CN105926160B - A kind of tack polysulfones aramid fiber/silicon rubber composite nano fiber perforated membrane - Google Patents
A kind of tack polysulfones aramid fiber/silicon rubber composite nano fiber perforated membrane Download PDFInfo
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- CN105926160B CN105926160B CN201610363293.9A CN201610363293A CN105926160B CN 105926160 B CN105926160 B CN 105926160B CN 201610363293 A CN201610363293 A CN 201610363293A CN 105926160 B CN105926160 B CN 105926160B
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- silicon rubber
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/54—Particle separators, e.g. dust precipitators, using ultra-fine filter sheets or diaphragms
- B01D46/543—Particle separators, e.g. dust precipitators, using ultra-fine filter sheets or diaphragms using membranes
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/54—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 by welding together the fibres, e.g. by partially melting or dissolving
- D04H1/541—Composite fibres, e.g. sheath-core, sea-island or side-by-side; Mixed fibres
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/54—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 by welding together the fibres, e.g. by partially melting or dissolving
- D04H1/542—Adhesive fibres
- D04H1/549—Polyamides
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/54—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 by welding together the fibres, e.g. by partially melting or dissolving
- D04H1/542—Adhesive fibres
- D04H1/551—Resins thereof not provided for in groups D04H1/544 - D04H1/55
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention provides a kind of tack polysulfones aramid fiber/silicon rubber composite nano fiber perforated membrane, and the nanofiber includes polysulfones aramid fiber and silicon rubber, and wherein silicon rubber is for making the nanofiber mutually bond；Tack polysulfones aramid fiber of the present invention/silicon rubber composite nano fiber perforated membrane has high intensity, resistant to chemical etching, resistance to high excellent properties, and preparation method is simple, cost is relatively low.
Description
Technical field
The invention belongs to polymeric material fields, more particularly it relates to a kind of tack polysulfones aramid fiber/silicon rubber
Composite nano fiber perforated membrane and preparation method thereof.
Background technology
As China is to the increasingly strict of environmental requirement, sack cleaner has been increasingly becoming important in air contaminant treatment
One of cleaner.There are many high-temperature conditions in dust removal process for sack cleaner, in steel, metallurgy, steam power plant, cement etc.
Industry, the flue-gas temperature discharged in production process is mostly more than 130 DEG C, referred to as high-temperature flue gas in removing dust project.High-temperature flue gas
Dedusting is difficult compared with room temperature dedusting and complicated, because flue-gas temperature height can cause a series of variations of smoke components and dust performance,
The problems such as easily causing low-temperature corrosion, abrasion cleaner, this proposes higher requirement to the filtering material of sack cleaner.
Polysulfones aramid fiber (Polysulfonamide, PSA) fiber, i.e., poly- paraphenylene terephthalamide -3,3 ', 4,4 '-diamino two
Benzene sulfone copolymer fibre, also known as aromatic polysulfonamide fiber belong to aromatic polyamide class high temperature resistant synthetic fibers.Polysulfones aramid fiber
Molecular structure be by amide groups (- CONH-), sulfuryl (- S02) and phenyl ring is bonded forms, bit architecture between monomer has 25%
With 75% aligning structure, due on high polymer main chain introduce to benzene structure and extremely strong electron-withdrawing group sulfuryl (- S02-),
By the double bond conjugated system of phenyl ring, the cloud density of nitrogen-atoms on amide groups is set to significantly reduce, to obtain heat resistanceheat resistant oxygen
The stability of aging makes polysulfones aramid fiber have the superior fire-retardant, heat resistance compared with other high-temperature fibres.It can make
It is widely used in the fields such as protective article, filtering material and battery diaphragm for nano fiber porous film.In the prior art, due to
Bad adhesion between fiber, polysulfones aramid nano-fiber perforated membrane need to heat at very high temperatures（Generally greater than 400
℃）So that bonding force is formed between fiber to improve the stability of perforated membrane, this not only improves technology difficulty, but also greatly increases
Cost, but will influence the qualification rate of product.
In view of the above-mentioned problems, existing, there is an urgent need for the improvement by technique and formula, can be in lower temperature and more easy work
Under skill so that polysulfones aramid fiber perforated membrane has stable porous network structure, widen polysulfones aramid fiber film development and
Using.
Invention content
To solve the above-mentioned problems, one aspect of the present invention provides a kind of tack polysulfones aramid fiber/silicon rubber is compound and receives
Rice fiber multihole film, the nanofiber include polysulfones aramid fiber and silicon rubber, and wherein silicon rubber is for making the nanofiber phase
Mutually bond.
