CN106012047A - Method using electrostatic spinning mode to manufacture shape-controllable poval composite fiber - Google Patents
Method using electrostatic spinning mode to manufacture shape-controllable poval composite fiber Download PDFInfo
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- CN106012047A CN106012047A CN201610347967.6A CN201610347967A CN106012047A CN 106012047 A CN106012047 A CN 106012047A CN 201610347967 A CN201610347967 A CN 201610347967A CN 106012047 A CN106012047 A CN 106012047A
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- polyvinyl alcohol
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- metal hydroxide
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- metal salt
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D1/00—Treatment of filament-forming or like material
- D01D1/02—Preparation of spinning solutions
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/50—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyalcohols, polyacetals or polyketals
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Artificial Filaments (AREA)
- Nonwoven Fabrics (AREA)
- Inorganic Fibers (AREA)
Abstract
The invention discloses a method using the electrostatic spinning mode to manufacture shape-controllable poval composite fibers; the method comprises the following steps: preparing layered double-metal hydroxide nanorods; mixing the layered double-metal hydroxide nanorods with deionized water, and evenly dispersing to obtain the dispersion liquid; adding poval into the dispersion liquid, stirring and resolving so as to obtain poval/layered double-metal hydroxide nanorod mixed liquid, and carrying out electrostatic spinning so as to obtain the shape-controllable poval composite fibers. The method uses the layered double-metal hydroxide nanorod as filling material, and the adding quantity of the filling material can be changed so as to adjust the mixed liquid viscosity, thus controlling the shape of the electrostatic spinning fibers, and widening the poval spinning concentration. The method uses one single filling material to control the shape of the electrostatic spinning fiber; the method is simple in operation, strong in controllability, and low in cost.
Description
Technical field
The present invention relates to electrostatic spinning technique field, be specifically related to one and utilize method of electrostatic spinning to prepare shape
The method of the polyvinyl alcohol composite fiber that looks are controlled.
Background technology
Electrostatic spinning is that one prepares submicron or the simple and effective technology of nano-scale fiber, can be used for
Prepare the monodimension nanometer materials such as polymer, metal, pottery.Its ultimate principle is: make at high voltage electric field
Under with, the polymer solution or the melt drop deformation that are suspended from capillary outlet are taylor cone.Work as electric-field strength
Degree improves further, drop surface the electrostatic repulsion forces of electrically charged formation exceed itself surface and open
Power, makes the top of taylor cone form liquid stream.Liquid stream with electric charge flows in the electric field,
It is stretched effect, solvent evaporation simultaneously or melt cooling further, becomes superfine fibre and be deposited on
Receive on device, form nonwoven superfine fibre film.At present, its application cover tissue engineering,
Wound coating, catalysis, separating and filtering and chemical sensor etc..
Polyvinyl alcohol is formed by vinylacetate hydrolysis, is a kind of polyhydric water-soluble polymer, tool
There are the excellent properties such as good chemical stability, biocompatibility, biodegradability, thermostability,
And possess good spinnability and film property, be the relatively conventional polymer for electrostatic spinning it
One, it is widely used in the fields such as filtration, pharmaceutical carrier and biomedical engineering.But, poly-
It is narrower that interaction of hydrogen bond strong between vinyl alcohol strand causes it can spin concentration range, fiber shape
Looks are also difficult to regulate and control, and limit the range of application of polyvinyl alcohol to a certain extent.
During electrostatic spinning, fiber morphology all can be produced by operating parameter and Polymer Solution Property
Tremendous influence.In above-mentioned influence factor, solution viscosity plays decisive role.Polymer solution sticks
Degree easily produces beading when can spunbond spend less than it.Though this phenomenon can be by introducing some salts, surface
Activating agent or polyelectrolyte are solved, but restricted application.On the other hand, polymer solution glues
Degree easily causes jet stretching higher than it when can spunbond spend not exclusively and pin hole blocks, and can only obtain few
Amount micron order and the uneven fiber of thickness.
Tan et al. (Y.Q.Tan, Y.H.Song and Q.Zheng, Nanoscale, 2012,4,
6997-7005.) next common by adding a small amount of graphene oxide and oxidoreduction Graphene respectively
The viscosity of regulation and control polyvinyl alcohol suspension, it is achieved that widening while polyvinyl alcohol can spin concentration range
Improve the regularity of electrospun fibers.But above-mentioned raw materials manufacturing cycle is long, expensive, and
Use two kinds of fillers to carry out viscosity regulation and control, operate relatively complicated.
Summary of the invention
The present invention provides a kind of polyvinyl alcohol composite fiber utilizing method of electrostatic spinning to prepare morphology controllable
Method, use single filler, i.e. layered duplex metal hydroxide nanometer rod regulate and control polyvinyl alcohol hang
The viscosity of supernatant liquid.Can be respectively increased or reduce the apparent glutinous of suspension by the addition changing filler
Degree, widens the concentration range spun of polyvinyl alcohol, obtains homogeneous regular electrospun fibers.The party
Method is easy and simple to handle, and controllability is strong.
A kind of method of the polyvinyl alcohol composite fiber utilizing method of electrostatic spinning to prepare morphology controllable, including
Following steps:
(1) layered duplex metal hydroxide nanometer rod is prepared；
(2) layered duplex metal hydroxide nanometer rod step (1) obtained mixes with deionized water,
It is uniformly dispersed and obtains dispersion liquid；In dispersion liquid, add polyvinyl alcohol, stirring and dissolving, obtain polyvinyl alcohol
/ layered duplex metal hydroxide nanometer rod mixed liquor；
(3) polyvinyl alcohol that step (2) obtains/layered duplex metal hydroxide nanometer rod mixed liquor warp
Electrostatic spinning, obtains the polyvinyl alcohol composite fiber of morphology controllable.
With layered duplex metal hydroxide nanometer rod as filler in the present invention, for one-dimentional structure, its major diameter
Ratio is between 20～100.It is different from the layered duplex metal hydroxide nanometer sheet of routine, the double gold of stratiform
Belong to and occur between hydroxide nanorod electrostatic interaction area less, sonicated after can be more uniformly
It is dispersed in suspension.On the other hand, polyvinyl alcohol passes through with layered duplex metal hydroxide nanometer rod
Hydrogen bond interacts, and when packing density is relatively low, nanometer rods can play the effect of physical crosslinking point,
Raising system viscosity；When packing density is higher, polyvinyl alcohol molecule chain was completely wound around in nanometer rods week
Enclose and be not involved in the formation of overall hydrogen bond network, cause system viscosity degradation.Therefore, received by regulation
The content of rice rod can effectively control system viscosity, the most significantly widens the concentration the spun model of polyvinyl alcohol
Enclose and regulate and control the pattern of polyvinyl alcohol composite fiber.
