CN107998897A - A kind of surface hydrophilic modification method of Pvdf Microporous Hollow Fiber Membrane - Google Patents
A kind of surface hydrophilic modification method of Pvdf Microporous Hollow Fiber Membrane Download PDFInfo
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- CN107998897A CN107998897A CN201711224843.XA CN201711224843A CN107998897A CN 107998897 A CN107998897 A CN 107998897A CN 201711224843 A CN201711224843 A CN 201711224843A CN 107998897 A CN107998897 A CN 107998897A
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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
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
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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
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/009—After-treatment of organic or inorganic membranes with wave-energy, particle-radiation or plasma
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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
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
Abstract
A kind of surface hydrophilic modification method of Pvdf Microporous Hollow Fiber Membrane belongs to Material Field, the invention discloses a kind of method for carrying out hydrophilic modification to Pvdf Microporous Hollow Fiber Membrane surface using efficient click chemistry method, introduces hydrophilic group in film surface to strengthen the resistance tocrocking of film surface.This method mild condition, method are simple, process is easily controllable.Concretely comprise the following steps and carry out processing generation elimination reaction removing C F key formation C=C double bonds to film with highly basic first；Then the hydrophilic radical carried sulfhydryl compound using the S H keys in sulfhydryl compound and the reaction of C=C double bonds under ultraviolet light environments and under the action of photoinitiator is anchored at the surface of film.The surface energy of polyvinylidene fluoride film is low and cannot form hydrogen bond with hydrone, will significantly strengthen the hydrophily and resistance to soiling of film after by hydrophilic radical introducing film surface.
Description
Technical field
It is that to be related to a kind of hydrophilic modification Kynoar ultrafiltration hollow further the invention belongs to Material Field
The preparation method of tunica fibrosa.
Background technology
Kynoar (PVDF) is one of material of preparing of greatest concern at present.PVDF is that a kind of semicrystalline linearly gathers
Compound, strand presentation-(CH2-CF2)n- alternating structure, since C-F key bond distances are short, bond energy is high, and it is excellent to make it have mechanical property
The various features such as good, heat-resisting, resistant to chemical etching, impact resistance, not degradable, easy film forming.Yet with Kynoar film surface
Can extremely low (25mN/m), and do not have on surface hydrophilic group such as hydroxyl (- OH), carboxyl (- COOH) or amino (-
NH2), hydrogen bond action cannot be produced with hydrone, therefore there is very strong hydrophobicity.During water separation, the strong of pvdf membrane is dredged
It is water-based that water can be made to add the required energy consumption of water treatment procedure through the required driving pressure increase of fenestra.It is meanwhile hydrophobic
Property the easy adsorbed proteins of film surface, microorganism, the organic substance such as colloid, so as to cause Pore Blocking, permeation flux declines,
Shorten the service life of film.The above problem constrains application of the pvdf membrane in aqueous phase separation system, in order to improve the water of film
Flux, the service life for reducing fouling membrane, extending film, have become current field of membrane science to the hydrophilic modification of pvdf membrane and grind
One of hot spot studied carefully, has very important practical significance.
106215723 A of Chinese invention patent application CN propose a kind of preparation of the compound PVDF ultrafiltration membrane of ultra-hydrophilic type
Method, by from poly-dopamine, grafting aromatic polycarboxylic acyl chlorides and being received the silica of ammonium salt end group modification on pvdf membrane surface
Rice grain is grafted to the acquisition compound PVDF ultrafiltration membrane of hydrophily, nanoparticle mass fraction on pvdf membrane and is contacted when being 0.08wt%
Angle is down to 46 °.
103127841 A of Chinese invention patent application CN propose a kind of preparation side of Kynoar hydrophilic modifying film
Method, hydrophilic PVDF film is prepared using directly hydrophilic polymer methyl methacrylate is blended into PVDF film systems.
In hydrophilic polymer additive amount mass fraction 25wt%, film contact angle is down to 64.2 °.
102516584 A of Chinese invention patent application CN propose a kind of changing for polyvinylidene fluoride film anti-protein-contamination
Property method.Amphion is formed in Kynoar film surface by two-stage polymerization Graft Method and is copolymerized layer.In amphion 3- (first
Base acrylamide) propyl group-dimethyl (3- sulphurs the third) amine grafting rate in 522 μ g/cm2 contact angle be down to 29.1 °.
