CN108905657B - Preparation method of amphiphilic triblock polymer blending modified polyvinylidene fluoride ultrafiltration membrane - Google Patents
Preparation method of amphiphilic triblock polymer blending modified polyvinylidene fluoride ultrafiltration membrane Download PDFInfo
- Publication number
- CN108905657B CN108905657B CN201811154984.3A CN201811154984A CN108905657B CN 108905657 B CN108905657 B CN 108905657B CN 201811154984 A CN201811154984 A CN 201811154984A CN 108905657 B CN108905657 B CN 108905657B
- Authority
- CN
- China
- Prior art keywords
- membrane
- preparation
- polyvinylidene fluoride
- ultrafiltration membrane
- triblock polymer
- 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.)
- Active
Links
Images
Classifications
-
- 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
- B01D71/80—Block polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/02—Hydrophilization
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/38—Graft polymerization
-
- 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 provides a preparation method of an amphiphilic triblock polymer blending modified polyvinylidene fluoride ultrafiltration membrane, which adopts polymethyl methacrylate (PMMA) and polyacryl morpholine (PACMO) as a hydrophobic chain segment and a hydrophilic chain segment of an amphiphilic block polymer respectively, prepares PACMO-b-PMMA-b-PACMO (PAMA) with a controllable structure by a reversible addition-fragmentation chain transfer polymerization method, and prepares the amphiphilic block copolymer modified ultrafiltration membrane by using the blend modifier and a non-solvent induced phase inversion method. The PMMA chain segment in the blending modifier PAMA is entangled with the PVDF chain segment, so that the modifier is more stable in the ultrafiltration membrane preparation and use processes; the PACMO is used as a chain segment to be enriched on the surface of the membrane and the surface of the membrane pore, so that the hydrophilicity of the membrane is improved, and the deposition and adhesion of pollutants on the surface of the membrane are reduced. The invention realizes the effective regulation and control of the membrane aperture and the porosity by adjusting the content of the membrane forming substances and the modifier in the membrane casting solution. The ultrafiltration membrane prepared by the invention has obviously improved permeability and keeps higher BSA retention rate and anti-fouling capability.
Description
Technical Field
The invention belongs to the field of high molecular material science, relates to an amphiphilic triblock copolymer modified ultrafiltration membrane, and particularly relates to a preparation method of an amphiphilic triblock copolymer blended and modified polyvinylidene fluoride ultrafiltration membrane.
Background
Solving the problems of water resource pollution and safe water use is one of the most important challenges in our times. Water is the most precious life resource on the earth, and the breeding and growth of all the organisms almost cannot be nourished by water resources. In recent years, along with population growth, industrial technology progress and climate change, the method forms a series of continuously expanding threats to the safety of water resources, and aggravates the shortage of water resources worldwide. To address this challenge, there is an urgent need to develop effective and sustainable technologies to increase water supply using unconventional water sources (e.g., seawater, brackish water, and wastewater) rather than obtaining water from hydrologic cycles. In addition to the use of seawater desalination for the production of fresh water, the recycling of municipal and industrial wastewater is also receiving increasing attention. In the next decades, water resource recovery will become an indispensable part of wastewater treatment, and development of new separation and purification technology will become an indispensable part of this work.
Based on the membrane treatment technology, compared with the traditional water treatment technologies such as adsorption, precipitation, filtration and the like, the membrane treatment technology can show strong advantages in water purification and seawater desalination. The membrane separation technology can produce water with excellent quality and occupies much smaller area. Furthermore, membrane-based desalination technology is inherently more energy efficient than thermal methods. For example, current thermal desalination techniques consume up to five times more energy than the most advanced Reverse Osmosis (RO) techniques require to desalinate seawater.
