CN106000120A - Preparation method for three-dimensional-network-shaped gradient composite functional film, and product thereof - Google Patents
Preparation method for three-dimensional-network-shaped gradient composite functional film, and product thereof Download PDFInfo
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- CN106000120A CN106000120A CN201610398890.5A CN201610398890A CN106000120A CN 106000120 A CN106000120 A CN 106000120A CN 201610398890 A CN201610398890 A CN 201610398890A CN 106000120 A CN106000120 A CN 106000120A
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- 239000002131 composite material Substances 0.000 title claims abstract description 112
- 238000002360 preparation method Methods 0.000 title claims abstract description 52
- 239000000463 material Substances 0.000 claims abstract description 135
- 239000002121 nanofiber Substances 0.000 claims abstract description 77
- 238000005507 spraying Methods 0.000 claims abstract description 71
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 56
- 239000000725 suspension Substances 0.000 claims abstract description 50
- 238000001035 drying Methods 0.000 claims abstract description 19
- 238000001179 sorption measurement Methods 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000011941 photocatalyst Substances 0.000 claims abstract description 7
- 230000003115 biocidal effect Effects 0.000 claims abstract description 5
- 229940016286 microcrystalline cellulose Drugs 0.000 claims abstract description 4
- 235000019813 microcrystalline cellulose Nutrition 0.000 claims abstract description 4
- 239000008108 microcrystalline cellulose Substances 0.000 claims abstract description 4
- 229920000168 Microcrystalline cellulose Polymers 0.000 claims abstract description 3
- 239000012528 membrane Substances 0.000 claims description 136
- 235000010980 cellulose Nutrition 0.000 claims description 68
- 239000001913 cellulose Substances 0.000 claims description 68
- 229920002678 cellulose Polymers 0.000 claims description 68
- 239000013081 microcrystal Substances 0.000 claims description 58
- 150000002500 ions Chemical class 0.000 claims description 52
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 38
- 239000000126 substance Substances 0.000 claims description 27
- 230000015556 catabolic process Effects 0.000 claims description 25
- 238000006731 degradation reaction Methods 0.000 claims description 25
- ASDLSKCKYGVMAI-UHFFFAOYSA-N 9,10-dioxoanthracene-2-carboxylic acid Chemical group C1=CC=C2C(=O)C3=CC(C(=O)O)=CC=C3C(=O)C2=C1 ASDLSKCKYGVMAI-UHFFFAOYSA-N 0.000 claims description 24
- 239000007921 spray Substances 0.000 claims description 10
- QGLZXHRNAYXIBU-WEVVVXLNSA-N aldicarb Chemical group CNC(=O)O\N=C\C(C)(C)SC QGLZXHRNAYXIBU-WEVVVXLNSA-N 0.000 claims description 9
- 229920000098 polyolefin Polymers 0.000 claims description 9
- 241000588724 Escherichia coli Species 0.000 claims description 7
- 241000191967 Staphylococcus aureus Species 0.000 claims description 7
- 229920001903 high density polyethylene Polymers 0.000 claims description 5
- 239000004700 high-density polyethylene Substances 0.000 claims description 5
- 229920002292 Nylon 6 Polymers 0.000 claims description 4
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 4
- 229920001684 low density polyethylene Polymers 0.000 claims description 4
- 239000004702 low-density polyethylene Substances 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 4
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 2
- 241000894006 Bacteria Species 0.000 claims 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 239000007900 aqueous suspension Substances 0.000 claims 1
- 229920006001 poly(vinyl alcohol-co-ethylene) Polymers 0.000 claims 1
- 229920000642 polymer Polymers 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 3
- 239000005416 organic matter Substances 0.000 abstract 2
- 239000002738 chelating agent Substances 0.000 abstract 1
- 230000000593 degrading effect Effects 0.000 abstract 1
- 229910021645 metal ion Inorganic materials 0.000 abstract 1
- 238000000465 moulding Methods 0.000 abstract 1
- 239000011148 porous material Substances 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- PXRKCOCTEMYUEG-UHFFFAOYSA-N 5-aminoisoindole-1,3-dione Chemical compound NC1=CC=C2C(=O)NC(=O)C2=C1 PXRKCOCTEMYUEG-UHFFFAOYSA-N 0.000 description 16
- 238000010521 absorption reaction Methods 0.000 description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 12
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 11
- 229920006395 saturated elastomer Polymers 0.000 description 9
- 239000000835 fiber Substances 0.000 description 8