There are additive and film matrix poor compatibility to cause raw material loss etc. to be asked as additive for blending hydrophilic polymer
Topic, and then existing process is cumbersome for graft modification, the inferior positions such as cost is higher.To solve the modification side of current hydrophilic PVDF film
Some problems existing for method, the present invention propose one kind by click chemistry method to introduce parent in film surface and internal channel surfaces
The modification mode of water-based group, realizes the persistent hydrophilic modification of PVDF hollow fiber ultrafiltration membranes.
The content of the invention
The property that low-surface-energy, hydrophobicity the present invention be directed to pvdf membrane are strong and resistance tocrocking is weak, proposes a kind of logical
The modification mode that click chemistry method to introduce hydrophilic radical in film surface and internal channel surfaces is crossed, realizes the hollow fibres of PVDF
The persistent hydrophilic and antipollution for tieing up ultrafiltration membrane are modified.
1. step is as described below：
(1) PVDF hollow fiber ultrafiltration membranes are cleaned：PVDF hollow fiber ultrafiltration membranes are immersed in 24h in absolute ethyl alcohol, so
Rinsed repeatedly with deionized water afterwards；
(2) lye is configured：Potassium hydroxide solid is added into ethanol and deionized water mixed liquor to stir evenly alkali is made
Liquid.
(3) hollow fiber ultrafiltration membrane after cleaning in step (1) is completely infused in the lye that step (2) is configured,
It is placed in 5~120min in 60 DEG C of environment.
(4) by the hollow fiber ultrafiltration membrane after alkali process in step (3) take out and use deionized water under ultrasonic vibration it is anti-
After backwashing wash to no longer in alkalescence, the alkali process hollow fiber ultrafiltration membrane after cleaning is placed in ethanol infiltrate it is stand-by.
(5) modification is prepared with solution：Solvent is ethanol.Compounds containing thiol groups, photoinitiator are added into solvent and is resisted
Form the reducing agent of disulfide bond.
(6) the PVDF hollow fiber ultrafiltration membranes that the ethanol in step (4) infiltrates are transferred to the solution prepared in step (5)
In, under conditions of stirring, it is placed under the ultraviolet lamp of a length of 365nm of light wave and is reacted in nitrogen atmosphere, the reaction time 1~
5h。
(7) the modification hollow fiber ultrafiltration membrane in step (6) is taken out, is cleaned repeatedly with ethanol and deionized water to go
Except responseless compounds containing thiol groups and initiator.
2. in a preferred embodiments of first way of the present invention, in the step (2) in lye solvent ethanol matter
Amount fraction is 50wt.%, and solute potassium hydroxide quality fraction is 5wt.%~20wt.%.
3. in a preferred embodiments of first way of the present invention, contain sulfydryl in modified solution in the step (5)
The mass fraction of polymer is 10wt.%~50wt.%, and initiator quality fraction is 0.2wt.%~1.0wt.%, reducing agent
Mass fraction is 0.2wt.%~1.0wt.%.
4. in a preferred embodiments of first way of the present invention, contain sulfydryl in modified solution in the step (5)
Polymer can be 2 mercapto ethanol, mercapto-acetaldehyde, 2- thioacetic acid, 3- mercaptopropionic acids, 4- mercaptobutyric acids, 2- sulfydryl propionic aldehyde,
3- sulfydryl -1- propylamine, 2- sulfydryl propyl- 1- alcohol, 3- sulfydryl -1- propyl alcohol, 1- sulfydryl -2- acetone, one kind in 2- mercapto-acetamides
It is or a variety of.
5. in a preferred embodiments of first way of the present invention, the initiator in the step (5) in modified solution
For 2- hydroxy-2-methyl -1- phenyl -1- acetone, benzoin dimethylether, 2,4,6- trimethylbenzoyls phosphinic acid ethyl ester, 2- first
Base -1- [4- methyl mercaptos phenyl] -2- Lin Ji -1- acetone, 1- hydroxycyclohexyl phenyl ketones and 2- phenyl benzyl -2- dimethyl
One or more in amine -1- (4- morpholine benzyls phenyl) butanone.
6. in a preferred embodiments of first way of the present invention, the reducing agent in the step (5) in modified solution
For triphenylphosphine, iodoacetamide, one kind in dithiothreitol (DTT).
7. beneficial effects of the present invention are：
(1) present invention illustrates the method mild condition of PVDF hollow fiber membrane surface hydrophilic modifications, method are simple, mistake
Journey is easily controllable.