The current design and preparation methods of membrane separation materials have certain defects, and further development of structure control technology for the selective layer of the membrane is needed. Membrane fouling will also reduce the performance and life of the membrane separation material, increasing the cost of water purification and desalination. Aiming at the existing modification method of a membrane separation material body, the method is designed to change the physical and chemical properties of the surface of a separation membrane so as to endow more functions to the traditional membrane material, wherein the improvement of the hydrophilicity, the anti-pollution performance and the like of the membrane has very important significance. The blending modification is widely used for preparing separation membrane materials due to the advantages of simple and easy method, easy industrial production and the like. The patent of CN105268331A discloses a PVDF separation membrane with better blood compatibility. Firstly, preparing a poly (acryloyl morpholine) -grafted polyvinylidene fluoride copolymer (PVDF-g-PACMO), and blending to prepare a PVDF separation membrane. The hydrophilicity of the separation membrane is improved, the adhesion of blood platelets and red blood cells on the surface of the membrane is obviously reduced, and the blood compatibility is improved. The preparation method of the graft copolymer is complicated, the grafting rate is difficult to control, and the problem is solved by directly blending the amphiphilic block copolymer. The introduction of the amphiphilic block copolymer has the advantages that the hydrophilic chain segment increases the membrane hydrophilicity and improves the anti-fouling effect of the membrane, and the hydrophobic anchoring chain segment improves the stability of the modifier in the membrane, so that the operation is simple and convenient, the method has industrial production conditions, and has very wide prospects in the field of membrane water treatment. In addition, the invention achieves the effects of high flux, high interception and high pollution resistance of the membrane by simply adjusting the concentration of the membrane forming substances and adjusting the porosity and the surface aperture of the membrane.
Disclosure of Invention
The invention provides an amphiphilic triblock polymer PAMA modified ultrafiltration membrane and a preparation method thereof, wherein PAMA is used as a blending additive, one-step modification is carried out to form a membrane by a non-solvent induced phase inversion method, and the surface aperture and porosity of the membrane are regulated and controlled by designing the concentration of a membrane forming substance, the length of a hydrophilic chain segment of a modifier and the concentration of the hydrophilic chain segment, so as to realize effective regulation on pure water flux and an anti-fouling effect. The membrane after blending modification has the advantages of good hydrophilicity, high flux and high pollution resistance.
In order to realize the performances, the invention provides a preparation method of an amphiphilic triblock polymer blending modified polyvinylidene fluoride ultrafiltration membrane, which is characterized by comprising the following steps:
1. preparation of amphiphilic triblock polymer PAMA
Dissolving methyl methacrylate, RAFT reagent and azobisisobutyronitrile into 60m L toluene, stirring and reacting for 24h at 70 ℃ under the protection of argon, removing part of solvent by rotary evaporation, adding the polymer solution into ice n-hexane for precipitation, collecting the precipitate, drying in vacuum to constant weight to obtain PMMA-RAFT, dissolving the PMMA-RAFT, acryloylmorpholine and azobisisobutyronitrile into 60m L of 1, 4-dioxane, repeatedly freezing and thawing for three times by double pipes to remove oxygen, stirring and reacting for 24h at 70 ℃ under the protection of argon, precipitating the polymer solution after removing part of solvent by rotary evaporation in n-hexane/ethyl acetate mixed solution, collecting the precipitate, and drying in vacuum to obtain the light yellow solid PAMA.
2. Preparation of amphiphilic triblock polymer PAMA modified ultrafiltration membrane
Putting a certain amount of PVDF, a modifier PAMA, a pore-forming agent and a solvent into a three-neck flask, mechanically stirring for 12-24 hours at 40-80 ℃, fully dissolving, and then defoaming in vacuum to obtain a homogeneous casting solution. And uniformly pouring the mixed solution onto a dry and clean glass plate, scraping the film by using a film scraping machine, then immersing into a coagulating bath, obtaining a PVDF modified film by non-solvent induced phase transformation, changing water twice every day until the solvent is completely removed, and immersing the film in distilled water for later use.
Preferably, the polymerization degree (X) of the polymethyl methacrylate segment and the polymerization degree (Y) of the polyacryloylmorpholine segment in the PAMA are controlled by controlling the amounts of methyl methacrylate and acryloylmorpholine to be added.
Preferably, the value of X is 70, and the values of Y are 14, 42, 70 and 99 respectively.