In one embodiment, the mass ratio of polysulfones aramid fiber and silicon rubber is in the nanofiber（1~9）：（1~
9）.
In one embodiment, the weight average molecular weight of the polysulfones aramid fiber is 1 × 105~1 × 107。
In one embodiment, the silicon rubber is at least 703 silicon rubber, 704 silicon rubber, 705 silicon rubber, 706 silicon
It is one or more in rubber.
Another aspect of the present invention provides a kind of preparation of tack polysulfones aramid fiber/silicon rubber composite nano fiber perforated membrane
Method at least includes the following steps：
（1）Sample dissolves：Silica gel is dissolved in 3 times of volume organic solvent As by mass fraction, polysulfones aramid fiber is dissolved in 5 times of bodies
In product organic solvent B；
（2）Electrostatic spinning：By step（1）Middle solution inclination, which is poured into, carries out electrostatic spinning in electrostatic spinning machine, form electrospinning
Polysulfones aramid fiber/silica gel composite nano fiber perforated membrane；
（3）Heat bonding：Polysulfones aramid fiber is thermally bonded with silicon rubber under the conditions of 80~180 DEG C, is formed between fiber certainly
The nano fiber porous film of bonding；
Wherein, A solvents are at least in ethyl acetate, toluene, dimethylbenzene, acetone a kind of；B solvents be at least DMAC, DMF,
It is a kind of in DMSO.
The present invention provides a kind of lithium Asia battery diaphragm, including polysulfones described above aramid fiber/silicon rubber composite nano fiber
Perforated membrane.
A kind of air-filtering membrane of present invention offer, including polysulfones described above aramid fiber/silicon rubber composite nano fiber are more
Pore membrane.
In one embodiment, the air-filtering membrane further includes industrial non-woven cloth.
In one embodiment, the polysulfones aramid fiber/silicon rubber composite nano fiber perforated membrane with the industry is non-knits
The mass ratio for making cloth is（1~10）：（1~100）.
The above-mentioned of the application and other features, aspect and advantage is more readily understood with reference to following detailed description.
Specific implementation mode
The detailed description for preferred implementation method of the invention below of participating in the election of and including embodiment this hair can be more easily understood
Bright content.Unless otherwise defined, all technologies used herein and scientific terminology have common with fields of the present invention
The normally understood identical meaning of technical staff.When there is a conflict, the definition in this specification shall prevail.
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 non-exclusionism includes.For example, the combination comprising listed elements
Object, step, method, product or device are not necessarily limited to those elements, but may include not expressly listed other elements or
Such composition, step, method, product or the intrinsic element of device.
Conjunction " Consists of " excludes any element that do not point out, step or component.If in claim, this
Phrase will make claim be closed, so that it is not included the material in addition to the material of those descriptions, but relative normal
Except rule impurity.When being rather than immediately following after theme in the clause that phrase " Consists of " appears in claim main body,
It is only limited to the element described in the clause；Other elements are not excluded except the claim as a whole.
Equivalent, concentration or other values or parameter are excellent with range, preferred scope or a series of upper limit preferred values and lower limit
When the Range Representation that choosing value limits, this, which should be understood as, specifically discloses by any range limit or preferred value and any range
Any pairing of lower limit or preferred value is formed by all ranges, regardless of whether the range separately discloses.For example, when open
When range " 1 to 5 ", described range should be interpreted as including range " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to
5 ", " 1 to 3 and 5 " etc..When numberical range is described herein, unless otherwise stated, otherwise range intention includes its end
Value and all integers and score in the range.
Singulative includes that plural number discusses object, unless the context clearly dictates otherwise." optional " or it is " arbitrary
It is a kind of " refer to that the item described thereafter or event may or may not occur, and the description include situation that event occurs and
The situation that event does not occur.
Approximate term in specification and claims is used for modifying quantity, and it is specific to indicate that the present invention is not limited to this
Quantity further includes the modified part of the acceptable change without lead to related basic function close to the quantity.Phase
It answers, modifies a numerical value with " about ", " about " etc., mean that the present invention is not limited to the exact numericals.In some examples, approximate
Term likely corresponds to the precision of the instrument of measured value.In present specification and claims, range limits can be with
Combination and/or exchange, these ranges include all subranges contained therebetween if not stated otherwise.
In addition, indefinite article "an" before element of the present invention or component and "one" quantitative requirement to element or component
(i.e. occurrence number) unrestriction.Therefore "one" or "an" should be read as including one or at least one, and odd number
The element or component of form also include plural form, unless the apparent purport of the quantity refers to singulative.
