CN110373814A - P-aramid fiber nano fibrous membrane and preparation method thereof - Google Patents
P-aramid fiber nano fibrous membrane and preparation method thereof Download PDFInfo
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- CN110373814A CN110373814A CN201910686371.2A CN201910686371A CN110373814A CN 110373814 A CN110373814 A CN 110373814A CN 201910686371 A CN201910686371 A CN 201910686371A CN 110373814 A CN110373814 A CN 110373814A
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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
- D01D5/0076—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
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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- D06C—FINISHING, DRESSING, TENTERING OR STRETCHING TEXTILE FABRICS
- D06C7/00—Heating or cooling textile fabrics
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Abstract
The present invention relates to a kind of p-aramid fiber nano fibrous membranes and preparation method thereof, belong to special fibre Material Field.The present invention provides a kind of preparation method of p-aramid fiber nano fibrous membrane, the preparation method is that: spinning-aid agent is first added in para-aramid fiber solution, uniform spinning solution is made, then p-aramid fiber nano fibrous membrane is made by the method for electrostatic spinning in gained spinning solution；Wherein, the spinning-aid agent is one of polyethylene oxide, polyethylene pyrrole network alkanone or polyvinyl alcohol, the mass ratio of para-aramid fiber in spinning-aid agent and para-aramid fiber solution are as follows: 10 parts by weight of para-aramid fiber, 1~12 parts by weight of spinning-aid agent.The present invention is successfully realized for the first time has prepared continuous p-aramid fiber nano fibrous membrane using the method for electrostatic spinning；And by the collection device for changing electrostatic spinning, random distribution and the film with certain two kinds of structural forms of the degree of orientation are obtained.
Description
Technical field
The present invention relates to a kind of p-aramid fiber nano fibrous membranes and preparation method thereof, belong to special fibre Material Field.
Background technique
The development of modern science and technology proposes increasingly higher demands to the performance of material, with the appearance of nanotechnology,
The property of nano material and application start to become the hot spot that scholars study.Nano material and nanotechnology are to carry out material instantly
One of research and the most potential field of change, and the basis of a new generation's advanced fiber and composite material is formed, it is micro-nano
The application of fibre structure also has become the core of many new industry technologies, will also become it from macroscopic view to microcosmic research
Trend afterwards.Continuous nano-fibre represents a kind of emerging nano material, above has key in the structure of material and using combining
Advantage, how to push material to structure nano and function nano be also one of present research hotspot.
Kevlar fiber, i.e. p -aromatic polyamide fiber, because having, intensity is high, modulus is high, density is low, hot steady for it
Qualitative good characteristic and be concerned.But the preparation process of PPTA fiber is more harsh, is by strictly equal mass ratioes to benzene two
First condensation polymerization or low temperature solution polymerization be (such as in highly polar amide solvent or solvent of strong for formyl chloride and p-phenylenediamine monomer
In the solvent of strong such as the highly polar system of the NMP containing LiCl or the concentrated sulfuric acid, chlorosulfonic acid and fluoroacetic acid), then solution carries out
Spinning obtains high-crystallinity, highly oriented micron order as-spun fibre.Kevlar fiber molecule interchain is there are two kinds of active forces, and one
It is that the hydrogen bound to nitrogen of different molecular interchain amide group interacts the hydrogen bond to be formed, the other is adjacent molecule interchain phenyl ring is mutual
It is superimposed the π-πconjugation formed；Just because of its extremely strong intermolecular force, high crystallinity, inert surface makes it
Using fento scale is rested on, its stable nanosizing can not be obtained p-aramid fiber nanofiber, to expand it using model
It encloses.
There has been no the relevant reports with preferable structure and the p-aramid fiber nano fibrous membrane of performance in the prior art.
Summary of the invention
In view of the foregoing drawbacks, the present invention provides a kind of preparation method of p-aramid fiber nano fibrous membrane, this method for the first time
The p-aramid fiber nano fibrous membrane with satisfactory texture and performance, and the preparation method simple process is successfully made, easily
In operation, there is breakthrough directive significance for the research of aramid nano-fiber.
Technical solution of the present invention:
The invention solves first technical problem be to provide the preparation method of p-aramid fiber nano fibrous membrane a kind of, institute
State the preparation method comprises the following steps: first in para-aramid fiber solution be added spinning-aid agent uniform spinning solution is made, then gained spinning solution
P-aramid fiber nano fibrous membrane is made by the method for electrostatic spinning；Wherein, the spinning-aid agent is polyethylene oxide, polyethylene pyrrole
The mass ratio of para-aramid fiber in one of network alkanone or polyvinyl alcohol, spinning-aid agent and para-aramid fiber solution are as follows: right
Position 10 parts by weight of aramid fiber, 1~12 parts by weight of spinning-aid agent.
Further, the weight average molecular weight of the spinning-aid agent is 30~7,000,000；If molecular weight is too small, can go out in fiber
Existing spindle structure；If molecular weight is excessive, fiber will appear the non-uniform situation of thickness, and go out with spindle structure
It is existing.
Further, in above-mentioned preparation method, the mass concentration of the para-aramid fiber solution is 0.5~2.5wt%；Such as
The concentration of fruit solution is too low, electrostatic spinning process then can because of spinning solution viscosity it is too low and can not carry out；If solution concentration
It is excessively high, then solution viscosity is bigger than normal, during electrostatic spinning electrostatic field drawing force not enough cause fibre diameter bigger than normal and thickness not
Uniformly.
