CN114405296A - Preparation method of aqueous-phase super-hydrophilic PTFE - Google Patents
Preparation method of aqueous-phase super-hydrophilic PTFE Download PDFInfo
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- CN114405296A CN114405296A CN202210062435.3A CN202210062435A CN114405296A CN 114405296 A CN114405296 A CN 114405296A CN 202210062435 A CN202210062435 A CN 202210062435A CN 114405296 A CN114405296 A CN 114405296A
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- polytetrafluoroethylene
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- 229920001343 polytetrafluoroethylene Polymers 0.000 title claims abstract description 89
- 239000004810 polytetrafluoroethylene Substances 0.000 title claims abstract description 87
- 239000008346 aqueous phase Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 55
- 229920002545 silicone oil Polymers 0.000 claims abstract description 23
- 239000007864 aqueous solution Substances 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 229920000974 Poly(dimethylsiloxane-ethylene oxide) Polymers 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 14
- 238000002791 soaking Methods 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 10
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 4
- 239000012071 phase Substances 0.000 claims description 4
- 239000012528 membrane Substances 0.000 abstract description 51
- 230000004048 modification Effects 0.000 abstract description 8
- 238000012986 modification Methods 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 5
- 239000007788 liquid Substances 0.000 abstract description 5
- 239000012510 hollow fiber Substances 0.000 abstract description 3
- 230000002209 hydrophobic effect Effects 0.000 description 7
- 239000012229 microporous material Substances 0.000 description 6
- 230000004907 flux Effects 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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Classifications
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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
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention relates to a preparation method of aqueous phase super-hydrophilic PTFE, which uses hydrophilic silicone oil aqueous solution as aqueous phase modification liquid, does not need alcohol and other alcohol substances to soak pretreatment, and places polytetrafluoroethylene powder, polytetrafluoroethylene membrane or polytetrafluoroethylene hollow fiber membrane and the like into the aqueous phase modification liquid to soak to prepare the super-hydrophilic polytetrafluoroethylene membrane material.
Description
Technical Field
The invention relates to the technical field of PTFE (polytetrafluoroethylene) water treatment, in particular to a preparation method of water-phase super-hydrophilic PTFE.
Background
The Polytetrafluoroethylene (PTFE) membrane separation material has wide application in the fields of wastewater treatment, pharmacy, chemical industry, food and the like due to the excellent physical and mechanical properties and chemical solvent corrosion resistance. However, because of the extremely low surface energy and strong hydrophobic property of polytetrafluoroethylene, and the polytetrafluoroethylene is difficult to be infiltrated, the pure water flux is low, the water production efficiency in the membrane separation process is not high, and higher pressure is needed for driving. Increasing the system operating costs and maintenance expenses. In addition, PTFE has extremely low surface energy, which makes it extremely hydrophobic, so that the membrane module made of the PTFE is easily polluted by organic matters such as oil, protein and the like to block the membrane pores when the membrane module is used in the sewage treatment field, which can reduce the filtering performance of the module and reduce the service life of the module.
Scholars at home and abroad carry out a great deal of relevant experimental research aiming at the hydrophilic modification of the polytetrafluoroethylene membrane, and the test methods comprise wet chemical modification, plasma treatment, radiation, ion radiation, ultraviolet treatment and the like, and the methods can improve the hydrophilicity of the surface of the flat membrane to a certain extent, but have the defects that the molecular structure and the form of the surface of the flat membrane are slightly damaged.
Therefore, simple hydrophilic modification of the hydrophobic polytetrafluoroethylene membrane is particularly important, and the pollution resistance, permeability and stability of the PTFE membrane can be greatly improved through the hydrophilic modification of the membrane. Therefore, the polytetrafluoroethylene membrane needs special hydrophilic modification treatment in the using process, the structure of PTFE is not damaged, and the practical application of the polytetrafluoroethylene membrane is improved.
Chinese patent CN 102872732 a discloses a hydrophilic modification method for polytetrafluoroethylene microporous material, which comprises pretreating polytetrafluoroethylene microporous material with absolute alcohol or analytically pure butanone, soaking in polyvinyl alcohol aqueous solution, and allowing the soaked polytetrafluoroethylene microporous material to firmly entangle hydrophilic material on the surface of polytetrafluoroethylene microporous material under the action of crosslinking agent and catalyst to realize hydrophilization of polytetrafluoroethylene microporous material.
