CN102140181B - Polyvinylidene fluoride (PVDF) hydrophilic modified membrane and preparation method thereof - Google Patents
Polyvinylidene fluoride (PVDF) hydrophilic modified membrane and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a polyvinylidene fluoride (PVDF) modified functional membrane and a preparation method thereof. The PVDF modified functional membrane is obtained by grafting a functional polymer on the surface of a PVDF membrane by adopting a water phase atom transfer free radical polymerization method. The invention has the advantages that: on the basis of keeping the advantages of the original PVDF, the hydrophilicity and pollution resistance of the membrane are enhanced. The method has a simple process, is environmental-friendly and is suitable for industrial production. By grafting of different monomers, various membranes with different functions can be obtained.
Description
Technical field
The present invention relates to a kind of polyvinylidene difluoride (PVDF) hydrophilic modifying film and preparation method thereof.
Background technology
In the water treatment field of 21 century, membrane separation technique is efficient owing to having, environmental protection, energy-conservation and process simple, can realize that the characteristic of automatization control becomes one of the one preferred technique in this field.Film is as the core of membrane technique, and its chemical property and structure play decisive role to the performance of membrane sepn.Polyvinylidene difluoride (PVDF) (PVDF) has good chemical stability, radiation resistance, thermotolerance and is easy to the advantages such as film forming.Therefore obtain researchist's common concern, be widely used in the fields such as chemical industry, electronics, weaving, food, biochemistry.But, because the PVDF surface energy is low, hydrophobicity is extremely strong, surface adsorption very easily occurs in carrying out sepn process pollute, cause separation performance to descend, cleaning and maintenance cost are strengthened, and limited the application at other field.At present, the modification direction of PVDF had: 1. the wetting ability and the biocompatibility that improve film improve film stain resistance and work-ing life; 2. pvdf membrane is carried out functionalization, the use field of expanded film.
Process for modifying surface is not because change material body character, and operational path is simple, is easy to introduce the Main Means that the advantage such as several functions group becomes the pvdf membrane modification.Membrane surface modification technology commonly used comprises that chemical conversion treatment modification, film are surface recombination modified, radiation modification and the graft modification of film surface chemistry etc.PVDF has good chemically-resistant character, and reagent is difficult to it is reacted in the chemical conversion treatment modification, and the bulk properties such as physical strength of modification caudacoria are affected; Composite modified top coat comes off easily; What radiation modification utilized energetic ray or ion is radiated at that film surface produces free radical and monomer reacts, but energetic ray can destroy the mechanical property of membrane body equally; The matter of utmost importance of surface chemistry graft modification is exactly how to realize the controllable growth of chain.Atom transfer radical polymerization (ATRP) has efficiency of initiation and monomer conversion is high, prepare the advantages such as polymericular weight is controlled, distribution is single, has become most widely used active free radical polymerization (LRP) technology (present all is the ATRP aspect about LRP research paper and patent about 75%).But the C-F bond energy of PVDF is higher, be difficult to fracture, so its ATRP initiating activity is lower.In a lot of situations, people introduce active higher Br end group by chemical reaction on the pvdf membrane surface, then carry out the ATRP graft reaction, cause the modifying process complexity to be difficult to operation.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, provide a kind of wetting ability height and stain resistance large polyvinylidene difluoride (PVDF) hydrophilic modifying film.
Second purpose of the present invention provides the simple environmental protection of a kind of technique, is suitable for the preparation method of the polyvinylidene difluoride (PVDF) hydrophilic modifying film of suitability for industrialized production.
Technical scheme of the present invention is summarized as follows:
Polyvinylidene fluoride modified functional membrane is that the method by the water atom transfer radical polymerization is grafted with functional polymer on the polyvinylidene fluoride film surface.
Described functional polymer is polymethacrylate or polyacrylamide water-soluble polymers.
