CN102423644A - Hydrophobic porous composite membrane, preparation method, and application thereof - Google Patents
Hydrophobic porous composite membrane, preparation method, and application thereof Download PDFInfo
- Publication number
- CN102423644A CN102423644A CN2011102323422A CN201110232342A CN102423644A CN 102423644 A CN102423644 A CN 102423644A CN 2011102323422 A CN2011102323422 A CN 2011102323422A CN 201110232342 A CN201110232342 A CN 201110232342A CN 102423644 A CN102423644 A CN 102423644A
- Authority
- CN
- China
- Prior art keywords
- hydrophobic
- copolymer
- hydrophobic porous
- porous composite
- membrane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- Y02E60/10—Energy storage using batteries
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Cell Separators (AREA)
Abstract
The present invention discloses a hydrophobic porous composite membrane, a preparation method, and an application thereof. According to the present invention, the substrate of the hydrophobic porous composite membrane is a hydrophobic porous membrane; a layer of a copolymer is compounded on the surface of the hydrophobic porous membrane; the copolymer is a random copolymer or a block copolymer, the hydrophobic end of the copolymer is polymethacrylic acid-2-ethyl cinnamate or polyacrylic acid-2-ethyl cinnamate, the hydrophilic end of the copolymer is one selected from polymethyl methacrylate, polymethyl acrylate, polyacrylamide, polyvinylpyrrolidone, polyacrylonitrile or polyglyceryl methacrylate. According to the present invention, with the method for the hydrophilic modification of the hydrophobic porous membrane, the hydrophilicity of the hydrophobic membrane is effectively improved; the hydrophobic porous membrane and the copolymer are subjected to cross-linking coupling, such that the prepared composite membrane has characteristics of good use stability and long aging; with the hydrophobic porous composite membrane of the present invention, defects of insufficient wettability of the hydrophobic membrane and low liquid absorption rate of the membrane in the existing lithium battery are overcome.
Description
Technical field
The invention belongs to field of materials, be specifically related to a kind of hydrophobic porous composite film and preparation method thereof and application.
Background technology
In a typical film separation process, exist two distinct requirements, both required high permeability, require to have high selectivity again.For the single polymers film, possess comparatively difficulty of above-mentioned two requirements simultaneously.Though it is quite extensive to be used to make the macromolecular material of film in theory; But the macromolecular material that really is used for diffusion barrier is very limited; Here except the reason of processing aspect, its chief reason is to a concrete separation system, needs the membrane material of special properties.The membrane material that for example separates Aquo System requires suitable hydrophilic/hydrophobic balance, to obtain high permeability and selectivity.This selection to membrane material has proposed strict requirement.In order to address this problem; People are when utilizing the membrane material of known structure; Also must notice be forwarded to the selection and the modified membrane aspect of membrane material, in the hope of through membrane material modified compatibility of coming between controlling diaphragm and penetrant, thereby it is unified with optionally to reach permeability.
In lithium battery applications, the wettability of hydrophobic membrane in electrolyte is not enough, and the barrier film pick up is low, causes battery efficiency lower.Be applied in the lithium battery diaphragm so hydrophobic membrane is carried out hydrophilic modifying, can improve the lyophily of barrier film, improve battery performance.
According to the hydrophilic and hydrophobic of membrane material, film can be divided into hydrophobic film and hydrophilic film.Hydrophobic membrane can be divided into dissimilar according to the difference of material of preparing, kind separately has corresponding characteristics.Using more hydrophobic membrane in the industry mainly contains: polypropylene (PP), Kynoar (PVDF), polysulfones (PSF), polyethylene (PE) and polyether sulfone (PES) etc.Hydrophilic membrane material mainly contains the macromolecular material that polymethyl methacrylate (PHEMA), polyacrylamide (PAM), polyvinylpyrrolidone (PVP), polyacrylonitrile (PAN) etc. have a large amount of hydrophilic radicals.
The method of at present hydrophobic membrane being carried out hydrophilic modifying has surface-coated hydrophilic polymer method; CN1153867C discloses a kind of hydrophobic polymer that has been coated with hydrophilic polymer material equably and has constituted the substrate of coating porous; But hydrophilic polymer and hydrophobic polymer interaction force are undesirable, and hydrophilic polymer is easy to come off in the use.
