CN108654410A - A kind of preparation method of hydrophilic modifying polyvinylidene fluoride film - Google Patents
A kind of preparation method of hydrophilic modifying polyvinylidene fluoride film Download PDFInfo
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- CN108654410A CN108654410A CN201710237898.8A CN201710237898A CN108654410A CN 108654410 A CN108654410 A CN 108654410A CN 201710237898 A CN201710237898 A CN 201710237898A CN 108654410 A CN108654410 A CN 108654410A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
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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
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0013—Casting processes
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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
- B01D71/08—Polysaccharides
- B01D71/10—Cellulose; Modified cellulose
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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
- B01D71/34—Polyvinylidene fluoride
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- 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
Abstract
The invention discloses a kind of preparation methods of hydrophilic modifying polyvinylidene fluoride film, first by hydrophilic cellulose dissolution in suitable ionic liquid, Kynoar (PVDF) is dissolved in the organic solvent containing inorganic salts, the two is blended again and forms homogeneous casting solution, using phase separation method, PVDF and cellulose blending film are obtained.One aspect of the present invention overcomes the problem of at present due to unsuitable solvent PVDF and cellulose co-dissolve, so that the two may be implemented that film forming is blended, on the other hand, hydrophilic modifying material of the cellulose of use as pvdf membrane, it can be easy to run off in film operational process to avoid current water soluble hydrophilic modified material, cause film to lose hydrophilic problem, realizes that the persistence of PVDF Modified Membranes is hydrophilic and anti-pollution.In addition, cellulose origin is extensive, of low cost, nontoxic, solvent resistant, good hydrophilic property, is rich in hydroxyl, good biocompatibility, there is significant advantage as hydrophilic modifying material, be suitable for the special separations applications such as medicine, biology.
Description
Technical field
The invention belongs to polymeric membrane separation technology fields, and in particular to a kind of preparation of hydrophilic modifying polyvinylidene fluoride film
Method.
Background technology
Membrane separation technique it is novel as one efficiently separate, concentrate, purifying and purification techniques is used widely, wherein
Micro-filtration (MF) and the development of ultrafiltration (UF) membrane technology are swift and violent, and market increases quick.Micro-filtration and ultrafiltration membrane (letter currently used for water process
Claim：Micro-/ultrafiltration membrane), mainly by Kynoar (PVDF), polyether sulfone (PES), polysulfones (PSF), polyvinyl chloride (PVC), poly-
The high molecular materials such as acrylonitrile (PAN) and polypropylene (PP) are made.In these membrane materials, PVDF is used to be prepared for membrane material
Micro-/ultrafiltration membrane has in cleaning etc. repeatedly of solvent resistance, resistance to acid and alkali, UV resistant and weatherability, oxidative resistance medicament
There is significant advantage, thus, the research that PVDF prepares micro-/ultrafiltration membrane as membrane material receives significant attention.
PVDF is to have very strong hydrophobic property for the shortcoming of water process, easily adsorb protein in water, oil droplet,
Colloid etc. blocks fenestra, causes the dramatic decrease of permeation flux.A large amount of studies have shown that if membrane material surface is in hydrophily, glue
The pollutants such as body, oil droplet, protein easily coalesce glomeration in film surface, and this spherical agglomerate is easy to be detached from from film surface, lead to
Crossing simple backwash can clean up, thus for water process when film have better anti-fouling performance.The parent of pvdf membrane
Water method of modifying can be divided into physical modification and chemical modification two major classes, and physical modification includes mainly surface coating and physical blending
Deng, and chemical modification has surface irradiation, grafting, polymerization and crosslinking etc..Usual chemical modification easily causes membrane structure (especially surface
Structure) damage, cause the decline of film mechanical strength, and complex process, it is of high cost, it is difficult to realize industrialization.Business at present
Frequently be that hydrophilic high molecular material such as polyvinylpyrrolidone (PVP) is blended film forming with PVDF, but PVP be it is water-soluble,
Operational process is easy to run off, and film is made to lose hydrophily.The PVDF that seeks persistence hydrophiling is micro-/and ultrafiltration membrane technique, improves the resistance to of film
Pollutant performance, be PVDF it is micro-/ultrafiltration membrane needs the key technical problem that solves.Cellulose is a kind of excellent natural height of hydrophily
Molecular material, but cellulose has the labyrinth that coexists of crystalline region and amorphous area, this make cellulose be difficult be dissolved in it is common molten
In agent, thus also it is difficult to that film forming is blended with PVDF.In consideration of it, the present invention provides a kind of high performance hydrophilic modifying polyvinylidene fluorides
The preparation method of alkene film.
