CN106824294A - A kind of polyimide/titanium dioxide compound fiber and its preparation method and application - Google Patents
A kind of polyimide/titanium dioxide compound fiber and its preparation method and application Download PDFInfo
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- CN106824294A CN106824294A CN201710132514.6A CN201710132514A CN106824294A CN 106824294 A CN106824294 A CN 106824294A CN 201710132514 A CN201710132514 A CN 201710132514A CN 106824294 A CN106824294 A CN 106824294A
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- fiber
- polyimide
- titanium dioxide
- temperature
- solution
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- 239000000835 fiber Substances 0.000 title claims abstract description 137
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 239000004642 Polyimide Substances 0.000 title claims abstract description 57
- 229920001721 polyimide Polymers 0.000 title claims abstract description 57
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 49
- -1 titanium dioxide compound Chemical class 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000002131 composite material Substances 0.000 claims abstract description 17
- 230000001699 photocatalysis Effects 0.000 claims abstract description 11
- 238000011065 in-situ storage Methods 0.000 claims abstract description 9
- 239000000428 dust Substances 0.000 claims abstract description 4
- 238000005342 ion exchange Methods 0.000 claims abstract description 4
- 239000011248 coating agent Substances 0.000 claims abstract description 3
- 238000000576 coating method Methods 0.000 claims abstract description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 46
- 239000000243 solution Substances 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 229910021529 ammonia Inorganic materials 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229910000831 Steel Inorganic materials 0.000 claims description 3
- 239000004568 cement Substances 0.000 claims description 3
- 239000010959 steel Substances 0.000 claims description 3
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229920005575 poly(amic acid) Polymers 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 239000010865 sewage Substances 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 230000000630 rising effect Effects 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 238000007146 photocatalysis Methods 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 5
- 239000002657 fibrous material Substances 0.000 abstract description 3
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- 230000008021 deposition Effects 0.000 abstract 2
- 239000003643 water by type Substances 0.000 description 14
- 150000002500 ions Chemical class 0.000 description 13
- 229910052719 titanium Inorganic materials 0.000 description 9
- 239000010936 titanium Substances 0.000 description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 8
- 238000005530 etching Methods 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 6
- 239000004952 Polyamide Substances 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000002341 toxic gas Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- VAEJJMYYTOYMLE-UHFFFAOYSA-N [O].OS(O)(=O)=O Chemical compound [O].OS(O)(=O)=O VAEJJMYYTOYMLE-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- 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
- B01D46/02—Particle separators, e.g. dust precipitators, having hollow filters made of flexible material
- B01D46/023—Pockets filters, i.e. multiple bag filters mounted on a common frame
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/80—Type of catalytic reaction
- B01D2255/802—Photocatalytic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Biomedical Technology (AREA)
- Catalysts (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The present invention relates to a kind of polyimide/titanium dioxide compound fiber and preparation method thereof, belong to functional form polyimide fiber Material Field.The preparation of the composite fibre is the method being combined with in-situ deposition using ion exchange in polyimide fiber surface deposition of titanium oxide Seed Layer; increase the deposit thickness of titanium dioxide layer through repeatedly circulation on this basis; under air atmosphere protection, heated up and the polyimide fiber that Surface coating anatase titanium dioxide is obtained after isothermal holding by staged.The preparation method that the present invention is provided is simple to operate, nontoxic pollution-free, low cost, obtained complex fiber material not only maintains the excellent resistance to elevated temperatures and mechanical performance of polyimide material, and the good photocatalysis performance of fiber is imparted, had broad application prospects in high-temperature dust removal, pollution control field.
Description
Technical field
The present invention relates to functional form polyimide fiber Material Field, in particular it relates to a kind of with photocatalysis effect
Polyimide/titanium dioxide compound fiber and its preparation method and application.
