CN101711950B - Flat separation membrane - Google Patents
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- CN101711950B CN101711950B CN2009102286638A CN200910228663A CN101711950B CN 101711950 B CN101711950 B CN 101711950B CN 2009102286638 A CN2009102286638 A CN 2009102286638A CN 200910228663 A CN200910228663 A CN 200910228663A CN 101711950 B CN101711950 B CN 101711950B
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Abstract
The invention discloses a flat separation membrane, belongs to the field of membrane technology and particularly relates to intelligent polymeric flat separation membrane technology. The invention adopts a technical scheme comprising: 1, carrying out alkali treatment to PVDF powder; 2, preparing temperature sensitive copolymer, copolymerizing the PVDF powder after alkali treatment and temperature sensitive monomer NIPAAm, and synthesizing PVDF-g-PNIPAAm copolymer; and 3, preparing the temperature response type PVDF flat separation membrane by a phase inversion method. A preparation method of membrane forming polymer has the characteristics of simple process, low cost, having no use for special equipment, easy industrial implementation and the like. An intelligent membrane product is a novel temperature sensitive type PVDF intelligent membrane capable of sensitively responding to environment temperature change.
Description
Technical field
The invention belongs to the membrane technology field, particularly a kind of intelligent polymer membrane technology.
Background technology
Since the fifties in last century, development along with polymer material science and engineering, having occurred is the new membrane separation technique of representative with the polymeric membrane for separation, and it has separative efficiency height, low, the simple operation and other advantages of energy consumption, has become to separate one of main means of purifying.But, be widely used at present producing polymeric membrane for separation with scientific research, fenestra size or permeability of the membrane can not the response environment variation of temperature, when separating the multiple constituents mixt of different molecular weight, need to adopt the different several films in aperture in batches, classification separated, the separation process complexity, the production cost height, thus limited its application in some fields.
Therefore, many in recent years diffusion barrier researchers are devoted to develop the temperature response type macromolecule diffusion barrier of energy response environment variations in temperature.So-called temperature response type macromolecule diffusion barrier, be exactly that fenestra size or permeability of the membrane can be according to the variations of environment temperature and a kind of intelligent film that changes automatically, such film can be realized by regulating variation of ambient temperature, only with the target of a kind of film with regard to gradable filtration different molecular quantity of material.The research and development of temperature response type macromolecule diffusion barrier have further enlarged the range of application of diffusion barrier and membrane separation technique, have become the emphasis of domestic and international research.
The core of membrane separation technique is a membrane material.In the membrane material of current polymeric membrane for separation research and application, Kynoar (PVDF) is owing to have performances such as good anti-corrosion, hydrophobicity, soil resistance, in numerous macromolecule member materials, become the outstanding person, and formed a series of comparatively ripe PVDF diffusion barrier goods.Therefore, carry out the temperature-responsive study on the modification with PVDF as the preferred material of temperature response type diffusion barrier and exploitation has important practical significance.
PVDF is with-CH
2-CF
2-be the chain crystalline polymer of construction unit, carbochain indention in its molecule is arranged, after hydrogen atom is replaced by the bigger fluorine atom of electronegativity, repel mutually with adjacent fluorine atom, thereby make fluorine atom not in same plane, and make spiral along carbochain and distribute, so being surrounded by the fluorine atom of a series of stable in properties all around of carbochain, this almost gapless space barrier makes any atom or group all can not enter its inside configuration and destroys carbochain.This just special structure makes pvdf membrane have the advantage of many uniquenesses, its piezoelectric modulus is big, frequency response is wide, mechanical strength is good, light weight, softness, shock-resistant, acoustic impedance is easily mated, easily be processed into large tracts of land, the pollution that is not subjected to water and chemicals, low price etc.
At present, from existing bibliographical information, the preparation method of temperature-responsive pvdf membrane mainly contains physical modification and chemical modification two big classes.
(1) physical modification method.Mainly comprise physical blending and face coat two classes.Physical blending is that the performance of each component of aggregative equilibrium is learnt from other's strong points to offset one's weaknesses with PVDF film forming polymer and other temperature sensitive polymer blend, obtains the comparatively desirable film forming polymer material of temperature response performance, gives PVDF unexistent temperature response performance.But the temperature sensitive property of the film that the physical blending method is prepared is limited by the character of blend temperature sensitive polymer and consumption, and the adding of blend affects to film forming procedure.
The face coat method of modifying then generally is meant to be coated with on the PVDF basement membrane and is covered with the temperature sensitive performance that temperature sensitive property material improves film.But face coat modification method exists coat easily to come off from the surface, and the modified effect persistence is relatively poor, and applies the easy fenestra that stops up in the modifying process, reduces defectives such as membrane flux.
(2) chemical modification method.Be a kind of simple and efficient ways, promptly, the PVDF film forming polymer carried out modifications such as graft copolymerization, make it have temperature-responsive by polymerisation.Usually, the chemical modification of pvdf membrane comprises membrane surface grafting and two kinds of methods of film forming matter modification by copolymerization.The membrane surface graft modification is by some means (as corona discharge or glow discharge, high-energy ray, ultraviolet light etc.), form the activated centre on the pvdf membrane surface, cause temperature sensitive monomer from this activated centre again and carry out glycerol polymerization on the film surface, on basement membrane, form the temperature sensitive polymer layer, thereby give the film temperature response.The characteristics of membrane surface graft modification are that modification occurs in the film superficial layer, and are little to the property effect of material body, but the size of temperature-responsive and stability are subjected to the influence of grafting degree bigger.
The film forming matter modification by copolymerization is to introduce temperature sensitive property group by copolyreaction on PVDF film forming matter strand, prepares temperature sensitive property copolymer, by certain film build method, obtains temperature-responsive PVDF diffusion barrier by this copolymer then.The advantage of this kind method is that the temperature-responsive of made film is stable, but the copolymer filming performance is affected.
