CN105970484A - PTFE/PI composite-nanometer-fiber porous membrane and preparing method thereof - Google Patents
PTFE/PI composite-nanometer-fiber porous membrane and preparing method thereof Download PDFInfo
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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
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- 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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- 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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- 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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- 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
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- 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
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- 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
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- 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
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Abstract
The invention relates to the membrane preparing technology, in particular to a PTFE/PI composite-nanometer-fiber porous membrane and a preparing method thereof. The preparing method of the PTFE/PI composite-nanometer-fiber porous membrane includes the following steps of 1, preparing a PEO solution, wherein PEO is dissolved in deionized water, stirring is carried out, and the PEO solution is prepared; 2, preparing PEO/PTFE mixing liquid, wherein a PTFE emulsion is added into the PEO solution in the step 1, stirring is carried out, and the PEO/PTFE mixing liquid is prepared; 3, preparing PEO/PTFE-PAAS mixing liquid, wherein PAAS and deionized water are added into the PEO/PTFE mixing liquid in the step 2, stirring is carried out, and the PEO/PTFE-PAAS mixing liquid is prepared; 4, preparing PTFE/PI composite-nanometer-fiber porous membrane, wherein the PEO/PTFE-PAAS mixing liquid is subjected to electrostatic spinning to prepare a PEO/PTFE-PAAS composite-fiber membrane, heat treatment is carried out, and the PTFE/PI composite-nanometer-fiber porous membrane is obtained. The PTFE/PI composite-nanometer-fiber porous membrane has the advantages of being resistant to high temperature and acid-and-alkali corrosion and excellent in mechanical performance.
Description
Technical field
The present invention relates to membrane preparation technology, more particularly it relates to PTFE/PI composite nano fiber perforated membrane and
Preparation method.
Background technology
Along with developing rapidly of industry has driven economic development, also bring some environmental problems to be solved simultaneously.As
The high-temp waste gas produced by industries such as thermal power generation, iron and steel, cement and the improvement of corrosive fume, this gives the development of high-temperature filter material
Bring fabulous opportunity.The core of high temperature gas medium dust removal by filtration technology is high-temperature-resistant filtering material, owing to operating temperature is high, gas
The features such as body corrosivity is strong, filtering material needs the most still to keep good performance.
Polytetrafluoroethylene (PTFE) is a kind of nonpolar line style crystalline polymer, has much unique physics and chemical
Can, such as good electrical insulating property and heat stability, excellent resistance to ag(e)ing, minimum water absorption rate, anti-ultraviolet radiation and excellent
Different chemical inertness etc..Therefore, electric, anticorrosion anti-attrition, machinery, petrochemical industry, weaving and aviation boat it are widely used in
My god, especially in fields such as high temperature resistant filter material and acid and alkali-resistances.But, owing to PTFE stability is high, indissoluble solution and also more than fusing point also
Do not flow, therefore directly can not prepare PTFE fiber by solvent spinning and melt spinning method.
The polyethylene glycol oxide (PEO) of super high molecular weight is normally used as that one " sacrifices " material and be used in can not spinning
Material prepare fiber by electrospinning during, PEO content in the fibre is little, and water processes and in heat treatment process
Can be easy to remove.
Polyimides (PI) refers on main chain containing a base polymer of imide ring, is optimal organic high of combination property
One of molecular material, life-time service temperature range, between-200-300 DEG C, does not has obvious fusing point.PI has the machine of excellence
The excellent properties such as tool performance, good thermostability (＞ 400 DEG C), radiation resistance, can be as high-performance fiber, high temperature composite wood
Material, selectivity, through film and high-temperature coatings etc., are widely used in the fields such as high temperature filtration film, battery diaphragm, space flight and aviation.But it is poly-
The poor processability of acid imide (PI), hydrophobicity and alkaline resistance properties are poor.
Therefore, research and develop high temperature resistant, the film of acid-alkali-corrosive-resisting and its technology of preparing is the most urgent and important.
Summary of the invention
The technical problem to be solved in the present invention is PTFE/PI composite nano fiber perforated membrane and preparation method thereof.