Invention content
The purpose of the present invention is the deficiencies for existing hydrophilic modifying pvdf membrane and its technology of preparing, provide a kind of high-performance
The preparation method of hydrophilic modifying polyvinylidene fluoride film obtained mainly by the way that film forming is blended with PVDF for hydrophilic cellulose
Obtain hydrophilic modifying polyvinylidene fluoride film.
Technical solution is used by the present invention solves above-mentioned technical problem：A kind of system of hydrophilic modifying polyvinylidene fluoride film
Preparation Method, it is characterised in that include the following steps：
1) Kynoar (PVDF) solution is prepared：It is 10%-25%, solvent quality percentage by PVDF mass percentages
Content is 60%-85%, and inorganic salts mass percentage is that 5%-15% configures suitable PVDF solution, first that inorganic salts are complete
In solvent PVDF is added, agitating and heating dissolving, nitrogen protection, at 50 DEG C -80 DEG C, constant temperature stirs solution temperature in fully dissolved later
2h-4h is mixed, standing and defoaming is kept the temperature, obtains homogeneous standard casting solution 1, is preserved under solution temperature for use；
2) cellulose-ionic liquid solution is prepared：It, in proportion will be fine using suitable ionic liquid as the solvent of cellulose
Dimension element is dissolved in ionic liquid, agitating and heating dissolving, nitrogen protection, and for solution temperature at 50 DEG C -80 DEG C, constant temperature stirs 2h-4h,
Standing and defoaming is kept the temperature, cellulose mass percentage is made in the homogeneous standard casting solution 2 of 3-15%, heat preservation for standby use；
3) by above-mentioned prepared PVDF solution (standard casting solution 1) and cellulose-ionic liquid solution (standard casting film
Liquid 2) it is mixed in a certain ratio, constant temperature stirring 2h-4h makes solution be uniformly mixed, and temperature at 50 DEG C -80 DEG C, protect by process nitrogen
Shield keeps the temperature standing and defoaming, obtains required homogeneous standard casting solution 3, heat preservation for standby use；
4) the homogeneous standard casting solution 3 that step 3) obtains is fallen on glass plate, then uses knifing machine striking at nascent
State film, then nascent state diaphragm plate is put into coagulation bath, so that nascent state film is separated, it is natural from homogeneous liquid phase film-forming
It falls off；
5) finally, film is placed in pure water, further the dissolution completely of the solvent in film is changed to get to the hydrophilic of the present invention
Property polyvinylidene fluoride film.
Inorganic salts must be contained in the step 1), inorganic salts are chloride and bromide, such as lithium chloride (LiCl), chlorine
Change zinc (ZnCl2), lithium bromide (LiBr) is without being limited thereto, and the mass percentage of inorganic salts is 5%-15%, and the solvent is
Dimethylformamide and dimethylacetylamide.
Cellulose in the step 2) is alpha-cellulose, purified cotton, without being limited thereto, and the ionic liquid is can be with
The ionic liquid of excellent dissolution cellulose, such as 1- butyl -3- methylimidazole villaumites, 1- allyl -3- methylimidazole villaumites, 1- second
Base -3- methylimidazole dimethyl phosphate salt, N- allyl pyridine villaumites are without being limited thereto.
The macromolecule in standard casting solution 3 in the step 3) is (i.e.：Cellulose and PVDF) account for total casting solution
For mass percentage in 7-20wt%, cellulose accounts for total macromolecule (i.e.：Cellulose and PVDF) mass percentage be 4%-
20%.
Coagulation bath in the step 4) is the non-solvent of standard casting solution 3, such as water, ethyl alcohol, solvent-laden water-soluble
Liquid, it is without being limited thereto.