Background technology
Titanium dioxide possesses chemical stability as a kind of typical semi-conducting material, nontoxic, and anti-light corrosivity is good,
Low cost, and the excellent performance such as efficient degradable organic pollutant, be widely used in sensor, solar cell,
The aspects such as photocatalysis, ARC, fiber waveguide and environmental protection.Wherein, nano titanium oxide is urged because of its excellent ultraviolet light
Change performance, the prospect of being widely applied is presented in terms of environmental protection, wastewater treatment can not only be applied to, in treatment indoor and outdoor air
Also there is application value very high in the research of pollutant.But there is dispersion in use in powdered nano titanium oxide
Property it is poor, be easy to reunite, utilization rate is low, the problems such as reclaim difficult.To solve the above problems, generally by titanium dichloride load certain
Matrix on, the matrix studied at present and reported is including glass material, porous ceramic film material, absorbent charcoal material etc..
Polyimide fiber has excellent mechanical performance, resistance to elevated temperatures, resistance to ultraviolet irradiation energy, low water absorption and height
The features such as insulating properties, as one of high-temperature flue gas filtration material optimal at present, steel, cement, combustion have been widely used in it
The aspects such as coal works.By photocatalyst in polyimide fiber surface, the effect of its high-temperature dust removal can not only be retained, also
Prestige further assign its degraded toxic and harmful function, for purification of air, reduce air in suspended particulate substance content, change
Kind air quality has very important significance.
Currently, the method in particular substrate area load titanic oxide material mainly has sol-gel process, hydro-thermal method, sinks
Shallow lake method etc..However, be directed to polyimide fiber matrix material, sol-gel process typically with Titanium alkoxides as presoma, using this
The fiber cost that method is obtained is higher, influences its large-scale promotion application；Hydro-thermal method is general to react under conditions of HTHP,
Reaction condition is harsher, is unfavorable for the continuous prodution of fiber；Precipitation rule is under the addition of precipitating reagent, by titanium dioxide
Presoma is deposited directly on fibrous matrix surface, although the efficiency of the method is higher, the thickness evenness of carried titanium dioxide
Poor, quality stability is not enough.
The content of the invention
For problem above, the polyamides that the present invention proposes controllable, the suitable continuous prodution of a kind of process is simple, cost is sub-
The preparation method of amine/titanium dioxide composite fibre, the method is using the characteristic of polyimides not hydrolysis by it in strong base solution
Middle hydrolysis, makes fiber surface open loop generate polyamic acid, then the fiber is placed in the inorganic salt solution of titanium and completes ion
Exchange, the fiber with titanium ion is placed in completion surface deposition process in ammonia precipitation process agent, wherein titanium ion and precipitation afterwards
Ammonium root cation exchange in agent, the titanium ion for exchanging further generates titanium dioxide with the hydroxide ion reaction in solution
The presoma of titanium.By washing the fiber for obtaining under the protection of air atmosphere, gentle insulating process is risen by staged, in fibre
While dimension imidization, the presoma dehydration generation titanium dioxide of titanium, and it is changed into Detitanium-ore-type by unformed.
By load nano-titanium dioxide, polyimide fiber matrix excellent machinery and thermal stability are being maintained
Outward, the excellent photocatalysis performance of fiber is also imparted, the multifunction of fiber is realized.On the other hand, the invention provides one
The preparation method of polyimide/titanium dioxide compound fiber is planted, the method specifically includes following steps:
1) polyimide fiber is placed on and certain hour is processed in constant temperature alkaline solution, its surface open loop is obtained polyamides
Amino acid salt；
2) by step 1) hydrochloric acid solution that the fiber for obtaining passes through uniform temperature is processed, neutralize the alkali of fiber surface remaining
Property solution, afterwards using deionized water be washed to fiber surface in neutrality；
3) by step 2) treatment obtain fiber immersion constant temperature aqueous solution of titanyle sulfate in carry out ion-exchange reactions；
4) by step 3) fiber that obtains for the treatment of fully washes molten to remove the titanyl sulfate of surface remaining through deionized water
Liquid；
5) by step 4) fiber that obtains further immerses ammonia spirit, and reaction certain hour completes precipitation process in situ,
Then neutrality is washed to using deionized water；
6) repeat step 3), 4), 5) 5-30 times；
7) by step 6) fiber for obtaining is processed under air atmosphere protection, by after the gentle heat preservation hot treatment of staged liter
Obtain the polyimide fiber of Surface coating anatase titania, namely polyimide/titanium dioxide compound fiber.