In order to realize foregoing invention purpose, this invention takes techniques below scheme:
The preparation method of PTFE/PI composite nano fiber perforated membrane, comprises the following steps:
1) preparation PEO solution: PEO is dissolved in deionized water, stirs, join to obtain PEO solution；
2) preparation PEO/PTFE mixed liquor: PTFE emulsion is joined in the PEO solution described in step 1), stir, join to obtain PEO/
PTFE mixed liquor；
3) preparation PEO/PTFE-PAAS mixed liquor: PAAS and deionized water are added step 2) described in PEO/PTFE mixed liquor
In, stir, join to obtain PEO/PTFE-PAAS mixed liquor；
4) PTFE/PI composite nano fiber perforated membrane is prepared: PEO/PTFE-PAAS mixed liquor prepares PEO/ by electrostatic spinning
PTFE-PAAS composite cellulosic membrane, thermally treated, obtain PTFE/PI composite nano fiber perforated membrane.
In one embodiment, PEO solution described in step 1) by super high molecular weight PEO powder is dissolved in 35～
In the water of 45 DEG C, obtain after stirring；The weight average molecular weight of described super high molecular weight PEO powder is 105～107 g/mol。
In one embodiment, step 2) described in the mass ratio of PEO Yu PTFE be 0.5～5:100.
In one embodiment, step 2) described in the mass ratio of PEO Yu PTFE be 2.5～5:100.
In one embodiment, described PEO solution contains the PEO of 3～6 wt%；Described PTFE emulsion contains 55～65
The PTFE of wt%.
In one embodiment, the mass ratio of PAAS Yu PTFE described in step 3) is 0.25-5:10.
In one embodiment, described PEO/PTFE-PAAS mixed liquor is the PEO/PTFE-PAAS mixing of 15-20wt%
Liquid.
In one embodiment, described in step 4), during electrostatic spinning, voltage is 10～30kV；Spinning-nozzle is to opposed
It is 15～25cm that electrode collects the distance of substrate；Spinning flow velocity is 0.001～0.005mm/s.
In one embodiment, described in step 4), heat treatment includes: first by PEO/PTFE-PAAS composite cellulosic membrane
It is placed under 50～80 DEG C of arbitrary temperature conditionss and is dried 0.5～1 h；Then heat treated under the temperature conditions of 330～450 DEG C
5～30min, make PEO decompose and remove.
Another object of the present invention is to provide the PTFE/PI composite nano fiber perforated membrane prepared by the method.
Compared with prior art, the invention have the benefit that
The present invention uses described PEO template to prepare PEO/PTFE-PAAS composite cellulosic membrane, successfully passes through electrostatic spinning skill
Art obtains PEO/PTFE-PAAS composite cellulosic membrane, and the PEO removed in fiber in high-temperature heat treatment, sintering process is prepared for
PTFE/PI composite nano fiber perforated membrane, this nano fiber porous film defect is few, continuous, even density, and the heat with excellence is steady
Qualitative, acid-alkali-corrosive-resisting performance and mechanical performance.The polyamic acid salt (PAAS) of water system and the PTFE emulsion of water system are raw material, body
System be water system, beneficially environment protection and ensure laboratory technician life and health；And, as the PAAS of the presoma of PI
Storage can be more long；Furthermore, the monomer of the PAAS of synthesis can be a variety of, are conducive to the PTFE-PI composite fibre that difference requires
Film.Such as, introduce the structures alone of rigid/flexible, obtain the PI of rigid/flexible, the PTFE-of rigid/flexible can be prepared
PI composite membrane.So, the method has environmental protection, economy advantage the most flexibly concurrently.
It is more readily understood the above-mentioned of the application and other features, aspect and advantage with reference to described further below.
Accompanying drawing explanation
Fig. 1: embodiment 1 fibrous membrane SEM figure after 380 DEG C of heat treatments
Fig. 2: embodiment 2 fibrous membrane SEM figure after 380 DEG C of heat treatments
Fig. 3: embodiment 3 fibrous membrane SEM figure after 380 DEG C of heat treatments
Fig. 4: embodiment 4 fibrous membrane SEM figure after 380 DEG C of heat treatments
Fig. 5: comparative example 1 fibrous membrane SEM figure after 380 DEG C of heat treatments
Fig. 6: comparative example 2 fibrous membrane SEM figure after 380 DEG C of heat treatments.
Detailed description of the invention
Unless otherwise defined, all technology used herein and scientific terminology have skill common with art of the present invention
The identical implication that art personnel are generally understood that.When there is contradiction, it is as the criterion with the definition in this specification.
