CN108939933A - A kind of preparation method of the amphipathic three block copolymer modified ultrafiltration membrane with pH responsiveness - Google Patents
A kind of preparation method of the amphipathic three block copolymer modified ultrafiltration membrane with pH responsiveness Download PDFInfo
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- CN108939933A CN108939933A CN201811144727.1A CN201811144727A CN108939933A CN 108939933 A CN108939933 A CN 108939933A CN 201811144727 A CN201811144727 A CN 201811144727A CN 108939933 A CN108939933 A CN 108939933A
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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
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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
- B01D71/30—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
- 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
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Abstract
The invention discloses a kind of preparation methods of amphipathic three block copolymer modified ultrafiltration membrane with pH responsiveness, first with methyl methacrylate (MMA) and acrylic acid (AA) for raw material, using the controllable PAA-b-PMMA-b-PAA (PAMA) of reversible addion-fragmentation chain transfer (RAFT) polymerization preparation structure.The amphipathic nature block polymer modified ultrafiltration membrane is directly prepared using immersion precipitation phase inversion process, and certain hydrophily and pollution resistance are made it have in the segregation behavior of film surface by modifying agent.The PMMA segment in modifying agent PAMA that the present invention uses has good compatibility with Kynoar, guarantees that it is more stable in use.On the one hand PAA is used as hydrophilic segment to be enriched in film surface and fenestra, improve the hydrophily of film, prevent pollutant in the adherency of film surface and fenestra.In addition, ultrafiltration membrane stain resistance with higher and retention rate of proteins, and there are the transformations of effective aperture between pH=3~8, realize under extraneous environmental stimulus to the Effective Regulation in aperture.
Description
Technical field
The invention belongs to polymer material science fields, are related to a kind of amphipathic three block copolymer modified ultrafiltration membrane, tool
Body is related to a kind of preparation side of the Amphipathilic block polymer modified polyvinilidene fluoride film of pH responsiveness segment as hydrophilic segment
Method.
Background technique
Water is Source of life.Now, ecological environment is seriously damaged, and water pollution is serious, and global freshwater resources are in short supply
Situation gradually show, in addition to active development freshwater resources, water resource secondary use becomes focus.With water process
The continuous development of technology, membrane water treatment technique reach its maturity, and may be implemented to be not necessarily to acid-alkali regeneration, continuously water processed, water outlet water
Matter is stablized, and the application in water treatment technology is increasingly extensive.And film is as a ring important in membrane separating process, it is desirable that its membrane material
Material itself has excellent mechanical performance and good hydrophily and chemical stability.
Polyvinylidene fluoride film shows in application process to the stronger tolerance of natural environment and climate, chemical stability and resists
The excellent performance such as ultraviolet light is widely applied in purification water and wastewater treatment.But because Kynoar has stronger dredge
Aqueous, resulting in can be such that its permeance property and separative efficiency significantly reduces by serious pollution in use, limit
Its further applying in separation membrane.Using amphipathic nature block polymer blending and modifying polyvinylidene fluoride film, table is utilized
Face segregation, realize to the hydrophilic modifying of film surface and fenestra be it is a kind of it is simple and easy can industrialized production method.In patent
In CN105457507A (preparation method of Amphipathilic block polymer nanofiltration membrane), it is prepared for that there is hydrophilic ethylene first
Base ether and its derivative and Styrene and its derivatives with hydrophobic chain segment, and cationic block copolymerization is carried out, then
Sulfonation processing is carried out to the hydrophobic chain segment of the Styrene and its derivatives, by purifying and being dried to obtain with hydrophily
The block copolymer of segment and sulfonic group segment is finally obtained using prepared block copolymer by forming film with phase transformation method
Amphipathilic block polymer nanofiltration membrane with sulfonic acid group.A kind of blending and modifying agent of the amphiphilic polymer as pvdf membrane,
During surface segregation, hydrophilic segment is enriched in fenestra and the hydrophily of film can be improved in film surface, as anchoring system
Hydrophobic segment guarantees that it can keep good stability in film.
