CN105442301A - Preparing method for polyimide fibrous membrane with surface coated with titanium dioxide nanolayer - Google Patents
Preparing method for polyimide fibrous membrane with surface coated with titanium dioxide nanolayer Download PDFInfo
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- CN105442301A CN105442301A CN201610050579.1A CN201610050579A CN105442301A CN 105442301 A CN105442301 A CN 105442301A CN 201610050579 A CN201610050579 A CN 201610050579A CN 105442301 A CN105442301 A CN 105442301A
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- Prior art keywords
- polyamic acid
- tunica fibrosa
- polyimide
- titanium dioxide
- fibrous membrane
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- 238000000034 method Methods 0.000 title claims abstract description 55
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000004642 Polyimide Substances 0.000 title claims abstract description 47
- 229920001721 polyimide Polymers 0.000 title claims abstract description 47
- 239000004408 titanium dioxide Substances 0.000 title abstract description 11
- 239000012528 membrane Substances 0.000 title abstract description 10
- 239000002052 molecular layer Substances 0.000 title abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 32
- 239000011248 coating agent Substances 0.000 claims abstract description 17
- 238000000576 coating method Methods 0.000 claims abstract description 17
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 14
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 5
- 229920005575 poly(amic acid) Polymers 0.000 claims description 56
- 239000000835 fiber Substances 0.000 claims description 32
- 238000002360 preparation method Methods 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 7
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical group [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 6
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical group [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical group CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical group Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical group [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 abstract description 12
- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000004952 Polyamide Substances 0.000 abstract 3
- 239000002253 acid Substances 0.000 abstract 3
- 229920002647 polyamide Polymers 0.000 abstract 3
- 230000007062 hydrolysis Effects 0.000 abstract 1
- 238000006460 hydrolysis reaction Methods 0.000 abstract 1
- 230000000630 rising effect Effects 0.000 abstract 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 27
- 238000009987 spinning Methods 0.000 description 15
- 239000002105 nanoparticle Substances 0.000 description 12
- 238000013019 agitation Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- 239000002131 composite material Substances 0.000 description 7
- -1 titanium dioxide compound Chemical class 0.000 description 6
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 5
- 238000013461 design Methods 0.000 description 5
- 239000005457 ice water Substances 0.000 description 5
- 238000009413 insulation Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011538 cleaning material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/46—Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic Table; Titanates; Zirconates; Stannates; Plumbates
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4326—Condensation or reaction polymers
- D04H1/4334—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
- D04H1/70—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
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Artificial Filaments (AREA)
- Laminated Bodies (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention relates to a preparing method for a polyimide fibrous membrane with the surface coated with a titanium dioxide nanolayer. The preparing method comprises the steps that firstly, a polyamide acid solution is prepared into a polyamide acid fibrous membrane through the electrostatic spinning technology; secondly, the polyamide acid fibrous membrane is put into a sealed container containing a titanium compound to be treated under the vacuum condition of 50 DEG C-70 DEG C; thirdly, the polyimide fibrous membrane with the surface coated with the titanium dioxide nanolayer is finally obtained through hydrolysis and gradient temperature rising heat imidization treatment. The preparing method is simple in implementing process, high in coating efficiency, free of damage to a matrix and good in application prospect due to the fact that the thickness of the titanium dioxide nanolayer is adjustable and controllable.
Description
Technical field
The invention belongs to polyimide fiber technical field of membrane, especially relate to a kind of preparation method of polyimide fiber film of Surface coating nano titania layer.
Background technology
Polyimides is the high-performance polymer containing imide ring structure on a class main chain, there is excellent high and low temperature resistance, mechanical performance, dielectric properties, chemical stability and the radiotolerant unique advantage of resistance to ultraviolet, all obtain application in high-tech areas such as Aero-Space, microelectronics and atomic energy.In recent years, along with the development of electrostatic spinning technique, take polyimides as the extensive concern that the micro/nano fibrous membrane material of matrix obtains people.This kind of material advantage that tunica fibrosa specific area is large owing to combining, porosity is high and polyimide high temperature-resistant and chemically stable characteristic, all show huge potential using value in fields such as tissue engineering bracket, Thermosensitive Material Used for Controlled Releasing of Medicine, sensor, catalysis, filtering material and battery diaphragms.Wherein, in order to give the more excellent surface property of polyimide fiber film and functional, surface inorganic particle being carried out to it and covers that to carry the polyimide-based organic/inorganic composite cellulosic membrane preparing Surface coating inorganic nano layer be the current research field received much concern.
