CN101985086B - Temperature response hollow fiber separation membrane - Google Patents
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- CN101985086B CN101985086B CN 200910228657 CN200910228657A CN101985086B CN 101985086 B CN101985086 B CN 101985086B CN 200910228657 CN200910228657 CN 200910228657 CN 200910228657 A CN200910228657 A CN 200910228657A CN 101985086 B CN101985086 B CN 101985086B
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 102
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 118
- 239000007788 liquid Substances 0.000 claims description 70
- 229910052757 nitrogen Inorganic materials 0.000 claims description 59
- 239000012153 distilled water Substances 0.000 claims description 46
- 239000000835 fiber Substances 0.000 claims description 46
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 45
- 238000003756 stirring Methods 0.000 claims description 36
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- 238000006243 chemical reaction Methods 0.000 claims description 34
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- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 7
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Abstract
The invention discloses a temperature response hollow fiber separation membrane, relating to a separation technology of an intelligent polymeric membrane and in particular to a temperature response separation membrane. The pure water flux of the membrane of a temperature response polyvinylidene fluoride (PVDF) hollow fiber separation membrane product is reduced sharply at 27-32DEG C. The temperature response hollow fiber separation membrane is prepared from the method comprising the following steps: carrying out alkali treatment on the PVDF powder in advance; and then carrying out copolymerization on the powder together with a temperature sensitive monomer N-isopropylacrylamide (NIPAAm) to synthesize the copolymer of PVDF-g-poly-N-isopropylacrylamide (PNIPAAm), and further preparing the temperature response PVDF hollow fiber separation membrane by using dry-wet spinning process. The preparation method of film-forming polymer has the advantages of simple process and low cost, and is easy to implement industrially; and the spinning performance of the copolymer is excellent, and the process of the spinning film-forming is simple. The intelligent membrane product is a novel temperature sensitive intelligent membrane which can sensitively respond to the ambient temperature change.
Description
Technical field
The present invention relates to a kind of Separation Membranes of Intelligent Polymer technology, particularly the temperature-responsive diffusion barrier.
Background technology
Polymeric membrane for separation has that separative efficiency is high, energy consumption is low, simple operation and other advantages, has become one of Main Means of separating-purifying.But, be widely used at present producing the polymeric membrane for separation with scientific research, fenestra size or permeability of the membrane can not the response environment temperature variation, when separating the Multiple components mixture of different molecular weight, need to adopt the different several films in aperture in batches, classification separated, separation process is complicated, and production cost is high, thereby has limited its application in some fields.Therefore, in recent years many diffusion barrier researchers be devoted to develop can the response environment variations in temperature the temperature response type macromolecule diffusion barrier, namely fenestra size or permeability of the membrane can change automatically according to the variation of environment temperature.Such film can be realized by the adjusting ambient variations in temperature, only with the target of a kind of film with regard to gradable filtration different molecular quantity of material.
In the membrane material of current polymeric membrane for separation research and application, PVDF has become the outstanding person owing to having the performances such as good corrosion resistance, hydrophobicity, soil resistance in numerous macromolecule member materials, and has 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 membrane has advantages of many uniquenesses, its piezoelectric modulus is large, mechanical strength 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., and PVDF has good spinnability, can be processed into hollow-fibre membrane.The PVDF hollow-fibre membrane is owing to having good pressure-resistant performance, need not supporter, membrane module can be made arbitrary size and shape, the advantages such as the loading density in membrane module is large, and the membrane area of unit volume is large, flux is large are classified as one of new and high technology of first developing by many countries.
At present, from existing bibliographical information, the preparation method of temperature-responsive PVDF hollow-fibre membrane mainly contains physical modification and chemical modification two large classes.
(1) physical modification method.Mainly comprise physical blending and face coat two classes.The Thermo-sensitive 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 exists coat easily to come off from the surface, and the modified effect persistence is relatively poor, and easily stops up fenestra in the coating modifying process, reduces the defectives such as membrane flux.
(2) chemical modification method.Be a kind of simple and effective method, namely by polymerisation, the PVDF film forming polymer carried out graft modification etc., make it have temperature-responsive.Usually, the chemical modification of pvdf membrane comprises membrane surface graft modification and two kinds of methods of film forming matter modification by copolymerization.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 impact of grafting degree larger.The advantage of film forming matter modification by copolymerization is that temperature-responsive is stable, but the copolymer filming performance is affected.
Can find out, above-mentioned several method all has advantage and defective in various degree.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 process, select suitable temperature sensitive monomer to carry out copolymerization, then can synthesize the filming performance impact 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 hollow-fibre 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 that the most often adopts.PNIPAAm has lower critical solution temperature (LCST), and its LCST and has faster response speed between 30 ℃～34 ℃.Therefore, in temperature-responsive PVDF diffusion barrier research field, utilize PNIPAAm to change the characteristic that changes with external environment, with its diffusion barrier of making, can realize reversible distortion.If keep the big or small constant of film, the contractility in the film can make fenestra swell or dwindle, thereby changes size and the permeability of the membrane of fenestra.
At present, adopt NIPA (NIPAAm) monomer more to the research that PVDF carries out the Thermo-sensitive modification, but be to adopt Flat Membrane membrane surface modification mostly.For example, the 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 is studied [huge dawn is clean, Chu Liangyin etc., biomedical engineering magazine, 2004,21 (5): 791].And the research of employing film forming matter modification by copolymerization method seldom.The research groups such as Lei will be dissolved in the corresponding solvent through PVDF powder and the polymerization single polymerization monomer of ozone treatment, carry out polymerization by the heat initiation, obtain intelligent PVDF material, pH sensitivity and temperature sensitive PVDF smart membrane [L.Ying have been prepared 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, Koon G Neoh.Macromol.Mater.Eng.2003,288:11].The application patent inventor once adopted the method for ATRP, take NIPAAm as grafted monomers, 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 is brought 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 hollow fiber intelligent membrane [ZL200410019992.9 of temperature, pH and temperature and pH sensitive; ZL200410019993.3].Research finds, PVDF is carried out alkali treatment method respond well, but the method 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 temperature response type hollow fiber separating film product.
