CN108854573A - A kind of hydrophilic modification method of seperation film - Google Patents
A kind of hydrophilic modification method of seperation film Download PDFInfo
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- CN108854573A CN108854573A CN201810792679.0A CN201810792679A CN108854573A CN 108854573 A CN108854573 A CN 108854573A CN 201810792679 A CN201810792679 A CN 201810792679A CN 108854573 A CN108854573 A CN 108854573A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
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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
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/78—Graft polymers
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- 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
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- 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
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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
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
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Abstract
The invention discloses a kind of hydrophilic modification methods of seperation film, and described method includes following steps：One, film is placed on LB film instrument sample stage, the dropwise addition of amphiphilic solution is formed into orderly aligned monolayer in the sink of LB film instrument, detect membrane pressure and with the position of the movement speed of 0.5 ~ 10mm/s adjustment two pieces of liquid level baffles of LB film instrument, when membrane pressure reaches critical value, adjustment LB film instrument liquid level baffle movement speed is 90 ~ 500 μm/s, and film is dipped vertically under the liquid level of LB film instrument with the decrease speed of 90 ~ 500 μm/s, so that film surface is equably adhered to the amphiphilic film of one layer of queueing discipline；Two, by film transfer obtained by step 1 into polymerizing reactor, the monomer polymerization reactions of film surface are carried out under liquid-phase condition, obtain the Modified Membrane of surface grafting hydrophilic radical and polymer.The present invention is significant for improving the performances such as membrane flux, stain resistance, membrane lifetime.
Description
Technical field
The present invention relates to a kind of method of modifying of seperation film, and in particular to a kind of hydrophilic modification method of seperation film.
Background technique
The materials such as polytetrafluoroethylene (PTFE), Kynoar have many advantages, such as corrosion-resistant, heat-resisting cold-resistant, and various aspects overall target is excellent
Show, film-formation result are good.
With the development of water process industry, film process becomes one of the important process of production high-quality water, but many suitable
It synthesizes the material hydrophilic difference of film or to be directly used in water treatment efficiency poor, such as polytetrafluoroethylene (PTFE), the contact angle that forms a film is up to 133 °,
It is limited to poor hydrophily and is difficult to be applied directly to water treatment field.
The hydrophilic method of film its number not to the utmost is improved, has chemical surface treatment modification, high-energy radiation graft modification, blending to change
Property etc., but often there is processing method complexity, equipment requirement are high, by-product is more etc. drawback.Plasma grafting it is modified by
To the favor of some researchers, but it is the failure to effectively solve modified imeliness problem.
So searching can effectively promote film hydrophily, reduce the method for modifying of fouling membrane and good timeliness to water
Processing industry has great significance.
Summary of the invention
In order to further increase the hydrophily of membrane material in prior art basis, and overcome common in film hydrophilically modified
Imeliness problem, to improve membrane flux, film filter effect and membrane lifetime, the present invention provides a kind of parent of new seperation film
Water method of modifying.
The purpose of the present invention is what is be achieved through the following technical solutions：
A kind of hydrophilic modification method of seperation film, includes the following steps：
One, the amphiphilic grafting of film surface
Film is placed on LB film instrument sample stage, the dropwise addition of amphiphilic solution is formed in the sink of LB film instrument orderly aligned
Monolayer is detected membrane pressure and is adjusted the position of two pieces of liquid level baffles of LB film instrument with the movement speed of 0.5 ~ 10mm/s, works as membrane pressure
When reaching critical value, adjustment LB film instrument liquid level baffle movement speed is 90 ~ 500 μm/s, and with the decrease speed of 90 ~ 500 μm/s
Film is dipped vertically under the liquid level of LB film instrument, film surface is made equably to adhere to the amphiphilic film of one layer of queueing discipline；
Two, the monomer polymerization reactions of film surface are carried out in liquid phase
By film transfer obtained by step 1 into polymerizing reactor, the monomer that film surface is carried out under anhydrous and oxygen-free liquid-phase condition is poly-
Reaction is closed, the Modified Membrane of surface grafting hydrophilic radical and polymer is obtained.
Three, subsequent graft reaction step：
The Modified Membrane of surface grafting that step 2 obtains hydrophilic radical and polymer is placed in plasma carry out etc. from
Daughter processing.
