CN106422821A - Preparing method of hydrophilically modified polyvinylidene fluoride ultrafiltration membrane - Google Patents
Preparing method of hydrophilically modified polyvinylidene fluoride ultrafiltration membrane Download PDFInfo
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- CN106422821A CN106422821A CN201610860439.0A CN201610860439A CN106422821A CN 106422821 A CN106422821 A CN 106422821A CN 201610860439 A CN201610860439 A CN 201610860439A CN 106422821 A CN106422821 A CN 106422821A
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- pvdf
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- ultrafiltration membrane
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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
- 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
- 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
- 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
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
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- Inorganic Chemistry (AREA)
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- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention provides a preparing method of a hydrophilically modified polyvinylidene fluoride (PVDF) ultrafiltration membrane, and relates to the preparing method of the PVDF ultrafiltration membrane. A chemical method is mainly adopted to hydrophilically modify the PVDF ultrafiltration membrane. The preparing method comprises two main steps which are preparation of a polyvinylidene fluoride spinning solution and electrostatic spinning and surface chemical modification respectively. To be more specific, the preparing method comprises the steps of putting PVDF powder into a mixed solution of N-N dimethylformamide (DMF) and acetone with a certain ratio to be prepared to the spinning solution, heating the spinning solution to 40 DEG C and stirring the spinning solution for 1-2 hours until the spinning solution is uniformly mixed, dissolving the spinning solution fully until the spinning solution is of a transparent state, testing and recording the viscosity of the spinning solution, and adopting the electrostatic spinning to obtain the PVDF membrane. A free radical polymerization method is adopted to conduct stem grafting of the crylic acid with a concentration of 10-20% to the surface of the PVDF ultrafiltration membrane obtained after alkali treatment, thus the hydrophilia of the surface of the membrane is improved. The hydrophilically modified polyvinylidene fluoride ultrafiltration membrane is prepared through the electrostatic spinning and has the advantages of being simple in device, convenient to operate, low in spinning cost and the like. Water flux of the membrane is remarkably improved after hydrophilical modifying.
Description
Technical field
The present invention relates to the preparation method of a kind of hydrophilic modifying Kynoar (PVDF) ultrafilter membrane.
Background technology
Kynoar (PVDF) has and five kinds of crystalline phases α, β, γ, δ and ε, wherein mainly based on two kinds of crystalline phases of α, β.α
It is the most common configuration of naturalness and most stable of crystalline phase that crystalline phase is nonpolar phase.Crystal formation β phase is a kind of ferroelectricity body phase, molecule
Chain is flat serrations (TT) configuration, is a kind of polarity configuration.Kynoar is a kind of organic material of excellent high molecular polymer
Material, the advantages of with excellent chemical stability, against weather, resistance tocrocking, radiation hardness and easy film forming, but PVDF surface energy
Low, hydrophobicity is strong, vulnerable to pollution in water process, increases membrane resistance, and bucket amount declines, so as to limit the application of pvdf membrane
Field.
Contain the group such as C, H, F in Kynoar structure, and do not possess-OH ,-COOH ,-NH2 isopolarity group, thus
Film obtained in it is hydrophobic.Therefore PVDF is significantly limit in many many applications, hydrophilic modifying is carried out to PVDF
Exactly replace the F atom on film using hydrophilic radical, be then bonded or cover upper hydroaropic substance, and then after enhancing modified
PVDF hydrophilic.
Hydrophilic film surface makes the water in film near-surface region be in due to there is interaction of hydrogen bond between hydrone
Ordered structure, therefore water Preferential adsorption, and hydrophobic substance is then required the expenditure of energy to destroy this ordered structure to be close to film surface.
Therefore, hydrophilic film is less susceptible to be contaminated.
Content of the invention
The purpose of the present invention aims to provide a kind of preparation method of hydrophilic modification method polyvinylidene fluoride (PVDF) ultrafiltration membrane, improves
The hydrophilic of pvdf membrane.
For achieving the above object, a kind of system of hydrophilic modification method polyvinylidene fluoride (PVDF) ultrafiltration membrane the technical scheme is that
Preparation Method, including two key steps, is followed successively by preparation and the surface chemical modification of PVDF ultrafiltration membrane.