As can be seen, all there is defective in various degree in above-mentioned several method.From present research, adopt the research of film forming matter modification by copolymerization method preparation temperature responsive polymer film less.And this kind method, if adopt appropriate copolymerization means, select for use suitable temperature sensitive monomer to carry out copolymerization, then can synthesize the filming performance influence little, and temperature-responsive is outstanding, the temperature-responsive PVDF copolymer of temperature sensitive excellent in stability, thereby is expected to prepare the temperature-responsive PVDF flat sheet membrane of function admirable.
In recent years, with regard to temperature sensing material was selected, poly-N-isopropyl acrylamide (PNIPAAm) became the temperature sensitive polymer of the most normal employing.PNIPAAm has lower critical solution temperature (LCST), and its LCST and has response speed faster between 30 ℃～34 ℃.Therefore,, utilize PNIPAAm to change the characteristic that changes,, can realize reversible distortion with its diffusion barrier made from external environment in temperature-responsive PVDF diffusion barrier research field.If keep the big or small constant of film, the contractility in the film can make fenestra swell or dwindle, thereby changes the size and the permeability of the membrane of fenestra.
At present, adopt N-N-isopropylacrylamide (NIPAAm) monomer more, but be the method that adopts the membrane surface modification mostly the research that PVDF carries out the modification of temperature sensitive property.For example, using plasma grafting filling perforation polymerizations such as Chu Liangyin are grafted to PNIPAAm in the fenestra of porous flat plate film, and its thermal switch performance carried out studying [huge dawn is clean, Chu Liangyin etc., biomedical engineering magazine, 2004,21 (5): 791].Ruben etc. adopt Co
60The method of-γ source irradiation is grafted to the PVDF surface with PNIPAAm, the hydrophily of pvdf membrane is improved and give film temperature response [M.Ruben, S.Eduardo, T.Daniel.Nuclear Instruments andMethods in Physics Research B, 2000,170:419].
But the research of employing film forming matter modification by copolymerization method seldom.Research groups such as Lei will be dissolved in the corresponding solvent through the PVDF powder and the polymerization single polymerization monomer of ozone treatment, carry out polymerization by the heat initiation, obtain intelligent PVDF material, prepared the responsive and temperature sensitive PVDF intelligence of pH film [L.Ying through the inversion of phases method again, E.T.Kand, K.G.Neoh.J Membr Sci., 2002,208:361; L.Ying, E.T.Kang, K.G.Neoh.Langmuir, 2002,18:6416; L.Ying, P Wang, E T Kang.Macromolecules, 2002,35:673; L.Ying, E.T.Kang, K.G.Neoh.J Membr Sci., 2004,243:253; L.Ying, En T Kang, KoonG Neoh.Macromol.Mater.Eng.2003,288:11].The application patent inventor once adopted the method for ATRP, was grafted monomers with NIPAAm, had synthesized temperature sensitive type PVDF intelligent membrane material PVDF-g-PNIPAAm copolymer [ZL200510015298.4].But these researchs are comparatively complicated aspect PVDF powder-processed or polymerization technique, for further application and development brings certain difficulty.
The application patent inventor once adopted the method for alkali treatment that graft modification is carried out on PVDF hollow-fibre membrane surface, prepared the PVDF doughnut intelligence film [ZL200410019992.9 of temperature, pH and temperature and pH Lazer sense; ZL200410019993.3].Discover that it is respond well that PVDF is carried out alkali treatment method, but this method is carried out grafting with the PVDF hollow-fibre membrane as basement membrane, has the defective of membrane surface graft-modification method.
Summary of the invention:
The technical problem that quasi-solution of the present invention is determined provides a kind of flat-plate separation film of temperature response type.
Product flat-plate separation film of the present invention, flat-plate separation film has temperature response characteristics at 27 ℃～32 ℃, and flat-plate separation film is prepared by following method: the alkali treatment of 1.PVDF powder; 2. the preparation of temperature sensitive copolymer: PVDF powder after the alkali treatment and temperature sensitive monomer NIPAAm are carried out copolymerization, synthetic PVDF-g-PNIPAAm copolymer; 3. the flat-plate separation film of inversion of phases method preparation temperature response type.
The alkali treatment of the powder of PVDF described in the present invention is as follows: additional proportion is the PVDF powder of 100g/L-180g/L in aqueous slkali.In above-mentioned aqueous slkali, add 14ml/L～45ml/L absolute ethyl alcohol and stirring subsequently, make PVDF in solution, fully disperse.Above-mentioned mixed solution reaction system is placed 50～80 ℃ of waters bath with thermostatic control, reacted 10～20 minutes.The suction filtration products therefrom, it is dry that washing back gained PVDF pulverulent solids product is put into 60 ℃ of baking ovens.
In suction filtration product process, constantly wash, to remove fluoride and the ethanol in the product with distilled water.
Described aqueous slkali is meant a kind of in potassium hydroxide, NaOH or the lithium hydroxide solution, and described alkaline concentration is 2-3mol/L.
The preparation method of temperature sensitive copolymer described in the present invention is as follows: the PVDF powder of getting after the alkali treatment adds in the there-necked flask, and logical nitrogen adds N, dinethylformamide (DMF), stirring and dissolving under 50～80 ℃ of condition of water bath heating again.Under the situation of logical nitrogen, add refining N-N-isopropylacrylamide (NIPAAm), initator azodiisobutyronitrile (AIBN) in there-necked flask, fully after the dissolving, logical again nitrogen 10～20 minutes continues stirring reaction and can obtain temperature sensitive type PVDF-g-PNIPAAm film forming copolymer in 8～12 hours.Reactant liquor is poured into from there-necked flask in the beaker, and the cooling back adds methanol extraction, and suction filtration washes repeatedly with distilled water, to remove unreacted little molecule, drains then, and it is stand-by that gained copolymer p VDF-g-PNIPAAm product is put into 60 ℃ of oven dryings.