Current, the method preparing polyimide-based organic/inorganic composite cellulosic membrane mainly contains direct blending, situ aggregation method and sol-gel process.Direct blending is directly directly mixed with the presoma of polyimides or polyimides by inorganic nano-particle, is dispersed in polymeric matrix by inorganic nano-particle, thus obtains composite.And in-situ polymerization rule is after being mixed with organic monomer by nano particle, then trigger monomer polymerization under suitable condition, thus obtain the composite polyimide material of doping inorganic nano-particle.Sol-gal process refers to and forms colloidal sol by after inorganic compound hydrolytic condensation, then with organic polymer solution or emulsion blending, occur to form Preparing Organic-inorganic Nano Hybrid Material after gelation.
Said method can realize dispersed in organic polymer matrix of inorganic nano-particle, therefore, has good effect, become the common method in this field in the polyimide fiber film preparing inorganic nano-particle doping.As patent CN102277648B once adopted direct blending successfully to prepare inorganic/organic composite polyimide based nano-fiber film; Patent CN101301592A once adopted sol-gel process to prepare polyimide/titanium dioxide compound submicron fiber film.But but there is larger deficiency when preparing the polyimide fiber film of Surface coating inorganic nano layer in these methods.This is mainly because inorganic nano-particle major part is in the inside of polyimide matrix fiber, the nano particle of seldom amount is only had to be attached to matrix fiber surface, cause inorganic nano-particle not high to the clad ratio on matrix fiber surface, inorganic nano layer fine and close continuously cannot be formed at fiber surface, and inorganic nano layer is in uneven thickness, be also difficult to realize controlled.Although can improve the coated degree of inorganic particulate on matrix fiber surface by the method for adding inorganic nano-particle or its presoma in a large number in preparation process, this often can cause again the larger change of polyimide matrix fiber bodies performance; Simultaneously, inorganic nano-particle or its presoma add the characteristic (as viscosity, density and electric conductivity etc.) that also can change polyimides and precursor solution itself thereof in a large number, thus cause the significantly change of electrospinning process parameter, even occur to prepare the problem of composite cellulosic membrane by Electrospun.
Summary of the invention
The object of the invention is to solve the deficiencies in the prior art, a kind of simple and effective process preparing the polyimide fiber film of Surface coating nano titania layer is provided.Method technical process of the present invention is simple, and coating efficiency is high, and to matrix not damaged, and the thickness of nano titania layer is adjustable controlled, and application prospect is good.
1. a preparation method for the polyimide fiber film of Surface coating nano titania layer, is characterized in that comprising the following steps:
A: adopt solid content to be the polyamic acid solution of 8% ~ 30%, obtain polyamic acid tunica fibrosa through method of electrostatic spinning;
B: polyamic acid tunica fibrosa steps A obtained is placed in the closed container filling titanium compound, processes 10min ~ 1h under the vacuum condition of 50 DEG C ~ 70 DEG C;
C: the polyamic acid tunica fibrosa that step B is obtained processes 0.5 ~ 3min in steam, and then 0.5 ~ 1h is left standstill under room temperature and condition of normal pressure;
D: order repeats step B and step C several times;
E: the polyamic acid tunica fibrosa that step D is obtained is placed in hot stove, is progressively warming up to 300-350 DEG C, and keeps 0.5 ~ 3h, namely obtain the polyimide fiber film of Surface coating nano titania layer with the programming rate of 2 ~ 6 DEG C/min.
2. the titanium compound wherein, described in step B is isopropyl titanate, butyl titanate, tetraethyl titanate, titanium tetrafluoride, titanium tetrachloride.
3. the number of repetition in step D is unrestricted, and the thickness of nano titania layer increases with the increase of number of repetition.
Compared with prior art, this method has following excellent results:
1. implementing process process is simple, and condition easily meets, the easy easy repetition of step, and to polyimide matrix fibrous zero damage in processing procedure, applied widely, can be used for the polyimide fiber film of all systems.