- -1 polyethylene terephthalate Polymers 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 230000001678 irradiating effect Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229920001707 polybutylene terephthalate Polymers 0.000 description 4
- 238000007592 spray painting technique Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 125000000532 dioxanyl group Chemical group 0.000 description 2
- 229920001038 ethylene copolymer Polymers 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 241000239290 Araneae Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 210000000576 arachnoid Anatomy 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-N benzene-dicarboxylic acid Natural products OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
-
- 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
-
- 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
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
-
- 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
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to a preparation method for a three-dimensional-network-shaped gradient composite functional film, and a product thereof. The preparation method comprises the following steps: spraying a nanometer microcrystalline cellulose suspension onto the surface of a nanofiber substrate, and carrying out drying and molding so as to form the gradient composite functional film. The prepared gradient composite functional film has a great specific surface area, a small pore size, high porosity and a large number of reaction bits. A heavy metal ion adsorption material prepared by subjecting the film and polybasic carboxylic acid to surface grafting has a heavy metal ion adsorption rate of no less than 99%; and the disadvantages of complex process, high cost and proneness to secondary pollution of common metal ion chelating agent processes are overcome. An organic matter degrading material prepared by subjecting the film and a photocatalyst to surface grafting has an organic matter removal rate of no less than 99% and has an antibiosis rate of 99.9999% after ultraviolet irradiation for 10 min.
Description
Technical field
The invention belongs to nano-fiber composite material functionalization preparing technical field, relate to ladder based on three-dimensional network shape
The preparation method of degree composite function film and goods thereof, particularly relate to nanofiber based on three-dimensional network shape and receive
Graded composite functional membrane of rice microcrystalline Cellulose and preparation method thereof.
Background technology
Nanofiber is a kind of superfine fibre, has that specific surface area is big, draw ratio big and is prone to the feature of film forming,
It is widely used in the fields such as medicine, food, industry and domestic, the filter material processed especially as air and water
Material.
Wang Dong, Sun Gang of Univ California-Davis USA et al., utilize and melt extrude phase disengagement method, will
TPO/CAB (acetylbutyrylcellulose) co-mixing system melt extrudes and is prepared for polyolefin copolymer
Nanofiber, and use high pressure draught forming technique, it is prepared for the nano fibrous membrane that different matrix material is carrier.
Nano fibrous membrane PVA-co-PE (polyvinyl alcohol-ethylene copolymer) surface prepared due to the method has
Hydroxyl reactive group, has bigger draw ratio and dimensional effect, and this nano fibrous membrane can be modified, and
Prepare the various nano fibrous membrane with specific function.
But the hydroxy radical content on this nano fibrous membrane is less, less than 10%, and activity is relatively low, needs in merit
Improving reactivity with naoh treatment film surface before energyization, the catalyst needing catalytic efficiency higher is urged
Change the carrying out of reaction.
Nano micro crystal cellulose has three hydroxyls, and wherein the primary hydroxyl reactivity on C6 position is the highest, with carboxyl
Esterification is easier simply to carry out.The a length of 90nm of nano micro crystal cellulose, diameter about 8nm,
Compared with nanofiber size much smaller.And nano fibrous membrane itself has more hole, specific surface area is big,
At film surface spraying nano micro crystal cellulose, bar-shaped nano micro crystal cellulose is dispersed in the Nanowire of 3 D stereo
On dimension film, direction is different, can form lamellar or arachnoid structure under certain condition between nanofiber,
Improve the specific surface area of nano fibrous membrane further, and higher reactivity can be obtained, prepare gradient
Functional composite membrane.