Chinese patent CN 112108009 a discloses a hydrophilic treatment method for polytetrafluoroethylene membrane, which is to treat the polytetrafluoroethylene membrane by using hydrophilic fluorine-containing polymer resin and epoxy polymer; wherein, the fluorine group in the polymer and the fluorine substance on the surface of the polytetrafluoroethylene membrane are firmly combined with each other by Van der Waals force, and the attached hydroxyl hydrophilic bond can perform crosslinking reaction with the epoxy polymer to realize the hydrophilization of the polytetrafluoroethylene microporous material.
However, in the above methods, alcohols are used for replacement, which causes damage to the structure of PTFE to a certain extent, has a risk of affecting the physicochemical properties of gas, and generates a large amount of waste liquid in the modification process, resulting in pollution and low practical application benefit.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a preparation method of aqueous-phase super-hydrophilic PTFE, which aims to solve the problems in the background art.
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of aqueous-phase super-hydrophilic PTFE comprises the following steps:
soaking the polytetrafluoroethylene material in a hydrophilic silicone oil aqueous solution, taking out, washing and drying.
Further, the hydrophilic silicone oil aqueous solution is a solution obtained by dissolving hydrophilic silicone oil in water.
Further, the hydrophilic silicone oil is poly (dimethylsiloxane) - (ethylene oxide) copolymer).
Further, the non-siloxane range of the hydrophilic silicone oil is 60-99%.
Further, the non-siloxane range of the hydrophilic silicone oil is 85%.
Further, the mass fraction of the hydrophilic silicone oil is 0.5-30%.
Further, the mass fraction of the hydrophilic silicone oil is 10-20%.
Further, the soaking time in the hydrophilic silicone oil aqueous solution is 0.001-48 h.
Further, the polytetrafluoroethylene material is polytetrafluoroethylene film, powder and tube.
Further, the drying step is drying or airing.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, the PTFE is modified by the hydrophilic silicone oil aqueous solution, the hydrophilic silicone oil is divided into the hydrophobic chain segment and the hydrophilic chain segment, when the PTFE is soaked in the aqueous solution, the hydrophobic chain segment in the hydrophilic silicone oil is close to the vicinity of the hydrophobic PTFE material and is in contact with the surface of the hydrophobic PTFE material, and then is physically entangled with the PTFE chain segment, and at the moment, the hydrophilic chain segment in the hydrophilic silicone oil is free outside, so that excellent hydrophilicity and hydrophilic stability are shown. The membrane has the advantages of improving the surface performance of the membrane, not influencing the inherent physical and chemical properties of the membrane, along with simple treatment process, no generation of a large amount of harmful waste liquid, energy conservation, environmental protection, high efficiency, economy and suitability for industrial production.
(2) The method does not need alcohol replacement, improves the surface performance of the membrane, does not influence the inherent physical and chemical properties of the membrane, has simple treatment process, does not generate a large amount of harmful waste liquid, is energy-saving, environment-friendly, efficient and economical, and is suitable for industrial production.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is a graph showing the hydrophilic effect of a PTFE membrane in example 1;
FIG. 2 is a contact angle test chart of the PTFE film of example 1.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Weighing a certain mass of poly (dimethylsiloxane) - (ethylene oxide) copolymer) to prepare 0.5 mass percent of aqueous solution;
soaking the polytetrafluoroethylene membrane in the poly (dimethylsiloxane) - (ethylene oxide) copolymer) solution for 12 hours, taking out, washing with water, and drying to obtain a hydrophilic polytetrafluoroethylene membrane finished product.
Example 2
A certain mass of poly (dimethylsiloxane) - (ethylene oxide) copolymer) was weighed to prepare a 5% mass fraction aqueous solution.
Soaking polytetrafluoroethylene fibers in the poly (dimethylsiloxane) - (ethylene oxide) copolymer) solution for 24 hours, taking out, washing with water, and drying to obtain the hydrophilic polytetrafluoroethylene fiber material.
Example 3
Weighing a certain mass of poly (dimethylsiloxane) - (ethylene oxide) copolymer) to prepare a 10 mass percent aqueous solution.
Soaking the polytetrafluoroethylene tubular membrane in the poly (dimethylsiloxane) - (ethylene oxide) copolymer) solution for 6 hours, taking out, washing with water, and drying to obtain the hydrophilic polytetrafluoroethylene tubular membrane material.
Example 4
A certain mass of poly (dimethylsiloxane) - (ethylene oxide) copolymer) was weighed to prepare a 20% mass fraction aqueous solution.
