CN105970484B - PTFE/PI composite nano fiber perforated membranes and preparation method thereof - Google Patents
PTFE/PI composite nano fiber perforated membranes and preparation method thereof Download PDFInfo
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- CN105970484B CN105970484B CN201610359125.2A CN201610359125A CN105970484B CN 105970484 B CN105970484 B CN 105970484B CN 201610359125 A CN201610359125 A CN 201610359125A CN 105970484 B CN105970484 B CN 105970484B
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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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- 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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- 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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- 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
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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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- D04H1/00—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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Abstract
The present invention relates to membrane preparation technology, more particularly it relates to PTFE/PI composite nano fiber perforated membranes and preparation method thereof.The preparation method of PTFE/PI composite nano fiber perforated membranes, comprises the following steps：（1）Prepare PEO solution；（2）Prepare PEO/PTFE mixed liquors；（3）Prepare PEO/PTFE PAAS mixed liquors；（4）Prepare PTFE/PI composite nano fiber perforated membranes.The PTFE/PI composite nano fiber perforated membranes have the characteristics of high temperature resistant, acid-alkali-corrosive-resisting and excellent mechanical performance.
Description
Technical field
The present invention relates to membrane preparation technology, more particularly it relates to PTFE/PI composite nano fibers perforated membrane and its
Preparation method.
Background technology
As developing rapidly for industry has driven economic development, while also bring some environmental problems to be solved.Such as
The improvement of high-temp waste gas and corrosive fume as caused by the industries such as thermal power generation, steel, cement, 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, because operating temperature is high, gas
The features such as body corrosivity is strong, filtering material need still to keep good performance under severe conditions.
Polytetrafluoroethylene (PTFE)（PTFE）It is a kind of nonpolar line style crystalline polymer, with many unique physics and chemically
Can, such as good electrical insulating property and heat endurance, excellent resistance to ag(e)ing, minimum water absorption rate, anti-ultraviolet radiation and excellent
Different chemical inertness etc..Therefore, it is widely used in electric, anti-corrosion anti-attrition, machinery, petrochemical industry, weaving and aviation boat
My god, especially in the field such as high temperature resistant filter material and acid and alkali-resistance.However, because PTFE stability is high, more than indissoluble solution and fusing point
Do not flow, therefore PTFE fiber directly can not be prepared by solution-polymerized SBR and melt spinning method.
The polyethylene glycol oxide of super high molecular weight（PEO）It is normally used as a kind of " sacrifice " material and is used in and is unable to spinning
Material fiber is prepared by electrospinning during, the contents of PEO in the fibre are seldom, and in water process and heat treatment process
It can be easy to remove.
Polyimides（PI）Refer to a kind of polymer containing imide ring on main chain, be optimal organic high of combination property
One of molecular material, long-term use of temperature range is between -200-300 DEG C, without obvious fusing point.PI has excellent machine
Tool performance, good heat resistance（400 DEG C of ＞）, the excellent properties such as radiation resistance, high-performance fiber, high temperature composite wood can be used as
Material, selectivity are widely used in the fields such as high temperature filtration film, battery diaphragm, space flight and aviation through film and high-temperature coatings etc..It is but poly-
Acid imide（PI）Poor processability, hydrophobicity and alkaline resistance properties are poor.
Therefore, it is very urgent and important to research and develop high temperature resistant, the film of acid-alkali-corrosive-resisting and its technology of preparing.
The content of the invention
The technical problem to be solved in the present invention is PTFE/PI composite nano fiber perforated membranes and preparation method thereof.
In order to realize foregoing invention purpose, this invention takes following technical scheme：
The preparation method of PTFE/PI composite nano fiber perforated membranes, comprises the following steps：
1）Prepare PEO solution：By PEO be dissolved in deionized water, stirring, with PEO solution；
2）Prepare PEO/PTFE mixed liquors：PTFE emulsion is added to step 1）In described PEO solution, stirring, with
PEO/PTFE mixed liquors；
3）Prepare PEO/PTFE-PAAS mixed liquors：PAAS and deionized water are added into step 2）Described PEO/PTFE is mixed
Close liquid in, stirring, with PEO/PTFE-PAAS mixed liquors；
4）Prepare PTFE/PI composite nano fiber perforated membranes：PEO/PTFE-PAAS mixed liquors are made by electrostatic spinning
PEO/PTFE-PAAS composite cellulosic membranes, it is thermally treated, produce PTFE/PI composite nano fiber perforated membranes.