Chinese patent CN 103861473A, patent name is: a kind of three-dimensional manometer fiber base cellulose is super close
The preparation method of water composite hyperfiltration membrane.Cellulose is coated on nano fibrous membrane by this invention, it is thus achieved that have
The filter membrane material of high-hydrophilic.But coated cellulose size is relatively big, and with scraper at nano fibrous membrane
On be coated with thicker one layer, it is impossible to utilize the bigger serface of the nano fibrous membrane of three-dimensional network-like structure, after coating
Form the Cellulose Plate film with nano fibrous membrane as base material, be only capable of improving hydrophilic and the filtration of nano fibrous membrane
Performance.
Summary of the invention
It is an object of the invention to provide a kind of graded composite functional membrane based on three-dimensional network shape preparation method and
Its goods, nanofiber and the graded composite function of the micro-crystalline cellulose based on three-dimensional network shape of nanometer in the present invention
Film can keep the advantage that the specific surface area of nano fibrous membrane is big, adds on this basis and a lot of is easier to reaction
Reaction site, it is achieved gradient function, and increase membrane material mechanical property.
The preparation method of the graded composite functional membrane based on three-dimensional network shape of the present invention, for: nanofiber-based
Material surface carries out spraying nano micro crystal cellulose suspension, drying forming, forms graded composite functional membrane.
As preferred technical scheme:
The preparation method of graded composite functional membrane based on three-dimensional network shape as above, described nanofiber-based
The thickness of material is 1-500 μm；Described nano fiber basis material is thermoplastic polymer nanofiber's fiber base material, specifically
For for polyester, polyamide, polyolefin or polyolefin copolymer nano fibrous membrane；
Described polyester be PTT (PTT), polyethylene terephthalate (PET),
Polybutylene terephthalate (PBT) (PBT) or poly terephthalic acid 1,4 cyclohexane dimethanol ester (PCT)；Institute
Stating polyamide is nylon 6 (nylon6), nylon66 fiber (nylon66) or nylon 1212 (nylon1212)；
Described polyolefin is Low Density Polyethylene (LDPE), isotactic polypropylene (iPP) or high density polyethylene (HDPE)
(HDPE)；Described polyolefin copolymer be polyvinyl alcohol-ethylene copolymer (PVA-co-PE), polyethylene-
Glycidyl methacrylate copolymer (PE-co-GMA), polyethylene methacrylic acid methyl ester
Or polyethylene-propylene acid copolymer (PE-co-AA) (PE-co-MMA).
The preparation method of graded composite functional membrane based on three-dimensional network shape as above, described spraying nanometer is micro-
The quantity for spray of crystalline cellulose suspension is 0.01-0.5g/m2, the concentration of described nano micro crystal cellulose suspension is
0.01wt%-4wt%.
The preparation method of graded composite functional membrane based on three-dimensional network shape as above, described nano microcrystalline is fine
Dimension element suspension is that the pH value of suspension is through suspension in water of the nano micro crystal cellulose of ultrasonic disperse
8-12。
The preparation method of graded composite functional membrane based on three-dimensional network shape as above, described nano microcrystalline is fine
The a length of 1-200nm, a diameter of 0.5-20nm of dimension element.
The preparation method of graded composite functional membrane based on three-dimensional network shape as above, the technique of described spraying
Parameter is: spraying swath is 50-150mm, air pressure 0.1-0.5MPa, and flow is 1-5mL/min, spraying
It is highly 10-50cm；The temperature of described drying is 10-50 DEG C.
The present invention additionally provides a kind of graded composite functional membrane, in described graded composite functional membrane, nano microcrystalline
Each strange land, cellulose direction intersperses among the shallow top layer of nano fiber basis material surface and nano fiber basis material；Described gradient
Composite function film contact angle rate of change is 50-80%, and described graded composite functional membrane varying aperture rate is
30-200%, strongly rate of change is 5-50%.