PVDF powder after the described alkali treatment and the mass ratio of NIPAAm are 1: 0.5-1.25, described N, the addition of dinethylformamide (DMF) are 6-12 times of PVDF powder quality.The addition of described initator azodiisobutyronitrile (AIBN) is the 1%-2.5% of PVDF powder quality.
The 10-25 that described methyl alcohol addition is the PVDF powder quality doubly.
The plate isolation film method of the method for inversion of phases described in the present invention preparation temperature response type is as follows:
Copolymer p VDF-g-PNIPAAm powder and pore-foaming agent polyethylene glycol (PEG) adding are filled in the container of DMF, and heating under 30～60 ℃ of conditions, stirring are until dissolving fully.Vacuum defoamation obtained casting solution in 20～40 minutes.Casting solution is inclined to glass plate glass bar striking film forming, immerse solidification forming in 25 ℃ the coagulating bath Water Tank with Temp.-controlled, treat film from glass plate be shaped come off after, placed again in the distilled water 18～36 hours, distilled water is cleaned the flat-plate separation film that promptly obtains temperature response type.
Described coagulating bath is that absolute ethyl alcohol quality percentage composition accounts for 10～40% distilled water solution.
Described pore-foaming agent polyethylene glycol addition is the 20%-75% of copolymer p VDF-g-PNIPAAm quality.
Described N, the addition of dinethylformamide (DMF) is 4-7 times for copolymer p VDF-g-PNIPAAm quality.
Beneficial effect:
Product of the present invention has characteristics such as technology is simple, cost is low, do not need special installation, industrializing implementation is easy, and the copolymer film forming is good, and film forming procedure technology is simple, cost is low, industrializing implementation is easy.This intelligent film product is can be to the flat-plate separation film of the responsive a kind of temperature response type that responds of variation of ambient temperature.
Compared with prior art, product of the present invention has that method is simple, cost is low, does not need special installation, industrializing implementation is easy; The temperature sensitive copolymer filming performance of the PVDF-g-PNIPAAm that the present invention synthesizes is good, and modification is little to the influence of PVDF filming performance; The present invention preparation be temperature response type PVDF flat-plate separation film, this film occurs sharply reducing at 27 ℃～32 ℃ pure water fluxs, and the rejection of bovine serum albumin is sharply raise, and reaches more than 99%, shows tangible temperature response characteristics.
The present invention preparation what be that flat-plate separation film adopts is film forming matter modification by copolymerization method, temperature-responsive is outstanding, temperature sensitive excellent in stability.Also prepared the temperature sensitive copolymer of PVDF-g-PNIPAAm in the application patent inventor's patent [ZL200510015298.4] formerly, but what adopt is the method for ATRP, polymerization process control is complicated, technology is loaded down with trivial details, cost is high, and the present invention adopts alkali treatment method, and is much then simple.[ZL200410019992.9 in the application patent inventor's patent formerly; ZL200410019993.3] also relate to alkali treatment method, but mainly be that basement membrane is carried out alkali treatment.The difference of two kinds of methods is: 1. prepare the product difference, what the present invention prepared is the temperature response type flat sheet membrane, rather than tunica fibrosa; 2. preparation method's difference, the present invention carries out alkali treatment to the PVDF powder, and then carries out graft copolymerization, prepares flat sheet membrane again, and the size and the stability that have overcome the existing temperature-responsive of tunica fibrosa graft modification are subjected to the grafting degree to influence bigger defective; 3. film temperature Response Mechanism difference, basement membrane grafting method mainly be by the expansion of temperature sensitive grafting layer in the fenestra with shrink the size that changes fenestra, and the present invention be by the expansion of the whole temperature influence of membrane material with shrink the size that changes fenestra; 4. product quality difference, the membrane surface graft modification, the size of temperature-responsive and stability are subjected to the influence of grafting degree bigger, and there is defective such as easily come off in the grafting layer, and the present invention is owing to be the direct film forming of copolymer, constant product quality.
The specific embodiment
The following examples can make those skilled in the art more fully understand the present invention, but do not limit the present invention in any way.
Embodiment 1: the preparation of flat sheet membrane product
(1) alkali treatment of PVDF powder: the preparation mol ratio is the sodium hydroxide solution of 2mol/L, this alkali lye of 350ml is poured in the beaker, added in this aqueous slkali of PVDF powder of 40g white, in reaction system, add the 5ml absolute ethyl alcohol subsequently again, stir, make PVDF in solution, fully disperse.Reaction system is placed 50 ℃ of waters bath with thermostatic control, reacted 10 minutes.With the products therefrom suction filtration, and constantly wash,, will wash back gained pulverulent solids product P VDF at last and put into 60 ℃ of baking oven dried for standby to remove NaF and the ethanol in the product with distilled water.
(2) preparation of temperature sensitive copolymer: the PVDF powder of getting after the 10g alkali treatment adds in the there-necked flask, and logical nitrogen adds the 120ml solvent DMF, stirring and dissolving under heating condition under 50 ℃ of water-baths again.Get the refining NIPAAm of 10g, 0.2g initiator A IBN joins in the there-necked flask under the situation of logical nitrogen, and after the dissolving, logical again nitrogen 10 minutes continues stirring reaction and can obtain temperature sensitive type PVDF-g-PNIPAAm copolymer in 8 hours fully.Reactant liquor is poured into from there-necked flask in the clean beaker, and the cooling back adds about 250ml methanol extraction, and suction filtration washes repeatedly with distilled water, to remove unreacted little molecule, drains then, and it is stand-by to put into 60 ℃ of oven dryings.
(3) preparation temperature response type flat sheet membrane: adopt phase inversion, with 3g copolymer p VDF-g-PNIPAAm powder, 1g pore-foaming agent PEG adding fills in the beaker of 21g solvent DMF, and heating under 30 ℃ of conditions, stirring obtained casting solution until dissolving fully in 20 minutes with this solution for vacuum deaeration.
