 1
(1) 14.034g of pyromellitic dianhydride (PMDA), 6.378g of 4,4 '-diaminodiphenyl ether (ODA) and 4.846g of 3,5' -diaminobenzoic acid (DABA) are weighed according to a molar ratio of dianhydride to diamine of 1.01:1, wherein the molar ratio of two different diamines is 1:1. Diamine ODA and DABA are all dissolved in 100mL of N, N-Dimethylformamide (DMF) solvent, mechanical stirring is carried out until the two diamines are completely dissolved in DMF, dianhydride PMDA is added in 10 times successively under the condition of ice water bath, after all the dianhydrides are reacted, the ice water bath is removed, stirring is continued for 2 hours, a certain volume of polyamide acid solution is taken in a 20mL injector, an electrostatic spinning technology is applied to prepare a polyamide acid fiber membrane, and the specific parameters of an electrostatic spinning machine are spinning voltage: positive pressure 22kV and negative pressure-3 kV; spinning temperature: room temperature; spinning humidity: 35-50%; syringe needle diameter: number 12; the propulsion amount is as follows: 0.004mL/min; receiving roller rotation speed: 400r/min; reception distance: 20cm; a receiving substrate: aluminum foil; spinning time is 10h. And placing the spun polyamide acid nanofiber membrane in an ultra-clean bench for standing for 12 hours.
(2) And (3) placing the nanofiber membrane in the last step in a high-temperature oven, and preserving heat for 2 hours at 300 ℃.
Finally, the polyimide nanofiber membrane with carboxyl functional primitives on the surface is obtained, the diameter of the nanofiber is 352.3nm, the thickness of the nanofiber membrane is 45.8 mu m, carboxyl accounts for 6.2 weight percent of the whole content of the nanofiber membrane, the porosity is 90%, the mechanical strength is 16.8MPa, and the contact angle with water is 132 degrees.
Example 1
(1) 14.034g of pyromellitic dianhydride (PMDA), 6.378g of 4,4 '-diaminodiphenyl ether (ODA) and 4.846g of 3,5' -diaminobenzoic acid (DABA) are weighed according to a molar ratio of dianhydride to diamine of 1.01:1, wherein the molar ratio of two different diamines is 1:1. Diamine ODA and DABA are all dissolved in 100mL of N, N-Dimethylformamide (DMF) solvent, mechanical stirring is carried out until the two diamines are completely dissolved in DMF, dianhydride PMDA is added in 10 times successively under the condition of ice water bath, after all the dianhydrides are reacted, the ice water bath is removed, stirring is continued for 2 hours, a certain volume of polyamide acid solution is taken in a 20mL injector, an electrostatic spinning technology is applied to prepare a polyamide acid fiber membrane, and the specific parameters of an electrostatic spinning machine are spinning voltage: positive pressure 22kV and negative pressure-3 kV; spinning temperature: room temperature; spinning humidity: 35-50%; syringe needle diameter: number 12; the propulsion amount is as follows: 0.004mL/min; receiving roller rotation speed: 400r/min; reception distance: 20cm; a receiving substrate: aluminum foil; spinning time is 10h. And placing the spun polyamide acid nanofiber membrane in an ultra-clean bench for standing for 12 hours.
(2) And (3) putting the nanofiber membrane in the last step into a high-temperature oven, and preserving the temperature for 2 hours at 150 ℃.
(3) The nanofiber membrane of the previous step was immersed in 0.006wt% aqueous ammonia solution for 30s and rapidly taken out.
(4) And (3) placing the nanofiber membrane in deionized water, and taking out after 1 h.
(5) The nanofiber membrane of the previous step is placed in 0.5wt% acetic acid solution, and after 3 hours, the nanofiber membrane is taken out and washed and dried by a large amount of deionized water.
(6) And (3) placing the nanofiber membrane in the last step in a high-temperature oven, and preserving heat for 2 hours at 300 ℃.
Finally, the polyimide nanofiber membrane with carboxyl functional primitives on the surface is obtained, the diameter of the nanofiber is 352.3nm, the thickness of the nanofiber membrane is 41.1um, carboxyl accounts for 6.2 weight percent of the whole content of the nanofiber membrane, the porosity is 81%, the mechanical strength is 25.7MPa, and the contact angle with water is 42 degrees.