In one embodiment, step 1）Described in PEO solution by super high molecular weight PEO powder is dissolved in 35~
In 45 DEG C of water, obtained after stirring；The weight average molecular weight of the super high molecular weight PEO powder is 105~107 g/mol。
In one embodiment, step 2）Described in PEO and PTFE mass ratio be 0.5~5：100.
In one embodiment, step 2）Described in PEO and PTFE mass ratio be 2.5~5：100.
In one embodiment, the PEO solution contains 3~6 wt% PEO；The PTFE emulsion contains 55~65
Wt% PTFE.
In one embodiment, step 3）Described in PAAS and PTFE mass ratio be 0.25-5：10.
In one embodiment, the PEO/PTFE-PAAS that the PEO/PTFE-PAAS mixed liquors are 15-20wt% is mixed
Liquid.
In one embodiment, step 4）Described in electrostatic spinning when voltage be 10~30kV；Spinning-nozzle is to opposed
The distance that electrode collects substrate is 15~25cm；Spinning flow velocity is 0.001~0.005mm/s.
In one embodiment, step 4）Described in be heat-treated and include：First by PEO/PTFE-PAAS composite cellulosic membranes
It is placed under 50~80 DEG C of any temperature conditionss and dries 0.5~1 h；Then heat under 330~450 DEG C of temperature conditionss
5~30min, decompose PEO and remove.
Another object of the present invention is to provide the PTFE/PI composite nano fiber perforated membranes prepared by this method.
Compared with prior art, beneficial effects of the present invention are：
The present invention uses described PEO templates to prepare PEO/PTFE-PAAS composite cellulosic membranes, successfully passes through Static Spinning
Silk technology obtains PEO/PTFE-PAAS composite cellulosic membranes, and by high-temperature heat treatment, the PEO systems in fiber are removed in sintering process
For PTFE/PI composite nano fiber perforated membranes, the nano fiber porous film defect is few, continuous, even density, has excellent
Heat endurance, acid-alkali-corrosive-resisting performance and mechanical performance.The polyamic acid salt of water system（PAAS）PTFE emulsion with water system is original
Material, system is water system, the life and health of protection and guarantee laboratory technician beneficial to environment；Moreover, the presoma as PI
PAAS storage can be more long；Furthermore the PAAS of synthesis monomer can be a variety of, and the PTFE-PI for being advantageous to different requirements is answered
Condensating fiber film.Such as the structures alone of rigid/flexible is introduced, the PI of rigid/flexible is obtained, rigid/flexible can be prepared
PTFE-PI composite membranes.So the method has the advantages of environmentally friendly, economic and flexible concurrently.
The above-mentioned of the application and other features, aspect and advantage is more readily understood with reference to described further below.
Brief description of the drawings
Fig. 1：SEM figure of the tunica fibrosa of embodiment 1 after 380 DEG C of heat treatment
Fig. 2：SEM figure of the tunica fibrosa of embodiment 2 after 380 DEG C of heat treatment
Fig. 3：SEM figure of the tunica fibrosa of embodiment 3 after 380 DEG C of heat treatment
Fig. 4：SEM figure of the tunica fibrosa of embodiment 4 after 380 DEG C of heat treatment
Fig. 5：SEM figure of the tunica fibrosa of comparative example 1 after 380 DEG C of heat treatment
Fig. 6：SEM figure of the tunica fibrosa of comparative example 2 after 380 DEG C of heat treatment.
Embodiment
Unless otherwise defined, all technologies used herein and scientific terminology have and the common skill of art of the present invention
The identical implication that art personnel are generally understood that.When contradiction be present, the definition in this specification is defined.