The distilled water 800g of configuration absolute ethyl alcohol quality percentage composition 10% places 25 ℃ Water Tank with Temp.-controlled as coagulating bath.Casting solution is inclined on drying, the smooth glass plate, with the even striking film forming of glass bar, immerse solidification forming in the coagulating bath at once, treat film from glass plate be shaped come off after, placed again in the distilled water 18 hours, and cleaned with distilled water then and promptly obtain the temperature response type flat sheet membrane.
This flat-plate separation film occurs sharply reducing at 27 ℃～29 ℃ pure water fluxs, and the rejection of bovine serum albumin is sharply raise, and reaches 99%, shows tangible temperature response characteristics.
Embodiment 2: the preparation of flat sheet membrane product
(1) alkali treatment of PVDF powder: the preparation mol ratio is the potassium hydroxide solution of 2mol/L, this alkali lye of 350ml is poured in the beaker, added in this aqueous slkali of PVDF powder of 60g white, in reaction system, add the 15ml absolute ethyl alcohol subsequently again, stir, make PVDF in solution, fully disperse.Reaction system is placed 80 ℃ of waters bath with thermostatic control, reacted 20 minutes.With the products therefrom suction filtration, and constantly wash,, will wash back gained pulverulent solids product at last and put into 60 ℃ of baking oven dried for standby to remove KF and the ethanol in the product with distilled water.
(2) preparation of temperature sensitive copolymer: the PVDF powder of getting after the 20g alkali treatment adds in the there-necked flask, and logical nitrogen adds the 120ml solvent DMF, stirring and dissolving under heating condition under 80 ℃ of water-baths again.Get the refining NIPAAm of 20g, 0.5g initiator A IBN joins in the there-necked flask under the situation of logical nitrogen, and after the dissolving, logical again nitrogen 20 minutes continues stirring reaction and can obtain temperature sensitive type PVDF-g-PNIPAAm copolymer in 12 hours fully.Reactant liquor is poured into from there-necked flask in the clean beaker, and the cooling back adds about 250ml methanol extraction, and suction filtration washes repeatedly with distilled water, to remove unreacted little molecule, drains then, and it is stand-by to put into 60 ℃ of oven dryings.
(3) preparation temperature response type flat sheet membrane: adopt phase inversion, with 5g copolymer p VDF-g-PNIPAAm powder, 3g pore-foaming agent PEG adding fills in the beaker of 21g solvent DMF, and heating under 60 ℃ of conditions, stirring obtained casting solution until dissolving fully in 40 minutes with this solution for vacuum deaeration.
The distilled water 800g of configuration absolute ethyl alcohol quality percentage composition 40% places 25 ℃ Water Tank with Temp.-controlled as coagulating bath.Casting solution is inclined on drying, the smooth glass plate, with the even striking film forming of glass bar, immerse solidification forming in the coagulating bath at once, treat film from glass plate be shaped come off after, placed again in the distilled water 36 hours, and cleaned with distilled water then and promptly obtain temperature response type PVDF flat sheet membrane.
This flat-plate separation film occurs sharply reducing at 28 ℃～30 ℃ pure water fluxs, and the rejection of bovine serum albumin is sharply raise, and reaches 99.1%, shows tangible temperature response characteristics.
Embodiment 3:
(1) alkali treatment of PVDF powder: the preparation mol ratio is the sodium hydroxide solution of 2mol/L, this alkali lye of 350ml is poured in the beaker, and the PVDF powder that adds 50g white adds the 10ml absolute ethyl alcohol subsequently again in reaction system in this aqueous slkali, stir, make PVDF in solution, fully disperse.Reaction system is placed 60 ℃ of waters bath with thermostatic control, reacted 20 minutes.With the products therefrom suction filtration, and constantly wash,, will wash back gained pulverulent solids product at last and put into 60 ℃ of baking oven dried for standby to remove NaF and the ethanol in the product with distilled water.
(2) preparation of temperature sensitive copolymer: the PVDF powder of getting after the 15g alkali treatment adds in the there-necked flask, and logical nitrogen adds the 120ml solvent DMF, stirring and dissolving under heating condition under 60 ℃ of water-baths again.Get the refining NIPAAm of 15g, 0.2g initiator A IBN joins in the there-necked flask under the situation of logical nitrogen, and after the dissolving, logical again nitrogen 20 minutes continues stirring reaction and can obtain temperature sensitive type PVDF-g-PNIPAAm copolymer in 12 hours fully.Reactant liquor is poured into from there-necked flask in the clean beaker, and the cooling back adds about 250ml methanol extraction, and suction filtration washes repeatedly with distilled water, to remove unreacted little molecule, drains then, and it is stand-by to put into 60 ℃ of oven dryings.
(3) preparation temperature response type flat sheet membrane: adopt phase inversion, with 4g copolymer p VDF-g-PNIPAAm powder, 3g pore-foaming agent PEG adding fills in the beaker of 21g solvent DMF, and heating under 60 ℃ of conditions, stirring obtained casting solution until dissolving fully in 40 minutes with this solution for vacuum deaeration.
The distilled water 800g of configuration absolute ethyl alcohol quality percentage composition 30% places 25 ℃ Water Tank with Temp.-controlled as coagulating bath.Casting solution is inclined on drying, the smooth glass plate, with the even striking film forming of glass bar, immerse solidification forming in the coagulating bath at once, treat film from glass plate be shaped come off after, placed again in the distilled water 36 hours, and cleaned with distilled water then and promptly obtain temperature response type PVDF flat sheet membrane.
This flat-plate separation film occurs sharply reducing at 29 ℃～30 ℃ pure water fluxs, and the rejection of bovine serum albumin is sharply raise, and reaches 99.3%, shows tangible temperature response characteristics.
