CN109722722A - A kind of equal hole nanofiber and its preparation method and application - Google Patents
A kind of equal hole nanofiber and its preparation method and application Download PDFInfo
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- CN109722722A CN109722722A CN201811388347.2A CN201811388347A CN109722722A CN 109722722 A CN109722722 A CN 109722722A CN 201811388347 A CN201811388347 A CN 201811388347A CN 109722722 A CN109722722 A CN 109722722A
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Abstract
The present invention provides a kind of preparation methods of equal hole nanofiber, comprising: provides the solution of polymer fiber and block copolymer containing, polymer fiber includes the first polymer fiber and/or the amine-modified second polymer fiber of DOPA of crosslinking；Entire polymeric fiber surface is set to adhere to the solution of one layer of block copolymer containing by the way of immersion or spraying, Uniform pore structure is formed on the surface that the surface of polymer fiber forms block copolymer layer and block copolymer layer after standing, obtains equal hole nanofiber.The preparation method is simple, easy to operate, process control, and the pore structure that the surface of equal hole nanofiber obtained has regularity high, mesoporous is up to 98% or more, has high specific surface area, and performance is stablized, and is conducive to the absorption and transmission to substance.
Description
Technical field
The present invention relates to technical field of polymer materials, in particular to a kind of equal hole nanofiber and preparation method thereof and answer
With.
Background technique
Porous nano-fibre as a kind of novel high polymer material, adsorbing separation field have excellent mass transfer rate and
Load factor.Currently, one-step method and multistep processes is mostly used to prepare porous nano-fibre.It is to pass through that one-step method, which prepares porous nano-fibre,
Hydrophobic polymer is dissolved in high volatile solvent, high molecular fine liquid stream is high in high-voltage electrostatic field in electrospinning
Speed stretches and solvent quickly volatilizees, and promotes the reduction of fiber surface temperature to lead to that Thermal inactive (TIPS) occurs, forms polymer
Enrichment phase and solvent-rich phase, the polymer-rich phase solidified skeleton for ultimately forming fiber, and solvent-rich phase forms fiber
Duct；Simultaneously when the vapor in air encounters the lower fiber surface of temperature, particle water can be liquefied as and be deposited on fiber table
Face, that is, so-called phase separation (NIPS).One-step method prepares the shortcomings that nano-porous fiber and is pore structure
The repetitive rate of inadequate, the porous pattern of regularity is not high；Secondly, the volatilization in electrostatic spinning process non-solvent is difficult to control, influence
Pore-forming.It is to dissolve one or more polymer in the solution that multistep processes, which prepares porous nano-fibre, can also be added a certain amount of
Pore-foaming agent (such as inorganic salts sodium chloride, sodium bicarbonate) prepares spinning solution, polymer fiber is obtained after electrospinning, then
By aftertreatment technology, one or more of them ingredient is removed, to form the fiber of porous structure.It is more that multistep processes prepares nanometer
The shortcomings that hole fiber, which is to operate, to be not easy, especially aftertreatment technology, needs to be related to solvent extraction, thermal degradation and ultraviolet light
The modes such as crosslinking Treatment are difficult to be controlled degree for the treatment of；Secondly aftertreatment technology removal partial polymer can destroy fiber
The continuity and integrity degree of film, mechanical property, stability and other reduced performances of fiber entirety.
Therefore, it is lacked in view of existing for current porous nano-fibre preparation method and the porous nano-fibre being prepared
It falls into, needs a kind of easy to operate, porous nano-fibre preparation method of process control, and porous nano-fibre obtained has height
The whole pore structure of metric, large specific surface area, performance are stablized.
Summary of the invention
In view of this, the present invention provides a kind of equal hole nanofiber, the pore structure that surface has height regular compares table
Area is big, and stability is good, to improve absorption to substance, transmittability, in catalysis industry, biological medicine, sensor, micro- anti-
It answers and is with a wide range of applications in device field.