Described polymethacrylate is poly--2-(dimethylamino) ethyl-methyl acrylate, poly--2-(diisopropylaminoethyl) ethyl-methyl acrylate, poly--2-(diethylamino) ethyl-methyl acrylate, poly-(polyoxyethylene glycol) methacrylic ester, poly--HEMA, poly--the 3-hydroxy propyl methacrylate, poly--2-hydroxy propyl methacrylate or poly--2,3-dihydroxypropyl methacrylic ester.
Described polyacrylamide water-soluble polymers is poly--NIPA, sodium polyacrylate, poly--N,N-DMAA or poly--2-methoxy ethyl acrylamide.
The preparation method of polyvinylidene fluoride modified functional membrane comprises the steps:
(1) be 9-25cm with the area that cleans up
2The aqueous solution, cupric chloride, atom transfer radical polymerization ligand and the deionized water of polyvinylidene fluoride microporous film, atom transfer free crowd monomer add in the container, obtain 20-200 ml water solution, making the atom transferred free radical monomer concentration is the 0.1-0.5 grams per milliliter, the concentration that makes cupric chloride is 0.44-2.2 micromole/milliliter, and the concentration that makes atom transfer radical polymerization ligand is 0.44-2.2 micromole/milliliter;
(2) inflated with nitrogen 5-10min gets rid of the oxygen in the container;
(3) adding 0.2-8 milliliter volumetric molar concentration is the vitamins C aqueous solution of 1-22 mmole/milliliter, continues inflated with nitrogen 5-10min;
(4) with container sealing, at 30-60 ℃ of reaction 0.5-7h;
(5) film is taken out, 40 ℃ of water-baths, put into dehydrated alcohol stirring and washing 2-24h, then use deionized water stirring and washing 2-24h, taking-up is dried, and namely makes polyvinylidene fluoride modified modified function film.
Described atom transfer free crowd monomer is 2-(dimethylamino) ethyl-methyl acrylate, 2-(diisopropylaminoethyl) ethyl-methyl acrylate, 2-(diethylamino) ethyl-methyl acrylate, poly-(polyoxyethylene glycol) methacrylic ester, HEMA, NIPA, sodium acrylate, 3-hydroxy propyl methacrylate, 2-hydroxy propyl methacrylate, 2,3-dihydroxypropyl methacrylic ester, N,N-DMAA or 2-methoxy ethyl acrylamide.
Described atom transfer free crowd part is 2,2-dipyridyl, 4,4 '-two (5-nonyls)-2,2 '-dipyridyl, 1, Isosorbide-5-Nitrae, 7,7-five methyl diethylentriamine or three-(N, N '-dimethylaminoethyl) amine.
The method of the described cleaning of described step (1) is: in 10-80 ℃ of water-bath, being placed on polyvinylidene fluoride microporous film in volumetric concentration is in the aqueous ethanolic solution of 10-90% rinsing 3-24 hour, the aqueous ethanolic solution that to change volumetric concentration in every 1-6 hour be 10-90%.
Advantage of the present invention is on the advantage basis that keeps original PVDF, has improved wetting ability and the stain resistance of film.The method technique is simple, and environmental protection is suitable for suitability for industrialized production, by obstructed monomer in the grafting, can obtain the film of various difference in functionalitys.
Description of drawings
Fig. 1 is the pvdf membrane photoelectron spectrum figure before and after the modification.
Among the figure: a is that the former film of PVDF is composed scintigram entirely; E is the former film C1s spectrum of PVDF scintigram;
B is that the modified membrane of embodiment 17 preparations is composed scintigram entirely; F is the modified membrane C1s spectrum scintigram of embodiment 17 preparations;
C is that the modified membrane of embodiment 16 preparations is composed scintigram entirely; G is the modified membrane C1s spectrum scintigram of embodiment 16 preparations;
D is that the modified membrane of embodiment 13 preparations is composed scintigram entirely; H is the modified membrane C1s spectrum scintigram of embodiment 13 preparations.
Fig. 2 is the pvdf membrane surface contact angle photo before and after the modification.
Among the figure: A, B are respectively the modified membrane surface contact angle photo of former film and embodiment 20 preparations.