(2) hydrophilic radical is introduced the surface of film by efficient click chemistry by the present invention, make film surface hydrophily,
Resistance tocrocking effectively improves.
(3) method provided by the invention can be used for PVDF hollow fiber membrane surface hydrophilicity-imparting treatments, and finished film can be applied to
Sewage disposal industry, has a extensive future.
Brief description of the drawings
Fig. 1 is unmodified PVDF hollow fiber ultrafiltration membranes surface static contact angle test chart.
Fig. 2 is the modification PVDF hollow fiber ultrafiltration membrane surface static contact angle test charts that the embodiment of the present invention 1 provides.
Fig. 3 is the modification PVDF hollow fiber ultrafiltration membrane surface static contact angle test charts that the embodiment of the present invention 2 provides.
Fig. 4 is the modification PVDF hollow fiber ultrafiltration membrane surface static contact angle test charts that the embodiment of the present invention 3 provides.
Fig. 5 is the modification PVDF hollow fiber ultrafiltration membrane surface static contact angle test charts that the embodiment of the present invention 4 provides.
Fig. 6 is the modification PVDF hollow fiber ultrafiltration membrane surface static contact angle test charts that comparative example 1 of the present invention provides.
Fig. 7 is the modification PVDF hollow fiber ultrafiltration membrane surface static contact angle test charts that comparative example 2 of the present invention provides.
Fig. 8 is the bovine serum protein suction of unmodified hollow fiber ultrafiltration membrane, the embodiment of the present invention 1~4, comparative example 1~2
Attached amount.
Fig. 9 is unmodified hollow fiber ultrafiltration membrane, the embodiment of the present invention 1~4, the pure water flux of comparative example 1~2.
Embodiment：
Embodiment 1
(1) PVDF hollow fiber ultrafiltration membranes are cleaned：PVDF hollow fiber ultrafiltration membranes are immersed in 24h in absolute ethyl alcohol, so
Rinsed repeatedly with deionized water afterwards；
(2) lye is configured：Potassium hydroxide solid is added to ethanol and deionized water quality ratio 1:Stirred in 1 mixed liquor
Lye uniformly is made, potassium hydroxide quality fraction is 5wt.% in solution.
(3) hollow fiber ultrafiltration membrane after cleaning in step (1) is completely infused in the lye that step (2) is configured,
It is placed in 5min in 60 DEG C of environment.
(4) by the hollow fiber ultrafiltration membrane after alkali process in step (3) take out and use deionized water under ultrasonic vibration it is anti-
After backwashing wash to no longer in alkalescence, the alkali process hollow fiber ultrafiltration membrane after cleaning is placed in ethanol infiltrate it is stand-by.
(5) modification is prepared with solution：Solvent is ethanol.Mercaptoethanol, 2- hydroxy-2-methyl -1- benzene are added into solvent
Base -1- acetone and triphenylphosphine.Mercaptoethanol, 2- hydroxy-2-methyl -1- phenyl -1- acetone and triphenylphosphine are in solution
In mass fraction be respectively 10wt.%, 0.2wt.%, 0.2wt.%.
(6) the PVDF hollow fiber ultrafiltration membranes that the ethanol in step (4) infiltrates are transferred to the solution prepared in step (5)
In, under conditions of stirring, it is placed under the ultraviolet lamp of a length of 365nm of light wave and is reacted in nitrogen atmosphere, reaction time 1h.
(7) the modification hollow fiber ultrafiltration membrane in step (6) is taken out, is cleaned repeatedly with ethanol and deionized water to go
Except responseless compounds containing thiol groups and initiator.
As Figure 1 and Figure 4, the static contact angle for being modified PVDF hollow fiber ultrafiltration membranes after tested is 63.2 °, with not changing
Property PVDF hollow fiber ultrafiltration membranes 88.1 ° of static contact angle significantly reduce compared to having.As shown in Figure 8, Figure 9, cow's serum
Protein adsorbance is by 22.3 μ g/cm3It is reduced to 12.5 μ g/cm3, pure water flux change unobvious, illustrate that structure does not occur substantially
Change, hydrophily enhancing.