" polymer " means the polymerizable compound prepared by the monomer by the identical or different type of polymerization.Generic term
" polymer " includes term " homopolymer ", " copolymer ", " terpolymer " and " copolymer ".
" copolymer " means the polymer prepared by polymerizeing at least two different monomers.Generic term " copolymer " includes
(it is general with term " terpolymer " for term " copolymer " (its generally to refer to the polymer prepared by two kinds of different monomers)
To refer to the polymer prepared by three kinds of different monomers).It also includes the polymer manufactured by polymerizeing more kinds of monomers.
" blend " means the polymer that two or more polymer is formed by mixing jointly by physics or chemical method.
One aspect of the present invention provides a kind of tack polysulfones aramid fiber/silicon rubber composite nano fiber perforated membrane, described
Nanofiber includes polysulfones aramid fiber and silicon rubber, and wherein silicon rubber is for making the nanofiber mutually bond.
In one embodiment, the mass ratio of polysulfones aramid fiber and silicon rubber is in the perforated membrane（1~9）：（1~9）.
In one embodiment, the mass ratio of polysulfones aramid fiber and silicon rubber is in the perforated membrane（1~8）：（1~8）.
Filtering is a kind of operation for the particulate material that trapping is scattered in gas or liquid, is heterogeneous point of substance
From.Filtering is completed by the way that filter medium and filter plant are mating, and manufacturing enterprise's filter medium is referred to as filtering material product,
It is component part critically important in fabrics for industrial use major class.Control pollution, environment protection are played by filtering, in work
Guarantee product quality is played in industry production, improves the technology acuracy of product, the important work such as recycles valuable raw material and reduce cost
With.
Using fibre as the filtering of filtering material, it is broadly divided into dry filter and wet filter two major classes.Dry type mistake
Filter refers to the solid particle that the floating type in gas suspends, the process that the dust in air is detached, also known as gas solid separation.
Bag type filtering in industrial process, the air filter in building ventilation, belongs to gas-particle separation（Filtering）Scope.Wet type mistake
Filter is the process for removing the solid particle for swimming or suspending in liquid from liquid.
The fiber of filter material is selected most important, is related to the service life of filter material, and heatproof, resistance are considered under service condition
The requirements such as wear-resisting, anti-folding, intensity height in the physical and mechanical property of combustion property, chemical-resistant stability and fibrous material.
As China is to the increasingly strict of environmental requirement, sack cleaner has been increasingly becoming important in air contaminant treatment
One of cleaner.There are many high-temperature conditions in dust removal process for sack cleaner, in steel, metallurgy, steam power plant, cement etc.
Industry, the flue-gas temperature discharged in production process is mostly more than 130 DEG C, referred to as high-temperature flue gas in removing dust project.High-temperature flue gas
Dedusting is difficult compared with room temperature dedusting and complicated, because flue-gas temperature height can cause a series of variations of smoke components and dust performance,
The problems such as easily causing low-temperature corrosion, abrasion cleaner.
Polysulfones aramid fiber belongs to aromatic co-polyamides class organic high temperature-resistant material, and structure is special, function admirable.Its
Anti-flammability is good, does not melt, do not shrink or seldom shrinks in burning, from flame self-extinguishment, rarely glows or remaining combustion phenomenon.
Polysulfones aramid fiber has stronger acid resistance and resistance to corrosive chemicals.Its fiber is by 80 DEG C a concentration of 30%
After sulfuric acid, hydrochloric acid, nitric acid treatment, except nitric acid makes fiber strength be slightly decreased, hydrochloric acid is with sulfuric acid to the strength of fiber without apparent
It influences.
In terms of anti-organic solvent, in addition to DMAC（N, N '-dimethyl acetamide), DMF（N, N '-dimethyl formamide),
Other than DMSO (dimethyl sulfoxide (DMSO)), hempa, N-Methyl pyrrolidone and several intensive polar solvents of the concentrated sulfuric acid, generally at normal temperatures
Aromatic polysulfonamide fiber can keep good stability to various chemicals.
Polysulfones aramid fiber filtrate has heat resistance outstanding and good resistance to chemical corrosion, meets filtrate professional standard
In to high temperature resistant and corrosion resistant specific technique requirement, be a kind of novel bag-type duster filtering material of resistance to 250 DEG C of high temperature.
Electrostatic spinning technique（Electrospinning technology）It is considered as a kind of simply and effectively prepare directly
Diameter has controlled diameter, high porosity, large specific surface area and can be with functionalization between the method for micrometer/nanometer grade fiber
The advantages that.