Fig. 3 is the pvdf membrane graph of pore diameter distribution before and after the modification.
Among the figure: a is the former film of PVDF; B is the modified membrane of embodiment 17 preparations; C is the modified membrane of embodiment 16 preparations; D is the modified membrane of embodiment 13 preparations;
Embodiment
The present invention is further illustrated below in conjunction with specific embodiment.
Embodiment 1
Polyvinylidene fluoride modified functional membrane, this film are that the method by the water atom transfer radical polymerization is grafted with poly--2-(dimethylamino) ethyl-methyl acrylate on the polyvinylidene fluoride film surface.
Embodiment 2
Polyvinylidene fluoride modified functional membrane, this film are that the method by the water atom transfer radical polymerization is grafted with poly--2-(diisopropylaminoethyl) ethyl-methyl acrylate on the polyvinylidene fluoride film surface.
Embodiment 3
Polyvinylidene fluoride modified functional membrane, this film are that the method by the water atom transfer radical polymerization is grafted with poly--2-(diethylamino) ethyl-methyl acrylate on the polyvinylidene fluoride film surface.
Embodiment 4
Polyvinylidene fluoride modified functional membrane, this film are that the method by the water atom transfer radical polymerization is grafted with poly-(polyoxyethylene glycol) methacrylic ester on the polyvinylidene fluoride film surface.
Embodiment 5
Polyvinylidene fluoride modified functional membrane, this film are that the method by the water atom transfer radical polymerization is grafted with poly--HEMA on the polyvinylidene fluoride film surface.
Embodiment 6
Polyvinylidene fluoride modified functional membrane, this film are that the method by the water atom transfer radical polymerization is grafted with poly--3-hydroxy propyl methacrylate on the polyvinylidene fluoride film surface.
Embodiment 7
Polyvinylidene fluoride modified functional membrane, this film are that the method by the water atom transfer radical polymerization is grafted with poly--2-hydroxy propyl methacrylate on the polyvinylidene fluoride film surface.
Embodiment 8
It is poly--2 that polyvinylidene fluoride modified functional membrane, this film are that the method by the water atom transfer radical polymerization is grafted with on the polyvinylidene fluoride film surface, 3-dihydroxypropyl methacrylic ester.
Embodiment 9
Polyvinylidene fluoride modified functional membrane, this film are that the method by the water atom transfer radical polymerization is grafted with poly--NIPA on the polyvinylidene fluoride film surface.
Embodiment 10
Polyvinylidene fluoride modified functional membrane, this film are that the method by the water atom transfer radical polymerization is grafted with sodium polyacrylate on the polyvinylidene fluoride film surface.
Embodiment 11
Polyvinylidene fluoride modified functional membrane, this film are that the method by the water atom transfer radical polymerization is grafted with poly--N,N-DMAA on the polyvinylidene fluoride film surface.
Embodiment 12
Polyvinylidene fluoride modified functional membrane, this film are that the method by the water atom transfer radical polymerization is grafted with poly--2-methoxy ethyl acrylamide on the polyvinylidene fluoride film surface.
Embodiment 13
The preparation method of polyvinylidene fluoride modified functional membrane comprises the steps:
(1) in 40 ℃ of water-baths, being placed on polyvinylidene fluoride microporous film in volumetric concentration is rinsing 10 hours in 70% the aqueous ethanolic solution, changes volumetric concentration in per 3 hours and be 70% aqueous ethanolic solution; Be 10cm with the area that cleans up
2Polyvinylidene fluoride microporous film, the aqueous solution, the cupric chloride, 2 of 2-(dimethylamino) ethyl-methyl acrylate, 2-dipyridyl and deionized water add in the container, obtain 100 ml water solution, making 2-(dimethylamino) ethyl-methyl acrylate concentration is 0.3 grams per milliliter, the concentration that makes cupric chloride is 1.0 micromole/milliliters, the concentration that makes 2,2-dipyridyl is 1.0 micromole/milliliters;
(2) inflated with nitrogen 8min gets rid of the oxygen in the container;
(3) add 1 milliliter of vitamins C aqueous solution that volumetric molar concentration is 15 mmole/milliliters, continue inflated with nitrogen 8min;
(4) with container sealing, at 45 ℃ of reaction 3h;
(5) film is taken out, 40 ℃ of water-baths, put into dehydrated alcohol stirring and washing 12h, then use deionized water stirring and washing 12h, taking-up is dried, and namely makes polyvinylidene fluoride modified modified function film.
