CN1095391C - Polymer membrane for mixing and ultrafilter and its preparing process - Google Patents
Polymer membrane for mixing and ultrafilter and its preparing process Download PDFInfo
- Publication number
- CN1095391C CN1095391C CN00130071A CN00130071A CN1095391C CN 1095391 C CN1095391 C CN 1095391C CN 00130071 A CN00130071 A CN 00130071A CN 00130071 A CN00130071 A CN 00130071A CN 1095391 C CN1095391 C CN 1095391C
- Authority
- CN
- China
- Prior art keywords
- chloromethyl
- chloromethyl polysulphone
- blend
- film
- polysulphone
- 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.)
- Expired - Fee Related
Links
Abstract
The present invention belongs to the technical field of the separation and the concentration of cathodal electrophoretic paint. The cathodal electrophoretic paint is composed of chloromethyl polysulphone and polyvinylidene difluoride which are dissolved in a selected solvent, wherein the content of chloromethyl of the chloromethyl polysulphone is about 1.1 to 3.5 milligram equivalent /g; the proportion of the chloromethyl polysulphone in the blending substance is from 10% to 60%; the concentration of the blending substance of the chloromethyl polysulphone and the polyvinylidene difluoride is from 8 to 20%; the solvent is dimethyl sulfoxide. A phase inversion method is used to prepare a blending ultra filtering film with chloromethyl polysulphone and polyvinylidene difluoride. The present invention opens up a new way for searching a better pollution resistant film.
Description
Technical field
The invention belongs to the separation and the concentration technique field of cathode electrodip painting, particularly the composition of milipore filter and filming technology.
Background technology
Polymer film has been widely used in ultra-filtration process.At special separation system, polymer film needs functionalization, to possess specific chemical structure or physical aspect structure.Chargedization and blending method are important channels wherein.
The character that blending method improves membrane material by complementarity between the composition polymer and cooperative effect is regulated membrane structure, controlling diaphragm performance by the compatibility difference of forming between polymer.Conclusion is got up, and blending method has several effects:
(1) structure of change film: by changing the composition and the filming technology condition of casting solution, can change the form and the situation that is separated of the composition polymer molecular chain of film, reach the purpose of change, adjusting membrane structure, thus the separating property and the permeance property of regulating film.
(2) change the hydrophily and the stain resistance of film: select polyblend of different nature, can reach the purpose of hydrophilic, the lipophile that changes film, thereby obtain certain intensity, high water flux and resistant to pollution film.
(3) improve the mechanical performance of film: blend polymer has the submicroscopic heterogeneous morphosis of microcosmic makes them present remarkable erosion-resisting characteristics.
Phase inversion prepares the polyblend film many exacting terms and difficulty.First: require to have certain intermiscibility between the polymer blend; Second: suitable dissolution with solvents blend polymer can be arranged, and formed blend polymer solution has relative stability, good film forming; The 3rd: behind some blend polymer solution film forming, because microphase-separated appears in evaporation, the diffusion of solvent between the polymer, occur white floccule in the film forming liquid or bleach fully, resulting film is wrinkling even break, and film is difficult to use in ultra-filtration process.
For these reasons, found at present and to be used to prepare the blend system of milipore filter very limited.The particularly ultrafiltration of some high concentrations, special composition solution, as cathode electrodip painting etc., milipore filter must have good resistance tocrocking.
Abcor company adopts Kynoar (PVDF) and dimethylaminoethyl acrylate methyl to handle cathode electrodip painting for the blend film of amino ethyl ester-methylmethacrylate copolymer, and permeation rate reaches 32GFD, and resistance tocrocking is better.Handle this blend film obtaining the cation group of quaternary ammonium type with methyl iodide, film properties further improve (European patent 54354).After handle the sulfonation Kynoar with polymine again composite membrane handle cathode electrodip painting, show good resistance tocrocking and long-time stability (United States Patent (USP) 4412922).The blend film that Tsukasa prepares with polysulfones and ethylene-vinyl alcohol copolymer, the hydrophily and the pure water flux of PS membrane have been improved significantly, stain resistance also obviously strengthens, and with cation paint ultrafiltration 500 hours, its permeability rate only reduced by 10% (Japan Patent 60206404).With respect to the single polymers milipore filter, these polyblend films have obvious must the raising to the resistance tocrocking of separation system.