Embodiment 4: the preparation of flat sheet membrane product
(1) alkali treatment of PVDF powder: the preparation mol ratio is the sodium hydroxide solution of 3mol/L, this alkali lye of 350ml is poured in the beaker, added in this aqueous slkali of PVDF powder of 40g white, in reaction system, add the 5ml absolute ethyl alcohol subsequently again, stir, make PVDF in solution, fully disperse.Reaction system is placed 50 ℃ of waters bath with thermostatic control, reacted 20 minutes.With the products therefrom suction filtration, and constantly wash,, will wash back gained pulverulent solids product at last and put into 60 ℃ of baking oven dried for standby to remove NaF and the ethanol in the product with distilled water.
(2) preparation of temperature sensitive copolymer: the PVDF powder of getting after the 20g alkali treatment adds in the there-necked flask, and logical nitrogen adds the 120ml solvent DMF, stirring and dissolving under heating condition under 60 ℃ of water-baths again.Get the refining NIPAAm of 10g, 0.2g initiator A IBN joins in the there-necked flask under the situation of logical nitrogen, and after the dissolving, logical again nitrogen 20 minutes continues stirring reaction and can obtain temperature sensitive type PVDF-g-PNIPAAm copolymer in 12 hours fully.Reactant liquor is poured into from there-necked flask in the clean beaker, and the cooling back adds about 250ml methanol extraction, and suction filtration washes repeatedly with distilled water, to remove unreacted little molecule, drains then, and it is stand-by to put into 60 ℃ of oven dryings.
(3) preparation temperature response type flat sheet membrane: adopt phase inversion, with 5g copolymer p VDF-g-PNIPAAm powder, 3g pore-foaming agent PEG adding fills in the beaker of 21g solvent DMF, and heating under 50 ℃ of conditions, stirring obtained casting solution until dissolving fully in 20～40 minutes with this solution for vacuum deaeration.
The distilled water 800g of configuration absolute ethyl alcohol quality percentage composition 10% places 25 ℃ Water Tank with Temp.-controlled as coagulating bath.Casting solution is inclined on drying, the smooth glass plate, with the even striking film forming of glass bar, immerse solidification forming in the coagulating bath at once, treat film from glass plate be shaped come off after, placed again in the distilled water 24 hours, and cleaned with distilled water then and promptly obtain temperature response type PVDF flat sheet membrane.
This flat-plate separation film occurs sharply reducing at 30 ℃～32 ℃ pure water fluxs, and the rejection of bovine serum albumin is sharply raise, and reaches 99.2%, shows tangible temperature response characteristics.
Embodiment 5:
(1) alkali treatment of PVDF powder: the preparation mol ratio is the sodium hydroxide solution of 2.5mol/L, this alkali lye of 350ml is poured in the beaker, added in this aqueous slkali of PVDF powder of 40g white, in reaction system, add the 12ml absolute ethyl alcohol subsequently again, stir, make PVDF in solution, fully disperse.Reaction system is placed 60 ℃ of waters bath with thermostatic control, reacted 20 minutes.With the products therefrom suction filtration, and constantly wash,, will wash back gained pulverulent solids product at last and put into 60 ℃ of baking oven dried for standby to remove NaF and the ethanol in the product with distilled water.
(2) preparation of temperature sensitive copolymer: the PVDF powder of getting after the 12g alkali treatment adds in the there-necked flask, and logical nitrogen adds the 120ml solvent DMF, stirring and dissolving under heating condition under 60 ℃ of water-baths again.Get the refining NIPAAm of 10～20g, 0.3g initiator A IBN joins in the there-necked flask under the situation of logical nitrogen, and after the dissolving, logical again nitrogen 20 minutes continues stirring reaction and can obtain temperature sensitive type PVDF-g-PNIPAAm copolymer in 12 hours fully.Reactant liquor is poured into from there-necked flask in the clean beaker, and the cooling back adds about 250ml methanol extraction, and suction filtration washes repeatedly with distilled water, to remove unreacted little molecule, drains then, and it is stand-by to put into 60 ℃ of oven dryings.
(3) preparation temperature response type flat sheet membrane: adopt phase inversion, with 4g copolymer p VDF-g-PNIPAAm powder, 2g pore-foaming agent PEG adding fills in the beaker of 21g solvent DMF, and heating under 60 ℃ of conditions, stirring obtained casting solution until dissolving fully in 30 minutes with this solution for vacuum deaeration.
The distilled water 800g of configuration absolute ethyl alcohol quality percentage composition 10% places 25 ℃ Water Tank with Temp.-controlled as coagulating bath.Casting solution is inclined on drying, the smooth glass plate, with the even striking film forming of glass bar, immerse solidification forming in the coagulating bath at once, treat film from glass plate be shaped come off after, placed again in the distilled water 24 hours, and cleaned with distilled water then and promptly obtain temperature response type PVDF flat sheet membrane.
This flat-plate separation film occurs sharply reducing at 29 ℃～31 ℃ pure water fluxs, and the rejection of bovine serum albumin is sharply raise, and reaches 99.0%, shows tangible temperature response characteristics.
Embodiment 6:
(1) preliminary treatment of PVDF powder: the preparation mol ratio is the potassium hydroxide solution of 3mol/L, this alkali lye of 350ml is poured in the beaker, added in this aqueous slkali of PVDF powder of 40g white, in reaction system, add the 12ml absolute ethyl alcohol subsequently again, stir, make PVDF in solution, fully disperse.Reaction system is placed 60 ℃ of waters bath with thermostatic control, reacted 20 minutes.With the products therefrom suction filtration, and constantly wash,, will wash back gained pulverulent solids product at last and put into 60 ℃ of baking oven dried for standby to remove KF and the ethanol in the product with distilled water.