As used herein term " by ... prepare " it is synonymous with "comprising".Term "comprising" used herein, " comprising ",
" having ", " containing " or its any other deformation, it is intended that cover including for non-exclusionism.For example, the combination comprising listed elements
Thing, step, method, product or device are not necessarily limited to those key elements, but can include not expressly listed other key elements or
Such a composition, step, method, product or the intrinsic key element of device.
Conjunction " Consists of " excludes any key element do not pointed out, step or component.If be used in claim, this
Phrase will make claim be closed, 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 in the clause that phrase " Consists of " appears in claim main body after theme,
It is only limited to the key element described in the clause；Other key elements are not excluded outside the claim as entirety.
Equivalent, concentration or other values or parameter are excellent with scope, preferred scope or a series of upper limit preferred values and lower limit
During the Range Representation that choosing value limits, this, which is appreciated that, specifically discloses by any range limit or preferred value and any scope
All scopes that any pairing of lower limit or preferred value is formed, regardless of whether the scope separately discloses.For example, 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 number range is described herein, unless otherwise indicated, otherwise the scope be intended to include its end value with
All integers and fraction within the range.
In addition, indefinite article " one kind " before key element of the present invention or component and "one" to key element or the quantitative requirement of component
(i.e. occurrence number) unrestriction.Therefore "one" or " one kind " should be read as including one or at least one, and odd number
The key element or component of form also include plural form, unless the quantity substantially refers to singulative.
In order to solve the above problems, the invention provides the preparation method of PTFE/PI composite nano fiber perforated membranes, including
Following steps：
1）Prepare PEO solution：By PEO be dissolved in deionized water, stirring, with PEO solution；
2）Prepare PEO/PTFE mixed liquors：PTFE emulsion is added to step 1）In described PEO solution, stirring, with
PEO/PTFE mixed liquors；
3）Prepare PEO/PTFE-PAAS mixed liquors：PAAS and deionized water are added into step 2）Described PEO/PTFE is mixed
Close liquid in, stirring, with PEO/PTFE-PAAS mixed liquors；
4）Prepare PTFE/PI composite nano fiber perforated membranes：PEO/PTFE-PAAS mixed liquors are made by electrostatic spinning
PEO/PTFE-PAAS composite cellulosic membranes, it is thermally treated, produce PTFE/PI composite nano fiber perforated membranes.
PTFE emulsion：
PTFE emulsion of the present invention is the aqueous dispersions that polytetrafluoroethylene (PTFE) is obtained by emulsion polymerization.
The PTFE emulsion can directly select commercially available, be preferably carried out mode as the present invention, the PTFE emulsion contains
There is 55~65 wt% PTFE.
PEO：
PEO of the present invention is polyethylene glycol oxide, also known as PEO, is a kind of crystallinity, thermoplastic water solubility
Polymer.PEO is the flowable powder of white, and molecular structure is (CH2CH2O), the concentration of such resin activity end group is relatively low, does not have
Obvious terminal reactive., can be with electron acceptor or some inorganic electrolytes generally with compliance because it has C-O-C keys
Form associated matter.The formation of this external cause hydrogen bond, a kind of water-soluble polymer is become again.As the present invention side of being preferably carried out
Formula, step 1）Described in PEO solution by the way that super high molecular weight PEO powder is dissolved in 35~45 DEG C of water, after stirring
Obtain；The weight average molecular weight of the super high molecular weight PEO powder is 105~107G/mol, and then preferably 5 × 106g/mol；Institute
State the PEO that PEO solution contains 3~6 wt%, and then preferably 4 wt% PEO.
Mode, step 2 are preferably carried out as the present invention）Described in PEO and PTFE mass ratio be 0.5~5：100；It is excellent
Selection of land, step 2）Described in PEO and PTFE mass ratio be 2.5~5：100；It is highly preferred that step 2）Described in PEO and PTFE
Mass ratio be 3：100.
PAAS：
PAAS of the present invention（Polyamic acid salt）Preparation method：
（1）Polyamic acid（PAA）Synthesis：Using DMAc as solvent, equimolar 4 are weighed, 4 '-diphenyldiamine（ODA）
And pyromellitic acid anhydride（PMDA）, successively it is dissolved in N2In 250 mL three-necked flasks of protection, the mechanical agitation at -5 DEG C
React 18 h, the polyamic acid that synthesis mass fraction is 12 wt%（PAA）Solution.