The film of required physical aspect structure is prepared in the polyblend of particular chemical structure, and the separation of special system is existed great potential and advantage.Seek and find physical chemistry excellent performance blend polymer, and adopt simple, fast, economy, effective method makes the milipore filter with required separating property and is subjected to people's attention always.
Summary of the invention
The objective of the invention is to prepare a kind of new type of polymer blended ultrafiltration membrane----chloromethyl polysulphone (ClCH2PSF) and polyvinylidene blending milipore filter, and utilize the chloromethyl polysulphone can be with the characteristics of the positive electrification of various amine lotuses, the blend film for preparing required morphosis, lotus positive electricity, be used for the cathode electrodip painting ultrafiltration, open up a new approach for seeking better pollution-resistant membrane.
The present invention proposes a kind of polyblend milipore filter, it is characterized in that, form by the chloromethyl polysulphone and the Kynoar that are dissolved in the selected solvent, wherein, about 1.1～3.5 moles/kilogram of the chloromethyl content of said chloromethyl polysulphone (milliequivalent/gram); The ratio of chloromethyl polysulphone in blend is 10%～60%; The concentration of chloromethyl polysulphone and polyvinylidene blending thing is 8～20%; Said solvent is a dimethyl sulfoxide (DMSO).
Another polyblend milipore filter that the present invention proposes, it is characterized in that, form with Kynoar and additive by the chloromethyl polysulphone that is dissolved in the selected solvent, wherein, about 1.1～3.5 moles/kilogram of the chloromethyl content of said chloromethyl polysulphone (milliequivalent/gram); The ratio of chloromethyl polysulphone in blend is 10%～60%; The concentration of chloromethyl polysulphone and polyvinylidene blending thing is 8～20%; Said solvent is a dimethyl sulfoxide (DMSO); Said additive is a polyethylene glycol, and its concentration is less than 20%.
A kind of method for preparing the polyblend milipore filter that the present invention proposes is characterized in that may further comprise the steps:
1), is dissolved in the selected solvent with chloromethyl polysulphone and polyvinylidene blending;
2) standing and defoaming after filtration;
3) be setting medium with ultrafiltration water, be prepared into chloromethyl polysulphone and polyvinylidene blending milipore filter with phase inversion.
Also can comprise in the said method;
4) amination in the aqueous solution of amine with said chloromethyl polysulphone and polyvinylidene fluoride blending film, the concentration of amine are 0.3～0.6 mol (N) aqueous solution, and the amination time is 6～24 hours, and temperature is 5～35 ℃.
Also can be added with additive in said chloromethyl polysulphone and polyvinylidene blending thing, said additive is a polyethylene glycol, and its concentration is less than 20%.
The polyethylene glycol additive that the present invention adds can be Macrogol 200, PEG400, Macrogol 600 etc. or does not add any additives, but can not influence the stability of solution.Prepare blended ultrafiltration membrane with phase inversion, the about 200 μ m of thickness.
Principle of the present invention:
PVDF has excellent hydrophobic property, mechanical performance and chemical stability, and can be dissolved in multiple solvents such as dimethyl formamide, dimethylacetylamide, dimethyl sulfoxide (DMSO), has good filming performance, in addition, PVDF itself is nontoxic, can operate in-50 ℃～140 ℃ scopes, therefore, pvdf membrane is widely used in technology (United States Patent (USP) 4399035) such as micro-filtration, ultrafiltration and film distillation.
Chloromethyl polysulphone is on the basis of the various good physical and chemical performances that keep polysulfones, because the existence of chloromethyl, further modification prepares the number of chemical structure, satisfies the material of different purposes, particularly be used for amberplex, ion exchange resin, charged milipore filter and charged reverse osmosis membrane etc. with the positive electrification of various amine reaction lotuses, separating property excellence not only, and show anti-solvent, withstand voltage characteristics (European patent 61424) such as close.