As preferably, in step (1), what layered duplex metal hydroxide nanometer was excellent specifically prepares step
Rapid as follows:
Cationic surfactant, cosurfactant and alkanes oil phase are at room temperature mixed all
Even, obtain reactant liquor；Will be containing soluble divalent metal salt, soluble trivalent metal salt and basic species
The aqueous solution of matter mixes with reactant liquor, obtains microemulsion system, hydro-thermal reaction 4～24 at 90～120 DEG C
H, obtains described layered duplex metal hydroxide nanometer rod；
Described alkanes oil phase includes normal hexane, normal heptane, normal octane or hexamethylene；
Described cationic surfactant includes cetyl trimethylammonium bromide, cetyl front three
Ammonium chloride, Tetradecyl Trimethyl Ammonium Bromide, tetradecyl trimethyl ammonium chloride, dodecyl three
Methyl bromide ammonium, Dodecyl trimethyl ammonium chloride, dodecyl dimethyl benzyl ammonium chloride, 14
Zephiran or cetalkonium chloride；
Described cosurfactant includes n-butyl alcohol, n-amyl alcohol or hexanol.
As preferably, described alkanes oil phase, cationic surfactant, cosurfactant and water
The mol ratio of solution is 1:0.1:0.3:1.3.
As preferably, the bivalent metal ion in described soluble divalent metal salt is Co2+、Ni2+、、
Mg2+In one or both；Trivalent metal ion in soluble trivalent metal salt is Al3+、、Cr3+
In one or both；The preferably soluble divalent metal salt of mentioned kind, soluble trivalent metal salt
Be conducive to preparing the layered double hydroxide that crystal structure is perfect.
Described soluble divalent metal salt, the anion of soluble trivalent metal salt independently selected from
Cl-、NO3 -Or SO4 2-；
Described alkaline matter is sodium hydroxide or potassium hydroxide；
In described aqueous solution, soluble divalent metal salt with the total concentration of soluble trivalent metal salt is
0.05～0.5mol/L, soluble divalent metal salt with the molal weight ratio of soluble trivalent metal salt is
0.5～5:1, soluble divalent metal salt and soluble trivalent metal salt total amount and mole matter of alkaline matter
Amount ratio is 1:1～10.
As preferably, the temperature of described hydro-thermal reaction is 100～110 DEG C, and the time is 8～20h.
As preferably, in step (2), described polyvinyl alcohol/layered duplex metal hydroxide nanometer
In rod mixed liquor, quality is polyvinyl alcohol quality 0.1～the 10 of layered duplex metal hydroxide nanometer rod
Wt%, the mass percentage concentration of polyvinyl alcohol is 2～25wt%.Further preferably, layered bi-metal hydrogen
The quality of oxide nano-rod is the 0.5～5wt% of polyvinyl alcohol quality, the percent mass of polyvinyl alcohol
Concentration is 5～20wt%.In this concentration range, relatively it is easily formed the fiber of regular appearance.
As preferably, in step (2), described polyvinyl alcohol is powder, and the degree of polymerization is 1600～2300,
Alcoholysis degree is 88～99%.
As preferably, in step (3), the technological parameter of described electrostatic spinning is as follows:
Voltage is 5～25kV, and charging rate is 0.1～1.0mL/h, and ambient humidity is 20～80%, connects
Receipts plate is 5～25cm to the distance of pin hole.Further preferably voltage is 10～20kV, and charging rate is
0.3～0.7mL/h, ambient humidity is 30～80%, and the distance of reception plate to pin hole is 10～20cm.
Compared with prior art, present invention have the advantage that
1, with layered duplex metal hydroxide nanometer rod as filler in the present invention, compared to the double gold of stratiform
Belonging to hydroxide nano sheet, layered duplex metal hydroxide nanometer rod disperses in poly-vinyl alcohol solution
Being more uniformly distributed, one-dimentional structure is conducive to filler to be orientated in spinning process simultaneously, then increases substantially
The combination property of spinning film.
2, the present invention uses the single filler i.e. viscosity of controllable polyvinyl alcohol, by changing filler
Addition can be respectively increased or reduce the apparent viscosity of suspension, thus by dense for spinning of polyvinyl alcohol
Degree scope is widened, and obtains homogeneous regular electrospun fibers.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the layered duplex metal hydroxide nanometer rod of embodiment 1 preparation；
Fig. 2 is the polyvinyl alcohol/layered duplex metal hydroxide nanometer rod composite fibre of embodiment 1 preparation
SEM schemes；
Fig. 3 is the polyvinyl alcohol/layered duplex metal hydroxide nanometer rod composite fibre of embodiment 2 preparation
SEM schemes；
Fig. 4 is the polyvinyl alcohol/layered duplex metal hydroxide nanometer rod composite fibre of embodiment 3 preparation
SEM schemes；
Fig. 5 is the polyvinyl alcohol/layered duplex metal hydroxide nanometer rod composite fibre of embodiment 4 preparation
SEM schemes；
Fig. 6 is the polyvinyl alcohol/layered duplex metal hydroxide nanometer rod composite fibre of embodiment 5 preparation
SEM schemes.
Detailed description of the invention
The invention will be further described with embodiment below in conjunction with the accompanying drawings.
Embodiment 1:
By normal hexane, cetyl trimethylammonium bromide, hexanol with the molar ratio of 1:0.1:0.3
Become cream.By 0.105g CoSO4、0.04g Al2(SO4)3Each with 0.15g sodium hydroxide molten
In 5mL deionized water and be added drop-wise in above-mentioned cream, by above-mentioned after continuously stirred 1h
Microemulsion system is transferred in water heating kettle, puts into vacuum drying oven in 110 DEG C of crystallization 12h, centrifugal, cold
Lyophilizing is dry, obtains layered duplex metal hydroxide nanometer rod.
Above-mentioned for 0.01g product is scattered in supersound process 1h in 18mL deionized water, is transferred to three
Mouth flask, adds 2g pva powder (the PVA degree of polymerization 1700, alcoholysis degree 99%) stirring,
Mixed liquor is obtained after polyvinyl alcohol is completely dissolved.
Being poured into by above-mentioned mixed liquor in 20mL syringe and carry out electrostatic spinning, arranging conditional parameter voltage is
15kV, charging rate is 0.5mL, and ambient humidity is 50%, and pin hole is 15cm to receiving plate distance.
Spinning process continues 10min, takes out and observe for fiber morphology after terminating.
The XRD spectra of layered duplex metal hydroxide nanometer rod prepared by the present embodiment is as shown in Figure 1.