The invariable aperture of conventional porous film and surface nature limit it and effectively apply.Seperation film during the separation process
Material inevitably by serious pollution, causes permeation flux and separative efficiency to drastically reduce, and can not be suitable for one
It is a little to need to automatically adjust selectivity and infiltrative situation.By the performance of environmental stimulus adjusting film under various circumstances, intelligence
Response film shows big advantage in Global Sustainable Development.Smart membrane by porous membrane substrate and can incude extraneous ring mostly
The polymers function of border stimulation switchs two parts composition.This kind of membrane material can according in external environment physically and/or chemically
Changing to change the conformation of polymers function switch for factor (such as temperature, pH value, magnetic field, electric field and light), is opened to change
Close effective aperture and the permeability of film.CN102068921A patent discloses a kind of pH sensitive polyvinylidene fluoride gel film and preparation
Method.It is prepared for first with pH sensitive polymer gel, this pH sensitive polymer gel is responded according to pH variation, real
The intelligent selection separation of existing separated object.Acrylic acid is important organic synthesis raw material and synthetic resin monomer, the present invention adopt
Use acrylic acid as hydrophilic and pH response monomer, hydrophilic segment of the polyacrylic acid as Amphipathilic block polymer, on surface
In segregation process, it is enriched in film and fenestra surface, optimizes the hydrophily and pollution resistance of hydrophobic membrane.Furthermore polyacrylic acid is a kind of band
The separation of pH responsiveness may be implemented in the polyelectrolyte of negative electricity.
Summary of the invention
In view of the foregoing deficiencies of prior art, it is an object of the invention to the simple and easy one kind that is prepared for have pH
The method of the high-throughput anti-pollution film of responsiveness solves the disadvantages such as traditional seperation film hydrophobicity is strong, and water flux is low, and to fenestra
Functionalization control is insufficient and during the separation process irreversible membrane fouling vulnerable to organic matters such as protein the problem of.
To solve above-mentioned deficiency, the present invention provides a kind of, and the amphipathic three block copolymer with pH responsiveness is modified super
The preparation method of filter membrane, it is characterised in that comprise the steps of:
1. the preparation method of the amphipathic three block copolymer with pH responsiveness, preparation method comprise the steps of:
1) methyl methacrylate, chain-transferring agent, azodiisobutyronitrile are dissolved in toluene solvant.Utilize biexhaust pipe freeze thawing
Remove oxygen three times, under inert gas protection 60~70 DEG C be stirred to react 20~for 24 hours, revolving removes partial solvent, by polymer
Solution is instilled in ice n-hexane dropwise and is precipitated, and precipitating is collected by filtration, is dried under vacuum to constant weight, obtains Macromolecular chain transfer agent
PMMA-RAFT。
2) PMMA-RAFT, acrylic acid, azodiisobutyronitrile are dissolved in n,N-Dimethylformamide solvent.Using double
Manage logical argon gas multigelation complete deoxygenation three times, under inert gas protection 60~70 DEG C be stirred to react 20~for 24 hours, be cooled to room
Temperature directly uses.
2. the preparation method of the amphipathic three block copolymer modified ultrafiltration membrane with pH responsiveness, preparation method are as follows:
Kynoar powder, pore-foaming agent and modifying agent are dissolved in polar solvent, the heating stirring 12~for 24 hours at 60 DEG C, vacuum
Deaeration obtains homogeneous casting solution；Casting solution is uniformly poured on dry, clean glass plate, goes out liquid with scraper at the uniform velocity striking
State film, is then immersed in coagulating bath, induces phase inversion to obtain modification film of polyvinylidene fluoride by non-solvent, refreshes the water periodically
To remove solvent, film is immersed in spare in distilled water.
Preferably, it prepares solvent selected by modifying agent and solvents all uses n,N-Dimethylformamide.
Preferably, the coagulating bath that non-solvent induction phase inversion uses is water and alcohol mixed solvent.
Preferably, invention adjusts the hydrophobe chain of modifying agent by the input amount of control methyl methacrylate and acrylic acid
Section ratio.
Preferably, the degree of polymerization for inventing the PAA is respectively 13 and 83.
As described above, the preparation side of the amphipathic three block copolymer modified ultrafiltration membrane with pH responsiveness of the invention
Method has the advantages that
1) modifying agent PAMA is prepared using RAFT polymerization, this method is easy to operate compared to existing technology, suitable monomers model
It encloses extensively, the harmful side products such as heavy metal free generate, and product structure is controllable, and molecular weight ranges are narrow.