The present invention proves that first chloromethyl polysulphone and Kynoar exist the part compatibility, and this characteristic is the basis of preparation ultrafiltration blend film.
The contribution of key of the present invention is to obtain suitable solvent after deliberation or mixed solvent dissolves chloromethyl polysulphone and Kynoar simultaneously, this solvent not only dissolves chloromethyl polysulphone and Kynoar mixture, and keep blend solution-stabilized, realize chloromethyl polysulphone and Kynoar part compatibility, prepare metastable chloromethyl polysulphone and polyvinylidene blending solution, adopt phase inversion to prepare the ultrafiltration blend film of suitable morphosis.
|=1.16, according to the solubility parameter principle, both can not be miscible with arbitrary proportion.For the preparation blend polymer membranes, be not complete miscibility between the requirement polymer, part is miscible can to satisfy the needs that inversion of phases prepares diffusion barrier.
The present invention is according to the characteristics of chloromethyl polysulphone, polyvinylidene fluoride material, choose N, N-dimethylacetylamide (DMAc), N, dinethylformamide (DMF), dimethyl sulfoxide (DMSO) (DMSO), N-methyl pyrrolidone (NMP), dichloroethanes, triethyl phosphate, ethanol, cyclohexanone, dioxane, methyl acetate equal solvent carry out dissolubility and compatibility experiment to the chloromethyl polysulphone and the Kynoar of different proportion, find that DMAc, DMF, DMSO and NMP are to ClCH
2The PSF/PVDF blend has certain dissolubility, but the ratio and the concentration of dissolving blend separately has than big difference, and the solution-stabilized lasting asynchronism(-nization) of formed polymer blend.These all are the keys of restriction inversion of phases legal system film.
NMP can dissolve or be partly dissolved ClCH
2The blend of PSF and PVDF forms transparent solution, but phase-splitting takes place stable extreme difference in a short period of time; DMAc, DMF are at whole C lCH
2Can only be partly dissolved blend in the proportion of PSF/PVDF but opaque, formed stability of solution is relatively poor; DMSO is with ClCH
2The ratio of PSF/PVDF changes, and can there be dissolving (ClCH in blend solution
2The ratio of PSF in blend is less than 25%), be partly dissolved (ClCH
2The ratio of PSF in blend is greater than 40%), the variation of swelling and phenomenon such as do not dissolve each other, but the good stability of blend solution.Therefore, selection DMSO is that the solvent or the double solvents of film making solution are preparation ClCH
2The key of PSF/PVDF blend film and basic.
Table 1. glass transition temperature
Pure PVDF ClCH
2The pure ClCH of PSF/PVDF (1/4)
2PSFTg (℃)-34-24 170.76Tm (℃) 166.18 164.63-
Measure the glass transition T of blend
gThe T that forms with blend not
gContrast is to determine the miscibility of polymer-blend polymer or the effective ways of part intermiscibility.Partial miscibility then between the transition point of pure component, the transformation of two separations occurred, rich component 1 phase of expression, another represents rich component 2 phases, to ClCH
2PSF/PVDF blend (C1CH
2The ratio of PSF in blend is 20%), the T of rich PVDF phase
gBe-24 ℃, pure relatively PVDF raises 10 ℃; Yet rich ClCH
2PSF is mutually because at 164.63 ℃ of melting peaks that have PVDF, with pure ClCH
2The T of PSF
gVery near, covered this T
gTransformation.
Fig. 1,2 has provided the infrared spectrogram of blend sample.Have interaction force between the xenogenesis macromolecule, relevant group can produce infrared absorption band frequency displacement or the asymmetric degree change of peak shape, but this variation is little usually, only is several wave numbers, and FT-IR is with its high resolution ratio (0.1cm
-1) and reappearance, provide another argument for judging xenogenesis macromolecule interphase interaction and compatibility.