It can be seen that curve baseline is steady, product diffraction maximum position and the feature of layered double hydroxide
Peak position coincide, and (003) and (006) two peak are relatively sharply, illustrate really to have synthesized stratiform double
Metal hydroxides, and degree of crystallinity is higher.
Polyvinyl alcohol prepared by the present embodiment/layered duplex metal hydroxide nanometer rod mixed liquor is 0.01
s-1Apparent viscosity under shear rate is that (pure polyvinyl alcohol water solution is at 0.01s for 2.25Pa s-1Shear
Apparent viscosity under speed is 1.22Pa s), the purer polyvinyl alcohol water solution of its viscosity improves 84.4%.
Sweeping of polyvinyl alcohol prepared by the present embodiment/layered duplex metal hydroxide nanometer rod composite fibre
Retouch electromicroscopic photograph as in figure 2 it is shown, as can be seen from Figure: fiber have slightly have thin, skewness, occur
Adhesive structure.This system viscosity is too high, and in spinning process, jet stretching not exclusively, causes fiber bending.
The average diameter of compounding fiber is that (average diameter of polyvinyl alcohol electrostatic spinning fiber is 625nm
409nm), relatively straight polymer fibre diameter increases.
The preparation process of pure polyvinyl alcohol water solution and electrospun fibers thereof is: by 2g polyvinyl alcohol
Powder joins heating for dissolving in 18mL deionized water, obtains aqueous solution after it is completely dissolved.By water
Solution is poured into and is carried out electrostatic spinning in 20mL syringe, and arranging conditional parameter voltage is 15kV, charging
Speed is 0.5mL, and ambient humidity is 50%, and pin hole is 15cm to receiving plate distance.Spinning process
Continue 10min, take out after terminating and observe for fiber morphology.
Embodiment 2:
By normal hexane, cetyl trimethylammonium bromide, n-butyl alcohol with the molar ratio of 1:0.1:0.3
Become cream.By 0.1g MgSO4、0.05g Al2(SO4)3Respectively it is dissolved in 0.12g sodium hydroxide
In 5mL deionized water and be added drop-wise in above-mentioned cream, by above-mentioned microemulsion after continuously stirred 1h
Liquid system is transferred in water heating kettle, puts into vacuum drying oven in 100 DEG C of crystallization 15h, centrifugal, freezing
It is dried, obtains layered duplex metal hydroxide nanometer rod.
Above-mentioned for 0.02g product is scattered in supersound process 1h in 18mL deionized water, is transferred to three
Mouth flask, adds 2g pva powder (the PVA degree of polymerization 1700, alcoholysis degree 99%) stirring,
Mixed liquor is obtained after polyvinyl alcohol is completely dissolved.
Being poured into by above-mentioned mixed liquor in 20mL syringe and carry out electrostatic spinning, arranging conditional parameter voltage is
10kV, charging rate is 0.3mL, and ambient humidity is 40%, and pin hole is 13cm to receiving plate distance.
Spinning process continues 10min, takes out and observe for fiber morphology after terminating.
Shown in the XRD spectra of layered duplex metal hydroxide nanometer rod prepared by the present embodiment and Fig. 1
Similar.In figure, curve baseline is steady, product diffraction maximum position and the feature of layered double hydroxide
Peak position coincide, and (003) and (006) two peak are relatively sharply, illustrate really to have synthesized stratiform double
Metal hydroxides, and degree of crystallinity is higher.
Polyvinyl alcohol prepared by the present embodiment/layered duplex metal hydroxide nanometer rod mixed liquor is 0.01
s-1Apparent viscosity under shear rate is 1.39Pa s, and the purer polyvinyl alcohol water solution of its viscosity improves
13.9%.
Sweeping of polyvinyl alcohol prepared by the present embodiment/layered duplex metal hydroxide nanometer rod composite fibre
Retouch electromicroscopic photograph as it is shown on figure 3, as can be seen from Figure: fiber thickness is more uniform, but still suffers from portion
Divide bending and adhesion structure.The average diameter of compounding fiber is 441nm, straight compared with straight polymer fiber
Footpath is slightly improved.
Embodiment 3:
By normal hexane, cetyl trimethylammonium bromide, n-amyl alcohol with the molar ratio of 1:0.1:0.3
Become cream.By 0.09g NiCl2、0.04g AlCl35mL respectively it is dissolved in 0.06g potassium hydroxide
In deionized water and be added drop-wise to above-mentioned suspension system, after continuously stirred 1h, above-mentioned microemulsion system is turned
Move in water heating kettle, put into vacuum drying oven in 105 DEG C of crystallization 10h, centrifugal, lyophilization,
To layered duplex metal hydroxide nanometer rod.
Above-mentioned for 0.03g product is scattered in supersound process 1h in 18mL deionized water, is transferred to three
Mouth flask, adds 2g pva powder (the PVA degree of polymerization 1700, alcoholysis degree 99%) stirring,
Mixed aqueous solution is obtained after polyvinyl alcohol is completely dissolved.
Being poured into by above-mentioned mixed liquor in 20mL syringe and carry out electrostatic spinning, arranging conditional parameter voltage is
12kV, charging rate is 0.4mL, and ambient humidity is 60%, and pin hole is 18cm to receiving plate distance.
Spinning process continues 10min, takes out and observe for fiber morphology after terminating.
Shown in the XRD spectra of the layered duplex metal hydroxide nanometer rod that the present embodiment prepares and Fig. 1
Similar.In figure, curve baseline is steady, product diffraction maximum position and the feature of layered double hydroxide
Peak position coincide, and (003) and (006) two peak are relatively sharply, illustrate really to have synthesized stratiform double
Metal hydroxides, and degree of crystallinity is higher.
Polyvinyl alcohol prepared by the present embodiment/layered duplex metal hydroxide nanometer rod mixed liquor is 0.01
s-1Apparent viscosity under shear rate is 1.18Pa s, and its viscosity is close with pure polyvinyl alcohol water solution.
Polyvinyl alcohol prepared by the present embodiment/layered duplex metal hydroxide nanometer rod electrospun fibers
Stereoscan photograph as shown in Figure 4, fiber thickness is consistent as can be seen from Figure, the most regular.Multiple
The average diameter of compound fiber is 390nm, close with straight polymer fibre diameter.
Embodiment 4:
By normal hexane, cetyl trimethylammonium bromide, n-amyl alcohol with the molar ratio of 1:0.1:0.3
Become cream.By 0.18g Mg (NO3)2、0.24g Cr(NO3)3Each with 0.15g sodium hydroxide
It is dissolved in 5mL deionized water and is added drop-wise to above-mentioned suspension system, by above-mentioned micro-after continuously stirred 1h
Emulsion system is transferred in water heating kettle, puts into vacuum drying oven in 110 DEG C of crystallization 8h, centrifugal, freezing
It is dried, obtains layered duplex metal hydroxide nanometer rod.