Example 2
(1) 14.034g of pyromellitic dianhydride (PMDA), 6.378g of 4,4 '-diaminodiphenyl ether (ODA) and 4.846g of 3,5' -diaminobenzoic acid (DABA) are weighed according to a molar ratio of dianhydride to diamine of 1.01:1, wherein the molar ratio of two different diamines is 1:1. Diamine ODA and DABA are all dissolved in 100mL of N, N-Dimethylformamide (DMF) solvent, mechanical stirring is carried out until the two diamines are completely dissolved in DMF, dianhydride PMDA is added in 10 times successively under the condition of ice water bath, after all the dianhydrides are reacted, the ice water bath is removed, stirring is continued for 2 hours, a certain volume of polyamide acid solution is taken in a 20mL injector, an electrostatic spinning technology is applied to prepare a polyamide acid fiber membrane, and the specific parameters of an electrostatic spinning machine are spinning voltage: positive pressure 22kV and negative pressure-3 kV; spinning temperature: room temperature; spinning humidity: 35-50%; syringe needle diameter: number 12; the propulsion amount is as follows: 0.004mL/min; receiving roller rotation speed: 400r/min; reception distance: 20cm; a receiving substrate: aluminum foil; spinning time is 10h. And placing the spun polyamide acid nanofiber membrane in an ultra-clean bench for standing for 12 hours.
(2) And (3) putting the nanofiber membrane in the last step into a high-temperature oven, and preserving heat for 2 hours at the temperature of 250 ℃.
(3) The nanofiber membrane obtained in the previous step is soaked in 0.006wt% ammonia water solution for 30s, and then taken out rapidly.
(4) And (3) placing the nanofiber membrane in deionized water, and taking out after 1 h.
(5) The nanofiber membrane of the previous step is placed in 0.5wt% acetic acid solution, and after 3 hours, the nanofiber membrane is taken out and washed and dried by a large amount of deionized water.
(6) And (3) placing the nanofiber membrane in the last step in a high-temperature oven, and preserving heat for 2 hours at 300 ℃.
Finally, the polyimide nanofiber membrane with carboxyl functional primitives on the surface is obtained, the diameter of the nanofiber is 352.1nm, the thickness of the nanofiber membrane is 31.2um, carboxyl accounts for 6.2 weight percent of the whole content of the nanofiber membrane, the porosity is 88%, the mechanical strength is 20.6MPa, and the contact angle with water is 38 degrees.
Example 3
(1) 14.034g of pyromellitic dianhydride (PMDA), 6.378g of 4,4 '-diaminodiphenyl ether (ODA) and 4.846g of 3,5' -diaminobenzoic acid (DABA) are weighed according to a molar ratio of dianhydride to diamine of 1.01:1, wherein the molar ratio of two different diamines is 1:1. Diamine ODA and DABA are all dissolved in 100mL of N, N-Dimethylformamide (DMF) solvent, mechanical stirring is carried out until the two diamines are completely dissolved in DMF, dianhydride PMDA is added in 10 times successively under the condition of ice water bath, after all the dianhydrides are reacted, the ice water bath is removed, stirring is continued for 2 hours, a certain volume of polyamide acid solution is taken in a 20mL injector, an electrostatic spinning technology is applied to prepare a polyamide acid fiber membrane, and the specific parameters of an electrostatic spinning machine are spinning voltage: positive pressure 22kV and negative pressure-3 kV; spinning temperature: room temperature; spinning humidity: 35-50%; syringe needle diameter: number 12; the propulsion amount is as follows: 0.004mL/min; receiving roller rotation speed: 400r/min; reception distance: 20cm; a receiving substrate: aluminum foil; spinning time is 10h. And placing the spun polyamide acid nanofiber membrane in an ultra-clean bench for standing for 12 hours.
(2) And (3) putting the nanofiber membrane in the last step into a high-temperature oven, and preserving heat for 2 hours at the temperature of 250 ℃.
(3) The nanofiber membrane obtained in the previous step is soaked in 0.023wt% ammonia water solution for 30s, and then is taken out rapidly.
(4) And (3) placing the nanofiber membrane in deionized water, taking out the nanofiber membrane after 1h, washing the nanofiber membrane with water and airing the nanofiber membrane.