Temperature response type hollow fiber separating film product is made by the spinning of PVDF-g-PNIPAAm copolymer, and this film occurs sharply reducing at 27 ℃～32 ℃ pure water fluxs, and the rejection of ovalbumin is sharply raise, and rejection raises more than 50%.Described temperature response type hollow fiber separating film is made by following method:
(1) PVDF powder alkali treatment; (2) preparation of temperature sensitive copolymer: the PVDF powder after the alkali treatment and temperature sensitive monomer NIPAAm are carried out copolymerization, synthetic PVDF-g-PNIPAAm copolymer; (3) temperature response type hollow fiber separating film preparation.
(1) alkali treatment of PVDF powder is as follows: additional proportion is the PVDF powder art of 100g/L-180g/L in aqueous slkali.In above-mentioned aqueous slkali, add 14ml/L～45ml/L absolute ethyl alcohol and stirring subsequently, so that PVDF fully disperses in solution.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, gained PVDF pulverulent solids product is put into 60 ℃ of baking ovens dryings after the washing.
In suction filtration product process, constantly wash with distilled water, to remove fluoride and the ethanol in the product.
Described aqueous slkali refers to a kind of in potassium hydroxide, NaOH or the lithium hydroxide solution, and described alkaline concentration is 2-3mol/L.
(2) preparation method of temperature sensitive copolymer is as follows: the PVDF powder of getting after the alkali treatment adds in the there-necked flask, and logical nitrogen adds DMF (DMF), stirring and dissolving under heating condition under 50～80 ℃ of water-baths again.In the situation that logical nitrogen adds refining NIPA (NIPAAm), initator azodiisobutyronitrile (AIBN) in there-necked flask, fully after the dissolving, logical nitrogen is 10～20 minutes again, 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, added methanol extraction after the cooling, suction filtration washes repeatedly with distilled water, to remove unreacted little molecule, then drains, 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, the addition of described DMF (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.
(3) temperature response type hollow fiber separating film preparation:
Thermo-sensitive PVDF-g-PNIPAAm copolymer and polyethylene glycol (PEG) are dissolved in the DMF solvent, under 40 ℃-70 ℃ temperature, add thermal agitation, then under 40 ℃-70 ℃ temperature, left standstill 30-60 minute, be made into consoluet PVDF-g-PNIPAAm spinning liquid.Spinning liquid is added in the spinning-drawing machine still, sealing spinning-drawing machine still, heating spinning-drawing machine still makes the spinning liquid temperature at 25 ℃-50 ℃, and vacuumizing and defoaming was processed 20-60 minute.
After the spinning liquid deaeration is disposed, open the still gate out switch, in still, pass into the nitrogen pressurization, open the measuring pump switch, 8-20 rev/min of measuring pump rotating speed, beginning spinning.The doughnut that to extrude from spinneret is wound up on the take up roll after by 20 ℃-30 ℃ coagulating bath, 10-25 rev/min of control take up roll rotating speed.The hollow-fibre membrane that spins out is soaked a week in distilled water, refresh the water periodically; Hollow-fibre membrane was soaked in the glycerine water solution 1-2 days, and taking-up is dried, and namely gets the temperature response type hollow fiber separating film.
The mass ratio of described Thermo-sensitive PVDF-g-PNIPAAm copolymer in DMF is 15-20%.
The mass ratio of described PEG in DMF is 5-10%.
Inject distilled water in coagulating bath water tank and the core flow container, coagulating bath water tank plays the freezing action of hollow-fibre membrane outer wall, and the core liquid in the core flow container leads in the hollow-fibre membrane inner tube, and the film inwall is played freezing action;
Glycerine and water ratio are 1: 1 in the described glycerine water solution.
Film dry-wet spinning machine and attached coagulating bath water tank thereof and core flow container, nitrogen pot, drafting system etc. are connected before the spinning.
The method is by designing first a kind of temperature response type PVDF copolymer, and then utilizes this copolymer to adopt dry-wet spinning technique preparation temperature response type hollow fiber separating film, comprises the steps:
Spinning technique is the chemical fibre spinning method that the characteristics with dry spinning and wet spinning combine among the present invention.The spinning speed of dried-wet spinning is high more than wet spinning, and can use the larger spinning head in aperture.High when spinning solution concentration and viscosity then can resemble dry-spinning, can also more effectively control the structure-forming process of fiber.Temperature response type hollow fiber separating film section is cirque structure, inside and outside wall is the dense layer surface structure, comprise outer compacted zone (1), inner compact layer layer (2), then present finger-like pore structure (2) below the cortex, the two-layer certain thickness spongelike structure of finger-like pore sandwich one deck (3).This intelligence hollow-fibre membrane is formed by Thermo-sensitive PVDF-g-PNIPAAm copolymer spinning.
