CN106467988B - Nylon 46/PVDF/PEO/ boric acid composite nano fiber and preparation method thereof - Google Patents
Nylon 46/PVDF/PEO/ boric acid composite nano fiber and preparation method thereof Download PDFInfo
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- CN106467988B CN106467988B CN201610846634.8A CN201610846634A CN106467988B CN 106467988 B CN106467988 B CN 106467988B CN 201610846634 A CN201610846634 A CN 201610846634A CN 106467988 B CN106467988 B CN 106467988B
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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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
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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
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/02—Heat treatment
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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
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
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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
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0069—Electro-spinning characterised by the electro-spinning apparatus characterised by the spinning section, e.g. capillary tube, protrusion or pin
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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
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0076—Electro-spinning characterised by the electro-spinning apparatus characterised by the collecting device, e.g. drum, wheel, endless belt, plate or grid
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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
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0092—Electro-spinning characterised by the electro-spinning apparatus characterised by the electrical field, e.g. combined with a magnetic fields, using biased or alternating fields
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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
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
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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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/12—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyamide as constituent
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
Abstract
The present invention relates to the technical fields of composite nano fiber and preparation method thereof, more particularly it relates to nylon 46/PVDF/PEO/ boric acid composite nano fiber and preparation method thereof.Composite nano fiber of the present invention includes nylon 46, PVDF, molecular adhesion agent, heat-resisting additive, and preparation method includes the following steps: a. prepares PEO solution: PEO being dissolved in deionized water, stirring, matches to obtain PEO solution；B. it prepares PEO/PVDF mixed liquor: PVDF aqueous emulsion is added in PEO solution described in step a, PEO/PVDF mixed liquor is matched to obtain in stirring；C. it prepares Electrospun solution: nylon 46 salt, boric acid is added in PEO/PVDF mixed liquor described in step b, Electrospun solution is matched to obtain in stirring；D. Electrospun prepares composite nano fiber: nylon 46 salt/PVDF/PEO/ boric acid precursor is made by electrostatic spinning in the Electrospun solution in step c, it is thermally treated to get nylon 46/PVDF/PEO/ boric acid composite nano fiber.Composite nano fiber of the present invention has the characteristics that high-modulus, high elongation at tear.
Description
Technical field
The present invention relates to the technical fields of composite nano fiber and preparation method thereof, more particularly it relates to nylon
46/PVDF/PEO/ boric acid composite nano fiber and preparation method thereof.
Background technique
Currently, it is increasingly mature by the technology that electrostatic spinning prepares nanosized polymer fiber, and nano grade polymer is fine
Dimension due to very big major diameter when recuperability, and to material mechanical performance and hot property have significant raising
Effect.The large-scale production of nanofiber industrially, for expand its industrially application provide possibility.Nylon is due to it
The feature that nanofiber diameter is small, toughness and intensity are high is all applied to day as a kind of good spinning material all the time
Often in life.Nylon is only soluble in a small number of solvents such as formic acid, dimethyl sulfoxide, and the smell of formic acid is big and toxic, is not suitable for big rule
The electrospinning of modelling prepares nylon nano fiber.
Kynoar (PVDF) is a kind of andwhite crystalline polymer, has good chemical stability, acidproof at room temperature
Caustic corrosion.Kynoar has preferable symmetrical structure, and crystal property is preferable, so that PVDF material has preferable intensity,
And non-crystallized part makes PVDF material have preferable toughness.
This year, composite material are extensive as a kind of brand-new material that is easily prepared and can significantly improving product properties
Be applied to various fields, when storeroom it is compound after, while also can change the preparation method and technique of homogenous material, because
This, developing a kind of aqueous solution electrospinning preparation high tenacity and the high nylon composite nano fiber method of intensity has highly important meaning
Justice.
Summary of the invention
The technical problem to be solved in the present invention is to provide nylon 46/PVDF/PEO/ boric acid composite nano fiber and its preparations
Method.