(5) The nanofiber membrane of the previous step is placed in 0.5wt% acetic acid solution, and after 3 hours, the nanofiber membrane is taken out and washed and dried by a large amount of deionized water.
(6) And (3) placing the nanofiber membrane in the last step in a high-temperature oven, and preserving heat for 2 hours at 300 ℃.
Finally, the polyimide nanofiber membrane with carboxyl functional primitives on the surface is obtained, the diameter of the nanofiber is 352.3nm, the thickness of the nanofiber membrane is 31.1um, carboxyl accounts for 6.2 weight percent of the whole content of the nanofiber membrane, the porosity is 86%, the mechanical strength is 22.3MPa, and the contact angle with water is 35 degrees.
Example 4
(1) 14.034g of pyromellitic dianhydride (PMDA), 6.378g of 4,4 '-diaminodiphenyl ether (ODA) and 4.846g of 3,5' -diaminobenzoic acid (DABA) are weighed according to a molar ratio of dianhydride to diamine of 1.01:1, wherein the molar ratio of two different diamines is 1:1. Diamine ODA and DABA are all dissolved in 100mL of N, N-Dimethylformamide (DMF) solvent, mechanical stirring is carried out until the two diamines are completely dissolved in DMF, dianhydride PMDA is added in 10 times successively under the condition of ice water bath, after all the dianhydrides are reacted, the ice water bath is removed, stirring is continued for 2 hours, a certain volume of polyamide acid solution is taken in a 20mL injector, an electrostatic spinning technology is applied to prepare a polyamide acid fiber membrane, and the specific parameters of an electrostatic spinning machine are spinning voltage: positive pressure 22kV and negative pressure-3 kV; spinning temperature: room temperature; spinning humidity: 35-50%; syringe needle diameter: number 12; the propulsion amount is as follows: 0.004mL/min; receiving roller rotation speed: 400r/min; reception distance: 20cm; a receiving substrate: aluminum foil; spinning time is 10h. And placing the spun polyamide acid nanofiber membrane in an ultra-clean bench for standing for 12 hours.
(2) And (3) putting the nanofiber membrane in the last step into a high-temperature oven, and preserving heat for 2 hours at the temperature of 250 ℃.
(3) Soaking the nanofiber membrane obtained in the previous step in 0.023wt% ammonia water solution for 3min, and rapidly taking out.
(4) And (3) placing the nanofiber membrane in deionized water, and taking out after 1 h.
(5) The nanofiber membrane of the previous step is placed in 0.5wt% acetic acid solution, and after 3 hours, the nanofiber membrane is taken out and washed and dried by a large amount of deionized water.
(6) And (3) placing the nanofiber membrane in the last step in a high-temperature oven, and preserving heat for 2 hours at 300 ℃.
Finally, the polyimide nanofiber membrane with carboxyl functional primitives on the surface is obtained, the diameter of the nanofiber is 352.2nm, the thickness of the nanofiber membrane is 31.3um, carboxyl accounts for 6.2 weight percent of the whole content of the nanofiber membrane, the porosity is 83%, the mechanical strength is 24.8MPa, and the contact angle with water is 40 degrees.
Example 5
(1) 14.034g of pyromellitic dianhydride (PMDA), 6.378g of 4,4 '-diaminodiphenyl ether (ODA) and 4.846g of 3,5' -diaminobenzoic acid (DABA) are weighed according to a molar ratio of dianhydride to diamine of 1.01:1, wherein the molar ratio of two different diamines is 1:1. Diamine ODA and DABA are all dissolved in 100mL of N, N-Dimethylformamide (DMF) solvent, mechanical stirring is carried out until the two diamines are completely dissolved in DMF, dianhydride PMDA is added in 10 times successively under the condition of ice water bath, after all the dianhydrides are reacted, the ice water bath is removed, stirring is continued for 2 hours, a certain volume of polyamide acid solution is taken in a 20mL injector, an electrostatic spinning technology is applied to prepare a polyamide acid fiber membrane, and the specific parameters of an electrostatic spinning machine are spinning voltage: positive pressure 22kV and negative pressure-3 kV; spinning temperature: room temperature; spinning humidity: 35-50%; syringe needle diameter: number 12; the propulsion amount is as follows: 0.004mL/min; receiving roller rotation speed: 400r/min; reception distance: 20cm; a receiving substrate: aluminum foil; spinning time is 10h. And placing the spun polyamide acid nanofiber membrane in an ultra-clean bench for standing for 12 hours.
