CN114870653B - Polytetrafluoroethylene porous membrane with asymmetric wettability and preparation method thereof - Google Patents
Polytetrafluoroethylene porous membrane with asymmetric wettability and preparation method thereof Download PDFInfo
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- CN114870653B CN114870653B CN202210577388.6A CN202210577388A CN114870653B CN 114870653 B CN114870653 B CN 114870653B CN 202210577388 A CN202210577388 A CN 202210577388A CN 114870653 B CN114870653 B CN 114870653B
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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
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
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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
- B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
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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
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/36—Polytetrafluoroethene
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Separation Using Semi-Permeable Membranes (AREA)
Abstract
An asymmetric wettability polytetrafluoroethylene porous membrane and a preparation method thereof, wherein the method comprises the following steps: 1) Placing a film substrate made of polytetrafluoroethylene and having a porous structure on a heat source to heat one side of the film substrate; 2) And (3) taking a perfluorinated sulfonic acid polymer solution containing a low-boiling point solvent as a modifier to coat on a non-heated surface of the film matrix, volatilizing the solvent, and preparing the polytetrafluoroethylene porous membrane with asymmetric wettability, wherein the polytetrafluoroethylene porous membrane is formed by compounding the film matrix and the fluorosulfonic acid membrane. The preparation method of the polytetrafluoroethylene porous membrane with asymmetric wettability is simple, efficient and controllable, and the perfluorinated sulfonic acid polymer solution containing the low-boiling point solvent is coated on one side, and in the single-side heating process, the low-boiling point solvent is utilized to volatilize rapidly at a certain temperature, so that the content of the perfluorinated sulfonic acid polymer is distributed in a gradient manner along the thickness direction of the film matrix, and the structure of asymmetric wettability in the ultrathin film matrix is realized.
Description
Technical Field
The invention relates to the field of preparation of high polymer materials, in particular to a polytetrafluoroethylene porous membrane with asymmetric wettability and a preparation method thereof.
Background
The asymmetric wettability porous membrane of the polymer has great application potential in the fields of membrane separation, membrane distillation, emulsification and the like, so the preparation method of the porous membrane is widely paid attention to. According to the application fields of the polymer asymmetric wettability porous membrane, the preparation of the membrane asymmetric wettability structure is an important point for the preparation of the polymer asymmetric wettability porous membrane. In the practical use process of the polymer asymmetric wettability porous separation membrane, the asymmetric wettability structure is prepared into a core problem of an asymmetric wettability membrane. The asymmetric wettability structure determines the efficiency of the fraction and the thickness of the film determines the film passing resistance, so that the film thickness and the asymmetric production cannot be simultaneously achieved.
Therefore, there is a need to develop an asymmetric wettability film excellent in performance and a method for manufacturing the same.
Disclosure of Invention
Based on the above, the invention provides an asymmetric wettability polytetrafluoroethylene porous membrane and a preparation method thereof, so as to solve the technical problem that the membrane thickness and asymmetric manufacture of the polymer asymmetric wettability porous membrane in the prior art cannot be considered.
In order to achieve the above object, the invention provides an asymmetric wettability polytetrafluoroethylene porous membrane, which comprises a film matrix and a perfluorinated sulfonic acid polymer compounded in the film matrix, wherein the film matrix is made of polytetrafluoroethylene and has a porous structure, and the content of the perfluorinated sulfonic acid polymer is distributed in a gradient manner along the thickness direction of the film matrix.
As a further preferable embodiment of the present invention, the thickness of the film base is 6 μm to 10. Mu.m.
According to another aspect of the present invention, there is also provided a method for preparing a polytetrafluoroethylene porous membrane having asymmetric wettability, comprising the steps of:
1) Placing a film substrate made of polytetrafluoroethylene and having a porous structure on a heat source to heat one side of the film substrate;
2) And taking a perfluorinated sulfonic acid polymer solution containing a low-boiling point solvent as a modifier to be coated on a non-heated surface of the film substrate, wherein the low-boiling point solvent is heated and volatilized rapidly, so that the asymmetric wettability polytetrafluoroethylene porous film formed by compounding the film substrate and the fluorosulfonic acid film is prepared.
As a further preferable embodiment of the present invention, the heat source is a heat stage, and the heating temperature of the heat stage is greater than the boiling point of the low boiling point solvent in the perfluorosulfonic acid polymer solution.
As a further preferable embodiment of the present invention, the heating temperature of the heat stage is 200 ℃.
As a further preferred embodiment of the present invention, in step 2), the film substrate is heated at a predetermined heating temperature for at least one minute and then coated with the perfluorosulfonic acid polymer solution.