Term as used herein " by ... preparation " and " comprising " synonym.Term used herein " comprises ", " including ",
" have ", " containing " or its other deformation any, it is intended that cover the including of non-exclusionism.Such as, the combination of listed elements is comprised
Thing, step, method, goods or device are not necessarily solely those key elements, but can include other not expressly listed key element or
The key element that this kind of compositions, step, method, goods or device are intrinsic.
Conjunction " Consists of " gets rid of any key element, step or component do not pointed out.If in claim, this
Phrase will make claim be closed so that it is does not comprise the material in addition to the material that those describe, but relative often
Except rule impurity.When being rather than immediately following during phrase " Consists of " occurs in the clause of claim main body after theme,
It is only limited to the key element described in this clause；Other key element is not excluded outside as overall described claim.
Equivalent, concentration or other value or parameter are excellent with scope, preferred scope or a series of upper limit preferred value and lower limit
During the Range Representation that choosing value limits, this is appreciated that and specifically discloses by any range limit or preferred value and any scope
All scopes that arbitrary pairing of lower limit or preferred value is formed, regardless of whether whether this scope separately discloses.Such as, when open
During scope " 1 to 5 ", described scope should be interpreted as including scope " 1 to 4 ", " 1 to 3 ", " 1-2 ", " 1-2 and 4-5 ",
" 1-3 and 5 " etc..When numerical range is described in this article, unless otherwise indicated, otherwise this scope be intended to include its end value and
All integers within the range and mark.
Additionally, indefinite article " a kind of " before key element of the present invention or component and " one " are to key element or the quantitative requirement of component
(i.e. occurrence number) unrestriction.Therefore " one " or " a kind of " should be read as including one or at least one, and odd number
The key element of form or component also include plural form, unless described quantity substantially refers to singulative.
In order to solve the problems referred to above, the invention provides the preparation method of PTFE/PI composite nano fiber perforated membrane, including
Following steps:
1) preparation PEO solution: PEO is dissolved in deionized water, stirs, join to obtain PEO solution；
2) preparation PEO/PTFE mixed liquor: PTFE emulsion is joined in the PEO solution described in step 1), stir, join to obtain PEO/
PTFE mixed liquor；
3) preparation PEO/PTFE-PAAS mixed liquor: PAAS and deionized water are added step 2) described in PEO/PTFE mixed liquor
In, stir, join to obtain PEO/PTFE-PAAS mixed liquor；
4) PTFE/PI composite nano fiber perforated membrane is prepared: PEO/PTFE-PAAS mixed liquor prepares PEO/ by electrostatic spinning
PTFE-PAAS composite cellulosic membrane, thermally treated, obtain PTFE/PI composite nano fiber perforated membrane.
PTFE emulsion:
PTFE emulsion of the present invention is the aqueous dispersions that politef passes through that emulsion polymerization obtains.
Described PTFE emulsion can directly select commercially available, is preferably carried out mode as the present invention, and described PTFE emulsion contains
There is the PTFE of 55～65 wt%.
PEO:
PEO of the present invention is polyethylene glycol oxide, also known as poly(ethylene oxide), is a kind of crystallinity, thermoplastic water-soluble polymeric
Thing.PEO is white flowable powder, and molecular structure is (CH2CH2O), the concentration of this type of resin activity end group is relatively low, the most substantially
Terminal reactive.Owing to it exists C-O-C key, it is generally of compliance, can be formed with electron acceptor or some inorganic electrolyte
Associated complex.The formation of this exopathogenic factor hydrogen bond, becomes again a kind of water-soluble polymer.It is preferably carried out mode as the present invention,
PEO solution described in step 1), by being dissolved in the water of 35～45 DEG C by super high molecular weight PEO powder, obtains after stirring
?；The weight average molecular weight of described super high molecular weight PEO powder is 105～107G/mol, and then preferably 5 × 106g/mol；Described
PEO solution contains the PEO of 3～6 wt%, and then the PEO of preferably 4 wt%.
Be preferably carried out mode, step 2 as the present invention) described in the mass ratio of PEO Yu PTFE be 0.5～5:100；Excellent
Selection of land, step 2) described in the mass ratio of PEO Yu PTFE be 2.5～5:100；It is highly preferred that step 2) described in PEO and PTFE
Mass ratio be 3:100.