2. the coating efficiency of titania nanoparticles to polyimide matrix fiber is high, and the compactness of the titanium oxide inorganic nanometer layer of formation is good, and adhesiveness is high.
3. the thickness of nano titania layer can realize controlled by changing process conditions.
The polyimide composite fiber film that carrying of titanium dioxide nanometer layer is covered on surface obtained by the present invention has inorganic layer dense uniform, adhesive force is high, thickness is controlled advantage, can be applicable in catalysis material, battery diaphragm, anti-ultraviolet material and self-cleaning material.
Accompanying drawing explanation
Fig. 1 is pyromellitic acid dianhydride/4, and 4 '-diaminodiphenyl ether (PMDA/ODA) polyamic acid tunica fibrosa is directly heated to 300 DEG C and is incubated the SEM shape appearance figure of the polyimide fiber film that 120min amidatioon obtains, and in figure, multiplication factor is 100,000 times;
Fig. 2 is that PMDA/ODA polyamic acid tunica fibrosa passes through process (circulating 1 time), and is heated to the SEM shape appearance figure of the polyimide fiber film that 300 DEG C of insulation 120min amidatioon obtains, and in figure, multiplication factor is 200,000 times;
Fig. 3 is that PMDA/ODA polyamic acid tunica fibrosa passes through process (circulating 4 times), and is heated to the SEM shape appearance figure of the polyimide fiber film that 300 DEG C of insulation 120min amidatioon obtains, and in figure, multiplication factor is 200,000 times;
Fig. 4 is that PMDA/ODA polyamic acid tunica fibrosa passes through process (circulating 20 times), and is heated to the SEM shape appearance figure of the polyimide fiber film that 320 DEG C of insulation 120min amidatioon obtains, and in figure, multiplication factor is 200,000 times;
Fig. 5 is that PMDA/ODA polyamic acid tunica fibrosa passes through process (circulating 30 times), and is heated to the SEM shape appearance figure of the polyimide fiber film that 300 DEG C of insulation 60min amidatioon obtains, and in figure, multiplication factor is 100,000 times;
Fig. 6 is that PMDA/ODA polyamic acid tunica fibrosa passes through process (circulating 50 times), and is heated to the SEM shape appearance figure of the polyimide fiber film that 300 DEG C of insulation 60min amidatioon obtains, and in figure, multiplication factor is 100,000 times;
Detailed description of the invention
Below in conjunction with specific embodiment, set forth invention further.Should be noted that: following examples are only in order to illustrate the present invention and and unrestricted technical scheme described in the invention.Therefore, although this description with reference to following embodiment to present invention has been detailed description, it will be understood by those of skill in the art that and still can modify to the present invention or equivalent to replace; And all do not depart from technical scheme and the improvement thereof of the spirit and scope of the present invention, it all should be encompassed in the middle of right of the present invention.
Embodiment 1
Preparation PMDA/ODA system polyamic acid tunica fibrosa, through process, then obtains the polyimide fiber film of Surface coating nano titania layer after hot imidization.(1) pyromellitic acid anhydride (PMDA) 2.0g that mol ratio is 1:1 is taken, 4, 4 '-diaminodiphenyl ether (ODA) 1.8g, ODA is all dissolved in the N of 30ml, in dinethylformamide (DMF) solvent, mechanical agitation, after ODA is all dissolved in DMF, under the condition of ice-water bath, substep adds PMDA, after obtaining the polyamic acid solution of modest viscosity, after mechanical agitation 2h, polyamic acid solution is loaded in the syringe of 20ml, application electrostatic spinning technique prepares polyamic acid tunica fibrosa, electrostatic spinning machine design parameter is spinning voltage: 20kV, spinning temperature: room temperature, spinning humidity: 20%, syringe needle diameter: No. 12, accepted roll rotating speed: 80.0m/min, receiving range: 20cm.The polyamic acid tunica fibrosa prepared is placed in super-clean bench 12h.(2) polyamic acid tunica fibrosa is placed in the closed container being placed with butyl titanate, in vacuum, under 60 DEG C of conditions, processes 0.5 hour; (3) polyamic acid tunica fibrosa is placed in after steam processes 1min and leaves standstill 0.5 hour under room temperature and condition of normal pressure.(4) treated polyamic acid tunica fibrosa is placed in hot stove, is progressively warming up to 300 DEG C with the programming rate of 2 DEG C/min, and keeps 2h, thus obtained polyimide/titanium dioxide compound tunica fibrosa, the pattern of the tunica fibrosa of gained is as shown in Figure 2.