Embodiment 2
(1) PVDF hollow fiber ultrafiltration membranes are cleaned：PVDF hollow fiber ultrafiltration membranes are immersed in 24h in absolute ethyl alcohol, so
Rinsed repeatedly with deionized water afterwards；
(2) lye is configured：Potassium hydroxide solid is added to ethanol and deionized water ethanol and deionized water quality ratio 1:1
Mixed liquor in stir evenly lye be made, potassium hydroxide quality fraction is 10wt.%.
(3) hollow fiber ultrafiltration membrane after cleaning in step (1) is completely infused in the lye that step (2) is configured,
It is placed in 10min in 60 DEG C of environment.
(4) by the hollow fiber ultrafiltration membrane after alkali process in step (3) take out and use deionized water under ultrasonic vibration it is anti-
After backwashing wash to no longer in alkalescence, the alkali process hollow fiber ultrafiltration membrane after cleaning is placed in ethanol infiltrate it is stand-by.
(5) modification is prepared with solution：Solvent is ethanol.Mercaptoethanol, 2- hydroxy-2-methyl -1- benzene are added into solvent
Base -1- acetone and triphenylphosphine.Mercaptoethanol, 2- hydroxy-2-methyl -1- phenyl -1- acetone and triphenylphosphine are in solution
In mass fraction be respectively 50wt.%, 1wt.%, 1wt.%.
(6) the PVDF hollow fiber ultrafiltration membranes that the ethanol in step (4) infiltrates are transferred to the solution prepared in step (5)
In, under conditions of stirring, it is placed under the ultraviolet lamp of a length of 365nm of light wave and is reacted in nitrogen atmosphere, reaction time 4h.
(7) the modification hollow fiber ultrafiltration membrane in step (6) is taken out, is cleaned repeatedly with ethanol and deionized water to go
Except responseless compounds containing thiol groups and initiator.
As shown in Figure 1, shown in Figure 5, the static contact angle for being modified PVDF hollow fiber ultrafiltration membranes after tested is 29.6 °, with not changing
Property PVDF hollow fiber ultrafiltration membranes 88.1 ° of static contact angle significantly reduce compared to having.As shown in Figure 8, Figure 9, cow's serum
Protein adsorbance is by 22.3 μ g/cm3It is reduced to 5.6 μ g/cm3, pure water flux change unobvious, illustrate that structure does not occur substantially
Change, hydrophily enhancing.
Embodiment 3
(1) PVDF hollow fiber ultrafiltration membranes are cleaned：PVDF hollow fiber ultrafiltration membranes are immersed in 24h in absolute ethyl alcohol, so
Rinsed repeatedly with deionized water afterwards；
(2) lye is configured：Potassium hydroxide solid is added to ethanol and deionized water ethanol and deionized water quality ratio 1:1
Mixed liquor in stir evenly lye be made, potassium hydroxide quality fraction is 20wt.%.
(3) hollow fiber ultrafiltration membrane after cleaning in step (1) is completely infused in the lye that step (2) is configured,
It is placed in 120min in 60 DEG C of environment.
(4) by the hollow fiber ultrafiltration membrane after alkali process in step (3) take out and use deionized water under ultrasonic vibration it is anti-
After backwashing wash to no longer in alkalescence, the alkali process hollow fiber ultrafiltration membrane after cleaning is placed in ethanol infiltrate it is stand-by.
(5) modification is prepared with solution：Solvent is ethanol.Mercaptoethanol, 2- hydroxy-2-methyl -1- benzene are added into solvent
Base -1- acetone and triphenylphosphine.Mercaptoethanol, 2- hydroxy-2-methyl -1- phenyl -1- acetone and triphenylphosphine are in solution
In mass fraction be respectively 50wt.%, 1wt.%, 1wt.%.
(6) the PVDF hollow fiber ultrafiltration membranes that the ethanol in step (4) infiltrates are transferred to the solution prepared in step (5)
In, under conditions of stirring, it is placed under the ultraviolet lamp of a length of 365nm of light wave and is reacted in nitrogen atmosphere, reaction time 5h.
(7) the modification hollow fiber ultrafiltration membrane in step (6) is taken out, is cleaned repeatedly with ethanol and deionized water to go
Except responseless compounds containing thiol groups and initiator.
As shown in Fig. 1, Fig. 6, the static contact angle for being modified PVDF hollow fiber ultrafiltration membranes after tested is 51.4 °, with not changing
Property PVDF hollow fiber ultrafiltration membranes 88.1 ° of static contact angle significantly reduce compared to having.As shown in Figure 8, Figure 9, cow's serum
Protein adsorbance is by 22.3 μ g/cm3It is reduced to 10.2 μ g/cm3, pure water flux change unobvious, illustrate that structure does not occur substantially
Change, hydrophily enhancing.