Beneficial effect:
The present invention is through more than a year research and development, up to a hundred experimental conditions have been carried out in the preparation of the alkali treatment of PVDF powder, temperature sensitive copolymer, temperature response type hollow fiber separating film preparation technology exploitation and raw material is selected and process optimization work, particularly temperature response type hollow fiber separating film preparation technology is without on the technical foundation formerly, experience the optimization of many experimental conditions and technique, finally realize the develop of technique.Compared with prior art, the present invention adopts the alkali treatment technology to be prepared into membrane polymer, and method is simple, cost is low, do not need special installation, industrializing implementation is easy; The temperature sensitive copolymer filming performance of the PVDF-g-PNIPAAm that the present invention synthesizes, good spinning property, modification is little on PVDF filming performance, spinning property impact; What the present invention prepared is temperature response type PVDF hollow fiber separating film, and this film occurs sharply reducing at 27 ℃～32 ℃ pure water fluxs, and the rejection of ovalbumin is sharply raise, and rejection raises more than 50%, shows obvious temperature response characteristics.
The present invention preparation what be that temperature-responsive PVDF hollow fiber separating 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, technique is loaded down with trivial details, cost is high, and the present invention adopts alkali treatment method, and is then simply too much.[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. the preparation method is different, and the present invention carries out alkali treatment to the PVDF powder, and then carries out graft copolymerization, the hollow fiber separating film processed of respinning; 2. the film temperature Response Mechanism is different, and the basement membrane Graft Method mainly is the size that changes fenestra by the Swelling and contraction of temperature sensitive grafting layer in the fenestra, and the present invention is the size that changes fenestra by the Swelling and contraction of the whole temperature influence of membrane material; 3. product quality is different, the membrane surface graft modification, and the size of temperature-responsive and stability are subjected to the impact of grafting degree larger, and there is the defective such as easily come off in the grafting layer, and the present invention is owing to being the copolymer direct formation of film at surface, constant product quality.
Film forming polymer preparation method of the present invention has the characteristics such as technique is simple, cost is low, do not need special installation, industrializing implementation is easy, and the copolymer spinning properties is good, is spun to that membrane process technique is simple, cost is low, industrializing implementation is easy.This intelligent film product is can be to a kind of Novel temperature-sensitive type PVDF smart membrane of the responsive response of variation of ambient temperature.
Description of drawings: Fig. 1 is the membrane structure schematic diagram.
The specific embodiment
The following examples can make the present invention of those skilled in the art comprehend, but do not limit the present invention in any way.
Embodiment 1:
(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 5ml absolute ethyl alcohol more subsequently, stir, so that PVDF fully disperses in solution.Reaction system is placed 50 ℃ of waters bath with thermostatic control, reacted 10 minutes.With the products therefrom suction filtration, and constantly wash with distilled water, to remove NaF and the ethanol in the product, gained pulverulent solids product is put into 60 ℃ of baking oven dried for standby after will washing at last.
(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, in the situation that logical nitrogen joins in the there-necked flask, after the dissolving, logical nitrogen is 10 minutes again, 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, added approximately 250ml methanol extraction after the cooling, suction filtration washes repeatedly with distilled water, to remove unreacted little molecule, then drains, and puts into 60 ℃ of oven dryings stand-by.
(3) preparation temperature response type hollow fiber separating film: be that 6% PEG is dissolved in the DMF solvent of 1000mL with the Thermo-sensitive PVDF-g-PNIPAAm copolymer of synthetic mass ratio 15% and mass ratio, be mixed with spinning liquid, under 60 ℃ temperature, add thermal agitation in the course of dissolution.Then spinning liquid was left standstill 30 minutes 60 ℃ temperature is lower, fully dissolving is made into consoluet PVDF-g-PNIPAAm spinning liquid.Spinning liquid is poured in the spinning-drawing machine still, behind the still good seal, utilized the circulation constant temperature device that still is heated, the spinning liquid temperature is controlled at about 30 ℃, vacuumize with vavuum pump again and carry out deaeration processing 30 minutes.
In coagulating bath water tank and core flow container, inject distilled water, film dry-wet spinning machine and attached coagulating bath water tank thereof and core flow container, nitrogen pot, drafting system etc. are connected.After the spinning liquid deaeration is disposed, open the still gate out switch, in still, pass into the nitrogen pressurization, open the measuring pump switch, adjust 12 rev/mins of rotating speeds, the beginning spinning.The doughnut that to extrude from spinneret is wound up on the take up roll after by 25 ℃ coagulating bath, 15 rev/mins of control take up roll rotating speeds.After spinning finishes coiler device is shut down, take off fiber, the hollow-fibre membrane that spins out is soaked a week in distilled water, refresh the water periodically, guarantee PEG is dissolved out.Configure the aqueous solution of 1: 1 glycerine, hollow-fibre membrane was soaked wherein 2 days, then take out and dry, namely get temperature sensitive type PVDF-g-PNIPAAm hollow fiber separating film.
This film occurs sharply reducing at 27 ℃～31 ℃ pure water fluxs, and the rejection of ovalbumin is sharply raise, and rejection raises 55%, shows obvious temperature response characteristics.
Embodiment 2:
(1) preliminary 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 more subsequently, stir, so that PVDF fully disperses in solution.Reaction system is placed 80 ℃ of waters bath with thermostatic control, reacted 20 minutes.With the products therefrom suction filtration, and constantly wash with distilled water, to remove KF and the ethanol in the product, gained pulverulent solids product is put into 60 ℃ of baking oven dried for standby after will washing at last.
(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, in the situation that logical nitrogen joins in the there-necked flask, after the dissolving, logical nitrogen is 20 minutes again, 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, added approximately 250ml methanol extraction after the cooling, suction filtration washes repeatedly with distilled water, to remove unreacted little molecule, then drains, and puts into 60 ℃ of oven dryings stand-by.
