CN104436760A - Magnetic response type high-efficiency oil-water separation fiber membrane and preparation method thereof - Google Patents
Magnetic response type high-efficiency oil-water separation fiber membrane and preparation method thereof Download PDFInfo
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- CN104436760A CN104436760A CN201410584912.8A CN201410584912A CN104436760A CN 104436760 A CN104436760 A CN 104436760A CN 201410584912 A CN201410584912 A CN 201410584912A CN 104436760 A CN104436760 A CN 104436760A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4326—Condensation or reaction polymers
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/49—Oxides or hydroxides of elements of Groups 8, 9, 10 or 18 of the Periodic System; Ferrates; Cobaltates; Nickelates; Ruthenates; Osmates; Rhodates; Iridates; Palladates; Platinates
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/61—Polyamines polyimines
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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/20—Polyalkenes, polymers or copolymers of compounds with alkenyl groups bonded to aromatic groups
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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/22—Polymers or copolymers of halogenated mono-olefins
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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/26—Polymers or copolymers of unsaturated carboxylic acids or derivatives thereof
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- D—TEXTILES; PAPER
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/32—Polyesters
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/38—Polyurethanes
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/10—Repellency against liquids
- D06M2200/12—Hydrophobic properties
Abstract
The invention discloses a magnetic response type high-efficiency oil-water separation fiber membrane and a preparation method thereof, and belongs to the field of functional micro-nano fiber materials. The magnetic response type high-efficiency oil-water separation fiber membrane disclosed by the invention is prepared by the following steps: dissolving hydrophobic polymers, such as polyvinylidene fluoride, polyurethane or polycaprolactone, as main raw materials into an organic solvent to form a polymer solution; preparing a non-woven fiber membrane material prepared from micro-nano structure fibers by adopting an electrospinning method; forming a sticky polydopamine membrane through polymerization of polydopamine in an alkaline solution, and firmly attaching magnetic nanoparticles onto the surface of an electrospinning fiber membrane by adopting the sticky polydopamine membrane, so as to prepare the magnetic response type high-efficiency oil-water separation fiber membrane. The fiber membrane disclosed by the invention has a super-hydrophobic/super-oleophilic property in air, and has an excellent adsorptive property on a plurality of common oils; the preparation method of the high-efficiency oil-water separation fiber membrane, disclosed by the invention, is simple, low in energy consumption, and high in efficiency,and can be widely applied to the fields such as remote controllable efficient separation of oily wastewater, and the magnetic responsiveness is realized.
Description
Technical field
The invention belongs to functional micro-nano complex fiber Material Field, be specifically related to a kind of to there is micro-nano composite cellulosic membrane of the efficient oil absorbency of magnetic response profit system and preparation method thereof.
Background technology
The discharge wantonly of industrial production and daily life oil-polluted water, and the frequent Crude Oil at Sea leakage accident occurred to the water resource that the mankind depend on for existence cause greatly pollute while also result in energy waste.Therefore, from the sustainable development of environment and the demand of oil recovery and Water warfare recycling, all require effectively to be separated oil-polluted water.Along with going deep into of investigation and application, on the one hand, it is found that there is special infiltrating material, such as super hydrophilic/super oleophobic, super-hydrophobic/super-oleophilic material many compared to other traditional in oil water separation process not only oil but also the water-oil separating material absorbed water, its separative efficiency not only significantly improves, and greatly facilitates recovery and the Reuse of materials of follow-up oil or water.On the other hand, along with the expansion in water-oil separating materials application field and the raising of requirement, the demand of intelligent response water-oil separating material is grown with each passing day.Intelligent response water-oil separating material can produce response to the effect in outfield (as power, heat, light, magnetic field etc.), thus realizes the recovery of the controlled separation of profit External field response and material.In multiple intelligent response material, from practical application area, the water-oil separating material with magnetic response performance is such as difficult to the fields such as close waters remote-controllable operation at extreme environment application due to the foul pollution mankind shows very high potential.Meanwhile, some traditional preparation methods also also exist the deficiencies such as process steps complexity, with high costs, the water-oil separating limited amounts of material once prepared, directly have influence on material application in practice.Therefore; based on the special infiltration of material; adopt that preparation process is simple and convenient, preparation condition is gentle, with low cost, the technological means that can accomplish scale production, the high efficiency oil-water parting material that design and preparation have magnetic response performance has important actual application value and meaning.