The step 5) obtains the thickness of the hydrophilic modifying polyvinylidene fluoride film of the present invention at 40 μm -200 μm, and aperture exists
0.01μm-1.0μm。
Compared with the prior art, the advantages of the present invention are as follows：
1. the method that the present invention is combined using common organic solvent, inorganic salts and the ionic liquid of PVDF, successfully prepares
Gone out PVDF and cellulose is blended homogeneous casting solution, is further prepared for being blended for PVDF and cellulose by phase separation method
Film.The problem of overcoming at present due to unsuitable solvent PVDF and cellulose co-dissolve so that the two may be implemented
Film forming is blended.In addition, the method that PVDF is remixed after respectively being dissolved with cellulose, improves rate of dissolution and the dissolving of cellulose
Amount, and present invention discover that inorganic salts presence, it is homogeneous phase solution that PVDF and cellulose can be promoted molten.
2. hydrophilic modifying macromolecule of the cellulose that the present invention uses as pvdf membrane, can be to avoid currently used hydrophilic
Modified material ----water-soluble polyethylene pyrrolidones (PVP) is easy to run off in operational process, and film is caused to lose hydrophilic problem,
Realize PVDF Modified Membranes persistence is hydrophilic and anti-pollution.In addition, cellulose origin is extensive, of low cost, nonhazardous, resistance to molten
Agent, good hydrophilic property apply also for the spies such as medicine, biology rich in hydroxyl, good biocompatibility if further carrying out chemical modification
Kind separation application.There is significant advantage as hydrophilic modifying material.
3. the cellulose dissolution process of the present invention is not required to need cellulose before dissolving into current common dissolving method
Activation, as a small amount of CoCl is added in document report in DMAc2Or KMnO4, 30min is heated in 160 DEG C of oil baths.This activation disappears
Weak intermolecular active force, destroys the fine structure of cellulose, cellulose is made although to may be dissolved in LiCl/ polar solvent bodies
In system, but cellulose degradation is apparent, influences the intensity of fiber.
Specific implementation mode
Present invention is further described in detail with reference to embodiments.
Embodiment 1
Step 1) prepares Kynoar (PVDF) solution：Weigh 11.28 grams of PVDF, 73.43 grams of dimethylacetylamide,
7.37 grams of lithium chloride configures PVDF solution, lithium chloride is dissolved completely in dimethylformamide first, PVDF is added later,
Nitrogen protection, agitating and heating keep the temperature standing and defoaming, obtain homogeneous standard casting solution 1 in 80 DEG C of dissolvings, constant temperature mechanical agitation 4h
Number, it is preserved in 80 DEG C for use；
Step 2) prepares cellulose-ionic liquid solution：Using 1- allyl -3- methylimidazole villaumites as the molten of cellulose
Agent, weighs 0.72 gram of alpha-cellulose, and 7.2 grams of 1- allyl -3- methylimidazole villaumites are molten by cellulose agitating and heating at 80 DEG C
Solution, nitrogen protection, constant temperature mechanical agitation 4h keep the temperature standing and defoaming, and homogeneous standard casting solution 2, heat preservation for standby use is made；
Step 3) is by above-mentioned prepared PVDF solution (standard casting solution 1) and cellulose-ionic liquid solution (standard
Casting solution 2) mixing, 80 DEG C of constant temperature, which stirs 4h, makes solution be uniformly mixed, and nitrogen protection keeps the temperature standing and defoaming, obtains homogeneous
Standard casting solution 3 so that the macromolecule in standard casting solution 3 is (i.e.：Cellulose and PVDF) account for total casting solution quality hundred
Divide content in 12wt%, cellulose accounts for total macromolecule (i.e.：Cellulose and PVDF) mass percentage be 6%.
And then fall homogeneous standard casting solution 3 on glass plate, then use knifing machine striking at nascent state film, then
Nascent state diaphragm plate is put into rapidly gel in room temperature water, nascent state film is made to be separated, it is natural from homogeneous liquid phase film-forming
Film is placed in pure water after falling off, further the solvent in film is dissolved out completely, obtains the hydrophilic modifying Kynoar of the present invention
Film.