（2）Polyamic acid salt（PAAS）Preparation：Into PAA solution, a certain amount of triethylamine is slowly added dropwise（The amount of material
For 1.5 times of-COOH in solution）, the h of mechanical agitation 5 at -5 DEG C, prepare polyamic acid salt（PAAS）.Ubbelohde viscometer surveys it
Viscosity is 2.3 dL g-1。
Mode, step 3 are preferably carried out as the present invention）Described in PAAS and PTFE mass ratio be 0.25-5：10；Tool
The PAAS and PTFE of body mass ratio are 1：5、1：4、1：3、1：2.
Mode is preferably carried out as the present invention, the PEO/PTFE-PAAS mixed liquors are 15-20wt% PEO/PTFE-
PAAS mixed liquors.
It is preferably carried out in one kind in mode, step 4）Described in electrostatic spinning when voltage be 10~30kV；Spinning-nozzle
The distance that substrate is collected to opposite electrode is 15~25cm；Spinning flow velocity is 0.001~0.005mm/s.
It is preferably carried out in one kind in mode, step 4）Described in be heat-treated and include：It is first that PEO/PTFE-PAAS is compound
Tunica fibrosa, which is placed under 50~80 DEG C of any temperature conditionss, dries 0.5~1 h；Then add under 330~450 DEG C of temperature conditionss
5~30min is heat-treated, PEO is decomposed and removes.
Mode is preferably carried out as the present invention, supporter collection step 4 is used as using 90 mesh steel wires）Electrostatic spinning obtains
PEO/PTFE-PAAS composite nano-fiber membranes, then place in an oven, 1 h dried under 70 DEG C of condition of normal pressure.
Another object of the present invention is to provide the PTFE/PI composite nano fiber perforated membranes prepared by this method.
The PTFE/PI composite nano fiber perforated membrane features prepared using method of the present invention are as follows：It is heat-resisting
Property：When temperature is higher than 550 DEG C, the weightlessness of PTFE/PI composite nano fiber perforated membranes is 5%, and tensile strength is 50~300
MPa；Elongation at break is 10~100%；The PTFE/PI composite nano fibers perforated membrane is continuous, even density, has excellent
Heat endurance, acid-alkali-corrosive-resisting performance and mechanical performance.
The present invention is specifically described below by embodiment.It is necessarily pointed out that following examples are only used
In the invention will be further described, it is impossible to be interpreted as limiting the scope of the invention, professional and technical personnel in the field
Some the nonessential modifications and adaptations made according to the content of foregoing invention, still fall within protection scope of the present invention.
In addition, if without other explanations, raw materials used is all commercially available.
PTFE emulsion used in the embodiment of the present invention contains 62 wt% PTFE, and PTFE particle 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
Solution contains 4 wt% PEO in the preparation method of PTFE/PI composite nano fiber perforated membranes, wherein PEO solution,
PEO and PTFE mass ratio is 3 in PEO/PTFE mixed liquors：PAAS and PTFE matter in 100, PEO/PTFE-PAAS mixed liquors
Amount is than being 2：8, PEO/PTFE-PAAS mixed liquors are 18wt% PEO/PTFE-PAAS mixed liquors；Comprise the following steps that：
PEO powder is dissolved in 40 DEG C of deionized water, the h of mechanical agitation 3 obtains the PEO that mass fraction is 4 wt%
Solution.Be cooled in room temperature and solution because of quick stirring and caused by bubble collapse.PTFE emulsion is added to described
In PEO solution, stirring, with PEO/PTFE mixed liquors；PAAS and deionized water are added in described PEO/PTFE mixed liquors,
Stirring, with PEO/PTFE-PAAS mixed liquors；When preparing PEO/PTFE-PAAS composite nano-fiber membranes by electrostatic spinning, electricity
Pressure, collection distance and flow velocity are respectively 13 kV, 20 cm and 0.002 mm/s；With steel wire（90 mesh）Collected as supporter
PEO/PTFE-PAAS composite cellulosic membranes, place in an oven, 70 DEG C of 1 h of baking, 380 DEG C are heat-treated in high temperature furnace, are removed
The PEO gone in fiber, obtain PTFE-PI composite cellulosic membranes.The tensile strength of PTFE-PI composite cellulosic membranes is 28.79MPa, bullet
Property modulus is 114.58 MPa, elongation at break 32.32%.