Further, in above-mentioned preparation method, the process conditions of the electrostatic spinning are as follows: the voltage of electrostatic spinning be 7~
15kv, spinning rate are 0.1~0.5ml/h, and the distance between spinning nozzle and reception device are 10~15cm, spinning temperature 35
~70 DEG C.
Further, in the above method, when the reception device in electrospinning process is flat receiver, gained contraposition virtue
The microstructure of synthetic fibre nano fibrous membrane shows themselves in that random distribution state is presented in the nanofiber in film；When reception device is rolling
When cylinder collector, the microstructure of gained p-aramid fiber nano fibrous membrane shows themselves in that the nanofiber in film along roller
Rotation direction has certain degree of orientation.
Further, the method that uniform spinning solution is made in spinning-aid agent is added in the above method, in para-aramid fiber solution
Are as follows: it is added spinning-aid agent in para-aramid fiber solution, heating stirring is completely dissolved spinning-aid agent to obtain uniform spinning solution；
Wherein, heating temperature is 25-70 DEG C, preferably 50 DEG C.
Further, in above-mentioned preparation method, the para-aramid fiber solution is made using following methods: by p-aramid fiber
Micrometer fibers stir to dissolve under the action of organic solvent and cosolvent, then remove extra cosolvent and completely molten
The para-aramid fiber of solution obtains uniform para-aramid fiber solution.
Further, in the preparation method of the para-aramid fiber solution, the organic solvent is dimethyl sulfoxide, N, N-
One of dimethyl acetamide, N,N-dimethylformamide, tetrahydrofuran or acetone.
Further, in the preparation method of the para-aramid fiber solution, the cosolvent is potassium hydroxide, hydroxide
One of sodium, potassium tert-butoxide or sec-butyl alcohol potassium.
Further, in the preparation method of the para-aramid fiber solution, p-aramid fiber micrometer fibers in organic solvent and
The method stirred to dissolve under the action of cosolvent are as follows: by p-aramid fiber micrometer fibers or it is added in organic solvent, then plus
Enter cosolvent, be then sealed, magnetic agitation 7~12 days or by 30-60 DEG C heating water bath 6~8 days.In the present invention, hydrotropy
The additional amount of agent and solvent needs to guarantee that para-aramid fiber can sufficiently dissolve, the mass ratio of para-aramid fiber and cosolvent
Are as follows: 1:1~2.
Further, in the preparation method of the para-aramid fiber solution, it is extra to be removed by the way of centrifugal treating
Cosolvent and the para-aramid fiber not being completely dissolved, wherein centrifugation rate be 5000~10000rad/min (preferably
8000rad/min), temperature is 18~30 DEG C (preferably 22 DEG C), 30~60min of centrifugation time (preferably 45min).
Further, in order to improve gained p-aramid fiber nano fibrous membrane mechanical property, by film made from method of electrostatic spinning
It is heat-treated, the heat treatment method are as follows: by p-aramid fiber nano fibrous membrane at 60~120 DEG C (preferably 100 DEG C), 0.2
5~60min of hot pressing (preferably 30min) under conditions of~2MPa (preferably 0.4MPa).
The invention solves second technical problem be to provide a kind of p-aramid fiber nano fibrous membrane, the p-aramid fiber
Nano fibrous membrane is made using the above method.
Further, the diameter of nanofiber is 80~200nm in the p-aramid fiber nano fibrous membrane.
Further, the porosity of the p-aramid fiber nano fibrous membrane are as follows: 50~90%.When film is that the quiet spinning of random distribution is thin
Porosity is 80~90% when film；When film is the quiet spinning film with certain degree of orientation, porosity is 50~60%.
Further, the water contact angle of the p-aramid fiber nano fibrous membrane are as follows: 17 ° -27 °.
Beneficial effects of the present invention:
1, the present invention is successfully realized for the first time has prepared continuous p-aramid fiber Nanowire using the method for electrostatic spinning
Tie up film；And by the collection device for changing electrostatic spinning, random distribution is obtained and there are two kinds of structure shapes of certain degree of orientation
The film of state.This not only avoids the concentrated sulfuric acid spinning systems of traditional aramid fiber, and under the assistance of spinning-aid agent, successfully make
It is standby to obtain p-aramid fiber nano-fiber film continuous, that structural form is excellent, realize the breakthrough of zero；P-aramid fiber is received
The research of rice fiber has breakthrough directive significance.
2, compared to traditional electrostatic spinning film, the quiet spinning film of p-aramid fiber nanofiber of the present invention has played virtue
The high-performance benefits of synthetic fibre fiber；Either random distribution still have the film of certain degree of orientation all have good heat resistance and
Excellent mechanical property, while good structural form has been still maintained, fibre structure is good, even thickness, and porosity is high, hole
Diameter is uniform.
3, certain heat treatment is carried out to preparation gained p-aramid fiber nano-fiber film, fibre structure shape can be being kept
State variation is less and in the case where high porosity, significantly promotion of the realization to the mechanical property of film, considerably beyond existing
Electrostatic spinning film mechanical strength.