In a first aspect, the present invention provides a kind of preparation methods of equal hole nanofiber, comprising:
The solution of polymer fiber and block copolymer containing is provided, the polymer fiber includes the first polymerization of crosslinking
Fibres and/or the amine-modified second polymer fiber of DOPA, the first polymer fiber and the second polymer fiber
Material independently selected from polymethyl methacrylate, polyacrylonitrile, polystyrene, polyvinylpyrrolidone and Kynoar
At least one of；The block copolymer includes polymethyl methacrylate, polyacrylonitrile, polystyrene, polyvinyl pyrrole
Alkanone, Kynoar, poly- 4-vinylpyridine, polyethylene glycol oxide, polymethylacrylic acid N, N- dimethylamino ethyl ester, polylactic acid
With at least two polymer blocks in polyisoprene；
The entire polymeric fiber surface is set to adhere to one layer of block copolymer containing by the way of immersion or spraying
Solution, the surface of block copolymer layer and the block copolymer layer is formed on the surface of the polymer fiber after standing
Uniform pore structure is formed, equal hole nanofiber is obtained.
In the present invention, after immersion or spraying, the surface of the polymer fiber is coated with described containing block copolymerization
The solution of object has chemical bond between that is, described polymer fiber and the block copolymer, by self assembly and non-solvent
Cause mutually separates, and can form block copolymer layer, the table of block copolymer layer on the surface of the polymer fiber after standing
Face forms equally distributed pore structure, ultimately forms the block copolymer layer of coated polymer fiber, and the block copolymer
The surface of layer has Uniform pore structure to get equal hole nanofiber is arrived.The surface of the equal hole nanofiber has height regular
Pore structure, performance stablizes, and has high specific surface area, to improve absorption of the fiber to substance, transmittability.
Preparation method of the invention solves the fiber mesoporous that one-step method is prepared compared with one-step method in the prior art
The not high problem of the repetitive rate of inadequate, the porous pattern of structural regularity, and preparation method of the invention is simple, easy to operate, mistake
Journey is controllable, is conducive to pore-forming；Compared with multistep processes, preparation method of the invention had not only needed the addition of pore-foaming agent, but also did not needed
Complicated aftertreatment technology, can be obtained the fiber with the regular pore structure of height by shirtsleeve operation, will not destroy fibre
Previous level can be kept by tieing up whole continuity and integrity degree, mechanical property, stability and other performances of fiber entirety.
Optionally, the preparation method of the polymer fiber can be, but not limited to are as follows:
First polymer is dissolved in organic solvent and is configured to the first spinning solution, is obtained after electrostatic spinning and vacuum drying
The first polymer fiber, then the first polymer fiber is crosslinked, the first polymer fiber being crosslinked or
Second polymer is dissolved in organic solvent and is configured to the second spinning solution, is obtained after electrostatic spinning and vacuum drying
The second polymer fiber, then the second polymer fiber is placed in dopamine modification liquid and is impregnated, it is obtained after washed
The second polymer fiber of poly-dopamine modification.
In the present invention, the material of the first polymer fiber and the second polymer fiber is independently selected from poly- first
At least one of base methyl acrylate, polyacrylonitrile, polystyrene, polyvinylpyrrolidone and Kynoar.
In the present invention, the organic solvent can dissolve the first polymer and second polymer.Optionally, described
Organic solvent includes at least one in dimethyl sulfoxide, chloroform, acetone, N,N-dimethylformamide and DMAC N,N' dimethyl acetamide
Kind.Specifically, the organic solvent can be, but not limited to as N, N- dimethyl when the second polymer is Kynoar
Formamide and acetone, wherein n,N-Dimethylformamide and the volume ratio of acetone are 9:(1-6).
Optionally, the mass concentration of first polymer described in first spinning solution is 15%-40%.It is further optional
, the mass concentration of first polymer described in first spinning solution is 20%-35%.Specifically, first spinning solution
Described in the mass concentration of first polymer can be, but not limited to be 18%, 22%, 27% or 35%.When the first polymer
When mixing for multiple polymers, the total mass concentration of multiple polymers is 15%-40%.