Electrostatic spinning is a kind of spining technology different from conventional method, and basic principle is：Polymer solution is molten
Body overcomes surface tension under high voltage electric field and generates electrified jet, and jet stream is dry in course of injection, cures, and falls and is receiving
Tunica fibrosa is formed on device.
In one embodiment, the weight average molecular weight of the polysulfones aramid fiber is 1 × 105~1 × 107；Preferably,
The weight average molecular weight of the polysulfones aramid fiber is 1 × 105~8 × 106。
In one embodiment, the silicon rubber is at least 703 silicon rubber, 704 silicon rubber, 705 silicon rubber, 706 silicon
It is one or more in rubber；Preferably, the silicon rubber be at least in 703 silicon rubber, 704 silicon rubber, 705 silicon rubber it is a kind of or
It is a variety of；Preferably, the silicon rubber is at least one or more in 703 silicon rubber, 704 silicon rubber.
Silicon rubber refers to that main chain is alternately made of silicon and oxygen atom, and the rubber there are two organic group is usually connected on silicon atom
Glue.Common silicon rubber is mainly made of the silica chain link containing methyl and a small amount of vinyl.Silicon rubber can be improved in the introducing of phenyl
High- and low-temperature resistance performance, the heatproof and oil resistance of silicon rubber then can be improved in the introducing of trifluoro propyl and cyano.Silicon rubber is resistance to low
Temperature is functional, generally remains to work at -55 DEG C.After introducing phenyl, reachable -73 DEG C.The heat resistance of silicon rubber is also very prominent
Go out, at 180 DEG C can long-term work, a little higher than 200 DEG C can also bear several weeks or longer time it is still flexible, be instantaneously resistant to 300
DEG C or more high temperature.The good permeability of silicon rubber, OTR oxygen transmission rate are highest in synthetic polymer.
Room temperature vulcanized silicone rubber is the relatively low one kind of silicon rubber middle-molecular-weihydroxyethyl, its molecular weight generally 1-10 ten thousand it
Between.Its main chain is the inorganic chain structure of-Si-O-Si-O-, end with hydroxyl, organic group is carried on silicon atom.
703 silicon rubber are that a kind of cementability is good, high intensity, free from corrosion single-component room-temperature-vulsilicone silicone rubber.It is by end
Hold fillers and the special curing agent such as dimethyl silicone polymer, the silica of hydroxyl（Without organotin）, formed appearance
For milky thick liquid matter.It, can be at -50 DEG C -+250 DEG C with excellent electrical insulation capability, sealing performance and ageing-resistant performance
In the range of be used for a long time.
703 room temperature vulcanized silicone rubbers not only have high- and low-temperature resistance outstanding and a resistance to ag(e)ing, excellent electrical apparatus insulation and
Moisture-proof shock resistance also has excellent cementability, it can bond various metals, nonmetallic, plastics and rubber extensively.With excellent
High temperature resistant and hot water resistance energy, be the ideal material of heat-resisting device sealing.Suitable for being bonded in for household electrical appliance electric heating appliances
Insulated enclosure, insulating protective coating and point spigot seal suitable for electric appliance are used.
704 silicon rubber are that a kind of cementability is good, high intensity, free from corrosion single-component room-temperature-vulsilicone silicone rubber.It is by end
End is fillers and suitable curing agent such as dimethyl silicone polymer, the silica of hydroxyl（Without organotin）Formed appearance is
The thick liquid matter of milky or red.With excellent electrical insulation capability, sealing performance and ageing-resistant performance, can -50 DEG C -+
It is used for a long time in the range of 250 DEG C.704 silica gel belong to the condensed type silica gel of dealcoholized type.704 room temperature vulcanized silicone rubbers not only have prominent
The high- and low-temperature resistance and resistance to ag(e)ing gone out, excellent electrical apparatus insulation and moisture-proof shock resistance also have excellent cementability, it
Various metals, nonmetallic, plastics and rubber can be bonded extensively.
705 glue, it is made of the dimethyl silicone polymer of end hydroxyl and suitable curing agent (being free of organotin),
Appearance is transparent not solvent-laden dilute thick body.It because tool viscosity, leakproofness it is preferable, more as moisture seal protective coating
It is suitble to.
706 silicon rubber can glue common metal（Aluminium, copper, nickel, zinc, titanium alloy, ferrite etc.）With various nonmetallic materials
（Ceramics, glass, cement）Plastics（Phenolic aldehyde, unsaturated polyester, organosilicon, hard polyvinyl chloride, organic glass, ABS, polystyrene
Glass）, therefore suitable between metal, between nonmetallic, metal and it is nonmetallic between seal bond.
