CN110327797B - Novel flexible organic porous polymer hollow fiber membrane containing carbazole active group and preparation method and application thereof - Google Patents
Novel flexible organic porous polymer hollow fiber membrane containing carbazole active group and preparation method and application thereof Download PDFInfo
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- CN110327797B CN110327797B CN201910629631.2A CN201910629631A CN110327797B CN 110327797 B CN110327797 B CN 110327797B CN 201910629631 A CN201910629631 A CN 201910629631A CN 110327797 B CN110327797 B CN 110327797B
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2325/00—Details relating to properties of membranes
- B01D2325/24—Mechanical properties, e.g. strength
Abstract
The invention relates to a novel flexible organic porous polymer hollow fiber membrane containing carbazole active groups, a preparation method and application thereof, wherein the method comprises the following steps: mixing an aromatic organic porous skeleton material monomer and dimethoxymethane, carrying out ice water bath, adding trifluoroacetic acid, pouring the mixture into ammonia water, filtering and collecting the obtained product; performing Soxhlet extraction on the product, and then drying to obtain powder; grinding the powder, dispersing the powder in N-methyl-2-pyrrolidone and stirring, adding polysulfone while stirring to obtain a suspension, adding ethanol and stirring; and spinning the PAF/PSF solution to obtain a symmetrical hollow fiber membrane, and drying to obtain the novel flexible organic porous polymer hollow fiber membrane containing the carbazole active group. According to the preparation method, the flexible group is added into the framework and then the hollow fiber membrane is processed, so that the solubility of the polymer can be increased, and the more uniform and compact hollow fiber membrane is formed.
Description
Technical Field
The invention belongs to the technical field of material synthesis, and particularly relates to a novel flexible organic porous polymer hollow fiber membrane containing carbazole active groups, and a preparation method and application thereof.
Background
The organic porous material can enable the organic small molecules to be connected and coupled with each other through specific polymerization reaction and the like among different functional groups to form polymer materials with infinite connection and stable pore channel structures. From the current POFs, we can find that the structure can be crystalline or long-range disordered, which has great relation with the selection of monomers and the selection of polymerization reaction for synthesizing the POFs. If the organic blocks of the synthesized POFs structure have high symmetry and the molecules have rigidity, the organic blocks can be polymerized to form a short-range ordered structure according to a certain connection mode even if the long-range order of the polymer is disordered, and then an ideal regular structure is formed on the microscopic size. POFs materials have been developed rapidly in the past decades, researchers have gained more and more organic porous materials in the processes of early design and subsequent modification, and have also expanded the application field of the materials, but the research on the synthesis of organic porous polymers is still less at present, and the research and development of an organic porous material with wide application is urgently needed.
Disclosure of Invention
The invention aims to provide a preparation method of a novel flexible organic porous polymer hollow fiber membrane containing carbazole active groups.
The invention relates to a preparation method of a novel flexible organic porous polymer hollow fiber membrane containing carbazole active groups, which comprises the following steps: s101: mixing an aromatic organic porous skeleton material monomer with dimethoxymethane, degassing by inert gas, carrying out ice water bath, adding trifluoroacetic acid, standing to room temperature, keeping the temperature for 68-78 h under the protection of inert gas, pouring the solution into ammonia water, filtering by a membrane filter, collecting the obtained product, and washing by acetone and ethanol respectively; wherein the molar ratio of the aromatic organic porous skeleton material monomer to the dimethoxymethane is 1: (2-12.5), wherein the volume ratio of the trifluoroacetic acid to the dimethoxymethane is 1 (2.2-7.5); s102: sequentially carrying out Soxhlet extraction on the product obtained in the step S101 for 20-29 h by using tetrahydrofuran and methanol respectively, and then carrying out vacuum drying for 1-3 h at the temperature of 110-130 ℃ to obtain powder; s103: grinding the powder in a ball milling tank for 0.8 h-1.2 h, dispersing 0.5-3.5 parts by weight of aromatic organic porous framework material monomer in 100-150 parts by weight of N-methyl-2-pyrrolidone, stirring for 22-26 h, treating for 0.8-1.2 h under ultrasonic conditions, adding 10-55 parts by weight of polysulfone while stirring to obtain a suspension, adding ethanol, and stirring for 10-24 h to homogenize the suspension to obtain a PAF/PSF solution; s104: spinning the PAF/PSF solution to obtain a self-supporting symmetrical hollow fiber membrane, exchanging residual solvents in the fiber membrane by water, methanol and hexane in sequence, and drying at room temperature for 8-16 h to obtain the novel flexible organic porous polymer hollow fiber membrane containing the carbazole active group.