Optionally, the mass concentration of second polymer described in second spinning solution is 15%-40%.It is further optional
, the mass concentration of second polymer described in second spinning solution is 20%-35%.Specifically, second spinning solution
Described in the mass concentration of second polymer can be, but not limited to be 15%, 24%, 30% or 37%.When the second polymer
When mixing for multiple polymers, the total mass concentration of multiple polymers is 15%-40%.
In the present invention, the organic solvent in first spinning solution with it is described organic in second spinning solution
Solvent may be the same or different.
Optionally, 20 DEG C -35 DEG C, humidity 20%-80% of the spinning temperature of the electrostatic spinning, sample introduction speed are
0.4ml/h-1.8ml/h。
Optionally, the voltage of the electrostatic spinning is 10kV-30kV, and roller rotation rate is that 50 turns/min-200 turns/min.
Optionally, the vacuum drying temperature is 40 DEG C -80 DEG C, drying time 6h-24h.
Optionally, the crosslinking includes at least one of chemical crosslinking and crosslinking with radiation.It is further alternative, describedization
Crosslinking is learned to impregnate 0.5h-10h in crosslinking agent.Further optional, the crosslinking agent includes that organic peroxide is handed over
Join at least one of agent, silane-type cross-linking agent, nitrine class crosslinking agent.It is further alternative, the technique item of the crosslinking with radiation
Part is in 10 μ W/cm2-100μW/cm20.5h-5h is irradiated under ultraviolet ray intensity.
Optionally, the dopamine modification liquid includes the aqueous solution containing dehydrated alcohol, ammonium hydroxide and Dopamine hydrochloride.It is described
Dopamine modification liquid specifically can be, but not limited to containing 5mL-15mL dehydrated alcohol, 0.3mL-0.8mL ammonium hydroxide, 0.05g-
0.25g Dopamine hydrochloride and 15mL-25mL distilled water.
Optionally, the soaking temperature impregnated in dopamine modification liquid that is placed in is 15 DEG C -35 DEG C, soaking time 6h-
24h.Specifically can be, but not limited to it is described be placed in dopamine modification liquid impregnate further include 50 turns/min-150 of revolving speed turn/
It is placed in the dopamine modification liquid and impregnates under the conditions of min.
In the present invention, it is more when second spinning solution is placed in dopamine modification liquid through the fiber that electrostatic spinning obtains
In fiber surface autohemagglutination occurs for bar amine, forms the second polymer fiber of poly-dopamine modification, wherein the adjacent benzene of dopamine
Diphenol and amido functional group can establish covalent and non-covalent interaction with organic and inorganic surface, to make poly-dopamine
Cross-linked layer strength is attached on second polymer fiber surface.
Optionally, it is described it is washed after obtain poly-dopamine modification the second polymer fiber, comprising: through water washing
It is repeatedly colourless to aqueous solution, and in aqueous isopropanol after immersion 10min-30min, then through water washing 3-5 times, obtain poly- DOPA
The amine-modified second polymer fiber.Further optional, the mass concentration of isopropanol is in the aqueous isopropanol
15%-30%.In the present invention, aqueous isopropanol is lesser poly- more for removing the second polymer fiber surface degree of polymerization
Bar amine and unreacted dopamine.
In the present invention, the block copolymer is that the segment alternating polymerization different by chemical structure, property is different forms
Copolymer.The block copolymer include polymethyl methacrylate, polyacrylonitrile, polystyrene, polyvinylpyrrolidone,
Kynoar, poly- 4-vinylpyridine, polyethylene glycol oxide, polymethylacrylic acid N, N- dimethylamino ethyl ester, polylactic acid and poly-
At least two polymer blocks in isoprene.
Optionally, containing in the block copolymer has same functional group with the material of the first polymer fiber
Polymer blocks.In the present invention, the polymer blocks in the material and block copolymer of first polymer fiber contain identical
When functional group, repulsive interaction is not generated because property is identical, so that the first polymer for being more advantageous to block copolymer and crosslinking is fine
Dimension combines.It is further alternative, the first polymer is contained in the block copolymer.In the present invention, second polymer
The second polymer fiber being prepared obtains the second polymer fiber of poly-dopamine modification after impregnating in dopamine solution,
Poly-dopamine can generate chemical bond with the group in the block copolymer, so that it can be preferably in conjunction with embedding
Section copolymer.