Invention further provides a kind of heavy metal ion adsorbing material, described heavy metal ion adsorbing material is for by institute
State graded composite functional membrane to carry out Surface grafting reaction with polybasic carboxylic acid and obtain；Described heavy metal ion adsorbing material
Heavy metal ionic adsorption rate >=99%；Described polybasic carboxylic acid is BTCA (BTCA) or citric acid
(CA)；Described heavy metal ion is Pb2+、Cr3+、Cr6+、Cd2+、Mn2+Or Hg2+。
Reactions steps (as a example by BTCA): BTCA is soluble in water, its mass fraction is 0.1wt%-50
Wt%.Adding catalyst sodium hypophosphite (SHP), wherein the molar ratio of SHP Yu BTCA is 0.1-5；
Graded composite functional membrane be impregnated in above-mentioned solution, wherein graded composite functional membrane and the mass ratio of BTCA
For 1:50-1:100, at 30-35 DEG C, impregnate 30-35min, then take out composite nano-fiber membrane, 100-120 DEG C
Under bake 1-3h, now BTCA upper part carboxyl reacts with the hydroxyl on nano micro crystal cellulose, carboxylic
Base has the effect of chelating heavy metal ion.The most at room temperature use deionized water rinsing three times, remove surface not
The BTCA of reaction, dries, i.e. obtains heavy metal ion adsorbing material.Then above-mentioned heavy metal ion adsorbed
Material is put in the heavy metal ion solution that concentration is 10-200ppm, after reaching saturated absorption, takes out film,
With 10mL deionized water rinsing film 3 times, collect residual liquid and mix with the heavy metal ion solution after absorption, survey
Try heavy metal ion content therein, subtract each other with initial solution heavy metal ion content, film absorption
Heavy metal ion content.
Invention further provides a kind of degradation of organic substances material, described degradation of organic substances material is that described gradient is multiple
Closing nano fibrous membrane to carry out Surface grafting reaction with photocatalyst and obtain, described degradation of organic substances material is at ultraviolet light
To organic clearance >=99% after irradiation 30min, after ultraviolet light irradiates 10min, antibiotic rate is
99.9999%.
Degradation of organic substances material as above, described photocatalyst is anthraquinone-2-carboxylic acid；Described Organic substance is
Aldicarb；Described antibiotic rate refers to the bacteriostasis rate to escherichia coli and staphylococcus aureus.
Reactions steps is: configuration concentration is the photocatalyst solution of 1-10mM, and vibrate at 55-65 DEG C 3-5h.
It is subsequently adding the quality of the graded composite nano fibrous membrane prepared, graded composite nano fibrous membrane and photocatalyst
Ratio is 1:1-1:10, reacts 5-7h, prepare degradation of organic substances material at a temperature of 58-62 DEG C；Then by above-mentioned
Degradation of organic substances material is put in the organic solution that concentration is 0.2mM, irradiates 30 under UVA 365nm
Min, obtains organic clearance.
The present invention is to utilize nano fibrous membrane for base material, sprays nano micro crystal cellulose, and nano micro crystal cellulose exists
Form lamellar or the same network structure of spider web between nanofiber, further increase the ratio table of nano fibrous membrane
Area and strength, aperture reduces simultaneously, and porosity improves, and improves the filter capacity of nano fibrous membrane.It addition,
Nano micro crystal cellulose has abundant hydroxyl, can react with other compound and carry out functional graft modification,
Give its special nature, expand the application of nano fibrous membrane further.
Beneficial effect:
The present invention compared with prior art, has an advantage in that:
1. the size of nano micro crystal cellulose is less, is sprayed on the porous nanofiber membrane that specific surface area is bigger,
It is possible not only to the advantage that the specific surface area of holding nano fibrous membrane is big, adds a lot of being easier to instead on this basis
The reaction site answered, it is achieved gradient function.
2. a kind of based on three-dimensional network shape the nanofiber selected by the present invention and the ladder of nano micro crystal cellulose
The preparation method of degree composite function film is composite nano-fiber membrane material surface modifying, does not change nano fibrous membrane material
The body construction of material, also will not impact the mechanical property of micro/nano fibrous membrane material itself, also can increase film
The mechanical property of material.