Comprise the following steps that:
PVDF powder is placed in the DMF of certain proportioning and acetone mixed solution spinning liquid is configured to, 40 DEG C of heating is simultaneously stirred
1-2h is mixed to the transparent shape of solution mix homogeneously, and its viscosity of test record, pvdf membrane is obtained using Static Spinning.
Using free radical polymerisation process concentration is the acrylic acid-grafted to through alkali process PVDF ultrafiltration membrane table of 10-20%
Face, improves the hydrophilic on film surface.
The pvdf membrane that Static Spinning is obtained is placed in soak in deionized water makes which fully infiltrate, and removes molten in preparation process
Agent and other materials.
By the pvdf membrane of complete wetting be placed in mass ratio for 8: 2 sodium hydroxide and potassium permanganate mixed solution in,
10-15min is stirred at 40 DEG C, make pvdf membrane surface occur elimination reaction to form C=C double bond.
The pvdf membrane for reacting is placed in water cleaning 10-15min, removes unreacted sodium hydroxide and potassium permanganate
And other materials.
PVDF ultrafiltration membrane after cleaning is placed in initiator that mass fraction is 2% and concentration be
Aqueous solution in occur graft reaction, response time 3-4h, reaction temperature is 40 DEG C.
Pvdf membrane after graft reaction is placed in 30min in deionized water, the material not reacted is removed, is placed in room temperature
Under dry, obtain modified hydrophilic PVDF membrane.
Electrostatic spinning technique is that polymer solution or melt are sprayed under the effect of high field power, stretched and obtained
The spinning process of nanofiber.Electrostatic spinning apparatus mainly include three below part:High-voltage DC power supply, syringe pump, ground connection
Reception device.
The configuration spinning liquid adds a certain amount of acetone, and fibrous membrane assumes loose structure.
Static Spinning process obtains Static Spinning pvdf membrane using Multi needle while working.
The use of initiator is methyl ethyl ketone peroxide.
Advantages of the present invention is to form free radical through the PVDF ultrafiltration membrane of alkali process in the presence of initiator, with propylene
Sour glycerol polymerization, film surface introduces hydroxyl and carboxylated hydrophilic group, improves the hydrophilic of pvdf membrane, improves film water and leads to
Amount.
Description of the drawings
Fig. 1 is electrostatic spinning apparatus sketch
In Fig. 1,1 is syringe
2 is PVDF spinning liquid
3 is dispensing needle head
4 is high-voltage DC power supply
5 is ground connection receiving device.
Specific embodiment
With reference to embodiment, technical scheme is described in further detail.
The present invention provides a kind of preparation method of hydrophilic modifying PVDF water filtration membrane, is changed PVDF ultrafiltration membrane hydrophilic
Kind, improve membrane flux.Concrete steps:
PVDF powder is placed in the DMF of certain proportioning and acetone mixed solution spinning liquid is configured to, 40 DEG C of heating is simultaneously stirred
1-2h is mixed to the transparent shape of solution mix homogeneously, and its viscosity of test record, pvdf membrane is obtained using Static Spinning.
Using free radical polymerisation process concentration is the acrylic acid-grafted to through alkali process PVDF ultrafiltration membrane table of 10-20%
Face, improves the hydrophilic on film surface.
The pvdf membrane that Static Spinning is obtained is placed in soak in deionized water makes which fully infiltrate, and removes molten in preparation process
Agent and other materials.
By the pvdf membrane of complete wetting be placed in mass ratio for 8: 2 sodium hydroxide and potassium permanganate mixed solution in,
10-15min is stirred at 40 DEG C, make pvdf membrane surface occur elimination reaction to form C=C double bond.
The pvdf membrane for reacting is placed in water cleaning 10-15min, removes unreacted sodium hydroxide and potassium permanganate
And other materials.
PVDF ultrafiltration membrane after cleaning is placed in initiator that mass fraction is 2% and concentration be
Aqueous solution in occur graft reaction, response time 3-4h, reaction temperature is 40 DEG C.
Pvdf membrane after graft reaction is placed in 30min in deionized water, the material not reacted is removed, is placed in room temperature
Under dry, obtain modified hydrophilic PVDF membrane.
Example 1:(1) electrostatic spinning:
1. the first step, the deionized waters such as reagent bottle, syringe is cleaned, then reagent bottle after cleaning etc. is put into baking
Case is dried, to be used.