Optionally, the block copolymer include polystyrene-poly 4-vinylpyridine block copolymer (PS-b-P4VP),
Polystyrene-poly ethylene oxide block copolymer (PS-b-PEO), polystyrene-poly methacrylic N, N-dimethylamino second
Ester block copolymer (PS-b-PDMAEMA), polystyrene-poly lactic acid block copolymer (PS-b-PLA), polyisoprene-are poly-
The poly- 4-vinylpyridine block copolymer (PI-b-PS-b-P4VP) of styrene-, Kynoar-polyvinylpyrrolidone block
Copolymer (PVDF-b-PVP), polyethylene glycol oxide-polyacrylonitrile block copolymer (PEO-b-PAN), the poly- methyl of polyethylene glycol oxide-
At least one of methyl acrylate block copolymer (PEO-b-PMMA).
Optionally, the concentration of the block copolymer in the solution of the block copolymer containing is 1%-10%.Into one
Step is optional, the concentration of the block copolymer in the solution of the block copolymer containing be 2%-9%, 2%-8%,
3.5%-8%.Specifically, the concentration of the block copolymer in the solution of the block copolymer containing can be, but not limited to for
1%, 2.5%, 5%, 7.3%, 9.5%.
Optionally, the solvent in the solution of the block copolymer containing includes tetrahydrofuran, Isosorbide-5-Nitrae-dioxane, N, N- bis-
At least one of methylformamide and chloroform.When the solvent in the solution of the block copolymer containing be tetrahydrofuran,
When two or more in Isosorbide-5-Nitrae-dioxane, n,N-Dimethylformamide and chloroform, two or more solvent quality ratios
It is not construed as limiting, the total mass concentration of two or more solvents is 1%-10%.Specifically, can be, but not limited to embedding to contain described in
When solvent in the solution of section copolymer is Isosorbide-5-Nitrae-dioxane and tetrahydrofuran, the volume of Isosorbide-5-Nitrae-dioxane and tetrahydrofuran
Than for 3:(2-7).
Optionally, the process conditions of the immersion are in 15 DEG C of -35 DEG C of immersion 2min-30min.It is further alternative, institute
The process conditions for stating immersion are in 20 DEG C of -30 DEG C of immersion 5min-25min.
Optionally, the process conditions of the spraying are in 15 DEG C of -35 DEG C of spraying 10min-60min.It is further alternative, institute
The process conditions for stating spraying are in 18 DEG C of -28 DEG C of immersion 10min-30min.
In the present invention, the solution of the block copolymer containing can be made to coat described gather by the way of immersion or spraying
Fibres are closed, purpose is for that block copolymer is made to be wrapped in polymeric fiber surface, while reducing the use of block copolymer
Amount reduces expense.
Optionally, described to stand to stand 0.5h-5h under the conditions of 5 DEG C -25 DEG C of temperature, humidity 5%-35%.Further
Optionally, described to stand as the time of repose 1h-5h under the conditions of 10 DEG C -25 DEG C of temperature, humidity 8%-35%.
In the present invention, the block copolymerization for being coated on the polymeric fiber surface is conducive to using above-mentioned standing mode
Object gradually forms order state from disordered state, is more advantageous to self assembly and phase separation, so that polymer is fine
The surface of dimension forms orderly block copolymer layer, the solvent volatilization after freeze-drying in block copolymer layer, then
The block copolymer layer with the regular pore structure of height is formed to surface, that is, forms equal hole nanofiber, performance is stablized, tool
There is high specific surface area, it is high to the absorption of substance, transmittability.
Optionally, described to obtain further including freeze-drying before equal hole nanofiber.The freeze-drying can be, but not limited to
0.5h-5h is saved in freeze dryer.