The pure ClCH of curve 11 expressions among Fig. 1
2PSF, curve 12 expression ClCH
2The PSF ratio is 30% PVDF/ClCH
2PSF blend, curve 13 expression ClCH
2The PSF ratio is 10% PVDF/ClCH
2PSF blend, the pure PVDF of curve 14 expressions.As seen from Figure 1, ClCH
2On the PSF
Displacement has taken place in the characteristic peak of vibration, by 1588cm
-1Move on to 1587cm
-1(ClCH
2The ratio of PSF in blend is 30%), and 1580cm
-1(ClCH
2The ratio of PSF in blend is 10%).Curve 21 expression ClCH wherein among Fig. 2
2The PSF ratio is 10% PVDF/ClCH
2PSF blend, curve 22 expression ClCH
2The PSF ratio is 30% PVDF/ClCH
2PSF blend, the pure ClCH of curve 23 expressions
2PSF, the pure PVDF of curve 24 expressions.Object line 24 is at 872cm among Fig. 2
-1For
Characteristic peak; Line 23 is at 879cm
-1For
Characteristic peak; ClCH in the blend
2The ratio of PSF is that 10% o'clock characteristic peak but moves to 882cm to high wave number direction
-1In blend, further increase ClCH
2PSF was by 30% o'clock, and this characteristic peak moves on to 881cm to the lower wave number direction again
-1, ClCH is described
2PSF/PVDF only is that part is compatible.
The present invention can add an amount of additive in chloromethyl polysulphone and polyvinylidene blending solution.The type of additive and addition can not influence the stability and the film forming of blend solution significantly.Additive is a polyethylene glycol, comprises Macrogol 200, PEG400, Macrogol 600, Macrogol 2000, Macrogol 6000 and Macrogol 2000 0 etc., and the adding of additive can further improve the separating property of film.
Chloromethyl polysulphone of the present invention can react with the mixture of amine, diamines or amine and two amine blends or different diamines with the polyvinylidene blending milipore filter, obtain polytype charged blend anion milipore filter, the charged type of film, carrying capacity combine with the morphosis of film and improve the separating property and the resistance tocrocking of film.Amine is 1,4-butanediamine, N, N-dimethyl-1,3-propane diamine (DMAPA) or N, N, N ', N '-tetramethyl-1,6-hexamethylene diamine (TMDAH) etc.Chloromethyl polysulphone in amine and chloromethyl polysulphone/polyvinylidene blending thing reacts, and forms quaternary ammonium ion, secondary amine ion and primary amine ion etc.Owing to the repulsive interaction of charged ion pair cathode electrodip painting, improved the resistance tocrocking of film.
Antifouling property be with in room temperature, cathode electrodip painting concentration be 1%, inlet pressure is the separating property rate of decay in time of measuring film under the 0.1Mpa.
Another index of film pollution level is that pure water flux attenuation coefficient m represents:
M=(J
0-J
1)/J
0J in * 100% formula
0: the pure water flux before polluting
J
1: the pure water flux after the pollution
The film cleaning performance is represented with pure water flux recovery coefficient γ:
γ＝J
2/J
0×100％
J
2: the pure water flux after the cleaning
The big more expression of general m value is polluted more serious; γ value big expression film easy cleaning or cleaning performance are better.
Effect of the present invention:
Of the present invention is the chloromethyl polysulphone and the polyvinylidene fluoride blending film of solvent preparation with the dimethyl sulfoxide (DMSO), when the ratio in the chloromethyl polysulphone blend is 50%, at operating pressure is under the 0.1MPa, film is to bovine serum albumin (concentration is 0.1 grams per liter) rejection only 3.9%, pure water flux 316.6L/m
2H; With the ratio in the chloromethyl polysulphone blend is 20% o'clock, and film is to bovine serum albumin rejection 86.2%, pure water flux 144.4L/m
2H.With N, N, N ', N '-tetramethyl-1,6-hexamethylene diamine (TMDAH) amination blend film (ClCH
2The ratio of PSF in blend is 40%) to bovine serum albumin rejection 78.0%, pure water flux 96.3L/m
2H.