After testing: film film surface water contact angle 72 degree that present embodiment is made, the water flux of film under 25 ℃ is 768L/m
2.h.bar
Embodiment 14
The preparation method of polyvinylidene fluoride modified functional membrane comprises the steps:
(1) in 40 ℃ of water-baths, being placed on polyvinylidene fluoride microporous film in volumetric concentration is rinsing 3 hours in 90% the aqueous ethanolic solution, changes volumetric concentration in per 1 hour and be 90% aqueous ethanolic solution; Be 9cm with the area that cleans up
2Polyvinylidene fluoride microporous film, the aqueous solution, the cupric chloride, 4 of 2-(diisopropylaminoethyl) ethyl-methyl acrylate, 4 '-two (5-nonyls)-2,2 '-dipyridyl and deionized water add in the container, obtain 20 ml water solution, making the concentration of 2-(diisopropylaminoethyl) ethyl-methyl acrylate is 0.1 grams per milliliter, and the concentration that makes cupric chloride is 0.44 micromole/milliliter, makes 4,4 '-two (5-nonyls)-2, the concentration of 2 '-dipyridyl are 0.44 micromole/milliliter;
(2) inflated with nitrogen 5min gets rid of the oxygen in the container;
(3) add 0.2 milliliter of vitamins C aqueous solution that volumetric molar concentration is 22 mmole/milliliters, continue inflated with nitrogen 5min;
(4) with container sealing, at 30 ℃ of reaction 7h;
(5) film is taken out, 40 ℃ of water-baths, put into dehydrated alcohol stirring and washing 2h, then use deionized water stirring and washing 2h, taking-up is dried, and namely makes polyvinylidene fluoride modified modified function film.
After testing: film film surface water contact angle 65 degree that present embodiment is made, the flux of film under 25 ℃ is 890L/m
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Embodiment 15
The preparation method of polyvinylidene fluoride modified functional membrane comprises the steps:
(1) in 60 ℃ of water-baths, being placed on polyvinylidene fluoride microporous film in volumetric concentration is rinsing 24 hours in 10% the aqueous ethanolic solution, changes volumetric concentration in per 6 hours and be 10% aqueous ethanolic solution; Be 25cm with the area that cleans up
2Polyvinylidene fluoride microporous film, the aqueous solution, the cupric chloride, 1 of 2-(diethylamino) ethyl-methyl acrylate, Isosorbide-5-Nitrae, 7,7-five methyl diethylentriamine and deionized water add in the container, obtain 200 ml water solution, and making the concentration of 2-(diethylamino) ethyl-methyl acrylate is 0.5 grams per milliliter, the concentration that makes cupric chloride is 2.2 micromole/milliliters, make 1, Isosorbide-5-Nitrae, the concentration of 7,7-five methyl diethylentriamine is 2.2 micromole/milliliters;
(2) inflated with nitrogen 10min gets rid of the oxygen in the container;
(3) add 8 milliliters of vitamins C aqueous solution that volumetric molar concentration is 1 mmole/milliliter, continue inflated with nitrogen 10min;
(4) with container sealing, at 60 ℃ of reaction 0.5h;
(5) film is taken out, 40 ℃ of water-baths, put into dehydrated alcohol stirring and washing 24h, then use deionized water stirring and washing 24h, taking-up is dried, and namely makes polyvinylidene fluoride modified modified function film.