First aspect present invention provides a kind of preparation method of equal hole nanofiber, is made by the way of immersion or spraying
The solution of the block copolymer containing coats the polymer fiber, and solution evaporation, remaining block copolymer is in the polymer
Fiber surface, after standing, block copolymer gradually forms order state from disordered state, causes phase using self assembly and non-solvent
Separation forms equal hole nanofiber, the pore structure that surface has height regular, and performance is stablized, and has high specific surface area, from
And improve absorption to substance, transmittability；The preparation method is simple, easy to operate, process control, is conducive to industrialized production.
Second aspect, the present invention provides a kind of equal hole nanofiber, the equal hole nanofiber is as described in first aspect
Equal hole nanofiber preparation method be prepared, the equal hole nanofiber includes polymer fiber and is supported on described poly-
The block copolymer layer on fibres surface is closed, the equal hole nanofiber surface has Uniform pore structure, mesoporous >=98%.
In the present invention, the equal hole nanofiber by polymer fiber and is coated on the block of polymeric fiber surface
Copolymer layer composition, and the surface of block copolymer layer has Uniform pore structure.According to International Association for Pure and Applied Chemistry
Definition, aperture less than 2nm be known as micropore, aperture greater than 50nm be known as macropore, aperture 2nm-50nm be known as mesoporous
Or it is mesoporous.The mesoporous of the equal hole nanofiber is up to 98% or more, has high specific surface area, to be more advantageous to substance
Absorption and transmission.
Optionally, the aperture of the pore structure is 10nm-60nm.
Optionally, the diameter of the equal hole nanofiber is 500nm-1100nm.
Optionally, the diameter of the polymer fiber is 490nm-1000nm.
Optionally, the block copolymer layer with a thickness of 10nm-100nm.
Optionally, the specific surface area of the equal hole nanofiber is 100m2/g-1000m2/g.It is further alternative, it is described
The specific surface area of equal hole nanofiber is 200m2/g-1000m2/g、220m2/g-1000m2/g、300m2/g-1000m2/ g or
450m2/g-1000m2/g.Specifically, the specific surface area of the equal hole nanofiber can be, but not limited to as 300m2/g、500m2/
g、880m2/g、1000m2/g。
Optionally, when the polymer fiber is the second polymer fiber of poly-dopamine modification, the equal hole
Nanofiber further includes poly-dopamine layer.In the present invention, the thickness of poly-dopamine layer is only 5nm-10nm.The poly-dopamine
Layer does not observe in Electronic Speculum.
The third aspect, it is being prepared the present invention provides equal hole nanofiber preparation method as described in relation to the first aspect or
Application of the equal hole nanofiber in catalysis industry, biological medicine, sensor, microreactor field as described in second aspect.
Specifically, can be, but not limited to as the equal hole nanofiber adsorbs noble metal granule shape as catalyst carrier
Load and release or the equal hole nanofiber at catalyst or sensor or the equal hole nanofiber applied to drug
Adsorption reaction object is used as microreactor.
Beneficial effects of the present invention:
(1) the present invention provides a kind of preparation methods of equal hole nanofiber, are made by the way of immersion or spraying described
The solution of block copolymer containing coats the polymer fiber, using self assembly and phase separation, forms equal hole nanometer
Fiber, the preparation method is simple, easy to operate, process control, is conducive to industrialized production；
(2) the present invention provides the pore structure that a kind of equal hole nanofiber, surface have regularity high, mesoporous is up to
98% or more, there is high specific surface area, performance is stablized, and is conducive to the absorption and transmission to substance, in catalysis industry, biology doctor
Medicine, sensor, microreactor are with a wide range of applications in field.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described.Specific embodiment described herein is only used to explain this
Invention, is not intended to limit the present invention.