(3) preparation temperature response type hollow fiber separating film: be that 8% PEG is dissolved in the DMF solvent of 1000mL with the Thermo-sensitive PVDF-g-PNIPAAm copolymer of synthetic mass ratio 16% and mass ratio, be mixed with spinning liquid, under 60 ℃ temperature, add thermal agitation in the course of dissolution.Then spinning liquid was left standstill 30 minutes 60 ℃ temperature is lower, fully dissolving is made into consoluet PVDF-g-PNIPAAm spinning liquid.Spinning liquid is poured in the spinning-drawing machine still, behind the still good seal, utilized the circulation constant temperature device that still is heated, the spinning liquid temperature is controlled at about 30 ℃, vacuumize with vavuum pump again and carry out deaeration processing 30 minutes.
In coagulating bath water tank and core flow container, inject distilled water, film dry-wet spinning machine and attached coagulating bath water tank thereof and core flow container, nitrogen pot, drafting system etc. are connected.After the spinning liquid deaeration is disposed, open the still gate out switch, in still, pass into the nitrogen pressurization, open the measuring pump switch, adjust 12 rev/mins of rotating speeds, the beginning spinning.The doughnut that to extrude from spinneret is wound up on the take up roll after by 25 ℃ coagulating bath, 15 rev/mins of control take up roll rotating speeds.After spinning finishes coiler device is shut down, take off fiber, the hollow-fibre membrane that spins out is soaked a week in distilled water, refresh the water periodically, guarantee PEG is dissolved out.Configure the aqueous solution of 1: 1 glycerine, hollow-fibre membrane was soaked wherein 2 days, then take out and dry, namely get temperature sensitive type PVDF-g-PNIPAAm hollow fiber separating film.
This film occurs sharply reducing at 28 ℃～31 ℃ pure water fluxs, and the rejection of ovalbumin is sharply raise, and rejection raises 50%, shows obvious temperature response characteristics.
Embodiment 3:
(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 50g white, in reaction system, add the 10ml absolute ethyl alcohol more subsequently, stir, so that PVDF fully disperses in solution.Reaction system is placed 60 ℃ of waters bath with thermostatic control, reacted 20 minutes.With the products therefrom suction filtration, and constantly wash with distilled water, to remove NaF and the ethanol in the product, gained pulverulent solids product is put into 60 ℃ of baking oven dried for standby after will washing at last.
(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, in the situation that logical nitrogen joins in the there-necked flask, after the dissolving, logical nitrogen is 20 minutes again, 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, added approximately 250ml methanol extraction after the cooling, suction filtration washes repeatedly with distilled water, to remove unreacted little molecule, then drains, and puts into 60 ℃ of oven dryings stand-by.
(3) preparation temperature response type hollow fiber separating film: be that 8% PEG is dissolved in the DMF solvent of 1000mL with the Thermo-sensitive PVDF-g-PNIPAAm copolymer of synthetic mass ratio 16% and mass ratio, be mixed with spinning liquid, under 60 ℃ temperature, add thermal agitation in the course of dissolution.Then spinning liquid was left standstill 30 minutes 60 ℃ temperature is lower, fully dissolving is made into consoluet PVDF-g-PNIPAAm spinning liquid.Spinning liquid is poured in the spinning-drawing machine still, behind the still good seal, utilized the circulation constant temperature device that still is heated, the spinning liquid temperature is controlled at about 35 ℃, vacuumize with vavuum pump again and carry out deaeration processing 40 minutes.
In coagulating bath water tank and core flow container, inject distilled water, film dry-wet spinning machine and attached coagulating bath water tank thereof and core flow container, nitrogen pot, drafting system etc. are connected.After the spinning liquid deaeration is disposed, open the still gate out switch, in still, pass into the nitrogen pressurization, open the measuring pump switch, adjust 13 rev/mins of rotating speeds, the beginning spinning.The doughnut that to extrude from spinneret is wound up on the take up roll after by 30 ℃ coagulating bath, 15 rev/mins of control take up roll rotating speeds.After spinning finishes coiler device is shut down, take off fiber, the hollow-fibre membrane that spins out is soaked a week in distilled water, refresh the water periodically, guarantee PEG is dissolved out.Configure the aqueous solution of 1: 1 glycerine, hollow-fibre membrane was soaked wherein 2 days, then take out and dry, namely get temperature sensitive type PVDF-g-PNIPAAm hollow fiber separating film.
This film occurs sharply reducing at 29 ℃～32 ℃ pure water fluxs, and the rejection of ovalbumin is sharply raise, and rejection raises 58%, shows obvious temperature response characteristics.
Embodiment 4:
(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 5ml absolute ethyl alcohol more subsequently, stir, so that PVDF fully disperses in solution.Reaction system is placed 50 ℃ of waters bath with thermostatic control, reacted 20 minutes.With the products therefrom suction filtration, and constantly wash with distilled water, to remove NaF and the ethanol in the product, gained pulverulent solids product is put into 60 ℃ of baking oven dried for standby after will washing at last.
(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, in the situation that logical nitrogen joins in the there-necked flask, after the dissolving, logical nitrogen is 20 minutes again, 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, added approximately 250ml methanol extraction after the cooling, suction filtration washes repeatedly with distilled water, to remove unreacted little molecule, then drains, and puts into 60 ℃ of oven dryings stand-by.