4, the water contact angle of present invention gained p-aramid fiber nano fibrous membrane are as follows: 17 ° -27 °, there is good hydrophily；
And gained p-aramid fiber nano fibrous membrane is heat-resist；After tested, decomposed can just occur for 320 DEG C；With 200 DEG C of heat
Platform directly heats 10~30min, and film will not deformation occurs, still maintains complete structural form.
Detailed description of the invention:
Fig. 1 is the transmission electron microscope picture of ANF/DMSO solution obtained by 1 step of embodiment (2), can be visible in detail in figure
The presence of nanofiber in ANF solution, and maintain better structural form.
In Fig. 2, (a) figure and (b) figure are respectively that the quiet spinning film surface of 3 gained flat panel collector of embodiment and truncation surface SEM scheme；
(c) figure and (d) figure is respectively that 2 gained roller of embodiment collects quiet spinnings film surface and truncation surface SEM figure.
In Fig. 3, (a) figure and (b) figure are respectively the quiet spinning film hot-pressing rear surface of 3 gained flat panel collector of embodiment and truncation surface
SEM figure；(c) figure and (d) figure is respectively that 2 gained roller of embodiment collects quiet spinnings film hot-pressing rear surface and truncation surface SEM figure.
In Fig. 4, (a) figure is stretching comparison diagram before and after the quiet spinning film hot-pressing of 3 gained flat panel collector of embodiment；(b) figure is real
It applies before and after 2 gained roller of example collects quiet spinning film hot-pressing and stretches comparison diagram.
In Fig. 5, (a) figure is the quiet SEM figure for spinning film surface of 1 gained flat panel collector of embodiment, and (b) figure is putting for (a) figure
Big figure.
In Fig. 6, (a) figure is the quiet SEM figure for spinning film surface of 4 gained flat panel collector of embodiment, and (b) figure is putting for (a) figure
Big figure.
In Fig. 7, (a) figure is the quiet SEM figure for spinning film surface of 2 gained flat panel collector of comparative example, and (b) figure is putting for (a) figure
Big figure.
Specific embodiment
The present invention provides a kind of p-aramid fiber nanometer with method of electrostatic spinning preparation with satisfactory texture and performance for the first time
The preparation method of fiber membrane provides new approaches for the current research about p-aramid fiber nanofiber.The present invention passes through
After para-aramid fiber is dissolved in organic solvent/alkali systems, adds certain spinning-aid agent and mixed through mechanical stirring equal
In the case where even, by regulating and controlling the parameters of electrostatic spinning, continuous p-aramid fiber nano fibrous membrane has been prepared.Gained
Film has even thickness, the nanofiber form of well-formed, and porosity is high, and uniform pore diameter is heat-resist, and mechanical property is excellent
It is different, there is potential application at many aspects.
The present invention provides a kind of with method of electrostatic spinning preparation structure and the p-aramid fiber nano-fiber film haveing excellent performance
Preparation method, specific steps are as follows: step 1: by micron order dissolving aramid fiber in DMSO/KOH system, in KOH deprotonation
Under the action of change, micron order aramid fiber is removed into nanofiber, the ANF suspension containing aramid nano-fiber is obtained, passed through
Centrifugation obtains ANF solution；Step 2: a certain amount of PEO is mixed with resulting ANF solution again, through heating water bath mechanical stirring
It is uniformly mixed, obtains spinning solution；Because having benzene radicals in the molecular backbone of para-aramid fiber, strand divides at rigidity
Entanglement power is weak between son, difficulty in spinning under the action of electrostatic field, and the PEO of certain mass and molecular weight is added, and can increase greatly
Add the entanglement effect between para-aramid fiber strand, to help to realize the electrostatic spinning of para-aramid fiber；Step 3:
P-aramid fiber nano-fiber film is prepared by electrostatic spinning；Step 4: to preparing resulting p-aramid fiber nanofiber
Film carries out certain heat treatment, obtains the quiet spinning film of more excellent performance of p-aramid fiber nanofiber.
In the present invention, the addition of the spinning-aid agents such as PEO can greatly improve the entanglement between 49 strand of Kevlar, improve
The viscosity and conductivity of solution, to guarantee the smooth implementation of electrostatic spinning process；Again to preparing resulting p-aramid fiber nanometer
The quiet spinning film of fiber carries out certain heat treatment process, is the bonding effect using PEO, greatly improves quiet spinning film-based fibre layer
Snap action between fibrous layer, to realize the quiet significantly promotion for spinning thin film mechanical performance.
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
It will be appreciated that the following example is merely to illustrate the present invention, and it is not construed as limiting the scope of the invention.