3. a kind of based on three-dimensional network shape the nanofiber of the present invention and the graded composite of nano micro crystal cellulose
The preparation method of functional membrane, preparation method technique is simple, has efficient, the easy and feature of environmental protection, and raw material is easy
, low cost, convenient operation and control, it is easy to accomplish industrialized production.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is expanded on further.Should be understood that these embodiments are only used for
The bright present invention rather than restriction the scope of the present invention.In addition, it is to be understood that reading the content that the present invention lectures
Afterwards, the present invention can be made various changes or modifications by those skilled in the art, and these equivalent form of values fall within equally
The application appended claims limited range.
Embodiment 1
The preparation method of a kind of graded composite functional membrane based on three-dimensional network shape, is 1 μm at thickness
PVA-co-PE nano fibrous membrane surface spraying concentration is the nano micro crystal cellulose suspension of 0.01wt%, wherein
The pH value of suspension is 8, a length of 1nm of nano micro crystal cellulose, a diameter of 0.5nm in suspension,
Quantity for spray is 0.01g/m2；The technological parameter of spraying is: spraying swath is 50mm, air pressure 0.1MPa, stream
Amount is 1mL/min, and spraying height is 10cm；Then drying forming at 10 DEG C, forms nano microcrystalline fine
Dimension element each strange land, direction intersperses among nano fiber basis material surface and the graded composite merit on the shallow top layer of nano fiber basis material
Can film；Test shows that the contact angle rate of change of the nano fiber basis material prepared is 50%, and varying aperture rate is
30%, strongly rate of change is 5%.
The preparation method of heavy metal ion adsorbing material, BTCA is soluble in water, and its mass fraction is
0.1wt%, adds catalyst SHP, and wherein the molar ratio of SHP Yu BTCA is 0.1；By graded composite
Functional membrane impregnated in above-mentioned solution, and wherein graded composite functional membrane is 1:50 with the mass ratio of BTCA, in
30min is impregnated at 30 DEG C；Then take out composite nano-fiber membrane, bake 1h at 100 DEG C, the most at room temperature
With deionized water rinsing three times, remove the unreacted BTCA in surface, dry, i.e. obtain heavy metal ion adsorbed
Material；It is the Pb of 200ppm by above-mentioned heavy metal ion adsorbing material immersion concentration2+Solution in, reach full
After absorption, take out film；Test shows that heavy metal ion adsorbing material is to Pb2+Adsorption rate be 99%.
Embodiment 2
The preparation method of a kind of graded composite functional membrane based on three-dimensional network shape, is 500 μm at thickness
PE-co-GMA nano fibrous membrane surface spraying concentration is the nano micro crystal cellulose suspension of 4wt%, wherein hangs
The pH value of supernatant liquid is 12, a length of 200nm of nano micro crystal cellulose, a diameter of 20nm in suspension,
Quantity for spray is 0.5g/m2；The technological parameter of spraying is: spraying swath is 150mm, air pressure 0.5MPa, stream
Amount is 5mL/min, and spraying height is 50cm；Then drying forming at 50 DEG C, forms nano microcrystalline fine
Dimension element each strange land, direction intersperses among nano fiber basis material surface and the graded composite merit on the shallow top layer of nano fiber basis material
Can film；Test shows that the contact angle rate of change prepared is 80%, and varying aperture rate is 200%, strongly rate of change
It is 50%.
The preparation method of degradation of organic substances material, by anthraquinone-2-carboxylic acid's molecular solution that concentration is 1mM, solvent
For oxolane, at 55 DEG C of 3h that vibrate；It is subsequently adding the graded composite nano fibrous membrane prepared, Qi Zhongti
Degree composite nano-fiber membrane is 1:1 with the mass ratio of anthraquinone-2-carboxylic acid's molecule, reacts 5h at a temperature of 58 DEG C；
Prepare degradation of organic substances material；Above-mentioned prepared degradation of organic substances material is put into the tears that concentration is 0.2mM go out
In prestige solution, irradiating after 30min the clearance to Aldicarb under ultraviolet light is 99%, irradiates at ultraviolet light
After 10min, the bacteriostasis rate to escherichia coli and staphylococcus aureus is 99.9999%.