Embodiment 2
Preparation PMDA/ODA system polyamic acid tunica fibrosa, through process, then obtains the polyimide fiber film of Surface coating nano titania layer after hot imidization.(1) pyromellitic acid anhydride (PMDA) 2.0g that mol ratio is 1:1 is taken, 4, 4 '-diaminodiphenyl ether (ODA) 1.8g, ODA is all dissolved in the N of 30ml, in dinethylformamide (DMF) solvent, mechanical agitation, after ODA is all dissolved in DMF, under the condition of ice-water bath, substep adds PMDA, after obtaining the polyamic acid solution of modest viscosity, after mechanical agitation 2h, polyamic acid solution is loaded in the syringe of 20ml, application electrostatic spinning technique prepares polyamic acid tunica fibrosa, electrostatic spinning machine design parameter is spinning voltage: 20kV, spinning temperature: room temperature, spinning humidity: 20%, syringe needle diameter: No. 12, accepted roll rotating speed: 80.0m/min, receiving range: 20cm.The polyamic acid tunica fibrosa prepared is placed in super-clean bench 12h.(2) polyamic acid tunica fibrosa is placed in the closed container being placed with butyl titanate, in vacuum, under 60 DEG C of conditions, processes 1 hour; (3) polyamic acid tunica fibrosa is placed in after steam processes 1min and leaves standstill 0.5 hour under room temperature and condition of normal pressure.(4) order repeats step (2) and (3) 4 times.(5) treated polyamic acid tunica fibrosa is placed in hot stove, is progressively warming up to 300 DEG C with the programming rate of 4 DEG C/min, and keeps 2h, thus obtained polyimide/titanium dioxide compound tunica fibrosa, the pattern of the tunica fibrosa of gained is as shown in Figure 3.
Embodiment 3
Preparation PMDA/ODA system polyamic acid tunica fibrosa, through process, then obtains the polyimide fiber film of Surface coating nano titania layer after hot imidization.(1) pyromellitic acid anhydride (PMDA) 2.0g that mol ratio is 1:1 is taken, 4, 4 '-diaminodiphenyl ether (ODA) 1.8g, ODA is all dissolved in the N of 30ml, in dinethylformamide (DMF) solvent, mechanical agitation, after ODA is all dissolved in DMF, under the condition of ice-water bath, substep adds PMDA, after obtaining the polyamic acid solution of modest viscosity, after mechanical agitation 2h, polyamic acid solution is loaded in the syringe of 20ml, application electrostatic spinning technique prepares polyamic acid tunica fibrosa, electrostatic spinning machine design parameter is spinning voltage: 20kV, spinning temperature: room temperature, spinning humidity: 20%, syringe needle diameter: No. 12, accepted roll rotating speed: 80.0m/min, receiving range: 20cm.The polyamic acid tunica fibrosa prepared is placed in super-clean bench 12h.(2) polyamic acid tunica fibrosa is placed in the closed container being placed with butyl titanate, in vacuum, under 65 DEG C of conditions, processes 1 hour; (3) polyamic acid tunica fibrosa is placed in after steam processes 2min and leaves standstill 1 hour under room temperature and condition of normal pressure.(4) order repeats step (2) and (3) 20 times.(5) treated polyamic acid tunica fibrosa is placed in hot stove, is progressively warming up to 320 DEG C with the programming rate of 4 DEG C/min, and keeps 2h, thus obtained polyimide/titanium dioxide compound tunica fibrosa, the pattern of the tunica fibrosa of gained is as shown in Figure 4.