In one embodiment, the base weight of the tack polysulfones aramid fiber/silicon rubber composite nano fiber perforated membrane is
15~30g/m2;Thickness is 20~60 μm;Surface average pore size is 1.0~3.0 μm.
In one embodiment, the base weight of the tack polysulfones aramid fiber/silicon rubber composite nano fiber perforated membrane is 8
~20 g/m2;Thickness is 10~40 μm;Average pore size is 0.5~1.5 μm.
In one embodiment, the electrospun fibers diameter range is 0.1~0.5 μm；Preferably, the electrostatic
Spinning fibre diameter range is 0.15~0.35 μm.
Polysulfones aramid fiber by model FEI Quanta 200 produced in USA scanning electron microscope（SEM）Table
Sign.Meanwhile passing through transmission electron microscope（JEM 2100, Japan）The front and back fiber morphology of analysis heat treatment.
Another aspect of the present invention provides a kind of preparation of tack polysulfones aramid fiber/silicon rubber composite nano fiber perforated membrane
Method at least includes the following steps：
Sample dissolves：Silica gel is dissolved in 3 times of volume organic solvent As by weight, it is organic that polysulfones aramid fiber is dissolved in 5 times of volumes
In solvent B；
Electrostatic spinning：By step（1）Middle solution inclination, which is poured into, carries out electrostatic spinning in electrostatic spinning machine, form electrospinning polysulfones
Aramid fiber/silicon rubber composite nano fiber perforated membrane；
Heat bonding：Polysulfones aramid fiber is thermally bonded with silicon rubber under the conditions of 80~180 DEG C, forms autoadhesion between fiber
Nano fiber porous film；
Wherein, A solvents are at least in ethyl acetate, toluene, dimethylbenzene, acetone a kind of；B solvents be at least DMAC, DMF,
It is a kind of in DMSO.
In one embodiment, the bonding temperature is 90~160 DEG C.
In one embodiment, the A solvents are at least in ethyl acetate, toluene, dimethylbenzene a kind of；The B solvents
It is a kind of at least in DMAC, DMF, DMSO；Preferably, the A solvents are at least in ethyl acetate, toluene a kind of；The B solvents
It is a kind of at least in DMAC, DMF.
The present invention provides a kind of lithium Asia battery diaphragm, including polysulfones described above aramid fiber/silicon rubber composite nano fiber
Perforated membrane.
A kind of air-filtering membrane of present invention offer, including polysulfones described above aramid fiber/silicon rubber composite nano fiber are more
Pore membrane.
In one embodiment, the air-filtering membrane further includes industrial non-woven cloth.
In one embodiment, the polysulfones aramid fiber/silicon rubber composite nano fiber perforated membrane with the industry is non-knits
The mass ratio for making cloth is（1~10）：（1~100）；Preferably, the polysulfones aramid fiber/silicon rubber composite nano fiber perforated membrane with
The mass ratio of the industry non-woven cloth is 1：（1~10）.
Industrial non-woven cloth is a kind of need not spin cotton and weave cloth and the fabric formed, only by textile staple or long filament
It is oriented or then random alignment, formation fibre net structure is reinforced using the methods of mechanical, hot sticky or chemical.It is directly
It is soft, ventilative by having of being formed of various web forming methods and concretion technology using high polymer slice, staple fiber or long filament
With the tencel product of planar structure.
Since the bad adhesion between fiber, polysulfones aramid nano-fiber perforated membrane are needed in very high temperature in the present invention
Lower hot melt（Generally greater than 400 DEG C）So that bonding force is formed between fiber to improve the stability of perforated membrane, after silicon rubber is added
By melting laminating process control at relatively low temperature, surface fiber and film surface bounding point is set to increase, molecule segment is handed over
Mutually stablize again on new position after migration, integration, forms the nano fiber porous film network structure of autoadhesion.
The nano fiber porous film of autoadhesion between the fiber formed is thermally bonded through high temperature by polysulfones aramid fiber and silicon rubber, is surpassed
Film is bonded with industrial non-woven cloth, and forming air purification film has heat resistance outstanding and good resistance to chemical corrosion,
It meets to high temperature resistant and corrosion resistant specific technique requirement in filtrate professional standard, is a kind of novel mistake of resistance to 250 DEG C of high temperature
Filter material material.
The equipment used when heretofore described electrostatic spinning is the FM- of the rich friendly horse science and technology limited Company production in Beijing
Type B electrospinning equipment（- 5~50kV）.Heat treatment SKGL-1200 high in the heat treatment step at 80~180 DEG C
Warm tube type resistance furnace is handled.