Fig. 1 is the electron-microscope scanning figure of polyvinylidene fluoride made from the embodiment of the present invention 1；
Fig. 2 is the electron-microscope scanning figure of equal hole nanofiber made from the embodiment of the present invention 1, and (a) is at 1 μm of scale in Fig. 2
The electron-microscope scanning figure of lower section, (b) is the electron-microscope scanning figure under 1 μm of scale in Fig. 2, and (c) is at scale 500nm in Fig. 2
Electron-microscope scanning figure；
Fig. 3 is the surface apertures analysis chart of equal hole nanofiber made from the embodiment of the present invention 1；
Fig. 4 is the effect experiment result figure of equal hole nanofiber made from the embodiment of the present invention 1.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
Embodiment 1
A kind of preparation method of equal hole nanofiber, comprising:
Kynoar is dissolved in n,N-Dimethylformamide (DMF) and acetone and prepares spinning solution, wherein spinning solution
The mass concentration of middle Kynoar is 28%, DMF and the volume ratio of acetone is 3:1.Spinning is carried out on electrostatic spinning machine, is spun
Silk temperature is 25 DEG C, humidity 30%, and sample introduction speed is 0.7ml/h, and voltage 15kV, roller rotation rate is 100 turns/min.Spinning
The dry 12h in 40 DEG C of vacuum drying ovens afterwards, obtains polyvinylidene fluoride, as a result as shown in Figure 1, poly- inclined through electron-microscope scanning
The diameter of vinyl fluoride fiber is 800nm.
By 22.5mL distilled water, 10mL dehydrated alcohol, 0.5mL ammonium hydroxide, 0.125g Dopamine hydrochloride is uniformly mixed, makes
Polyvinylidene fluoride is placed in dopamine modified solution by dopamine modification liquid, is placed on setting shaking speed on shaking table and is
It 100 turns/min, is washed with water after 20 DEG C of immersion 12h, until after aqueous solution is colourless, then with the isopropanol water of mass fraction 15%
Solution impregnates 20min, removes unreacted dopamine, and water rinses 3-5 times, and the poly- DOPA that brownish black can be obtained is lyophilized in freeze dryer
Amine-modified polyvinylidene fluoride.
4% polystyrene-poly 4-vinylpyridine block copolymer (PS-b-P4VP) solution is prepared, wherein solvent is Isosorbide-5-Nitrae-
The polyvinylidene fluoride that poly-dopamine is modified is placed in by the mixed solvent of dioxane and tetrahydrofuran (volume ratio 7:3)
It is taken out after impregnating 10min in above-mentioned solution, the solution of excess surface is wiped with filter paper, is being placed in 20 DEG C of temperature, humidity 20%
2h is stood under part, it is freeze-dried to obtain equal hole nanofiber.Through electron-microscope scanning, as shown in Fig. 2, finding the equal hole nanofiber
Diameter be 870nm, can significantly see that the equal hole nanofiber is double-layer structure in Fig. 2 (a), be poly- inclined through detection internal layer
Vinyl fluoride fiber, outer layer are polystyrene-poly 4-vinylpyridine block copolymer, and polystyrene-poly 4-vinylpyridine block
The surface of copolymer has Uniform pore structure, in Fig. 2 shown in (c) and (d), can be clearly seen that the pore structure on surface.
The aperture of the pore structure of the equal hole nanofiber surface is measured, as a result as shown in Figure 3, it can be seen that average pore size is
34.54nm, mesoporous are up to 99%, and regularity is high.
Embodiment 2
A kind of preparation method of equal hole nanofiber, comprising:
Polyacrylonitrile is dissolved in DMF and acetone and prepares spinning solution, wherein in spinning solution polyacrylonitrile mass concentration
It is 3:2 for the volume ratio of 15%, DMF and acetone.Spinning is carried out on electrostatic spinning machine, spinning temperature is 20 DEG C, and humidity is
30%, sample introduction speed is 1ml/h, and voltage 20kV, roller rotation rate is 120 turns/min, obtains polyacrylonitrile fibre.
By 25mL distilled water, 5mL dehydrated alcohol, 0.8mL ammonium hydroxide, 0.2g Dopamine hydrochloride is uniformly mixed, and makes DOPA
Polyacrylonitrile fibre is placed in dopamine modification, is washed after impregnating 10h at 30 DEG C with water, until aqueous solution by amine modification liquid
After colourless, then with the isopropanol water solution of mass fraction 25% 15min is impregnated, removes unreacted dopamine, water rinses 3-5
Secondary, the polyacrylonitrile fibre of the poly-dopamine cladding of black can be obtained in freeze dryer freeze-drying.