Above-mentioned for 0.04g product is scattered in supersound process 1h in 18mL deionized water, is transferred to three
Mouth flask, adds 2g pva powder (the PVA degree of polymerization 1700, alcoholysis degree 99%) stirring,
Mixed aqueous solution is obtained after polyvinyl alcohol is completely dissolved.
Being poured into by above-mentioned mixed liquor in 20mL syringe and carry out electrostatic spinning, arranging conditional parameter voltage is
14kV, charging rate is 0.5mL, and ambient humidity is 50%, and pin hole is 16cm to receiving plate distance.
Spinning process continues 10min, takes out and observe for fiber morphology after terminating.
Shown in the XRD spectra of layered duplex metal hydroxide nanometer rod prepared by the present embodiment and Fig. 1
Similar.In figure, curve baseline is steady, product diffraction maximum position and the feature of layered double hydroxide
Peak position coincide, but (003) and (006) two peak be not sharp-pointed, shows the double gold of stratiform of synthesis
Belong to hydroxide crystallization imperfection.
Polyvinyl alcohol prepared by the present embodiment/layered duplex metal hydroxide nanometer rod mixed liquor is 0.01
s-1Apparent viscosity under shear rate is 0.69Pa s, and the purer polyvinyl alcohol water solution of its viscosity declines
43.4%.
Sweeping of polyvinyl alcohol prepared by the present embodiment/layered duplex metal hydroxide nanometer rod composite fibre
Retouch electromicroscopic photograph as it is shown in figure 5, as can be seen from Figure fiber thickness consistent, the most regular.Complex
The average diameter of fiber is 324nm, and relatively straight polymer fibre diameter is decreased obviously.
Embodiment 5:
By normal heptane, cetyl trimethylammonium bromide, hexanol with the molar ratio of 1:0.1:0.3
Become cream.By 0.5g Co (NO3)2、0.12g Al(NO3)3Respectively it is dissolved in 0.3g sodium hydroxide
In 5mL deionized water and be added drop-wise to above-mentioned suspension system, by above-mentioned Emulsions after continuously stirred 1h
System is transferred in water heating kettle, puts into vacuum drying oven in 100 DEG C of crystallization 20h, centrifugal, lyophilization,
Obtain layered duplex metal hydroxide nanometer rod.
Above-mentioned for 0.06g product is scattered in supersound process 1h in 18mL deionized water, is transferred to three
Mouth flask, adds 2g pva powder (the PVA degree of polymerization 2100, alcoholysis degree 99%) stirring,
Mixed aqueous solution is obtained after polyvinyl alcohol is completely dissolved.
Being poured into by above-mentioned mixed liquor in 20mL syringe and carry out electrostatic spinning, arranging conditional parameter voltage is
13kV, charging rate is 0.6mL, and ambient humidity is 60%, and pin hole is 17cm to receiving plate distance.
Spinning process continues 10min, takes out and observe for fiber morphology after terminating.
Shown in the XRD spectra of layered duplex metal hydroxide nanometer rod prepared by the present embodiment and Fig. 1
Similar.In figure, curve baseline is steady, product diffraction maximum position and the feature of layered double hydroxide
Peak position coincide, and (003) and (006) two peak are relatively sharply, shows the double gold of stratiform of synthesis
Belong to hydroxide degree of crystallinity higher.
Polyvinyl alcohol prepared by the present embodiment/layered duplex metal hydroxide nanometer rod mixed liquor is 0.01
s-1Apparent viscosity under shear rate is 0.82Pa s, and the purer polyvinyl alcohol water solution of its viscosity declines
32.8%.Viscosity of mixed liquid the most slightly rises may come from layered duplex metal hydroxide nanometer rod
Reunite.
Sweeping of polyvinyl alcohol prepared by the present embodiment/layered duplex metal hydroxide nanometer rod composite fibre
Retouching electromicroscopic photograph as shown in Figure 6, fiber thickness is consistent as can be seen from Figure, the most regular, and part is fine
The diameter of dimension increases the most suddenly, should be caused by layered duplex metal hydroxide nanometer rod aggregate.
The average diameter of compounding fiber is 356nm, and relatively straight polymer fibre diameter is declined slightly.
Embodiment 6:
By hexamethylene, tetradecyl trimethyl ammonium chloride, hexanol with the molar ratio of 1:0.1:0.3
Become cream.By 0.2g Ni (NO3)2、0.36g Al(NO3)3Each with 0.6g sodium hydroxide molten
In 5mL deionized water and be added drop-wise to above-mentioned suspension system, by above-mentioned microemulsion after continuously stirred 1h
Liquid system is transferred in water heating kettle, puts into vacuum drying oven in 110 DEG C of crystallization 20h, centrifugal, freezing dry
Dry, obtain layered duplex metal hydroxide nanometer rod.
Above-mentioned for 0.1g product is scattered in supersound process 1h in 18mL deionized water, is transferred to three mouthfuls
Flask, adds 2g pva powder (the PVA degree of polymerization 1700, alcoholysis degree 99%) stirring,
Mixed aqueous solution is obtained after polyvinyl alcohol is completely dissolved.
Being poured into by above-mentioned mixed liquor in 20mL syringe and carry out electrostatic spinning, arranging conditional parameter voltage is
10kV, charging rate is 0.5mL, and ambient humidity is 80%, and pin hole is 15cm to receiving plate distance.
Spinning process continues 10min, takes out and observe for fiber morphology after terminating.
In the XRD spectra of layered duplex metal hydroxide nanometer rod prepared by the present embodiment, curve base
Line is steady, and the characteristic peak positions of product diffraction maximum position and layered double hydroxide is coincide, and
(003) and (006) two peak is relatively more sharp-pointed, the layered double hydroxide crystallization of synthesis is shown
Spend higher.Spectrogram additionally also occurs Al (OH)3Miscellaneous peak, should be caused by trivalent metal ion excess.
Polyvinyl alcohol prepared by the present embodiment/layered duplex metal hydroxide nanometer rod mixed liquor is 0.01
s-1Apparent viscosity under shear rate is 1.16Pa s, and its viscosity is close with pure polyvinyl alcohol water solution.
Along with the increase of filer content, mixed liquor viscosity again rises and comes from layered duplex metal hydroxide nanometer
The reunion of rod.