Surface grafting hydrophilic polymer method; CN100366666C discloses a kind of method of polyvinylidene fluoride film being carried out hydrophilic modifying; This method combines blend and surface grafting technology, earlier PVDF is processed microporous barrier or dense film with another photosensitive polymers, adopts the surface grafting method at blend film surface grafting hydrophilic monomer then; But its complex process, the graft reaction condition is harsh.
With the hydrophilic polymer blending method; CN101773789A discloses a kind of preparation method of hydrophilic film material; Be mixed with uniform solution film forming later on by amorphous macromolecule and hydrophilic macromolecule, two kinds of macromolecules twine mutually, but do not take place crosslinked; Membrane material may be separated, and the hydrophilic polymer large usage quantity.
The surfactant treatment method, JP63-277251 discloses a kind of method of modifying of hydrophobic perforated membrane, coats the hydrophobic polysulfones membrane surface of porous with surfactant, improves its hydrophily; But ageing not long, surfactant peels off easily.
The hygrometric state preservation method for fear of the film bone dry, keeps the activity of film; It also is the hydrophilic method that keeps film that film is carried out the hygrometric state preservation; But the hygrometric state film is in case dry, and meeting dwindles fenestra because dehydration produces the contraction distortion phenomenon significantly; Or membrane structure is destroyed, the quality of film is become fragile.
Summary of the invention
For the shortcoming and deficiency that overcome prior art, primary and foremost purpose of the present invention is to provide a kind of hydrophobic porous composite film through hydrophilic modifying.
Another object of the present invention is to provide the preparation method of above-mentioned hydrophobic porous composite film; This method is to be substrate with hydrophobic perforated membrane, but obtains the hydrophobic composite membrane material that the surface is a hydrophilic radical with physical method with the copolymer that contains ultraviolet light cross-linking group and hydrophilic radical simultaneously is compound.
A purpose more of the present invention is to provide the purposes of above-mentioned hydrophobic porous composite film.
The object of the invention is realized through following technical proposals:
A kind of hydrophobic porous composite film, its substrate are hydrophobic perforated membrane, surface recombination one deck copolymer of hydrophobic perforated membrane;
The aperture of said hydrophobic perforated membrane is 0.1～1 μ m, and thickness is 10～100 μ m, and porosity is 20～65%;
The material of said hydrophobic perforated membrane is a kind of in polypropylene (PP), Kynoar (PVDF), polyethylene (PE) or the polysulfones (PSF);
But described copolymer is to contain the group of ultraviolet light cross-linking and the random or block copolymer of hydrophilic radical; Its hydrophobic side group of ultraviolet light cross-linking (can) is polymethylacrylic acid-2-cinnamic acid ethyl ester (PCEMA) or polyacrylic acid-2-cinnamic acid ethyl ester (PCEA), and water-wet side (being hydrophilic radical) is a kind of in polymethyl methacrylate (PHEMA), PMA (PHEA), polyacrylamide (PAM), polyvinylpyrrolidone (PVP), polyacrylonitrile (PAN) or the poly (glycidyl methacrylate) (PGMA); Wherein but the mol ratio of ultraviolet light cross-linking group and hydrophilic radical is 0.2～8: 1;
A kind of in the block copolymer of the random copolymer of the block copolymer of the random copolymer of the preferred polymethylacrylic acid of described copolymer-2-cinnamic acid ethyl ester (PCEMA) and polymethyl methacrylate (PHEMA), polyacrylic acid-2-cinnamic acid ethyl ester (PCEA) and polyacrylamide (PAM), polymethylacrylic acid-2-cinnamic acid ethyl ester (PCEMA) and polyacrylonitrile (PAN) or polyacrylic acid-2-cinnamic acid ethyl ester (PCEA) and poly (glycidyl methacrylate) (PGMA).
The preparation method of above-mentioned hydrophobic porous composite film may further comprise the steps:
(1) hydrophobic perforated membrane was soaked in copolymer solution 3-20 hour;
(2) the hydrophobic perforated membrane after will soaking shone 3-48 hour under ultraviolet light, removed and obtained the hydrophobic porous composite film be made up of fine and close hydrophilic layer and porous hydrophobic layer behind the uncrosslinked polymer;
The mass concentration of the said polymer solution of step (1) is 1～20%, and solvent is a kind of in oxolane, dioxane, N ' dinethylformamide, N-methyl pyrrolidone, dimethyl sulfoxide (DMSO), carrene, chloroform, methyl alcohol or the ethanol;
Step (2) is said, and to remove uncrosslinked polymer be the method that adopts solvent wash, and used solvent is a kind of in oxolane, dioxane, N ' dinethylformamide, N-methyl pyrrolidone, dimethyl sulfoxide (DMSO), carrene, chloroform, methyl alcohol or the ethanol.