In the present invention, film described in step 1 is aperture in 0.0002~1 μm of microfiltration membranes, ultrafiltration membrane, nanofiltration membrane or anti-
Permeable membrane.
In the present invention, film component described in step 1 at least contains polytetrafluoroethylene (PTFE), Kynoar, polypropylene, polysulfones
One of film, polyimides.
May include the pretreatment process of film in the present invention, before step 1, in the pretreatment process, using nitrogen and/
Or argon gas carries out corona treatment to membrane material.The pretreatment process makes film surface generate a large amount of free radicals, can become step 2
The initiation conditions of middle polymerization reaction.
In the present invention, the plasma processing time is 10 ~ 300s, and plasma electrons energy is 2 ~ 6ev.
In the present invention, amphiphilic solution described in step 1 is acrylic acid solution, the content of acrylic acid is 5 ~
40wt%。
In the present invention, liquid phase described in step 2 is the solution containing initiator, wherein：Initiator can be two isobutyl of azo
Nitrile, content are 0.01 ~ 1wt%；Initiator content should be suitably reduced if reinforced polypropylene acid molecule length；Solvent can be chloroform.
In the present invention, liquid phase described in step 2 can contain molecular weight regulator, wherein：Molecular weight regulator can be second two
Alcohol dimethylacrylate, ethylene glycol dimethacrylate concentration are 0.1 ~ 20wt% of liquid phase.
In the present invention, reaction terminating condition is provided for heat polymerization system using low temperature in step 2, cryogenic temperature is situated between
In 277.15 ~ 0K.
In the present invention, treatment temperature >=45 DEG C of polymerization reaction described in step 2 handle time >=2h.
The invention has the advantages that：
The present invention by LB embrane method in conjunction with liquid-phase polymerization in the way of, as shown in Figure 1, first membrane material surface grafting arrange advise
Amphiphilic then recycles liquid-phase polymerization to form thickness uniformly and the polymer of firm attachment on membrane material surface, greatly
The big hydrophily for improving membrane material, modified polytetrafluoroethylene film surface water contact angle are down to 81 ° from 133 °, polyvinylidene fluoride film table
Face water contact angle is down to 76 ° from 92 °.It is significant for improving the performances such as membrane flux, stain resistance, membrane lifetime.
Detailed description of the invention
Fig. 1 is the hydrophilic modifying schematic diagram of seperation film of the present invention.
Specific embodiment
Further description of the technical solution of the present invention with reference to the accompanying drawing, but is not so limited, all to this
Inventive technique scheme is modified or replaced equivalently, and without departing from the spirit and scope of the technical solution of the present invention, should all be covered
Within the protection scope of the present invention.
Embodiment 1
A kind of hydrophilic modification method of film is present embodiments provided, the method mainly includes the following steps that：
One, pre-treatment step：
（1）Polytetrafluoroethylene film is cleaned using deionized water and is impregnated in acetone, ultrasound（Power 100W, 30 DEG C of temperature）Processing
2h is transferred to baking oven（80℃）Dry 2h, then in vacuum oven（22℃）Middle dry 3h；
（2）Two electrode plates are mounted on corresponding hanger, by what is cleaned by open plasma cavity by spacing 5cm
PTFE film sample is placed on the center of grounding electrode plate, is then shut off cavity and locks；
（3）Start AP-600 plasma, preheat 5 ~ 10min, open plasma gas valve starts gas pump and vacuum
Pump；
（4）On operation panel start vacuum pump vacuumize, while be arranged processing sample needed for plasma gas type be
Nitrogen, processing power 50W, time 50s；
（5）Stop vacuumizing when air pressure is lower than 40Pa in cavity, be put into plasma gas, adjustment flow makes intracavitary plasma
Pressure is stablized generates plasma-treated samples in 100mTorr, star t-up discharge program, cavity.
Two, the amphiphilic grafting step of film surface：
Film obtained by step 1 is placed on the sample stage of LB film instrument, amphiphilic solution is added dropwise in LB film instrument sink, inspection
Survey membrane pressure and with the position of the movement speed of 1 ~ 5mm/s adjustment two pieces of liquid level baffles of LB film instrument；When membrane pressure reaches critical value, adjust
Whole LB film instrument liquid level baffle movement speed is 120 μm/s, and film is dipped vertically into LB film instrument with the decrease speed of 120 μm/s
Under liquid level, film surface is made equably to adhere to one layer of amphiphilic film.