(3) preparation temperature response type hollow fiber separating film: be that 10% PEG is dissolved in the DMF solvent of 1000mL with the Thermo-sensitive PVDF-g-PNIPAAm copolymer of synthetic mass ratio 18% and mass ratio, be mixed with spinning liquid, under 60 ℃ temperature, add thermal agitation in the course of dissolution.Then spinning liquid was left standstill 30 minutes 60 ℃ temperature is lower, fully dissolving is made into consoluet PVDF-g-PNIPAAm spinning liquid.Spinning liquid is poured in the spinning-drawing machine still, behind the still good seal, utilized the circulation constant temperature device that still is heated, the spinning liquid temperature is controlled at about 35 ℃, vacuumize with vavuum pump again and carry out deaeration processing 40 minutes.
In coagulating bath water tank and core flow container, inject distilled water, film dry-wet spinning machine and attached coagulating bath water tank thereof and core flow container, nitrogen pot, drafting system etc. are connected.After the spinning liquid deaeration is disposed, open the still gate out switch, in still, pass into the nitrogen pressurization, open the measuring pump switch, adjust 12 rev/mins of rotating speeds, the beginning spinning.The doughnut that to extrude from spinneret is wound up on the take up roll after by 25 ℃ coagulating bath, 15 rev/mins of control take up roll rotating speeds.After spinning finishes coiler device is shut down, take off fiber, the hollow-fibre membrane that spins out is soaked a week in distilled water, refresh the water periodically, guarantee PEG is dissolved out.Configure the aqueous solution of 1: 1 glycerine, hollow-fibre membrane was soaked wherein 2 days, then take out and dry, namely get temperature sensitive type PVDF-g-PNIPAAm hollow fiber separating film.
This film occurs sharply reducing at 30 ℃～32 ℃ pure water fluxs, and the rejection of ovalbumin is sharply raise, and rejection raises 51%, shows obvious temperature response characteristics.
Embodiment 5:
(1) preliminary 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, add in this aqueous slkali of PVDF powder of 40g white, in reaction system, add the 12ml absolute ethyl alcohol more subsequently, stir, so that PVDF fully disperses in solution.Reaction system is placed 60 ℃ of waters bath with thermostatic control, reacted 20 minutes.With the products therefrom suction filtration, and constantly wash with distilled water, to remove NaF and the ethanol in the product, gained pulverulent solids product is put into 60 ℃ of baking oven dried for standby after will washing at last.
(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, in the situation that logical nitrogen joins in the there-necked flask, after the dissolving, logical nitrogen is 20 minutes again, 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, added approximately 250ml methanol extraction after the cooling, suction filtration washes repeatedly with distilled water, to remove unreacted little molecule, then drains, and puts into 60 ℃ of oven dryings stand-by.
(3) preparation temperature response type hollow fiber separating film: be that 8% PEG is dissolved in the DMF solvent of 1000mL with the Thermo-sensitive PVDF-g-PNIPAAm copolymer of synthetic mass ratio 16% and mass ratio, be mixed with spinning liquid, under 60 ℃ temperature, add thermal agitation in the course of dissolution.Then spinning liquid was left standstill 30 minutes 60 ℃ temperature is lower, fully dissolving is made into consoluet PVDF-g-PNIPAAm spinning liquid.Spinning liquid is poured in the spinning-drawing machine still, behind the still good seal, utilized the circulation constant temperature device that still is heated, the spinning liquid temperature is controlled at about 35 ℃, vacuumize with vavuum pump again and carry out deaeration processing 60 minutes.
In coagulating bath water tank and core flow container, inject distilled water, film dry-wet spinning machine and attached coagulating bath water tank thereof and core flow container, nitrogen pot, drafting system etc. are connected.After the spinning liquid deaeration is disposed, open the still gate out switch, in still, pass into the nitrogen pressurization, open the measuring pump switch, adjust 15 rev/mins of rotating speeds, the beginning spinning.The doughnut that to extrude from spinneret is wound up on the take up roll after by 28 ℃ coagulating bath, 18 rev/mins of control take up roll rotating speeds.After spinning finishes coiler device is shut down, take off fiber, the hollow-fibre membrane that spins out is soaked a week in distilled water, refresh the water periodically, guarantee PEG is dissolved out.Configure the aqueous solution of 1: 1 glycerine, hollow-fibre membrane was soaked wherein 2 days, then take out and dry, namely get temperature sensitive type PVDF-g-PNIPAAm hollow fiber separating film.
This film occurs sharply reducing at 28 ℃～32 ℃ pure water fluxs, and the rejection of ovalbumin is sharply raise, and rejection raises 52%, shows obvious 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 more subsequently, stir, so that PVDF fully disperses in solution.Reaction system is placed 60 ℃ of waters bath with thermostatic control, reacted 20 minutes.With the products therefrom suction filtration, and constantly wash with distilled water, to remove KF and the ethanol in the product, gained pulverulent solids product is put into 60 ℃ of baking oven dried for standby after will washing at last.
(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, in the situation that logical nitrogen joins in the there-necked flask, after the dissolving, logical nitrogen is 20 minutes again, 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, added approximately 250ml methanol extraction after the cooling, suction filtration washes repeatedly with distilled water, to remove unreacted little molecule, then drains, and puts into 60 ℃ of oven dryings stand-by.
(3) preparation temperature response type hollow fiber separating film: be that 8% PEG is dissolved in the DMF solvent of 1000mL with the Thermo-sensitive PVDF-g-PNIPAAm copolymer of synthetic mass ratio 20% and mass ratio, be mixed with spinning liquid, under 60 ℃ temperature, add thermal agitation in the course of dissolution.Then spinning liquid was left standstill 30 minutes 70 ℃ temperature is lower, fully dissolving is made into consoluet PVDF-g-PNIPAAm spinning liquid.Spinning liquid is poured in the spinning-drawing machine still, behind the still good seal, utilized the circulation constant temperature device that still is heated, the spinning liquid temperature is controlled at about 50 ℃, vacuumize with vavuum pump again and carry out deaeration processing 60 minutes.