Soaking the polytetrafluoroethylene hollow fiber membrane in the poly (dimethylsiloxane) - (ethylene oxide) copolymer) solution for 12h, taking out, washing with water, and drying to obtain the hydrophilic polytetrafluoroethylene hollow fiber membrane material.
Example 5
Weighing a certain mass of poly (dimethylsiloxane) - (ethylene oxide) copolymer) to prepare a 30 mass percent aqueous solution.
Soaking polytetrafluoroethylene powder in the poly (dimethylsiloxane) - (ethylene oxide) copolymer) solution for 12 hours, taking out, washing with water, and drying to obtain a hydrophilic polytetrafluoroethylene powder finished product.
Example 6
A certain mass of poly (dimethylsiloxane) - (ethylene oxide) copolymer) was weighed to prepare a 0.5 mass% aqueous solution.
Soaking the polytetrafluoroethylene membrane in the poly (dimethylsiloxane) - (ethylene oxide) copolymer) solution for 48 hours, taking out, washing with water, and drying to obtain the hydrophilic polytetrafluoroethylene membrane.
Example 7
Weighing a certain mass of poly (dimethylsiloxane) - (ethylene oxide) copolymer) to prepare a 10 mass percent aqueous solution.
Soaking the polytetrafluoroethylene membrane in the poly (dimethylsiloxane) - (ethylene oxide) copolymer) solution for 48 hours, taking out, washing with water, and drying to obtain the hydrophilic polytetrafluoroethylene membrane.
Example 8
Weighing a certain mass of poly (dimethylsiloxane) - (ethylene oxide) copolymer) to prepare a 30 mass percent aqueous solution.
Soaking the polytetrafluoroethylene membrane in the poly (dimethylsiloxane) - (ethylene oxide) copolymer) solution for 0.001h, taking out, washing with water, and drying to obtain the hydrophilic polytetrafluoroethylene membrane.
Experimental example 1
Placing the finished product of the hydrophilic polytetrafluoroethylene membrane obtained in example 1 and one end of the polytetrafluoroethylene membrane which is not subjected to hydrophilic treatment into water, observing the shapes of the finished product and the polytetrafluoroethylene membrane, and testing the hydrophilicity, wherein as can be seen from a figure 1 (a), the polytetrafluoroethylene membrane which is not subjected to hydrophilic treatment floats on the water surface and gathers in a bundle shape, and the water inlet end and the water outlet end have the same color state and are both white sheets; the water inlet end of the finished product of the hydrophilic polytetrafluoroethylene membrane obtained in the embodiment 1 floats in water in an unfolded state, and the water inlet end is changed from white to semitransparent;
as shown in fig. 1 (b), one end of the ptfe membrane was subjected to the hydrophilic treatment in example 1, wherein the one end of the ptfe membrane was a hydrophilic end, the other end was an untreated end, and the middle of the hydrophilic end and the untreated end was a semi-treated sample, which was placed in water, and the shape of the sample was observed, wherein the untreated end floated on the water surface and bunched up, the hydrophilic end floated on the water in an expanded form, and the semi-treated sample floated on the water in an expanded form, wherein both the semi-treated sample and the hydrophilic end were translucent and had a distinct boundary with the untreated end.
Experimental example 2
The contact angle test of the finished hydrophilic polytetrafluoroethylene membrane obtained in example 1 and the polytetrafluoroethylene membrane which is not subjected to hydrophilic treatment is carried out, and as shown in fig. 2, the contact angle of the finished hydrophilic polytetrafluoroethylene membrane which is subjected to modification is about 39 degrees, which is obviously smaller than that of the polytetrafluoroethylene membrane which is not subjected to hydrophilic treatment;
therefore, the preparation method of the aqueous-phase super-hydrophilic PTFE provided by the invention can effectively improve the hydrophilicity of the polytetrafluoroethylene material.
Experimental example 3
The pure water flux of the finished hydrophilic polytetrafluoroethylene membrane obtained in example 1 was measured by using a membrane filtration apparatus comprising a diaphragm pump, a pressure gauge, a membrane module and a flow meter, and the sample was soaked in pure water for 2 hours or more, and the influence of the running time on the pure water flux was measured under the conditions of an operating pressure of 0.1MPa and a water temperature of 25 ℃, and the results are shown in table 1.