PAAS:
PAAS(polyamic acid salt of the present invention) preparation method:
(1) synthesis of polyamic acid (PAA): with DMAc as solvent, weighs equimolar 4,4 '-diphenyldiamine (ODA) and all
PMDA (PMDA), is successively dissolved in N2In 250 mL there-necked flasks of protection, mechanic whirl-nett reaction 18 at-5 DEG C
H, synthesis mass fraction is polyamic acid (PAA) solution of 12 wt%.
(2) preparation of polyamic acid salt (PAAS): in PAA solution, slowly drips a certain amount of triethylamine (amount of material
For in solution 1.5 times of-COOH), mechanical agitation 5 h at-5 DEG C, prepares polyamic acid salt (PAAS).Ubbelohde viscometer surveys it
Viscosity is 2.3 dL g-1。
Being preferably carried out mode as the present invention, the mass ratio of PAAS Yu PTFE described in step 3) is 0.25-5:10；Tool
The mass ratio of PAAS Yu PTFE of body is 1:5,1:4,1:3,1:2.
Being preferably carried out mode as the present invention, described PEO/PTFE-PAAS mixed liquor is the PEO/PTFE-of 15-20wt%
PAAS mixed liquor.
In one is preferably carried out mode, described in step 4), during electrostatic spinning, voltage is 10～30kV；Spinning-nozzle
The distance collecting substrate to opposite electrode is 15～25cm；Spinning flow velocity is 0.001～0.005mm/s.
In one is preferably carried out mode, described in step 4), heat treatment includes: be first combined by PEO/PTFE-PAAS
Fibrous membrane is placed under 50～80 DEG C of arbitrary temperature conditionss and is dried 0.5～1 h；Then add under the temperature conditions of 330～450 DEG C
Heat treatment 5～30min, makes PEO decompose and removes.
It is preferably carried out mode as the present invention, collects step 4) electrostatic spinning using 90 mesh steel wires as supporter and obtain
PEO/PTFE-PAAS composite nano-fiber membrane, then place in an oven, under 70 DEG C of condition of normal pressure, be dried 1 h.
Another object of the present invention is to provide the PTFE/PI composite nano fiber perforated membrane prepared by the method.
The PTFE/PI composite nano fiber perforated membrane feature using method of the present invention to prepare is as follows: thermostability: when
When temperature is higher than 550 DEG C, the weightlessness of PTFE/PI composite nano fiber perforated membrane is 5%, and hot strength is 50～300 MPa；Disconnected
Splitting percentage elongation is 10～100%；Described PTFE/PI composite nano fiber perforated membrane is continuous, even density, and the heat with excellence is steady
Qualitative, acid-alkali-corrosive-resisting performance and mechanical performance.
Below by embodiment, the present invention is specifically described.Be necessary it is pointed out here that, following example are served only for right
The present invention is described further, it is impossible to be interpreted as limiting the scope of the invention, professional and technical personnel in the field according to
Some nonessential improvement and adjustment that the content of foregoing invention is made, still fall within protection scope of the present invention.
It addition, illustrate without other, raw materials used is all commercially available.
PTFE emulsion used in the embodiment of the present invention contains the PTFE of 62 wt%, and the granule of PTFE is 80nm, is purchased from
Dongguan City Dong Zhan plastics trade Co., Ltd；PEO powder (MW=5 × 106G/mol), purchased from lark prestige Science and Technology Ltd..
Embodiment 1
The preparation method of PTFE/PI composite nano fiber perforated membrane, wherein in PEO solution, solution contains the PEO, PEO/ of 4 wt%
The mass ratio of PAAS Yu PTFE during the mass ratio of PEO Yu PTFE is 3:100, PEO/PTFE-PAAS mixed liquor in PTFE mixed liquor
For the PEO/PTFE-PAAS mixed liquor that 2:8, PEO/PTFE-PAAS mixed liquor is 18wt%；Specifically comprise the following steps that
Being dissolved in the deionized water of 40 DEG C by PEO powder, it is molten that mechanical agitation 3 h obtains the PEO that mass fraction is 4 wt%
Liquid.It is cooled in room temperature and solution the bubble collapse produced because quickly stirring.PTFE emulsion is joined described PEO
In solution, stir, join to obtain PEO/PTFE mixed liquor；In PEO/PTFE mixed liquor described in PAAS and deionized water are added, stir
Mix, join to obtain PEO/PTFE-PAAS mixed liquor；When preparing PEO/PTFE-PAAS composite nano-fiber membrane by electrostatic spinning, electricity
Pressure, collection distance and flow velocity are respectively 13 kV, 20 cm and 0.002 mm/s；Collect using steel wire (90 mesh) as supporter
PEO/PTFE-PAAS composite cellulosic membrane, places in an oven, and 70 DEG C are dried 1 h, and in high temperature furnace, 380 DEG C carry out heat treatment, remove
Remove the PEO in fiber, obtain PTFE-PI composite cellulosic membrane.The hot strength of PTFE-PI composite cellulosic membrane is 28.79MPa, bullet
Property modulus is 114.58 MPa, and elongation at break is 32.32%.