After testing: film film surface water contact angle 88 degree that present embodiment is made, the flux of film under 25 ℃ is 1050L/m
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Embodiment 16
The preparation method of polyvinylidene fluoride modified functional membrane comprises the steps:
(1) disclosing method with embodiment 13 polyvinylidene fluoride microporous film is cleaned, is 15cm with the area that cleans up
2Polyvinylidene fluoride microporous film, the aqueous solution, the cupric chloride, three-(N of poly-(polyoxyethylene glycol) methacrylic ester, N '-dimethylaminoethyl) amine and deionized water add in the container, obtain 60 ml water solution, making poly-(polyoxyethylene glycol) methacrylic acid ester concentration is 0.3 grams per milliliter, the concentration that makes cupric chloride is 1.2 micromole/milliliters, making the concentration of three-(N, N '-dimethylaminoethyl) amine is 1.2 micromole/milliliters;
(2) inflated with nitrogen 8min gets rid of the oxygen in the container;
(3) add 3 milliliters of vitamins C aqueous solution that volumetric molar concentration is 10 mmole/milliliters, continue inflated with nitrogen 8min;
(4) with container sealing, at 45 ℃ of reaction 3h;
(5) film is taken out, 40 ℃ of water-baths, put into dehydrated alcohol stirring and washing 12h, then use deionized water stirring and washing 12h, taking-up is dried, and namely makes polyvinylidene fluoride modified modified function film.
After testing: film film surface water contact angle 47 degree that present embodiment is made, the flux of film under 25 ℃ is 486L/m
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Embodiment 17
The preparation method of polyvinylidene fluoride modified functional membrane comprises the steps:
(1) disclosing method with embodiment 14 polyvinylidene fluoride microporous film is cleaned, is 15cm with the area that cleans up
2Polyvinylidene fluoride microporous film, the aqueous solution of HEMA, cupric chloride, 2,2-dipyridyl and deionized water add in the container, obtain 80 ml water solution, the concentration that makes HEMA is 0.3 grams per milliliter, the concentration that makes cupric chloride is 1.2 micromole/milliliters, the concentration that makes 2,2-dipyridyl is 1.2 micromole/milliliters;
(2), (3), (4) and (5) are with embodiment 16.
After testing: film film surface water contact angle 57 degree that present embodiment is made, the flux of film under 25 ℃ is 770L/m
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Embodiment 18
The preparation method of polyvinylidene fluoride modified functional membrane comprises the steps:
(1) disclosing method with embodiment 15 polyvinylidene fluoride microporous film is cleaned, is 15cm with the area that cleans up
2Polyvinylidene fluoride microporous film, the aqueous solution of NIPA, cupric chloride, 4,4 '-two (5-nonyls)-2,2 '-dipyridyl and deionized water add in the container, obtain 100 ml water solution, making the concentration of NIPA is 0.3 grams per milliliter, and the concentration that makes cupric chloride is 1.2 micromole/milliliters, makes 4,4 '-two (5-nonyls)-2, the concentration of 2 '-dipyridyl are 12 micromole/milliliters; (2), (3), (4) and (5) are with embodiment 16.
After testing: film film surface water contact angle 79 degree that present embodiment is made, the flux of film under 25 ℃ is 590L/m
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Embodiment 19
The preparation method of polyvinylidene fluoride modified functional membrane comprises the steps:
(1) disclosing method with embodiment 13 polyvinylidene fluoride microporous film is cleaned, is 15cm with the area that cleans up
2Polyvinylidene fluoride microporous film, the aqueous solution (alkalescence) of sodium acrylate, cupric chloride, 2,2-dipyridyl and deionized water add in the container, obtain 100 ml water solution, the concentration that makes sodium acrylate is 0.3 grams per milliliter, the concentration that makes cupric chloride is 1.2 micromole/milliliters, the concentration that makes 2,2-dipyridyl is 1.2 micromole/milliliters;
(2), (3), (4) and (5) are with embodiment 16.