Electrostatic spinning technique is called for short electrospinning, and it is subject to extensive concern and application as the technology efficiently preparing micro nanometer fiber grown up in the last few years.Electrospinning is the injection being used for realizing spinning solution utilizing high voltage electric field, is placed in high-voltage electrostatic field by polymer solution or melt, and charged polymer liquid is stretched under dropping in the effect of electric field Coulomb force.When electric field force is enough large, polymer solution or melt overcome capillary effect and form spurting thread.Thread solidifies along with solvent volatilization in course of injection, falls within negative pole collecting board, forms micron, the nano-scale fiber film of nonwoven cloth-like.Because electrospinning is simple to operate, can accomplish scale production, be generally used in and prepared micron, nanofiber, material relates to polymer, inorganic oxide, metal and organic/inorganic hybridization material etc.Have larger specific surface area and porosity by the tunica fibrosa obtained by electrospinning, this is not only conducive to the water-oil separating performance improving fiber felt magnetic response water-oil separating tunica fibrosa, and is easier to the recovery of material than nano particle sorbing material.
Summary of the invention
The object of this invention is to provide and a kind of there is electrospun fiber membrane of the super-hydrophobic/super-oleophilic micro-nano compound structure of magnetic response performance and preparation method thereof.
The preparation of magnetic response high efficiency oil-water defibre film provided by the present invention mainly adopts electrostatic spinning technique, specifically comprises following step:
(1) be dissolved in solvent orange 2 A by analytically pure polymer A in 20 ~ 30 DEG C of room temperature environments, be stirred well to polymer A and dissolve completely, obtain the solution of polymer A, gained solution is 10 ~ 35% containing the mass percentage of polymer A.
Described polymer A is the polymer with hydrophobic property, as any one in Kynoar, polyurethane, polystyrene, polymethyl methacrylate or polycaprolactone etc.
The solvent orange 2 A of described dissolve polymer A is analytically pure DMF, analytically pure oxolane or analytically pure chloroform etc., specifically can be selected from a kind of solvent wherein or two kinds of solvents formation mixed solvents.
(2) using the solution of above-mentioned polymer A as electrostatic spinning precursor solution, be placed in the syringe of electro-spinning equipment, high-voltage electrostatic field is applied between the metal spinning head and reception substrate of syringe, high-pressure electrostatic field voltage is 10 ~ 35KV, the diameter of metal spinning head is 0.4mm ~ 1.8mm, and reception substrate is non-woven fabrics, steel wire, aluminium foil etc.Adjustment metal spinning head and the distance received between substrate are 10 ~ 35cm, and the high-voltage electrostatic field of applying makes electrospinning precursor solution produce jet under electrostatic interaction, are receiving electrospun fiber membrane substrate obtaining random arrangement, uniform fold.In described electrospun fiber membrane, fibre diameter is 150nm ~ 800nm.
(3) configure the Tris salting liquid (DOPA-Tris) of dopamine, regulate it to be alkalescent, preferable ph is 7.5 ~ 8.5.
(4) magnetic nano-particle is added in above-mentioned DOPA-Tris salting liquid, and magnetic nano-particle is uniformly dispersed in the solution.Wherein, the magnetic nano-particle added is the diameter of the described magnetic nano-particles such as magnetic oxide such as iron, cobalt, nickel is 30nm ~ 80nm.