Embodiment 2
The preparation method of PTFE/PI composite nano fiber perforated membrane, wherein in PEO solution, solution contains the PEO, PEO/ of 4 wt%
The mass ratio of PAAS Yu PTFE during the mass ratio of PEO Yu PTFE is 3:100, PEO/PTFE-PAAS mixed liquor in PTFE mixed liquor
For the PEO/PTFE-PAAS mixed liquor that 1:4, PEO/PTFE-PAAS mixed liquor is 18wt%；Specifically comprise the following steps that
Being dissolved in the deionized water of 40 DEG C by PEO powder, it is molten that mechanical agitation 3 h obtains the PEO that mass fraction is 4 wt%
Liquid.It is cooled in room temperature and solution the bubble collapse produced because quickly stirring.PTFE emulsion is joined described PEO
In solution, stir, join to obtain PEO/PTFE mixed liquor；In PEO/PTFE mixed liquor described in PAAS and deionized water are added, stir
Mix, join to obtain PEO/PTFE-PAAS mixed liquor；When preparing PEO/PTFE-PAAS composite nano-fiber membrane by electrostatic spinning, electricity
Pressure, collection distance and flow velocity are respectively 13 kV, 20 cm and 0.002 mm/s；Collect using steel wire (90 mesh) as supporter
PEO/PTFE-PAAS composite cellulosic membrane, places in an oven, and 70 DEG C are dried 1h, and in high temperature furnace, 380 DEG C carry out heat treatment, remove
PEO in fiber, obtains PTFE-PI composite cellulosic membrane.The hot strength of PTFE-PI composite cellulosic membrane is 39.91MPa, elastic
Modulus is 197.38 MPa, and elongation at break is 26.88%.
Embodiment 3
The preparation method of PTFE/PI composite nano fiber perforated membrane, wherein in PEO solution, solution contains the PEO, PEO/ of 4 wt%
The mass ratio of PAAS Yu PTFE during the mass ratio of PEO Yu PTFE is 3:100, PEO/PTFE-PAAS mixed liquor in PTFE mixed liquor
For the PEO/PTFE-PAAS mixed liquor that 1:5, PEO/PTFE-PAAS mixed liquor is 18wt%；Specifically comprise the following steps that
Being dissolved in the deionized water of 40 DEG C by PEO powder, it is molten that mechanical agitation 3 h obtains the PEO that mass fraction is 4 wt%
Liquid.It is cooled in room temperature and solution the bubble collapse produced because quickly stirring.PTFE emulsion is joined described PEO
In solution, stir, join to obtain PEO/PTFE mixed liquor；In PEO/PTFE mixed liquor described in PAAS and deionized water are added, stir
Mix, join to obtain PEO/PTFE-PAAS mixed liquor；When preparing PEO/PTFE-PAAS composite nano-fiber membrane by electrostatic spinning, electricity
Pressure, collection distance and flow velocity are respectively 13 kV, 20 cm and 0.002 mm/s；Collect using steel wire (90 mesh) as supporter
PEO/PTFE-PAAS composite cellulosic membrane, places in an oven, and 70 DEG C are dried 1 h, and in high temperature furnace, 380 DEG C carry out heat treatment, remove
Remove the PEO in fiber, obtain PTFE-PI composite cellulosic membrane.The hot strength of PTFE-PI composite cellulosic membrane is 57.10MPa, bullet
Property modulus is 233.62 MPa, and elongation at break is 26.24%.