Three, the monomer polymerization reactions step of film surface is carried out in liquid phase：
6.280g ethylene glycol dimethacrylate is accurately weighed in 40mL chloroform, is uniformly mixed, 0.128g azo two is added
Isobutyronitrile is uniformly mixed, is transferred in reaction kettle, then surface obtained by step 2 is attached with to the modification film transfer of acrylic acid LB film
It into reaction kettle, vacuumizes, leads to nitrogen, seal afterwards repeatedly for three times, be placed in 60 DEG C of water-baths and react for 24 hours, take out reaction kettle, be placed in
Reaction is terminated in ice salt bath.Modified Membrane successively, which is washed, with toluene, dehydrated alcohol and deionized water removes extra acrylic acid, 110
The hydrophilic modifying seperation film for obtaining surface grafting hydrophilic radical and polymer for 24 hours is dried in vacuo at DEG C, and in deionized water
Storage.
Four, subsequent graft reaction step：
The hydrophilic modifying film that step 3 obtains is placed in plasma described in step 1, adjustment plasma gas type is
Nitrogen, processing power 50W, time 300s.
In the present embodiment, the aperture of the polytetrafluoroethylene film is 0.3 μm.
In the present embodiment, the amphiphilic solution is acrylic acid solution, wherein：Solvent is chloroform, and acrylic acid contains
Amount is 3.5wt%.
Modified polytetrafluoroethylene film surface water contact angle is down to 81 ° from 133 °.
Embodiment 2
The present embodiment is unlike the first embodiment, modified using the polyvinylidene fluoride film that aperture is 0.25 μm as hydrophilic modifying object
Polyvinylidene fluoride film surface water contact angle is down to 76 ° from 92 ° afterwards.
Embodiment 3
The present embodiment unlike the first embodiment, is pre-processed in step 1 using argon plasma, and processing power is adjusted
For 100W, intracavitary plasma pressure is 200mTorr, and the processing time is 50s.
Embodiment 4
The present embodiment unlike the first embodiment, is further modified in step 4 using argon plasma, and processing power is adjusted
For 100W, intracavitary plasma pressure is 200mTorr, and the processing time is 300s.
Embodiment 5
The present embodiment unlike the first embodiment, no pre-treatment step.Modified polytetrafluoroethylene film surface water contact angle from
133 ° are down to 83 °.
Embodiment 6
The present embodiment unlike the first embodiment, without subsequent grafting step.Modified polytetrafluoroethylene film surface water contact angle from
133 ° are down to 84 °.
Claims (10)
1. a kind of hydrophilic modification method of seperation film, it is characterised in that described method includes following steps：
One, the amphiphilic grafting of film surface
Film is placed on LB film instrument sample stage, the dropwise addition of amphiphilic solution is formed in the sink of LB film instrument orderly aligned
Monolayer is detected membrane pressure and is adjusted the position of two pieces of liquid level baffles of LB film instrument with the movement speed of 0.5 ~ 10mm/s, works as membrane pressure
When reaching critical value, adjustment LB film instrument liquid level baffle movement speed is 90 ~ 500 μm/s, and with the decrease speed of 90 ~ 500 μm/s
Film is dipped vertically under the liquid level of LB film instrument, film surface is made equably to adhere to the amphiphilic film of one layer of queueing discipline；
Two, the monomer polymerization reactions of film surface are carried out in liquid phase
By film transfer obtained by step 1 into polymerizing reactor, the monomer that film surface is carried out under anhydrous and oxygen-free liquid-phase condition is poly-
Reaction is closed, the Modified Membrane of surface grafting hydrophilic radical and polymer is obtained.
2. the hydrophilic modification method of seperation film according to claim 1, it is characterised in that the method also includes walking as follows
Suddenly：
Three, subsequent graft reaction step：
The Modified Membrane of surface grafting that step 2 obtains hydrophilic radical and polymer is placed in plasma carry out etc. from
Daughter processing.