The PVDF and the ClCH of the present invention's preparation
2The PSF blend film is worked as ClCH
2The ratio of PSF in blend is 20% o'clock, and not only to the pure water flux attenuation coefficient m minimum of bovine serum albumin, and the water flux of target electrophoretic paint is higher, and rate of decay is low, pure water flux recovery coefficient γ maximum.
The amination blend film of the present invention's preparation, compare with the blend film of not amination, m diminishes, resistance tocrocking to bovine serum albumin strengthens, and the water flux of the target electrophoretic paint aqueous solution increases, the pure water flux recovery coefficient is higher, illustrates that the positive electrification of lotus of film has further improved the resistance tocrocking of blend film target electrophoretic paint.
Fig. 3,4 is respectively PVDF/ClCH
2The surface of PSF blend film and fracture morphology structure.Section structure is irregular finger-like pore or spongy hole, the fibrous or granular tissue that wherein is scattered here and there and causes because of limited compatibility.
Description of drawings
Fig. 1 is the infrared spectrogram of blend sample of the present invention.
Fig. 2 is the infrared spectrogram of blend sample of the present invention.
Fig. 3 is PVDF/ClCH of the present invention
2The configuration of surface structure chart of PSF blend film.
Fig. 4 is PVDF/ClCH of the present invention
2The fracture morphology structure chart of PSF blend film.
The specific embodiment
Following embodiment is used for illustrating protection scope of the present invention, but is not limited thereto.
Embodiment 1.
2.5 gram chloromethyl polysulphones and 7.5 gram Kynoar are dissolved in 88 milliliters of dimethyl sulfoxide (DMSO)s, and the chloromethyl content of chloromethyl polysulphone is 2.2 moles/kilogram (milliequivalents/gram); Treating that polymer all dissolves, after filtration, standing and defoaming, is setting medium with ultrafiltration water, prepares milipore filter with phase inversion, the about 200 μ m of thickness.This film is 0.1MPa at operating pressure, pure water flux 445.6L/m
2H is to the rejection 82.7% of the bovine serum albumin aqueous solution of 0.1 grams per liter.
Embodiment 2.
4 gram chloromethyl polysulphones and 8 gram Kynoar are dissolved in 86 milliliters of dimethyl sulfoxide (DMSO)s, and the chloromethyl content of chloromethyl polysulphone is 2.2 moles/kilogram (milliequivalents/gram); Treat that polymer all dissolves, add 3 gram Macrogol 600s, treat dissolving evenly after, after filtration, standing and defoaming, be setting medium with ultrafiltration water, the temperature of setting medium is 10 ℃, prepares milipore filter with phase inversion, the about 200 μ m of thickness.This film is 0.1MPa at operating pressure, pure water flux 380.2L/m
2H is to the rejection 65.4% of the bovine serum albumin aqueous solution of 0.1 grams per liter.
Embodiment 3.
2.5 gram chloromethyl polysulphones and 10 gram Kynoar are dissolved in 88 milliliters of dimethyl sulfoxide (DMSO)s, and the chloromethyl content of chloromethyl polysulphone is 2.2 moles/kilogram (milliequivalents/gram); Treating that polymer all dissolves, after filtration, standing and defoaming, is setting medium with ultrafiltration water, prepares milipore filter with phase inversion, the about 200 μ m of thickness.This film is 0.1MPa at operating pressure, pure water flux 144.4L/m
2H is to the rejection 86.1% of the bovine serum albumin aqueous solution of 0.1 grams per liter, pure water flux attenuation coefficient m
1Be 16.8; The pure water flux recovery coefficient of target electrophoretic paint is 204.5.
Embodiment 4.