Sweeping of polyvinyl alcohol prepared by the present embodiment/layered duplex metal hydroxide nanometer rod composite fibre
Retouching electromicroscopic photograph similar to that shown in Fig. 6, fiber is the most regular as can be seen from Figure, but there is adhesion knot
Structure, should be that ambient humidity is excessive, and solvent volatilization is the most caused.The diameter of few fibers is dashed forward somewhere
So increase, should be caused by layered duplex metal hydroxide nanometer rod aggregate.Compounding fiber average
A diameter of 382nm, relatively straight polymer fibre diameter is declined slightly.
Embodiment 7:
By normal octane, dodecyl dimethyl benzyl ammonium chloride, hexanol with the mol ratio of 1:0.1:0.3
It is configured to cream.By 0.3g NiSO4、0.15g Al2(SO4)3Each with 0.1g sodium hydroxide
It is dissolved in 5mL deionized water and is added drop-wise to above-mentioned suspension system, by above-mentioned micro-after continuously stirred 1h
Emulsion system is transferred in water heating kettle, puts into vacuum drying oven in 105 DEG C of crystallization 16h, centrifugal, cold
Lyophilizing is dry, obtains layered duplex metal hydroxide nanometer rod.
Above-mentioned for 0.005g product is scattered in supersound process 1h in 19mL deionized water, is transferred to three
Mouth flask, adds 1g pva powder (the PVA degree of polymerization 1900, alcoholysis degree 88%) stirring,
Mixed aqueous solution is obtained after polyvinyl alcohol is completely dissolved.
Being poured into by above-mentioned mixed liquor in 20mL syringe and carry out electrostatic spinning, arranging conditional parameter voltage is
16kV, charging rate is 0.5mL, and ambient humidity is 40%, and pin hole is 15cm to receiving plate distance.
Spinning process continues 10min, takes out and observe for fiber morphology after terminating.
Shown in the XRD spectra of layered duplex metal hydroxide nanometer rod prepared by the present embodiment and Fig. 1
Similar.In figure, curve baseline is steady, product diffraction maximum position and the feature of layered double hydroxide
Peak position coincide, and (003) and (006) two peak are relatively sharply, shows the double gold of stratiform of synthesis
Belong to hydroxide degree of crystallinity higher.
Polyvinyl alcohol prepared by the present embodiment/layered duplex metal hydroxide nanometer rod mixed liquor is 0.01
s-1Apparent viscosity under shear rate is 0.26Pa s, and polyvinyl alcohol concentration reduction causes system viscosity big
Amplitude declines.
Sweeping of polyvinyl alcohol prepared by the present embodiment/layered duplex metal hydroxide nanometer rod composite fibre
Retouching in electromicroscopic photograph, major part fiber exists with beading form.Viscosity of mixed liquid is relatively low, it is difficult to formed
The spinning jet of continuous-stable, thus cause beading to produce.Compounding fiber is deposited due to bead structure
, its average diameter is difficult to add up.
Embodiment 8:
By normal hexane, myristyl benzyl dimethyl ammonium chloride, hexanol with the mol ratio of 1:0.1:0.3
It is configured to cream.By 0.06g CoCl2、0.03g AlCl3Each with 0.05g sodium hydroxide molten
In 5mL deionized water and be added drop-wise to above-mentioned suspension system, by above-mentioned microemulsion after continuously stirred 1h
Liquid system is transferred in water heating kettle, puts into vacuum drying oven in 110 DEG C of crystallization 15h, centrifugal, freezing dry
Dry, obtain layered duplex metal hydroxide nanometer rod.
Above-mentioned for 0.0065g product is scattered in supersound process 1h in 18.7mL deionized water, transfer
To there-necked flask, add 1.3g pva powder (the PVA degree of polymerization 1700, alcoholysis degree 99%)
Stirring, obtains mixed aqueous solution after polyvinyl alcohol is completely dissolved.
Being poured into by above-mentioned mixed liquor in 20mL syringe and carry out electrostatic spinning, arranging conditional parameter voltage is
13kV, charging rate is 0.7mL, and ambient humidity is 60%, and pin hole is 20cm to receiving plate distance.
Spinning process continues 10min, takes out and observe for fiber morphology after terminating.
Shown in the XRD spectra of layered duplex metal hydroxide nanometer rod prepared by the present embodiment and Fig. 1
Similar.In figure, curve baseline is steady, product diffraction maximum position and the feature of layered double hydroxide
Peak position coincide, and (003) and (006) two peak are relatively sharply, shows the double gold of stratiform of synthesis
Belong to hydroxide degree of crystallinity higher.
Polyvinyl alcohol prepared by the present embodiment/layered duplex metal hydroxide nanometer rod mixed liquor is 0.01
s-1Apparent viscosity under shear rate is 0.45Pa s, and polyvinyl alcohol concentration reduction causes system viscosity big
Amplitude declines.
Sweeping of polyvinyl alcohol prepared by the present embodiment/layered duplex metal hydroxide nanometer rod composite fibre
Retouching electromicroscopic photograph similar with shown in Fig. 5, fiber thickness is consistent as can be seen from Figure, the most regular.Multiple
The average diameter of compound fiber is 175nm.
Embodiment 9:
By normal hexane, cetyl trimethylammonium bromide, hexanol with the molar ratio of 1:0.1:0.3
Become cream.By 0.08g Mg (NO3)2、0.02g Cr(NO3)3Each with 0.02g sodium hydroxide
It is dissolved in 5mL deionized water and is added drop-wise to above-mentioned suspension system, by above-mentioned micro-after continuously stirred 1h
Emulsion system is transferred in water heating kettle, puts into vacuum drying oven in 100 DEG C of crystallization 16h, centrifugal, cold
Lyophilizing is dry, obtains layered duplex metal hydroxide nanometer rod.
Above-mentioned for 0.072g product is scattered in supersound process 1h in 16.4mL deionized water, is transferred to
There-necked flask, adds 3.6g pva powder (the PVA degree of polymerization 2300, alcoholysis degree 99%) and stirs
Mix, after polyvinyl alcohol is completely dissolved, obtains mixed aqueous solution.
Being poured into by above-mentioned mixed liquor in 20mL syringe and carry out electrostatic spinning, arranging conditional parameter voltage is
17kV, charging rate is 0.5mL, and ambient humidity is 50%, and pin hole is 18cm to receiving plate distance.
Spinning process continues 10min, takes out and observe for fiber morphology after terminating.
In the XRD spectra of layered duplex metal hydroxide nanometer rod prepared by the present embodiment, curve base
Line is steady, and the characteristic peak positions of product diffraction maximum position and layered double hydroxide is coincide, and
(003) and (006) two peak is relatively more sharp-pointed, the layered double hydroxide crystallization of synthesis is shown
Spend higher.Spectrogram additionally also occurs Mg (OH)2Miscellaneous peak, should be caused by bivalent metal ion excess.