(2) preparation of temperature sensitive copolymer: the PVDF powder of getting after the 15g alkali treatment adds in the there-necked flask, and logical nitrogen adds the 120ml solvent DMF, stirring and dissolving under heating condition under 60 ℃ of water-baths again.Get the refining NIPAAm of 12g, 0.2g initiator A IBN joins in the there-necked flask under the situation of logical nitrogen, and after the dissolving, logical again nitrogen 20 minutes continues stirring reaction and can obtain temperature sensitive type PVDF-g-PNIPAAm copolymer in 12 hours fully.Reactant liquor is poured into from there-necked flask in the clean beaker, and the cooling back adds about 250ml methanol extraction, and suction filtration washes repeatedly with distilled water, to remove unreacted little molecule, drains then, and it is stand-by to put into 60 ℃ of oven dryings.
(3) preparation temperature response type flat sheet membrane: adopt phase inversion, with 4g copolymer p VDF-g-PNIPAAm powder, 2g pore-foaming agent PEG adding fills in the beaker of 21g solvent DMF, and heating under 60 ℃ of conditions, stirring obtained casting solution until dissolving fully in 40 minutes with this solution for vacuum deaeration.
The distilled water 800g of configuration absolute ethyl alcohol quality percentage composition 10% places 25 ℃ Water Tank with Temp.-controlled as coagulating bath.Casting solution is inclined on drying, the smooth glass plate, with the even striking film forming of glass bar, immerse at once in the coagulating bath and to coagulate with being shaped, treat film from glass plate be shaped come off after, placed again in the distilled water 20 hours, and cleaned with distilled water then and promptly obtain temperature response type PVDF flat sheet membrane.
Embodiment 7:
(1) preliminary treatment of PVDF powder: the preparation mol ratio is the potassium hydroxide solution of 2.5mol/L, this alkali lye of 350ml is poured in the beaker, added in this aqueous slkali of PVDF powder of 45g white, in reaction system, add the 12ml absolute ethyl alcohol subsequently again, stir, make PVDF in solution, fully disperse.Reaction system is placed 50～80 ℃ of waters bath with thermostatic control, reacted 10～20 minutes.With the products therefrom suction filtration, and constantly wash,, will wash back gained pulverulent solids product at last and put into 60 ℃ of baking oven dried for standby to remove KF and the ethanol in the product with distilled water.
(2) preparation of temperature sensitive copolymer: the PVDF powder of getting after the 16g alkali treatment adds in the there-necked flask, and logical nitrogen adds the 120ml solvent DMF, stirring and dissolving under heating condition under 70 ℃ of water-baths again.Get the refining NIPAAm of 20g, 0.4g initiator A IBN joins in the there-necked flask under the situation of logical nitrogen, and after the dissolving, logical again nitrogen 20 minutes continues stirring reaction and can obtain temperature sensitive type PVDF-g-PNIPAAm copolymer in 12 hours fully.Reactant liquor is poured into from there-necked flask in the clean beaker, and the cooling back adds about 250ml methanol extraction, and suction filtration washes repeatedly with distilled water, to remove unreacted little molecule, drains then, and it is stand-by to put into 60 ℃ of oven dryings.
(3) preparation temperature response type flat sheet membrane: adopt phase inversion, with 3g copolymer p VDF-g-PNIPAAm powder, 1g pore-foaming agent PEG adding fills in the beaker of 21g solvent DMF, and heating under 60 ℃ of conditions, stirring obtained casting solution until dissolving fully in 40 minutes with this solution for vacuum deaeration.
The distilled water 800g of configuration absolute ethyl alcohol quality percentage composition 20% places 25 ℃ Water Tank with Temp.-controlled as coagulating bath.Casting solution is inclined on drying, the smooth glass plate, with the even striking film forming of glass bar, immerse solidification forming in the coagulating bath at once, treat film from glass plate be shaped come off after, placed again in the distilled water 24 hours, and cleaned with distilled water then and promptly obtain temperature response type PVDF flat sheet membrane.
Embodiment 8:
(1) preliminary treatment of PVDF powder: the preparation mol ratio is the sodium hydroxide solution of 3mol/L, this alkali lye of 350ml is poured in the beaker, added in this aqueous slkali of PVDF powder of 40g white, in reaction system, add the 6ml absolute ethyl alcohol subsequently again, stir, make PVDF in solution, fully disperse.Reaction system is placed 60 ℃ of waters bath with thermostatic control, reacted 20 minutes.With the products therefrom suction filtration, and constantly wash,, will wash back gained pulverulent solids product at last and put into 60 ℃ of baking oven dried for standby to remove NaF and the ethanol in the product with distilled water.
(2) preparation of temperature sensitive copolymer: the PVDF powder of getting after the 15g alkali treatment adds in the there-necked flask, and logical nitrogen adds the 120ml solvent DMF, stirring and dissolving under heating condition under 50 ℃ of water-baths again.Get the refining NIPAAm of 15g, 0.3g initiator A IBN joins in the there-necked flask under the situation of logical nitrogen, and after the dissolving, logical again nitrogen 20 minutes continues stirring reaction and can obtain temperature sensitive type PVDF-g-PNIPAAm copolymer in 12 hours fully.Reactant liquor is poured into from there-necked flask in the clean beaker, and the cooling back adds about 250ml methanol extraction, and suction filtration washes repeatedly with distilled water, to remove unreacted little molecule, drains then, and it is stand-by to put into 60 ℃ of oven dryings.
(3) preparation temperature response type flat sheet membrane: adopt phase inversion, with 5g copolymer p VDF-g-PNIPAAn powder, 2g pore-foaming agent PEG adding fills in the beaker of 21g solvent DMF, and heating under 50 ℃ of conditions, stirring obtained casting solution until dissolving fully in 30 minutes with this solution for vacuum deaeration.
The distilled water 800g of configuration absolute ethyl alcohol quality percentage composition 30% places 25 ℃ Water Tank with Temp.-controlled as coagulating bath.Casting solution is inclined on drying, the smooth glass plate, with the even striking film forming of glass bar, immerse solidification forming in the coagulating bath at once, treat film from glass plate be shaped come off after, placed again in the distilled water 36 hours, and cleaned with distilled water then and promptly obtain temperature response type PVDF flat sheet membrane.