In order to achieve the above-mentioned object of the invention, this invention takes following technical schemes:
Nylon 46/PVDF/PEO/ boric acid composite nano fiber, the composite nano fiber include nylon 46, PVDF, molecule
Adhesive, heat-resisting additive, the molecular adhesion agent are PEO, and the heat-resisting additive is boric acid；
The nylon 46/PVDF/PEO/ boric acid composite nano fiber preparation method, comprising the following steps:
A. it prepares PEO solution: PEO being dissolved in deionized water, stirring, matches to obtain PEO solution；
B. it prepares PEO/PVDF mixed liquor: PVDF aqueous emulsion is added in PEO solution described in step a, stirring is matched
PEO/PVDF mixed liquor；
C. it prepares Electrospun solution: nylon 46 salt, boric acid being added in PEO/PVDF mixed liquor described in step b, stirred
It mixes, match to obtain Electrospun solution；
D. Electrospun prepares composite nano fiber: nylon 46 is made by electrostatic spinning in the Electrospun solution in step c
Salt/PVDF/PEO/ boric acid precursor, it is thermally treated to get nylon 46/PVDF/PEO/ boric acid composite nano fiber.
In one embodiment, in step a, the PEO solution by super high molecular weight PEO powder is dissolved in 35~
In 45 DEG C of water, obtain after mixing evenly；The weight average molecular weight of the super high molecular weight PEO powder is 105~107g/mol。
In one embodiment, the weight average molecular weight of the super high molecular weight PEO powder is 5 × 106g/mol。
In one embodiment, the nylon 46 salt, PVDF, PEO mass ratio be (3-5): (4-6): 1.
In one embodiment, the mass ratio of the PEO and boric acid is 1-2.3.
In one embodiment, the PEO solution contains the PEO of 3~6wt%.
In one embodiment, the PVDF aqueous emulsion contains the PVDF of 30~50wt%.
In one embodiment, voltage is 10~40kV when electrostatic spinning described in the step d；Spinning-nozzle to pair
Setting electrode and collecting the distance of substrate is 15~30cm；Spinning flow velocity is 0.001~0.005mm/s.
In one embodiment, heat treatment described in the step d includes: first by nylon 46 salt/PVDF/PEO/ boron
Sour precursor is dried in vacuo 1~2h under conditions of being placed in 50~80 DEG C；Then heat under the conditions of 150-300 DEG C of temperature
0.5-1h.It is another object of the present invention to provide the nylon 46/PVDF/PEO/ boric acid composite nano fibers in nanometer
Application in fiber non-woven field.
Compared with prior art, the invention has the benefit that the present invention mixes nylon 46 salt with PVDF aqueous emulsion, and
Molecular adhesion agent, heat-resisting additive is added, obtains Electrospun solution, and by electrostatic spinning and heat treatment obtains having excellent
Mechanical property nylon 46/PVDF/PEO/ boric acid composite nano fiber, this solves nylon, and to be only soluble in formic acid, dimethyl sub-
In the minority solvents such as sulfone, the smell of formic acid is big and toxic, is not suitable for electrospinning the problem of preparing nylon nano fiber of large-scale,
Nylon 46/PVDF/PEO/ boric acid composite nano fiber of high-modulus, high elongation at tear is prepared simultaneously.
The above-mentioned of the application and other features, aspects and advantages are more readily understood with reference to following detailed description.
Specific embodiment
Unless otherwise defined, all technologies used herein and scientific term have and the common skill of fields of the present invention
The normally understood identical meaning of art personnel.When there is a conflict, the definition in this specification shall prevail.
As used herein term " by ... preparation " it is synonymous with "comprising".Term "comprising" used herein, " comprising ",
" having ", " containing " or its any other deformation, it is intended that cover non-exclusionism includes.For example, the combination comprising listed elements
Object, step, method, product or device are not necessarily limited to those elements, but may include not expressly listed other elements or
Such composition, step, method, product or the intrinsic element of device.