Embodiment 3
The preparation method of a kind of graded composite functional membrane based on three-dimensional network shape, is 100 μm at thickness
PTT nano fibrous membrane surface spraying concentration is 1wt% nano micro crystal cellulose suspension, the wherein pH of suspension
Value is 9, a length of 50nm of nano micro crystal cellulose in suspension, a diameter of 2nm, and quantity for spray is 0.1
g/m2；The technological parameter of spraying is: spraying swath is 100mm, air pressure 0.29MPa, and flow is 2mL/min,
Spraying height is 15cm；Then drying forming at 20 DEG C, forms each strange land, nano micro crystal cellulose direction and dissipates
It is distributed in nano fiber basis material surface and the graded composite functional membrane on the shallow top layer of nano fiber basis material；Test shows to prepare
Nano fiber basis material contact angle rate of change be 60%, varying aperture rate is 50%, and strongly rate of change is 20%.
The preparation method of heavy metal ion adsorbing material, CA is soluble in water, and its mass fraction is 50wt%；
Adding catalyst SHP, wherein the molar ratio of SHP Yu CA is 5；Graded composite functional membrane be impregnated in
Stating in solution, wherein graded composite functional membrane is 1:100 with the mass ratio of CA, impregnates 35min at 35 DEG C,
Then take out composite nano-fiber membrane, at 120 DEG C, bake 3h, now CA upper part carboxyl and nano microcrystalline
Hydroxyl on cellulose reacts；The most at room temperature use deionized water rinsing three times, remove surface unreacted
CA, dry, i.e. obtain heavy metal ion adsorbing material；Above-mentioned heavy metal ion adsorbing material is immersed dense
Degree is the Cr of 180ppm3+Solution in, after reaching saturated absorption, take out film；Test shows heavy metal ion
Adsorbing material is to Cr3+Adsorption rate be 99.2%.
Embodiment 4
The preparation method of a kind of graded composite functional membrane based on three-dimensional network shape, is 200 μm at thickness
LDPE nano fibrous membrane surface spraying concentration is the nano micro crystal cellulose suspension of 3wt%, wherein suspension
PH value be 10, a length of 100nm of nano micro crystal cellulose, a diameter of 15nm in suspension, spraying
Amount is 0.3g/m2；The technological parameter of spraying is: spraying swath is 80mm, air pressure 0.29MPa, and flow is
3mL/min, spraying height is 35cm；Then drying forming at 35 DEG C, forms nano micro crystal cellulose side
Nano fiber basis material surface and the graded composite functional membrane on the shallow top layer of nano fiber basis material is interspersed among to each strange land；Survey
Bright prepared nano fiber basis material contact angle rate of change of taking temperature is 70%, and varying aperture rate is 150%, and strength becomes
Rate is 40%.
The preparation method of degradation of organic substances material, by anthraquinone-2-carboxylic acid's molecular solution that concentration is 10mM, molten
Agent is dioxane, at 65 DEG C of 5h that vibrate；It is subsequently adding the graded composite nano fibrous membrane prepared, wherein
Graded composite nano fibrous membrane is 1:10 with the mass ratio of anthraquinone-2-carboxylic acid's molecule, reacts 7h at a temperature of 62 DEG C；
Prepare degradation of organic substances material；Above-mentioned prepared degradation of organic substances material is put into the tears that concentration is 0.2mM go out
In prestige solution, irradiating after 30min the clearance to Aldicarb under ultraviolet light is 99.2%, at ultraviolet lighting
After penetrating 10min, the bacteriostasis rate to escherichia coli and staphylococcus aureus is 99.9999%.