Embodiment 1
(1) 7g Kevlar 49 is weighed respectively and 7g KOH is added in 500ml DMSO, after being sealed with sealant
Magnetic agitation one week or so at room temperature, obtain wine-colored ANF suspension；It is found in experimentation, aramid fiber is dissolving
The different state of the presentation of different time sections system, aramid fiber gradually dissolve in the process, and system color is gradually deepened, and is finally become
Laking obtains ANF suspension；
It (2) is 8000rad/min in revolving speed by the ANF suspension in step (1), temperature is centrifuged under conditions of being 25 DEG C
45min removes undissolved KOH and aramid fiber in suspension, and it is molten that the ANF/DMSO that concentration is 2.159wt% is prepared
Liquid；Fig. 1 is the transmission electron microscope picture of 1 gained ANF/DMSO solution of embodiment, can be with nanometer in ANF solution visible in detail in figure
The presence of fiber, and maintain better structural form；Show micron order aramid fiber in DMSO/KOH system because
The deprotonation of KOH, the amido bond between the para-aramid fiber molecule of part are destroyed, and realize micron order p-aramid fiber
The removing of fiber, to obtain p-aramid fiber nanofiber in ANF solution；
(3) the ANF solution that step (2) resulting concentration is 2.159wt% is diluted to 0.7wt% concentration, adds 200
The PEO of ten thousand molecular weight, para-aramid fiber: the mass ratio of PEO is 10:3, and it is equal to obtain mixing through 50 DEG C of heating water bath mechanical stirrings
Even spinning solution；
(4) spinning solution that appropriate step (3) are taken with the syringe that the diameter of 5ml is 12.5mm, uses internal diameter for 0.2mm,
The syringe needle that outer diameter is 0.80mm implements electrostatic spinning；The parameter setting of electrostatic spinning is as follows: voltage: 7kv, spinning rate:
0.1ml/h, the distance between spinning nozzle and collector be 150mm, spinning temperature: 45 DEG C, spinning humidity: 3%.With this condition
The spinning time is set as 60h, and using flat panel collector, the quiet spinning film of p-aramid fiber nanofiber of random distribution is prepared；
(5) by the quiet dry 12h of vacuum drying oven for spinning film and being put into 60 DEG C of step (4) preparation gained, it is extra in film to remove
Solvent and a small amount of moisture；Fig. 5 is the quiet spinning film surface SEM figure of 1 gained of embodiment, it can be seen that fibre morphology structure is non-
Chang Hao, fiber thickness is uniform, and fibre diameter is between 150-250nm.
Embodiment 2
(1) 8g Kevlar 49 is weighed respectively and 10g KOH is added in 500ml DMSO, after being sealed with sealant
Magnetic agitation one week or so at room temperature, obtain wine-colored ANF suspension.
It (2) is 8000rad/min in revolving speed by the ANF suspension in step (1), temperature is centrifuged under conditions of being 22 DEG C
45min removes undissolved KOH and aramid fiber in suspension, the ANF/DMSO solution of 2.365wt% concentration is prepared.
(3) the ANF solution of the resulting 2.365wt% concentration of step (2) is diluted to 1.5wt% concentration, added and ANF
The PEO of 1,000,000 molecular weight of phase homogenous quantities, i.e. para-aramid fiber: the mass ratio of PEO is 1:1, through 50 DEG C of heating water bath machinery
Stir to get uniformly mixed spinning solution.
(4) spinning solution that appropriate step (3) are taken with the syringe that the diameter of 5ml is 12.5mm, uses internal diameter for 0.2mm,
The syringe needle that outer diameter is 0.80mm implements electrostatic spinning；The parameter setting of electrostatic spinning is as follows: voltage: 10kv, spinning rate:
0.3ml/h, the distance between spinning nozzle and collector be 150mm, spinning temperature: 45 DEG C, spinning humidity: 3%；With this condition
The spinning time is set as 40h, is collected using roller, and it is thin that the quiet spinning of the p-aramid fiber nanofiber with certain degree of orientation is prepared
Film.
(5) by the quiet dry 12h of vacuum drying oven for spinning film and being put into 60 DEG C of step (4) preparation gained, it is extra in film to remove
Solvent and a small amount of moisture.
(6) the quiet spinning film after again will be dry in step (5) is at 100 DEG C, hot pressing 30min under conditions of 0.4MPa, into one
Step promotes the mechanical property of film.
Embodiment 3
(1) 8g Kevlar 49 is weighed respectively and 10g KOH is added in 500ml DMSO, after being sealed with sealant
Magnetic agitation one week or so at room temperature, obtain wine-colored ANF suspension.
It (2) is 8000rad/min in revolving speed by the ANF suspension in step (1), temperature is centrifuged under conditions of being 22 DEG C
45min removes undissolved KOH and aramid fiber in suspension, the ANF/DMSO solution of 2.365wt% concentration is prepared.
(3) the ANF solution of the resulting 2.365wt% concentration of step (2) is diluted to 1.5wt% concentration, added and ANF
The PEO of 1,000,000 molecular weight of phase homogenous quantities, i.e. para-aramid fiber: the mass ratio of PEO is 1:1, through 50 DEG C of heating water bath machinery
Stir to get uniformly mixed spinning solution.
(4) spinning solution that appropriate step (3) are taken with the syringe that the diameter of 5ml is 12.5mm, uses internal diameter for 0.2mm,
The syringe needle that outer diameter is 0.80mm implements electrostatic spinning；The parameter setting of electrostatic spinning is as follows: voltage: 10kv, spinning rate:
0.3ml/h, the distance between spinning nozzle and collector be 150mm, spinning temperature: 45 DEG C, spinning humidity: 3%；With this condition
The spinning time is set as 20h, and using flat panel collector, the quiet spinning film of p-aramid fiber nanofiber of random distribution is prepared.