2. second step, weighs the PVDF powder of certain mass, after dried, is dissolved in DMF and acetone mixing is molten
In agent, it is 8% to prepare PVDF solution concentration, heats 40 DEG C in thermostat water bath and stirs 1-2h to solution mix homogeneously so as to
Transparent shape is fully dissolved, tests and record its viscosity.
3. the 3rd step, takes appropriate PVDF spinning liquid and is injected in syringe, place a syringe on syringe pump, high
Pressure DC power anode is clipped on syringe needle, and negative pole is connected with reception device, spinning voltage 16KV needed for adjusting, spinning flow velocity
1.0ml/h, spinning obtain Static Spinning pvdf membrane apart from 15cm.
(2) hydrophilic modifying:
1. being placed in soak the pvdf membrane that Static Spinning is obtained in deionized water makes which fully infiltrate, and removes in preparation process
Solvent and other materials.
2. by the pvdf membrane of complete wetting be placed in mass ratio for 8: 2 sodium hydroxide and potassium permanganate mixed solution in,
10-15min is stirred at 40 DEG C, make pvdf membrane surface occur elimination reaction to form C=C double bond.
3. the pvdf membrane for reacting is placed in water cleaning 10-15min, removes unreacted sodium hydroxide and permanganic acid
Potassium and other materials.
4. the PVDF ultrafiltration membrane after cleaning is placed in initiator that mass fraction is 2% and concentration is 10% acrylic acid
Generation graft reaction, response time 3-4h in aqueous solution, reaction temperature is 40 DEG C.
5. the pvdf membrane after graft reaction is placed in 30min in deionized water, the material not reacted is removed, is placed in room
Dry under temperature, obtain modified hydrophilic PVDF membrane
Example 2:(1) electrostatic spinning:
1. the deionized waters such as reagent bottle, syringe are cleaned, are then put reagent bottle after cleaning etc. by the first step first
Enter oven for drying, to be used.
2. second step, weighs the PVDF powder of certain mass, after dried, is dissolved in DMF and acetone mixing is molten
In agent, it is 10% to prepare PVDF solution concentration, heats 40 DEG C in thermostat water bath and stirs 1-2h to solution mix homogeneously so as to
Transparent shape is fully dissolved, tests and record its viscosity.
3. the 3rd step, takes appropriate PVDF spinning liquid and is injected in syringe, place a syringe on syringe pump, high
Pressure DC power anode is clipped on syringe needle, and negative pole is connected with reception device, spinning voltage 16KV needed for adjusting, spinning flow velocity
1.0ml/h, spinning obtain Static Spinning pvdf membrane apart from 15cm.
(2) hydrophilic modifying:
1. being placed in soak the pvdf membrane that Static Spinning is obtained in deionized water makes which fully infiltrate, and removes in preparation process
Solvent and other materials.
2. by the pvdf membrane of complete wetting be placed in mass ratio for 8: 2 sodium hydroxide and potassium permanganate mixed solution in,
10-15min is stirred at 40 DEG C, make pvdf membrane surface occur elimination reaction to form C=C double bond.
3. the pvdf membrane for reacting is placed in water cleaning 10-15min, removes unreacted sodium hydroxide and permanganic acid
Potassium and other materials.
4. the PVDF ultrafiltration membrane after cleaning is placed in initiator that mass fraction is 2% and concentration is 10% acrylic acid
Generation graft reaction, response time 3-4h in aqueous solution, reaction temperature is 40 DEG C.
5. the pvdf membrane after graft reaction is placed in 30min in deionized water, the material not reacted is removed, is placed in room
Dry under temperature, obtain modified hydrophilic PVDF membrane.
Example 3:(1) electrostatic spinning:
1. the deionized waters such as reagent bottle, syringe are cleaned, are then put reagent bottle after cleaning etc. by the first step first
Enter oven for drying, to be used.
2. second step, weighs the PVDF powder of certain mass, after dried, is dissolved in DMF and acetone mixing is molten
In agent, it is 10% to prepare PVDF solution concentration, heats 40 DEG C in thermostat water bath and stirs 1-2h to solution mix homogeneously, makes
Which fully dissolves transparent shape, tests and record its viscosity.
3. the 3rd step, takes appropriate PVDF spinning liquid and is injected in syringe, place a syringe on syringe pump, high
Pressure DC power anode is clipped on syringe needle, and negative pole is connected with reception device, spinning voltage 16KV needed for adjusting, spinning flow velocity
1.0ml/h, spinning obtain Static Spinning pvdf membrane apart from 15cm.