TABLE 1 Effect of run time on pure Water flux
Therefore, the pure water flux of the finished product of the hydrophilic polytetrafluoroethylene membrane is stable, the preparation method of the aqueous-phase super-hydrophilic PTFE provided by the invention has better pure water circulation performance within a certain time, and the hydrophilicity is stable.
While there have been shown and described what are at present considered the fundamental principles and essential features of the invention and its advantages, it will be apparent to those skilled in the art that the invention is not limited to the details of the foregoing exemplary embodiments, but is capable of other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (10)
1. A preparation method of water-phase super-hydrophilic PTFE is characterized by comprising the following steps:
soaking the polytetrafluoroethylene material in a hydrophilic silicone oil aqueous solution, taking out, washing and drying.
2. The method for preparing the aqueous-phase super-hydrophilic PTFE according to claim 1, wherein the aqueous solution of the hydrophilic silicone oil is a solution of the hydrophilic silicone oil dissolved in water.
3. The method for preparing the aqueous-phase super-hydrophilic PTFE according to claim 2, wherein the hydrophilic silicone oil is poly (dimethylsiloxane) - (ethylene oxide) copolymer).
4. The method for preparing water-phase super-hydrophilic PTFE according to claim 2, wherein the non-siloxane range of the hydrophilic silicone oil is 60 to 99 percent.
5. The method for preparing aqueous-phase super-hydrophilic PTFE according to claim 2, wherein the non-siloxane range of the hydrophilic silicone oil is 85%.
6. The method for preparing the aqueous-phase super-hydrophilic PTFE according to claim 2, wherein the mass fraction of the hydrophilic silicone oil is 0.5-30%.
7. The method for preparing the aqueous-phase super-hydrophilic PTFE according to claim 2, wherein the mass fraction of the hydrophilic silicone oil is 10-20%.
8. The preparation method of the water-phase super-hydrophilic PTFE as set forth in claim 1, wherein the soaking time in the hydrophilic silicone oil aqueous solution is 0.001h-48 h.
9. The method for preparing the aqueous-phase super-hydrophilic PTFE according to claim 1, wherein the polytetrafluoroethylene material is polytetrafluoroethylene film, powder or tube.
10. The method for preparing the aqueous-phase super-hydrophilic PTFE according to claim 1, wherein the drying step is drying or airing.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210062435.3A CN114405296A (en) | 2022-01-19 | 2022-01-19 | Preparation method of aqueous-phase super-hydrophilic PTFE |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210062435.3A CN114405296A (en) | 2022-01-19 | 2022-01-19 | Preparation method of aqueous-phase super-hydrophilic PTFE |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1905930A (en) * | 2004-01-07 | 2007-01-31 | 美国海德能公司 | Method for wetting hydrophobic porous polymeric membranes to improve water flux without alcohol treatment |
| US20110244215A1 (en) * | 2009-01-16 | 2011-10-06 | Sartorius Stedim Biotech Gmbh | Electron beam induced modification of membranes by polymers |
| CN103418254A (en) * | 2012-05-21 | 2013-12-04 | 中国科学院化学研究所 | Method of hydrophilic modification of polyvinylidene fluoride membrane |
| JP2017080674A (en) * | 2015-10-28 | 2017-05-18 | 日東電工株式会社 | Separation membrane, and protein separation-recovery system |
| US20200030750A1 (en) * | 2017-01-05 | 2020-01-30 | Centre National De La Recherche Scientifique | Process for manufacturing a multilayer membrane on a solid support using an amphiphilic block copolymer |
-
2022
- 2022-01-19 CN CN202210062435.3A patent/CN114405296A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1905930A (en) * | 2004-01-07 | 2007-01-31 | 美国海德能公司 | Method for wetting hydrophobic porous polymeric membranes to improve water flux without alcohol treatment |
| US20110244215A1 (en) * | 2009-01-16 | 2011-10-06 | Sartorius Stedim Biotech Gmbh | Electron beam induced modification of membranes by polymers |
| CN103418254A (en) * | 2012-05-21 | 2013-12-04 | 中国科学院化学研究所 | Method of hydrophilic modification of polyvinylidene fluoride membrane |
| JP2017080674A (en) * | 2015-10-28 | 2017-05-18 | 日東電工株式会社 | Separation membrane, and protein separation-recovery system |
| US20200030750A1 (en) * | 2017-01-05 | 2020-01-30 | Centre National De La Recherche Scientifique | Process for manufacturing a multilayer membrane on a solid support using an amphiphilic block copolymer |
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Application publication date: 20220429 |