(5) electrospun fiber membrane obtained for step (2) is immersed in by step (4) prepare containing in the alkalescent DOPA-Tris solution of magnetic nano-particle, stirring reaction 12h.Wherein, the quality adding magnetic particle is no more than 50% of electrospinning fibre film quality.In process, dopamine is spontaneous polymerization in alkaline environment, all can form one deck viscosity at the fiber of electrospun fiber membrane and magnetic nano particle sub-surface and gather dopamine film, magnetic nano-particle and electrospun fiber membrane be adhered to, obtains magnetic response high efficiency oil-water defibre film of the present invention.
Magnetic response high efficiency oil-water defibre film prepared by the present invention has the composite mesh loose structure be made up of micron or nanofiber, and the micro-meter scale fiber mesh be interweaved and the particle of nanoscale have convexed to form coarse surface texture.This water-oil separating tunica fibrosa not only in atmosphere to external world magnetic field there is response performance, in oil mixing with water system, too there is magnetic field responsiveness.In atmosphere 150 ° are greater than to the contact angle of water, to the contact angle of oil close to 0 °, there is the special wellability of super-hydrophobic super-oleophylic.Substrate can be received by non-woven fabrics etc. after described water-oil separating tunica fibrosa electrospinning to peel off, can self-supporting be realized.
The magnetic responsiveness remote-controllable that this magnetic response high efficiency oil-water defibre film can be used for oil in oil-polluted water efficiently absorbs the aspects such as removal and water body purification fast.Meanwhile, this water-oil separating tunica fibrosa has selective height in profit system, separative efficiency is high, speed is fast, all have the features such as good separation removal effect to oil water mixtures such as diesel oil, gasoline, silicone oil, machine oil, is applicable to the aspects such as water body purification.
Water-oil separating tunica fibrosa provided by the invention is using intensity more much higher kind of polymer as primary raw material, and the oil of absorption can be separated out by centrifugal, extruding etc. physics or chemical method after using, material can realize repeatedly reusing.This preparation method is simple, and experimental implementation is easy, can accomplish scale production.
Accompanying drawing explanation
Fig. 1 is electrostatic spinning apparatus schematic diagram of the present invention.
In figure: 1. for liquid syringe; 2. metal spinning head; 3. electrospinning fibre; 4. receive substrate; 5. high voltage source.
Fig. 2 is that 8,000 times of topography scan electromicroscopic photograph is amplified on magnetic response water-oil separating electrospun fiber membrane surface prepared by embodiment 1;
Fig. 3 is the photo that the magnetic response water-oil separating electrospun fiber membrane of embodiment 1 preparation is adsorbed on additional magnet;
Fig. 4 be the embodiment of the present invention 1 in atmosphere water droplet (2 μ L) at the contact angle photo on magnetic response water-oil separating electrospun fiber membrane surface of preparation, contact angle=162 ° of water.
Fig. 5 be embodiment 1 in atmosphere oil droplet (2 μ L) at the contact angle photo on magnetic response water-oil separating electrospun fiber membrane surface of preparation, contact angle=0 ° of oil.
Fig. 6 is that the magnetic response water-oil separating electrospun fiber membrane of embodiment 1 preparation is for separating of oil mixing with water system photo before the separation of oil water mixture.
Fig. 7 is the effect photo of magnetic response water-oil separating electrospun fiber membrane for separating of water body and magnet adsorption sample after the experiment of oil water mixture of embodiment 1 preparation.
Detailed description of the invention
Below in conjunction with drawings and Examples, the present invention is elaborated, but the present invention is not limited thereto.
Reagent and material described in following embodiment, if no special instructions, all can obtain from commercial channels.
embodiment 1
(1) Kynoar (weight average molecular weight is 170,000) is dissolved in analytically pure DMF solution, is configured to the DMF solution that mass fraction is 18% Kynoar.