The present invention is specifically described below by embodiment.It is necessarily pointed out that following embodiment is only used
In the invention will be further described, it should not be understood as limiting the scope of the invention, professional and technical personnel in the field
Some the nonessential modifications and adaptations made according to the content of aforementioned present invention, still fall within protection scope of the present invention.
In addition, if without other explanations, it is raw materials used to be all commercially available, it is purchased from traditional Chinese medicines chemical reagent.
Raw material：
A1：Polysulfones aramid fiber, weight average molecular weight 1.5 × 106, Dupont；
A2：Polysulfones aramid fiber, weight average molecular weight 5 × 104, Dupont；
A3：Polysulfones aramid fiber, weight average molecular weight 2 × 107, Dupont；
B1：703 silicon rubber；
B2：704 silicon rubber；
B3：705 silicon rubber；
B4：706 silicon rubber.
Embodiment 1
A kind of tack polysulfones aramid fiber/silicon rubber composite nano fiber perforated membrane, polysulfones aramid fiber are with silicon rubber mass ratio
1.25：1, preparation method includes the following steps：
（1）Sample dissolves：703 silicon rubber B1 of 1g are dissolved in 30ml organic solvent ethyl acetate, 10g polysulfones aramid fibers A1
It is dissolved in 70ml organic solvents DMAC, after mixing, stirs evenly；
（2）Electrostatic spinning：By step（1）Middle solution inclination, which is poured into, carries out electrostatic spinning in electrostatic spinning machine, the electrostatic
Voltage when spinning is 25kV, and the distance that spinning-nozzle to opposite electrode collects substrate is 20cm, and spinning flow velocity is 0.003mm/
s；Form the silicon rubber composite nano fiber perforated membrane of electrospinning polysulfones aramid fiber/703；
（3）Heat bonding：Polysulfones aramid fiber and 703 silicon rubber are thermally bonded 15min under the conditions of 80 DEG C, remove solvent,
The nano fiber porous film of autoadhesion between formation fiber.
Embodiment 2：
A kind of tack polysulfones aramid fiber/silicon rubber composite nano fiber perforated membrane, polysulfones aramid fiber are with silicon rubber mass ratio
9：1, preparation method includes the following steps：
（1）Sample dissolves：705 silicon rubber B3 of 1g are dissolved in 30ml organic solvent toluenes, 9g polysulfones aramid fibers A2 is dissolved in
In 70ml organic solvents DMF, after mixing, stir evenly；
（2）Electrostatic spinning：By step（1）Middle solution inclination, which is poured into, carries out electrostatic spinning in electrostatic spinning machine, the electrostatic
Voltage when spinning is 25kV, and the distance that spinning-nozzle to opposite electrode collects substrate is 20cm, and spinning flow velocity is 0.003mm/
s；Form the silicon rubber composite nano fiber perforated membrane of electrospinning polysulfones aramid fiber/705；
（3）Heat bonding：Polysulfones aramid fiber and 705 silicon rubber are thermally bonded 15min under the conditions of 180 DEG C, remove solvent,
The nano fiber porous film of autoadhesion between formation fiber.
Embodiment 3
A kind of tack polysulfones aramid fiber/silicon rubber composite nano fiber perforated membrane, polysulfones aramid fiber are with silicon rubber mass ratio
8：1, preparation method includes the following steps：
（1）Sample dissolves：1g704 silicon rubber B2 is dissolved in 30ml organic solvent ethyl acetate, 8g polysulfones aramid fibers A1 is molten
In 65ml organic solvents DMAC, after mixing, stir evenly；
（2）Electrostatic spinning：By step（1）Middle solution inclination, which is poured into, carries out electrostatic spinning in electrostatic spinning machine, the electrostatic
Voltage when spinning is 25kV, and the distance that spinning-nozzle to opposite electrode collects substrate is 20cm, and spinning flow velocity is 0.003mm/
s；Form the silicon rubber composite nano fiber perforated membrane of electrospinning polysulfones aramid fiber/704；
（3）Heat bonding：Polysulfones aramid fiber and 704 silicon rubber are thermally bonded 15min under the conditions of 160 DEG C, remove solvent,
The nano fiber porous film of autoadhesion between formation fiber；
Embodiment 4
A kind of tack polysulfones aramid fiber/silicon rubber composite nano fiber perforated membrane, polysulfones aramid fiber are with silicon rubber mass ratio
1：1, preparation method includes the following steps：
（1）Sample dissolves：2g706 silicon rubber B4 is dissolved in 60ml organic solvent toluenes, 2g polysulfones aramid fibers A3 is dissolved in 10
In ml organic solvents DMSO, after mixing, stir evenly；
（2）Electrostatic spinning：By step（1）Middle solution inclination, which is poured into, carries out electrostatic spinning in electrostatic spinning machine, the electrostatic
Voltage when spinning is 25kV, and the distance that spinning-nozzle to opposite electrode collects substrate is 20cm, and spinning flow velocity is 0.003mm/
s；Form the silicon rubber composite nano fiber perforated membrane of electrospinning polysulfones aramid fiber/706；
（3）Heat bonding：Polysulfones aramid fiber and 706 silicon rubber are thermally bonded 15min under the conditions of 70 DEG C, remove solvent,
The nano fiber porous film of autoadhesion between formation fiber.