Further, the step 1) in alkali lye be potassium hydroxide solution or sodium hydroxide solution, concentration 5-8mol/L, temperature
25-40 DEG C of degree.It is preferred that potassium hydroxide solution.
Further, the step 2) in concentration of hydrochloric acid solution 0.5-2mol/L, 25-40 DEG C of temperature.
Further, the step 3) in titanyl sulfate solution concentration 0.2-1mol/L, 25-40 DEG C of temperature.
Further, the step 5) in ammonia concn 0.2-1mol/L, 25-40 DEG C of temperature.
Further, the step 7) under air atmosphere protection, staged rises gentle insulation program and is：With 2-5 DEG C/
The heating rate of min is incubated 1h from room temperature to 135 DEG C, is then warmed up to 350 DEG C, insulation according to identical heating rate
2-4h。
On the other hand, answered present invention also offers the polyimide/titanium dioxide that a kind of use above method is prepared
Condensating fiber.The fiber has excellent hot property and mechanical performance, its 10% heat decomposition temperature more than 550 DEG C, tensile strength
More than 2GPa, the titanium dioxide of load is Detitanium-ore-type, with good photocatalytic effect.
Additionally, the present invention still further provides the polyimide/titanium dioxide compound fiber that the above method is prepared
Application, high-temperature dust removal that it can be applied not only to the factories such as cement plant, steel plant, chemical plant, power plant bag field, Neng Gou
The toxic gases such as nitrogen oxides, sulfide are degraded to non-toxic gas while dedusting, it may also be used for pollution control field is (for example
Sewage disposal).
Compared with prior art, the present invention has the advantage that：
(1) with polyimide fiber as matrix, with titanium dioxide nano-particle as functional layer, fiber bodies are not only maintained
Excellent mechanical performance, hot property, also imparts the good ultraviolet catalytic performance of fiber, realizes many of polyimide fiber
Functionalization.
(2) operating process is simply easily implemented, and reaction condition is simple, with cheap inorganic matter as presoma, by sky
Atmosphere encloses heat treatment process, the presoma generation anatase titania of titanium while fiber imidizate, without extra
Heat treatment process, reduces reaction cost.
(3) titanium dioxide granule for being obtained using the method is good with the adhesiveness of polyimide fiber matrix, build-up of particles
Densification, and the content of titanium dioxide can control by changing cycle-index.
Brief description of the drawings
Fig. 1 be embodiment 1 in when titanyl sulfate concentration be 0.1mol/L when, by 15 times circulate obtain polyimides/
The SEM shape appearance figures (10,000 times of multiplication factor) of titanium dioxide composite fibre；
Fig. 2 be embodiment 2 in when titanyl sulfate concentration be 0.2mol/L when, by 15 times circulate obtain polyimides/
The SEM shape appearance figures (10,000 times of multiplication factor) of titanium dioxide composite fibre；
Fig. 3 be embodiment 3 in when titanyl sulfate concentration be 0.3mol/L when, by 15 times circulate obtain polyimides/
The SEM shape appearance figures (10,000 times of multiplication factor) of titanium dioxide composite fibre；
Fig. 4 be embodiment 4 in when titanyl sulfate concentration be 0.4mol/L when, by 15 times circulate obtain polyimides/
The SEM shape appearance figures (10,000 times of multiplication factor) of titanium dioxide composite fibre；
Fig. 5 be in embodiment 5 when titanyl sulfate concentration is 0.3mol/L, circulate polyimides/bis- that obtain by 1 time
The SEM shape appearance figures (10,000 times of multiplication factor) of titanium oxide composite fibre；
Fig. 6 be in embodiment 6 when titanyl sulfate concentration is 0.3mol/L, circulate polyimides/bis- that obtain by 5 times
The SEM shape appearance figures (10,000 times of multiplication factor) of titanium oxide composite fibre；
Fig. 7 be embodiment 7 in when titanyl sulfate concentration be 0.3mol/L when, by 10 times circulate obtain polyimides/
The SEM shape appearance figures (10,000 times of multiplication factor) of titanium dioxide composite fibre；
Fig. 8 is the XRD of gained polyimide/titanium dioxide compound fiber in embodiment 3；
Fig. 9 be embodiment 3 in when titanyl sulfate concentration be 0.3mol/L when, by 15 times circulate obtain polyimides/
The photocatalysis UV images of titanium dioxide composite fibre.