Conjunction " Consists of " excludes any element that do not point out, step or component.If in claim, this
Phrase will make claim closed, so that it is not included the material in addition to the material of those descriptions, but relative normal
Except rule impurity.When being rather than immediately following after theme in the clause that phrase " Consists of " appears in claim main body,
It is only limited to element described in the clause；Other elements are not excluded except the claim as a whole.
Equivalent, concentration or other values or parameter are excellent with range, preferred scope or a series of upper limit preferred values and lower limit
When the Range Representation that choosing value limits, this should be understood as specifically disclosing by any range limit or preferred value and any range
Any pairing of lower limit or preferred value is formed by all ranges, regardless of whether the range separately discloses.For example, when open
When range " 1 to 5 ", described range should be interpreted as including range " 1 to 4 ", " 1 to 3 ", " 1-2 ", " 1-2 and 4-5 ",
" 1-3 and 5 " etc..When numberical range is described herein, unless otherwise stated, otherwise the range be intended to include its end value and
All integers and score in the range.
In addition, indefinite article "an" before element of the present invention or component and "one" quantitative requirement to element or component
(i.e. frequency of occurrence) unrestriction.Therefore "one" or "an" should be read as including one or at least one, and odd number
The element or component of form also include plural form, unless the quantity obviously refers to singular.
To solve the above-mentioned problems, described multiple the present invention provides nylon 46/PVDF/PEO/ boric acid composite nano fiber
Closing nanofiber includes nylon 46, PVDF, molecular adhesion agent, heat-resisting additive, and the molecular adhesion agent is PEO, described heat-resisting
Additive is boric acid；
The nylon 46/PVDF/PEO/ boric acid composite nano fiber preparation method, comprising the following steps:
A. it prepares PEO solution: PEO being dissolved in deionized water, stirring, matches to obtain PEO solution；
B. it prepares PEO/PVDF mixed liquor: PVDF aqueous emulsion is added in PEO solution described in step a, stirring is matched
PEO/PVDF mixed liquor；
C. it prepares Electrospun solution: nylon 46 salt, boric acid being added in PEO/PVDF mixed liquor described in step b, stirred
It mixes, match to obtain Electrospun solution；
D. Electrospun prepares composite nano fiber: nylon 46 is made by electrostatic spinning in the Electrospun solution in step c
Salt/PVDF/PEO/ boric acid precursor, it is thermally treated to get nylon 46/PVDF/PEO/ boric acid composite nano fiber.
Electrospun solution of the present invention is the Electrospun solution of concentration 10-25wt%, the absolute viscosity of Electrospun solution
For 1-3.6Pa/s.
PVDF aqueous emulsion:
PVDF aqueous emulsion of the present invention is the aqueous dispersions that Kynoar is obtained by emulsion polymerization.
The PVDF aqueous emulsion can directly select commercially available, be preferably carried out mode, the PVDF water and milk as the present invention
Liquid contains the PVDF of 30~50wt%.
PEO:
PEO of the present invention is polyethylene glycol oxide, also known as polyethylene oxide, is a kind of crystallinity, thermoplastic water solubility
Polymer.PEO is the flowable powder of white, and molecular structure is (CH2CH2O), the concentration of this kind of resin active end group is lower, does not have
Apparent terminal reactive.Since there are C-O-C keys for it, usually there is flexibility, it can be with electron acceptor or certain inorganic electrolytes
Form associated matter.The formation of this external cause hydrogen bond, and become a kind of water-soluble polymer.As the present invention side of being preferably carried out
Formula, in step a, the PEO solution is by the way that super high molecular weight PEO powder to be dissolved in 35~45 DEG C of water, after mixing evenly
It obtains；The weight average molecular weight of the super high molecular weight PEO powder is 105~107g/mol；And then preferably, the super high molecular weight
The weight average molecular weight of PEO powder is 5 × 106g/mol；The PEO solution contains the PEO of 3~6wt%, and then preferably 4wt%
PEO。
Be preferably carried out mode as the present invention, the nylon 46 salt, PVDF, PEO mass ratio be (3-5): (4-6):
1。
Mode is preferably carried out as the present invention, and the mass ratio of the PEO and boric acid is 1-2.3.