Above-mentioned hydrophobic porous composite film can be used for making lithium battery.
The present invention has following advantage and effect with respect to prior art:
(1) the present invention is easy to the method that hydrophobic perforated membrane carries out hydrophilic modifying, cost is low, be easy to suitability for industrialized production.
(2) the base material range of choice of the hydrophobic porous composite film of the present invention is wide, can obtain containing the composite membrane of different hydrophilic property group through the change copolymer structure simultaneously, thereby satisfies the requirement of preparation different performance lithium battery.
(3) the present invention's method that hydrophobic perforated membrane is carried out hydrophilic modifying has improved the hydrophily of hydrophobic membrane effectively, and hydrophobic perforated membrane passes through crosslinked riveted with copolymer simultaneously, makes that the composite membrane stability in use that obtains is better, timeliness is long.
(4) the present invention can supply further reaction at the functional group of hydrophobic porous film surface introducing, the preparation functional membrane.
The specific embodiment
Below in conjunction with embodiment the present invention is described in further detail, but embodiment of the present invention is not limited thereto.
Embodiment 1
A kind of preparation method of hydrophobic porous composite film may further comprise the steps:
(1) A, add the 10mmol hydroxyethyl methacrylate in the round-bottomed flask; Add the 10ml pyridine then; Slowly drip the 15mmol cinnamoyl chloride; Keep 0 ℃ of reaction 2 hours, be warming up to 25 ℃ of reactions 5 hours then, obtain methacrylic acid-2-cinnamic acid ethyl ester (CEMA) after the filtration of product process, washing and the distillation;
B, add 1mmol 4-bromomethyl benzophenone, 50mmol hydroxyethyl methacrylate (HEMA), 10mmol methacrylic acid-2-cinnamic acid ethyl ester (CEMA), 1mmol cuprous bromide, 1mmol pentamethyl-diethylenetriamine and 6.0g toluene solution in the round-bottomed flask; Reaction system is carried out liquid nitrogen frozen-vacuumize-the fill out argon gas-repeatable operation of thawing 3 times, and logical argon gas sealed after 10 minutes.Reacted 5 hours down at 20 ℃.Cessation reaction, product is centrifugal, get deposition, washing precipitation obtains the random copolymer PCEMA-co-PHEMA of polymethylacrylic acid-2-cinnamic acid ethyl ester (PCEMA) and poly hydroxy ethyl acrylate (PHEMA);
(2) adopting average pore size is 0.1 μ m, and thickness is 10 μ m, and porosity is that 20% porous polypropylene (PP) film is hydrophobic porous membrane substrate.Copolymer adopts the polymethylacrylic acid-2-cinnamic acid ethyl ester (PCEMA) of step (1) and the random copolymer (PCEMA-co-PHEMA) of polymethyl methacrylate (PHEMA);
(3) copolymer is dissolved in the oxolane, is mixed with the solution of mass fraction 1%, the porous PP film is soaked in copolymer solution, kept 3 hours.Take out the PP film, irradiation is crosslinked 3 hours under ultraviolet light.With film with the oxolane flushing repeatedly, remove uncrosslinked copolymer on film after crosslinked, the PP porous composite film of hydroxyl is contained on the surface that obtains film.
Resulting hydrophobic porous composite film substrate is porous polypropylene (PP) film, the surface recombination of porous polypropylene (PP) film the random copolymer (PCEMA-co-PHEMA) of one deck polymethylacrylic acid-2-cinnamic acid ethyl ester (PCEMA) and polymethyl methacrylate (PHEMA).The water contact angle of hydrophobic porous composite film is 70 °, and permeability improves 20% before than modification.