2) since the segment in additive PMMA has good compatibility with Kynoar, in the use process of film
It is more stable, it not easily runs off；PAA segment has good hydrophily and pH responsiveness, can be effectively improved the hydrophily and tune of film
Aperture is controlled, and then controls flux.
3) a small amount of modifying agent (1.125%) can make film have preferable hydrophily, when the hydrophilic segment degree of polymerization is 83, performance
Significant pH responsiveness out.
Detailed description of the invention
Fig. 1 is amphipathic three block copolymer PAA prepared by the embodiment of the present invention 113-b-PMMA80-b-PAA13And PAA83-
b-PMMA80-b-PAA83Nuclear-magnetism characterize map；
Fig. 2 is surface and the section SEM figure for responding polyvinylidene fluoride film M-2.0 described in the embodiment of the present invention 1 with pH；
Fig. 3 is the pH responsiveness for responding polyvinylidene fluoride film M-3 film described in the embodiment of the present invention 2 with pH；
Fig. 4 is pure pvdf membrane described in the embodiment of the present invention 3, the poly- pvdf membrane M-3 and PAA with pH response83-b-
PMMA80-b-PAA83ATR-FTIR spectrogram.
Specific embodiment
Below in conjunction with specific embodiments and drawings, elaborate to the present invention.It should be understood that these embodiments are only used for
It is bright the present invention rather than limit the scope of the invention, except illustrate, this experiment use technological means belong to the field
Generally acknowledged technical method.
Embodiment 1
PVDF/PAA13-b-PMMA80-b-PAA13The preparation of film
It uses PAMA as blending and modifying agent, prepares pH by immersion precipitation phase inversion process and responds amphiphilic block
Object modified polyvinilidene fluoride film, wherein comprising the steps of:
1. refining methacylic acid methyl esters, RAFT reagent, azodiisobutyronitrile is taken to dissolve in toluene.It is vacuumized using water pump
30min, to remove the air in reaction solution.Lead to argon gas multigelation using biexhaust pipe and removes oxygen three times, under protection of argon gas 70
It DEG C is stirred to react for 24 hours, revolving removes partial solvent, and polymer solution is added in ice n-hexane and be precipitated, and collects precipitating, and vacuum is dry
It is dry to constant weight, obtain PMMA-RAFT.A certain amount of PMMA-RAFT, acrylic acid, azodiisobutyronitrile is taken to be dissolved in the N of 60mL, N-
In dimethylformamide, it is stirred to react under protection of argon gas and obtains uniform polymer solution for 24 hours for 70 DEG C.
2. being respectively the PAA of the PVDF powder of 9.0g, the lithium chloride of 4.0g, 2.0g by mass fraction13-b-PMMA80-b-
PAA13And solvent is placed in three-necked flask, and the mechanical stirring 12h at 60 DEG C, is sufficiently dissolved, being configured to mass concentration is 15%
Homogeneous casting solution, casting solution is stood at room temperature or vacuum defoamation.Casting solution is uniformly poured into dry, clean glass
On plate, 200 μm of films are spread to using knifing machine, after standing 5s in air, glass plate is placed in parallel into coagulating bath water-bath, temperature
Degree is 25 DEG C, is fallen off from glass plate to film, by Modified Membrane from being taken out in immersion deionized water in coagulating bath, is changed daily twice
Water is freeze-dried until solvent is replaced completely, and amphiphilic block copolymer modified polyvinilidene fluoride film M-2.0 is made.
Embodiment 2
PVDF/PAA83-b-PMMA80-b-PAA83The preparation of film
PAA is prepared according to embodiment 183-b-PMMA80-b-PAA83, thrown with specific reference to methyl methacrylate and acrylic acid
The degree of polymerization of the molar ratio control PMMA and PAA entered.