(2) N of Kynoar step (1) configured, dinethylformamide solution supplies in liquid syringe 1 as electrostatic spinning apparatus (shown in Fig. 1), select metal spinning head 2 diameter to be 0.6mm, high voltage source 5 provides supply voltage to be 20KV.Distance between adjustment metal spinning head 2 and reception substrate 4 is at 25cm.In preparation process, electrospun solution produces jet under electrostatic interaction, when electric field force is higher than the N of Kynoar, during the surface tension of dinethylformamide solution (electrospun solution), electrospun solution is stretched refinement, along with solvent N in dropping process, the volatilization of dinethylformamide, forms Kynoar electrospinning fibre 3.This electrospinning fibre 3 diameter is about 150nm, and the stacking film forming uniform fold of fiber random arrangement receives in substrate 4 in non-woven fabrics etc.
(3) configure the dopamine Tris salting liquid (DOPA-Tris) of 10mmol, regulate it to be alkalescent, pH=7.5.
(4) diameter is about the magnetic nano ferroferric oxide (Fe of 30nm
3o
4) particle adds in the DOPA-Tris salting liquid that step (3) configures, stir and magnetic nano-particle is uniformly dispersed in the solution.
(5) electrospun fiber membrane obtained for step (2) is immersed in by step (4) prepare containing magnetic Fe
3o
4in the alkalescent DOPA-Tris solution of nano particle, stirring reaction 12h.Wherein, magnetic Nano Fe is added
3o
4the mass ratio of particle and polyvinylidene fluoride film is 1:4.In stirring reaction process, dopamine is spontaneous polymerization in alkaline environment, in polyvinylidene fluoride and magnetic Fe
3o
4nanoparticle surface forms one deck viscosity and gathers dopamine film, magnetic nano-particle and electrospinning fibre is adhered to.
Described electrospinning device structure as shown in Figure 1, comprises for liquid syringe 1, metal spinning head 2, receives substrate 4, between reception substrate 4 and metal spinning head 2, connect high voltage source 5, and the electrospinning fibre 3 sprayed from metal spinning head 2 is undertaken on reception substrate 4 surface.
In the tunica fibrosa that this said method prepares, the fibre diameter of Kynoar is about 150nm, magnetic Nano Fe attached to it
3o
4owing to there is polymer overmold to a certain degree in particle, particle size is about 40nm, and magnetic Nano Fe
3o
4particles coat is in polyvinylidene fluoride surface, and as shown in Figure 2, fiber is nonwoven cloth-like intertexture random distribution, fiber surface attachment Fe
3o
4nano particle.As shown in Figure 3, by magnet near prepared electrospun fiber membrane, its can adsorb by magnet, illustrate that the water-oil separating electrospun fiber membrane prepared by the present invention has magnetic response performance.Measure in atmosphere water droplet (2 μ L) divides tunica fibrosa surface contact angle CA=162 ° (as Fig. 4) at described magnetic response profit, measure in atmosphere oil droplet (2 μ L) divides tunica fibrosa surface contact angle OCA=0 ° (as Fig. 5) at described magnetic response profit, magnetic response water-oil separating tunica fibrosa prepared by visible the present invention has the special wellability of super-hydrophobic super-oleophylic.
Above-mentioned magnetic response water-oil separating tunica fibrosa is put into oil mixing with water system (as shown in Figure 6), and demonstration oil wherein used is the machine oil after oil red O stain.This water-oil separating composite cellulosic membrane has selection removal capacity (as shown in Figure 7) to the oil in oil mixing with water system.
embodiment 2
(1) by polystyrene, (weight average molecular weight is 230,000) analytically pure N is dissolved in, in dinethylformamide/oxolane mixed solution, wherein N, the mass ratio of dinethylformamide and oxolane is 9:1, be configured to DMF/tetrahydrofuran solution that mass fraction is the polystyrene of 25%.