Embodiment 2
A kind of preparation method of hydrophobic porous composite film may further comprise the steps:
(1) A, add the 10mmol hydroxy-ethyl acrylate in the round-bottomed flask; Add the 10ml pyridine then; Slowly drip the 15mmol cinnamoyl chloride; Keep 0 ℃ of reaction 2 hours, be warming up to 25 ℃ of reactions 5 hours then, obtain acrylic acid-2-cinnamic acid ethyl ester (CEA) after the filtration of product process, washing and the distillation;
B, add 1mmol 4-bromomethyl benzophenone, 50mmol acrylamide, 30mmol acrylic acid-2-cinnamic acid ethyl ester (CEA), 1mmol cuprous bromide, 1mmol pentamethyl-diethylenetriamine and 6.0g toluene solution in the round-bottomed flask; Reaction system is carried out liquid nitrogen frozen-vacuumize-the fill out argon gas-repeatable operation of thawing 3 times, and logical argon gas sealed after 10 minutes.Reacted 5 hours down at 20 ℃.Cessation reaction, product is centrifugal, get deposition, washing precipitation obtains the block copolymer PCEA-b-PAM of polyacrylic acid-2-cinnamic acid ethyl ester (PCEA) and polyacrylamide (PAM);
(2) adopting average pore size is 0.3 μ m, and thickness is 30 μ m, and porosity is that 40% porous polyethylene (PE) film is hydrophobic porous membrane substrate.Copolymer adopts the polyacrylic acid-2-cinnamic acid ethyl ester (PCEA) of step (1) and the block copolymer (PCEA-b-PAM) of polyacrylamide (PAM);
(3) copolymer is dissolved in the dioxane, is mixed with the solution of mass fraction 5%, porous PE film is soaked in copolymer solution, kept 6 hours.Take out the PE film, irradiation is crosslinked 8 hours under ultraviolet light.With film with the dioxane flushing repeatedly, remove uncrosslinked copolymer on film after crosslinked, the PE porous composite film of amido link is contained on the surface that obtains film.
Resulting hydrophobic porous composite film substrate is porous polyethylene (PE) film, the surface recombination of porous polyethylene (PE) film the block copolymer (PCEA-b-PAM) of one deck polyacrylic acid-2-cinnamic acid ethyl ester (PCEA) and polyacrylamide (PAM).The water contact angle of hydrophobic porous composite film is 85 °, and permeability improves 50% before than modification.
Embodiment 3
A kind of preparation method of hydrophobic porous composite film may further comprise the steps:
(1) A, add the 10mmol hydroxyethyl methacrylate in the round-bottomed flask; Add the 10ml pyridine then; Slowly drip the 15mmol cinnamoyl chloride; Keep 0 ℃ of reaction 2 hours, be warming up to 25 ℃ of reactions 5 hours then, obtain methacrylic acid-2-cinnamic acid ethyl ester (CEMA) after the filtration of product process, washing and the distillation;
B, add 1mmol 4-bromomethyl benzophenone, 50mmol acrylonitrile, 200mmol methacrylic acid-2-cinnamic acid ethyl ester (CEMA), 1mmol cuprous bromide, 1mmol pentamethyl-diethylenetriamine and 6.0g toluene solution in the round-bottomed flask; Reaction system is carried out liquid nitrogen frozen-vacuumize-the fill out argon gas-repeatable operation of thawing 3 times, and logical argon gas sealed after 10 minutes.Reacted 5 hours down at 20 ℃.Cessation reaction, product is centrifugal, get deposition, washing precipitation obtains the random copolymer PCEMA-co-PAN of polymethylacrylic acid-2-cinnamic acid ethyl ester (PCEMA) and polyacrylonitrile (PAN);
(2) adopting average pore size is 0.7 μ m, and thickness is 50 μ m, and porosity is that 50% porous Kynoar (PVDF) film is hydrophobic porous membrane substrate.Copolymer adopts the polymethylacrylic acid-2-cinnamic acid ethyl ester (PCEMA) of step (1) and the random copolymer (PCEMA-co-PAN) of polyacrylonitrile (PAN);
(3) copolymer is dissolved in the N ' dinethylformamide, is mixed with the solution of mass fraction 10%, the porous pvdf membrane is soaked in copolymer solution, kept 10 hours.Take out pvdf membrane, irradiation is crosslinked 24 hours under ultraviolet light, during film maintenance hygrometric state.After crosslinked film is used in the N ' dinethylformamide flushing repeatedly, remove uncrosslinked copolymer on film, the PVDF porous composite film of itrile group is contained on the surface that obtains film.
Resulting hydrophobic porous composite film substrate is porous Kynoar (PVDF) film, the surface recombination of porous Kynoar (PVDF) film the random copolymer (PCEMA-co-PAN) of one deck polymethylacrylic acid-2-cinnamic acid ethyl ester (PCEMA) and polyacrylonitrile (PAN).The water contact angle of hydrophobic porous composite film is 55 °, and permeability improves 80% before than modification.