Above-mentioned hydrophilic modifying pvdf membrane is placed in membrane performance tester under 0.1MPa and is tested, the thickness of film is 110 μ
M, for average pore size at 0.12 μm, the water flux of film is 1375L/ (m2H), water contact angle is 76 °, and tensile elongation is
56.1%, the stain resistance of film is good.
Embodiment 2
Step 1) prepares Kynoar (PVDF) solution：Weigh 11.16 grams of PVDF, 73.34 grams of dimethylacetylamide,
7.26 grams of lithium chloride configures PVDF solution, lithium chloride is dissolved completely in dimethylformamide first, PVDF is added later,
Nitrogen protection, agitating and heating keep the temperature standing and defoaming, obtain homogeneous standard casting solution 1 in 60 DEG C of dissolvings, constant temperature mechanical agitation 4h
Number, it is preserved in 60 DEG C for use；
Step 2) prepares cellulose-ionic liquid solution：Using 1- allyl -3- methylimidazole villaumites as the molten of cellulose
Agent, weighs 0.84 gram of alpha-cellulose, and 8.4 grams of 1- allyl -3- methylimidazole villaumites are molten by cellulose agitating and heating at 60 DEG C
Solution, nitrogen protection, constant temperature mechanical agitation 4h keep the temperature standing and defoaming, and homogeneous standard casting solution 2, heat preservation for standby use is made；
Step 3) is by above-mentioned prepared PVDF solution (standard casting solution 1) and cellulose-ionic liquid solution (standard
Casting solution 2) mixing, 60 DEG C of constant temperature, which stirs 4h, makes solution be uniformly mixed, and nitrogen protection keeps the temperature standing and defoaming, obtains homogeneous
Standard casting solution 3 so that the macromolecule in standard casting solution 3 is (i.e.：Cellulose and PVDF) account for total casting solution quality hundred
Divide content in 12wt%, cellulose accounts for total macromolecule (i.e.：Cellulose and PVDF) mass percentage be 7%.And then it will
Homogeneous standard casting solution 3 falls on glass plate, is then put rapidly at nascent state film, then by nascent state diaphragm plate with knifing machine striking
Enter gel in room temperature water, nascent state film is made to be separated, from homogeneous liquid phase film-forming, film is placed in pure water after falling off naturally
In further the solvent in film is dissolved out completely, obtain the present invention hydrophilic modifying polyvinylidene fluoride film.
Above-mentioned hydrophilic modifying pvdf membrane is placed in membrane performance tester under 0.1MPa and is tested, the thickness of film is 100 μ
M, for average pore size at 0.1 μm, the water flux of film is 1670L/ (m2H), water contact angle is 72 °, tensile elongation 34.5%,
The stain resistance of film is good.
Embodiment 3
Step 1) prepares Kynoar (PVDF) solution：Weigh 10.8 grams of PVDF, 71.3 grams of dimethylacetylamide, chlorine
7.1 grams of compound configures PVDF solution, chloride is dissolved completely in dimethylformamide first, PVDF, nitrogen are added later
Protection, agitating and heating keep the temperature standing and defoaming, obtain homogeneous standard casting solution 1 in 70 DEG C of dissolvings, constant temperature mechanical agitation 4h,
It is preserved in 70 DEG C for use；
Step 2) prepares cellulose-ionic liquid solution：Using 1- allyl -3- methylimidazole villaumites as the molten of cellulose
Agent, weighs 1.2 grams of purified cotton, and 9.6 grams of 1- allyl -3- methylimidazole villaumites stir cellulose (purified cotton) at 70 DEG C
It dissolves by heating, nitrogen protection, constant temperature mechanical agitation 4h, keeps the temperature standing and defoaming, homogeneous standard casting solution 2, heat preservation for standby use is made；
Step 3) is by above-mentioned prepared PVDF solution (standard casting solution 1) and cellulose-ionic liquid solution (standard
Casting solution 2) mixing, 70 DEG C of constant temperature, which stirs 4h, makes solution be uniformly mixed, and nitrogen protection keeps the temperature standing and defoaming, obtains homogeneous
Standard casting solution 3 so that the macromolecule in standard casting solution 3 is (i.e.：Cellulose and PVDF) account for total casting solution quality hundred
Divide content in 12wt%, cellulose accounts for total macromolecule (i.e.：Cellulose and PVDF) mass percentage be 10%.Later, will
Homogeneous standard casting solution 3 falls on glass plate, and at nascent state film, gel solidification forms a film in room temperature water, falls off naturally for striking
Film is placed in pure water afterwards and dissolves out film internal solvent completely, obtains the hydrophilic modifying polyvinylidene fluoride film of the present invention.