Embodiment 9:
(1) preliminary treatment of PVDF powder: the preparation mol ratio is the sodium hydroxide solution of 2mol/L, this alkali lye of 350ml is poured in the beaker, added in this aqueous slkali of PVDF powder of 40g white, in reaction system, add the 15ml absolute ethyl alcohol subsequently again, stir, make PVDF in solution, fully disperse.Reaction system is placed 50～80 ℃ of waters bath with thermostatic control, reacted 15 minutes.With the products therefrom suction filtration, and constantly wash,, will wash back gained pulverulent solids product at last and put into 60 ℃ of baking oven dried for standby to remove NaF and the ethanol in the product with distilled water.
(2) preparation of temperature sensitive copolymer: the PVDF powder of getting after the 15g alkali treatment adds in the there-necked flask, and logical nitrogen adds the 120ml solvent DMF, stirring and dissolving under heating condition under 60 ℃ of water-baths again.Get the refining NIPAAm of 10g, 0.3g initiator A IBN joins in the there-necked flask under the situation of logical nitrogen, and after the dissolving, logical again nitrogen 15 minutes continues stirring reaction and can obtain temperature sensitive type PVDF-g-PNIPAAm copolymer in 10 hours fully.Reactant liquor is poured into from there-necked flask in the clean beaker, and the cooling back adds about 250ml methanol extraction, and suction filtration washes repeatedly with distilled water, to remove unreacted little molecule, drains then, and it is stand-by to put into 60 ℃ of oven dryings.
(3) preparation temperature response type flat sheet membrane: adopt phase inversion, with 5g copolymer p VDF-g-PNIPAAm powder, 1g pore-foaming agent PEG adding fills in the beaker of 21g solvent DMF, and heating under 50 ℃ of conditions, stirring obtained casting solution until dissolving fully in 30 minutes with this solution for vacuum deaeration.
The distilled water 800g of configuration absolute ethyl alcohol quality percentage composition 25% places 25 ℃ Water Tank with Temp.-controlled as coagulating bath.Casting solution is inclined on drying, the smooth glass plate, with the even striking film forming of glass bar, immerse solidification forming in the coagulating bath at once, treat film from glass plate be shaped come off after, placed again in the distilled water 20 hours, and cleaned with distilled water then and promptly obtain temperature response type PVDF flat sheet membrane.
Embodiment 10:
(1) preliminary treatment of PVDF powder: the preparation mol ratio is the lithium hydroxide solution of 3mol/L, this alkali lye of 350ml is poured in the beaker, added in this aqueous slkali of PVDF powder of 60g white, in reaction system, add the 15ml absolute ethyl alcohol subsequently again, stir, make PVDF in solution, fully disperse.Reaction system is placed 60 ℃ of waters bath with thermostatic control, reacted 15 minutes.With the products therefrom suction filtration, and constantly wash,, will wash back gained pulverulent solids product at last and put into 60 ℃ of baking oven dried for standby to remove LiF and the ethanol in the product with distilled water.
(2) preparation of temperature sensitive copolymer: the PVDF powder of getting after the 16g alkali treatment adds in the there-necked flask, and logical nitrogen adds the 120ml solvent DMF, stirring and dissolving under heating condition under 60 ℃ of water-baths again.Get the refining NIPAAm of 18g, 0.4g initiator A IBN joins in the there-necked flask under the situation of logical nitrogen, and after the dissolving, logical again nitrogen 20 minutes continues stirring reaction and can obtain temperature sensitive type PVDF-g-PNIPAAm copolymer in 10 hours fully.Reactant liquor is poured into from there-necked flask in the clean beaker, and the cooling back adds about 250ml methanol extraction, and suction filtration washes repeatedly with distilled water, to remove unreacted little molecule, drains then, and it is stand-by to put into 60 ℃ of oven dryings.
(3) preparation temperature response type flat sheet membrane: adopt phase inversion, with 4g copolymer p VDF-g-PNIPAAm powder, 2g pore-foaming agent PEG adding fills in the beaker of 21g solvent DMF, and heating under 60 ℃ of conditions, stirring obtained casting solution until dissolving fully in 30 minutes with this solution for vacuum deaeration.
The distilled water 800g of configuration absolute ethyl alcohol quality percentage composition 15% places 25 ℃ Water Tank with Temp.-controlled as coagulating bath.Casting solution is inclined on drying, the smooth glass plate, with the even striking film forming of glass bar, immerse solidification forming in the coagulating bath at once, treat film from glass plate be shaped come off after, placed again in the distilled water 30 hours, and cleaned with distilled water then and promptly obtain temperature response type PVDF flat sheet membrane.
Claims (6)
1. a flat-plate separation film is characterized in that described flat-plate separation film has temperature response characteristics at 27 ℃～32 ℃, and described flat-plate separation film is prepared by following method:
(1) PVDF powder alkali treatment: additional proportion is the PVDF powder of 100g/L-180g/L in aqueous slkali; In above-mentioned aqueous slkali, add 14ml/L～45ml/L absolute ethyl alcohol and stirring, above-mentioned mixed solution reaction system is placed 50～80 ℃ of waters bath with thermostatic control, reacted 10～20 minutes; The suction filtration products therefrom, it is dry that distilled water washing back gained PVDF pulverulent solids product is put into 60 ℃ of baking ovens;
(2) preparation of temperature sensitive copolymer: the PVDF powder after the alkali treatment adds in the there-necked flask, logical nitrogen, add N, dinethylformamide, in 50～80 ℃ of stirring in water bath dissolvings, under the situation of logical nitrogen, add refining NIPAAm, the initator azodiisobutyronitrile is in there-necked flask, wherein the mass ratio of PVDF powder after the alkali treatment and NIPAAm is 1: 0.5-1.25, fully after the dissolving, logical again nitrogen 10～20 minutes continues stirring reaction and can obtain temperature sensitive type PVDF-g-PNIPAAm film forming copolymer in 8～12 hours; Reactant liquor is poured into from there-necked flask in the beaker, and the cooling back adds methanol extraction, and suction filtration is used distilled water flushing, drains, and it is stand-by to put into 60 ℃ of oven dryings;
(3) the inversion of phases method prepares flat-plate separation film: copolymer p VDF-g-PNIPAAm powder and the adding of pore-foaming agent polyethylene glycol are filled in the container of DMF, and heating under 30～60 ℃ of conditions, stirring are until dissolving fully; Vacuum defoamation obtained casting solution in 20～40 minutes; Casting solution is inclined to glass plate with glass bar striking film forming, immerses solidification forming in 25 ℃ the coagulating bath Water Tank with Temp.-controlled, treat film from glass plate be shaped come off after, placed in the distilled water the clean flat-plate separation film that promptly obtains of distilled water again 18～36 hours.