In coagulating bath water tank and core flow container, inject distilled water, film dry-wet spinning machine and attached coagulating bath water tank thereof and core flow container, nitrogen pot, drafting system etc. are connected.After the spinning liquid deaeration is disposed, open the still gate out switch, in still, pass into the nitrogen pressurization, open the measuring pump switch, adjust 12 rev/mins of rotating speeds, the beginning spinning.The doughnut that to extrude from spinneret is wound up on the take up roll after by 25 ℃ coagulating bath, 20 rev/mins of control take up roll rotating speeds.After spinning finishes coiler device is shut down, take off fiber, the hollow-fibre membrane that spins out is soaked a week in distilled water, refresh the water periodically, guarantee PEG is dissolved out.Configure the aqueous solution of 1: 1 glycerine, hollow-fibre membrane was soaked wherein 1 day, then take out and dry, namely get temperature sensitive type PVDF-g-PNIPAAm hollow fiber separating film.
This film occurs sharply reducing at 28 ℃～32 ℃ pure water fluxs, and the rejection of ovalbumin is sharply raise, and rejection raises 59%, shows obvious temperature response characteristics.
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, add in this aqueous slkali of PVDF powder of 45g white, in reaction system, add the 12ml absolute ethyl alcohol more subsequently, stir, so that PVDF fully disperses in solution.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 with distilled water, to remove KF and the ethanol in the product, gained pulverulent solids product is put into 60 ℃ of baking oven dried for standby after will washing at last.
(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, in the situation that logical nitrogen joins in the there-necked flask, after the dissolving, logical nitrogen is 20 minutes again, 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, added approximately 250ml methanol extraction after the cooling, suction filtration washes repeatedly with distilled water, to remove unreacted little molecule, then drains, and puts into 60 ℃ of oven dryings stand-by.
(3) preparation temperature response type hollow fiber separating film: preparation temperature response type hollow fiber separating film: be that 10% PEG is dissolved in the DMF solvent of 1000mL with the Thermo-sensitive PVDF-g-PNIPAAm copolymer of synthetic mass ratio 16% and mass ratio, be mixed with spinning liquid, under 60 ℃ temperature, add thermal agitation in the course of dissolution.Then spinning liquid was left standstill 60 minutes 70 ℃ temperature is lower, fully dissolving is made into consoluet PVDF-g-PNIPAAm spinning liquid.Spinning liquid is poured in the spinning-drawing machine still, behind the still good seal, utilized the circulation constant temperature device that still is heated, the spinning liquid temperature is controlled at about 45 ℃, vacuumize with vavuum pump again and carry out deaeration processing 60 minutes.
In coagulating bath water tank and core flow container, inject distilled water, film dry-wet spinning machine and attached coagulating bath water tank thereof and core flow container, nitrogen pot, drafting system etc. are connected.After the spinning liquid deaeration is disposed, open the still gate out switch, in still, pass into the nitrogen pressurization, open the measuring pump switch, adjust 20 rev/mins of rotating speeds, the beginning spinning.The doughnut that to extrude from spinneret is wound up on the take up roll after by 25 ℃ coagulating bath, 25 rev/mins of control take up roll rotating speeds.After spinning finishes coiler device is shut down, take off fiber, the hollow-fibre membrane that spins out is soaked a week in distilled water, refresh the water periodically, guarantee PEG is dissolved out.Configure the aqueous solution of 1: 1 glycerine, hollow-fibre membrane was soaked wherein 1 day, then take out and dry, namely get temperature sensitive type PVDF-g-PNIPAAm hollow fiber separating film.
This film occurs sharply reducing at 29 ℃～32 ℃ pure water fluxs, and the rejection of ovalbumin is sharply raise, and rejection raises 53%, shows obvious temperature response characteristics.
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 more subsequently, stir, so that PVDF fully disperses in solution.Reaction system is placed 60 ℃ of waters bath with thermostatic control, reacted 20 minutes.With the products therefrom suction filtration, and constantly wash with distilled water, to remove NaF and the ethanol in the product, gained pulverulent solids product is put into 60 ℃ of baking oven dried for standby after will washing at last.
(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, in the situation that logical nitrogen joins in the there-necked flask, after the dissolving, logical nitrogen is 20 minutes again, 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, added approximately 250ml methanol extraction after the cooling, suction filtration washes repeatedly with distilled water, to remove unreacted little molecule, then drains, and puts into 60 ℃ of oven dryings stand-by.
(3) preparation temperature response type hollow fiber separating film: preparation temperature response type hollow fiber separating film: be that 8% PEG is dissolved in the DMF solvent of 1000mL with the Thermo-sensitive PVDF-g-PNIPAAm copolymer of synthetic mass ratio 18% and mass ratio, be mixed with spinning liquid, under 60 ℃ temperature, add thermal agitation in the course of dissolution.Then spinning liquid was left standstill 60 minutes 70 ℃ temperature is lower, fully dissolving is made into consoluet PVDF-g-PNIPAAm spinning liquid.Spinning liquid is poured in the spinning-drawing machine still, behind the still good seal, utilized the circulation constant temperature device that still is heated, the spinning liquid temperature is controlled at about 26 ℃, vacuumize with vavuum pump again and carry out deaeration processing 30 minutes.