Above-mentioned hydrophilic modifying pvdf membrane is placed in membrane performance tester under 0.1MPa and is tested, the thickness of film is 105 μ
M, for average pore size at 0.18 μm, the water flux of film is 2610L/ (m2H), water contact angle is 63 °, and tensile elongation is
33.1%, permanent hydrophilic, the anti-fouling performance of film are good.
Comparative example 1
Inorganic salts (i.e. the quality of inorganic salts is substituted by solvent) are free of in step 1), remaining is the same as the step 1) of embodiment 1, step
It is rapid 2) with the step 2) of embodiment 1, as a result after standard solution 1 and standard solution 2 are stirred by step 3), stand process
Middle stratified-phase-separable can not form homogeneous phase solution, cause to be unable to knifing.
Comparative example 2
Step 1)：With the step 1) of embodiment 2；
Later, without the step 2) and step 3) of embodiment 2, directly homogeneous standard casting solution 1 is fallen in glass plate
On, it is then put into gel in room temperature water rapidly at nascent state film, then by nascent state diaphragm plate with knifing machine striking, nascent state film is made to send out
Film is placed in pure water further that the solvent in film is completely molten by raw phase separation from homogeneous liquid phase film-forming, after falling off naturally
Go out, obtains the hydrophilic modifying polyvinylidene fluoride film of the present invention.
Above-mentioned pvdf membrane is placed in membrane performance tester under 0.1MPa and is tested, the water flux of film is 870L/ (m2·
H), water contact angle is 83 °, tensile elongation 23.6%, the low contamination resistance of film.
Comparative example 3
Step 1)：With the step 1) of embodiment 3；
Step 2) and remaining step：Except composition not containing cellulose (i.e. the quality of cellulose is all substituted by ionic liquid)
Outside, remaining step 2) and remaining step with embodiment 3；
Above-mentioned pvdf membrane is placed in membrane performance tester under 0.1MPa and is tested, the water flux of film is 1030L/
(m2H), water contact angle is 84 °, tensile elongation 12.2%, the low contamination resistance of film.
Comparative example 4
PVDF10.8 grams, 1.2 grams of cellulose is placed in the mixed solution of 81.9 grams of dimethylacetylamides and 7.1 grams of chlorides
In, as a result heating stirring can not be dissolved into homogeneous phase solution.
Comparative example 5
PVDF11.28 grams, 0.72 gram of cellulose is placed in heating stirring in 88 grams of 1- allyl -3- methylimidazole villaumites, knot
Fruit can not be dissolved into homogeneous phase solution.
Claims (5)
1. a kind of preparation method of hydrophilic modifying polyvinylidene fluoride film, it is characterised in that include the following steps：
1) Kynoar (PVDF) solution is prepared：It is 10%-25%, solvent quality percentage composition by PVDF mass percentages
For 60%-85%, inorganic salts mass percentage is that 5%-15% configures suitable PVDF solution, first that inorganic salts are completely molten
In solvent PVDF is added, agitating and heating dissolving, nitrogen protection, for solution temperature at 50 DEG C -80 DEG C, constant temperature stirs 2h- in solution later
4h keeps the temperature standing and defoaming, obtains homogeneous standard casting solution 1, is preserved under solution temperature for use；
2) cellulose-ionic liquid solution is prepared：Using suitable ionic liquid as the solvent of cellulose, in proportion by cellulose
It is dissolved in ionic liquid, agitating and heating dissolving, nitrogen protection, for solution temperature at 50 DEG C -80 DEG C, constant temperature stirs 2h-4h, heat preservation
Cellulose mass percentage is made in the homogeneous standard casting solution 2 of 3-15%, heat preservation for standby use in standing and defoaming；
3) by above-mentioned prepared PVDF solution (standard casting solution 1) and cellulose-ionic liquid solution (standard casting solution 2
Number) be mixed in a certain ratio, constant temperature stirring 2h-4h makes solution be uniformly mixed, and temperature is protected in 50 DEG C -80 DEG C, process nitrogen protection
Warm standing and defoaming obtains required homogeneous standard casting solution 3, heat preservation for standby use；
4) the homogeneous standard casting solution obtained step 3) 3 fall on glass plate, then use knifing machine striking at nascent state film,
Nascent state diaphragm plate is put into coagulation bath again, nascent state film is made to be separated, from homogeneous liquid phase film-forming, is fallen off naturally；
5) finally, film is placed in pure water, further the dissolution completely of the solvent in film is gathered to get the hydrophilic modifying to the present invention
Vinylidene fluoride film.