(2) DMF/tetrahydrofuran solution of polystyrene step (1) configured is placed in the confession liquid syringe of electrostatic spinning apparatus, and select metal spinnerette diameters to be 1.0mm, applying voltage is 25KV.Distance between adjustment metal spinning head and reception substrate is at 30cm.In preparation process, above-mentioned electrospun solution produces jet under electrostatic interaction, when electric field force is higher than the N of polystyrene, during the surface tension of dinethylformamide/tetrahydrofuran solution, solution is stretched refinement, along with solvent N in dropping process, the volatilization of dinethylformamide/oxolane, forms polystyrene electrospun fiber membrane.In this electrospun fiber membrane, fibre diameter is about 350nm, and the stacking film forming uniform fold of fiber random arrangement receives in substrate in non-woven fabrics etc.
(3) configure the dopamine Tris salting liquid (DOPA-Tris) of 8.5mmol, regulate it to be alkalescent, pH=8.
(4) magnetic Nano nickel oxide (NiO) particle diameter being about 50nm adds in the DOPA-Tris salting liquid that step (3) configures, and stirs and magnetic nano-particle is uniformly dispersed in the solution.
(5) electrospun fiber membrane obtained for step (2) is immersed in by step (4) prepare containing in the alkalescent DOPA-Tris solution of magnetic Nano NiO particle, stirring reaction 12h.Wherein, the mass ratio adding magnetic Nano NiO particle and styroflex film is 1:3.In stirring reaction process, dopamine is spontaneous polymerization in alkaline environment, form one deck viscosity at styroflex and magnetic Nano NiO particle surface and gather dopamine film, magnetic nano-particle and electrospinning fibre are adhered to, obtain magnetic response high efficiency oil-water defibre film of the present invention.
In this tunica fibrosa, the fibre diameter of polystyrene is about 350nm, owing to there is polymer overmold to a certain degree in magnetic Nano NiO particle attached to it, particle size is about 65nm, and magnetic Nano NiO particles coat is in styroflex surface, and fiber is nonwoven cloth-like intertexture random distribution.By magnet near prepared electrospun fiber membrane, its can adsorb by magnet, illustrate that the water-oil separating electrospun fiber membrane prepared by the present invention has magnetic response performance.Measure water droplet (2 μ L) divides tunica fibrosa surface contact angle CA=156 ° at described magnetic response profit in atmosphere, measure oil droplet (2 μ L) divides tunica fibrosa surface contact angle OCA=0 ° at described magnetic response profit in atmosphere, magnetic response water-oil separating tunica fibrosa prepared by visible the present invention has the special wellability of super-hydrophobic super-oleophylic.
Above-mentioned magnetic response water-oil separating tunica fibrosa is put into oil mixing with water system, and demonstration oil wherein used is the machine oil after oil red O stain.This water-oil separating composite cellulosic membrane has selection removal capacity to the oil in oil mixing with water system.
embodiment 3
(1) polyurethane (Sigma-Aldirich) is dissolved in analytically pure DMF solution, is configured to the DMF solution that mass fraction is 35% polyurethane.
(2) the DMF solution of polyurethane step (1) configured is placed in the confession liquid syringe of electrostatic spinning apparatus, and select metal spinnerette diameters to be 1.8mm, applying voltage is 35KV.Distance between adjustment spinning head and reception substrate is at 35cm.In preparation process, above-mentioned electrospun solution produces jet under electrostatic interaction, when the surface tension of electric field force higher than the DMF solution of polyurethane, solution is stretched refinement, along with the volatilization of solvent DMF in dropping process, form polyurethane electrospun fiber membrane.In this electrospun fiber membrane, fibre diameter is about 800nm, and the stacking film forming uniform fold of fiber random arrangement receives in substrate in steel wire etc.
(3) configure the dopamine Tris salting liquid (DOPA-Tris) of 12mmol, regulate it to be alkalescent, pH=8.5.
(4) diameter is about the magnetic Nano cobaltosic oxide (Co of 80nm
3o
4) particle adds in the DOPA-Tris salting liquid that step (3) configures, stir and magnetic nano-particle is uniformly dispersed in the solution.