In coagulating bath water tank and core flow container, inject distilled water, film dry-wet spinning machine and attached coagulating bath water tank thereof and core flow container, nitrogen pot, drafting system etc. are connected.After the spinning liquid deaeration is disposed, open the still gate out switch, in still, pass into the nitrogen pressurization, open the measuring pump switch, adjust 13 rev/mins of rotating speeds, the beginning spinning.The doughnut that to extrude from spinneret is wound up on the take up roll after by 28 ℃ coagulating bath, 18 rev/mins of control take up roll rotating speeds.After spinning finishes coiler device is shut down, take off fiber, the hollow-fibre membrane that spins out is soaked a week in distilled water, refresh the water periodically, guarantee PEG is dissolved out.Configure the aqueous solution of 1: 1 glycerine, hollow-fibre membrane was soaked wherein 1 day, then take out and dry, namely get temperature sensitive type PVDF-g-PNIPAAm hollow fiber separating film.
This film occurs sharply reducing at 29 ℃～31 ℃ pure water fluxs, and the rejection of ovalbumin is sharply raise, and rejection raises 59%, shows obvious temperature response characteristics.
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 more subsequently, stir, so that PVDF fully disperses in solution.Reaction system is placed 50～80 ℃ of waters bath with thermostatic control, reacted 15 minutes.With the products therefrom suction filtration, and constantly wash with distilled water, to remove NaF and the ethanol in the product, gained pulverulent solids product is put into 60 ℃ of baking oven dried for standby after will washing at last.
(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, in the situation that logical nitrogen joins in the there-necked flask, after the dissolving, logical nitrogen is 15 minutes again, 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, added approximately 250ml methanol extraction after the cooling, suction filtration washes repeatedly with distilled water, to remove unreacted little molecule, then drains, and puts into 60 ℃ of oven dryings stand-by.
(3) preparation temperature response type hollow fiber separating film: preparation temperature response type hollow fiber separating film: be that 5% PEG is dissolved in the DMF solvent of 1000mL with the Thermo-sensitive PVDF-g-PNIPAAm copolymer of synthetic mass ratio 20% and mass ratio, be mixed with spinning liquid, under 70 ℃ temperature, add thermal agitation in the course of dissolution.Then spinning liquid was left standstill 30 minutes 70 ℃ temperature is lower, fully dissolving is made into consoluet PVDF-g-PNIPAAm spinning liquid.Spinning liquid is poured in the spinning-drawing machine still, behind the still good seal, utilized the circulation constant temperature device that still is heated, the spinning liquid temperature is controlled at about 50 ℃, vacuumize with vavuum pump again and carry out deaeration processing 60 minutes.
In coagulating bath water tank and core flow container, inject distilled water, film dry-wet spinning machine and attached coagulating bath water tank thereof and core flow container, nitrogen pot, drafting system etc. are connected.After the spinning liquid deaeration is disposed, open the still gate out switch, in still, pass into the nitrogen pressurization, open the measuring pump switch, adjust 15 rev/mins of rotating speeds, the beginning spinning.The doughnut that to extrude from spinneret is wound up on the take up roll after by 30 ℃ coagulating bath, 18 rev/mins of control take up roll rotating speeds.After spinning finishes coiler device is shut down, take off fiber, the hollow-fibre membrane that spins out is soaked a week in distilled water, refresh the water periodically, guarantee PEG is dissolved out.Configure the aqueous solution of 1: 1 glycerine, hollow-fibre membrane was soaked wherein 2 days, then take out and dry, namely get temperature sensitive type PVDF-g-PNIPAAm hollow fiber separating film.
This film occurs sharply reducing at 30 ℃～32 ℃ pure water fluxs, and the rejection of ovalbumin is sharply raise, and rejection raises 58%, shows obvious temperature response characteristics.
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 50g white, in reaction system, add the 15ml absolute ethyl alcohol more subsequently, stir, so that PVDF fully disperses in solution.Reaction system is placed 60 ℃ of waters bath with thermostatic control, reacted 15 minutes.With the products therefrom suction filtration, and constantly wash with distilled water, to remove LiF and the ethanol in the product, gained pulverulent solids product is put into 60 ℃ of baking oven dried for standby after will washing at last.
(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, in the situation that logical nitrogen joins in the there-necked flask, after the dissolving, logical nitrogen is 20 minutes again, 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, added approximately 250ml methanol extraction after the cooling, suction filtration washes repeatedly with distilled water, to remove unreacted little molecule, then drains, and puts into 60 ℃ of oven dryings stand-by.
(3) preparation temperature response type hollow fiber separating film: preparation temperature response type hollow fiber separating film: be that 6% PEG is dissolved in the DMF solvent of 1000mL with the Thermo-sensitive PVDF-g-PNIPAAm copolymer of synthetic mass ratio 16% and mass ratio, be mixed with spinning liquid, under 70 ℃ temperature, add thermal agitation in the course of dissolution.Then spinning liquid was left standstill 30 minutes 70 ℃ temperature is lower, fully dissolving is made into consoluet PVDF-g-PNIPAAm spinning liquid.Spinning liquid is poured in the spinning-drawing machine still, behind the still good seal, utilized the circulation constant temperature device that still is heated, the spinning liquid temperature is controlled at about 35 ℃, vacuumize with vavuum pump again and carry out deaeration processing 60 minutes.
In coagulating bath water tank and core flow container, inject distilled water, film dry-wet spinning machine and attached coagulating bath water tank thereof and core flow container, nitrogen pot, drafting system etc. are connected.After the spinning liquid deaeration is disposed, open the still gate out switch, in still, pass into the nitrogen pressurization, open the measuring pump switch, adjust 10 rev/mins of rotating speeds, the beginning spinning.The doughnut that to extrude from spinneret is wound up on the take up roll after by 30 ℃ coagulating bath, 15 rev/mins of control take up roll rotating speeds.After spinning finishes coiler device is shut down, take off fiber, the hollow-fibre membrane that spins out is soaked a week in distilled water, refresh the water periodically, guarantee PEG is dissolved out.Configure the aqueous solution of 1: 1 glycerine, hollow-fibre membrane was soaked wherein 2 days, then take out and dry, namely get temperature sensitive type PVDF-g-PNIPAAm hollow fiber separating film.