Embodiment 4
A kind of preparation method of hydrophobic porous composite film may further comprise the steps:
(1) A, add the 10mmol hydroxy-ethyl acrylate in the round-bottomed flask; Add the 10ml pyridine then; Slowly drip the 15mmol cinnamoyl chloride; Keep 0 ℃ of reaction 2 hours, be warming up to 25 ℃ of reactions 5 hours then, obtain acrylic acid-2-cinnamic acid ethyl ester (CEA) after the filtration of product process, washing and the distillation;
B, add 1mmol 4-bromomethyl benzophenone, 50mmol GMA, 400mmol acrylic acid-2-cinnamic acid ethyl ester (CEA), 1mmol cuprous bromide, 1mmol pentamethyl-diethylenetriamine and 6.0g toluene solution in the round-bottomed flask; Reaction system is carried out liquid nitrogen frozen-vacuumize-the fill out argon gas-repeatable operation of thawing 3 times, and logical argon gas sealed after 10 minutes.Reacted 5 hours down at 20 ℃.Cessation reaction, product is centrifugal, get deposition, washing precipitation obtains the block copolymer PCEA-b-PGMA of polyacrylic acid-2-cinnamic acid ethyl ester (PCEA) and poly (glycidyl methacrylate) (PGMA);
(2) adopting average pore size is 1.0 μ m, and thickness is 100 μ m, and porosity is that 65% porous polyether sulfone (PES) film is hydrophobic porous membrane substrate.Copolymer adopts the polyacrylic acid-2-cinnamic acid ethyl ester (PCEA) of step (1) and the block copolymer (PCEA-b-PGMA) of poly (glycidyl methacrylate) (PGMA);
(3) copolymer is dissolved in the chloroform, is mixed with the solution of mass fraction 20%, porous PES film is soaked in copolymer solution, kept 20 hours.Take out the PES film, irradiation is crosslinked 48 hours under ultraviolet light.With film with the chloroform flushing repeatedly, remove uncrosslinked copolymer on film after crosslinked, the PES porous composite film of epoxide group is contained on the surface that obtains film.
Resulting hydrophobic porous composite film substrate is porous polyether sulfone (PES) film, the surface recombination of porous polyether sulfone (PES) film the block copolymer (PCEA-b-PGMA) of one deck polyacrylic acid-2-cinnamic acid ethyl ester (PCEA) and poly (glycidyl methacrylate) (PGMA).The water contact angle of hydrophobic porous composite film is 70 °, and permeability improves 100% before than modification.
The foregoing description is a preferred implementation of the present invention; But embodiment of the present invention is not restricted to the described embodiments; Other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; All should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (7)
1. hydrophobic porous composite film, it is characterized in that: substrate is hydrophobic perforated membrane, surface recombination one deck copolymer of hydrophobic perforated membrane;
The material of said hydrophobic perforated membrane is a kind of in polypropylene, Kynoar, polyethylene or the polysulfones;
Described copolymer is random or block copolymer; Its hydrophobic side is polymethylacrylic acid-2-cinnamic acid ethyl ester or polyacrylic acid-2-cinnamic acid ethyl ester; Water-wet side is a kind of in polymethyl methacrylate, PMA, polyacrylamide, polyvinylpyrrolidone, polyacrylonitrile or the poly (glycidyl methacrylate), and the mol ratio of hydrophobic side group and water-wet side group is 0.2～8: 1.
2. hydrophobic porous composite film according to claim 1 is characterized in that: the aperture of said hydrophobic perforated membrane is 0.1～1 μ m, and thickness is 10～100 μ m, and porosity is 20～65%.
3. hydrophobic porous composite film according to claim 1 is characterized in that: described copolymer is a kind of in the block copolymer of random copolymer or polyacrylic acid-2-cinnamic acid ethyl ester and poly (glycidyl methacrylate) of block copolymer, polymethylacrylic acid-2-cinnamic acid ethyl ester and polyacrylonitrile of random copolymer, polyacrylic acid-2-cinnamic acid ethyl ester and polyacrylamide of polymethylacrylic acid-2-cinnamic acid ethyl ester and polymethyl methacrylate.