(5) by the quiet dry 12h of vacuum drying oven for spinning film and being put into 60 DEG C of step (4) preparation gained, it is extra in film to remove
Solvent and a small amount of moisture；Gained after tested, the water contact angle of film is 17 ° at this time.
(6) the quiet spinning film after again will be dry in step (5) is at 100 DEG C, hot pressing 30min under conditions of 0.4MPa, into one
Step promotes the mechanical property of film；Gained after tested, the water contact angle of film is 27 ° at this time, and 200 DEG C of thermal station heat 30min, thin
Film will not deformation occurs, still maintains complete structural form；Show the heat resistance of gained p-aramid fiber nano-fiber film
It is good.
Fig. 2 (a) and Fig. 2 (b) is respectively that the quiet spinning film surface of 3 gained flat panel collector of embodiment and truncation surface SEM scheme；Fig. 2
(c) and Fig. 2 (d) is respectively that 2 gained roller of embodiment collects quiet spinning film surface and truncation surface SEM figure；As shown in Figure 2, this hair
The bright resulting random distribution and the p-aramid fiber nano-fiber film with certain degree of orientation of preparing all has good fiber shape
State, fiber thickness is uniform, is mainly distributed between 100~200nm, and the quiet porosity for spinning film obtained by flat panel collector reaches
87% or so, the quiet spinning film porosity that roller is collected also has 50% or so；And the quiet spinning film that roller is collected is very bright
Aobvious to have certain degree of orientation, the overlap joint between fibrous layer will more closely compared to the obtained film of flat panel collector, this is
Because drum rotation speed is higher when roller is collected, 3000rad/min is reached, when spinning solution is sprayed from spinning nozzle, through electrostatic field force
Stretching Cheng Sihou by drawing will also be subjected to the shearing force along roller rotation direction, the distance between such fibrous layer and fibrous layer
Can be smaller, the overlap joint between fibrous layer and fibrous layer also can be closer, and mechanical property also can be much better.
Fig. 3 (a) and Fig. 3 (b) is respectively the quiet spinning film hot-pressing rear surface of 3 gained flat panel collector of embodiment and truncation surface SEM
Figure；Fig. 3 (c) and Fig. 3 (d) is respectively that 2 gained roller of embodiment collects quiet spinning film hot-pressing rear surface and truncation surface SEM figure；Fig. 3
It is found that either flat panel collector or roller collect the quiet spinning film of gained, after hot pressing, the fibre morphology in film is protected substantially
Hold constant, fiber thickness is uniform, and being computed the quiet spinning film of flat panel collector porosity after hot pressing is 82% or so, and roller is collected quiet
Spinning film porosity is 50% or so, and before hot pressing, porosity does not change substantially；Generally speaking, quiet before and after hot pressing
The structural form of spinning film is (c) shown substantially there is no variation such as figure (a).However, two kinds of film fibrous layers after hot pressing
Overlap joint between fibrous layer becomes even closer, almost without gap such as figure (b), (d) shown in, while from figure (a), (b) in
As can be seen that there is the thing similar to node at the overlapped points of fiber and fiber in the film after hot pressing, that be because
During high temperature hot pressing, fiber middles divide PEO to flow out from fiber, and the process being then cold-pressed is transformed to PEO again
Condensed state, so as to form point of contact so-called in this way；Exactly these points of contact promote quiet spinning film-based fibre layer and fibrous layer
Between overlap joint so that the quiet spinning film of high porosity becomes more closely, the mechanical property of film is also big compared to having before
The promotion of amplitude.
In addition the present invention also compares the tensile property of 3 gained film of embodiment 2 and embodiment, and structure is as shown in Figure 4；Figure
In 4, (a) figure is stretching comparison diagram before and after the quiet spinning film hot-pressing of 3 gained flat panel collector of embodiment；(b) figure is to roll obtained by embodiment 2
Cylinder stretches comparison diagram before and after collecting quiet spinning film hot-pressing；As shown in Figure 4, spinning film quiet for flat panel collector, without hot-pressing processing
Tensile strength be 10MPa, the tensile strength after hot-pressing processing has reached 35MPa, has improved 3.5 times, though and elongation at break
It so reduces, but still has 10%；Quiet spinning film is collected for roller, the tensile strength without hot-pressing processing is 36MPa, hot pressing
Treated, and tensile strength has reached 66MPa, improves nearly twice, and elongation at break is improved extremely by original 3%
Nearly 4%；Because the quiet spinning film that roller is collected has certain degree of orientation, then compared to the quiet spinning film of flat panel collector,
Tensile strength is relatively high, and elongation at break is relatively low.It is received it can be seen that preparing resulting p-aramid fiber by electrostatic spinning
The rice quiet spinning film itself of fiber just has excellent mechanical property, but after hot-pressing processing, due to the bonding effect of PEO, makes
The mechanical property for obtaining film has obtained significantly being promoted, considerably beyond the mechanical property of existing electrostatic spinning film.
Embodiment 4
(1) 7g Kevlar 49 is weighed respectively and 7g KOH is added in 500ml DMSO, after being sealed with sealant
Magnetic agitation one week or so at room temperature, obtain wine-colored ANF suspension.
It (2) is 8000rad/min in revolving speed by the ANF suspension in step (1), temperature is centrifuged under conditions of being 25 DEG C
45min removes undissolved KOH and aramid fiber in suspension, the ANF/DMSO solution of 2.159wt% concentration is prepared.