After testing: film film surface water contact angle 49 degree that present embodiment is made, the flux of film under 25 ℃ is 590L/m
2.h.bar
The preparation method of polyvinylidene fluoride modified functional membrane comprises the steps:
(1) disclosing method with embodiment 13 polyvinylidene fluoride microporous film is cleaned, is 15cm with the area that cleans up
2Polyvinylidene fluoride microporous film, the aqueous solution of 3-hydroxy propyl methacrylate, cupric chloride, 4,4 '-two (5-nonyls)-2,2 '-dipyridyl and deionized water add in the container, obtain 80 ml water solution, making the concentration of 3-hydroxy propyl methacrylate is 0.3 grams per milliliter, and the concentration that makes cupric chloride is 1.2 micromole/milliliters, makes 4,4 '-two (5-nonyls)-2, the concentration of 2 '-dipyridyl are 1.2 micromole/milliliters;
(2), (3), (4) and (5) are with embodiment 16.
After testing: film film surface water contact angle 67 degree that present embodiment is made, the flux of film under 25 ℃ is 670L/m
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Embodiment 21
The preparation method of polyvinylidene fluoride modified functional membrane comprises the steps:
(1) disclosing method with embodiment 13 polyvinylidene fluoride microporous film is cleaned, is 15cm with the area that cleans up
2Polyvinylidene fluoride microporous film, the aqueous solution of 2-hydroxy propyl methacrylate, cupric chloride, 2,2-dipyridyl and deionized water add in the container, obtain 100 ml water solution, the concentration that makes the 2-hydroxy propyl methacrylate is 0.3 grams per milliliter, the concentration that makes cupric chloride is 1.2 micromole/milliliters, the concentration that makes 2,2-dipyridyl is 1.2 micromole/milliliters;
(2), (3), (4) and (5) are with embodiment 16.
After testing: film film surface water contact angle 72 degree that present embodiment is made, the flux of film under 25 ℃ is 635L/m
2.h.bar
The preparation method of polyvinylidene fluoride modified functional membrane comprises the steps:
(1) disclosing method with embodiment 13 polyvinylidene fluoride microporous film is cleaned, is 15cm with the area that cleans up
2Polyvinylidene fluoride microporous film, 2, the aqueous solution of 3-dihydroxypropyl methacrylic ester, cupric chloride, 1,1,4,7,7-five methyl diethylentriamine and deionized water add in the container, obtain 100 ml water solution, the concentration that makes 2,3-dihydroxypropyl methacrylic ester is 0.3 grams per milliliter, the concentration that makes cupric chloride is 1.2 micromole/milliliters, make 1, Isosorbide-5-Nitrae, the concentration of 7,7-five methyl diethylentriamine is 1.2 micromole/milliliters;
(2), (3), (4) and (5) are with embodiment 16.
After testing: film film surface water contact angle 36 degree that present embodiment is made, the flux of film under 25 ℃ is 890L/m
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Embodiment 23
The preparation method of polyvinylidene fluoride modified functional membrane comprises the steps:
(1) disclosing method with embodiment 13 polyvinylidene fluoride microporous film is cleaned, is 12cm with the area that cleans up
2Polyvinylidene fluoride microporous film, N, the aqueous solution of N-DMAA, cupric chloride, 2,2-dipyridyl and deionized water add in the container, obtain 100 ml water solution, making the concentration of N,N-DMAA is 0.3 grams per milliliter, and the concentration that makes cupric chloride is 1.2 micromole/milliliters, the concentration that makes 2,2-dipyridyl is 1.2 micromole/milliliters;
(2), (3), (4) and (5) are with embodiment 16.
After testing: the flux of film film under 25 ℃ that present embodiment is made is 1150L/m
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Embodiment 24
The preparation method of polyvinylidene fluoride modified functional membrane comprises the steps:
(1) disclosing method with embodiment 13 polyvinylidene fluoride microporous film is cleaned, is 12cm with the area that cleans up
2Polyvinylidene fluoride microporous film, the aqueous solution of 2-methoxy ethyl acrylamide, cupric chloride, 1, Isosorbide-5-Nitrae, 7,7-five methyl diethylentriamine and deionized water add in the container, obtain 100 ml water solution, and the concentration that makes 2-methoxy ethyl acrylamide is 0.3 grams per milliliter, the concentration that makes cupric chloride is 1.2 micromole/milliliters, make 1, Isosorbide-5-Nitrae, the concentration of 7,7-five methyl diethylentriamine is 1.2 micromole/milliliters;
(2), (3), (4) and (5) are with embodiment 16.