According to the preparation method of the novel flexible organic porous polymer hollow fiber membrane containing the carbazole active group, the flexible group is added into the skeleton and then processed into the hollow fiber membrane, and the solubility of the polymer can be increased by the flexible group, so that the hollow fiber membrane can be better formed. Overcomes the defects that the prior solid particles need to be ground into fine particles, but even the fine particles are easy to crack the surface of the film in the film forming process. The solubility of the polymer is increased, so that the polymer and the solution are fully mixed, and active groups are fully doped in the film forming process without changing the permeability and integrity of the film.
In addition, the preparation method of the novel flexible organic porous polymer hollow fiber membrane containing the carbazole active group can also have the following additional technical characteristics:
further, the carbazole group-containing monomer includes at least one of 3, 6-diamino-9-ethylcarbazole, 3, 6-diamino-9-propylcarbazole, 3, 6-diamino-9-butylcarbazole, and 3, 6-diamino-9-isopropylcarbazole.
Further, in step S104, the spinning method is a dry spray wet quenching method.
Further, in step S104, the specific steps of sequentially exchanging the solvent remaining in the fiber membrane with water, methanol, and hexane are as follows: firstly, the fiber membrane is immersed in deionized water for 3 to 4 days, then is immersed in methanol for three times, each time is 280 to 320 minutes, and then is immersed in n-hexanol for three times, each time is 280 to 320 minutes.
Further, in the step S101, the washing is performed three times with acetone and ethanol, respectively.
Further, in step S101, the inert gas is argon.
Further, in the step S103, after the ethanol solution is added, the loading amount of the PAF is 1 wt% to 8 wt% of the total PSF.
The invention also aims to provide a novel flexible organic porous polymer hollow fiber membrane containing carbazole active groups, which is prepared by the method.
The invention also aims to provide application of the novel flexible organic porous polymer hollow fiber membrane containing the carbazole active group in the technical fields of chemical industry, biomedicine and aviation.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
FIG. 1 is a synthesis reaction formula of a novel flexible organic porous polymer hollow fiber membrane containing carbazole active groups according to the present invention;
FIG. 2 is an electron microscope image of the cross section of the novel flexible organic porous polymer hollow fiber membrane containing carbazole active groups of the present invention;
FIGS. 3a and 3b are scanning electron microscope images of the novel flexible organic porous polymer hollow fiber membrane containing carbazole active groups according to the present invention;
FIG. 4 is a thermogravimetric plot of POF-c1, c2, c3 of FIG. 1;
fig. 5 is an infrared view of POF-c1 of fig. 1.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
Example 1
Embodiment 1 provides a novel flexible organic porous polymer hollow fiber membrane containing carbazole active groups, and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) mixing an aromatic organic porous skeleton material monomer with dimethoxymethane, then carrying out argon degassing, then carrying out ice water bath, adding trifluoroacetic acid, standing to room temperature, then carrying out heat preservation for 68 hours under the protection of argon, then pouring the mixture into ammonia water, filtering by using a membrane filter, collecting the obtained product, and then washing with acetone and ethanol for three times respectively; wherein the molar ratio of the aromatic organic porous skeleton material monomer to the dimethoxymethane is 1: 12.5, and the volume ratio of the trifluoroacetic acid to the dimethoxymethane is 1: 2.2. The aromatic organic porous skeleton material monomer at least comprises one of 3, 6-diamino-9-ethyl carbazole, 3, 6-diamino-9-propyl carbazole, 3, 6-diamino-9-butyl carbazole or 3, 6-diamino-9-isopropyl carbazole.
(2) Sequentially carrying out Soxhlet extraction on the product obtained in the step (1) by using tetrahydrofuran and methanol for 29h respectively, and then carrying out vacuum drying at the temperature of 110 ℃ for 3h to obtain powder.
(3) The powder was ground in a ball mill pot for 0.8h, then 3.5 parts by weight of aromatic organic porous framework material monomer was dispersed in 100 parts by weight of N-methyl-2-pyrrolidone and stirred for 26h, then treated under ultrasonic conditions for 0.8h, and 55 parts by weight of polysulfone was added while stirring to obtain a suspension, then ethanol was added, and stirred for 10h to homogenize the suspension, resulting in a PAF/PSF solution. After addition of the ethanol solution, the PAF loading was 8 wt% of the total PSF.