4. the preparation method of each described hydrophobic porous composite film of claim 1-3 is characterized in that may further comprise the steps:
(1) hydrophobic perforated membrane was soaked in copolymer solution 3-20 hour;
(2) the hydrophobic perforated membrane after will soaking shone 3-48 hour under ultraviolet light, obtained hydrophobic porous composite film after removing uncrosslinked polymer.
5. the preparation method of hydrophobic porous composite film according to claim 4; It is characterized in that: the mass concentration of the described polymer solution of step (1) is 1～20%, and solvent is a kind of in oxolane, dioxane, N ' dinethylformamide, N-methyl pyrrolidone, dimethyl sulfoxide (DMSO), carrene, chloroform, methyl alcohol or the ethanol.
6. the preparation method of hydrophobic porous composite film according to claim 4; It is characterized in that: step (2) is said, and to remove uncrosslinked polymer be the method that adopts solvent wash, and used solvent is a kind of in oxolane, dioxane, N ' dinethylformamide, N-methyl pyrrolidone, dimethyl sulfoxide (DMSO), carrene, chloroform, methyl alcohol or the ethanol.
7. each described hydrophobic porous composite film of claim 1-3 is used to make lithium battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102323422A CN102423644A (en) | 2011-08-15 | 2011-08-15 | Hydrophobic porous composite membrane, preparation method, and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102323422A CN102423644A (en) | 2011-08-15 | 2011-08-15 | Hydrophobic porous composite membrane, preparation method, and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102423644A true CN102423644A (en) | 2012-04-25 |
Family
ID=45957722
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011102323422A Pending CN102423644A (en) | 2011-08-15 | 2011-08-15 | Hydrophobic porous composite membrane, preparation method, and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102423644A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN106632922A (en) * | 2016-10-21 | 2017-05-10 | 苏州科技大学 | Preparation method of block polymer containing hydrophilic segment and method for modifying polyvinylidene fluoride (PVDF) micro-filtration membrane by block polymer |
| CN106745457A (en) * | 2016-12-26 | 2017-05-31 | 深圳大学 | Hollow-fibre membrane of selective absorption gold ion and preparation method and application |
| CN111341974A (en) * | 2020-03-13 | 2020-06-26 | 江苏厚生新能源科技有限公司 | PVDF (polyvinylidene fluoride) coated diaphragm and preparation method thereof, PVDF coated layer and lithium battery |
| CN112316751A (en) * | 2020-10-29 | 2021-02-05 | 南京工业大学 | Separation method of circulating tumor cells |
| CN113061276A (en) * | 2021-04-19 | 2021-07-02 | 威海泉成新材料科技有限公司 | High-hydrophobicity polyethylene composite film and preparation method thereof |
| CN114024089A (en) * | 2020-07-16 | 2022-02-08 | 湖南农业大学 | Hydrophilic modified polymer composite membrane and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4944879A (en) * | 1989-07-27 | 1990-07-31 | Millipore Corporation | Membrane having hydrophilic surface |
| CN100584437C (en) * | 2007-06-13 | 2010-01-27 | 海南立昇净水科技实业有限公司 | Hydrophilic polyvinylidene fluoride hollow fiber microporous membrane and preparation method thereof |
| CN101663057A (en) * | 2007-04-23 | 2010-03-03 | 东洋纺织株式会社 | Hollow fiber membrane-type artificial lung |
| CN102131568A (en) * | 2008-06-30 | 2011-07-20 | 3M创新有限公司 | Method of forming rewettable asymmetric membrane |
-
2011
- 2011-08-15 CN CN2011102323422A patent/CN102423644A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4944879A (en) * | 1989-07-27 | 1990-07-31 | Millipore Corporation | Membrane having hydrophilic surface |
| CN101663057A (en) * | 2007-04-23 | 2010-03-03 | 东洋纺织株式会社 | Hollow fiber membrane-type artificial lung |
| CN100584437C (en) * | 2007-06-13 | 2010-01-27 | 海南立昇净水科技实业有限公司 | Hydrophilic polyvinylidene fluoride hollow fiber microporous membrane and preparation method thereof |
| CN102131568A (en) * | 2008-06-30 | 2011-07-20 | 3M创新有限公司 | Method of forming rewettable asymmetric membrane |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103418254B (en) * | 2012-05-21 | 2015-07-08 | 中国科学院化学研究所 | Method of hydrophilic modification of polyvinylidene fluoride membrane |