After testing: the flux of film film under 25 ℃ that present embodiment is made is 833L/m
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Claims (8)
1. polyvinylidene fluoride modified functional membrane is characterized in that being grafted with functional polymer by the method for water atom transfer radical polymerization on the polyvinylidene fluoride film surface, and described method comprises the steps:
(1) be 9-25cm with the area that cleans up
2The aqueous solution, cupric chloride, atom transfer radical polymerization ligand and the deionized water of polyvinylidene fluoride microporous film, atom transfer free crowd monomer add in the container, obtain 20-200 ml water solution, making the atom transferred free radical monomer concentration is the 0.1-0.5 grams per milliliter, the concentration that makes cupric chloride is 0.44-2.2 micromole/milliliter, and the concentration that makes atom transfer radical polymerization ligand is 0.44-2.2 micromole/milliliter;
(2) inflated with nitrogen 5-10min gets rid of the oxygen in the container;
(3) adding 0.2-8 milliliter volumetric molar concentration is the vitamins C aqueous solution of 1-22 mmole/milliliter, continues inflated with nitrogen 5-10min;
(4) with container sealing, at 30-60 ℃ of reaction 0.5-7h;
(5) film is taken out, 40 ℃ of water-baths, put into dehydrated alcohol stirring and washing 2-24h, then use deionized water stirring and washing 2-24h, taking-up is dried, and namely makes polyvinylidene fluoride modified functional membrane.
2. polyvinylidene fluoride modified functional membrane according to claim 1 is characterized in that described functional polymer is polymethacrylate or polyacrylamide water-soluble polymers.
3. polyvinylidene fluoride modified functional membrane according to claim 2, it is characterized in that described polymethacrylate is poly--2-(dimethylamino) ethyl-methyl acrylate, poly--the 2-(diisopropylaminoethyl) ethyl-methyl acrylate, poly--the 2-(diethylamino) ethyl-methyl acrylate, poly-(polyoxyethylene glycol) methacrylic ester, poly--HEMA, poly--the 3-hydroxy propyl methacrylate, poly--2-hydroxy propyl methacrylate or poly--2,3-dihydroxypropyl methacrylic ester.
4. polyvinylidene fluoride modified functional membrane according to claim 2, it is characterized in that described polyacrylamide water-soluble polymers is poly--NIPA, sodium polyacrylate, poly--N,N-DMAA or poly--2-methoxy ethyl acrylamide.
5. the preparation method of polyvinylidene fluoride modified functional membrane is characterized in that comprising the steps:
(1) be 9-25cm with the area that cleans up
2The aqueous solution, cupric chloride, atom transfer radical polymerization ligand and the deionized water of polyvinylidene fluoride microporous film, atom transfer free crowd monomer add in the container, obtain 20-200 ml water solution, making the atom transferred free radical monomer concentration is the 0.1-0.5 grams per milliliter, the concentration that makes cupric chloride is 0.44-2.2 micromole/milliliter, and the concentration that makes atom transfer radical polymerization ligand is 0.44-2.2 micromole/milliliter;
(2) inflated with nitrogen 5-10min gets rid of the oxygen in the container;
(3) adding 0.2-8 milliliter volumetric molar concentration is the vitamins C aqueous solution of 1-22 mmole/milliliter, continues inflated with nitrogen 5-10min;
(4) with container sealing, at 30-60 ℃ of reaction 0.5-7h;
(5) film is taken out, 40 ℃ of water-baths, put into dehydrated alcohol stirring and washing 2-24h, then use deionized water stirring and washing 2-24h, taking-up is dried, and namely makes polyvinylidene fluoride modified functional membrane.