Polyvinyl alcohol prepared by the present embodiment/layered duplex metal hydroxide nanometer rod mixed liquor is 0.01
s-1Apparent viscosity under shear rate is 16.5Pa s, and polyvinyl alcohol concentration rising causes system viscosity big
Amplitude increases.
Sweeping of polyvinyl alcohol prepared by the present embodiment/layered duplex metal hydroxide nanometer rod composite fibre
Retouching in electromicroscopic photograph, fiber thickness is basically identical, produces without bending, adhesion structure.Compounding fiber
Average diameter be 1.35 μm.
Embodiment 10:
By normal hexane, cetyl trimethylammonium bromide, hexanol with the molar ratio of 1:0.1:0.3
Become cream.By 0.3g MgSO4、0.18g Cr2(SO4)3Respectively it is dissolved in 0.2g sodium hydroxide
In 5mL deionized water and be added drop-wise to above-mentioned suspension system, by above-mentioned Emulsions after continuously stirred 1h
System is transferred in water heating kettle, puts into vacuum drying oven in 105 DEG C of crystallization 16h, centrifugal, lyophilization,
Obtain layered duplex metal hydroxide nanometer rod.
Above-mentioned for 0.08g product is scattered in supersound process 1h in 16mL deionized water, is transferred to three
Mouth flask, adds 4g pva powder (the PVA degree of polymerization 1700, alcoholysis degree 99%) stirring,
Mixed aqueous solution is obtained after polyvinyl alcohol is completely dissolved.
Being poured into by above-mentioned mixed liquor in 20mL syringe and carry out electrostatic spinning, arranging conditional parameter voltage is
20kV, charging rate is 0.6mL, and ambient humidity is 60%, and pin hole is 17cm to receiving plate distance.
Spinning process continues 10min, takes out and observe for fiber morphology after terminating.
Shown in the XRD spectra of layered duplex metal hydroxide nanometer rod prepared by the present embodiment and Fig. 1
Similar.In figure, curve baseline is steady, product diffraction maximum position and the feature of layered double hydroxide
Peak position coincide, and (003) and (006) two peak are relatively sharply, shows the double gold of stratiform of synthesis
Belong to hydroxide degree of crystallinity higher.
Polyvinyl alcohol prepared by the present embodiment/layered duplex metal hydroxide nanometer rod mixed liquor is 0.01
s-1Apparent viscosity under shear rate is 30.2Pa s, and polyvinyl alcohol concentration rising causes system viscosity big
Amplitude increases.
Sweeping of polyvinyl alcohol prepared by the present embodiment/layered duplex metal hydroxide nanometer rod composite fibre
Retouching in electromicroscopic photograph, fiber content is less, substantially in bending, the structure of adhesion.Mixed liquid concentration mistake
Height, causes fluid to be dried rapidly at syringe needle, it is difficult to form the spinning jet of continuous-stable.Complex
The average diameter of fiber is 2.12 μm.
Embodiment 11:
By normal hexane, cetyl trimethylammonium bromide, hexanol with the molar ratio of 1:0.1:0.3
Become cream.By 0.15g CoSO4、0.05g Al2(SO4)3Respectively it is dissolved in 0.1g sodium hydroxide
In 5mL deionized water and be added drop-wise to above-mentioned suspension system, by above-mentioned Emulsions after continuously stirred 1h
System is transferred in water heating kettle, puts into vacuum drying oven in 105 DEG C of crystallization 16h, centrifugal, lyophilization,
Obtain layered duplex metal hydroxide nanometer rod.
Above-mentioned for 0.01g product is scattered in supersound process 1h in 18mL deionized water, is transferred to three
Mouth flask, adds 2g pva powder (the PVA degree of polymerization is 1700, alcoholysis degree 88%) and stirs
Mix, after polyvinyl alcohol is completely dissolved, obtains mixed aqueous solution.
Being poured into by above-mentioned mixed liquor in 20mL syringe and carry out electrostatic spinning, arranging conditional parameter voltage is
12kV, charging rate is 0.4mL, and ambient humidity is 40%, and pin hole is 12cm to receiving plate distance.
Spinning process continues 10min, takes out and observe for fiber morphology after terminating.
Shown in the XRD spectra of the layered duplex metal hydroxide nanometer rod that the present embodiment prepares and Fig. 1
Similar.In figure, curve baseline is steady, product diffraction maximum position and the feature of layered double hydroxide
Peak position coincide, and (003) and (006) two peak are relatively sharply, shows the double gold of stratiform of synthesis
Belong to hydroxide degree of crystallinity higher.
Polyvinyl alcohol prepared by the present embodiment/layered duplex metal hydroxide nanometer rod mixed liquor is 0.01
s-1Apparent viscosity under shear rate is 1.05Pa s.Polyvinyl alcohol alcoholysis degree declines, molecules in solution
Hydrogen bond action between chain weakens, and may result in system viscosity and declines.Add a small amount of layered bi-metal simultaneously
Hydroxide nanorod can play the effect of physical crosslinking point, thus finally makes viscosity of mixed liquid poly-with pure
Vinyl alcohol aqueous solution viscosity is close.
Sweeping of polyvinyl alcohol prepared by the present embodiment/layered duplex metal hydroxide nanometer rod composite fibre
Retouching electromicroscopic photograph similar with shown in Fig. 4, fiber thickness is consistent, the most regular.Putting down of compounding fiber
The most a diameter of 403nm, with pure vinal similar diameters.
Embodiment 12:
By normal hexane, cetyl trimethylammonium bromide, hexanol with the molar ratio of 1:0.1:0.3
Become cream.By 0.25g MgCl2、0.15g CrCl35mL respectively it is dissolved in 0.34g sodium hydroxide
In deionized water and be added drop-wise to above-mentioned suspension system, after continuously stirred 1h, above-mentioned microemulsion system is turned
Move in water heating kettle, put into vacuum drying oven in 100 DEG C of crystallization 18h, centrifugal, lyophilization,
To layered duplex metal hydroxide nanometer rod.
Above-mentioned for 0.04g product is scattered in supersound process 1h in 18mL deionized water, is transferred to three
Mouth flask, adds 2g pva powder (the PVA degree of polymerization 1700, alcoholysis degree 88%) stirring,
Mixed aqueous solution is obtained after polyvinyl alcohol is completely dissolved.
Being poured into by above-mentioned mixed liquor in 20mL syringe and carry out electrostatic spinning, arranging conditional parameter voltage is
17kV, charging rate is 0.6mL, and ambient humidity is 60%, and pin hole is 20cm to receiving plate distance.