Embodiment 5
A kind of tack polysulfones aramid fiber/silicon rubber composite nano fiber perforated membrane, polysulfones aramid fiber are with silicon rubber mass ratio
10：1, preparation method includes the following steps：
（1）Sample dissolves：1g704 silicon rubber B2 is dissolved in 30ml organic solvent-acetones, 10g polysulfones aramid fibers A3 is dissolved in
In 90ml organic solvents DMAC, after mixing, stir evenly；
（2）Electrostatic spinning：By step（1）Middle solution inclination, which is poured into, carries out electrostatic spinning in electrostatic spinning machine, the electrostatic
Voltage when spinning is 25kV, and the distance that spinning-nozzle to opposite electrode collects substrate is 20cm, and spinning flow velocity is 0.003mm/
s；Form the silicon rubber composite nano fiber perforated membrane of electrospinning polysulfones aramid fiber/704；
（3）Heat bonding：Polysulfones aramid fiber and 704 silicon rubber are thermally bonded 15min under the conditions of 200 DEG C, remove solvent,
The nano fiber porous film of autoadhesion between formation fiber.
Embodiment 6
A kind of tack polysulfones aramid fiber/silicon rubber composite nano fiber perforated membrane, polysulfones aramid fiber are with silicon rubber mass ratio
8：1, preparation method includes the following steps：
（1）Sample dissolves：1g704 silicon rubber B2 is dissolved in 30ml organic solvent ethyl acetate, 10g polysulfones aramid fibers A1 is molten
In 90ml organic solvents DMAC, after mixing, stir evenly；
（2）Electrostatic spinning：By step（1）Middle solution inclination, which is poured into, carries out electrostatic spinning in electrostatic spinning machine, the electrostatic
Voltage when spinning is 25kV, and the distance that spinning-nozzle to opposite electrode collects substrate is 20cm, and spinning flow velocity is 0.003mm/
s；Form the silicon rubber composite nano fiber perforated membrane of electrospinning polysulfones aramid fiber/704；
（3）Heat bonding：Polysulfones aramid fiber and 704 silicon rubber are thermally bonded 15min under the conditions of 160 DEG C, remove solvent,
The nano fiber porous film of autoadhesion between formation fiber；
（4）By step（3）The nano fiber porous film of autoadhesion carries out hot sticky with industrial non-woven cloth between obtained fiber
Close 30min（The mass ratio of polysulfones aramid fiber/silicon rubber composite nano fiber perforated membrane and the Industry non-woven cloth is 1：
7）, obtain a kind of air purification film.
Test and evaluation：Mechanical performance and resistance toization are carried out to the nano fiber porous film that embodiment, comparative example prepare
The test of corrosive nature is learned, wherein mechanical performance thinks carefully Science and Technology Co., Ltd.'s offer in length and breadth by using Shenzhen
UTM6500 electronic universal testers are tested.Specifically, the nano fibrous membrane of acquisition is cut into 1 × 5cm2Rectangle, claim
Weight, with the width and length of vernier caliper correct amount membrane, according to the density 1.4g/cm of polysulfones aramid fiber3Its thickness is calculated, is drawn
It stretches speed and is set as 5 mm/min, carry out extension test.
Acid processing：Nano fiber porous film is placed in 30% H2SO4In 12 h are handled at 80 DEG C；
Alkali process：Nano fiber porous film is placed in 6 mol/L-112 h are handled in NaOH at 80 DEG C.