Embodiment 4
The preparation method of PTFE/PI composite nano fiber perforated membrane, wherein in PEO solution, solution contains the PEO, PEO/ of 4 wt%
The mass ratio of PAAS Yu PTFE during the mass ratio of PEO Yu PTFE is 3:100, PEO/PTFE-PAAS mixed liquor in PTFE mixed liquor
For the PEO/PTFE-PAAS mixed liquor that 1:2, PEO/PTFE-PAAS mixed liquor is 18wt%；Specifically comprise the following steps that
Being dissolved in the deionized water of 40 DEG C by PEO powder, it is molten that mechanical agitation 3 h obtains the PEO that mass fraction is 4 wt%
Liquid.It is cooled in room temperature and solution the bubble collapse produced because quickly stirring.PTFE emulsion is joined described PEO
In solution, stir, join to obtain PEO/PTFE mixed liquor；In PEO/PTFE mixed liquor described in PAAS and deionized water are added, stir
Mix, join to obtain PEO/PTFE-PAAS mixed liquor；When preparing PEO/PTFE-PAAS composite nano-fiber membrane by electrostatic spinning, electricity
Pressure, collection distance and flow velocity are respectively 13 kV, 20 cm and 0.002 mm/s；Collect using steel wire (90 mesh) as supporter
PEO/PTFE-PAAS composite cellulosic membrane, places in an oven, and 70 DEG C are dried 1h, and in high temperature furnace, 380 DEG C carry out heat treatment, remove
PEO in fiber, obtains PTFE-PI composite cellulosic membrane.The hot strength of PTFE-PI composite cellulosic membrane is 81.96MPa, elastic
Modulus is 444.73 MPa, and elongation at break is 23.87%.
Comparative example 1
The preparation method of PTFE nano fiber porous film, wherein in PEO solution, solution contains PEO, the PEO/PTFE mixing of 4 wt%
During in liquid, the mass ratio of PEO Yu PTFE is 3:100, PEO/PTFE-PAAS mixed liquor, the mass ratio of PAAS Yu PTFE is 0:10,
PEO/PTFE-PAAS mixed liquor is the PEO/PTFE-PAAS mixed liquor of 18wt%；Specifically comprise the following steps that
Being dissolved in the deionized water of 40 DEG C by PEO powder, it is molten that mechanical agitation 3 h obtains the PEO that mass fraction is 4 wt%
Liquid.It is cooled in room temperature and solution the bubble collapse produced because quickly stirring.PTFE emulsion is joined described PEO
In solution, stir, join to obtain PEO/PTFE mixed liquor；When preparing PEO/PTFE composite nano-fiber membrane by electrostatic spinning, voltage,
Collect distance and flow velocity is respectively 13 kV, 20 cm and 0.002 mm/s；PEO/ is collected as supporter using steel wire (90 mesh)
PTFE composite cellulosic membrane, places in an oven, and 70 DEG C are dried 1 h, and in high temperature furnace, 380 DEG C carry out heat treatment, remove in fiber
PEO, obtains PTFE fiber film.The hot strength of PTFE-PI composite cellulosic membrane is 14.52MPa, and elastic modelling quantity is 65.89 MPa,
Elongation at break is 658.40%.
Comparative example 2
The preparation method of PI nano fiber porous film, wherein in PEO solution, solution contains PEO, the PEO/PAAS mixed liquor of 4 wt%
The mass ratio of middle PEO Yu PAAS is that in 3:100, PEO/PTFE-PAAS mixed liquor, the mass ratio of PAAS Yu PTFE is 10:0, PEO/
PTFE-PAAS mixed liquor is the PEO/PTFE-PAAS mixed liquor of 18wt%；Specifically comprise the following steps that
Being dissolved in the deionized water of 40 DEG C by PEO powder, it is molten that mechanical agitation 3 h obtains the PEO that mass fraction is 4 wt%
Liquid.It is cooled in room temperature and solution the bubble collapse produced because quickly stirring.PAAS is joined described PEO solution
In, stir, join to obtain PEO/PAAS mixed liquor；When preparing PEO/ PAAS composite nano-fiber membrane by electrostatic spinning, voltage, receipts
Collection distance and flow velocity are respectively 13 kV, 20 cm and 0.002 mm/s；PEO/ is collected as supporter using steel wire (90 mesh)
PAAS composite cellulosic membrane, places in an oven, and 70 DEG C are dried 1 h, and in high temperature furnace, 380 DEG C carry out heat treatment, remove in fiber
PEO, obtains PI fibrous membrane.The hot strength of PTFE-PI composite cellulosic membrane is 106.43MPa, and elastic modelling quantity is 652.64 MPa,
Elongation at break is 20.14%.