(5) electrospun fiber membrane obtained for step (2) is immersed in by step (4) prepare containing magnetic Nano Co
3o
4in the alkalescent DOPA-Tris solution of particle, stirring reaction 12h.Wherein, magnetic Nano Co is added
3o
4the mass percent that film tieed up by particle and polyurethane is 1:5.In stirring reaction process, dopamine is spontaneous polymerization in alkaline environment, at styroflex and magnetic Nano Co
3o
4particle surface forms one deck viscosity and gathers dopamine film, magnetic nano-particle and electrospinning fibre is adhered to, and forms final magnetic response high efficiency oil-water defibre film.
In this tunica fibrosa, the fibre diameter of polyurethane is about 800nm, magnetic Nano Co attached to it
3o
4owing to there is polymer overmold to a certain degree in particle, particle size is about 92nm, and magnetic Nano Co
3o
4particle is coated on polyurethane fiber surface, and fiber is nonwoven cloth-like intertexture random distribution.By magnet near prepared electrospun fiber membrane, its can adsorb by magnet, illustrate that the water-oil separating electrospun fiber membrane prepared by the present invention has magnetic response performance.Measure water droplet (2 μ L) divides tunica fibrosa surface contact angle CA=150 ° at described magnetic response profit in atmosphere, measure oil droplet (2 μ L) divides tunica fibrosa surface contact angle OCA=0 ° at described magnetic response profit in atmosphere, magnetic response water-oil separating tunica fibrosa prepared by visible the present invention has the special wellability of super-hydrophobic super-oleophylic.
Above-mentioned magnetic response water-oil separating tunica fibrosa is put into oil mixing with water system, and demonstration oil wherein used is the machine oil after oil red O stain.This water-oil separating composite cellulosic membrane has selection removal capacity to the oil in oil mixing with water system.
embodiment 4
(1) polycaprolactone (weight average molecular weight 270,000) is dissolved in analytically pure chloroform soln, is configured to the chloroform soln that mass fraction is 10% polycaprolactone.
(2) chloroform soln of polycaprolactone step (1) configured is placed in the confession liquid syringe of electrostatic spinning apparatus, and select metal spinnerette diameters to be 0.4mm, applying voltage is 10KV.Distance between adjustment spinning head and reception substrate is at 10cm.In preparation process, above-mentioned electrospun solution produces jet under electrostatic interaction, when the surface tension of electric field force higher than the chloroform soln of polycaprolactone, solution is stretched refinement, along with the volatilization of solvent chloroform in dropping process, forms polycaprolactone electrospinning fibre.This fibre diameter is about 200nm, and the stacking film forming uniform fold of fiber random arrangement receives in substrate in aluminium foil etc., obtains electrospun fiber membrane.
(3) configure the dopamine Tris salting liquid (DOPA-Tris) of 10mmol, regulate it to be alkalescent, pH=8.5.
(4) diameter is about the magnetic nano ferroferric oxide (Fe of 50nm
3o
4) particle adds in the DOPA-Tris salting liquid that step (3) configures, stir and magnetic nano-particle is uniformly dispersed in the solution.
(5) electrospun fiber membrane obtained for step (2) is immersed in by step (4) prepare containing magnetic nano ferroferric oxide (Fe
3o
4) particle alkalescent DOPA-Tris solution in, stirring reaction 12h.Wherein, magnetic Nano Fe is added
3o
4the mass ratio that particle and polycaprolactone tie up film is 1:1.In process, dopamine is spontaneous polymerization in alkaline environment, at polycaprolactone fiber and magnetic Nano Fe
3o
4particle surface forms one deck viscosity and gathers dopamine film, magnetic nano-particle and electrospinning fibre is adhered to, and obtains final magnetic response high efficiency oil-water defibre film of the present invention.