Spinning process continues 10min, takes out and observe for fiber morphology after terminating.
Shown in the XRD spectra of the layered duplex metal hydroxide nanometer rod that the present embodiment prepares and Fig. 1
Similar.In figure, curve baseline is steady, product diffraction maximum position and the feature of layered double hydroxide
Peak position coincide, and (003) and (006) two peak are relatively sharply, shows the double gold of stratiform of synthesis
Belong to hydroxide degree of crystallinity higher.
Polyvinyl alcohol prepared by the present embodiment/layered duplex metal hydroxide nanometer rod mixed liquor is 0.01
s-1Apparent viscosity under shear rate is 0.58Pa s.When packing density is higher, polyvinyl alcohol molecule chain is complete
Entirely it is wrapped in around nanometer rods the formation being not involved in overall hydrogen bond network, causes system viscosity degradation.
Sweeping of polyvinyl alcohol prepared by the present embodiment/layered duplex metal hydroxide nanometer rod composite fibre
Retouching electromicroscopic photograph similar with shown in Fig. 5, fiber thickness is consistent as can be seen from Figure, the most regular.Multiple
The average diameter of compound fiber is 286nm.
Comparative example 1:
1.3g pva powder (the PVA degree of polymerization 1700, alcoholysis degree 99%) is joined 18.7
ML deionized water dissolves, obtains aqueous solution.Aqueous solution is poured into 20mL syringe carries out Static Spinning
Silk, arranging conditional parameter voltage is 13kV, and charging rate is 0.7mL, and ambient humidity is 60%,
Pin hole is 20cm to receiving plate distance.Spinning process continues 10min, takes out for fiber after terminating
Morphology observation.
Contrasting this comparative example and embodiment 8, polyvinyl alcohol water solution prepared by this comparative example is at 0.01s-1
Apparent viscosity under shear rate is 0.29Pa s, and the polyvinyl alcohol/stratiform of relatively embodiment 8 preparation is double
Metal hydroxides nanometer rods mixed liquor declines 35.5%, and this phenomenon shows to add a small amount of layered bi-metal
Hydroxide nanorod is remarkably improved the apparent viscosity of system.
In the stereoscan photograph of polyvinyl alcohol electrostatic spinning fiber prepared by this comparative example, major part is fine
Tie up and exist with beading form, thus be difficult to add up its average diameter.Show to add a small amount of layered bi-metal
Hydroxide nanorod can reduce the spun concentration value that polyvinyl alcohol is minimum.
Comparative example 2
3.6g pva powder (the PVA degree of polymerization 2300, alcoholysis degree 99%) is joined 16.4
ML deionized water dissolves, after it is completely dissolved, obtains aqueous solution.Aqueous solution is poured into 20mL pin
Carrying out electrostatic spinning in Tong, arranging conditional parameter voltage is 17kV, and charging rate is 0.5mL, ring
Border humidity is 50%, and pin hole is 18cm to receiving plate distance.Spinning process continues 10min, terminates
Rear taking-up is observed for fiber morphology.
Contrasting this comparative example and embodiment 9, polyvinyl alcohol water solution prepared by this comparative example is at 0.01s-1
Apparent viscosity under shear rate is 22.8Pa s, and the polyvinyl alcohol/stratiform of relatively embodiment 9 preparation is double
The apparent viscosity of metal hydroxides nanometer rods mixed liquor rises 38.2%, shows to add more content
Layered duplex metal hydroxide nanometer rod can obviously reduce the apparent viscosity of system.
In the stereoscan photograph of polyvinyl alcohol electrostatic spinning fiber prepared by this comparative example, fiber content
Less, substantially in bending, the structure of adhesion.Show to add the laminated type bimetal hydroxide of more content
Thing nanometer rods can improve the spun concentration value that polyvinyl alcohol is maximum.
Comparative example 3
By 0.3g MgCl2、0.2g AlCl35mL deionized water respectively it is dissolved in 0.15g sodium hydroxide
In, mix rapidly afterwards and continuously stirred 1h.Above-mentioned suspension is transferred in water heating kettle, puts into
Vacuum drying oven in 100 DEG C of crystallization 12h, centrifugal, lyophilization, obtain laminated type bimetal hydroxide
Thing nanometer sheet.
Above-mentioned for 0.01g product is scattered in supersound process 1h in 18mL deionized water, is transferred to three
Mouth flask, adds 2g pva powder (the PVA degree of polymerization 1700, alcoholysis degree 99%) stirring,
Mixed aqueous solution is obtained after polyvinyl alcohol is completely dissolved.
Being poured into by above-mentioned mixed liquor in 20mL syringe and carry out electrostatic spinning, arranging conditional parameter voltage is
15kV, charging rate is 0.5mL, and ambient humidity is 50%, and pin hole is 15cm to receiving plate distance.
Spinning process continues 10min, takes out and observe for fiber morphology after terminating.
Shown in the XRD spectra of the layered duplex metal hydroxide nanometer sheet that this comparative example prepares and Fig. 1
Similar.In figure, curve baseline is steady, product diffraction maximum position and the feature of layered double hydroxide
Peak position coincide, and (003) and (006) two peak are relatively sharply, shows the double gold of stratiform of synthesis
Belong to hydroxide degree of crystallinity higher.
Polyvinyl alcohol prepared by this comparative example/layered duplex metal hydroxide nanometer sheet mixed liquor is 0.01
s-1Apparent viscosity under shear rate is 1.45Pa s, and purer polyvinyl alcohol water solution improves 18.8%.
Show that adding a small amount of layered duplex metal hydroxide nanometer sheet also can play the effect of physical crosslinking point, and
Improve system viscosity, but the layered double hydroxide that its amplitude of variation relatively adds equal quality is received
Rice rod is little.
Polyvinyl alcohol prepared by this comparative example/layered duplex metal hydroxide nanometer sheet electrospun fibers
Stereoscan photograph similar with shown in Fig. 3, fiber thickness is consistent as can be seen from Figure, the most regular.
The average diameter of compounding fiber is 452nm.
Comparative example 4
By 0.45g NiCl2、0.18g AlCl35mL deionized water respectively it is dissolved in 0.35g potassium hydroxide
In, mix rapidly afterwards and continuously stirred 1h.Above-mentioned suspension is transferred in water heating kettle, puts into
Vacuum drying oven in 105 DEG C of crystallization 16h, centrifugal, lyophilization, obtain laminated type bimetal hydroxide
Thing nanometer sheet.
Above-mentioned for 0.04g product is scattered in supersound process 1h in 18mL deionized water, is transferred to three
Mouth flask, adds 2g pva powder (the PVA degree of polymerization 1700, alcoholysis degree 99%) stirring,
Mixed aqueous solution is obtained after polyvinyl alcohol is completely dissolved.