Embodiment 4
(1) PVDF hollow fiber ultrafiltration membranes are cleaned：PVDF hollow fiber ultrafiltration membranes are immersed in 24h in absolute ethyl alcohol, so
Rinsed repeatedly with deionized water afterwards；
(2) lye is configured：Potassium hydroxide solid is added to ethanol and deionized water ethanol and deionized water quality ratio 1:1
Mixed liquor in stir evenly lye be made, potassium hydroxide quality fraction is 10wt.%.
(3) hollow fiber ultrafiltration membrane after cleaning in step (1) is completely infused in the lye that step (2) is configured,
It is placed in 10min in 60 DEG C of environment.
(4) by the hollow fiber ultrafiltration membrane after alkali process in step (3) take out and use deionized water under ultrasonic vibration it is anti-
After backwashing wash to no longer in alkalescence, the alkali process hollow fiber ultrafiltration membrane after cleaning is placed in ethanol infiltrate it is stand-by.
(5) modification is prepared with solution：Solvent is ethanol.Mercaptoethanol, 2- hydroxy-2-methyl -1- benzene are added into solvent
Base -1- acetone and triphenylphosphine.Mercaptoethanol, 2- hydroxy-2-methyl -1- phenyl -1- acetone and triphenylphosphine are in solution
In mass fraction be respectively 20wt.%, 0.4wt.%, 0.4wt.%.
(6) the PVDF hollow fiber ultrafiltration membranes that the ethanol in step (4) infiltrates are transferred to the solution prepared in step (5)
In, under conditions of stirring, it is placed under the ultraviolet lamp of a length of 365nm of light wave and is reacted in nitrogen atmosphere, reaction time 2h.
(7) the modification hollow fiber ultrafiltration membrane in step (6) is taken out, is cleaned repeatedly with ethanol and deionized water to go
Except responseless compounds containing thiol groups and initiator.
As shown in Figure 1, Figure 7 shows, the static contact angle for being modified PVDF hollow fiber ultrafiltration membranes after tested is 31.7 °, with not changing
Property PVDF hollow fiber ultrafiltration membranes 88.1 ° of static contact angle significantly reduce compared to having.As shown in Figure 8, Figure 9, cow's serum
Protein adsorbance is by 22.3 μ g/cm3It is reduced to 5.7 μ g/cm3, pure water flux change unobvious, illustrate that structure does not occur substantially
Change, hydrophily enhancing.
Comparative example 1
(1) PVDF hollow fiber ultrafiltration membranes are cleaned：PVDF hollow fiber ultrafiltration membranes are immersed in 24h in absolute ethyl alcohol, so
Rinsed repeatedly with deionized water afterwards；
(2) lye is configured：Potassium hydroxide solid is added to ethanol and deionized water ethanol and deionized water quality ratio 1:1
Mixed liquor in stir evenly lye be made, potassium hydroxide quality fraction is 10wt.%.
(3) hollow fiber ultrafiltration membrane after cleaning in step (1) is completely infused in the lye that step (2) is configured,
It is placed in 2min in 60 DEG C of environment.
(4) by the hollow fiber ultrafiltration membrane after alkali process in step (3) take out and use deionized water under ultrasonic vibration it is anti-
After backwashing wash to no longer in alkalescence, the alkali process hollow fiber ultrafiltration membrane after cleaning is placed in ethanol infiltrate it is stand-by.
(5) modification is prepared with solution：Solvent is ethanol.Mercaptoethanol, 2- hydroxy-2-methyl -1- benzene are added into solvent
Base -1- acetone and triphenylphosphine.Mercaptoethanol, 2- hydroxy-2-methyl -1- phenyl -1- acetone and triphenylphosphine are in solution
In mass fraction be respectively 50wt.%, 1wt.%, 1wt.%.
(6) the PVDF hollow fiber ultrafiltration membranes that the ethanol in step (4) infiltrates are transferred to the solution prepared in step (5)
In, under conditions of stirring, it is placed under the ultraviolet lamp of a length of 365nm of light wave and is reacted in nitrogen atmosphere, reaction time 4h.