In this tunica fibrosa, the fibre diameter of polycaprolactone is about 200nm, magnetic Nano Fe attached to it
3o
4owing to there is polymer overmold to a certain degree in particle, particle size is about 56nm, and magnetic Nano Fe
3o
4particle is coated on polycaprolactone fiber surface, and fiber is nonwoven cloth-like intertexture random distribution.By magnet near prepared electrospun fiber membrane, its can adsorb by magnet, illustrate that the water-oil separating electrospun fiber membrane prepared by the present invention has magnetic response performance.Measure water droplet (2 μ L) divides tunica fibrosa surface contact angle CA=158 ° at described magnetic response profit in atmosphere, measure oil droplet (2 μ L) divides tunica fibrosa surface contact angle OCA=0 ° at described magnetic response profit in atmosphere, magnetic response water-oil separating tunica fibrosa prepared by visible the present invention has the special wellability of super-hydrophobic super-oleophylic.
Above-mentioned magnetic response water-oil separating tunica fibrosa is put into oil mixing with water system, and demonstration oil wherein used is the machine oil after oil red O stain.This water-oil separating composite cellulosic membrane has selection removal capacity to the oil in oil mixing with water system.
embodiment 5
(1) polymethyl methacrylate (weight average molecular weight 300,000) is dissolved in analytically pure DMF solution, is configured to the DMF solution that mass fraction is 20% polymethyl methacrylate.
(2) the DMF solution of polymethyl methacrylate step (1) configured is placed in the confession liquid syringe of electrostatic spinning apparatus, and select metal spinnerette diameters to be 0.8mm, applying voltage is 30KV.Distance between adjustment spinning head and reception substrate is at 20cm.In preparation process, above-mentioned electrospun solution produces jet under electrostatic interaction, when electric field force is higher than the N of polymethyl methacrylate, during the surface tension of dinethylformamide solution, solution is stretched refinement, along with solvent N in dropping process, the volatilization of dinethylformamide, forms polymethyl methacrylate electrospinning fibre.This fibre diameter is about 500nm, and the stacking film forming uniform fold of fiber random arrangement receives in substrate in aluminium foil etc., obtains electrospun fiber membrane.
(3) configure the dopamine Tris salting liquid (DOPA-Tris) of 10mmol, regulate it to be alkalescent, pH=8.5.
(4) diameter is about the magnetic nano ferroferric oxide (Fe of 80nm
3o
4) particle adds in the DOPA-Tris salting liquid that step (3) configures, stir and magnetic nano-particle is uniformly dispersed in the solution.
(5) electrospun fiber membrane obtained for step (2) is immersed in by step (4) prepare containing magnetic nano ferroferric oxide (Fe
3o
4) particle alkalescent DOPA-Tris solution in, stirring reaction 12h.Wherein, magnetic Nano Fe is added
3o
4the mass ratio of particle and polymethyl methacrylate tunica fibrosa is 1:3.In stirring reaction process, dopamine is spontaneous polymerization in alkaline environment, at polymethyl methacrylate fiber and magnetic Nano Fe
3o
4particle surface forms one deck viscosity and gathers dopamine film, magnetic nano-particle and electrospinning fibre is adhered to, and obtains magnetic of the present invention and answers high efficiency oil-water defibre film.
In this tunica fibrosa, the fibre diameter of polymethyl methacrylate is about 500nm, magnetic Nano Fe attached to it
3o
4owing to there is polymer overmold to a certain degree in particle, particle size is about 85nm, and magnetic Nano Fe
3o
4particle is coated on polymethyl methacrylate fiber surface, and fiber is nonwoven cloth-like intertexture random distribution.By magnet near prepared electrospun fiber membrane, its can adsorb by magnet, illustrate that the water-oil separating electrospun fiber membrane prepared by the present invention has magnetic response performance.Measure water droplet (2 μ L) divides tunica fibrosa surface contact angle CA=155 ° at described magnetic response profit in atmosphere, measure oil droplet (2 μ L) divides tunica fibrosa surface contact angle OCA=0 ° at described magnetic response profit in atmosphere, magnetic response water-oil separating tunica fibrosa prepared by visible the present invention has the special wellability of super-hydrophobic super-oleophylic.