The table 1 PTFE/PI composite nano fiber perforated membrane (PAAS: PTFE=2:8) machinery before and after acid-alkali treatment
Performance
Table 2 PTFE/PI composite nano fiber perforated membrane (PAAS: PTFE=1:4) and PI film mechanicalness before and after alkali processes
Can contrast
Illustrate: PI is completely dissolved in the highly basic of 100 DEG C, it is impossible to survey its mechanical performance.
Aforesaid example is merely illustrative, for explaining some features of inventive feature.Appended claim
It is intended to the widest scope that requirement it is contemplated that, and embodiments as presented herein is only according to all possible embodiment
The explanation of embodiment of selection of combination.Therefore, the purpose of applicant is that appended claim is not by the explanation present invention
The selectional restriction of example of feature.And the progress in science and technology will be formed due to language performance inaccurate reason and not
The possible equivalent or the son that are presently considered are replaced, and these changes also should be interpreted in the conceived case by appended
Claim covers.
Claims (10)
- The preparation method of 1.PTFE/PI composite nano fiber perforated membrane, it is characterised in that comprise the following steps:1) preparation PEO solution: PEO is dissolved in deionized water, stirs, join to obtain PEO solution；2) preparation PEO/PTFE mixed liquor: PTFE emulsion is joined in the PEO solution described in step 1), stir, join to obtain PEO/ PTFE mixed liquor；3) preparation PEO/PTFE-PAAS mixed liquor: PAAS and deionized water are added step 2) described in PEO/PTFE mixed liquor In, stir, join to obtain PEO/PTFE-PAAS mixed liquor；4) PTFE/PI composite nano fiber perforated membrane is prepared: PEO/PTFE-PAAS mixed liquor prepares PEO/ by electrostatic spinning PTFE-PAAS composite cellulosic membrane, thermally treated, obtain PTFE/PI composite nano fiber perforated membrane.
- The preparation method of PTFE/PI composite nano fiber perforated membrane the most according to claim 1, it is characterised in that step 1) PEO solution described in, by being dissolved in by super high molecular weight PEO powder in the water of 35～45 DEG C, obtains after stirring；Institute The weight average molecular weight stating super high molecular weight PEO powder is 105～107 g/mol。
- The preparation method of PTFE/PI composite nano fiber perforated membrane the most according to claim 1, it is characterised in that step 2) mass ratio of PEO Yu PTFE described in is 0.5～5:100.
- The preparation method of PTFE/PI composite nano fiber perforated membrane the most according to claim 3, it is characterised in that step 2) mass ratio of PEO Yu PTFE described in is 2.5～5:100.
- The preparation method of PTFE/PI composite nano fiber perforated membrane the most according to claim 1, it is characterised in that described PEO solution contains the PEO of 3～6 wt%；Described PTFE emulsion contains the PTFE of 55～65 wt%.
- The preparation method of PTFE/PI composite nano fiber perforated membrane the most according to claim 1, it is characterised in that step 3) mass ratio of PAAS Yu PTFE described in is 0.25-5:10.
- The preparation method of PTFE/PI composite nano fiber perforated membrane the most according to claim 1, it is characterised in that described PEO/PTFE-PAAS mixed liquor is the PEO/PTFE-PAAS mixed liquor of 15-20wt%.
- The preparation method of PTFE/PI composite nano fiber perforated membrane the most according to claim 1, it is characterised in that step 4) described in, during electrostatic spinning, voltage is 10～30kV；The distance that spinning-nozzle collects substrate to opposite electrode is 15～25cm； Spinning flow velocity is 0.001～0.005mm/s.
- The preparation method of PTFE/PI composite nano fiber perforated membrane the most according to claim 1, it is characterised in that step 4) described in, heat treatment includes: be first placed in by PEO/PTFE-PAAS composite cellulosic membrane under 50～80 DEG C of arbitrary temperature conditionss dry Dry 0.5～1 h；Then heat treated 5～30min under the temperature conditions of 330～450 DEG C, make PEO decompose and remove.
- 10. according to the method system preparing PTFE/PI composite nano fiber perforated membrane described in any one in claim 1～9 The standby PTFE/PI composite nano fiber perforated membrane obtained.
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