Preferably, the modifier PAMA adopted by the invention adopts RAFT polymerization, and the method has the advantages of simple operation, low cost, wide range of applicable monomers for RAFT polymerization and controllable and diversified structure. The modified membrane is modified by blending, and is formed by one step through a phase inversion method, so that the operation is simple, the performance of the membrane is stable, and the industrial production is easy.
Compared with the prior art, the preparation method of the modified membrane has the following beneficial effects:
a) the invention solves the problems of complicated preparation method, unstable quality, incapability of mass production and the like of the existing membrane hydrophilic modifier. In addition, compared with other polymerization methods, the chain transfer agent adopted by the reversible addition-fragmentation chain transfer polymerization does not need metal salt as a catalyst, so that the environmental pollution and the post-treatment cost are reduced.
b) The invention obtains the optimal chain segment length by designing and preparing the amphiphilic block copolymers with different hydrophilic chain segment lengths and a series of characteristics of the modified membrane, so that the modified membrane has the optimal hydrophilicity, thereby optimizing the anti-fouling capability of the modified membrane.
c) The invention regulates and controls the aperture by regulating the concentration of the film forming substance, achieves the effect of small aperture and high anti-fouling, ensures the pure water flux and simultaneously has higher protein retention rate and anti-fouling capability.
Drawings
FIG. 1 is a contact angle characterization of a polyvinylidene fluoride membrane and a PVDF/PAMA modified membrane prepared in example 1 of the present invention;
FIG. 2 shows the pure water flux and protein rejection of the PVDF/PAMA modified membrane and the polyvinylidene fluoride membrane prepared in example 1 of the present invention;
FIG. 3 is an IR spectrum of a polyvinylidene fluoride membrane and a PVDF/PAMA modified membrane prepared in example 1 of the present invention;
FIG. 4 is a scanning electron microscope image of a polyvinylidene fluoride membrane and a PVDF/PAMA modified membrane prepared in example 2 of the present invention;
Detailed Description
The present invention will be further described with reference to the following embodiments and the accompanying drawings. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
Example 1
a) The amphiphilic block copolymer PAMA is prepared by dissolving 5g of methyl methacrylate, 0.29g of RAFT reagent and 47mg of azobisisobutyronitrile into 60m L of toluene, stirring and reacting for 24h at 70 ℃ under the protection of argon, dropwise adding a polymer solution obtained by rotary evaporation of a part of solvent into ice n-hexane for precipitation, carrying out suction filtration, collecting the precipitate, carrying out vacuum drying to constant weight to obtain PMMA-RAFT, dissolving 5g of PMMA-RAFT, 10g of acryloyl morpholine and 47mg of azobisisobutyronitrile prepared in the above step into 60m L of 1, 4-dioxane, stirring and reacting for 24h at 70 ℃ under the protection of argon, carrying out rotary evaporation to remove a part of solvent, adding the polymer solution into n-hexane/ethyl acetate mixed solution for precipitation, collecting the precipitate, and carrying out vacuum drying to obtain a light yellow solid PAMA, wherein the X value and the Y value are controlled according to the change of the molar ratio of methyl methacrylate to acryloyl morpholine, the X value is 70, and the Y value is respectively 14, 42, 70 and 99.
b) Preparation of PVDF/PAMA modified film: respectively weighing 8-11 g of PVDF powder, 4g of lithium chloride, 10% by mass of PAMA-99 and N, N-dimethylformamide, putting into a three-neck flask, stirring at 60 ℃ for 12 hours until the materials are completely dissolved into a homogeneous casting solution, and standing or defoaming in vacuum at room temperature; and uniformly pouring the homogeneous casting film liquid onto a dry and clean glass plate, scraping out a liquid membrane with the thickness of 300 mu m, standing in the air for 10s, putting the flat membrane into a solidification water bath in parallel, soaking the prepared flat membrane in distilled water at the temperature of 25 ℃ for a period of time, and freeze-drying to obtain the amphiphilic block copolymer modified polyvinylidene fluoride ultrafiltration membrane, which is marked as PVDF-10/0, PVDF-8/0.8, PVDF-9/0.9, PVDF-10/1.0 and PVDF-11/1.1.