The blend film of embodiment 3 is immersed 0.5 mol (N) the butanediamine aqueous solution, amination at room temperature 12 hours, film is 0.1MPa at operating pressure, pure water flux 85.0L/m
2H is to the rejection 77.9% of the bovine serum albumin aqueous solution of 0.1 grams per liter, pure water flux attenuation coefficient m
1Be 0.4; The pure water flux recovery coefficient of target electrophoretic paint is 268.7.
Embodiment 5.
The blend film of embodiment 3 is immersed 0.5 mol (N) N, N, N ', N '-tetramethyl-1, the 6-hexamethylene diamine aqueous solution, amination at room temperature 12 hours, film is 0.1MPa at operating pressure, pure water flux 96.8L/m
2H is to the rejection 78.0% of the bovine serum albumin aqueous solution of 0.1 grams per liter, pure water flux attenuation coefficient m
1Be 0.9; The pure water flux recovery coefficient of target electrophoretic paint is 219.8.
Claims (5)
1, a kind of polyblend milipore filter is characterized in that, form by the chloromethyl polysulphone and the Kynoar that are dissolved in the selected solvent, wherein, about 1.1～3.5 moles/kilogram of the chloromethyl content of said chloromethyl polysulphone (milliequivalent/gram); The ratio of chloromethyl polysulphone in blend is 10%～60%; The concentration of chloromethyl polysulphone and polyvinylidene blending thing is 8～20%; Said solvent is a dimethyl sulfoxide (DMSO).
2, a kind of polyblend milipore filter, it is characterized in that, form with Kynoar and additive by the chloromethyl polysulphone that is dissolved in the selected solvent, wherein, about 1.1～3.5 moles/kilogram of the chloromethyl content of said chloromethyl polysulphone (milliequivalent/gram); The ratio of chloromethyl polysulphone in blend is 10%～60%; The concentration of chloromethyl polysulphone and polyvinylidene blending thing is 8～20%; Said solvent is a dimethyl sulfoxide (DMSO); Said additive is a polyethylene glycol, and its concentration is less than 20%.
3, a kind of method for preparing polyblend milipore filter as claimed in claim 1 is characterized in that may further comprise the steps:
1), is dissolved in the selected solvent with chloromethyl polysulphone and polyvinylidene blending;
2) standing and defoaming after filtration;
3) be setting medium with ultrafiltration water, be prepared into chloromethyl polysulphone and polyvinylidene blending milipore filter with phase inversion.
4, the method for polyblend milipore filter as claimed in claim 3 is characterized in that, also comprises;
4) amination in the aqueous solution of amine with said chloromethyl polysulphone and polyvinylidene fluoride blending film, the concentration of amine are 0.3～0.6 mol (N) aqueous solution, and the amination time is 6～24 hours, and temperature is 5～35 ℃.
As the method for claim 3 or 4 described polyblend milipore filters, it is characterized in that 5, also be added with additive in said chloromethyl polysulphone and polyvinylidene blending thing, said additive is a polyethylene glycol, its concentration is less than 20%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00130071A CN1095391C (en) | 2000-10-27 | 2000-10-27 | Polymer membrane for mixing and ultrafilter and its preparing process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00130071A CN1095391C (en) | 2000-10-27 | 2000-10-27 | Polymer membrane for mixing and ultrafilter and its preparing process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1289633A CN1289633A (en) | 2001-04-04 |
| CN1095391C true CN1095391C (en) | 2002-12-04 |
Family
ID=4593943
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN00130071A Expired - Fee Related CN1095391C (en) | 2000-10-27 | 2000-10-27 | Polymer membrane for mixing and ultrafilter and its preparing process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1095391C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100382876C (en) * | 2003-09-15 | 2008-04-23 | 上海一鸣过滤技术有限公司 | Complex pore structured micropore membrane and its preparation method |