(3) the ANF solution of the resulting 2.159wt% concentration of step (2) is diluted to 2.0wt% concentration, adds 4,000,000
The PEO of molecular weight, para-aramid fiber: the mass ratio of PEO is 5:6, is uniformly mixed through 50 DEG C of heating water bath mechanical stirrings
Spinning solution.
(4) spinning solution that appropriate step (3) are taken with the syringe that the diameter of 5ml is 12.5mm, uses internal diameter for 0.2mm,
The syringe needle that outer diameter is 0.80mm implements electrostatic spinning；The parameter setting of electrostatic spinning is as follows: voltage: 15kv, spinning rate:
0.5ml/h, the distance between spinning nozzle and collector be 150mm, spinning temperature: 45 DEG C, spinning humidity: 3%；With this condition
The spinning time is set as 15h, is collected using roller, and it is thin that the quiet spinning of the p-aramid fiber nanofiber with certain degree of orientation is prepared
Film.
(5) by the quiet dry 12h of vacuum drying oven for spinning film and being put into 60 DEG C of step (4) preparation gained, it is extra in film to remove
Solvent and a small amount of moisture；Fig. 6 is the quiet spinning film surface SEM figure of 4 gained of embodiment, as can be seen from the figure.Fibre morphology
It is basic to keep good.
Embodiment 5
(1) 8g Kevlar 49 is weighed respectively and 10g KOH is added in 500ml DMSO, after being sealed with sealant
Magnetic agitation one week or so at room temperature, obtain wine-colored ANF suspension.
It (2) is 8000rad/min in revolving speed by the ANF suspension in step (1), temperature is centrifuged under conditions of being 22 DEG C
45min removes undissolved KOH and aramid fiber in suspension, the ANF/DMSO solution of 2.365wt% concentration is prepared.
(3) the ANF solution of the resulting 2.365wt% concentration of step (2) is diluted to 1.5wt% concentration, added and ANF
The PEO of 1,000,000 molecular weight of phase homogenous quantities, i.e. para-aramid fiber: the mass ratio of PEO is 1:1, through 50 DEG C of heating water bath machinery
Stir to get uniformly mixed spinning solution.
(4) spinning solution that appropriate step (3) are taken with the syringe that the diameter of 5ml is 12.5mm, uses internal diameter for 0.2mm,
The syringe needle that outer diameter is 0.80mm implements electrostatic spinning；The parameter setting of electrostatic spinning is as follows: voltage: 10kv, spinning rate:
0.3ml/h, the distance between spinning nozzle and collector be 150mm, spinning temperature: 45 DEG C, spinning humidity: 3%；With this condition
The spinning time is set as 20h, and using flat panel collector, the quiet spinning film of p-aramid fiber nanofiber of random distribution is prepared.
(5) by the quiet dry 12h of vacuum drying oven for spinning film and being put into 60 DEG C of step (4) preparation gained, it is extra in film to remove
Solvent and a small amount of moisture.
(6) the quiet spinning film after will be dry in step (5) impregnates 6h under 80 DEG C of heating water bath mechanical stirring, removes
Part PEO obtains the quiet spinning film of p-aramid fiber nanofiber that ANF content is 75%.
(7) the quiet spinning film after again will be dry in step (6) is at 100 DEG C, hot pressing 30min under conditions of 0.4MPa, into one
Step promotes the mechanical property of film.The porosity of gained hot pressing rear film is 80%, tensile strength 28MPa, elongation at break
It is 7.2%.
Embodiment 6
(1) 8g Kevlar 49 is weighed respectively and 10g KOH is added in 500ml DMSO, after being sealed with sealant
Magnetic agitation one week or so at room temperature, obtain wine-colored ANF suspension.
It (2) is 8000rad/min in revolving speed by the ANF suspension in step (1), temperature is centrifuged under conditions of being 22 DEG C
45min removes undissolved KOH and aramid fiber in suspension, the ANF/DMSO solution of 2.365wt% concentration is prepared.
(3) the ANF solution of the resulting 2.365wt% concentration of step (2) is diluted to 1.5wt% concentration, added and ANF
The PEO of 1,000,000 molecular weight of phase homogenous quantities, i.e. para-aramid fiber: the mass ratio of PEO is 1:1, through 50 DEG C of heating water bath machinery
Stir to get uniformly mixed spinning solution.
(4) spinning solution that appropriate step (3) are taken with the syringe that the diameter of 5ml is 12.5mm, uses internal diameter for 0.2mm,
The syringe needle that outer diameter is 0.80mm implements electrostatic spinning；The parameter setting of electrostatic spinning is as follows: voltage: 10kv, spinning rate:
0.3ml/h, the distance between spinning nozzle and collector be 150mm, spinning temperature: 45 DEG C, spinning humidity: 3%；With this condition
The spinning time is set as 10h, and using flat panel collector, the quiet spinning film of p-aramid fiber nanofiber of random distribution is prepared.
(5) by the quiet dry 12h of vacuum drying oven for spinning film and being put into 60 DEG C of step (4) preparation gained, it is extra in film to remove
Solvent and a small amount of moisture.