Mode is preferably carried out as the present invention, and voltage is 10~40kV when electrostatic spinning described in the step d；Spinning
Nozzle collects the distance of substrate to opposite electrode as 15~30cm；Spinning flow velocity is 0.001~0.005mm/s.
Be preferably carried out mode as the present invention, described in the step d heat treatment include: first by nylon 46 salt/
PVDF/PEO/ boric acid precursor is dried in vacuo 1~2h under conditions of being placed in 50~80 DEG C；Then in 150-300 DEG C of temperature condition
Lower heat treatment 0.5-1h, makes nylon 46 salt be converted into nylon 46.
It is another object of the present invention to provide the nylon 46/PVDF/PEO/ boric acid composite nano fibers to receive
Application in rice fiber non-woven field.
The nylon 46 prepared using method of the present invention /PVDF/PEO/ boric acid composite nano fiber feature is such as
Under: fibre diameter: 50-300nm；Tensile strength: 300-1500MPa；Young's modulus: 2-20GPa；Elongation at break: 100-
400%.Embodiment:
Embodiment 1, nylon 46/PVDF/PEO/ boric acid composite nano fiber, the composite nano fiber includes nylon
46, PVDF, molecular adhesion agent, heat-resisting additive, the molecular adhesion agent are PEO, and the heat-resisting additive is boric acid；
Embodiment 2, the nylon 46/PVDF/PEO/ boric acid composite nano fiber preparation method, including following step
It is rapid:
A. it prepares PEO solution: PEO being dissolved in deionized water, stirring, matches to obtain PEO solution；
B. it prepares PEO/PVDF mixed liquor: PVDF aqueous emulsion is added in PEO solution described in step a, stirring is matched
PEO/PVDF mixed liquor；
C. it prepares Electrospun solution: nylon 46 salt, boric acid being added in PEO/PVDF mixed liquor described in step b, stirred
It mixes, match to obtain Electrospun solution；
D. Electrospun prepares composite nano fiber: nylon 46 is made by electrostatic spinning in the Electrospun solution in step c
Salt/PVDF/PEO/ boric acid precursor, it is thermally treated to get nylon 46/PVDF/PEO/ boric acid composite nano fiber.
Embodiment 3, identical as embodiment 2, different places is in step a, and the PEO solution is by dividing superelevation
Son amount PEO powder is dissolved in 35~45 DEG C of water, is obtained after mixing evenly；The super high molecular weight PEO powder is divided equally again
Son amount is 105~107g/mol。
Embodiment 4, identical as embodiment 3, different places are that the super high molecular weight PEO powder is divided equally again
Son amount is 5 × 106g/mol。
Embodiment 5, identical as embodiment 2, different places are, in step (1), the nylon 46 salt, PVDF,
The mass ratio of PEO is (3-5): (4-6): 1.
Embodiment 6, identical as embodiment 2, different places are that the mass ratio of the PEO and boric acid is 1-2.3.
Embodiment 7, identical as embodiment 2, different places are that the PEO solution contains the PEO of 3~6wt%.
Embodiment 8, identical as embodiment 2, different places are that the PVDF aqueous emulsion contains 30~50wt%'s
PVDF。
Embodiment 9, identical as embodiment 2, different places are, voltage when electrostatic spinning described in the step d
For 10~40kV；Spinning-nozzle collects the distance of substrate to opposite electrode as 15~30cm；Spinning flow velocity be 0.001~
0.005mm/s.Embodiment 10, identical as embodiment 1, different places are that heat treatment described in the step d includes:
1~2h is dried in vacuo under conditions of nylon 46 salt/PVDF/PEO/ boric acid precursor is placed in 50~80 DEG C first；Then in 150-
Heat 0.5-1h under the conditions of 300 DEG C of temperature.