(7) the modification hollow fiber ultrafiltration membrane in step (6) is taken out, is cleaned repeatedly with ethanol and deionized water to go
Except responseless compounds containing thiol groups and initiator.
As shown in Figure 1 and Figure 2, the static contact angle for being modified PVDF hollow fiber ultrafiltration membranes after tested is 81.9 °, with not changing
88.1 ° of the static contact angle of property PVDF hollow fiber ultrafiltration membranes compares range of decrease very little.As shown in Figure 8, Figure 9, bovine serum protein
Adsorbance is by 22.3 μ g/cm3It is reduced to 21.9 μ g/cm3, pure water flux change unobvious, illustrate that significant change does not occur for structure,
Hydrophily slightly strengthens.
Comparative example 2
(1) PVDF hollow fiber ultrafiltration membranes are cleaned：PVDF hollow fiber ultrafiltration membranes are immersed in 24h in absolute ethyl alcohol, so
Rinsed repeatedly with deionized water afterwards；
(2) lye is configured：Potassium hydroxide solid is added to ethanol and deionized water ethanol and deionized water quality ratio 1:1
Mixed liquor in stir evenly lye be made, potassium hydroxide quality fraction is 10wt.%.
(3) hollow fiber ultrafiltration membrane after cleaning in step (1) is completely infused in the lye that step (2) is configured,
It is placed in 10min in 60 DEG C of environment.
(4) by the hollow fiber ultrafiltration membrane after alkali process in step (3) take out and use deionized water under ultrasonic vibration it is anti-
After backwashing wash to no longer in alkalescence, the alkali process hollow fiber ultrafiltration membrane after cleaning is placed in ethanol infiltrate it is stand-by.
(5) modification is prepared with solution：Solvent is ethanol.Mercaptoethanol, 2- hydroxy-2-methyl -1- benzene are added into solvent
Base -1- acetone and triphenylphosphine.Mercaptoethanol, 2- hydroxy-2-methyl -1- phenyl -1- acetone and triphenylphosphine are in solution
In mass fraction be respectively 5wt.%, 0.1wt.%, 0.1wt.%.
(6) the PVDF hollow fiber ultrafiltration membranes that the ethanol in step (4) infiltrates are transferred to the solution prepared in step (5)
In, under conditions of stirring, it is placed under the ultraviolet lamp of a length of 365nm of light wave and is reacted in nitrogen atmosphere, reaction time 4h.
(7) the modification hollow fiber ultrafiltration membrane in step (6) is taken out, is cleaned repeatedly with ethanol and deionized water to go
Except responseless compounds containing thiol groups and initiator.
As shown in Figure 1 and Figure 2, the static contact angle for being modified PVDF hollow fiber ultrafiltration membranes after tested is 84.9 °, with not changing
88.1 ° of the static contact angle of property PVDF hollow fiber ultrafiltration membranes compares range of decrease very little.As shown in Figure 8, Figure 9, bovine serum protein
Adsorbance is by 22.3 μ g/cm3It is reduced to 21.6 μ g/cm3, pure water flux change unobvious, illustrate that significant change does not occur for structure,
Hydrophily slightly strengthens.
Claims (6)
1. a kind of surface hydrophilic modification method of Pvdf Microporous Hollow Fiber Membrane, it is characterised in that comprise the following steps：
(1) PVDF hollow fiber ultrafiltration membranes are cleaned：PVDF hollow fiber ultrafiltration membranes are immersed in 24h in absolute ethyl alcohol, Ran Houyong
Deionized water is rinsed repeatedly；
(2) lye is configured：Potassium hydroxide solid is added into ethanol and deionized water mixed liquor to stir evenly lye is made；
(3) hollow fiber ultrafiltration membrane after cleaning in step (1) is completely infused in the lye that step (2) is configured, be placed in
5~120min in 60 DEG C of environment；
(4) hollow fiber ultrafiltration membrane after alkali process in step (3) is taken out and is washed repeatedly under ultrasonic vibration with deionized water
Wash to no longer in alkalescence, the alkali process hollow fiber ultrafiltration membrane after cleaning is placed in ethanol infiltrate it is stand-by；
(5) modification is prepared with solution：Solvent is ethanol；Compounds containing thiol groups, photoinitiator and anti-formation are added into solvent
The reducing agent of disulfide bond；
(6) the PVDF hollow fiber ultrafiltration membranes that the ethanol in step (4) infiltrates are transferred in the solution prepared in step (5),
Under conditions of stirring, it is placed under the ultraviolet lamp of a length of 365nm of light wave and is reacted in nitrogen atmosphere, 1~5h of reaction time；
(7) the modification hollow fiber ultrafiltration membrane in step (6) is taken out, is cleaned with ethanol and deionized water and do not had to remove repeatedly
There are the compounds containing thiol groups and initiator of reaction.