As a further preferred embodiment of the present invention, the low boiling point solvent in the perfluorosulfonic acid polymer solution comprises ethanol.
As a further preferable embodiment of the present invention, the concentration of the perfluorosulfonic acid polymer solution is 6 to 10%.
As a further preferable embodiment of the present invention, the concentration of the perfluorosulfonic acid polymer solution is 8%.
As a further preferable technical scheme of the invention, the film substrate is flatly paved above a heat source when being heated, the bottom surface of the film substrate is a heating surface, the top surface of the film substrate is a non-heating surface, and the perfluorinated sulfonic acid polymer solution is coated on the top surface of the film substrate.
According to the asymmetric wettability polytetrafluoroethylene porous membrane and the preparation method thereof, the following beneficial effects can be achieved by adopting the technical scheme:
1) The polytetrafluoroethylene porous membrane has better chemical corrosion resistance and supporting property, and can realize opposite wettability to oil under water;
2) The polytetrafluoroethylene porous membrane provided by the invention has an asymmetric wettability membrane, the membrane can carry out unidirectional transmission on oil, and the membrane has better oil separation performance in an oil-water mixing system;
3) The polytetrafluoroethylene porous membrane can be used in the fields of environmental protection, industry and the like, and the specific wettability degree can be adjusted according to the application;
4) The preparation method is simple, efficient and controllable, and the perfluorinated sulfonic acid polymer solution containing the low-boiling point solvent is coated on one side, and in the single-side heating process, the low-boiling point solvent is utilized to volatilize rapidly at a certain temperature, so that the content of the perfluorinated sulfonic acid polymer is distributed in a gradient manner along the thickness direction of the film substrate, and an asymmetric wettability structure in the ultrathin film substrate is realized.
Drawings
The invention will be described in further detail with reference to the drawings and the detailed description.
FIG. 1 shows the morphology of a polytetrafluoroethylene porous membrane of the invention before and after macroscopic coating;
FIG. 2 is a front and back scan of a polytetrafluoroethylene porous membrane of the invention prior to coating, with a scale of 10 μm;
FIG. 3 is a front and back scan of the polytetrafluoroethylene porous membrane of the invention after coating, with a scale of 10 μm;
FIG. 4 is a view showing the contact angle of the front and back sides of the polytetrafluoroethylene porous membrane of the invention with water, wherein the oil is selected from carbon tetrachloride as heavy oil;
FIG. 5 shows the contact angle of the water on the front and back surfaces of the polytetrafluoroethylene porous membrane coated by the invention, wherein the oil is selected from heavy oil carbon tetrachloride.
The achievement of the objects, functional features and advantages of the present invention will be further described with reference to the accompanying drawings, in conjunction with the embodiments.
Detailed Description
The invention will be further described with reference to the drawings and detailed description. The terms such as "upper", "lower", "left", "right", "middle" and "a" in the preferred embodiments are merely descriptive, but are not intended to limit the scope of the invention, as the relative relationship changes or modifications may be otherwise deemed to be within the scope of the invention without substantial modification to the technical context.
The invention provides a polytetrafluoroethylene porous membrane (called polytetrafluoroethylene porous membrane for short) with asymmetric wettability, which comprises a film matrix and perfluorinated sulfonic acid polymers compounded in the film matrix, wherein the perfluorinated sulfonic acid polymers are distributed in a gradient manner along the thickness direction of the film matrix, the film matrix is made of polytetrafluoroethylene and has a porous structure, the thickness of the film matrix is 6-10 mu m, and the film matrix determines the thickness of the polytetrafluoroethylene porous membrane.
The polytetrafluoroethylene porous membrane of the invention has the following characteristics by having the structure: hydrophilicity is provided by the wettability of the perfluorosulfonic acid polymer, hydrophobicity is provided by the wettability of the polytetrafluoroethylene material, and asymmetric wettability is provided by the gradient distribution of the content of the perfluorosulfonic acid polymer.
The invention also provides a preparation method of the polytetrafluoroethylene porous membrane with asymmetric wettability, which comprises the following steps:
1) Spreading a film substrate made of polytetrafluoroethylene and provided with a porous structure above a heat source, and heating one side of the film substrate by taking the bottom surface of the film substrate as a heating surface;
2) The top surface of the film substrate is taken as a non-heating surface, a perfluorinated sulfonic acid polymer solution containing low-boiling point solvent which is ethanol is taken as a modifier to be coated on the non-heating surface of the film substrate, and the low-boiling point solvent is heated to volatilize rapidly, so that the polytetrafluoroethylene porous membrane with asymmetric wettability, which is formed by compounding the film substrate and the fluorinated sulfonic acid membrane, is prepared.