Embodiment 2
Solution contains 4 wt% PEO in the preparation method of PTFE/PI composite nano fiber perforated membranes, wherein PEO solution,
PEO and PTFE mass ratio is 3 in PEO/PTFE mixed liquors：PAAS and PTFE matter in 100, PEO/PTFE-PAAS mixed liquors
Amount is than being 1：4, PEO/PTFE-PAAS mixed liquors are 18wt% PEO/PTFE-PAAS mixed liquors；Comprise the following steps that：
PEO powder is dissolved in 40 DEG C of deionized water, the h of mechanical agitation 3 obtains the PEO that mass fraction is 4 wt%
Solution.Be cooled in room temperature and solution because of quick stirring and caused by bubble collapse.PTFE emulsion is added to described
In PEO solution, stirring, with PEO/PTFE mixed liquors；PAAS and deionized water are added in described PEO/PTFE mixed liquors,
Stirring, with PEO/PTFE-PAAS mixed liquors；When preparing PEO/PTFE-PAAS composite nano-fiber membranes by electrostatic spinning, electricity
Pressure, collection distance and flow velocity are respectively 13 kV, 20 cm and 0.002 mm/s；With steel wire（90 mesh）Collected as supporter
PEO/PTFE-PAAS composite cellulosic membranes, place in an oven, 70 DEG C of baking 1h, 380 DEG C are heat-treated in high temperature furnace, are removed
PEO in fiber, obtain PTFE-PI composite cellulosic membranes.The tensile strength of PTFE-PI composite cellulosic membranes is 39.91MPa, elasticity
Modulus is 197.38 MPa, elongation at break 26.88%.
Embodiment 3
Solution contains 4 wt% PEO in the preparation method of PTFE/PI composite nano fiber perforated membranes, wherein PEO solution,
PEO and PTFE mass ratio is 3 in PEO/PTFE mixed liquors：PAAS and PTFE matter in 100, PEO/PTFE-PAAS mixed liquors
Amount is than being 1：5, PEO/PTFE-PAAS mixed liquors are 18wt% PEO/PTFE-PAAS mixed liquors；Comprise the following steps that：
PEO powder is dissolved in 40 DEG C of deionized water, the h of mechanical agitation 3 obtains the PEO that mass fraction is 4 wt%
Solution.Be cooled in room temperature and solution because of quick stirring and caused by bubble collapse.PTFE emulsion is added to described
In PEO solution, stirring, with PEO/PTFE mixed liquors；PAAS and deionized water are added in described PEO/PTFE mixed liquors,
Stirring, with PEO/PTFE-PAAS mixed liquors；When preparing PEO/PTFE-PAAS composite nano-fiber membranes by electrostatic spinning, electricity
Pressure, collection distance and flow velocity are respectively 13 kV, 20 cm and 0.002 mm/s；With steel wire（90 mesh）Collected as supporter
PEO/PTFE-PAAS composite cellulosic membranes, place in an oven, 70 DEG C of 1 h of baking, 380 DEG C are heat-treated in high temperature furnace, are removed
The PEO gone in fiber, obtain PTFE-PI composite cellulosic membranes.The tensile strength of PTFE-PI composite cellulosic membranes is 57.10MPa, bullet
Property modulus is 233.62 MPa, elongation at break 26.24%.