The present invention is specifically described below by embodiment.It is necessarily pointed out that following embodiment is only used
In the invention will be further described, it should not be understood as limiting the scope of the invention, professional and technical personnel in the field
The some nonessential modifications and adaptations made according to the content of foregoing invention, still fall within protection scope of the present invention.
In addition, if illustrated without other, it is raw materials used to be all commercially available.
Embodiment 1
Nylon 46/PVDF/PEO/ boric acid composite nano fiber: PVDF aqueous emulsion contains the PVDF of 45wt%, of PVDF
Grain is 80nm, and PEO solution contains the PEO of 3wt%, and the weight average molecular weight of PEO powder is 5 × 106G/mol, nylon 46 salt,
The mass ratio of PVDF, PEO are 3:4:1, and the mass ratio of PEO and boric acid is 1, and Electrospun solution is that the Electrospun of concentration 10wt% is molten
Liquid；It is specific the preparation method is as follows:
PEO powder is dissolved in 40 DEG C of deionized water, it is molten that mechanical stirring 3h obtains the PEO that mass fraction is 3wt%
Liquid.The bubble collapse for being cooled to room temperature and being generated in solution because quickly stirring.PVDF aqueous emulsion is added to described
In PEO solution, PEO/PVDF mixed liquor is matched to obtain in stirring；Nylon 46 salt, boric acid are added in the PEO/PVDF mixed liquor,
Electrospun solution is matched to obtain in stirring；When preparing nylon 46 salt/PVDF/PEO/ boric acid precursor by electrostatic spinning, voltage, collect away from
From being respectively 13kV, 20cm and 0.002mm/s with flow velocity；Nylon 46 salt/PVDF/ is collected using steel wire (90 mesh) as supporter
PEO/ boric acid precursor, is placed in vacuum drying oven, and 70 DEG C of baking 1.8h carry out heat treatment 30min for 200 DEG C in high temperature furnace, obtain
Nylon 46/PVDF/PEO/ boric acid composite nano fiber.
Embodiment 2
Nylon 46/PVDF/PEO/ boric acid composite nano fiber: PVDF aqueous emulsion contains the PVDF of 48wt%, of PVDF
Grain is 80nm, and PEO solution contains the PEO of 4wt%, and the weight average molecular weight of PEO powder is 1 × 107G/mol, nylon 46 salt,
The mass ratio of PVDF, PEO are 3:6:1, and the mass ratio of PEO and boric acid is 1, and Electrospun solution is that the Electrospun of concentration 13wt% is molten
Liquid；It is specific the preparation method is as follows:
PEO powder is dissolved in 40 DEG C of deionized water, it is molten that mechanical stirring 3h obtains the PEO that mass fraction is 4wt%
Liquid.The bubble collapse for being cooled to room temperature and being generated in solution because quickly stirring.PVDF aqueous emulsion is added to described
In PEO solution, PEO/PVDF mixed liquor is matched to obtain in stirring；Nylon 46 salt, boric acid are added in the PEO/PVDF mixed liquor,
Electrospun solution is matched to obtain in stirring；When preparing nylon 46 salt/PVDF/PEO/ boric acid precursor by electrostatic spinning, voltage, collect away from
From being respectively 13kV, 20cm and 0.002mm/s with flow velocity；Nylon 46 salt/PVDF/ is collected using steel wire (90 mesh) as supporter
PEO/ boric acid precursor, is placed in vacuum drying oven, and 70 DEG C of baking 2h are heat-treated for 200 DEG C in high temperature furnace, obtain nylon 46/
PVDF/PEO/ boric acid composite nano fiber.