(4) Spinning the PAF/PSF solution by adopting a dry-spray wet-quenching method to obtain a self-supporting symmetrical hollow fiber membrane, exchanging residual solvents in the fiber membrane by using water, methanol and hexane in sequence, and drying at room temperature for 8 hours to obtain the novel flexible organic porous polymer hollow fiber membrane containing the carbazole active group. Wherein, the specific steps of sequentially exchanging the residual solvent in the fiber membrane by water, methanol and hexane are as follows: the fiber membrane was first immersed in deionized water for 4 days, then soaked three times with methanol, 280min each time, and then soaked three times with n-hexanol, 320min each time. As shown in fig. 1-5.
Example 2
Embodiment 2 provides a novel flexible organic porous polymer hollow fiber membrane containing carbazole active groups, and a preparation method thereof, including the following steps:
(1) mixing an aromatic organic porous skeleton material monomer with dimethoxymethane, then carrying out argon degassing, then carrying out ice water bath, adding trifluoroacetic acid, standing to room temperature, then carrying out heat preservation for 78 hours under the protection of argon, then pouring the mixture into ammonia water, filtering by using a membrane filter, collecting the obtained product, and then washing with acetone and ethanol for three times respectively; wherein the molar ratio of the aromatic organic porous skeleton material monomer to the dimethoxymethane is 1:2, the volume ratio of the trifluoroacetic acid to the dimethoxymethane is 1: 7.5. The aromatic organic porous skeleton material monomer at least comprises one of 3, 6-diamino-9-ethyl carbazole, 3, 6-diamino-9-propyl carbazole, 3, 6-diamino-9-butyl carbazole or 3, 6-diamino-9-isopropyl carbazole.
(2) Sequentially carrying out Soxhlet extraction on the product obtained in the step (1) by using tetrahydrofuran and methanol for 20h respectively, and then carrying out vacuum drying at the temperature of 130 ℃ for 1h to obtain powder.
(3) The powder was ground in a ball mill pot for 1.2h, then 0.5 parts by weight of aromatic organic porous framework material monomer was dispersed in 150 parts by weight of N-methyl-2-pyrrolidone and stirred for 22h, then treated under ultrasonic conditions for 1.2h, and 10 parts by weight of polysulfone was added while stirring to obtain a suspension, then ethanol was added, and stirred for 24h to homogenize the suspension, resulting in a PAF/PSF solution. After addition of the ethanol solution, the PAF loading was 1 wt% of the total PSF.
(4) Spinning the PAF/PSF solution by adopting a dry-spray wet-quenching method to obtain a self-supporting symmetrical hollow fiber membrane, exchanging residual solvents in the fiber membrane by using water, methanol and hexane in sequence, and drying at room temperature for 16 hours to obtain the novel flexible organic porous polymer hollow fiber membrane containing the carbazole active group. Wherein, the specific steps of sequentially exchanging the residual solvent in the fiber membrane by water, methanol and hexane are as follows: the fiber membrane was first immersed in deionized water for 3 days, then soaked three times with methanol, 320min each time, and then soaked three times with n-hexanol, 280min each time.
Example 3
Embodiment 3 provides a novel flexible organic porous polymer hollow fiber membrane containing carbazole active groups, and a preparation method thereof, including the following steps:
(1) mixing an aromatic organic porous skeleton material monomer with dimethoxymethane, then carrying out argon degassing, then carrying out ice water bath, adding trifluoroacetic acid, standing to room temperature, then carrying out heat preservation for 73 hours under the protection of argon, then pouring the mixture into ammonia water, filtering by using a membrane filter, collecting the obtained product, and then washing with acetone and ethanol for three times respectively; wherein the molar ratio of the aromatic organic porous skeleton material monomer to the dimethoxymethane is 1:7, the volume ratio of the trifluoroacetic acid to the dimethoxymethane is 1: 5. The aromatic organic porous skeleton material monomer at least comprises one of 3, 6-diamino-9-ethyl carbazole, 3, 6-diamino-9-propyl carbazole, 3, 6-diamino-9-butyl carbazole or 3, 6-diamino-9-isopropyl carbazole.
(2) Sequentially carrying out Soxhlet extraction on the product obtained in the step (1) by using tetrahydrofuran and methanol for 24h respectively, and then carrying out vacuum drying at the temperature of 120 ℃ for 2h to obtain powder.
(3) The powder was ground in a ball mill pot for 1h, then 2 parts by weight of aromatic organic porous framework material monomer was dispersed in 125 parts by weight of N-methyl-2-pyrrolidone and stirred for 24h, then treated under ultrasonic conditions for 1h, and 30 parts by weight of polysulfone was added while stirring to obtain a suspension, then ethanol was added, and stirred for 17h to homogenize the suspension, to obtain a PAF/PSF solution. After addition of the ethanol solution, the PAF loading was 4 wt% of the total PSF.