It prepares 6% polystyrene-poly lactic acid block copolymer solution and sprays 50min at 20 DEG C and poly-dopamine is modified
Polyacrylonitrile fibre surface be coated with polystyrene-poly lactic acid block copolymer solution, under the conditions of 10 DEG C, humidity 10%
5h is stood, it is freeze-dried to obtain equal hole nanofiber.Through electron-microscope scanning, it is found that the diameter of the equal hole nanofiber is 600nm,
Meanwhile the aperture of its surface pore structure is measured, average pore size 40.53nm, mesoporous is up to 99%, and specific surface area is
600m2/ g, regularity are high.
Embodiment 3
A kind of preparation method of equal hole nanofiber, comprising:
Crosslinked polymethylmethacrylaparticles are dissolved in n,N-dimethylacetamide and prepare spinning solution, wherein in spinning solution
The mass concentration of crosslinked polymethylmethacrylaparticles is 35%.Spinning is carried out on electrostatic spinning machine, spinning temperature is 35 DEG C, wet
Degree is 60%, and sample introduction speed is 0.4ml/h, and voltage 10kV, roller rotation rate is 60 turns/min, is dried after spinning then at 60 DEG C of vacuum
Dry 18h, obtains crosslinked polymethylmethacrylaparticles fiber in case.
8% polystyrene-poly n,N-dimethylaminoethyl methacrylate block copolymer solution is prepared, crosslinking is poly-
Methyl methacrylate fiber is placed in above-mentioned solution and takes out after 35 DEG C of immersion 5min, and the solution of excess surface is wiped with filter paper,
It is placed under the conditions of 15 DEG C of temperature, humidity 25% again and stands 3h, obtain equal hole nanofiber.Through electron-microscope scanning, the equal Kong Na is found
The diameter of rice fiber is 950nm, and surface pore structure regularity is good, and mesoporous is up to 98.5%, specific surface area 300m2/g。
Embodiment 4
A kind of preparation method of equal hole nanofiber, comprising:
Crosslinked polystyrene is dissolved in chloroform and prepares spinning solution, wherein the quality of crosslinked polystyrene is dense in spinning solution
Degree is 22%.Spinning is carried out on electrostatic spinning machine, spinning temperature is 23 DEG C, and humidity 75%, sample introduction speed is 1.5ml/h,
Voltage is 27kV, and roller rotation rate is 180 turns/min, obtains crosslinked polystyrene fiber.
10% polyisoprene-polystrene-poly- 4-vinylpyridine block copolymer solution is prepared to spray at 30 DEG C
20min makes crosslinked polystyrene fiber surface be coated with the poly- 4-vinylpyridine block copolymer of polyisoprene-polystrene-
Solution stands 1h under the conditions of 25 DEG C, humidity 20%, freeze-dried to obtain equal hole nanofiber.Through electron-microscope scanning, discovery
The diameter of the equal hole nanofiber is 1050nm, meanwhile, the aperture of its surface pore structure is measured, aperture is respectively less than
50nm, average pore size 35.46nm, specific surface area 800m2/g。
In order to prove beneficial effects of the present invention, following effect example is carried out:
Effect example 1
The equal hole nanofiber for taking 60mg embodiment 1 to prepare is placed in chlorauric acid solution and takes out after immersion, and in boron hydrogen
Change after being restored in sodium solution, obtains the equal hole nanofiber of load gold nano grain, place it in 3mL p-nitrophenyl phenol solution
(concentration 10-5Mol/L in), the changes of contents of p-nitrophenol in solution is detected by ultraviolet-visible spectrophotometer, as a result
As shown in Figure 4, it can be seen that p-nitrophenol after 8min in solution can be completely by catalytic production hypotoxicity, degradable
Para-aminophenol shows that equal hole nanofiber provided by the invention has high specific surface area, can load a large amount of noble metals
Grain, improves whole catalytic performance, is with a wide range of applications in catalysis industry field.