Embodiment 3
Nylon 46/PVDF/PEO/ boric acid composite nano fiber: PVDF aqueous emulsion contains the PVDF of 50wt%, of PVDF
Grain is 80nm, and PEO solution contains the PEO of 4wt%, and the weight average molecular weight of PEO powder is 5 × 106G/mol, nylon 46 salt,
The mass ratio of PVDF, PEO are 4:4:1, and the mass ratio of PEO and boric acid is 2, and Electrospun solution is that the Electrospun of concentration 15wt% is molten
Liquid；It is specific the preparation method is as follows:
PEO powder is dissolved in 40 DEG C of deionized water, it is molten that mechanical stirring 3h obtains the PEO that mass fraction is 4wt%
Liquid.The bubble collapse for being cooled to room temperature and being generated in solution because quickly stirring.PVDF aqueous emulsion is added to described
In PEO solution, PEO/PVDF mixed liquor is matched to obtain in stirring；Nylon 46 salt, boric acid are added in the PEO/PVDF mixed liquor,
Electrospun solution is matched to obtain in stirring；When preparing nylon 46 salt/PVDF/PEO/ boric acid precursor by electrostatic spinning, voltage, collect away from
From being respectively 13kV, 20cm and 0.002mm/s with flow velocity；Nylon 46 salt/PVDF/ is collected using steel wire (90 mesh) as supporter
PEO/ boric acid precursor, is placed in vacuum drying oven, and 70 DEG C of baking 2h are heat-treated for 200 DEG C in high temperature furnace, obtain nylon 46/
PVDF/PEO/ boric acid composite nano fiber.
Embodiment 4
Nylon 46/PVDF/PEO/ boric acid composite nano fiber: PVDF aqueous emulsion contains the PVDF of 50wt%, of PVDF
Grain is 80nm, and PEO solution contains the PEO of 4wt%, and the weight average molecular weight of PEO powder is 5 × 106G/mol, nylon 46 salt,
The mass ratio of PVDF, PEO are 4:5:1, and the mass ratio of PEO and boric acid is 2, and Electrospun solution is that the Electrospun of concentration 20wt% is molten
Liquid；It is specific the preparation method is as follows:
PEO powder is dissolved in 40 DEG C of deionized water, it is molten that mechanical stirring 3h obtains the PEO that mass fraction is 4wt%
Liquid.The bubble collapse for being cooled to room temperature and being generated in solution because quickly stirring.PVDF aqueous emulsion is added to described
In PEO solution, PEO/PVDF mixed liquor is matched to obtain in stirring；Nylon 46 salt, boric acid are added in the PEO/PVDF mixed liquor,
Electrospun solution is matched to obtain in stirring；When preparing nylon 46 salt/PVDF/PEO/ boric acid precursor by electrostatic spinning, voltage, collect away from
From being respectively 13kV, 20cm and 0.002mm/s with flow velocity；Nylon 46 salt/PVDF/ is collected using steel wire (90 mesh) as supporter
PEO/ boric acid precursor, is placed in vacuum drying oven, and 70 DEG C of baking 2h are heat-treated for 200 DEG C in high temperature furnace, obtain nylon 46/
PVDF/PEO/ boric acid composite nano fiber.
Embodiment 5
Nylon 46/PVDF/PEO/ boric acid composite nano fiber: PVDF aqueous emulsion contains the PVDF of 50wt%, of PVDF
Grain is 80nm, and PEO solution contains the PEO of 4wt%, and the weight average molecular weight of PEO powder is 5 × 106G/mol, nylon 46 salt,
The mass ratio of PVDF, PEO are 5:6:1, and the mass ratio of PEO and boric acid is 1, and Electrospun solution is that the Electrospun of concentration 25wt% is molten
Liquid；It is specific the preparation method is as follows:
PEO powder is dissolved in 40 DEG C of deionized water, it is molten that mechanical stirring 3h obtains the PEO that mass fraction is 4wt%
Liquid.The bubble collapse for being cooled to room temperature and being generated in solution because quickly stirring.PVDF aqueous emulsion is added to described
In PEO solution, PEO/PVDF mixed liquor is matched to obtain in stirring；Nylon 46 salt, boric acid are added in the PEO/PVDF mixed liquor,
Electrospun solution is matched to obtain in stirring；When preparing nylon 46 salt/PVDF/PEO/ boric acid precursor by electrostatic spinning, voltage, collect away from
From being respectively 13kV, 20cm and 0.002mm/s with flow velocity；Nylon 46 salt/PVDF/ is collected using steel wire (90 mesh) as supporter
PEO/ boric acid precursor, is placed in vacuum drying oven, and 70 DEG C of baking 2h are heat-treated for 200 DEG C in high temperature furnace, obtain nylon 46/
PVDF/PEO/ boric acid composite nano fiber.