This film occurs sharply reducing at 29 ℃～32 ℃ pure water fluxs, and the rejection of ovalbumin is sharply raise, and rejection raises 59%, shows obvious temperature response characteristics.
Claims (6)
1. temperature response type hollow fiber separating film, it is characterized in that described temperature response type hollow fiber separating film is made by the spinning of PVDF-g-PNIPAAm copolymer, described temperature response type hollow fiber separating film occurs sharply reducing at 27 ℃～32 ℃ pure water fluxs, rejection to ovalbumin sharply raises, and rejection raises more than 50%; Described temperature response type hollow fiber separating film is made by following method: the alkali treatment of (1) PVDF powder; (2) preparation of temperature sensitive copolymer: the PVDF powder after the alkali treatment and temperature sensitive monomer NIPAAm are carried out copolymerization, synthetic PVDF-g-PNIPAAm copolymer; (3) temperature response type hollow fiber separating film preparation; The alkali treatment of described PVDF powder 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, 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, gained PVDF pulverulent solids product is put into 60 ℃ of baking ovens dryings after the washing; The preparation method of temperature sensitive copolymer is as follows in described (2): the PVDF powder of getting after the alkali treatment adds in the there-necked flask, and logical nitrogen adds DMF, stirring and dissolving under heating condition under 50～80 ℃ of water-baths; In the situation that logical nitrogen adds refining NIPA, initator azodiisobutyronitrile in there-necked flask, fully after the dissolving, logical nitrogen is 10～20 minutes again, 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, added methanol extraction after the cooling, suction filtration is used distilled water flushing, drains, and it is stand-by that gained copolymer p VDF-g-PNIPAAm product is put into 60 ℃ of oven dryings; The temperature response type hollow fiber separating film is prepared as follows in described (3): Thermo-sensitive PVDF-g-PNIPAAm copolymer and polyethylene glycol are dissolved in the DMF solvent, under 40 ℃-70 ℃ temperature, add thermal agitation, then spinning liquid was left standstill 30-60 minute under 40 ℃-70 ℃ temperature, be made into consoluet PVDF-g-PNIPAAm spinning liquid; Spinning liquid is poured in the spinning-drawing machine still, sealing spinning-drawing machine still, heating spinning-drawing machine still makes the spinning liquid temperature at 25 ℃-50 ℃, and vacuumizing and defoaming was processed 20-60 minute; After the spinning liquid deaeration is disposed, open the still gate out switch, in still, pass into the nitrogen pressurization, open the measuring pump switch, adjust 8-20 rev/min of rotating speed, the beginning spinning; The doughnut that to extrude from spinneret is wound up on the take up roll after by 20 ℃-30 ℃ coagulating bath, 10-25 rev/min of control take up roll rotating speed; Coiler device is shut down, and takes off fiber, and the hollow-fibre membrane that spins out is soaked a week in distilled water, refreshes the water periodically; Hollow-fibre membrane was soaked in the glycerine water solution 1-2 days, and taking-up is dried, and namely gets temperature sensitive type PVDF-g-PNIPAAm hollow fiber separating film.
2. temperature response type hollow fiber separating film as claimed in claim 1 is characterized in that the PVDF powder after alkali treatment and the mass ratio of NIPAAm are 1 in described (2): 0.5-1.25.
3. a temperature response type hollow fiber separating film as claimed in claim 1 is characterized in that the addition of initator azodiisobutyronitrile (AIBN) in described (2) is the 1%-2.5% of PVDF powder quality.
4. a temperature response type hollow fiber separating film as claimed in claim 1 is characterized in that the mass ratio of described (3) Thermo-sensitive PVDF-g-PNIPAAm copolymer in DMF is 15-20%.
5. a temperature response type hollow fiber separating film as claimed in claim 1 is characterized in that the mass ratio of described (3) polyethylene glycol in DMF is 5-10%.
6. temperature response type hollow fiber separating film as claimed in claim 1 is characterized in that glycerine and water ratio are 1: 1 in described (3) glycerine water solution..
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| CN102580574B (en) * | 2012-02-29 | 2013-12-04 | 福州大学 | Antipollution self-cleaning polyvinylidene fluoride membrane and method for producing same |
| CN103007770A (en) * | 2012-09-28 | 2013-04-03 | 天津大学 | Solvent-free preparation method of temperature-sensitive separation film |
| CN103055710A (en) * | 2012-12-20 | 2013-04-24 | 天津工业大学 | Hollow fiber membrane for chiral separation and preparation method thereof |
| CN107602891B (en) * | 2017-09-08 | 2020-11-03 | 哈尔滨工业大学 | Preparation method of composite PNIPAM-based microgel PDMS (polydimethylsiloxane) film |
| CN107684834B (en) * | 2017-09-19 | 2020-11-24 | 北京航空航天大学 | Intelligent response type graphene-based separation membrane for mixed molecular separation and preparation method thereof |
| CN114832647B (en) * | 2022-05-25 | 2023-08-11 | 中国海洋大学 | Preparation method and application of temperature-sensitive switchable emulsion type oil-water separation membrane |
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| 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 |
| 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 |
| CN101711951A (en) * | 2009-11-23 | 2010-05-26 | 天津工业大学 | Method for preparing fiber separation film |
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| 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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