3. the hydrophilic modification method of seperation film according to claim 1, it is characterised in that the film is microfiltration membranes, ultrafiltration
Film, nanofiltration membrane or reverse osmosis membrane, aperture are 0.0002~1 μm, and film component at least contains polytetrafluoroethylene (PTFE), Kynoar, gathers
One of propylene, PS membrane, polyimides.
4. the hydrophilic modification method of seperation film according to claim 1 or 3, it is characterised in that the film is amphiphilic in progress
Following pretreatment process is carried out before molecule grafting：Corona treatment is carried out to membrane material using nitrogen and/or argon gas.
5. the hydrophilic modification method of seperation film according to claim 2 or 4, it is characterised in that the plasma processing time
For 10 ~ 300s, plasma electrons energy is 2 ~ 6ev.
6. the hydrophilic modification method of seperation film according to claim 1, it is characterised in that the amphiphilic solution is
Acrylic acid solution, the content of acrylic acid are 5 ~ 40wt%.
7. the hydrophilic modification method of seperation film according to claim 1, it is characterised in that contain initiator in the liquid phase,
The initiator is azodiisobutyronitrile, and content is 0.01 ~ 1wt%.
8. the hydrophilic modification method of seperation film according to claim 7, it is characterised in that also contain molecule in the liquid phase
Regulator is measured, the molecular weight regulator is ethylene glycol dimethacrylate, and ethylene glycol dimethacrylate content is 0.1
~20wt%。
9. the hydrophilic modification method of seperation film according to claim 1, it is characterised in that the heat polymerization system makes
Termination condition is provided for polymerization reaction with low temperature, cryogenic temperature is between 277.15 ~ 0K.
10. the hydrophilic modification method of seperation film according to claim 1, it is characterised in that the processing temperature of the polymerization reaction
>=45 DEG C of degree handles time >=2h.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810792679.0A CN108854573B (en) | 2018-07-18 | 2018-07-18 | Hydrophilic modification method of separation membrane |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810792679.0A CN108854573B (en) | 2018-07-18 | 2018-07-18 | Hydrophilic modification method of separation membrane |
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| CN108854573A true CN108854573A (en) | 2018-11-23 |
| CN108854573B CN108854573B (en) | 2021-06-01 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101890314A (en) * | 2010-07-20 | 2010-11-24 | 东华大学 | Surface hydrophilic modification method for polytetrafluoroethylene bulked membrane |
| CN103263861A (en) * | 2013-05-30 | 2013-08-28 | 哈尔滨工业大学 | Hydrophilic modification method for polyvinylidene fluoride hollow fiber membrane |
| CN103831027A (en) * | 2014-02-28 | 2014-06-04 | 东华大学 | Method for improving pollution resistance of PVDF (polyvinylidene fluoride) porous membrane based on plasmas technology |
| EP3088450A1 (en) * | 2015-04-30 | 2016-11-02 | VITO NV (Vlaamse Instelling voor Technologisch Onderzoek NV) | Plasma assisted hydrophilicity enhancement of polymer materials |
| CN106268370A (en) * | 2016-08-29 | 2017-01-04 | 同济大学 | Poly tetrafluoroethylene low temperature plasma hydrophilic modifying and timeliness modification processing method |
-
2018
- 2018-07-18 CN CN201810792679.0A patent/CN108854573B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101890314A (en) * | 2010-07-20 | 2010-11-24 | 东华大学 | Surface hydrophilic modification method for polytetrafluoroethylene bulked membrane |
| CN103263861A (en) * | 2013-05-30 | 2013-08-28 | 哈尔滨工业大学 | Hydrophilic modification method for polyvinylidene fluoride hollow fiber membrane |
| CN103831027A (en) * | 2014-02-28 | 2014-06-04 | 东华大学 | Method for improving pollution resistance of PVDF (polyvinylidene fluoride) porous membrane based on plasmas technology |
| EP3088450A1 (en) * | 2015-04-30 | 2016-11-02 | VITO NV (Vlaamse Instelling voor Technologisch Onderzoek NV) | Plasma assisted hydrophilicity enhancement of polymer materials |
| CN106268370A (en) * | 2016-08-29 | 2017-01-04 | 同济大学 | Poly tetrafluoroethylene low temperature plasma hydrophilic modifying and timeliness modification processing method |
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