Comparative example 1 is commercially available nylon 46 fiber, is purchased from Dongguan City Dong Zhan plastics trade Co., Ltd.
The nylon 46 being prepared using embodiment 1-5/PVDF/PEO/ boric acid composite nano fiber utilizes melting as raw material
Legal system obtains non-woven cloth.Comprising the following steps:
Melt simultaneously force feed melt to polymer chips using screw extruder；Polymer melt enter spinneret die it
It is preceding to be filtered through multilayer detailed catalogue metallic sieve；Gear wheel metering pump carries out melt-stoichiometry, and high polymer molten is sent after accurately measuring to molten
Jet mould head；After melt is transported to die head, it is evenly dispersed by runner to each spinneret orifice, and sprayed through spinneret orifice；From mould
While the melt stream generation extruding that head spinneret orifice squeezes out swells, by the drawing-off of two sides high velocity heated air streams, it is in viscosity flow
The melt stream of state is drawn and attenuated rapidly, meanwhile, the air at room temperature of two sides mixes drawing-off stream of hot air, cools and solidifies melt stream
Forming forms superfine fibre；Superfine fibre through drawing-off and cooling and solidifying blows to solidifying lace curtaining or rolling under the action of attenuating blast
Cylinder, fiber are collected on solidifying lace curtaining or roller, and nano-fiber for production of non-woven is formed.
Performance test:
1. fibre diameter measures
Pattern and fibre diameter use scanning electron microscope (VEGA3LMU, Tescan company of Czech) to carry out observation survey
It is fixed；
2. the measurement of the tensile strength of fibre single thread (measurement standard uses GB 9997-88)
It is measured, the result of every kind of sample using JQ03new type Miniature tension instrument (upper marine morning Digital Equipment Co., Ltd)
It is obtained by the average value of 10 this group of samples
3. the measurement of fibre single thread elongation at break (measurement standard uses GB 9997-88)
It is measured with the miniature control electronic universal tester of CMT8102 (Shenzhen SANS material tests Co., Ltd)；
4. the measurement of Young's modulus
It is measured using YMC-1 measure apparatus of youngs modulus (Changchun Great Wall instruments used for education Co., Ltd).
5. the measurement of electro spinning nano fiber non-woven cloth elongation at break
It is measured with the miniature control electronic universal tester of CMT8102 (Shenzhen SANS material tests Co., Ltd)；
6. the measurement of electro spinning nano fiber non-woven cloth tensile strength
It is measured with the miniature control electronic universal tester of CMT8102 (Shenzhen SANS material tests Co., Ltd)；
7. the measurement of electro spinning nano fiber non-woven cloth Young's modulus
It is measured using YMC-1 measure apparatus of youngs modulus (Changchun Great Wall instruments used for education Co., Ltd).Test result is shown in Table 1
Table 1
Example above-mentioned is merely illustrative, some features of feature for explaining the present invention.The attached claims
It is intended to the range as wide as possible for requiring to be contemplated that, and embodiments as presented herein is only according to all possible embodiment
Combined selection embodiment explanation.Therefore, the purpose of applicant is that the attached claims are not illustrated the present invention
Feature exemplary selectional restriction.And the progress in science and technology will be formed language express it is inaccurate due to and not
The possible equivalent being presently considered or son replacement, and these variations should also be interpreted in the conceived case by appended
Claim covering.