2. a kind of preparation method of hydrophilic modifying polyvinylidene fluoride film according to claim 1, which is characterized in that step 1)
In must contain inorganic salts, inorganic salts are chloride and bromide, such as lithium chloride (LiCl), zinc chloride (ZnCl2), lithium bromide
(LiBr), without being limited thereto, the mass percentage of inorganic salts is 5%-15%, and the solvent is dimethylformamide and diformazan
Yl acetamide.
3. a kind of preparation method of hydrophilic modifying polyvinylidene fluoride film according to claim 1, which is characterized in that step 2)
In cellulose be alpha-cellulose, purified cotton, without being limited thereto, the ionic liquid is can be with the ion of excellent dissolution cellulose
Liquid, such as 1- butyl -3- methylimidazole villaumites, 1- allyl -3- methylimidazole villaumites, 1- ethyl-3-methylimidazole di(2-ethylhexyl)phosphates
Methyl esters salt, N- allyl pyridine villaumites are without being limited thereto.
4. a kind of preparation method of hydrophilic modifying polyvinylidene fluoride film according to claim 1, which is characterized in that step 3)
Standard casting solution 3 in macromolecule (i.e.：Cellulose and PVDF) total casting solution quality percentage is accounted for containing degree in 7-20wt%,
Cellulose accounts for total macromolecule (i.e.：Cellulose and PVDF) mass percentage be 4%-20%.
5. a kind of preparation method of hydrophilic modifying polyvinylidene fluoride film according to claim 1, which is characterized in that step 5)
The thickness of the hydrophilic modifying polyvinylidene fluoride film of the present invention is obtained at 40 μm -200 μm, aperture is at 0.01 μm -1.0 μm.
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| CN114950169A (en) * | 2021-12-30 | 2022-08-30 | 昆明理工大学 | Ionic liquid-based high-performance conductive composite membrane and preparation method and application thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109433027A (en) * | 2018-12-20 | 2019-03-08 | 长春工业大学 | A kind of hydrophilic antipollution ultrafiltration membrane and preparation method thereof |
| CN110846306A (en) * | 2019-12-09 | 2020-02-28 | 江苏省中国科学院植物研究所 | Amphiphilic enzyme immobilization carrier |
| CN110846306B (en) * | 2019-12-09 | 2021-08-17 | 江苏省中国科学院植物研究所 | Amphiphilic enzyme immobilization carrier |
| CN111495207A (en) * | 2020-04-23 | 2020-08-07 | 北京赛诺膜技术有限公司 | Hydrophilic modification method of polymer ultrafiltration membrane |
| CN111617641A (en) * | 2020-05-07 | 2020-09-04 | 天津工业大学 | Imidazole functionalized ionic liquid copolymer synthesis and alloy ultrafiltration membrane preparation method |
| CN111617641B (en) * | 2020-05-07 | 2021-12-10 | 天津工业大学 | Imidazole functionalized ionic liquid copolymer synthesis and alloy ultrafiltration membrane preparation method |
| CN114950169A (en) * | 2021-12-30 | 2022-08-30 | 昆明理工大学 | Ionic liquid-based high-performance conductive composite membrane and preparation method and application thereof |
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