Weigh 15g PVDF, 7.25g PEG, 1.125g PAA83-b-PMMA80-b-PAA83With and N, N- dimethyl methyl
Amide is put into three-necked flask, and 12h is sufficiently stirred at 60 DEG C, makes it dissolve, and obtains homogeneous casting solution, vacuum defoamation, by casting film
Liquid is uniformly poured on dry, clean glass plate, scrapes 200 μm of film manually using scraper, glass plate is placed in parallel into
In coagulating bath, coagulating bath is that ethanol/water (V/V) is 1/3, and temperature is 25 DEG C.The plate membrane of preparation is impregnated in deionized water
A period of time, freeze-drying prepared the amphipathic nature block polymer modified polyvinilidene fluoride with pH responsiveness to remove solvent
Film M-3.
Embodiment 3
PVDF/PAA83-b-PMMA80-b-PAA83The preparation of Modified Membrane
Weigh 15g PVDF, 7.25g PEG, 1.125g PAA83-b-PMMA80-b-PAA83With and N, N- dimethyl methyl
Amide is put into three-necked flask, and 12h is sufficiently stirred at 60 DEG C, makes it dissolve, and obtains homogeneous casting solution, vacuum defoamation, by casting film
Liquid is uniformly poured on dry, clean glass plate, scrapes 200 μm of film manually using scraper, glass plate is placed in parallel into
It solidifies in water-bath, temperature is 25 DEG C.It falls off from glass plate to film, Modified Membrane is taken out from coagulating bath and immerses deionized water
In, water twice is changed daily, until solvent is replaced substantially, is freeze-dried, the amphipathic nature block polymer that pH responsiveness is made changes
Property polyvinylidene fluoride film M-4.
For the pH responsiveness for characterizing Modified Membrane, the Modified Membrane M-3 circulation flux for carrying out pH=3/8 is tested.It can be with by Fig. 5
It obtains, Modified Membrane has apparent variations of flux under condition of different pH, passes through the circulation experiment of pH=3/8, it can be deduced that knot
By: the responsiveness of Modified Membrane has the characteristics that quick, lasting, reversible.
Claims (8)
1. a kind of preparation method of the amphipathic three block copolymer modified ultrafiltration membrane with pH responsiveness, it is characterised in that with
PAMA has the amphipathic triblock polymer of pH responsiveness modified as additive, using non-solvent induction phase inversion preparation
Ultrafiltration membrane.
2. the preparation method of the amphipathic three block copolymer modified ultrafiltration membrane with pH responsiveness according to claim 1,
Preparation method comprises the steps of:
1) methyl methacrylate, chain-transferring agent, azodiisobutyronitrile are dissolved in polar solvent, stirs 5- under vacuum condition
10min, and under inert gas protection 60~70 DEG C be stirred to react 20~for 24 hours, revolving removes partial solvent, by polymer solution
It instills in ice n-hexane and precipitates dropwise, precipitating is collected by filtration, is dried under vacuum to constant weight, obtains Macromolecular chain transfer agent PMMA-
RAFT。
2) PMMA-RAFT, acrylic acid, azodiisobutyronitrile are dissolved in polar solvent, are vacuumized, to remove the sky in reaction solution
Gas.Lead to the complete deoxygenation three times of argon gas multigelation using biexhaust pipe, under inert gas protection 60~70 DEG C be stirred to react 20~
For 24 hours, it is cooled to room temperature, directly uses.
3. polar solvent according to claim 2 be toluene, n,N-Dimethylformamide, n,N-dimethylacetamide, two
Methyl sulfoxide, one of N-Methyl pyrrolidone or its mixed solvent.
4. the preparation side of the amphipathic three block copolymer modified ultrafiltration membrane according to claim 1 with pH responsiveness
Method, preparation method are as follows: by 12~15% PVDF powder, 1~6% pore-foaming agent and modifying agent are dissolved in polar solvent,
Heating stirring 12 at 60 DEG C~for 24 hours, vacuum defoamation obtains homogeneous casting solution；Casting solution is uniformly poured on to dry, clean glass
In glass plate, go out liquid film with scraper at the uniform velocity striking, be then immersed in coagulating bath, phase transition method preparation is induced by non-solvent
Modification film of polyvinylidene fluoride is refreshed the water periodically to remove solvent, and prepared polyvinylidene fluoride film is immersed in spare in distilled water.