(2) And putting the nanofiber membrane in the last step into a high-temperature oven at 250 ℃ for 2 hours.
(3) Soaking the nanofiber membrane obtained in the previous step in 0.023wt% ammonia water solution for 3min, and rapidly taking out.
(4) And (3) placing the nanofiber membrane in deionized water, and taking out after 1 h.
(5) The nanofiber membrane of the previous step is placed in 0.9wt% acetic acid solution, and after 3 hours, the nanofiber membrane is taken out and washed and dried by a large amount of deionized water.
(6) And (3) placing the nanofiber membrane in the last step in a high-temperature oven, and preserving heat for 2 hours at 300 ℃.
Finally, the polyimide nanofiber membrane with carboxyl functional primitives on the surface is obtained, the diameter of the nanofiber is 352.3nm, the thickness of the nanofiber membrane is 31.2um, carboxyl accounts for 6.2 weight percent of the whole content of the nanofiber membrane, the porosity is 84%, the mechanical strength is 24.1MPa, and the contact angle with water is 37 degrees.
Claims (8)
1. The polyimide nanofiber membrane with the carboxyl functional units on the surface is characterized in that the diameter of the nanofiber is 50-600 nm, the thickness of the nanofiber membrane is 15-100 mu m, carboxyl accounts for 0.5-10% of the total content of the nanofiber membrane, and the content of polyamine containing the carboxyl functional units in a polyamine monomer is 2-40 mol%; the tensile strength of the polyimide nanofiber membrane with carboxyl functional primitives on the surface is 20.6-50MPa, and the porosity of the fiber membrane is 50-95%;
the preparation method of the polyimide nanofiber membrane with carboxyl functional motifs on the surface comprises the following steps:
a: synthesizing a polyamic acid solution containing carboxyl functional motifs by a solution polycondensation method, and preparing a polyamic acid nanofiber membrane containing the carboxyl functional motifs by electrostatic spinning;
b: performing heat treatment on the polyamic acid nanofiber membrane obtained in the step A to obtain a partially cyclized polyamic acid nanofiber membrane;
c: placing the partially cyclized polyamide acid nanofiber membrane obtained in the step B into a dilute ammonia water solution with the concentration of 0.005-0.025 wt% for 8 s-5 min, wherein the dilute ammonia water solution is used in excess;
d: immersing the polyamide acid nanofiber membrane treated in the step C into deionized water for standing for 0.5-12 h, wherein the deionized water is used excessively;
e: placing the polyamide acid nanofiber membrane treated in the step D into an acid solution with the concentration of 0.3-1wt% for acidification for 10 min-5 h, wherein the acid solution is used excessively;
f: and E, performing heat treatment on the polyamide acid nanofiber membrane treated in the step E to obtain the polyimide nanofiber membrane with carboxyl functional elements on the surface of the polyimide nanofiber.
2. The polyimide nanofiber membrane according to claim 1, wherein the polyimide nanofiber membrane having carboxyl functional motifs on the surface has a porosity of 60 to 92%.
3. The polyimide nanofiber membrane according to claim 1, wherein the thickness of the fiber membrane is 15 to 80um, and the carboxyl group content is 0.5 to 8% by weight of the total content of the fiber membrane.
4. The polyimide nanofiber membrane according to claim 1, wherein the content of the polyamine containing the carboxyl functional unit in the polyamine monomer in the step A is 2 to 40mol%.
5. The polyimide nanofiber membrane according to claim 1, wherein the heat treatment temperature in the step B is 120 to 350 ℃ and the holding time is 0.5 to 4 hours.
6. The polyimide nanofiber membrane according to claim 1, wherein the concentration of the dilute ammonia water in the step C is 0.006 to 0.023wt% and the treatment time is 8s to 3min.
7. The polyimide nanofiber membrane according to claim 1, wherein the deionized water temperature in the step D is 20-55 ℃ and the standing time is 0.6-10 h.
8. The polyimide nanofiber membrane according to claim 1, wherein the concentration of the acid solution in the step E is 0.4 to 0.9wt% and the acidification time is 15min to 4h.
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