(6) the quiet spinning film after again will be dry in step (5) is at 100 DEG C, hot pressing 30min under conditions of 0.4MPa, into one
Step promotes the mechanical property of film.The porosity of gained hot pressing rear film is 78%, tensile strength 30MPa, elongation at break
It is 8.2%.
Embodiment 7
(1) 8g Kevlar 49 is weighed respectively and 10g KOH is added in 500ml DMSO, after being sealed with sealant
Magnetic agitation one week or so at room temperature, obtain wine-colored ANF suspension.
It (2) is 8000rad/min in revolving speed by the ANF suspension in step (1), temperature is centrifuged under conditions of being 22 DEG C
45min removes undissolved KOH and aramid fiber in suspension, the ANF/DMSO solution of 2.365wt% concentration is prepared.
(3) the ANF solution of the resulting 2.365wt% concentration of step (2) is diluted to 1.5wt% concentration, added and ANF
The PEO of 1,000,000 molecular weight of phase homogenous quantities, i.e. para-aramid fiber: PEO 1:1 are obtained through 50 DEG C of heating water bath mechanical stirrings
Uniformly mixed spinning solution.
(4) spinning solution that appropriate step (3) are taken with the syringe that the diameter of 5ml is 12.5mm, uses internal diameter for 0.2mm,
The syringe needle that outer diameter is 0.80mm implements electrostatic spinning；The parameter setting of electrostatic spinning is as follows: voltage: 10kv, spinning rate:
0.3ml/h, the distance between spinning nozzle and collector be 150mm, spinning temperature: 45 DEG C, spinning humidity: 3%；With this condition
The spinning time is set as 10h, and using flat panel collector, the quiet spinning film of p-aramid fiber nanofiber of random distribution is prepared.
(5) by the quiet dry 12h of vacuum drying oven for spinning film and being put into 60 DEG C of step (4) preparation gained, it is extra in film to remove
Solvent and a small amount of moisture.
(6) the quiet spinning film after will be dry in step (5) impregnates 6h under 80 DEG C of heating water bath mechanical stirring, removes
Part PEO obtains the quiet spinning film of p-aramid fiber nanofiber that ANF content is 75%.
(7) the quiet spinning film after again will be dry in step (6) is at 100 DEG C, hot pressing 30min under conditions of 0.4MPa, into one
Step promotes the mechanical property of film.The porosity of gained hot pressing rear film is 75%, tensile strength 24MPa, elongation at break
It is 6.4%.
Comparative example 1 is not added with spinning-aid agent PEO
(1) 8g Kevlar 49 is weighed respectively and 10g KOH is added in 500ml DMSO, after being sealed with sealant
Magnetic agitation one week or so at room temperature, obtain wine-colored ANF suspension.
It (2) is 8000rad/min in revolving speed by the ANF suspension in step (1), temperature is centrifuged under conditions of being 22 DEG C
45min removes undissolved KOH and aramid fiber in suspension, the ANF/DMSO solution of 2.365wt% concentration is prepared.
(3) the ANF solution of the resulting 2.365wt% concentration of step (2) is diluted to 1.5wt% concentration, through 50 DEG C of water-baths
Heated mechanical mixer obtains spinning solution.
(4) spinning solution that appropriate step (3) are taken with the syringe that the diameter of 5ml is 12.5mm, uses internal diameter for 0.2mm,
The syringe needle that outer diameter is 0.80mm implements electrostatic spinning.The parameter setting of electrostatic spinning is as follows: voltage: 10kv, spinning rate:
0.3ml/h, the distance between spinning nozzle and collector be 150mm, spinning temperature: 45 DEG C, spinning humidity: 3%.
Because para-aramid fiber strand is in rigidly, substantially without entanglement between strand, electrostatic spinning is in the process quiet
It cannot mostly be dripped in droplets well at silk under electric field force effect, and cannot be continuous well, so can not obtain at all
To the continuous whole quiet spinning film of p-aramid fiber nanofiber.
Comparative example 2
(1) 15g Kevlar 49 is weighed respectively and 15g KOH is added in 500ml DMSO, it is sealed with sealant
At room temperature magnetic agitation one week or so afterwards, obtain wine-colored ANF suspension.
It (2) is 8000rad/min in revolving speed by the ANF suspension in step (1), temperature is centrifuged under conditions of being 22 DEG C
45min removes undissolved KOH and aramid fiber in suspension, the ANF/DMSO solution of 3.128wt% concentration is prepared.
(3) the ANF solution of the resulting 3.128wt% concentration of step (2) is diluted to 2.7wt% concentration, added and ANF
The PEO of 7,000,000 molecular weight of phase homogenous quantities, i.e. para-aramid fiber: the mass ratio of PEO is 1:1, through 50 DEG C of heating water bath machinery
It is uniformly mixed to obtain spinning solution.
(4) spinning solution that appropriate step (3) are taken with the syringe that the diameter of 5ml is 12.5mm, uses internal diameter for 0.2mm,
The syringe needle that outer diameter is 0.80mm implements electrostatic spinning；The parameter setting of electrostatic spinning is as follows: voltage: 10kv, spinning rate:
0.3ml/h, the distance between spinning nozzle and collector be 150mm, spinning temperature: 45 DEG C, spinning humidity: 3%.