Above-mentioned magnetic response water-oil separating tunica fibrosa is put into oil mixing with water system, and demonstration oil wherein used is the machine oil after oil red O stain.This water-oil separating composite cellulosic membrane has selection removal capacity to the oil in oil mixing with water system.
Claims (9)
1. a preparation method for magnetic response high efficiency oil-water defibre film, is characterized in that: concrete steps are,
The first step, is dissolved in solvent orange 2 A by analytically pure polymer A in 20 ~ 30 DEG C of room temperature environments, is stirred well to polymer A and dissolves completely, obtains the solution of polymer A, and gained solution is 10 ~ 35% containing the mass percentage of polymer A;
Second step, using the solution of above-mentioned polymer A as electrostatic spinning precursor solution, be placed in the syringe of electro-spinning equipment, high-voltage electrostatic field is applied between the metal spinning head and reception substrate of syringe, high-pressure electrostatic field voltage is 10 ~ 35KV, the diameter of metal spinning head is 0.4mm ~ 1.8mm, adjustment metal spinning head and the distance received between substrate are 10 ~ 35cm, the high-voltage electrostatic field applied makes electrospinning precursor solution produce jet under electrostatic interaction, is receiving electrospun fiber membrane substrate obtaining random arrangement, uniform fold;
3rd step, the Tris salting liquid of configuration dopamine, regulates it to be alkalescent;
4th step, adds magnetic nano-particle in the Tris salting liquid of above-mentioned dopamine, and magnetic nano-particle is uniformly dispersed in the solution;
5th step, the electrospun fiber membrane obtained by second step is immersed in the Tris salting liquid of the alkalescent dopamine containing magnetic nano-particle prepared by the 4th step, stirring reaction 12h; In stirring reaction process, dopamine is spontaneous polymerization in alkaline environment, all can form one deck viscosity at the fiber of electrospun fiber membrane and magnetic nano particle sub-surface and gather dopamine film, magnetic nano-particle and electrospun fiber membrane be adhered to, obtains magnetic response high efficiency oil-water defibre film.
2. preparation method according to claim 1, is characterized in that: the quality adding magnetic particle in the 4th step is no more than 50% of electrospinning fibre film quality.
3. preparation method according to claim 1, is characterized in that: described polymer A is any one in Kynoar, polyurethane, polystyrene, polymethyl methacrylate or polycaprolactone;
The solvent orange 2 A of described dissolve polymer A is analytically pure DMF, analytically pure oxolane or analytically pure chloroform, is specifically selected from a kind of solvent wherein or two kinds of solvents formation mixed solvents.
4. preparation method according to claim 1, is characterized in that: described reception substrate is non-woven fabrics, steel wire or aluminium foil.
5. preparation method according to claim 1, is characterized in that: in the described electrospun fiber membrane of second step, fibre diameter is 150nm ~ 800nm.
6. preparation method according to claim 1, is characterized in that: described magnetic nano-particle is the magnetic oxides such as iron, cobalt, nickel; The diameter of described magnetic nano-particle is 30nm ~ 80nm.
7. preparation method according to claim 1, is characterized in that: the Tris salting liquid pH value of described dopamine is 7.5 ~ 8.5.
8. a magnetic response high efficiency oil-water defibre film, it is characterized in that: described tunica fibrosa has magnetic field responsiveness in air and oil mixing with water system, in atmosphere 150 ° are greater than to the contact angle of water, to the contact angle of oil close to 0 °, there is the special wellability of super-hydrophobic super-oleophylic; Can be peeled off by reception substrate after described water-oil separating tunica fibrosa electrospinning, can self-supporting be realized.
9. a kind of magnetic response high efficiency oil-water defibre film according to claim 8, it is characterized in that: the fibre diameter of this tunica fibrosa is 150nm ~ 800nm, magnetic nano-particle attached to it is of a size of 40 ~ 92nm, and magnetic nanoparticle is coated on fiber surface, fiber is nonwoven cloth-like intertexture random distribution.
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