Example 2
a) The same as example 1;
b) preparation of PVDF/PAMA modified film: respectively weighing 10g of PVDF powder, 4g of lithium chloride, 10% by mass of PAMA-70 and N, N-dimethylformamide, putting into a three-neck flask, stirring for 12 hours at 60 ℃, preparing a homogeneous casting solution with the mass concentration of 21.33% after the PVDF powder, the lithium chloride and the PAMA-70 and the N, N-dimethylformamide are completely dissolved, and standing or defoaming in vacuum at room temperature; and (2) uniformly pouring the homogeneous casting film liquid onto a dry and clean glass plate, scraping a liquid film with the thickness of 200 mu M, standing in the air for 10s, putting the flat film into coagulating bath water in parallel, soaking the prepared flat film in distilled water at the temperature of 25 ℃ for a period of time, and freeze-drying to obtain the amphiphilic block copolymer modified polyvinylidene fluoride ultrafiltration membrane marked as M-5 k.
Example 3
a) The same as example 1;
b) preparation of PVDF/PAMA modified film: weighing 9.5g of PVDF, 4g of lithium chloride, 1.5g of PAMA-70 and 63g N, putting N-dimethylformamide into a three-neck flask, fully stirring for 12 hours at 60 ℃, fully dissolving to obtain homogeneous casting solution, and standing or defoaming the casting solution in vacuum at room temperature; uniformly pouring the homogeneous casting film liquid onto a dry and clean glass plate, scraping out a liquid film with the thickness of 200 mu m, standing in air for 30s, putting the flat film into a coagulating bath in parallel, wherein the coagulating bath is water, the temperature is 25 ℃, after the film falls off from the glass plate, putting the prepared flat film into distilled water, soaking for a period of time, and freeze-drying to obtain the amphiphilic block copolymer modified polyvinylidene fluoride ultrafiltration membrane.
Claims (9)
1. A preparation method of an amphiphilic triblock polymer blending modified polyvinylidene fluoride ultrafiltration membrane is characterized by comprising the following steps: the PAMA is used as an additive to prepare the amphiphilic triblock polymer modified ultrafiltration membrane, wherein the modifier is prepared by the following synthetic route:
2. the preparation method of the amphiphilic triblock polymer blended and modified polyvinylidene fluoride ultrafiltration membrane according to claim 1, which is characterized by comprising the following steps of: the PAMA synthesis method comprises the following steps:
a) dissolving methyl methacrylate, RAFT reagent and azodiisobutyronitrile in a polar solvent; reacting for 12-24 h at 60-70 ℃ under the protection of inert gas; after the reaction is finished, evaporating part of the solvent in a rotary manner at 25-40 ℃, precipitating the evaporated solution in a normal hexane solution, collecting the precipitate, and drying in vacuum to constant weight to obtain a macromolecular chain transfer agent PMMA-RAFT;
b) dissolving the prepared macromolecular chain transfer agent PMMA-RAFT, acryloyl morpholine and azobisisobutyronitrile in a polar solvent; and (3) reacting for 12-24 h at 60-70 ℃ under the protection of inert gas, after the reaction is finished, rotationally evaporating part of the solvent at 25-40 ℃, precipitating the rotationally evaporated solution in a normal hexane/ethyl acetate solution, collecting the precipitate, and drying in vacuum to constant weight to obtain light yellow solid PAMA.
3. The preparation method of the amphiphilic triblock polymer blended and modified polyvinylidene fluoride ultrafiltration membrane according to claim 2, which is characterized by comprising the following steps of: the polar solvent is one of N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone and 1, 4-dioxane.