Being poured into by above-mentioned mixed liquor in 20mL syringe and carry out electrostatic spinning, arranging conditional parameter voltage is
16kV, charging rate is 0.4mL, and ambient humidity is 60%, and pin hole is 18cm to receiving plate distance.
Spinning process continues 10min, takes out and observe for fiber morphology after terminating.
Shown in the XRD spectra of the layered duplex metal hydroxide nanometer sheet that this comparative example prepares and Fig. 1
Similar.In figure, curve baseline is steady, product diffraction maximum position and the feature of layered double hydroxide
Peak position coincide, and (003) and (006) two peak are relatively sharply, shows the double gold of stratiform of synthesis
Belong to hydroxide degree of crystallinity higher.
Polyvinyl alcohol prepared by this comparative example/layered duplex metal hydroxide nanometer sheet mixed liquor is 0.01
s-1Apparent viscosity under shear rate is 1.55Pa s, and purer polyvinyl alcohol water solution improves 27.1%,
Show that the layered duplex metal hydroxide nanometer sheet adding more content improves system viscosity the most only, should
Phenomenon is different from the nanometer rods adding more content in system, and the reason causing this difference should be owing to
The change of layered double hydroxide topological structure.
Polyvinyl alcohol prepared by this comparative example/layered duplex metal hydroxide nanometer sheet electrospun fibers
Stereoscan photograph similar with shown in Fig. 3, fiber thickness is consistent as can be seen from Figure, the most regular.
The average diameter of compounding fiber is 467nm.
Claims (9)
1. utilize method of electrostatic spinning to prepare the method for polyvinyl alcohol composite fiber for morphology controllable,
It is characterized in that, comprise the steps:
(1) layered duplex metal hydroxide nanometer rod is prepared；
(2) layered duplex metal hydroxide nanometer rod step (1) obtained mixes with deionized water,
It is uniformly dispersed and obtains dispersion liquid；In dispersion liquid, add polyvinyl alcohol, stirring and dissolving, obtain polyvinyl alcohol
/ layered duplex metal hydroxide nanometer rod mixed liquor；
(3) polyvinyl alcohol that step (2) obtains/layered duplex metal hydroxide nanometer rod mixed liquor warp
Electrostatic spinning, obtains the polyvinyl alcohol composite fiber of morphology controllable.
The polyvinyl alcohol utilizing method of electrostatic spinning to prepare morphology controllable the most according to claim 1
The method of composite fibre, it is characterised in that in step (1), layered duplex metal hydroxide nanometer
The concrete preparation process of rod is as follows:
Cationic surfactant, cosurfactant and alkanes oil phase are at room temperature mixed all
Even, obtain reactant liquor；Will be containing soluble divalent metal salt, soluble trivalent metal salt and basic species
The aqueous solution of matter mixes with reactant liquor, obtains microemulsion system, hydro-thermal reaction 4～24 at 90～120 DEG C
H, obtains described layered duplex metal hydroxide nanometer rod；
Described alkanes oil phase includes normal hexane, normal heptane, normal octane or hexamethylene；
Described cationic surfactant includes cetyl trimethylammonium bromide, cetyl front three
Ammonium chloride, Tetradecyl Trimethyl Ammonium Bromide, tetradecyl trimethyl ammonium chloride, dodecyl three
Methyl bromide ammonium, Dodecyl trimethyl ammonium chloride, dodecyl dimethyl benzyl ammonium chloride, 14
Zephiran or cetalkonium chloride；
Described cosurfactant includes n-butyl alcohol, n-amyl alcohol or hexanol.
The polyvinyl alcohol utilizing method of electrostatic spinning to prepare morphology controllable the most according to claim 2
The method of composite fibre, it is characterised in that described alkanes oil phase, cationic surfactant, help
Surfactant is 1:0.1:0.3:1.3 with the mol ratio of aqueous solution.
The polyvinyl alcohol utilizing method of electrostatic spinning to prepare morphology controllable the most according to claim 2
The method of composite fibre, it is characterised in that the bivalent metal ion in described soluble divalent metal salt
For Co2+、Ni2+、、Mg2+In one or both；Trivalent metal in soluble trivalent metal salt
Ion is Al3+、、Cr3+In one or both；
Described soluble divalent metal salt, the anion of soluble trivalent metal salt independently selected from
Cl-、NO3 -Or SO4 2-；
Described alkaline matter is sodium hydroxide or potassium hydroxide；
In described aqueous solution, soluble divalent metal salt with the total concentration of soluble trivalent metal salt is
0.05～0.5mol/L, soluble divalent metal salt with the molal weight ratio of soluble trivalent metal salt is
0.5～5:1, soluble divalent metal salt and soluble trivalent metal salt total amount and mole matter of alkaline matter
Amount ratio is 1:1～10.
The polyvinyl alcohol utilizing method of electrostatic spinning to prepare morphology controllable the most according to claim 2
The method of composite fibre, it is characterised in that the temperature of described hydro-thermal reaction is 100～110 DEG C, the time
It is 8～20h.
The polyvinyl alcohol utilizing method of electrostatic spinning to prepare morphology controllable the most according to claim 1
The method of composite fibre, it is characterised in that in step (2), the double gold of described polyvinyl alcohol/stratiform
Belonging in hydroxide nanorod mixed liquor, the quality of layered duplex metal hydroxide nanometer rod is polyethylene
The 0.1～10wt% of alcohol quality, the mass percentage concentration of polyvinyl alcohol is 2～25wt%.
The polyvinyl alcohol utilizing method of electrostatic spinning to prepare morphology controllable the most according to claim 6
The method of composite fibre, it is characterised in that described polyvinyl alcohol is powder, the degree of polymerization is
1600～2300, alcoholysis degree is 88～99%.
The polyvinyl alcohol utilizing method of electrostatic spinning to prepare morphology controllable the most according to claim 7
The method of composite fibre, it is characterised in that described polyvinyl alcohol/layered duplex metal hydroxide nanometer
In rod mixed liquor, quality is polyvinyl alcohol quality 0.5～the 5 of layered duplex metal hydroxide nanometer rod
Wt%, the mass percentage concentration of polyvinyl alcohol is 5～20wt%.
The polyvinyl alcohol utilizing method of electrostatic spinning to prepare morphology controllable the most according to claim 1
The method of composite fibre, it is characterised in that in step (3), the technological parameter of described electrostatic spinning
As follows:
Voltage is 5～25kV, and charging rate is 0.1～1.0mL/h, and ambient humidity is 20～80%, connects
Receipts plate is 5～25cm to the distance of pin hole.
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