6. the preparation method of polyvinylidene fluoride modified functional membrane according to claim 5, it is characterized in that described atom transfer free crowd monomer is the 2-(dimethylamino) the ethyl-methyl acrylate, the 2-(diisopropylaminoethyl) ethyl-methyl acrylate, the 2-(diethylamino) ethyl-methyl acrylate, (polyoxyethylene glycol) methacrylic ester, HEMA, NIPA, sodium acrylate, the 3-hydroxy propyl methacrylate, the 2-hydroxy propyl methacrylate, 2,3-dihydroxypropyl methacrylic ester, N, N methacrylamide or 2-methoxy ethyl acrylamide.
7. the preparation method of polyvinylidene fluoride modified functional membrane according to claim 5, it is characterized in that described atom transfer free crowd part is 2,2-dipyridyl, 4,4 '-two (5-nonyls)-2,2 '-dipyridyl, 1,1,4,7,7-five methyl diethylentriamine or three-(N, N '-dimethylaminoethyl) amine.
8. the preparation method of polyvinylidene fluoride modified functional membrane according to claim 5, the method that it is characterized in that the described cleaning of described step (1) is: in 10-80 ℃ of water-bath, being placed on polyvinylidene fluoride microporous film in volumetric concentration is in the aqueous ethanolic solution of 10-90% rinsing 3-24 hour, the aqueous ethanolic solution that to change volumetric concentration in every 1-6 hour be 10-90%.
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| JP6377633B2 (en) * | 2012-12-21 | 2018-08-22 | ソルベイ スペシャルティ ポリマーズ イタリー エス．ピー．エー． | Hydrophilic fluoropolymer |
| JP6065689B2 (en) * | 2013-03-25 | 2017-01-25 | 日本ゼオン株式会社 | Method for producing secondary battery electrode binder, method for producing secondary battery electrode, and method for producing secondary battery |
| CN104548961B (en) * | 2014-12-24 | 2016-10-05 | 福州大学 | A kind of preparation method of hydrophilic anti-pollution polyvinylidene fluoride film |
| US9849428B2 (en) * | 2015-04-30 | 2017-12-26 | Pall Corporation | Hydrophilically modified fluorinated membrane (VI) |
| CN104877278B (en) * | 2015-06-29 | 2017-08-15 | 北京化工大学 | A kind of Vinalac 5920/polyvinylidene fluoride compound dielectric film and preparation method thereof |
| CN105056776B (en) * | 2015-08-27 | 2018-01-02 | 中国科学院宁波材料技术与工程研究所 | The method that electrochemistry triggers surface atom transition free radical aggregation modified hollow fibre membrane |
| CN105642127B (en) * | 2016-01-13 | 2018-01-05 | 厦门理工学院 | A kind of preparation method of anthraquinone functionalization polyvinylidene fluoride (PVDF) ultrafiltration membrane |
| CN106496465B (en) * | 2016-10-22 | 2018-09-04 | 宁波大学 | A kind of environment-friendly preparation method thereof of hydrophiling PVDF membrane material |
| CN106890577B (en) * | 2017-03-14 | 2019-09-20 | 天津工业大学 | A kind of preparation method of antipollution anticoagulation pvdf membrane |
| CN108579447B (en) * | 2018-04-30 | 2020-07-21 | 天津工业大学 | Super-hydrophilic electrostatic spinning fiber membrane for oil-water separation and preparation method thereof |
| CN110066415B (en) * | 2019-04-23 | 2021-07-20 | 吕剑阳 | Preparation method of porous membrane with functionalized surface |
| CN110527430A (en) * | 2019-08-26 | 2019-12-03 | 佛山科学技术学院 | A kind of modified polyvinylidene fluoride fluorocarbon coating and preparation method thereof |
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| CN100467506C (en) * | 2005-09-30 | 2009-03-11 | 天津工业大学 | Method for preparing temperature-sensitive polyvinylidene fluoride intelligent membrane material and its product |
| CN101792510B (en) * | 2010-01-18 | 2012-04-04 | 苏州大学 | Method for carrying out controllable hydrophilic modification on polyvinylidene fluoride (PVDF) |
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