5. polar solvent according to claim 4 is n,N-Dimethylformamide, n,N-dimethylacetamide, dimethyl Asia
Sulfone, N-Methyl pyrrolidone, one of triethyl phosphate or its mixed liquor.
6. the preparation side of the amphipathic three block copolymer modified ultrafiltration membrane according to claim 3 with pH responsiveness
Method, preparation method feature are as follows: pore-foaming agent is respectively polyethylene glycol and lithium chloride, and molecular weight polyethylene glycol is respectively 2000g/
Mol, 4000g/mol, 6000g/mol, 10000g/mol.
7. the preparation side of the amphipathic three block copolymer modified ultrafiltration membrane according to claim 3 with pH responsiveness
Method, preparation method feature are as follows: coagulating bath be ethanol/water mixed liquor (volume ratio of water and ethyl alcohol is less than 4), temperature be 20~
30℃。
8. the preparation of the amphipathic three block copolymer modified ultrafiltration membrane according to claim 1 or 2 with pH responsiveness
Method, it is characterised in that: it is 1000~6000 that PMMA molecular weight, which is 2000~20000, PAA molecular weight, in PAMA.
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Cited By (8)
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| 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 |
| CN109663510A (en) * | 2019-01-25 | 2019-04-23 | 苏州科技大学 | Amphoteric ion random copolymer P (MMAx-r-CBMAy) it is modified PVDF anti-pollution film and preparation method thereof |
| CN111223687A (en) * | 2020-01-13 | 2020-06-02 | 常州大学 | Preparation method of MXene/PANI-based high-capacity linear supercapacitor electrode |
| 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 |
| CN115178097A (en) * | 2022-08-15 | 2022-10-14 | 无锡零界净化设备股份有限公司 | PVDF (polyvinylidene fluoride) microporous filter membrane and preparation process thereof |
| CN115286805A (en) * | 2022-09-30 | 2022-11-04 | 宁德时代新能源科技股份有限公司 | BAB type block copolymer, preparation method, binder, positive pole piece, secondary battery and electric device |
| CN115364683A (en) * | 2022-08-24 | 2022-11-22 | 天津大学 | Method for preparing anti-pollution ultrafiltration membrane by one-step method in-situ assembly of polyelectrolyte |
| CN117181024A (en) * | 2023-04-04 | 2023-12-08 | 赛普(杭州)过滤科技有限公司 | Ultrafiltration membrane with pH response switchable pore diameter and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN109663510A (en) * | 2019-01-25 | 2019-04-23 | 苏州科技大学 | Amphoteric ion random copolymer P (MMAx-r-CBMAy) it is modified PVDF anti-pollution film and preparation method thereof |
| CN111223687A (en) * | 2020-01-13 | 2020-06-02 | 常州大学 | Preparation method of MXene/PANI-based high-capacity linear supercapacitor electrode |
| 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 |
| CN115178097A (en) * | 2022-08-15 | 2022-10-14 | 无锡零界净化设备股份有限公司 | PVDF (polyvinylidene fluoride) microporous filter membrane and preparation process thereof |
| CN115178097B (en) * | 2022-08-15 | 2024-02-23 | 无锡零界净化设备股份有限公司 | PVDF microporous filter membrane and preparation process thereof |
| CN115364683A (en) * | 2022-08-24 | 2022-11-22 | 天津大学 | Method for preparing anti-pollution ultrafiltration membrane by one-step method in-situ assembly of polyelectrolyte |
| CN115364683B (en) * | 2022-08-24 | 2023-08-25 | 天津大学 | Method for preparing anti-pollution ultrafiltration membrane by in-situ polyelectrolyte assembly through one-step method |
| CN115286805A (en) * | 2022-09-30 | 2022-11-04 | 宁德时代新能源科技股份有限公司 | BAB type block copolymer, preparation method, binder, positive pole piece, secondary battery and electric device |
| CN117181024A (en) * | 2023-04-04 | 2023-12-08 | 赛普(杭州)过滤科技有限公司 | Ultrafiltration membrane with pH response switchable pore diameter and preparation method thereof |
| CN117181024B (en) * | 2023-04-04 | 2024-02-20 | 赛普(杭州)过滤科技有限公司 | Ultrafiltration membrane with pH response switchable pore diameter and preparation method thereof |
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