(4) Spinning the PAF/PSF solution by adopting a dry-spray wet-quenching method to obtain a self-supporting symmetrical hollow fiber membrane, exchanging residual solvents in the fiber membrane by using water, methanol and hexane in sequence, and drying at room temperature for 12 hours to obtain the novel flexible organic porous polymer hollow fiber membrane containing the carbazole active group. Wherein, the specific steps of sequentially exchanging the residual solvent in the fiber membrane by water, methanol and hexane are as follows: the fiber membrane was first immersed in deionized water for 3 days, then soaked three times with methanol, 300min each time, and then soaked three times with n-hexanol, 300min each time.
In conclusion, according to the preparation method of the novel flexible organic porous polymer hollow fiber membrane containing the carbazole active group, the flexible group is added into the skeleton and then processed into the hollow fiber membrane, and the flexible group can increase the solubility of the polymer, so that the hollow fiber membrane is formed better. Overcomes the defects that the prior solid particles need to be ground into fine particles, but even the fine particles are easy to crack the surface of the film in the film forming process. The solubility of the polymer is increased, so that the polymer and the solution are fully mixed, and active groups are fully doped in the film forming process without changing the permeability and integrity of the film.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (3)
1. A preparation method of a novel flexible organic porous polymer hollow fiber membrane containing carbazole active groups is characterized by comprising the following steps:
s101: mixing an aromatic organic porous skeleton material monomer with dimethoxymethane, degassing by inert gas, carrying out ice water bath, adding trifluoroacetic acid, standing to room temperature, keeping the temperature for 68-78 h under the protection of inert gas, pouring the solution into ammonia water, filtering by a membrane filter, collecting the obtained product, and washing by acetone and ethanol respectively; wherein the molar ratio of the aromatic organic porous skeleton material monomer to the dimethoxymethane is 1: (2-12.5), wherein the volume ratio of the trifluoroacetic acid to the dimethoxymethane is 1 (2.2-7.5);
s102: sequentially carrying out Soxhlet extraction on the product obtained in the step S101 for 20-29 h by using tetrahydrofuran and methanol respectively, and then carrying out vacuum drying for 1-3 h at the temperature of 110-130 ℃ to obtain powder;
s103: grinding the powder in a ball milling tank for 0.8-1.2 h, then dispersing 0.5-3.5 parts by weight of the ground powder in 100-150 parts by weight of N-methyl-2-pyrrolidone and stirring for 22-26 h, then treating for 0.8-1.2 h under ultrasonic conditions, adding 10-55 parts by weight of polysulfone while stirring to obtain a suspension, then adding ethanol and stirring for 10-24 h to homogenize the suspension to obtain a PAF/PSF solution;
s104: spinning the PAF/PSF solution to obtain a self-supporting symmetrical hollow fiber membrane, exchanging residual solvents in the fiber membrane by water, methanol and hexane in sequence, and drying at room temperature for 8-16 h to obtain a novel flexible organic porous polymer hollow fiber membrane containing carbazole active groups;
the monomer containing the carbazole group at least comprises one of 3, 6-diamino-9-ethyl carbazole, 3, 6-diamino-9-propyl carbazole, 3, 6-diamino-9-butyl carbazole or 3, 6-diamino-9-isopropyl carbazole;
in the step S101, washing with acetone and ethanol respectively for three times;
in the step S101, the inert gas is argon;
in the step S103, after the ethanol solution is added, the load capacity of the PAF is 1 wt% -8 wt% of the whole PSF;
in the step S104, the spinning method is a dry spraying and wet quenching method;
in step S104, the specific steps of sequentially exchanging the solvent remaining in the fiber membrane with water, methanol, and hexane are: firstly, the fiber membrane is immersed in deionized water for 3 to 4 days, then is immersed in methanol for three times, each time is 280 to 320 minutes, and then is immersed in n-hexanol for three times, each time is 280 to 320 minutes.
2. The novel flexible organic porous polymer hollow fiber membrane containing carbazole active groups prepared by the method of claim 1.
3. The application of the novel flexible organic porous polymer hollow fiber membrane containing carbazole active groups as claimed in claim 2 in the fields of chemical engineering, biomedicine and aeronautics.
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| CN1441693A (en) * | 2000-04-17 | 2003-09-10 | 陶氏环球技术公司 | Composite membrane and method for making same |
| US9457318B2 (en) * | 2010-12-12 | 2016-10-04 | Ben-Gurion University Of The Negev Research And Development Authority | Anion exchange membranes, methods of preparation and uses |
| CN105536579A (en) * | 2016-01-29 | 2016-05-04 | 天津工业大学 | Preparation method of asymmetric porous membrane based on electrostatic spinning technology |
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