Embodiment 4
Preparation PMDA/ODA system polyamic acid tunica fibrosa, through process, then obtains the polyimide fiber film of Surface coating nano titania layer after hot imidization.(1) pyromellitic acid anhydride (PMDA) 2.0g that mol ratio is 1:1 is taken, 4, 4 '-diaminodiphenyl ether (ODA) 1.8g, ODA is all dissolved in the N of 30ml, in dinethylformamide (DMF) solvent, mechanical agitation, after ODA is all dissolved in DMF, under the condition of ice-water bath, substep adds PMDA, after obtaining the polyamic acid solution of modest viscosity, after mechanical agitation 2h, polyamic acid solution is loaded in the syringe of 20ml, application electrostatic spinning technique prepares polyamic acid tunica fibrosa, electrostatic spinning machine design parameter is spinning voltage: 20kV, spinning temperature: room temperature, spinning humidity: 20%, syringe needle diameter: No. 12, accepted roll rotating speed: 80.0m/min, receiving range: 20cm.The polyamic acid tunica fibrosa prepared is placed in super-clean bench 12h.(2) polyamic acid tunica fibrosa is placed in the closed container being placed with isopropyl titanate, in vacuum, under 70 DEG C of conditions, processes 1 hour; (3) polyamic acid tunica fibrosa is placed in after steam processes 2min and leaves standstill 0.5 hour under room temperature and condition of normal pressure.(4) order repeats step (2) and (3) 30 times.(5) treated polyamic acid tunica fibrosa is placed in hot stove, is progressively warming up to 300 DEG C with the programming rate of 5 DEG C/min, and keeps 1h, thus obtained polyimide/titanium dioxide compound tunica fibrosa, the pattern of the tunica fibrosa of gained is as shown in Figure 5.
Embodiment 5
Preparation PMDA/ODA system polyamic acid tunica fibrosa, through process, then obtains the polyimide fiber film of Surface coating nano titania layer after hot imidization.(1) pyromellitic acid anhydride (PMDA) 2.0g that mol ratio is 1:1 is taken, 4, 4 '-diaminodiphenyl ether (ODA) 1.8g, ODA is all dissolved in the N of 30ml, in dinethylformamide (DMF) solvent, mechanical agitation, after ODA is all dissolved in DMF, under the condition of ice-water bath, substep adds PMDA, after obtaining the polyamic acid solution of modest viscosity, after mechanical agitation 2h, polyamic acid solution is loaded in the syringe of 20ml, application electrostatic spinning technique prepares polyamic acid tunica fibrosa, electrostatic spinning machine design parameter is spinning voltage: 20kV, spinning temperature: room temperature, spinning humidity: 20%, syringe needle diameter: No. 12, accepted roll rotating speed: 80.0m/min, receiving range: 20cm.The polyamic acid tunica fibrosa prepared is placed in super-clean bench 12h.(2) polyamic acid tunica fibrosa is placed in the closed container being placed with butyl titanate, in vacuum, under 70 DEG C of conditions, processes 1 hour; (3) polyamic acid tunica fibrosa is placed in after steam processes 1min and leaves standstill 1 hour under room temperature and condition of normal pressure.(4) order repeats step (2) and (3) 50 times.(5) treated polyamic acid tunica fibrosa is placed in hot stove, is progressively warming up to 300 DEG C with the programming rate of 5 DEG C/min, and keeps 1h, thus obtained polyimide/titanium dioxide compound tunica fibrosa, the pattern of the tunica fibrosa of gained is as shown in Figure 6.
Claims (3)
1. a preparation method for the polyimide fiber film of Surface coating nano titania layer, is characterized in that comprising the following steps:
A: adopt solid content to be the polyamic acid solution of 8% ~ 30%, obtain polyamic acid tunica fibrosa through method of electrostatic spinning;
B: polyamic acid tunica fibrosa steps A obtained is placed in the closed container being placed with titanium compound, processes 10min ~ 1h under the vacuum condition of 50 DEG C ~ 70 DEG C;
C: the polyamic acid tunica fibrosa that step B is obtained processes 0.5 ~ 3min in steam, and then 0.5 ~ 1h is left standstill under room temperature and condition of normal pressure;
D: order repeats step B and step C several times;
E: the polyamic acid tunica fibrosa that step D is obtained is placed in hot stove, is progressively warming up to 300-350 DEG C, and keeps 0.5 ~ 3h, namely obtain the polyimide fiber film of Surface coating nano titania layer with the programming rate of 2 ~ 6 DEG C/min.
2. in accordance with the method for claim 1, it is characterized in that, the titanium compound described in step B is isopropyl titanate, butyl titanate, tetraethyl titanate, titanium tetrafluoride, titanium tetrachloride.