2. flat-plate separation film according to claim 1 is characterized in that (1) described aqueous slkali is meant a kind of in potassium hydroxide, NaOH or the lithium hydroxide solution, and described alkaline concentration is 2-3mol/L.
3. flat-plate separation film according to claim 1, it is characterized in that (2) described N, the addition of dinethylformamide is 6-12 a times of PVDF powder quality, the addition of described initator azodiisobutyronitrile is the 1%-2.5% of PVDF powder quality, and the 10-25 that described methyl alcohol addition is the PVDF powder quality doubly.
4. flat-plate separation film according to claim 1 is characterized in that (3) described coagulating bath is that absolute ethyl alcohol quality percentage composition accounts for 10～40% distilled water solution.
5. flat-plate separation film according to claim 1, it is characterized in that (3) described pore-foaming agent polyethylene glycol addition is the 20%-75% of copolymer p VDF-g-PNIPAAm quality, described N, the addition of dinethylformamide are 4-7 times of copolymer p VDF-g-PNIPAAm quality.
6. the preparation method of a flat-plate separation film as claimed in claim 1, comprise the steps: the alkali treatment of (1) PVDF powder: additional proportion is the PVDF powder of 100g/L-180g/L in aqueous slkali; In above-mentioned aqueous slkali, add 14ml/L～45ml/L absolute ethyl alcohol and stirring, above-mentioned mixed solution reaction system is placed 50～80 ℃ of waters bath with thermostatic control, reacted 10～20 minutes; The suction filtration products therefrom, it is dry that distilled water washing back gained PVDF pulverulent solids product is put into 60 ℃ of baking ovens; (2) preparation of temperature sensitive copolymer: PVDF powder after the alkali treatment and temperature sensitive monomer NIPAAm are carried out copolymerization, synthetic PVDF-g-PNIPAAm copolymer; (3) the inversion of phases method prepares flat-plate separation film.
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| PCT/CN2010/072091 WO2011060631A1 (en) | 2009-11-23 | 2010-04-23 | Temperature responsive membrane and preparation method thereof |
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| CN102008908A (en) * | 2010-12-29 | 2011-04-13 | 天津工业大学 | PVDF flat membrane for preventing microbial contamination and preparing method thereof |
| CN102091536A (en) * | 2010-12-29 | 2011-06-15 | 天津工业大学 | Method for preparing structure controlled temperature-sensitive polyvinylidene fluoride flat separation membrane and product |
| CN102553464A (en) * | 2011-12-30 | 2012-07-11 | 江苏大孚膜科技有限公司 | Preparation method of modified polyvinylidene fluoride ultrafiltration membrane |
| CN103418255B (en) * | 2012-05-22 | 2016-01-20 | 宁波大学 | A kind of thermo-sensitive type ultrafiltration membrane and preparation method thereof |
| CN102728241B (en) * | 2012-07-18 | 2014-10-15 | 天津工业大学 | Anti-pollution separation membrane and preparation method |
| CN103007774A (en) * | 2012-12-19 | 2013-04-03 | 天津工业大学 | Flat sheet membrane for chiral separation of amino acid and preparation method thereof |
| CN104190273B (en) * | 2014-09-12 | 2016-05-11 | 天津工业大学 | A kind of PVDF-g-PNIPAAm film Thermo-sensitive and hydrophilic preparation method of improving |
| CN104307389B (en) * | 2014-10-11 | 2016-08-24 | 四川大学 | Polyether sulfone thermal stimulus response film and preparation method thereof |
| CN105289329A (en) * | 2015-11-14 | 2016-02-03 | 常州大学 | Preparation method of PVDF/nanometer TiO2 blending modified flat sheet membrane module |
| CN112403294A (en) * | 2019-08-21 | 2021-02-26 | 天津理工大学 | Preparation method of composite membrane with photoresponse and temperature-sensitive characteristics and membrane cleaning method |
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| CN1594405A (en) * | 2004-07-16 | 2005-03-16 | 天津工业大学 | Method for making PH value-sensitive polyvinylidene fluoride hollow fibre intelligent film and products thereby |
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| CN101239283A (en) * | 2008-03-21 | 2008-08-13 | 北京碧水源科技股份有限公司 | Convenient for cleaning hollow fiber membrane, preparation of the same and products produced thereby |
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| CN1594405A (en) * | 2004-07-16 | 2005-03-16 | 天津工业大学 | Method for making PH value-sensitive polyvinylidene fluoride hollow fibre intelligent film and products thereby |
| CN1594404A (en) * | 2004-07-16 | 2005-03-16 | 天津工业大学 | Method for making temperature-sensitive polyvinylidene fluoride hollow fibre intelligent film and products thereby |
| CN1743351A (en) * | 2005-09-30 | 2006-03-08 | 天津工业大学 | Method for preparing temperature-sensitive polyvinylidene fluoride intelligent membrane material and its product |
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