In one embodiment, the heat source is a heat stage and the heating temperature of the heat stage is greater than the boiling point of the low boiling point solvent in the perfluorosulfonic acid polymer solution.
In the actual heating process, if the temperature is too low, the solvent with low boiling point is not volatilized quickly, so that the perfluorinated sulfonic acid polymer solution can quickly permeate to the other side of the film matrix after coating, and the prepared film is a symmetrical wetting film instead of an asymmetrical wetting film; if the temperature is too high, damage to the membrane itself can result, and the modifier perfluorosulfonic acid polymer solution tends to accumulate on the surface and plug the pores. The temperature is thus chosen so that it has asymmetric wettability characteristics without damaging the membrane itself or blocking the pores resulting in a decrease in flux. In specific implementation, the heating temperature is 150-250 ℃. Preferably, the heating temperature of the heat stage is 200 ℃. In the process of adding, the film substrate is heated for at least one minute at a preset heating temperature, and then the perfluorinated sulfonic acid polymer solution is coated.
In actual use, if the concentration of the perfluorinated sulfonic acid polymer solution is too high, the membrane hole blocking phenomenon can be caused, the same effect can be achieved if the concentration is too thin, and the perfluorinated sulfonic acid polymer solution needs to be coated for more times, so that the cost is increased and the energy is wasted. In a specific implementation, the concentration of the perfluorinated sulfonic acid polymer solution is 6-10%. Preferably, the concentration of the perfluorinated sulfonic acid polymer solution is 8%.
In the preparation process, the heat source is added below the film substrate, the film substrate is coated with the solvent of the perfluorinated sulfonic acid polymer solution, so that the ethanol can volatilize rapidly under the heating of the heat source below, the heat source temperature is higher, the solvent volatilizes rapidly when the perfluorinated sulfonic acid polymer solution does not permeate to the bottom surface of the film substrate, the perfluorinated sulfonic acid polymer is distributed in a gradient manner along the thickness direction of the film substrate, and the wettability of the front side and the back side of the prepared polytetrafluoroethylene porous membrane is asymmetric. The low boiling point solvent is utilized to volatilize rapidly at a certain temperature, and after single-sided coating, the content of the perfluorinated sulfonic acid polymer is distributed in a gradient manner along the thickness direction of the film matrix, which is a main innovative technical feature of the invention.
In order to better understand the advantages of the present invention, those skilled in the art will perform the following tests on the polytetrafluoroethylene porous membrane prepared in one example of the preparation method of the present invention:
referring to fig. 1, in the macroscopic view, the surface of the film substrate after modification is not blocked, and if so, the film substrate is not pure white but transparent when being watched.
Referring to fig. 2-5, in the microscopic view, the surface of the film substrate after modification treatment has no obvious change of pore diameter and pores, no pore blocking phenomenon occurs, and the material is not destroyed; the film substrate before and after coating shows wettability of pure polytetrafluoroethylene film, both sides show underwater oleophilic state, and after coating modification, the film substrate shows underwater oleophobic state of coated side (front side shown in the figure) and uncoated side (back side shown in the figure), so as to achieve the characteristic of asymmetric wettability of both sides of the film, and fig. 5 is a contact angle diagram of the phenomenon, wherein the wettability of polytetrafluoroethylene porous film under water for oil is 36 degrees, and the oleophilic side is 133.7 degrees.
In practical application, the wettability degree of the polytetrafluoroethylene porous membrane can be adjusted according to requirements, and the wettability degree is respectively as follows: the wettability of the coated surface can be regulated and controlled by using different modifier concentrations, the wettability of the coated surface can be regulated and controlled by using different temperatures, the wettability of the coated surface can be regulated and controlled by using different coating times, and the wettability of the uncoated surface can be regulated and controlled by using different base films to replace polytetrafluoroethylene films.
Polytetrafluoroethylene has excellent chemical corrosion resistance, high temperature resistance and excellent flexibility, so that the polytetrafluoroethylene is often used as a material for selecting a polymer separation membrane. The invention adopts a film matrix which is made of polytetrafluoroethylene material and has a porous structure and is lower than ten micrometers, and adopts a heating table to heat one side, and a non-heating surface is coated to prepare the porous separation film with asymmetric wettability.
While particular embodiments of the present invention have been described above, it will be appreciated by those skilled in the art that these are merely illustrative, and that many variations or modifications may be made to the embodiments without departing from the principles and spirit of the invention, the scope of which is defined only by the appended claims.