Claims (8)
1. nylon 46/PVDF/PEO/ boric acid composite nano fiber, which is characterized in that the composite nano fiber include nylon 46,
PVDF, molecular adhesion agent, heat-resisting additive, the molecular adhesion agent are PEO, and the heat-resisting additive is boric acid；
The nylon 46/PVDF/PEO/ boric acid composite nano fiber preparation method, comprising the following steps:
A. it prepares PEO solution: PEO being dissolved in deionized water, stirring, matches to obtain PEO solution；
B. it prepares PEO/PVDF mixed liquor: PVDF aqueous emulsion is added in PEO solution described in step a, PEO/ is matched to obtain in stirring
PVDF mixed liquor；
C. it prepares Electrospun solution: nylon 46 salt, boric acid being added in PEO/PVDF mixed liquor described in step b, stirs, match
Obtain Electrospun solution；
D. Electrospun prepares composite nano fiber: by the Electrospun solution in step c by electrostatic spinning be made nylon 46/
PVDF/PEO/ boric acid precursor, it is thermally treated to get nylon 46/PVDF/PEO/ boric acid composite nano fiber；
The nylon 46 salt, PVDF, PEO mass ratio be (3-5): (4-6): 1.
2. nylon 46 according to claim 1/PVDF/PEO/ boric acid composite nano fiber, which is characterized in that in step a,
The PEO solution is obtained after mixing evenly by the way that super high molecular weight PEO powder to be dissolved in 35~45 DEG C of water；It is described super
The weight average molecular weight of high molecular weight PEO powder is 105~107g/moL。
3. nylon 46 according to claim 2/PVDF/PEO/ boric acid composite nano fiber, which is characterized in that the superelevation
The weight average molecular weight of molecular weight PEO powder is 5 × 106g/moL。
4. nylon 46 according to claim 1/PVDF/PEO/ boric acid composite nano fiber, which is characterized in that the PEO
Mass ratio with boric acid is 1-2.3.
5. nylon 46 according to claim 1/PVDF/PEO/ boric acid composite nano fiber, which is characterized in that the PEO
Solution contains the PEO of 3~6wt%.
6. nylon 46 according to claim 1/PVDF/PEO/ boric acid composite nano fiber, which is characterized in that the PVDF
Aqueous emulsion contains the PVDF of 30~50wt%.
7. nylon 46 according to claim 1/PVDF/PEO/ boric acid composite nano fiber, which is characterized in that the step
Voltage is 10~40kV when electrostatic spinning described in d；Spinning-nozzle collects the distance of substrate to opposite electrode as 15~30cm；It spins
Silk flow velocity is 0.001~0.005mm/s.
8. nylon 46 according to claim 1/PVDF/PEO/ boric acid composite nano fiber, which is characterized in that the step
Heat treatment includes: nylon 46/PVDF/PEO/ boric acid precursor to be placed under conditions of 50~80 DEG C to be dried in vacuo 1 first described in d
~2h；Then heat 0.5-1h under the conditions of 150-300 DEG C of temperature.
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| CN1367276A (en) * | 2001-01-26 | 2002-09-04 | 韩国科学技术研究院 | Method for producing fine fibrous polymer fabric |
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| CN1367276A (en) * | 2001-01-26 | 2002-09-04 | 韩国科学技术研究院 | Method for producing fine fibrous polymer fabric |
| CN101104970A (en) * | 2007-07-19 | 2008-01-16 | 东华大学 | Continuous preparation method for ultra-fine electrostatic spinning fibre yarn |
| CN103938288A (en) * | 2014-04-10 | 2014-07-23 | 北京石油化工学院 | Preparation of fatty acid phase change energy storage luminescent material and nanofibers of material |
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