CN116199931B - Nanofiber composite aerogel and preparation method and application thereof - Google Patents
Nanofiber composite aerogel and preparation method and application thereof Download PDFInfo
- Publication number
- CN116199931B CN116199931B CN202310227958.3A CN202310227958A CN116199931B CN 116199931 B CN116199931 B CN 116199931B CN 202310227958 A CN202310227958 A CN 202310227958A CN 116199931 B CN116199931 B CN 116199931B
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- Prior art keywords
- nanofiber
- water
- composite aerogel
- polyacrylonitrile
- oil
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- 239000002121 nanofiber Substances 0.000 title claims abstract description 139
- 239000004964 aerogel Substances 0.000 title claims abstract description 128
- 239000002131 composite material Substances 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 112
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 86
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 76
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 70
- 238000000926 separation method Methods 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000002105 nanoparticle Substances 0.000 claims abstract description 33
- 239000004952 Polyamide Substances 0.000 claims abstract description 29
- 229920002647 polyamide Polymers 0.000 claims abstract description 29
- 238000007710 freezing Methods 0.000 claims abstract description 24
- 230000008014 freezing Effects 0.000 claims abstract description 24
- 239000002253 acid Substances 0.000 claims abstract description 21
- 239000011148 porous material Substances 0.000 claims abstract description 16
- 230000009435 amidation Effects 0.000 claims abstract description 6
- 238000007112 amidation reaction Methods 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims description 32
- 229920005575 poly(amic acid) Polymers 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 24
- 239000006185 dispersion Substances 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 238000004108 freeze drying Methods 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 11
- 239000005457 ice water Substances 0.000 claims description 9
- 238000006068 polycondensation reaction Methods 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 7
- 150000003863 ammonium salts Chemical class 0.000 claims description 6
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 5
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 5
- 238000010041 electrostatic spinning Methods 0.000 claims description 5
- 238000006386 neutralization reaction Methods 0.000 claims description 5
- 239000002798 polar solvent Substances 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 239000003921 oil Substances 0.000 abstract description 34
- 239000000835 fiber Substances 0.000 abstract description 33
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 15
- 230000008569 process Effects 0.000 abstract description 12
- 239000004642 Polyimide Substances 0.000 abstract description 8
- 230000004907 flux Effects 0.000 abstract description 8
- 229920001721 polyimide Polymers 0.000 abstract description 8
- 239000011230 binding agent Substances 0.000 abstract description 4
- 239000003431 cross linking reagent Substances 0.000 abstract description 4
- 239000011259 mixed solution Substances 0.000 abstract description 3
- 230000003746 surface roughness Effects 0.000 abstract description 3
- 235000019198 oils Nutrition 0.000 description 29
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 19
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 18
- 238000009826 distribution Methods 0.000 description 17
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 238000012360 testing method Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000295 fuel oil Substances 0.000 description 11
- 229910004298 SiO 2 Inorganic materials 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000004626 scanning electron microscopy Methods 0.000 description 8
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 7
- 235000019476 oil-water mixture Nutrition 0.000 description 7
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 6
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 230000003075 superhydrophobic effect Effects 0.000 description 6
- 238000000635 electron micrograph Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- 206010061592 cardiac fibrillation Diseases 0.000 description 4
- 230000002600 fibrillogenic effect Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000001493 electron microscopy Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000005304 optical glass Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001612 separation test Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WEHZNZTWKUYVIY-UHFFFAOYSA-N 3-oxabicyclo[3.2.2]nona-1(7),5,8-triene-2,4-dione Chemical compound O=C1OC(=O)C2=CC=C1C=C2 WEHZNZTWKUYVIY-UHFFFAOYSA-N 0.000 description 1
- WXAIEIRYBSKHDP-UHFFFAOYSA-N 4-phenyl-n-(4-phenylphenyl)-n-[4-[4-(4-phenyl-n-(4-phenylphenyl)anilino)phenyl]phenyl]aniline Chemical compound C1=CC=CC=C1C1=CC=C(N(C=2C=CC(=CC=2)C=2C=CC=CC=2)C=2C=CC(=CC=2)C=2C=CC(=CC=2)N(C=2C=CC(=CC=2)C=2C=CC=CC=2)C=2C=CC(=CC=2)C=2C=CC=CC=2)C=C1 WXAIEIRYBSKHDP-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000001926 trapping method Methods 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/14—Other self-supporting filtering material ; Other filtering material
- B01D39/16—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres
- B01D39/1607—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous
- B01D39/1623—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous of synthetic origin
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28047—Gels
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0066—Use of inorganic compounding ingredients
- C08J9/0071—Nanosized fillers, i.e. having at least one dimension below 100 nanometers
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/18—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/048—Elimination of a frozen liquid phase
- C08J2201/0484—Elimination of a frozen liquid phase the liquid phase being aqueous
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/02—Foams characterised by their properties the finished foam itself being a gel or a gel being temporarily formed when processing the foamable composition
- C08J2205/026—Aerogel, i.e. a supercritically dried gel
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/18—Homopolymers or copolymers of nitriles
- C08J2333/20—Homopolymers or copolymers of acrylonitrile
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/20—Controlling water pollution; Waste water treatment
- Y02A20/204—Keeping clear the surface of open water from oil spills
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Analytical Chemistry (AREA)
- Toxicology (AREA)
- Textile Engineering (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Silicon Compounds (AREA)
Abstract
The invention provides a nanofiber composite aerogel and a preparation method and application thereof. According to the preparation method, the water-soluble polyamide acid nanofiber, the pre-oxidized polyacrylonitrile nanofiber, the silicon dioxide nanoparticle and water are mixed and frozen to obtain the macroporous orientation structure, the shrinkage of the pore structure of the aerogel is small in the imidization treatment process, so that the polyacrylonitrile/polyimide-silicon dioxide macroporous orientation nanofiber composite aerogel has a higher specific surface area, the oil-water mixed solution passing path is obviously reduced, and the oil flux of the aerogel is improved; after directional freezing and amidation treatment, the water-soluble polyamide acid nanometer fiber is changed into polyimide, which is used as a binder and a cross-linking agent to ensure that silicon dioxide is uniformly distributed on the fiber, thereby increasing the surface roughness of the fiber and obtaining a reentrant structure, and ensuring that a stable oil film or water film can be maintained in the separation process. The aerogel can not only show underwater oleophobic property, but also show oil-under-oil hydrophobicity, and can be used for oil-water separation as required.
Description
Technical Field
The invention belongs to the technical field of aerogel, and particularly relates to nanofiber composite aerogel as well as a preparation method and application thereof.
Background
The permselective material, especially the super-wetting permselective material, has the advantages of high separation efficiency, large flux, high cost efficiency, easy recovery of separated liquid and the like, and has become a main research object for adsorption and separation in the current oil-water separation field. The double super-hydrophobic oil-water separation material can alternately realize oil removal and water removal through a single porous material, so that the oil-water separation according to needs is realized, and the cost is saved to a great extent. Theoretically, however, the underwater oil contact angle and the oil-water contact angle of the same interface are complementary. Thus, underwater oleophilic interfaces generally exhibit hydrophobic properties under oil, while underwater hydrophilic interfaces generally exhibit oleophobic properties under water. The same solid surface can not only show underwater superoleophobic property, but also show oil-under-super-hydrophobic property, and is difficult to realize in thermodynamics. Generally, the underwater super oleophobic surface has a fish scale effect, namely a texture surface with high surface energy, so that water can pass preferentially; the super-hydrophobic surface under the oil has a lotus effect, namely a surface with low surface energy, and can retain the oil in the filter material to prevent water from passing through. Since the surface energy of a solid is generally lower than the surface tension of water and higher than the surface tension of oil, it is difficult to make the solid surface amphiphobic by a method of coating a smooth layer on a single surface.
It is difficult to prepare an amphiphobic material based on the current technology, and thus an improvement is necessary.
Disclosure of Invention
In view of the above, the invention provides a nanofiber composite aerogel and a preparation method and application thereof, so as to solve the technical problems in the prior art.
In a first aspect, the present invention provides a method for preparing a nanofiber composite aerogel, comprising the steps of:
mixing pre-oxidized polyacrylonitrile nanofiber, water-soluble polyamide acid nanofiber, silica nanoparticle and water to obtain a mixed dispersion liquid;
sequentially carrying out directional freezing and freeze drying on the mixed dispersion liquid to obtain polyacrylonitrile/polyamide acid-silicon dioxide macroporous oriented nanofiber aerogel;
and carrying out imidization treatment on the polyacrylonitrile/polyamide acid-silicon dioxide macroporous oriented nanofiber aerogel to obtain the polyacrylonitrile/polyimide-silicon dioxide macroporous oriented nanofiber composite aerogel.
Preferably, the preparation method of the nanofiber composite aerogel, the imidization treatment sequentially comprises:
heating to a first temperature at a first heating rate, and performing first imidization treatment;
raising the temperature to a second temperature at a second heating rate, and performing a second imidization treatment;
raising the temperature to a third temperature at a third heating rate, and performing third amidation treatment;
wherein the first temperature is 80-120 ℃, and the first imidization treatment time is 45-90 min;
the second temperature is 180-220 ℃, and the second imidization treatment time is 45-90 min;
the third temperature is 280-320 ℃, and the first imidization treatment time is 45-90 min;
the first heating rate, the second heating rate and the third heating rate are independently 2-10 ℃/min.
Preferably, in the preparation method of the nanofiber composite aerogel, the mass of the water-soluble polyamide acid nanofiber is 5-15% of the total mass of the pre-oxidized polyacrylonitrile nanofiber and the water-soluble polyamide acid nanofiber;
and/or the mass of the silica nano particles is 40-60% of the mass of the pre-oxidized polyacrylonitrile nano fiber.
Preferably, the preparation method of the nanofiber composite aerogel comprises the steps of freeze drying at the temperature of-20 to-60 ℃ for 24 to 72 hours.
Preferably, in the preparation method of the nanofiber composite aerogel, the directional freezing is performed by adopting a directional freezing method of an oriented ice crystal template.
Preferably, the preparation method of the nanofiber composite aerogel comprises the following steps:
and (3) placing the mixed dispersion liquid in a mould, and placing the bottom surface of the mould in a cold source for directional freezing, wherein the time of directional freezing is 5-15 min.
Preferably, the preparation method of the nanofiber composite aerogel comprises the following steps of:
carrying out electrostatic spinning on the polyacrylonitrile solution to obtain polyacrylonitrile nanofibers;
oxidizing the polyacrylonitrile nanofiber in an air atmosphere at 200-300 ℃ for 1-3 h to obtain the pre-oxidized polyacrylonitrile nanofiber.
Preferably, the preparation method of the nanofiber composite aerogel comprises the following steps:
mixing 4,4' -diaminodiphenyl ether, pyromellitic dianhydride and a polar solvent, and performing polycondensation reaction to obtain non-water-soluble polyamide acid ammonium salt;
mixing the non-water-soluble polyamic acid ammonium salt with triethylamine, and carrying out neutralization reaction to obtain a water-soluble polyamic acid solution;
and carrying out ice water precipitation on the water-soluble polyamic acid solution to obtain the water-soluble polyamic acid nanofiber.
In a second aspect, the invention also provides a nanofiber composite aerogel, which is prepared by the preparation method, wherein the nanofiber composite aerogel has a multi-stage pore structure, the multi-stage pore structure comprises macropores, mesopores and micropores, and the macropores are arranged on the same axis.
In a third aspect, the invention also provides a nanofiber composite aerogel prepared by the preparation method or an application of the nanofiber composite aerogel as an oil-water separation material or an air filtering material.
Compared with the prior art, the nanofiber composite aerogel and the preparation method and application thereof have the following beneficial effects:
1. the preparation method of the nanofiber composite aerogel comprises the following steps: mixing pre-oxidized polyacrylonitrile nanofiber, water-soluble polyamide acid nanofiber, silica nanoparticle and water to obtain a mixed dispersion liquid; sequentially carrying out directional freezing and freeze drying on the mixed dispersion liquid to obtain polyacrylonitrile/polyamide acid-silicon dioxide macroporous oriented nanofiber aerogel; and performing imidization treatment on the polyacrylonitrile/polyamide acid-silicon dioxide macroporous oriented nanofiber aerogel to obtain the polyacrylonitrile/polyimide-silicon dioxide macroporous oriented nanofiber composite aerogel. According to the preparation method, the water-soluble polyamide acid nanofiber, the pre-oxidized polyacrylonitrile nanofiber, the silicon dioxide nanoparticle and water are mixed and then directionally frozen to obtain the macroporous orientation structure, the shrinkage of the pore structure of the aerogel is smaller in the subsequent imidization treatment process, so that the polyacrylonitrile/polyimide-silicon dioxide macroporous orientation nanofiber composite aerogel has a higher specific surface area, the oil-water mixed solution passing path is obviously reduced, and the oil flux of the aerogel is improved; furthermore, after directional freezing and amidation treatment, the water-soluble polyamide acid nano fiber is changed into polyimide, and the polyimide is used as a binder and a cross-linking agent to ensure that silicon dioxide is uniformly distributed on the fiber, so that the surface roughness of the fiber is increased, a re-entrant structure is obtained, and a stable oil film or water film can be kept in the separation process. The aerogel can not only show underwater oleophobic property, but also show oil-under-oil hydrophobicity, and can be used for oil-water separation as required. The composite aerogel with the three-dimensional space structure and the oriented macropores ensure that the aerogel keeps high filtration efficiency and high flux in the process of oil-water separation;
2. the polyacrylonitrile/polyimide-silicon dioxide macroporous oriented nanofiber composite aerogel provided by the invention has the advantages of macroporous orientation, multistage pore structure, high specific surface area, switchable amphiphobicity and stable physical and chemical properties, is an ideal high-performance oil-water separation material and air filtering material, and has good application prospects in the fields of oil-water separation, oily sewage treatment, air filtering, gas adsorption and storage, gas separation and sensing.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the following description will briefly explain the drawings used in the embodiments or the description of the prior art, and it is obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings can be obtained according to these drawings without inventive effort to a person skilled in the art.
FIG. 1 is a graph of OPAN/PI-SiO in comparative example 1 2 -0 scanning electron microscopy at different magnifications;
FIG. 2 is an OPAN/PI-SiO of example 3 2 -15 scanning electron microscopy at different magnifications;
FIG. 3 is an OPAN/PI-SiO of example 2 2 -50 scanning electron microscopy at different magnifications;
FIG. 4 is an OPAN/PI-SiO of example 1 2 -400 scanning electron microscopy at different magnifications;
FIG. 5 is an OPAN/PI-SiO of comparative example 1 2 -0 particle size distribution profile;
FIG. 6 is an OPAN/PI-SiO of example 3 2 -15 particle size distribution profile;
FIG. 7 is an OPAN/PI-SiO of example 2 2 -a particle size distribution profile of 50;
FIG. 8 is an OPAN/PI-SiO of example 1 2 -400 particle size distribution profile.
FIG. 9 is an OPAN/PI-SiO of example 1 2 -400 partial fiber surface silica distribution electron microscopy images;
FIG. 10 is an OPAN/PI-SiO of example 2 2 -50 partial fiber surface silica distribution electron microscopy images; FIG. 11 is an OPAN/PI-SiO of example 3 2 -15 partial fiber surface silica distribution electron microscopy; FIG. 12 is an OPAN/PI-SiO of comparative example 1 2 -0 a partial fiber surface silica distribution electron microscopy image;
FIGS. 13 to 14 are graphs showing experimental results of contact angles of polyacrylonitrile/polyimide-silica macroporous oriented nanofiber composite aerogels prepared in examples 1 to 3 and comparative example 1;
FIG. 15 is an oil-water separation performance test apparatus;
FIG. 16 is a composite aerogel OPAN/PI-SiO prepared in example 1 2 -400 oil-water separation test result graph;
FIG. 17 is a composite aerogel OPAN/PI-SiO prepared in example 1 2 -400 resilience test result graph;
FIG. 18 is a composite aerogel OPAN/PI-SiO prepared in example 1 2 -400 continuous switching of separation efficiency of light oil/water mixture 50 times;
FIG. 19 is a composite aerogel OPAN/PI-SiO prepared in example 1 2 -400 continuous switching of the separation efficiency of the heavy oil/water mixture 50 times.
Detailed Description
For the purposes of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, are intended to fall within the scope of the present invention.
For a better understanding of the present invention, and not to limit its scope, all numbers expressing quantities, percentages, and other values used in the present application are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated otherwise, the numerical parameters set forth in the specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained. Each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
The following description of the embodiments is not intended to limit the preferred embodiments. In addition, in the description of the present application, the term "comprising" means "including but not limited to". Various embodiments of the invention may exist in a range of forms; it should be understood that the description in a range format is merely for convenience and brevity and should not be construed as a rigid limitation on the scope of the invention; it is therefore to be understood that the range description has specifically disclosed all possible sub-ranges and individual values within that range. For example, it should be considered that a description of a range from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the ranges, such as 1, 2, 3, 4, 5, and 6, wherever applicable. In addition, whenever a numerical range is referred to herein, it is meant to include any reference number (fractional or integer) within the indicated range.
The invention provides a preparation method of nanofiber composite aerogel, which comprises the following steps:
s1, mixing pre-oxidized polyacrylonitrile nanofiber, water-soluble polyamide acid nanofiber, silica nanoparticle and water to obtain a mixed dispersion liquid;
s2, sequentially carrying out directional freezing and freeze drying on the mixed dispersion liquid to obtain polyacrylonitrile/polyamide acid-silicon dioxide macroporous oriented nanofiber aerogel;
s3, carrying out imidization treatment on the polyacrylonitrile/polyamide acid-silicon dioxide macroporous orientation nanofiber aerogel to obtain the polyacrylonitrile/polyimide-silicon dioxide macroporous orientation nanofiber composite aerogel.
In the preparation method of the nanofiber composite aerogel, a micro/nano structure is introduced on the surface of the filter material, and water or oil enters the micro/nano structure to form a liquid film by combining a polar-non-polar theory and a liquid injection theory, so that a stable solid-oil-water interface is formed, thermodynamic contradiction can be avoided, and double super-hydrophobicity of the filter material is realized. By adjusting the content of hydrophobic and hydrophilic components on the surface and finely controlling the surface chemistry, the surface with double super-hydrophobic property can be prepared; specifically, the silicon dioxide is a hydrophilic material, and the hydrophilic pre-oxidized polyacrylonitrile nanofiber and the hydrophobic polyimide are used for regulating the overall hydrophilicity and hydrophobicity of the aerogel together, so that the spherical silicon dioxide nanoparticle and the surface of the fiber can form a reentrant structure, and the preparation of the double super-hydrophobic nanofiber aerogel is facilitated.
According to the preparation method, the water-soluble polyamide acid nanofiber, the pre-oxidized polyacrylonitrile nanofiber, the silicon dioxide nanoparticle and water are mixed and then directionally frozen to obtain the macroporous orientation structure, the shrinkage of the pore structure of the aerogel is smaller in the subsequent imidization treatment process, so that the polyacrylonitrile/polyimide-silicon dioxide macroporous orientation nanofiber composite aerogel has a higher specific surface area, the oil-water mixed solution passing path is obviously reduced, and the oil flux of the aerogel is improved; furthermore, after directional freezing and amidation treatment, the water-soluble polyamide acid nano fiber is changed into polyimide, and the polyimide is used as a binder and a cross-linking agent to ensure that silicon dioxide is uniformly distributed on the fiber, so that the surface roughness of the fiber is increased, a re-entrant structure is obtained, and a stable oil film or water film can be kept in the separation process. The aerogel can not only show underwater oleophobic property, but also show oil-under-oil hydrophobicity, and can be used for oil-water separation as required. The composite aerogel with the three-dimensional space structure and the oriented macropores enable the aerogel to keep high filtration efficiency and high flux in the process of oil-water separation.
In the process of obtaining the macroporous orientation structure by utilizing the orientation freezing technology, the polyamic acid is distributed at the node of the pre-oxidized polyacrylonitrile nanofiber and the joint of the fiber and the silicon dioxide, and in the subsequent imidization treatment process, the polyamic acid is still intensively distributed at the node of the pre-oxidized polyacrylonitrile nanofiber and the joint of the fiber and the silicon dioxide after being converted into polyimide, so that the silicon dioxide nanoparticles are uniformly distributed on the surface of the fiber. When the aerogel is subjected to external pressure, the stress is concentrated at the node, so that the stress crushing of the pre-oxidized polyacrylonitrile nanofiber is effectively relieved, and the aerogel shows excellent rebound resilience. The invention utilizes hydrophilic pre-oxidized polyacrylonitrile nanofiber, hydrophilic spherical silica nanoparticle and hydrophobic polyamic acid to adjust the hydrophilicity and hydrophobicity of aerogel, so that the aerogel shows underwater super-oleophobic property and oil super-hydrophobic property. The preparation method provided by the invention is simple to operate, low in toxicity of the preparation raw materials, environment-friendly, low in production cost and suitable for industrial production.
In some embodiments, the imidization treatment sequentially comprises:
heating to a first temperature at a first heating rate, and performing first imidization treatment;
raising the temperature to a second temperature at a second heating rate, and performing a second imidization treatment;
raising the temperature to a third temperature at a third heating rate, and performing third amidation treatment;
wherein the first temperature is 80 to 120 ℃, more preferably 90 to 110 ℃, still more preferably 100 ℃;
the first imidization treatment time is 45 to 90 minutes, more preferably 50 to 80 minutes, still more preferably 60 to 70 minutes;
the second temperature is 180 to 220 ℃, more preferably 190 to 210 ℃, still more preferably 200 ℃; the second imidization treatment time is 45 to 90 minutes, more preferably 50 to 80 minutes, still more preferably 60 to 70 minutes;
the third temperature is 280 to 320 ℃, more preferably 290 to 310 ℃, still more preferably 300 ℃; the first imidization treatment time is 45 to 90 minutes, more preferably 50 to 80 minutes, still more preferably 60 to 70 minutes;
the first heating rate, the second heating rate and the third heating rate are independently 2-10 ℃/min, preferably 5-8 ℃/min.
In some embodiments, the mass of the water-soluble polyamic acid nanofiber is 5 to 15%, preferably 9 to 10%, of the total mass of the pre-oxidized polyacrylonitrile nanofiber and the water-soluble polyamic acid nanofiber.
In some embodiments, the mass of the silica nanoparticles is 40-60%, preferably 50% of the mass of the pre-oxidized polyacrylonitrile nanofibers; further, the silica nanoparticles are spherical silica nanoparticles, and the average particle diameter of the silica nanoparticles is 10-400 nm.
In some embodiments, the temperature of freeze-drying is-20 to-60 ℃, more preferably-45 to-60 ℃, and even more preferably-55 to-60 ℃; the freeze-drying time is 24 to 72 hours, preferably 30 to 60 hours, more preferably 35 to 48 hours.
In some embodiments, directional freezing is a method of directional freezing of oriented ice crystal templates.
In some embodiments, directional freezing comprises the steps of:
and (3) placing the mixed dispersion liquid in a mould, and placing the bottom surface of the mould in a cold source for directional freezing, wherein the time of directional freezing is 5-15 min.
Specifically, in the above embodiment, the material of the mold is preferably a heat conductive metal, and more preferably includes copper or iron; the cold source preferably comprises liquid nitrogen, and the directional freezing time is preferably 7-13 min.
In some embodiments, the method of preparing the pre-oxidized polyacrylonitrile nanofiber comprises the steps of:
s11, carrying out electrostatic spinning on a polyacrylonitrile solution to obtain polyacrylonitrile nanofibers;
s12, oxidizing the polyacrylonitrile nanofiber in an air atmosphere at 200-300 ℃ for 1-3 hours to obtain the pre-oxidized polyacrylonitrile nanofiber.
Specifically, in step S11, the concentration of the polyacrylonitrile solution is preferably 5 to 15wt%, more preferably 9 to 10wt%, the polyacrylonitrile solution is preferably obtained by dissolving polyacrylonitrile powder in an organic solvent, the organic solvent preferably includes an amide-based solvent, more preferably includes N, N' -Dimethylformamide (DMF), the dissolution temperature is preferably room temperature, and the dissolution time is preferably 6 to 12 hours, more preferably 10 hours.
In step S11, the operating parameters of electrospinning preferably include: the extrusion speed is preferably 0.005 to 0.03mL/min, more preferably 0.01 to 0.02mL/min; the distance between the needle and the roller is preferably 8-15 cm, more preferably 10-12 cm; the voltage is preferably 18 to 25kV, more preferably 20 to 22kV.
In step S12, the temperature of the pre-oxidation is preferably 200 to 300 ℃, more preferably 250 to 300 ℃, and the pre-oxidation time is preferably 1 to 3, more preferably 1.5 to 2.5 hours, and the pre-oxidation atmosphere is preferably air.
In some embodiments, the diameter of the pre-oxidized polyacrylonitrile nanofibers is 320 to 460nm, more preferably 350 to 450nm.
In some embodiments, the pre-oxidized polyacrylonitrile nanofiber is a fibrillated pre-oxidized polyacrylonitrile nanofiber, which is prepared by a method comprising: homogenizing the mixture in deionized water containing the pre-oxidized polyacrylonitrile nanofiber by using a homogenizer at a speed of 15000rpm for 30-45 min to obtain the fibrillated pre-oxidized polyacrylonitrile nanofiber.
In some embodiments, the method of preparing the water-soluble polyamic acid includes the steps of:
s21, mixing 4,4' -diaminodiphenyl ether, pyromellitic dianhydride and a polar solvent (marked as first mixing), and performing polycondensation reaction to obtain non-water-soluble polyamic acid ammonium salt;
s22, mixing the non-water-soluble polyamic acid ammonium salt with triethylamine (marked as second mixing), and carrying out a neutralization reaction to obtain a water-soluble polyamic acid solution;
s23, carrying out ice water precipitation on the water-soluble polyamic acid solution to obtain the water-soluble polyamic acid nanofiber.
Specifically, in the above examples, the molar ratio of 4,4' -diaminodiphenyl ether (ODA) and pyromellitic dianhydride (PMDA) is preferably 1:1; the polar solvent preferably includes an amide-based solvent, N' -dimethylacetamide (DMAc); the invention is not particularly limited in the amount of the polar solvent, and can ensure that the polycondensation reaction proceeds smoothly. In the above-described embodiments, the temperatures of the first mixing, the polycondensation reaction, the neutralization reaction, and the second mixing are independently preferably-10 to 0 ℃, more preferably-5 to 0 ℃; the time of the polycondensation reaction and the neutralization reaction is independently preferably 5 to 6 hours, more preferably 5.5 hours; the polycondensation reaction is preferably carried out under a protective atmosphere, preferably an inert gas, more preferably comprising argon or helium; the time of the first mixing and the second mixing is not particularly limited in the present invention, and the raw materials may be uniformly mixed. In the present invention, the molar ratio of 4,4' -diaminodiphenyl ether to triethylamine is preferably 1: (0.5 to 1), more preferably 1: (0.8-1). The invention is not particularly limited to the amount of ice water, and the ice water precipitation product is not increased. After the ice water precipitation is finished, the invention preferably further comprises freeze-drying the obtained ice water precipitation product to obtain the water-soluble polyamide acid nanofiber; the temperature of freeze drying is preferably-20 to-60 ℃, more preferably-55 to-60 ℃; the time for freeze-drying is preferably 24 to 72 hours, more preferably 48 to 60 hours.
In some embodiments, in step S1, pre-oxidized polyacrylonitrile nanofibers, water-soluble polyamic acid nanofibers, silica nanoparticles, and water are mixed to obtain a mixed dispersion; preferably, the pre-oxidized polyacrylonitrile nano-fiber is mixed with water (marked as a third mixture) and then subjected to a fibrillation treatment, so as to obtain a pre-oxidized polyacrylonitrile nano-staple fiber dispersion; and mixing the obtained pre-oxidized polyacrylonitrile nano short fiber dispersion liquid with water-soluble polyamide acid nano fiber (marked as fourth mixing), and adding silica nano particles to obtain mixed dispersion liquid. Specifically, the fibrillation treatment is preferably performed by a cell disruption apparatus, the temperature of the fibrillation treatment is preferably room temperature, the power is preferably 100 to 400W, and more preferably 200 to 300W; the time for the fibrillation treatment is preferably 60 to 200 minutes, more preferably 90 to 120 minutes. In this embodiment, the length of the pre-oxidized polyacrylonitrile nano-staple is preferably 40 to 55 μm.
Based on the same inventive concept, the embodiment of the application also provides the nanofiber composite aerogel, which is prepared by adopting the preparation method, and the nanofiber composite aerogel has a multi-stage pore structure, wherein the multi-stage pore structure comprises macropores, mesopores and micropores, and the macropores are arranged on the same axis.
Based on the same inventive concept, the nanofiber composite aerogel prepared by the preparation method or the application of the nanofiber composite aerogel as an oil-water separation material is provided.
The invention provides application of the polyacrylonitrile/polyimide-silicon dioxide macroporous oriented nanofiber composite aerogel as an oil-water separation material or an air filtering material. The polyacrylonitrile/polyimide-silicon dioxide macroporous oriented nanofiber composite aerogel provided by the invention has the advantages of macroporous orientation, multistage pore structure, high specific surface area, switchable amphiphobicity and stable physical and chemical properties, is an ideal high-performance oil-water separation material and air filtering material, and has good application prospects in the fields of oil-water separation, oily sewage treatment, air filtering, gas adsorption and storage, gas separation and sensing.
The nanofiber composite aerogel of the present application, and a method for preparing the same and applications thereof are further described in specific examples below. This section further illustrates the summary of the invention in connection with specific embodiments, but should not be construed as limiting the invention. The technical means employed in the examples are conventional means well known to those skilled in the art, unless specifically stated. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art.
Example 1
The embodiment of the application provides a preparation method of nanofiber composite aerogel, which comprises the following steps:
s1, adding polyacrylonitrile powder into N, N' -dimethylformamide, and stirring and mixing for 10 hours at room temperature (25 ℃) to obtain a polyacrylonitrile solution with the concentration of 10 wt%;
s2, transferring the polyacrylonitrile solution in the S1 into a 10mL needle tube for electrostatic spinning to obtain polyacrylonitrile nanofiber (with the diameter of 320-460 nm); wherein, the process conditions of electrostatic spinning are as follows: the extrusion speed is 0.015mL/min, the distance from the needle head to the roller is 25cm, and the voltage is 20kV;
s3, placing the polyacrylonitrile nanofiber in the S2 into a high-temperature furnace, and pre-oxidizing for 2 hours in an air atmosphere at 300 ℃ to obtain a pre-oxidized polyacrylonitrile nanofiber;
s4, dispersing the pre-oxidized polyacrylonitrile nanofiber in the S3 in deionized water, and carrying out short-fiber treatment for 120min at room temperature and 200W by using a cell disruption instrument to obtain a pre-oxidized polyacrylonitrile nanofiber dispersion (the concentration is 0.75wt% and the length of the staple fiber is 40-55 mu m);
s5, dissolving 4.31g of 4,4 '-diamine diphenyl ether in 51g of N, N' -dimethylacetamide, adding 4.69g of terephthalic anhydride, placing in an ice water bath (0 ℃) and carrying out polycondensation reaction for 5 hours under the argon atmosphere; then adding 2.18g of triethylamine, and continuing to react for 5 hours to obtain a water-soluble polyamide acid solution; adding 2000mL of ice water into the obtained water-soluble polyamic acid solution for precipitation, washing the obtained solid component with water, and freeze-drying the solid component to constant weight at the temperature of-57 ℃ to obtain water-soluble polyamic acid;
s6, placing spherical silicon dioxide nano particles with the mass being half of that of the polyacrylonitrile nano short fiber dispersion liquid in the S4, and performing ultrasonic treatment for 10min to obtain stable dispersion liquid of the pre-oxidized polyacrylonitrile nano fibers and the silicon dioxide nano particles; the average particle diameter of the silica nanoparticles is 400nm;
s7, placing the water-soluble polyamide acid in the S5 into the dispersion liquid of the pre-oxidized polyacrylonitrile nanofiber and the silicon dioxide nanoparticle in the S6, and stirring at room temperature until the water-soluble polyamide acid is completely dissolved, so as to obtain a mixed dispersion liquid;
s8, transferring the mixed dispersion liquid in the S7 into an iron mold, contacting the bottom surface of the iron mold with liquid nitrogen, directionally freezing for 30min by using an oriented ice crystal template method, and then freeze-drying for 48h at the temperature of-57 ℃ to obtain the polyacrylonitrile-polyamide acid macroporous oriented nanofiber aerogel (marked as OPAN/PAA-SiO) 2 -400); wherein the mass fraction of the water-soluble polyamic acid in the polyacrylonitrile-polyamic acid macroporous oriented nanofiber aerogel is 10%;
s9, macroporous polyacrylonitrile-polyamide acid in S8The oriented nanofiber aerogel is placed in a tubular furnace, and is subjected to program imidization treatment in an air atmosphere to obtain polyacrylonitrile/polyimide-silicon dioxide macroporous oriented nanofiber composite aerogel (marked as OPAN/PI-SiO) 2 -400); wherein, imidization treatment is as follows: the temperature is raised to 100 ℃ from room temperature at a heating rate of 5 ℃/min, then the temperature is kept for 1h, the temperature is raised to 200 ℃ at a heating rate of 5 ℃/min, then the temperature is kept for 1h, and the temperature is raised to 300 ℃ at a heating rate of 5 ℃/min.
Example 2
The preparation method of the nanofiber composite aerogel provided in this embodiment is the same as that in embodiment 1, except that in step S6, the average particle size of the silica nanoparticles is 50nm, and the other process parameters are the same as those in embodiment 1, to obtain the polyacrylonitrile/polyimide-silica macroporous oriented nanofiber composite aerogel (denoted as OPAN/PI-SiO 2 -50)。
Example 3
The preparation method of the nanofiber composite aerogel provided in this embodiment is the same as that in embodiment 1, except that in step S6, the average particle size of the silica nanoparticles is 15nm, and the other process parameters are the same as those in embodiment 1, so as to obtain the polyacrylonitrile/polyimide-silica macroporous oriented nanofiber composite aerogel (denoted as OPAN/PI-SiO 2 -15)。
Comparative example 1
The preparation method of the nanofiber composite aerogel provided in this comparative example is the same as that in example 1, except that in step S6, no silica nanoparticles are added, and the other process parameters are the same as those in example 1, to obtain the polyacrylonitrile/polyimide-silica macroporous oriented nanofiber composite aerogel (denoted as OPAN/PI-SiO 2 -0)。
Performance testing
(1) Scanning electron microscope test
In FIG. 1 (a) 1 )～(a 3 ) For OPAN/PI-SiO in comparative example 1 2 -0 scanning electron microscopy at different magnifications; in FIG. 2 (b) 1 )～(b 3 ) For OPAN/PI-SiO in example 3 2 -15 scanning electron microscopy at different magnifications; in FIG. 3 (c 1 )～(c 3 ) For OPAN/PI-SiO in example 2 2 -50 scanning electron microscopy at different magnifications; in FIG. 4 (d 1 )～(d 3 ) For OPAN/PI-SiO in example 1 2 -400 scanning electron microscopy at different magnifications.
FIG. 5 is an OPAN/PI-SiO of comparative example 1 2 -0 particle size distribution profile; FIG. 6 is an OPAN/PI-SiO of example 3 2 -15 particle size distribution profile; FIG. 7 is an OPAN/PI-SiO of example 2 2 -a particle size distribution profile of 50; FIG. 8 is an OPAN/PI-SiO of example 1 2 -400 particle size distribution profile.
FIG. 9 is an OPAN/PI-SiO of example 1 2 -400 partial fiber surface silica distribution electron microscopy images; FIG. 10 is an OPAN/PI-SiO of example 2 2 -50 partial fiber surface silica distribution electron microscopy images; FIG. 11 is an OPAN/PI-SiO of example 3 2 -15 partial fiber surface silica distribution electron microscopy; FIG. 12 is an OPAN/PI-SiO of comparative example 1 2 -0 partial fiber surface silica distribution electron microscopy.
As can be seen from figures 1-12, the polyacrylonitrile/polyimide-silicon dioxide nanofiber composite aerogel prepared by the invention has skeleton macroporous orientation, the composite aerogel internally contains a small pore structure formed by electrospun polyacrylonitrile fibers, the silicon dioxide nanoparticles are attached to the surfaces of the fibers to form a reentrant structure, polyimide is used as a binder and a cross-linking agent, and the polyacrylonitrile nanofibers are constructed into the skeleton oriented macroporous multistage pore structure aerogel. As the nanoparticle size increases, the average pore size of the oriented macropores decreases and the pore size distribution decreases. When the particle size of the nano particles is proper, OPAN/PI-SiO 2 -400 the nanoparticles on the fiber surface are uniformly distributed. When the particle size of the nano particles is too small, OPAN/PI-SiO 2 -50、OPAN/PI-SiO 2 -15 nanoparticles on the surface of the fiber are non-uniform.
(2) Contact angle test
Fig. 13 to 14 are graphs showing the experimental results of contact angles of polyacrylonitrile/polyimide-silica macroporous oriented nanofiber composite aerogels prepared in examples 1 to 3 and comparative example 1. The test method is as follows:
1) Contact angle with water in air: 3 μl of water was dropped on the aerogel surface, and the water drop contact angle was observed by a video optical contact angle (OCA 25) test instrument.
2) Contact angle of water under oil: the aerogel was sequentially soaked with dichloromethane and n-hexane for 1h so that the inside of the aerogel was completely filled with n-hexane, then the aerogel was placed in an optical glass square box filled with n-hexane, 3 μl of water was dropped on the surface of the sample using a bubble trapping method, and the contact angle of the water drop was observed.
3) Underwater oil contact angle: the aerogel is soaked in ethanol and water for 1h in sequence, so that the inside of the aerogel is completely filled with water, then the aerogel is placed in an optical glass square box filled with water, 5 mu l of n-hexane is dripped on the surface of a sample, and the contact angle of the n-hexane is observed.
As can be seen from fig. 13 to 14, the polyacrylonitrile/polyimide-silica nanofiber composite aerogel prepared in example 1 of the present invention has both an underwater oil contact angle and an oil-under-water contact angle greater than 150 °, which indicates that the composite aerogel has amphiphobicity, whereas the underwater oil contact angle and the oil-under-water contact angle of examples 2 to 3 and comparative example 1 are both less than 150 ° and greater than 90 ° only achieve amphiphobicity. Description of OPAN/PI-SiO 2 The reentrant structure formed by the spherical nano particles with uniform surfaces of the 400 fibers is beneficial to the stability of the liquid film on the surface of the aerogel, so that the surface energy of the liquid film is close to that of wetting liquid, the capability of rejecting another liquid is enhanced, and the aerogel is beneficial to presenting double super-hydrophobic property. And OPAN/PI-SiO 2 -50、OPAN/PI-SiO 2 And 15, the silica on the surface of the fiber is clustered together due to the small particle size, so that a uniform re-entrant structure cannot be formed on the surface of the fiber, a liquid film formed on the surface of the aerogel is unstable, and the amphiphobic property cannot be realized. OPAN/PI-SiO 2 The surface of the fiber 0 has no reentrant structure, a liquid film can be formed only by virtue of holes among the fibers, the formed liquid film is relatively unstable, and the amphiphobicity cannot be realized.
(3) Oil-water separation performance test
The testing method comprises the following steps: oil-water separation is carried out under the drive of the gravity of the liquid, and various oily liquids (including heavy oil and light oil) are adopted for testing; heavy oils include tetrachloroethane, tetrachloroethylene, and methylene chloride, and light oils include n-hexane, n-heptane, isopropyl alcohol, vegetable oils, and liquid paraffin. When the light oil/water system is separated, the volume ratio of the light oil to the water is 1:4, and the aerogel is pre-wetted by ethanol and water in turn in advance; in separating the heavy oil/water system, the volume ratio of heavy oil to water was 4:1, and the aerogel was pre-wetted with methylene chloride and n-hexane in sequence. The apparatus is shown in fig. 15. Specifically, in the test process, adding the composite aerogel in the application into a container, then dripping an oil-water mixture (namely the light oil/water system and the heavy oil/water system), and if the oil-water mixture is the light oil/water system, as the composite aerogel is pre-wetted by ethanol and water in turn in advance, water in the oil-water mixture is separated out through the composite aerogel, and most of light oil in the oil-water mixture is blocked by the composite aerogel, so that the separation of the light oil and the water is realized; if the oil-water mixture is a heavy oil/water system, because the composite aerogel is pre-wetted by dichloromethane and n-hexane in turn in advance, heavy oil in the oil-water mixture is separated out through the composite aerogel, and most of water in the oil-water mixture is blocked by the composite aerogel, so that the separation of heavy oil and water is realized.
FIG. 16 is a composite aerogel OPAN/PI-SiO prepared in example 1 2 -400 graph of oil-water separation test results obtained according to the test method described above.
As can be seen from FIG. 16, the average filtration efficiency of the composite aerogel prepared in example 1 for filtering different oils is greater than 99%, and the oil flux of the polyacrylonitrile/polyimide-silica macroporous oriented nanofiber composite aerogel prepared in example 1 of the present invention is (8.39.+ -. 0.52). Times.10 4 L m -2 h -1 The water flux is (2.87+/-0.51) multiplied by 10 4 L m -2 h -1 。
(4) Rebound resilience test
The testing method comprises the following steps: samples were tested using a high and low temperature materials universal tester (i.e., composite aerogel OPAN/PI-SiO prepared in example 1) 2 -400) compression resilience, compression rate of 1.0mm min using a 50N pressure sensor -1 The results are shown in FIG. 17. In fig. 17, 15%, 30%, 45%, 60% represent different strains, respectively.
As can be seen from fig. 17, the polyacrylonitrile/polyimide-silica macroporous oriented nanofiber composite aerogel prepared by the present invention has excellent rebound resilience before being strained to 30%.
(1) Reusable performance test
The composite aerogel was tested for reusability with reference to the test methods described above. Specifically, sequentially pre-wetting the aerogel with ethanol and water, testing the separation efficiency of a light oil/water mixture of the aerogel, and circularly testing for 50 times; the aerogel was pre-wetted with dichloromethane and n-hexane in sequence, tested for separation efficiency of the heavy oil/water mixture, and tested for 50 cycles.
FIG. 18 is a composite aerogel OPAN/PI-SiO prepared in example 1 2 -400 separation efficiency of light oil/water mixture with 50 consecutive cycles; FIG. 19 is a composite aerogel OPAN/PI-SiO prepared in example 1 2 400 separation efficiency of the heavy oil/water mixture, which is continuously circulated 50 times.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (10)
1. The preparation method of the nanofiber composite aerogel is characterized by comprising the following steps of:
mixing pre-oxidized polyacrylonitrile nanofiber, water-soluble polyamide acid nanofiber, silica nanoparticle and water to obtain a mixed dispersion liquid;
sequentially carrying out directional freezing and freeze drying on the mixed dispersion liquid to obtain polyacrylonitrile/polyamide acid-silicon dioxide macroporous oriented nanofiber aerogel;
imidizing the polyacrylonitrile/polyamide acid-silicon dioxide macroporous oriented nanofiber aerogel to obtain a polyacrylonitrile/polyimide-silicon dioxide macroporous oriented nanofiber composite aerogel;
the silica nanoparticles had an average particle diameter of 400nm.
2. The method for preparing a nanofiber composite aerogel according to claim 1, wherein the imidization treatment sequentially comprises:
heating to a first temperature at a first heating rate, and performing first imidization treatment;
raising the temperature to a second temperature at a second heating rate, and performing a second imidization treatment;
raising the temperature to a third temperature at a third heating rate, and performing third amidation treatment;
wherein the first temperature is 80-120 ℃, and the first imidization treatment time is 45-90 min;
the second temperature is 180-220 ℃, and the second imidization treatment time is 45-90 min;
the third temperature is 280-320 ℃, and the first imidization treatment time is 45-90 min;
the first heating rate, the second heating rate and the third heating rate are independently 2-10 ℃/min.
3. The method for preparing the nanofiber composite aerogel according to claim 1, wherein the mass of the water-soluble polyamic acid nanofiber is 5-15% of the total mass of the pre-oxidized polyacrylonitrile nanofiber and the water-soluble polyamic acid nanofiber;
and/or the mass of the silica nanoparticles is 40-60% of the mass of the pre-oxidized polyacrylonitrile nanofiber.
4. The method for preparing the nanofiber composite aerogel according to claim 1, wherein the freeze-drying temperature is-20 to-60 ℃ and the time is 24-72 hours.
5. The method of preparing a nanofiber composite aerogel according to claim 1 wherein the directional freezing is directional freezing by an oriented ice crystal template method.
6. The method of preparing a nanofiber composite aerogel according to claim 1, wherein the directional freezing comprises the steps of:
and placing the mixed dispersion liquid in a mold, and placing the bottom surface of the mold in a cold source for directional freezing, wherein the time of directional freezing is 5-15 min.
7. The method for preparing the nanofiber composite aerogel according to any one of claims 1 to 6, wherein the method for preparing the pre-oxidized polyacrylonitrile nanofiber comprises the following steps:
carrying out electrostatic spinning on the polyacrylonitrile solution to obtain polyacrylonitrile nanofibers;
and oxidizing the polyacrylonitrile nanofiber in an air atmosphere at 200-300 ℃ for 1-3 hours to obtain the pre-oxidized polyacrylonitrile nanofiber.
8. The method for preparing the nanofiber composite aerogel according to any one of claims 1 to 6, wherein the method for preparing the water-soluble polyamic acid comprises the following steps:
mixing 4,4' -diaminodiphenyl ether, pyromellitic dianhydride and a polar solvent, and performing polycondensation reaction to obtain non-water-soluble polyamide acid ammonium salt;
mixing the non-water-soluble polyamic acid ammonium salt with triethylamine, and carrying out neutralization reaction to obtain a water-soluble polyamic acid solution;
and carrying out ice water precipitation on the water-soluble polyamic acid solution to obtain the water-soluble polyamic acid nanofiber.
9. The nanofiber composite aerogel is characterized by being prepared by the preparation method according to any one of claims 1-8, wherein the nanofiber composite aerogel has a multi-stage pore structure, the multi-stage pore structure comprises macropores, mesopores and micropores, and the macropores are arranged on the same axis.
10. The use of the nanofiber composite aerogel prepared by the preparation method according to any one of claims 1 to 8 or the nanofiber composite aerogel according to claim 9 as an oil-water separation material or an air filtration material.
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