Embodiment 4
Solution contains 4 wt% PEO in the preparation method of PTFE/PI composite nano fiber perforated membranes, wherein PEO solution,
PEO and PTFE mass ratio is 3 in PEO/PTFE mixed liquors：PAAS and PTFE matter in 100, PEO/PTFE-PAAS mixed liquors
Amount is than being 1：2, PEO/PTFE-PAAS mixed liquors are 18wt% PEO/PTFE-PAAS mixed liquors；Comprise the following steps that：
PEO powder is dissolved in 40 DEG C of deionized water, the h of mechanical agitation 3 obtains the PEO that mass fraction is 4 wt%
Solution.Be cooled in room temperature and solution because of quick stirring and caused by bubble collapse.PTFE emulsion is added to described
In PEO solution, stirring, with PEO/PTFE mixed liquors；PAAS and deionized water are added in described PEO/PTFE mixed liquors,
Stirring, with PEO/PTFE-PAAS mixed liquors；When preparing PEO/PTFE-PAAS composite nano-fiber membranes by electrostatic spinning, electricity
Pressure, collection distance and flow velocity are respectively 13 kV, 20 cm and 0.002 mm/s；With steel wire（90 mesh）Collected as supporter
PEO/PTFE-PAAS composite cellulosic membranes, place in an oven, 70 DEG C of baking 1h, 380 DEG C are heat-treated in high temperature furnace, are removed
PEO in fiber, obtain PTFE-PI composite cellulosic membranes.The tensile strength of PTFE-PI composite cellulosic membranes is 81.96MPa, elasticity
Modulus is 444.73 MPa, elongation at break 23.87%.
Comparative example 1
Solution contains 4 wt% PEO, PEO/PTFE in the preparation method of PTFE nano fiber porous films, wherein PEO solution
PEO and PTFE mass ratio is 3 in mixed liquor：PAAS and PTFE mass ratio is 0 in 100, PEO/PTFE-PAAS mixed liquors：
10, PEO/PTFE-PAAS mixed liquors are 18wt% PEO/PTFE-PAAS mixed liquors；Comprise the following steps that：
PEO powder is dissolved in 40 DEG C of deionized water, the h of mechanical agitation 3 obtains the PEO that mass fraction is 4 wt%
Solution.Be cooled in room temperature and solution because of quick stirring and caused by bubble collapse.PTFE emulsion is added to described
In PEO solution, stirring, with PEO/PTFE mixed liquors；When preparing PEO/PTFE composite nano-fiber membranes by electrostatic spinning, electricity
Pressure, collection distance and flow velocity are respectively 13 kV, 20 cm and 0.002 mm/s；With steel wire（90 mesh）Collected as supporter
PEO/PTFE composite cellulosic membranes, place in an oven, 70 DEG C of 1 h of baking, 380 DEG C are heat-treated in high temperature furnace, remove fiber
In PEO, obtain PTFE fiber film.The tensile strength of PTFE-PI composite cellulosic membranes is 14.52MPa, modulus of elasticity 65.89
MPa, elongation at break 658.40%.
Comparative example 2
Solution contains 4 wt% PEO in the preparation method of PI nano fiber porous films, wherein PEO solution, and PEO/PAAS is mixed
The mass ratio for closing PEO and PAAS in liquid is 3：PAAS and PTFE mass ratio is 10 in 100, PEO/PTFE-PAAS mixed liquors：0,
PEO/PTFE-PAAS mixed liquors are 18wt% PEO/PTFE-PAAS mixed liquors；Comprise the following steps that：
PEO powder is dissolved in 40 DEG C of deionized water, the h of mechanical agitation 3 obtains the PEO that mass fraction is 4 wt%
Solution.Be cooled in room temperature and solution because of quick stirring and caused by bubble collapse.It is molten that PAAS is added to described PEO
In liquid, stirring, with PEO/PAAS mixed liquors；When preparing PEO/ PAAS composite nano-fiber membranes by electrostatic spinning, voltage,
It is respectively 13 kV, 20 cm and 0.002 mm/s to collect distance and flow velocity；With steel wire（90 mesh）PEO/ is collected as supporter
PAAS composite cellulosic membranes, place in an oven, 70 DEG C of 1 h of baking, 380 DEG C are heat-treated in high temperature furnace, are removed in fiber
PEO, obtain PI tunica fibrosas.The tensile strength of PTFE-PI composite cellulosic membranes is 106.43MPa, and modulus of elasticity is 652.64 MPa,
Elongation at break is 20.14%.