Therefore, the hole that surface has regularity high is made by simple, easy to operate, process control preparation process in the present invention
Structure, mesoporous are up to 98% or more, high specific surface area, the stable equal hole nanofiber of performance, in catalysis industry, biology doctor
Medicine, sensor, microreactor are with a wide range of applications in field.
The above is a preferred embodiment of the present invention, and but it cannot be understood as to the invention patent range
Limitation.It should be pointed out that for those skilled in the art, without departing from the principle of the present invention, also
Several improvements and modifications can be made, these modifications and embellishments are also considered to be within the scope of the present invention.
Claims (10)
1. a kind of preparation method of equal hole nanofiber characterized by comprising
The solution of polymer fiber and block copolymer containing is provided, the polymer fiber includes that the first polymer of crosslinking is fine
Dimension and/or the amine-modified second polymer fiber of DOPA, the material of the first polymer fiber and the second polymer fiber
Matter is independently selected from polymethyl methacrylate, polyacrylonitrile, polystyrene, polyvinylpyrrolidone and Kynoar
It is at least one；The block copolymer include polymethyl methacrylate, polyacrylonitrile, polystyrene, polyvinylpyrrolidone,
Kynoar, poly- 4-vinylpyridine, polyethylene glycol oxide, polymethylacrylic acid N, N- dimethylamino ethyl ester, polylactic acid and poly-
At least two polymer blocks in isoprene；
The entire polymeric fiber surface is set to adhere to the molten of one layer of block copolymer containing by the way of immersion or spraying
Liquid is formed after standing on the surface that the surface of the polymer fiber forms block copolymer layer and the block copolymer layer
Uniform pore structure obtains equal hole nanofiber.
2. the preparation method of hole nanofiber as described in claim 1, which is characterized in that described to stand as in 5 DEG C of temperature-
25 DEG C, 0.5h-5h is stood under the conditions of humidity 5%-35%.
3. the preparation method of hole nanofiber as described in claim 1, which is characterized in that the block copolymer containing it is molten
The concentration of the block copolymer in liquid is 1%-10%.
4. the preparation method of hole nanofiber as described in claim 1, which is characterized in that the block copolymer containing it is molten
Solvent in liquid includes at least one of tetrahydrofuran, 1,4- dioxane, N,N-dimethylformamide and chloroform.
5. the preparation method of hole nanofiber as described in claim 1, which is characterized in that the process conditions of the immersion are
In 15 DEG C of -35 DEG C of immersion 2min-30min, the process conditions of the spraying are in 15 DEG C of -35 DEG C of spraying 10min-60min.
6. the preparation method of hole nanofiber as described in claim 1, which is characterized in that the of the poly-dopamine modification
The preparation method of dimerization fibres includes:
Second polymer fiber is provided, the second polymer fiber is placed in dopamine modification liquid and is impregnated, is obtained after washed
The second polymer fiber modified to poly-dopamine.
7. the preparation method of hole nanofiber as claimed in claim 6, which is characterized in that the dopamine modification liquid includes
Aqueous solution containing dehydrated alcohol, ammonium hydroxide and Dopamine hydrochloride, the soaking temperature impregnated in dopamine modification liquid that is placed in are
15 DEG C -35 DEG C, soaking time 6h-24h.
8. a kind of equal hole nanofiber, which is characterized in that the equal hole nanofiber is described in any item by claim 1-7
Hole nanofiber preparation method is prepared, and the equal hole nanofiber includes polymer fiber and is coated on the polymer
The surface of the block copolymer layer of fiber surface, the equal hole nanofiber has Uniform pore structure, mesoporous >=98%.
9. hole nanofiber as claimed in claim 8, which is characterized in that the diameter of the equal hole nanofiber is 500nm-
1100nm。
10. be prepared such as the described in any item equal hole nanofiber preparation methods of claim 1-7 or such as claim 8-9
Application of described in any item equal hole nanofibers in catalysis industry, biological medicine, sensor, microreactor field.
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