4. The preparation method of the amphiphilic triblock polymer blended and modified polyvinylidene fluoride ultrafiltration membrane according to claim 1, which is characterized by comprising the following steps of: the preparation method of the casting solution comprises the following steps:
a) dissolving a certain amount of polyvinylidene fluoride powder, a pore-forming agent and 10% by mass of an amphiphilic block copolymer in a polar solvent, heating and stirring at 25-80 ℃ for 12-24 h, and preparing a homogeneous casting solution with the concentration of 15-25%;
b) pouring the casting solution on a clean glass plate, scraping out a liquid membrane with the thickness of 100-300 mu m, standing in the air for 0-30 s, and parallelly placing the flat membrane in a coagulating bath for curing to form a membrane; and soaking the prepared flat membrane in distilled water, and drying to obtain the amphiphilic block copolymer PAMA modified polyvinylidene fluoride flat membrane.
5. The preparation method of the amphiphilic triblock polymer blended and modified polyvinylidene fluoride ultrafiltration membrane according to claim 4, wherein the preparation method comprises the following steps: the polar solvent is one or a mixture of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone and triethyl phosphate.
6. The preparation method of the amphiphilic triblock polymer blended and modified polyvinylidene fluoride ultrafiltration membrane according to claim 4, wherein the preparation method comprises the following steps: the coagulating bath is a mixed solvent of water and ethanol, wherein the proportion of the ethanol is 0-100%.
7. The preparation method of the amphiphilic triblock polymer blended and modified polyvinylidene fluoride ultrafiltration membrane according to claim 3, which is characterized by comprising the following steps of: the lengths of the segments of the polyacryloylmorpholine and the polymethyl methacrylate can be adjusted according to the charge ratio.
8. The preparation method of the amphiphilic triblock polymer blended and modified polyvinylidene fluoride ultrafiltration membrane according to claim 1 or 2, which is characterized by comprising the following steps of: the polymerization degree of the polymethyl methacrylate is 40-200, and the polymerization degree of the polyacryloylmorpholine is 10-100.
9. An amphiphilic triblock polymer blending modified polyvinylidene fluoride ultrafiltration membrane is prepared according to any one of claims 1 to 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811154984.3A CN108905657B (en) | 2018-09-28 | 2018-09-28 | Preparation method of amphiphilic triblock polymer blending modified polyvinylidene fluoride ultrafiltration membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811154984.3A CN108905657B (en) | 2018-09-28 | 2018-09-28 | Preparation method of amphiphilic triblock polymer blending modified polyvinylidene fluoride ultrafiltration membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108905657A CN108905657A (en) | 2018-11-30 |
| CN108905657B true CN108905657B (en) | 2020-07-14 |
Family
ID=64408997
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811154984.3A Active CN108905657B (en) | 2018-09-28 | 2018-09-28 | Preparation method of amphiphilic triblock polymer blending modified polyvinylidene fluoride ultrafiltration membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108905657B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109529637B (en) * | 2018-12-18 | 2021-08-03 | 曲靖师范学院 | Preparation method of polyvinylidene fluoride separation membrane resisting microbial contamination |
| CN112090288A (en) * | 2020-08-05 | 2020-12-18 | 杭州晟聚环保科技有限公司 | Preparation method of amphiphilic sulfone polymer and blend membrane |
| CN112108015A (en) * | 2020-10-10 | 2020-12-22 | 天津工业大学 | Preparation method of structurally controllable amphiphilic hyperbranched polymer in-situ modified ultrafiltration membrane |
| CN113750804B (en) * | 2021-09-15 | 2022-07-19 | 北京理工大学 | Modified polyisophthaloyl metaphenylene diamine ultrafiltration membrane as well as preparation method and application thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100496683C (en) * | 2007-04-28 | 2009-06-10 | 浙江大学 | Method of modifying surface of polytetrafluoroethylene porous membrane by amphipathic fluorine-contained copolymer |