The PTFE/PI composite nano fiber perforated membranes of table 1（PAAS ：PTFE =2：8）By the machinery of soda acid before and after the processing
Performance
The PTFE/PI composite nano fiber perforated membranes of table 2（PAAS ：PTFE =1：4）And PI films are through the machine before and after alkali process
Tool performance comparison
Explanation:PI has been completely dissolved in 100 DEG C of highly basic, can not survey its mechanical performance.
Foregoing example is merely illustrative, some features of the feature for explaining the present invention.Appended claim
It is intended to require the scope as wide as possible being contemplated that, and embodiments as presented herein is only according to all possible embodiment
Combination selection embodiment explanation.Therefore, the purpose of applicant is appended claim not by the explanation present invention
Feature example selectional restriction.And the progress in science and technology will not formed due to the inaccuracy of language performance and not
The possible equivalent or son being presently considered are replaced, and these changes should also be interpreted by appended in the conceived case
Claim covers.
Claims (10)
- The preparation method of 1.PTFE/PI composite nano fiber perforated membranes, it is characterised in that comprise the following steps：1）Prepare PEO solution：By PEO be dissolved in deionized water, stirring, with PEO solution；2）Prepare PEO/PTFE mixed liquors：PTFE emulsion is added to step 1）In described PEO solution, stirring, with PEO/ PTFE mixed liquors；3）Prepare PEO/PTFE-PAAS mixed liquors：PAAS and deionized water are added into step 2）Described PEO/PTFE mixed liquors In, stirring, with PEO/PTFE-PAAS mixed liquors；4）Prepare PTFE/PI composite nano fiber perforated membranes：PEO/ is made by electrostatic spinning in PEO/PTFE-PAAS mixed liquors PTFE-PAAS composite cellulosic membranes, it is thermally treated, produce PTFE/PI composite nano fiber perforated membranes.
- 2. the preparation method of PTFE/PI composite nano fibers perforated membrane according to claim 1, it is characterised in that step 1）Described in PEO solution by the way that super high molecular weight PEO powder is dissolved in 35~45 DEG C of water, obtained after stirring；Institute The weight average molecular weight for stating super high molecular weight PEO powder is 105~107 g/mol。
- 3. the preparation method of PTFE/PI composite nano fibers perforated membrane according to claim 1, it is characterised in that step 2）Described in PEO and PTFE mass ratio be 0.5~5：100.
- 4. the preparation method of PTFE/PI composite nano fibers perforated membrane according to claim 3, it is characterised in that step 2）Described in PEO and PTFE mass ratio be 2.5~5：100.
- 5. the preparation method of PTFE/PI composite nano fibers perforated membrane according to claim 1, it is characterised in that described PEO solution contains 3~6 wt% PEO；The PTFE emulsion contains 55~65 wt% PTFE.
- 6. the preparation method of PTFE/PI composite nano fibers perforated membrane according to claim 1, it is characterised in that step 3）Described in PAAS and PTFE mass ratio be 0.25-5：10.
- 7. the preparation method of PTFE/PI composite nano fibers perforated membrane according to claim 1, it is characterised in that described PEO/PTFE-PAAS mixed liquors are 15-20wt% PEO/PTFE-PAAS mixed liquors.
- 8. the preparation method of PTFE/PI composite nano fibers perforated membrane according to claim 1, it is characterised in that step 4）Described in electrostatic spinning when voltage be 10~30kV；The distance that spinning-nozzle collects substrate to opposite electrode is 15~25cm； Spinning flow velocity is 0.001~0.005mm/s.
- 9. the preparation method of PTFE/PI composite nano fibers perforated membrane according to claim 1, it is characterised in that step 4）Described in be heat-treated and include：PEO/PTFE-PAAS composite cellulosic membranes are placed under 50~80 DEG C of any temperature conditionss first and done Dry 0.5~1 h；Then heat 5~30min under 330~450 DEG C of temperature conditionss, decompose PEO and remove.
- 10. the method system for preparing PTFE/PI composite nano fiber perforated membranes according to any one in claim 1~9 The standby PTFE/PI composite nano fiber perforated membranes obtained.
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