Specific embodiment
Below in conjunction with example, the present invention is further illustrated, but the present invention is not limited to following examples.
Embodiment 1
(1) configure the KOH solution of 8mol/L and be placed in 30 DEG C of water bath with thermostatic control, 20 μm of polyimide fiber is placed in
In KOH solution, taken out after etching 18min, the hydrochloric acid solution that fiber is passed through into 2mol/L neutralizes the alkalescence of fiber surface remaining
Solution, afterwards using a large amount of deionized water rinsing fibers to neutrality；
(2) configuration concentration is the aqueous solution of titanyle sulfate of 0.1mol/L, is placed it in 30 DEG C of water bath with thermostatic control, treats that its is complete
After portion's dissolving, the fiber in step (1) is placed therein, with manual time-keeping, is taken out after 10min, rushed with a large amount of deionized waters
The ion for going fiber surface to adhere to；
(3) ammonia spirit of 0.2mol/L is configured, and is positioned in 30 DEG C of water bath with thermostatic control, the fibre that step (2) is obtained
Dimension is placed wherein, with manual time-keeping, is taken out after 5min, and neutrality is washed till with a large amount of deionized waters；
(4) repeat step (2) exchanged with (3) intermediate ion and in-situ precipitate process 15 times；
(5) fiber obtained in step (4) is placed in convection oven and is heat-treated, heating schedule is:Room temperature is passed through
1h is raised to 135 DEG C, is incubated 1h, then is warmed up to 350 DEG C by 2h, is incubated 2h, fine so as to obtain polyimide/titanium dioxide compound
Dimension.
Embodiment 2
(1) configure the KOH solution of 8mol/L and be placed in 30 DEG C of water bath with thermostatic control, 20 μm of polyimide fiber is placed in
In KOH solution, taken out after etching 18min, the hydrochloric acid solution that fiber is passed through into 2mol/L neutralizes the alkalescence of fiber surface remaining
Solution, afterwards using a large amount of deionized water rinsing fibers to neutrality；
(2) configuration concentration is the aqueous solution of titanyle sulfate of 0.2mol/L, is placed it in 30 DEG C of water bath with thermostatic control, treats that its is complete
After portion's dissolving, the fiber in step (1) is placed therein, with manual time-keeping, is taken out after 10min, rushed with a large amount of deionized waters
The ion for going fiber surface to adhere to；
(3) ammonia spirit of 0.2mol/L is configured, and is positioned in 30 DEG C of water bath with thermostatic control, the fibre that step (2) is obtained
Dimension is placed wherein, with manual time-keeping, is taken out after 5min, and neutrality is washed till with a large amount of deionized waters；
(4) repeat step (2) exchanged with (3) intermediate ion and in-situ precipitate process 15 times；
(5) fiber obtained in step (4) is placed in convection oven and is heat-treated, heating schedule is:Room temperature is passed through
1h is raised to 135 DEG C, is incubated 1h, then is warmed up to 350 DEG C by 2h, is incubated 2h, fine so as to obtain polyimide/titanium dioxide compound
Dimension.
Embodiment 3
(1) configure the KOH solution of 8mol/L and be placed in 30 DEG C of water bath with thermostatic control, 20 μm of polyimide fiber is placed in
In KOH solution, taken out after etching 18min, the hydrochloric acid solution that fiber is passed through into 2mol/L neutralizes the alkalescence of fiber surface remaining
Solution, afterwards using a large amount of deionized water rinsing fibers to neutrality；
(2) configuration concentration is the aqueous solution of titanyle sulfate of 0.3mol/L, is placed it in 30 DEG C of water bath with thermostatic control, treats that its is complete
After portion's dissolving, the fiber in step (1) is placed therein, with manual time-keeping, is taken out after 10min, rushed with a large amount of deionized waters
The ion for going fiber surface to adhere to；
(3) ammonia spirit of 0.2mol/L is configured, and is positioned in 30 DEG C of water bath with thermostatic control, the fibre that step (2) is obtained
Dimension is placed wherein, with manual time-keeping, is taken out after 5min, and neutrality is washed till with a large amount of deionized waters；
(4) repeat step (2) exchanged with (3) intermediate ion and in-situ precipitate process 15 times；
(5) fiber obtained in step (4) is placed in convection oven and is heat-treated, heating schedule is:Room temperature is passed through
1h is raised to 135 DEG C, is incubated 1h, then is warmed up to 350 DEG C by 2h, is incubated 2h, fine so as to obtain polyimide/titanium dioxide compound
Dimension.
Embodiment 4
(1) configure the KOH solution of 8mol/L and be placed in 30 DEG C of water bath with thermostatic control, 20 μm of polyimide fiber is placed in
In KOH solution, taken out after etching 18min, the hydrochloric acid solution that fiber is passed through into 2mol/L neutralizes the alkalescence of fiber surface remaining
Solution, afterwards using a large amount of deionized water rinsing fibers to neutrality；
(2) configuration concentration is the aqueous solution of titanyle sulfate of 0.4mol/L, is placed it in 30 DEG C of water bath with thermostatic control, treats that its is complete
After portion's dissolving, the fiber in step (1) is placed therein, with manual time-keeping, is taken out after 10min, rushed with a large amount of deionized waters
The ion for going fiber surface to adhere to；
(3) ammonia spirit of 0.2mol/L is configured, and is positioned in 30 DEG C of water bath with thermostatic control, the fibre that step (2) is obtained
Dimension is placed wherein, with manual time-keeping, is taken out after 5min, and neutrality is washed till with a large amount of deionized waters；
(4) repeat step (2) exchanged with (3) intermediate ion and in-situ precipitate process 15 times；
(5) fiber obtained in step (4) is placed in convection oven and is heat-treated, heating schedule is:Room temperature is passed through
1h is raised to 135 DEG C, is incubated 1h, then is warmed up to 350 DEG C by 2h, is incubated 2h, fine so as to obtain polyimide/titanium dioxide compound
Dimension.
Embodiment 5
(1) configure the KOH solution of 8mol/L and be placed in 30 DEG C of water bath with thermostatic control, 20 μm of polyimide fiber is placed in
In KOH solution, taken out after etching 18min, the hydrochloric acid solution that fiber is passed through into 2mol/L neutralizes the alkalescence of fiber surface remaining
Solution, afterwards using a large amount of deionized water rinsing fibers to neutrality；
(2) configuration concentration is the aqueous solution of titanyle sulfate of 0.3mol/L, is placed it in 30 DEG C of water bath with thermostatic control, treats that its is complete
After portion's dissolving, the fiber in step (1) is placed therein, with manual time-keeping, is taken out after 10min, rushed with a large amount of deionized waters
The ion for going fiber surface to adhere to；
(3) ammonia spirit of 0.2mol/L is configured, and is positioned in 30 DEG C of water bath with thermostatic control, the fibre that step (2) is obtained
Dimension is placed wherein, with manual time-keeping, is taken out after 5min, and neutrality is washed till with a large amount of deionized waters；
(4) fiber obtained in step (3) is placed in convection oven and is heat-treated, heating schedule is:Room temperature is passed through
1h is raised to 135 DEG C, is incubated 1h, then is warmed up to 350 DEG C by 2h, is incubated 2h, fine so as to obtain polyimide/titanium dioxide compound
Dimension.
Embodiment 6
(1) configure the KOH solution of 8mol/L and be placed in 30 DEG C of water bath with thermostatic control, 20 μm of polyimide fiber is placed in
In KOH solution, taken out after etching 18min, the hydrochloric acid solution that fiber is passed through into 2mol/L neutralizes the alkalescence of fiber surface remaining
Solution, afterwards using a large amount of deionized water rinsing fibers to neutrality；
(2) configuration concentration is the aqueous solution of titanyle sulfate of 0.3mol/L, is placed it in 30 DEG C of water bath with thermostatic control, treats that its is complete
After portion's dissolving, the fiber in step (1) is placed therein, with manual time-keeping, is taken out after 10min, rushed with a large amount of deionized waters
The ion for going fiber surface to adhere to；
(3) ammonia spirit of 0.2mol/L is configured, and is positioned in 30 DEG C of water bath with thermostatic control, the fibre that step (2) is obtained
Dimension is placed wherein, with manual time-keeping, is taken out after 5min, and neutrality is washed till with a large amount of deionized waters；
(4) repeat step (2) exchanged with (3) intermediate ion and in-situ precipitate process 5 times；
(5) fiber obtained in step (4) is placed in convection oven and is heat-treated, heating schedule is:Room temperature is passed through
1h is raised to 135 DEG C, is incubated 1h, then is warmed up to 350 DEG C by 2h, is incubated 2h, fine so as to obtain polyimide/titanium dioxide compound
Dimension.
Embodiment 7
(1) configure the KOH solution of 8mol/L and be placed in 30 DEG C of water bath with thermostatic control, 20 μm of polyimide fiber is placed in
In KOH solution, taken out after etching 18min, the hydrochloric acid solution that fiber is passed through into 2mol/L neutralizes the alkalescence of fiber surface remaining
Solution, afterwards using a large amount of deionized water rinsing fibers to neutrality；
(2) configuration concentration is the aqueous solution of titanyle sulfate of 0.3mol/L, is placed it in 30 DEG C of water bath with thermostatic control, treats that its is complete
After portion's dissolving, the fiber in step (1) is placed therein, with manual time-keeping, is taken out after 10min, rushed with a large amount of deionized waters
The ion for going fiber surface to adhere to；
(3) ammonia spirit of 0.2mol/L is configured, and is positioned in 30 DEG C of water bath with thermostatic control, the fibre that step (2) is obtained
Dimension is placed wherein, with manual time-keeping, is taken out after 5min, and neutrality is washed till with a large amount of deionized waters；
(4) repeat step (2) exchanged with (3) intermediate ion and in-situ precipitate process 10 times；
(5) fiber obtained in step (4) is placed in convection oven and is heat-treated, heating schedule is:Room temperature is passed through
1h is raised to 135 DEG C, is incubated 1h, then is warmed up to 350 DEG C by 2h, is incubated 2h, fine so as to obtain polyimide/titanium dioxide compound
Dimension.
Embodiment 8
(1) the methyl orange solution 200ml of 10mg/L is configured, after standby after its all dissolving；
(2) methyl orange solution that some obtained polyimide/titanium dioxide compound fibers are placed in step (1)
In, and ensure titanium dioxide content be 0.2g/100ml methyl orange solutions；
(3) methyl orange solution containing composite fibre in step (2) is placed under the ultraviolet Hg lamps of 500W, carries out ultraviolet light
Catalysis experiments, take out 10ml degradation solutions and do ultraviolet spectral analysis every 30min.
Above example 1-4 tests the titanyl sulfate of various concentrations to polyimide/titanium dioxide compound fibre morphology
Influence, the sulfuric acid oxygen of 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L has been selected in wherein embodiment 1-4 respectively
Titanium, in the case of other conditions are the same from, from accompanying drawing 1-4 as can be seen that when titanyl sulfate concentration be 0.1mol/L and
During 0.2mol/L, the content of titanium dioxide of composite fiber surface is less；And work as titanyl sulfate concentration for 0.4mol/L, titanium dioxide
Pile up, cementability is poor；When titanyl sulfate concentration is 0.3mol/L, titanium dioxide can preferably be coated on fiber table
Face.
Using the titanyl sulfate of 0.3mol/L as presoma, it is sub- to polyamides that embodiment 5,6,7 and 3 tests cycle-index
It is 1,5,10,15 that the influence of amine/titanium dioxide composite fibre form, wherein embodiment 5,6,7 and 3 test cycle-index respectively
When fiber surface titanium dioxide form change, from accompanying drawing 5,6,7 and 3 as can be seen that with the increase of cycle-index, titanium dioxide
The quantity of titanium is continuously increased.
Accompanying drawing 8 shows the XRD of gained polyimide/titanium dioxide compound fiber in embodiment 3, can by XRD
To find out, can obtain crystallizing preferable Detitanium-ore-type titanium dioxide under 350 DEG C of heat treatment conditions, while fiber hot imidization
Titanium, composite fibre has manifested preferable photocatalysis performance under the irradiation of ultraviolet light.
Accompanying drawing 9 shown in embodiment 3 when titanyl sulfate concentration is 0.3mol/L, and the polyamides for obtaining is circulated by 15 times
The photocatalysis UV images of imines/titanium dioxide composite fibre, when be can be seen that with ultraviolet light by photocatalysis UV images
Between increase, calibration curve of the composite fibre at 500nm wavelength gradually reduce, and indicates area load anatase dioxy
The polyimide fiber for changing titanium has manifested certain photocatalytic activity under the irradiation of ultraviolet light.
Claims (10)
1. a kind of preparation method of polyimide/titanium dioxide compound fiber, it is characterised in that comprise the following steps:
1) polyimide fiber is placed on and certain hour is processed in constant temperature alkaline solution, its surface open loop is obtained polyamic acid
Salt；
2) by step 1) hydrochloric acid solution that the fiber for obtaining passes through uniform temperature is processed, neutralize the alkaline molten of fiber surface remaining
Liquid, is washed to fiber surface in neutrality using deionized water afterwards；
3) by step 2) treatment obtain fiber immersion constant temperature aqueous solution of titanyle sulfate in carry out ion-exchange reactions；
4) by step 3) fiber that obtains for the treatment of fully washes to remove the titanyl sulfate solution of surface remaining through deionized water；
5) by step 4) fiber that obtains further immerses ammonia spirit, and reaction certain hour completes precipitation process in situ, then
Neutrality is washed to using deionized water；
6) repeat step 3), 4), 5) 5-30 times；
7) by step 6) fiber for obtaining is processed under air atmosphere protection, obtained after staged rises gentle heat preservation hot treatment
The polyimide fiber of Surface coating anatase titanium dioxide, namely polyimide/titanium dioxide compound fiber.
2. method according to claim 1, it is characterised in that the step 1) in alkali lye be potassium hydroxide solution or hydrogen
Sodium hydroxide solution, concentration 5-8mol/L, 25-40 DEG C of temperature.
3. method according to claim 2, it is characterised in that the step 1) in the preferred potassium hydroxide solution of alkali lye.
4. method according to claim 1, it is characterised in that the step 2) in concentration of hydrochloric acid solution 0.5-2mol/
L, 25-40 DEG C of temperature.
5. method according to claim 1, it is characterised in that the step 3) in titanyl sulfate solution concentration 0.2-
1mol/L, 25-40 DEG C of temperature.
6. method according to claim 1, it is characterised in that the step 5) in ammonia concn 0.2-1mol/L, temperature
25-40℃。
7. method according to claim 1, it is characterised in that the step 7) under air atmosphere protection, staged
Rising gentle insulation program is：Heating schedule is, from room temperature to 135 DEG C, to be incubated 1h, then with the heating rate of 2-5 DEG C/min
350 DEG C are warmed up to according to identical heating rate, 2-4h is incubated.
8. a kind of polyimide/titanium dioxide compound fiber prepared according to claim 1-7 either method, its feature exists
In the composite fibre has excellent hot property and mechanical performance, and its 10% heat decomposition temperature is more than 550 DEG C, and stretching is strong
Degree is more than 2GPa, density 4.9-5.3g/cm3, the titanium dioxide of polyimide fiber area load is Detitanium-ore-type, with good
Photocatalytic effect.
9. a kind of application of the fiber of polyimide/titanium dioxide compound according to claim 8, it is characterised in that described multiple
Condensating fiber can be applied not only to the high-temperature dust removal bag field of the factories such as cement plant, steel plant, chemical plant, power plant, can also apply
In pollution control field.
10. application according to claim 9, it is characterised in that the pollution control field is sewage treatment area.
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Effective date of registration: 20221014 Address after: No. 882, Songxia Road, Fushan District, Yantai, Shandong 265599 Patentee after: Yantai huaweitefang New Material Co.,Ltd. Address before: 100029, No. 15 East Third Ring Road, Chaoyang District, Beijing Patentee before: BEIJING University OF CHEMICAL TECHNOLOGY |