(2) hydrophilic modifying:
1. being placed in soak the pvdf membrane that Static Spinning is obtained in deionized water makes which fully infiltrate, and removes in preparation process
Solvent and other materials.
2. by the pvdf membrane of complete wetting be placed in mass ratio for 8: 2 sodium hydroxide and potassium permanganate mixed solution in,
10-15min is stirred at 40 DEG C, make pvdf membrane surface occur elimination reaction to form C=C double bond.
3. the pvdf membrane for reacting is placed in water cleaning 10-15min, removes unreacted sodium hydroxide and permanganic acid
Potassium and other materials.
4. the PVDF ultrafiltration membrane after cleaning is placed in initiator that mass fraction is 2% and concentration is 15% acrylic acid
Generation graft reaction, response time 3-4h in aqueous solution, reaction temperature is 40 DEG C.
5. the pvdf membrane after graft reaction is placed in 30min in deionized water, the material not reacted is removed, is placed in room
Dry under temperature, obtain modified hydrophilic PVDF membrane.
Claims (12)
1. a kind of preparation method of hydrophilic modifying polyvinylidene fluoride (PVDF) ultrafiltration membrane, the preparation including polyvinylidene fluoride (PVDF) ultrafiltration membrane and its table
Face chemical modification.Characterized in that, preparation of the preparation of described polyvinylidene fluoride (PVDF) ultrafiltration membrane comprising Kynoar spinning liquid
With electrostatic spinning;Described surface chemical modification mode is the acrylic acid-grafted technique after alkali process.
2. the preparation method of Kynoar spinning liquid as claimed in claim 1, it is characterised in that by Kynoar powder
It is placed in the DMF of certain proportioning and acetone mixed solution, spinning liquid is configured to, 40 DEG C of heating simultaneously stirs 1-2
Hour controls its viscosity 70-75mPa s by the volatilization of acetone, using method of electrostatic spinning to the transparent shape of solution mix homogeneously
Obtain polyvinylidene fluoride film.
3. a kind of preparation method of hydrophilic modifying polyvinylidene fluoride (PVDF) ultrafiltration membrane as claimed in claim 1, it is characterised in that adopt
Concentration is the acrylic acid-grafted to polyvinylidene fluoride (PVDF) ultrafiltration membrane surface after alkali process of 10-20% by free radical polymerisation process,
Improve the hydrophilic on film surface.
4. a kind of electrostatic spinning apparatus and technique as claimed in claim 2, the device for spinning of employing mainly includes HVDC
Power supply, multigroup syringe pump, multiple rows of spinning syringe needle and ground connection four part of reception device.Described high-voltage DC power supply running voltage is
12-15kV, connects a 20G specification spinning syringe needle per platform syringe pump by communicating pipe, and ejection of syringe pump speed is 1-1.2ml/
H, spinning syringe needle is arranged in a row with 2.2-2.5cm spacing parallel vertical, and reception device is the conductive rubber conveyer belt of ground connection, transmission
Speed is 20mm/min.
5. a kind of preparation method of hydrophilic modifying polyvinylidene fluoride (PVDF) ultrafiltration membrane as claimed in claim 2, it is characterised in that will be quiet
The pvdf membrane that electrospinning is obtained is placed in soak in deionized water makes which fully infiltrate, and removes the solvent in preparation process and other things
Matter.
6. a kind of preparation method of hydrophilic modifying polyvinylidene fluoride (PVDF) ultrafiltration membrane as claimed in claim 5, it is characterised in that will be complete
The pvdf membrane of full infiltration is placed in mass ratio for, in 8: 2 sodium hydroxide and the mixed solution of potassium permanganate, stirring 10- at 40 DEG C
15min, makes pvdf membrane surface occur elimination reaction to form C=C double bond.
7. a kind of preparation method of hydrophilic modifying polyvinylidene fluoride (PVDF) ultrafiltration membrane as claimed in claim 6, it is characterised in that will send out
The pvdf membrane of raw reaction is placed in water cleaning 10-15min, removes unreacted sodium hydroxide and potassium permanganate and other things
Matter.