1 the performance test results of table
In conclusion using tack polysulfones aramid fiber of the present invention/silicon rubber composite nano fiber perforated membrane, success
Ground obtains polysulfones aramid fiber/silicon rubber composite nano-fiber membrane by electrostatic spinning technique, is heat-treated by heat bonding, is prepared for gathering
Sulfone aramid fiber/silicon rubber composite nano fiber perforated membrane has better mechanical performance.And polysulfones aramid fiber/silicon rubber composite Nano
Fiber multihole film impregnates 12 h, the pattern of fiber and the mechanicalness of film under the severe chemical environment of 80 DEG C of strong acid and strong base
It can compare, vary less, in addition, polysulfones aramid fiber/silicon rubber composite nano fiber perforated membrane is the same as polysulfones aramid fiber/silicon with before impregnating
Rubber composite nano fiber perforated membrane is compared with the air purification film after industrial non-woven cloth heat bonding, and performance change is also little,
But cost is reduced, illustrates that polysulfones aramid fiber/silicon rubber composite nano fiber perforated membrane and electrospinning polysulfones aramid fiber/silicon rubber are compound
The air purification film that nano fiber porous film and industrial non-woven cloth are thermally bonded all has excellent chemical resistance, electricity
Spin polysulfones aramid fiber/silicon rubber composite nano fiber perforated membrane has very greatly in high temperature filtration and harsh chemical environments filtration art
Potential application.
Example above-mentioned is merely illustrative, some features of the feature for explaining the disclosure, those skilled in the art
Present disclosure can be used for reference, technological parameter realization is suitably modified.In particular, it should be pointed out that all similar substitutions and modifications pair
It is it will be apparent that they are considered as being included in the present invention for those skilled in the art.The method of the present invention and application are
Be described through passing through preferred embodiment, related personnel obviously can not depart from the content of present invention, in spirit and scope to this
Methods and applications described in text are modified or suitably change and combine, to realize and apply the technology of the present invention.
Claims (7)
1. a kind of tack polysulfones aramid fiber/silicon rubber composite nano fiber perforated membrane, which is characterized in that the nanofiber includes
Polysulfones aramid fiber and silicon rubber, wherein silicon rubber are for making the nanofiber mutually bond；
The mass ratio of polysulfones aramid fiber and silicon rubber is 8 in the nanofiber：1；
The weight average molecular weight of the polysulfones aramid fiber is 1 × 105~1 × 107；
The silicon rubber is at least one or more in 703 silicon rubber, 704 silicon rubber, 705 silicon rubber, 706 silicon rubber.
2. a kind of preparation method of tack polysulfones aramid fiber described in claim 1/silicon rubber composite nano fiber perforated membrane,
It is characterized in that, at least includes the following steps：
(1) sample dissolves：Silica gel is dissolved in 3 times of volume organic solvent As by mass fraction, polysulfones aramid fiber, which is dissolved in 5 times of volumes, to be had
In solvent B；
(2) electrostatic spinning：Solution inclination in step (1) is poured into and carries out electrostatic spinning in electrostatic spinning machine, forms electrospinning polysulfones
Aramid fiber/silica gel composite nano fiber perforated membrane；
(3) it is thermally bonded：Polysulfones aramid fiber is thermally bonded with silicon rubber under the conditions of 80~180 DEG C, forms autoadhesion between fiber
Nano fiber porous film；
Wherein, A solvents are at least in ethyl acetate, toluene, dimethylbenzene, acetone a kind of；B solvents are at least DMAC, DMF, DMSO
Middle one kind.
3. the preparation method of the aramid fiber of tack polysulfones described in claim 2/silicon rubber composite nano fiber perforated membrane, feature
It is, the bonding temperature is 90~160 DEG C, and A solvents are at least in ethyl acetate, toluene, dimethylbenzene a kind of；B solvents are extremely
It is a kind of in DMAC, DMF, DMSO less.
4. a kind of lithium Asia battery diaphragm, which is characterized in that including polysulfones aramid fiber/silicon rubber composite Nano described in claim 1
Fiber multihole film.
5. a kind of air-filtering membrane, which is characterized in that fine including polysulfones aramid fiber described in claim 1/silicon rubber composite Nano
Tie up perforated membrane.
6. the air-filtering membrane described in claim 5, which is characterized in that the air-filtering membrane further includes industrial non-woven cloth.
7. the air-filtering membrane described in claim 6, which is characterized in that the polysulfones aramid fiber/silicon rubber composite nano fiber is more
The mass ratio of pore membrane and the industrial non-woven cloth is (1~10)：(1~100).
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| CN1883779A (en) * | 2006-05-19 | 2006-12-27 | 广州美能材料科技有限公司 | Process for preparing composite hollow fiber membrane |
| CN102947499A (en) * | 2010-06-21 | 2013-02-27 | 可隆株式会社 | Porous nanoweb and method for manufacturing the same |
| CN102050954A (en) * | 2010-11-12 | 2011-05-11 | 北京工业大学 | Preparation method of environment-friendly silicone rubber composite membrane |
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