2. according to a kind of surface hydrophilic modification method of Pvdf Microporous Hollow Fiber Membrane of claim 1, it is characterised in that institute
The mass fraction for stating ethanol in lye solvent in step (2) is 50wt.%, solute potassium hydroxide quality fraction for 5wt.%~
20wt.%.
3. according to a kind of surface hydrophilic modification method of Pvdf Microporous Hollow Fiber Membrane of claim 1, it is characterised in that institute
The mass fraction for stating the polymer containing sulfydryl in step (5) in modified solution is 10wt.%~50wt.%, and initiator quality is divided
Number is 0.2wt.%~1.0wt.%, and reducing agent mass fraction is 0.2wt.%~1.0wt.%.
4. according to a kind of surface hydrophilic modification method of Pvdf Microporous Hollow Fiber Membrane of claim 1, it is characterised in that institute
It is 2 mercapto ethanol to state the polymer containing sulfydryl in step (5) in modified solution, mercapto-acetaldehyde, 2- thioacetic acid, 3- sulfydryls third
Acid, 4- mercaptobutyric acids, 2- sulfydryl propionic aldehyde, 3- sulfydryl -1- propylamine, 2- sulfydryl propyl- 1- alcohol, 3- sulfydryl -1- propyl alcohol, 1- sulfydryls -2-
Acetone, the one or more in 2- mercapto-acetamides.
5. according to a kind of surface hydrophilic modification method of Pvdf Microporous Hollow Fiber Membrane of claim 1, it is characterised in that institute
Initiator in step (5) in modified solution is stated as 2- hydroxy-2-methyl -1- phenyl -1- acetone, benzoin dimethylether, 2,4,
6- trimethylbenzoyls phosphinic acid ethyl ester, 2- methyl isophthalic acids-[4- methyl mercaptos phenyl] -2- Lin Ji -1- acetone, 1- hydroxy-cyclohexyls
One or more in phenyl ketone and 2- phenyl benzyl -2- dimethyl amines -1- (4- morpholine benzyls phenyl) butanone.
6. according to a kind of surface hydrophilic modification method of Pvdf Microporous Hollow Fiber Membrane of claim 1, it is characterised in that institute
It is triphenylphosphine to state the reducing agent in step (5) in modified solution, iodoacetamide, one kind in dithiothreitol (DTT).
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110694487A (en) * | 2019-11-27 | 2020-01-17 | 大连交通大学 | Device and method for electrochemically modifying polyvinylidene fluoride membrane |
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| CN110801739A (en) * | 2019-11-25 | 2020-02-18 | 济南大学 | Blending modification method of polyvinylidene fluoride membrane |
| CN110801741A (en) * | 2019-11-25 | 2020-02-18 | 济南大学 | Surface modification method of polyvinylidene fluoride membrane |
| CN110801739B (en) * | 2019-11-25 | 2022-10-25 | 济南大学 | Blending modification method of polyvinylidene fluoride membrane |
| CN110694487A (en) * | 2019-11-27 | 2020-01-17 | 大连交通大学 | Device and method for electrochemically modifying polyvinylidene fluoride membrane |
| CN110694487B (en) * | 2019-11-27 | 2021-12-17 | 大连交通大学 | Device and method for electrochemically modifying polyvinylidene fluoride membrane |
| CN112973472A (en) * | 2021-02-19 | 2021-06-18 | 武汉大学苏州研究院 | Functionalization method of thin-layer composite membrane |
| CN112973472B (en) * | 2021-02-19 | 2022-07-19 | 武汉大学苏州研究院 | Functionalization method of thin-layer composite 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 |
| CN117358076A (en) * | 2023-12-07 | 2024-01-09 | 新乡学院 | Hydrophilic high-performance polyvinylidene fluoride/MOFs composite membrane and preparation method thereof |
| CN117358076B (en) * | 2023-12-07 | 2024-04-12 | 新乡学院 | Hydrophilic high-performance polyvinylidene fluoride/MOFs composite membrane and preparation method thereof |
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