| FR3047244B1 (en) * | 2016-02-01 | 2020-04-03 | Arkema France | DIBLOC AMPHIPHILIC COPOLYMER AND ITS USE FOR THE MANUFACTURE OF POLYMERIC FILTRATION MEMBRANES |
| CN105709618B (en) * | 2016-04-19 | 2019-08-09 | 贵阳学院 | By the Pvdf Microporous Hollow Fiber Membrane of amphipathic three block copolymer blending and modifying |
| CN107486043A (en) * | 2017-09-14 | 2017-12-19 | 天津工业大学 | A kind of preparation method of amphipathic three block copolymer modified polyvinilidene fluoride film |
-
2018
- 2018-09-28 CN CN201811154984.3A patent/CN108905657B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN108905657A (en) | 2018-11-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108905657B (en) | Preparation method of amphiphilic triblock polymer blending modified polyvinylidene fluoride ultrafiltration membrane | |
| Huang et al. | Improved antifouling performance of ultrafiltration membrane via preparing novel zwitterionic polyimide | |
| CN107715700B (en) | Corrosion-resistant and stain-resistant membrane for treating high-salinity wastewater and preparation method and application thereof | |
| US10940445B2 (en) | Doping of inorganic minerals to hydrophobic membrane surface | |
| KR101436175B1 (en) | Fouling resistant membranes formed with polyacrylonitrile graft copolymers | |
| CN108939933A (en) | A kind of preparation method of the amphipathic three block copolymer modified ultrafiltration membrane with pH responsiveness | |
| KR20090071548A (en) | Isoporous membrane and method of production thereof | |
| CN101905125B (en) | Preparation method of polystyrolsulfon acid salt/polyethyleneimine crosslinking nanofiltration membrane | |
| CN108452684A (en) | A kind of metal organic frame reverse osmosis membrane and preparation method thereof | |
| CN108043242B (en) | Preparation method of graphene oxide film with adjustable surface wettability | |
| CN107970789B (en) | Hydrophobic membrane with micro-nano structure surface functional layer and preparation method thereof | |
| Du et al. | Polymerizable ionic liquid copolymer P (MMA-co-BVIm-Br) and its effect on the surface wettability of PVDF blend membranes | |
| CN109351207B (en) | Sunlight-driven water purification material and preparation method and application thereof | |
| Velu et al. | Development, characterization and application studies of cellulose acetate–activated carbon blend ultra filtration membranes | |
| CN113304618B (en) | MOFs (metal-organic frameworks) -based in-situ growth forward osmosis membrane and preparation method thereof | |
| CN112957932B (en) | Preparation and application of amphiphilic graft copolymer homogeneous-pore ultrafiltration membrane with high permeability and pH response | |
| CN1673272A (en) | Hydrophilic porous PTFE film and its production process | |
| CN104801209A (en) | Ultralow-pressure nanofiltration membrane prepared from imidazole sulfonate grafted polyether sulfone | |
| CN109745878B (en) | Preparation method of polypiperazine amide/amphiphilic block polymer nanofiltration membrane | |
| Hwang et al. | Characteristics and separation efficiencies of PPSU/PEI/PEG blend membranes with different compositions for water treatment | |
| CN113083043A (en) | Self-assembly and interface induction phase separation membrane based on block copolymer and preparation method and application thereof | |
| CN107998899B (en) | Method for preparing PVDF (polyvinylidene fluoride) blended membrane by using activated carbon and cross-linking agent | |
| Zhang et al. | Synthesis and characterization of cinnamic acid-grafted poly (Vinylidene Fluoride) microporous membranes | |
| CN110681264B (en) | Preparation method of amphiphilic terpolymer modified ultrafiltration membrane | |
| CN117181024B (en) | Ultrafiltration membrane with pH response switchable pore diameter and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210818 Address after: 5 / F, 277 Huqingping Road, Minhang District, Shanghai, 201100 Patentee after: Shanghai Hailuo Environment Group Co.,Ltd. Address before: No. 399 Bingshui Road, Xiqing District, Tianjin, Tianjin Patentee before: TIANJIN POLYTECHNIC University |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220225 Address after: 266700 No. 13, Luoyang Road, Tonghe sub district office, Pingdu City, Qingdao City, Shandong Province Patentee after: Qingdao Hailuo Intelligent Technology Co.,Ltd. Address before: 5 / F, 277 Huqingping Road, Minhang District, Shanghai, 201100 Patentee before: Shanghai Hailuo Environment Group Co.,Ltd. |