Claims (9)
1. The preparation method of the polytetrafluoroethylene porous membrane with asymmetric wettability is characterized in that the polytetrafluoroethylene porous membrane with asymmetric wettability comprises a film matrix with the thickness being lower than ten micrometers and a perfluorinated sulfonic acid polymer compounded in the film matrix, wherein the film matrix is made of polytetrafluoroethylene and has a porous structure, and the content of the perfluorinated sulfonic acid polymer is distributed in a gradient manner along the thickness direction of the film matrix;
the preparation method comprises the following steps:
1) Placing a film substrate made of polytetrafluoroethylene and having a porous structure on a heat source to heat one side of the film substrate;
2) And taking a perfluorinated sulfonic acid polymer solution containing a low-boiling point solvent as a modifier to be coated on a non-heated surface of the film substrate, wherein the low-boiling point solvent is heated and volatilized rapidly, so that the asymmetric wettability polytetrafluoroethylene porous film formed by compounding the film substrate and the fluorosulfonic acid film is prepared.
2. The method for producing an asymmetric wettable polytetrafluoroethylene porous membrane according to claim 1, wherein the thickness of said thin film substrate is 6 μm to 10 μm.
3. The method for producing an asymmetric wettable porous polytetrafluoroethylene membrane according to claim 1, wherein said heat source is a heat stage and the heating temperature of the heat stage is greater than the boiling point of the low boiling point solvent in the perfluorosulfonic acid polymer solution.
4. The method for producing an asymmetric wettable porous polytetrafluoroethylene membrane according to claim 2, wherein the heating temperature of said heat stage is 200 ℃.
5. The method for preparing an asymmetric wettable polytetrafluoroethylene porous membrane according to claim 1, wherein in step 2), the membrane substrate is coated with a perfluorosulfonic acid polymer solution after being heated at a predetermined heating temperature for at least one minute.
6. The method for preparing an asymmetric wettable polytetrafluoroethylene porous membrane according to claim 1 wherein the low boiling point solvent in said perfluorosulfonic acid polymer solution comprises ethanol.
7. The method for producing an asymmetric wettability porous polytetrafluoroethylene membrane according to claim 1, wherein the concentration of said perfluorosulfonic acid polymer solution is 6 to 10%.
8. The method for producing an asymmetric wettable polytetrafluoroethylene porous membrane according to claim 1 wherein the concentration of said perfluorosulfonic acid polymer solution is 8%.
9. The method for preparing an asymmetric wettability polytetrafluoroethylene porous membrane according to any one of claims 1 to 8, wherein the thin film substrate is laid flat on top of a heat source when heated, the bottom surface of the thin film substrate is a heated surface, the top surface of the thin film substrate is a non-heated surface, and the perfluorosulfonic acid polymer solution is coated on the top surface of the thin film substrate.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102068924A (en) * | 2010-12-22 | 2011-05-25 | 中国科学院长春应用化学研究所 | Polytetrafluoroethylene composite membrane and preparation method thereof |
| US20110186437A1 (en) * | 2010-02-02 | 2011-08-04 | James Huang | Polymeric Electret Film and Method of Manufacturing the Same |
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| WO1995002447A1 (en) * | 1993-07-16 | 1995-01-26 | E.I. Du Pont De Nemours And Company | Asymmetric membranes of polytetrafluoroethylene and their preparation |
| US20100143611A1 (en) * | 2008-12-05 | 2010-06-10 | General Electric Company | Methods for making an asymmetric composite membrane |
| CN101733016B (en) * | 2009-12-10 | 2011-04-06 | 山东东岳神舟新材料有限公司 | Functional group grafted porous membrane compound perfluorinated ion exchange membrane |
| CN101961608B (en) * | 2010-10-12 | 2013-02-06 | 浙江理工大学 | Method for controlling aperture of polytetrafluoroethylene hollow fibrous membrane |
| CN107096390B (en) * | 2017-05-17 | 2019-12-06 | 四川理工学院 | preparation method of modified copolymer porous membrane |
| CN108511777A (en) * | 2018-04-04 | 2018-09-07 | 华南理工大学 | The construction method of proton exchange membrane with three-dimensional high-specific surface area surface and its high-performance membrane electrode based on this proton exchange membrane |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20110186437A1 (en) * | 2010-02-02 | 2011-08-04 | James Huang | Polymeric Electret Film and Method of Manufacturing the Same |
| CN102068924A (en) * | 2010-12-22 | 2011-05-25 | 中国科学院长春应用化学研究所 | Polytetrafluoroethylene composite membrane and preparation method thereof |
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