Because of the excessive concentration of ANF solution, viscosity is excessive, and electrostatic field force can not guarantee well during electrostatic spinning
Wire vent state, preparation-obtained fiber thickness is uneven, and occurs with spindle structure, and solution can also be due to viscous once in a while
Spending cannot drip at silk greatly in droplets in time.Fig. 7 is the quiet spinning film surface SEM figure of 2 gained of comparative example, can from figure
To find out, fiber thickness is uneven in film, and occurs with spindle structure, illustrates that ANF solution concentration is excessively high, leads to institute
Membrane structure form cannot reach perfect condition.
Claims (10)
1. a kind of preparation method of p-aramid fiber nano fibrous membrane, which is characterized in that the preparation method is that: first in p-aramid fiber
Spinning-aid agent is added in fiber solution, uniform spinning solution is made, then contraposition is made by the method for electrostatic spinning in gained spinning solution
Aramid nano-fiber film；Wherein, the spinning-aid agent is one of polyethylene oxide, polyethylene pyrrole network alkanone or polyvinyl alcohol,
The mass ratio of para-aramid fiber in spinning-aid agent and para-aramid fiber solution are as follows: 10 parts by weight of para-aramid fiber, spinning-aid agent 1
~12 parts by weight.
2. the preparation method of p-aramid fiber nano fibrous membrane according to claim 1, which is characterized in that the p-aramid fiber
The mass concentration of fiber solution is 0.5~2.5wt%.
3. the preparation method of p-aramid fiber nano fibrous membrane according to claim 1 or 2, which is characterized in that described to help spinning
The weight average molecular weight of agent is 30~7,000,000.
4. the preparation method of described in any item p-aramid fiber nano fibrous membranes according to claim 1~3, which is characterized in that institute
State the process conditions of electrostatic spinning are as follows: the voltage of electrostatic spinning is 7~15kv, and spinning rate is 0.1~0.5ml/h, spinning nozzle
The distance between reception device is 10~15cm, and spinning temperature is 35~70 DEG C.
5. the preparation method of p-aramid fiber nano fibrous membrane according to any one of claims 1 to 4, which is characterized in that when
When reception device in electrospinning process is flat receiver, the microstructure performance of gained p-aramid fiber nano fibrous membrane
Are as follows: random distribution state is presented in the nanofiber in film；When reception device is roller collector, gained p-aramid fiber nanometer
The microstructure of tunica fibrosa shows themselves in that the nanofiber in film has certain degree of orientation along roller rotation direction.
6. the preparation method of described in any item p-aramid fiber nano fibrous membranes according to claim 1~5, which is characterized in that right
The method that uniform spinning solution is made in spinning-aid agent is added in the aramid fiber solution of position are as follows: be added and help in para-aramid fiber solution
Agent is spun, heating stirring is completely dissolved spinning-aid agent to obtain uniform spinning solution；Wherein, heating temperature is 25-70 DEG C, preferably
50℃。
7. the preparation method of described in any item p-aramid fiber nano fibrous membranes according to claim 1~6, which is characterized in that institute
State para-aramid fiber solution using following methods be made: by p-aramid fiber micrometer fibers organic solvent and cosolvent effect
Under stir to dissolve, the para-aramid fiber for then removing extra cosolvent and not being completely dissolved is uniformly aligned
Aramid fiber solution；
Further, in the preparation method of the para-aramid fiber solution, the organic solvent is dimethyl sulfoxide, N, N- diformazan
One of yl acetamide, N,N-dimethylformamide, tetrahydrofuran or acetone；
Further, in the preparation method of the para-aramid fiber solution, the cosolvent be potassium hydroxide, sodium hydroxide,
One of potassium tert-butoxide or sec-butyl alcohol potassium；
Further, in the preparation method of the para-aramid fiber solution, p-aramid fiber micrometer fibers are in organic solvent and hydrotropy
The method stirred to dissolve under the action of agent are as follows: by p-aramid fiber micrometer fibers or be added in organic solvent, add and help
Then solvent is sealed, magnetic agitation 7~12 days or by 30-60 DEG C heating water bath 6~8 days；
Further, in the preparation method of the para-aramid fiber solution, extra hydrotropy is removed by the way of centrifugal treating
Agent and the para-aramid fiber not being completely dissolved, wherein centrifugation rate is 5000~10000rad/min, and temperature is 18~30
DEG C, 30~60min of centrifugation time.
8. the preparation method of described in any item p-aramid fiber nano fibrous membranes according to claim 1~7, which is characterized in that right
Gained p-aramid fiber nano fibrous membrane is heat-treated, the heat treatment method are as follows: by p-aramid fiber nano fibrous membrane 60~
120 DEG C, 5~60min of hot pressing under conditions of 0.2~2MPa.
9. a kind of p-aramid fiber nano fibrous membrane, which is characterized in that the p-aramid fiber nano fibrous membrane using claim 1~
8 described in any item methods are made.
10. p-aramid fiber nano fibrous membrane according to claim 9, which is characterized in that the p-aramid fiber nanofiber
The diameter of nanofiber is 80~200nm in film；
Further, the porosity of the p-aramid fiber nano fibrous membrane are as follows: 50~90%；
Further, the water contact angle of the p-aramid fiber nano fibrous membrane are as follows: 17 °~27 °.
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