Embodiment 5
The preparation method of a kind of graded composite functional membrane based on three-dimensional network shape, at the iPP that thickness is 400 μm
Nano fibrous membrane surface spraying concentration is the nano micro crystal cellulose suspension of 2.5wt%, the wherein pH of suspension
Value is 10.5, and a length of 80nm of nano micro crystal cellulose in suspension, a diameter of 12nm, quantity for spray is
0.4g/m2；The technological parameter of spraying is: spraying swath is 100mm, air pressure 0.4MPa, and flow is 4.5
ML/min, spraying height is 25cm；Then drying forming at 30 DEG C, forms nano micro crystal cellulose side
Nano fiber basis material surface and the graded composite functional membrane on the shallow top layer of nano fiber basis material is interspersed among to each strange land；Survey
The contact angle rate of change of bright prepared nano fiber basis material of taking temperature is 65%, and varying aperture rate is 130%, strongly
Rate of change is 30%.
The preparation method of heavy metal ion adsorbing material, BTCA is soluble in water, and its mass fraction is 30wt%；
Adding catalyst SHP, wherein the molar ratio of SHP Yu BTCA is 4；Graded composite functional membrane is impregnated
In above-mentioned solution, wherein graded composite functional membrane is 1:75 with the mass ratio of BTCA, impregnates at 30 DEG C
30min；Then take out composite nano-fiber membrane, at 110 DEG C, bake 2h, now BTCA upper part carboxylic
Base reacts with the hydroxyl on nano micro crystal cellulose；The most at room temperature use deionized water rinsing three times, remove
Remove the unreacted BTCA in surface, dry, i.e. obtain heavy metal ion adsorbing material；By above-mentioned heavy metal ion
It is the Cr of 150ppm that adsorbing material immerses concentration6+Solution in, after reaching saturated absorption, take out film；Test
Show that heavy metal ion adsorbing material is to Cr6+Adsorption rate be 99.4%.
Embodiment 6
The preparation method of a kind of graded composite functional membrane based on three-dimensional network shape, is 450 μm at thickness
Nylon6 nano fibrous membrane surface spraying concentration is the nano micro crystal cellulose suspension of 3wt%, wherein suspension
PH value be 11.5, a length of 140nm of nano micro crystal cellulose, a diameter of 10nm in suspension, spray
Painting amount is 0.25g/m2；The technological parameter of spraying is: spraying swath is 120mm, air pressure 0.2MPa, flow
For 2.5mL/min, spraying height is 40cm；Then drying forming at 38 DEG C, forms nano microcrystalline fiber
Element each strange land, direction intersperses among nano fiber basis material surface and the graded composite function on the shallow top layer of nano fiber basis material
Film；Test shows that the contact angle rate of change of the nano fiber basis material prepared is 68%, and varying aperture rate is 160%,
Strongly rate of change is 27%.
The preparation method of degradation of organic substances material, by anthraquinone-2-carboxylic acid's molecular solution that concentration is 5mM, solvent
For DMF, at 60 DEG C of 4h that vibrate；It is subsequently adding the graded composite nano fibrous membrane prepared,
Wherein graded composite nano fibrous membrane is 1:5 with the mass ratio of anthraquinone-2-carboxylic acid's molecule, reacts at a temperature of 60 DEG C
6h；Prepare degradation of organic substances material；Above-mentioned prepared degradation of organic substances material is put into concentration is 0.2mM's
In Aldicarb solution, irradiating after 30min the clearance to Aldicarb under ultraviolet light is 99.4%, in ultraviolet
After light irradiation 10min, the bacteriostasis rate to escherichia coli and staphylococcus aureus is 99.9999%.
Embodiment 7
The preparation method of a kind of graded composite functional membrane based on three-dimensional network shape, is 1 μm at thickness
Nylon1212 nano fibrous membrane surface spraying concentration is the nano micro crystal cellulose suspension of 0.01wt%, wherein
The pH value of suspension is 8, a length of 1nm of nano micro crystal cellulose, a diameter of 0.5nm in suspension,
Quantity for spray is 0.01g/m2；The technological parameter of spraying is: spraying swath is 140mm, air pressure 0.25MPa,
Flow is 1mL/min, and spraying height is 30cm；Then drying forming at 10 DEG C, forms nano microcrystalline
Each strange land, cellulose direction intersperses among nano fiber basis material surface and the graded composite on the shallow top layer of nano fiber basis material
Functional membrane；Test shows that the contact angle rate of change that the nano fiber basis material prepared is sent out is 50%, and varying aperture rate is
30%, strongly rate of change is 5%.