| CN100357350C (en) * | 2005-03-16 | 2007-12-26 | 福州大学 | The pH sensitive film with polyvinylidene fluoride/polyurethane mixture film as base film and its prepn process |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4203848A (en) * | 1977-05-25 | 1980-05-20 | Millipore Corporation | Processes of making a porous membrane material from polyvinylidene fluoride, and products |
| US4399035A (en) * | 1979-10-15 | 1983-08-16 | Asahi Kasei Kogyo Kabushiki Kaisha | Polyvinylidene fluoride type resin hollow filament microfilter and process for producing the same |
| JPS60206404A (en) * | 1984-03-30 | 1985-10-18 | Nitto Electric Ind Co Ltd | Permselective membrane and its prepration |
-
2000
- 2000-10-27 CN CN00130071A patent/CN1095391C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4203848A (en) * | 1977-05-25 | 1980-05-20 | Millipore Corporation | Processes of making a porous membrane material from polyvinylidene fluoride, and products |
| US4399035A (en) * | 1979-10-15 | 1983-08-16 | Asahi Kasei Kogyo Kabushiki Kaisha | Polyvinylidene fluoride type resin hollow filament microfilter and process for producing the same |
| JPS60206404A (en) * | 1984-03-30 | 1985-10-18 | Nitto Electric Ind Co Ltd | Permselective membrane and its prepration |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1289633A (en) | 2001-04-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | Characteristics and performance of PVDF membrane prepared by using NaCl coagulation bath: Relationship between membrane polymorphous structure and organic fouling | |
| JP6018790B2 (en) | Separation membrane, manufacturing method thereof, and water treatment apparatus including separation membrane | |
| CN111013391B (en) | Modified nanofiltration membrane and preparation method thereof | |
| CN104607063B (en) | PVDF permanently hydrophilic ultrafiltration membrane and modification method thereof | |
| US9868834B2 (en) | Polymer blend for membranes | |
| Zhu et al. | Preparation and characterization of improved fouling-resistant PPESK ultrafiltration membranes with amphiphilic PPESK-graft-PEG copolymers as additives | |
| Baig et al. | Sustainable Aqueous Phase Separation membranes prepared through mild pH shift induced polyelectrolyte complexation of PSS and PEI | |
| CN106345318A (en) | Composite membrane for water treatment, and preparation method thereof | |
| US20190209973A1 (en) | Multilayer hollow fibre membranes | |
| JP3215512B2 (en) | Durable filtration membrane with optimal molecular weight | |
| CN1261547A (en) | High permeability composite reverse osmosis film and its producing method | |
| Joshi et al. | Multipurpose tight ultrafiltration membrane through controlled layer-by-layer assembly for low pressure molecular separation | |
| WO2021191043A1 (en) | Solution of polysulfons in n-n-butyl-2-pyrrolidone for the use of membranes | |
| Gao et al. | A prebiotic chemistry inspired one-step functionalization of zwitterionic nanofiltration membranes for efficient molecular separation | |
| Burts et al. | Modification of polysulfone ultrafiltration membranes using block copolymer Pluronic F127 | |
| CN1095391C (en) | Polymer membrane for mixing and ultrafilter and its preparing process | |
| Xiang et al. | Poly (acrylic acid-co-acrylonitrile) copolymer modified polyethersulfone hollow fiber membrane with pH-sensitivity | |
| Nazri et al. | A facile modification approach for polyacrylonitrile-based UF hollow fiber membrane utilizing polyacrylonitrile-g-poly (vinyl alcohol) graft copolymer | |
| Sforca et al. | Composite nanofiltration membranes prepared by in situ polycondensation of amines in a poly (ethylene oxide-b-amide) layer | |
| US5942120A (en) | Composite microporous ultrafiltration membrane, method of making thereof, and separation methods | |
| Pacharasakoolchai et al. | Improved permeation performance and fouling-resistance of Poly (vinyl chloride)/Polycarbonate blend membrane with added Pluronic F127. | |
| JPH04227824A (en) | Hydrophilic membrane and its manufacture | |
| CN1772358A (en) | Composite nanofiltering film of polyacrylonitrile and poly (p,p-diamino diphenylmethane amide) and its prepn process | |
| WO1996027429A1 (en) | Improved membrane | |
| CN115779697B (en) | Hydrophilic modification method of hollow fiber separation membrane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |