CN111686593A - Novel adjustable and controllable ultrathin organic polymer composite membrane and preparation method thereof - Google Patents
Novel adjustable and controllable ultrathin organic polymer composite membrane and preparation method thereof Download PDFInfo
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- CN111686593A CN111686593A CN201910189144.9A CN201910189144A CN111686593A CN 111686593 A CN111686593 A CN 111686593A CN 201910189144 A CN201910189144 A CN 201910189144A CN 111686593 A CN111686593 A CN 111686593A
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- organic polymer
- composite membrane
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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
- B01D69/12—Composite membranes; Ultra-thin membranes
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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
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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
- B01D67/0023—Organic membrane manufacture by inducing porosity into non porous precursor membranes
- B01D67/0025—Organic membrane manufacture by inducing porosity into non porous precursor membranes by mechanical treatment, e.g. pore-stretching
- B01D67/0027—Organic membrane manufacture by inducing porosity into non porous precursor membranes by mechanical treatment, e.g. pore-stretching by stretching
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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
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
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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
- B01D69/087—Details relating to the spinning process
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/39—Electrospinning
Abstract
The invention relates to a novel controllable ultrathin organic polymer composite film and a preparation method thereof, which comprises the steps of depositing a polymer on a base film by utilizing an electrostatic spinning technology, and then partially melting a fibrous polymer deposited on the base film by utilizing a solvent by utilizing the dissolvability of the polymer to form a layer of compact ultrathin organic polymer film on the base film. Compared with the prior art, the preparation method has low preparation cost, can effectively control the thickness and the membrane aperture size of the organic polymer composite membrane, and reduces the resistance of the organic polymer composite membrane so as to improve the performance of the membrane.
Description
Technical Field
The invention belongs to the technical field of membrane preparation, relates to a preparation method of a composite membrane, and particularly relates to an organic polymer composite membrane with adjustable thickness and membrane pore size and a preparation method thereof.
Technical Field
Membrane technology is a new separation technology developed in recent years, and can be used for separating, purifying, concentrating and the like various components in a mixture by utilizing the selective permeability of a membrane. Inorganic films and organic films in the film technology have advantages and disadvantages respectively. Such as: the separation principle of the pervaporation technology is a process of separating components by utilizing the difference of solubility and diffusion coefficient of components in a feed liquid in a membrane matrix and further utilizing the difference of pressure difference of the components on two sides of the membrane. Organic pervaporation membranes generally have lower flux in practical applications of organic pervaporation membranes compared to inorganic pervaporation membranes, although the cheapness of cost is a significant advantage of them. Practice shows that the control of the membrane thickness and the membrane pore diameter is a great technical difficulty in the application of the organic pervaporation membrane.
Disclosure of Invention
The invention provides a novel adjustable ultrathin organic polymer composite membrane and a preparation method thereof aiming at the regulation and control of the membrane thickness and the membrane aperture, and the method is a novel regulation and control preparation method of electrostatic spinning deposition-solvent remelting.
The invention is realized by the following technical scheme:
1. a preparation method of a novel adjustable ultrathin organic polymer composite membrane is characterized by comprising the following process steps:
1) preparation of polymer solution: mixing and dissolving the high polymer and the surfactant;
2) electrostatic spinning: extruding the dissolved materials in a microsyringe, regulating and controlling the sampling rate of the microsyringe, and setting the operating parameters of the electrostatic spinning machine;
3) re-dissolving the solvent: placing the prepared electrostatic spinning membrane in a solvent steam range, and controlling the solvent steam treatment time to control the re-dissolution degree of the surface high polymer of the base membrane (polysulfone, polyethersulfone and the like);
4) rolling: setting the temperature of a calender and the speed (300rpm) of a rotating shaft, and re-calendering the film to form a more compact and smooth organic film;
5) surface crosslinking: and carrying out surface chemical crosslinking modification on the high polymer on the surface of the base film by using a crosslinking agent.
Further, the polymer in the step (1) is PVA, and the concentration of the PVA is 6-12 wt%.
Further, the surfactant in the step (1) is sodium dodecyl benzene sulfonate.
Further, the method is characterized in that the solvent in the step (3) is high-purity water.
Further, it is characterized in that the distance between the film in the step (3) and the solvent interface is 5-15 cm.
Further, the solvent vapor treatment time in the step (3) is 0 to 10 minutes, preferably 0, 5, 10 minutes, respectively.
Further, the temperature of the calender in the step (4) is 100 ℃.
Further, the cross-linking agent in the step (5) is glutaraldehyde with the concentration of 0.5 wt%, and the solution environment is as follows: PH 1.5.
Further, the electrostatic spinning machine operating parameters of step (2): electrostatic voltage: 14-18KV, spindle speed: 300rpm, the distance between the electrostatic spinning needle head and the rotating shaft is 15cm, and the swing width of the electrostatic spinning manipulator is 15 cm.
The invention also provides a novel controllable ultrathin organic polymer composite membrane prepared by the preparation method.
Detailed description of the invention:
a preparation method of a novel adjustable ultrathin organic polymer composite membrane comprises the following steps:
1) polymer (PVA) solution preparation: mixing and dissolving a high Polymer (PVA) and a surfactant (increasing the conductivity of the mixed solution and preventing the phenomenon of electrostatic spinning yarn flying);
2) electrostatic spinning: and (3) extruding the dissolved materials in a microsyringe, regulating and controlling the sample injection rate of the microsyringe, and setting the operating parameters (rotating shaft rate, electrostatic voltage, distance between an electrostatic spinning needle head and a rotating shaft, and swing width of an electrostatic spinning manipulator) of the electrostatic spinning machine.
3) Re-dissolving the solvent: and placing the prepared electrostatic spinning membrane in a solvent steam range, wherein the solvent steam treatment time is used for controlling the re-dissolution degree of the high polymer on the surface of the polyether sulfone base membrane.
4) Rolling: setting the temperature of the calender and the speed of the rotating shaft, and re-calendering the film to form a more compact and smooth organic polymer film.
5) Surface crosslinking: in order to improve the stability of the organic membrane, a high Polymer (PVA) on the surface of the base membrane is subjected to surface chemical crosslinking modification by using a crosslinking agent (glutaraldehyde GA).
Preferably, the mass concentration of PVA in step 1) described in the above production method is 8% by weight.
Preferably, the mass concentration of the surfactant (sodium dodecylbenzenesulfonate) in step 1) described in the above production method is 0.1 wt%.
Preferably, the sample injection rate of the sample injector of step 2) described in the above preparation method is 0.7ml/h, and the operating parameters of the electrospinning machine (electrostatic voltage: 14-18KV, spindle speed: 300rpm), the distance between the electrostatic spinning needle head and the rotating shaft is 15cm, and the swing width of the electrostatic spinning manipulator is 15 cm.
Preferably, the distance between the film and the solvent interface in step 3) described in the above production method is 10cm, and the heating temperature of the solvent in the beaker is controlled to 90 ℃.
Preferably, the temperature of the calender in step 4) described in the above preparation method is controlled to be 100 ℃.
The prepared organic composite membrane can effectively control the aperture size and the surface roughness of the membrane by controlling the preparation conditions; the prepared composite membrane can be used as a base membrane of microfiltration, ultrafiltration, nanofiltration and other membranes, and can improve the performance of various membranes. (the specific regulation and control results are shown in the attached drawings as examples).
The preparation method of the invention has the advantages that: for example, low cost; the thickness of the later steam-treated film can be controlled by the amount of the electrostatic spinning polymer deposited on the rotating shaft receiving film; the aperture of the effective active layer of the composite membrane and the roughness of the membrane surface are regulated and controlled by controlling the steam treatment time, the steam treatment temperature and the like.
The invention has low preparation cost, can effectively control the thickness of the organic polymer composite membrane, and reduces the resistance of the organic polymer composite membrane so as to improve the performance of the membrane.
Description of the drawings:
FIG. 1 is an electron micrograph (magnification. times.10000) of a sample obtained in example 1.
FIG. 2 is an electron micrograph (magnification. times.10000) of a sample obtained in example 2.
FIG. 3 is an electron micrograph (magnification. times.10000) of a sample obtained in example 3.
Detailed Description
The following examples are intended to illustrate the invention and are not to be construed as limiting the scope of the invention
Example 1
Preparing an aqueous solution containing 8 wt% of PVA and 0.1 wt% of sodium dodecyl benzene sulfonate. The advancing speed of the sample feeding device is controlled to be 0.7ml/h, the rotating speed of the rotating shaft is controlled to be 300rpm, the distance between the electrostatic spinning needle head and the rotating shaft and the swinging width of the electrostatic spinning mechanical arm are both 15cm, and the spinning deposition time of the electrostatic spinning PVA is 2 h. The samples were taken in electron micrographs (magnification x 10000).
Example 2
Electrospun nanofiber membranes were prepared as in example 1, but with post-steaming. Processing steam parameters: the steam is required to be kept in a constant temperature water bath at 90 ℃, and the distance between the membrane and the liquid phase water surface is kept constant at 10 cm. And (3) redissolving PVA on the surface of the polyether sulfone base film by using water vapor to form a compact ultrathin skin layer: the holding time was 5 minutes. The samples were taken in electron micrographs (magnification x 10000).
Example 3
The preparation process of the electrostatic spinning nanofiber membrane is the same as that of example 1, and the post-steam treatment step is the same as that of example 2; but the treatment time of the water vapor of the film was kept at 10 minutes. The samples were taken in electron micrographs (magnification x 10000).
The attached drawings fully illustrate that the remelting degree of the polymer can be effectively controlled by changing the steam treatment time, and the pore size in the organic film layer can be regulated and controlled; the processing time of fig. 3 has melt formed the polymer electrospun onto the base film into a denser organic active layer.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and decorations can be made without departing from the concept of the present invention, and these modifications and decorations should also be regarded as being within the protection scope of the present invention.
Claims (10)
1. A preparation method of a novel adjustable ultrathin organic polymer composite membrane is characterized by comprising the following process steps:
1) preparation of polymer solution: mixing and dissolving the high polymer and the surfactant;
2) electrostatic spinning: extruding the dissolved materials in a microsyringe, regulating and controlling the sampling rate of the microsyringe, and setting the operating parameters of the electrostatic spinning machine;
3) re-dissolving the solvent: placing the prepared electrostatic spinning film in a solvent steam range, and controlling the solvent steam treatment time to control the re-dissolution degree of the high polymer on the surface of the base film;
4) rolling: setting the temperature of a calender and the speed of a rotating shaft, and re-calendering the film to form a more compact and smooth organic film;
5) surface crosslinking: and carrying out surface chemical crosslinking modification on the high polymer on the surface of the base film by using a crosslinking agent.
2. The method for preparing a controllable ultrathin organic polymer composite membrane as claimed in claim 1, wherein the polymer in step (1) is PVA with a concentration of 6-12 wt%.
3. The method for preparing the novel controllable ultrathin organic polymer composite membrane according to claim 1, wherein the surfactant in the step (1) is sodium dodecyl benzene sulfonate.
4. The method for preparing a controllable ultrathin organic polymer composite membrane as claimed in claim 1, wherein the solvent in step (3) is high purity water.
5. The method for preparing a novel controllable ultrathin organic polymer composite membrane according to claim 1, wherein the distance between the membrane in the step (3) and a solvent interface is 5-15 cm.
6. The method for preparing a controllable ultrathin organic polymer composite membrane as claimed in claim 1, wherein the solvent vapor treatment time in step (3) is 0, 5 and 10 minutes respectively.
7. The method for preparing the novel controllable ultrathin organic polymer composite membrane according to claim 1, wherein the temperature of the calender in the step (4) is 100 ℃.
8. The method for preparing a controllable ultrathin organic polymer composite membrane as claimed in claim 1, wherein the crosslinking agent in step (5) is glutaraldehyde with a concentration of 0.5 wt%, and the solution environment is: PH 1.5.
9. The method for preparing the novel controllable ultrathin organic polymer composite membrane as claimed in claim 1, wherein the electrostatic spinning machine operating parameters in step (2) are as follows: electrostatic voltage: 14-18KV, spindle speed: 300rpm, the distance between the electrostatic spinning needle head and the rotating shaft is 15cm, and the swing width of the electrostatic spinning manipulator is 15 cm.
10. A novel controllable ultrathin organic polymer composite membrane prepared by the preparation method of any one of claims 1 to 9.
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| CN201910189144.9A CN111686593A (en) | 2019-03-13 | 2019-03-13 | Novel adjustable and controllable ultrathin organic polymer composite membrane and preparation method thereof |
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| CN201910189144.9A CN111686593A (en) | 2019-03-13 | 2019-03-13 | Novel adjustable and controllable ultrathin organic polymer composite membrane and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114197202A (en) * | 2021-12-21 | 2022-03-18 | 西安交通大学 | Polyelectrolyte grafted polyvinyl alcohol spinning membrane for oil-water emulsion separation, and preparation method and application thereof |
| CN115154659A (en) * | 2022-01-30 | 2022-10-11 | 爱美客技术发展股份有限公司 | Implant and preparation method thereof |
| CN115154660A (en) * | 2022-01-30 | 2022-10-11 | 爱美客技术发展股份有限公司 | High-strength implant and preparation method thereof |
| CN116920638A (en) * | 2023-08-29 | 2023-10-24 | 上海翊科聚合物科技有限公司 | Novel composite micro-filtration membrane and preparation method thereof |
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| CN103386257A (en) * | 2012-05-08 | 2013-11-13 | 北京服装学院 | Nano-fiber composite ultrafiltration membrane preparation method based on electrostatic spinning technology |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114197202A (en) * | 2021-12-21 | 2022-03-18 | 西安交通大学 | Polyelectrolyte grafted polyvinyl alcohol spinning membrane for oil-water emulsion separation, and preparation method and application thereof |
| CN115154659A (en) * | 2022-01-30 | 2022-10-11 | 爱美客技术发展股份有限公司 | Implant and preparation method thereof |
| CN115154660A (en) * | 2022-01-30 | 2022-10-11 | 爱美客技术发展股份有限公司 | High-strength implant and preparation method thereof |
| CN116920638A (en) * | 2023-08-29 | 2023-10-24 | 上海翊科聚合物科技有限公司 | Novel composite micro-filtration membrane and preparation method thereof |
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