3. in accordance with the method for claim 1, it is characterized in that, the number of repetition in step D is unrestricted, and the thickness of nano titania layer increases with the increase of number of repetition.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610050579.1A CN105442301B (en) | 2016-01-25 | 2016-01-25 | A kind of preparation method of the polyimide fiber film of surface cladding titanium dioxide nano layer |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610050579.1A CN105442301B (en) | 2016-01-25 | 2016-01-25 | A kind of preparation method of the polyimide fiber film of surface cladding titanium dioxide nano layer |
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Cited By (7)
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| CN106046409A (en) * | 2016-08-05 | 2016-10-26 | 北京化工大学常州先进材料研究院 | Method for preparing surface-silvered polyimide film |
| CN106049028A (en) * | 2016-06-06 | 2016-10-26 | 北京化工大学常州先进材料研究院 | Method for covering polyimide nanofiber surface with titanium dioxide nano-layer |
| CN108774808A (en) * | 2018-06-12 | 2018-11-09 | 北京化工大学常州先进材料研究院 | A kind of polyimide nanofiber membrane and preparation method thereof that there is the surface of crosslinking pattern to coat zirconium dioxide |
| CN109853135A (en) * | 2018-11-02 | 2019-06-07 | 北京化工大学常州先进材料研究院 | A kind of nuclear shell structure nano tunica fibrosa and preparation method thereof of polybenzimidazoles cladding polyimide nano-fiber |
| CN110247005A (en) * | 2019-05-28 | 2019-09-17 | 浙江大学 | A kind of preparation method of the difunctional composite diaphragm for lithium-sulfur cell |
| CN111455476A (en) * | 2020-04-07 | 2020-07-28 | 北京化工大学常州先进材料研究院 | Polyimide nanofiber membrane coaxially coated with aluminum oxide and preparation method thereof |
| CN113956658A (en) * | 2021-10-21 | 2022-01-21 | 北京宇程科技有限公司 | Polyimide/titanium dioxide composite microsphere and preparation method thereof |
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| CN103981634A (en) * | 2014-05-30 | 2014-08-13 | 北京化工大学常州先进材料研究院 | Polyimide/silicon dioxide composite nanofiber film and preparation thereof |
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| CN106049028A (en) * | 2016-06-06 | 2016-10-26 | 北京化工大学常州先进材料研究院 | Method for covering polyimide nanofiber surface with titanium dioxide nano-layer |
| CN106046409A (en) * | 2016-08-05 | 2016-10-26 | 北京化工大学常州先进材料研究院 | Method for preparing surface-silvered polyimide film |
| CN106046409B (en) * | 2016-08-05 | 2019-02-12 | 北京化工大学常州先进材料研究院 | A method of preparing surface patina Kapton |
| CN108774808A (en) * | 2018-06-12 | 2018-11-09 | 北京化工大学常州先进材料研究院 | A kind of polyimide nanofiber membrane and preparation method thereof that there is the surface of crosslinking pattern to coat zirconium dioxide |
| CN109853135A (en) * | 2018-11-02 | 2019-06-07 | 北京化工大学常州先进材料研究院 | A kind of nuclear shell structure nano tunica fibrosa and preparation method thereof of polybenzimidazoles cladding polyimide nano-fiber |
| CN109853135B (en) * | 2018-11-02 | 2021-02-19 | 北京化工大学常州先进材料研究院 | Polybenzimidazole coated polyimide nanofiber core-shell structure nanofiber membrane and preparation method thereof |
| CN110247005A (en) * | 2019-05-28 | 2019-09-17 | 浙江大学 | A kind of preparation method of the difunctional composite diaphragm for lithium-sulfur cell |
| CN111455476A (en) * | 2020-04-07 | 2020-07-28 | 北京化工大学常州先进材料研究院 | Polyimide nanofiber membrane coaxially coated with aluminum oxide and preparation method thereof |
| CN113956658A (en) * | 2021-10-21 | 2022-01-21 | 北京宇程科技有限公司 | Polyimide/titanium dioxide composite microsphere and preparation method thereof |
| CN113956658B (en) * | 2021-10-21 | 2024-01-30 | 北京宇程科技有限公司 | Polyimide/titanium dioxide composite microsphere and preparation method thereof |
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