| CN106632922A (en) * | 2016-10-21 | 2017-05-10 | 苏州科技大学 | Preparation method of block polymer containing hydrophilic segment and method for modifying polyvinylidene fluoride (PVDF) micro-filtration membrane by block polymer |
| CN106632922B (en) * | 2016-10-21 | 2018-12-21 | 苏州科技大学 | The method of the preparation method and its modified polyvinilidene fluoride microfiltration membranes of block polymer containing hydrophilic segment |
| CN106745457A (en) * | 2016-12-26 | 2017-05-31 | 深圳大学 | Hollow-fibre membrane of selective absorption gold ion and preparation method and application |
| CN106745457B (en) * | 2016-12-26 | 2019-12-17 | 深圳大学 | Hollow fiber membrane for selectively adsorbing gold ions and preparation method and application thereof |
| CN111341974A (en) * | 2020-03-13 | 2020-06-26 | 江苏厚生新能源科技有限公司 | PVDF (polyvinylidene fluoride) coated diaphragm and preparation method thereof, PVDF coated layer and lithium battery |
| CN114024089A (en) * | 2020-07-16 | 2022-02-08 | 湖南农业大学 | Hydrophilic modified polymer composite membrane and preparation method and application thereof |
| CN112316751A (en) * | 2020-10-29 | 2021-02-05 | 南京工业大学 | Separation method of circulating tumor cells |
| CN113061276A (en) * | 2021-04-19 | 2021-07-02 | 威海泉成新材料科技有限公司 | High-hydrophobicity polyethylene composite film and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102423644A (en) | Hydrophobic porous composite membrane, preparation method, and application thereof | |
| Sun et al. | Novel mussel-inspired zwitterionic hydrophilic polymer to boost membrane water-treatment performance | |
| CN102423642B (en) | Permanent hydrophilic modification method for surface of porous membrane and porous membrane obtained by same | |
| Zhang et al. | Supramolecular chemistry assisted construction of ultra-stable solvent-resistant membranes for angstrom-sized molecular separation | |
| CN103446897B (en) | Chemical and ionic cross-linked alginate hydrogel flat membrane for filtration and preparation method thereof | |
| CN110475602B (en) | Homogeneous pore self-assembled block copolymer membrane containing high molecular weight hydrophilic additive and preparation method thereof | |
| CN109758907A (en) | A kind of method that LBL self-assembly interfacial polymerization prepares compound forward osmosis membrane | |
| CN1077804C (en) | Porous composite membrane and making process | |
| CN110449048B (en) | Nanofiltration membrane, preparation method and dye separation method | |
| KR101580702B1 (en) | Composite separation membrane | |
| JP2015529555A (en) | Membrane having isoporous separation active layer and method for producing membrane | |
| CN101678279A (en) | Modified porous membranes, methods of membrane pore modification, and methods of use thereof | |
| CN105642129A (en) | Positively charged nano-filtration membrane based on tertiary amine type amphiphilic copolymer and preparation method thereof | |
| US20200222860A1 (en) | Method for preparing membrane selective layers by interfacial free radical polymerization | |
| CN101905125B (en) | Preparation method of polystyrolsulfon acid salt/polyethyleneimine crosslinking nanofiltration membrane | |
| CN102068912A (en) | Method for preparing negatively charged nanofiltration membrane through grafting induced after plasma radiation | |
| WO2021139094A1 (en) | Room-temperature selective swelling method of pore generation used for preparation of separation membrane | |
| CN104415667A (en) | Method of modifying polyolefin ultrafiltration membrane through polyaniline in-situ polymerization method | |
| CN111659268A (en) | Preparation method of low-pressure multi-electrolyte-layer hollow fiber nanofiltration membrane | |
| JP2011069011A (en) | Fiber assembly | |
| Tang et al. | Ultrafiltration membranes with ultrafast water transport tuned via different substrates | |
| CN102000511A (en) | Method for preparing positive charge hollow fiber nanofiltration membrane through surface UV irradiation grafting | |
| Zhai et al. | Stable fouling resistance of polyethylene (PE) separator membrane via oxygen plasma plus zwitterion grafting | |
| CN101284214B (en) | Preparation method of uni-endodermis hollow fiber infiltrating and vaporizing membrane | |
| CN113578061B (en) | Method for preparing composite nanofiltration membrane by using polluted polyethersulfone ultrafiltration membrane and composite nanofiltration membrane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20120425 |