8. a kind of preparation method of hydrophilic modifying polyvinylidene fluoride (PVDF) ultrafiltration membrane as claimed in claim 7, it is characterised in that will be clear
It is to send out in the acrylic acid aqueous solution of 10-20% that PVDF ultrafiltration membrane after washing is placed in the initiator that mass fraction is 2% and concentration
Raw graft reaction, response time 3-4h, reaction temperature is 40 DEG C.
9. a kind of preparation method of hydrophilic modifying polyvinylidene fluoride (PVDF) ultrafiltration membrane as claimed in claim 8, it is characterised in that will connect
The reacted pvdf membrane of branch is placed in 30min in deionized water, removes the material not reacted, puts and dry at room temperature, obtain
Modified hydrophilic PVDF membrane.
10. a kind of preparation method of hydrophilic modifying Kynoar PVDF ultrafiltration membrane as claimed in claim 1, its feature exists
In configuration spinning liquid adds a certain amount of acetone, and fibrous membrane assumes loose structure.
A kind of preparation method of the 11. hydrophilic modifying polyvinylidene fluoride (PVDF) ultrafiltration membranes as described in claim 1 or 3, it is characterised in that
Static Spinning pvdf membrane is obtained while working using Multi needle.
12. a kind of preparation methoies of hydrophilic modifying PVDF ultrafiltration membrane as claimed in claim 8, it is characterised in that using initiation
Agent is methyl ethyl ketone peroxide.
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107602740A (en) * | 2017-10-31 | 2018-01-19 | 北京化工大学 | A kind of modified dielectric fluoropolymer and its thin-film material, and preparation method thereof |
CN108786486A (en) * | 2018-07-02 | 2018-11-13 | 上海城市水资源开发利用国家工程中心有限公司 | A kind of coating Raolical polymerizable method preparation PES/PVDF function ultrafiltration film methods |
CN111939773A (en) * | 2020-08-18 | 2020-11-17 | 武汉高正新材料科技有限公司 | Preparation method of PVDF (polyvinylidene fluoride) film |
CN112593341A (en) * | 2020-11-17 | 2021-04-02 | 广州市天河区暨南大学附属实验学校 | Underwater self-powered sensor and preparation method and application thereof |
CN113644378A (en) * | 2021-08-10 | 2021-11-12 | 深圳市鼎泰祥新能源科技有限公司 | Functional coating diaphragm and preparation method and application thereof |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103194820A (en) * | 2013-04-27 | 2013-07-10 | 青岛大学 | Method for preparing micro-nanofiber through solvent curing type electrostatic spinning |
CN104174302A (en) * | 2014-07-31 | 2014-12-03 | 北京碧水源膜科技有限公司 | Hydrophilic modification method for PVDF (Polyvinylidene Fluoride) ultra-filtration film |
-
2016
- 2016-09-27 CN CN201610860439.0A patent/CN106422821A/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103194820A (en) * | 2013-04-27 | 2013-07-10 | 青岛大学 | Method for preparing micro-nanofiber through solvent curing type electrostatic spinning |
CN104174302A (en) * | 2014-07-31 | 2014-12-03 | 北京碧水源膜科技有限公司 | Hydrophilic modification method for PVDF (Polyvinylidene Fluoride) ultra-filtration film |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107602740A (en) * | 2017-10-31 | 2018-01-19 | 北京化工大学 | A kind of modified dielectric fluoropolymer and its thin-film material, and preparation method thereof |
CN107602740B (en) * | 2017-10-31 | 2019-12-31 | 北京化工大学 | Modified dielectric fluorine-containing polymer and film material thereof, and preparation method thereof |
CN108786486A (en) * | 2018-07-02 | 2018-11-13 | 上海城市水资源开发利用国家工程中心有限公司 | A kind of coating Raolical polymerizable method preparation PES/PVDF function ultrafiltration film methods |
CN111939773A (en) * | 2020-08-18 | 2020-11-17 | 武汉高正新材料科技有限公司 | Preparation method of PVDF (polyvinylidene fluoride) film |
CN112593341A (en) * | 2020-11-17 | 2021-04-02 | 广州市天河区暨南大学附属实验学校 | Underwater self-powered sensor and preparation method and application thereof |
CN113644378A (en) * | 2021-08-10 | 2021-11-12 | 深圳市鼎泰祥新能源科技有限公司 | Functional coating diaphragm and preparation method and application thereof |
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