The preparation method of heavy metal ion adsorbing material, BTCA is soluble in water, and its mass fraction is 10wt%,
Adding catalyst SHP, wherein the molar ratio of SHP Yu BTCA is 3；Graded composite functional membrane is impregnated
In above-mentioned solution, wherein graded composite functional membrane is 1:60 with the mass ratio of BTCA, impregnates at 30 DEG C
33min；Then take out composite nano-fiber membrane, at 110 DEG C, bake 2h, the most at room temperature use deionized water
Rinse three times, remove the unreacted BTCA in surface, dry, i.e. obtain heavy metal ion adsorbing material；By upper
Stating heavy metal ion adsorbing material immersion concentration is the Cd of 100ppm2+Solution in, after reaching saturated absorption,
Take out film；Test shows that heavy metal ion adsorbing material is to Cd2+Adsorption rate be 99.5%.
Embodiment 8
The preparation method of a kind of graded composite functional membrane based on three-dimensional network shape, is 100 μm at thickness
PE-co-MMA nano fibrous membrane surface spraying concentration is 1wt% nano micro crystal cellulose suspension, wherein hangs
The pH value of supernatant liquid is 9, a length of 50nm of nano micro crystal cellulose, a diameter of 2nm in suspension, spray
Painting amount is 0.1g/m2；The technological parameter of spraying is: spraying swath is 100mm, air pressure 0.2MPa, flow
For 2mL/min, spraying height is 35cm；Then drying forming at 20 DEG C, forms nano microcrystalline fiber
Element each strange land, direction intersperses among nano fiber basis material surface and the graded composite function on the shallow top layer of nano fiber basis material
Film；Test shows that the contact angle rate of change of the nano fiber basis material prepared is 60%, and varying aperture rate is 50%,
Strongly rate of change is 20%.
The preparation method of heavy metal ion adsorbing material, CA is soluble in water, and its mass fraction is 30wt%；
Adding catalyst SHP, wherein the molar ratio of SHP Yu CA is 3；Graded composite functional membrane be impregnated in
Stating in solution, wherein graded composite functional membrane is 1:70 with the mass ratio of CA, impregnates 30min at 35 DEG C,
Then take out composite nano-fiber membrane, at 120 DEG C, bake 1h, now CA upper part carboxyl and nano microcrystalline
Hydroxyl on cellulose reacts；The most at room temperature use deionized water rinsing three times, remove surface unreacted
CA, dry, i.e. obtain heavy metal ion adsorbing material；Above-mentioned heavy metal ion adsorbing material is immersed dense
Degree is the Mn of 50ppm2+Solution in, after reaching saturated absorption, take out film；Test shows heavy metal ion
Adsorbing material is to Mn2+Adsorption rate be 99.6%.
Embodiment 9
The preparation method of a kind of graded composite functional membrane based on three-dimensional network shape, is 400 μm at thickness
Nylon66 nano fibrous membrane surface spraying concentration is the nano micro crystal cellulose suspension of 2.5wt%, wherein suspends
The pH value of liquid is 10.5, a length of 80nm of nano micro crystal cellulose, a diameter of 12nm in suspension,
Quantity for spray is 0.4g/m2；The technological parameter of spraying is: spraying swath is 90mm, air pressure 0.4MPa, stream
Amount is 4.5mL/min, and spraying height is 30cm；Then drying forming at 30 DEG C, forms nano microcrystalline fine
Dimension element each strange land, direction intersperses among nano fiber basis material surface and the graded composite merit on the shallow top layer of nano fiber basis material
Can film；Test shows that the contact angle rate of change of the nano fiber basis material prepared is 65%, and varying aperture rate is
130%, strongly rate of change is 30%.
The preparation method of heavy metal ion adsorbing material, BTCA is soluble in water, and its mass fraction is 30wt%；
Adding catalyst SHP, wherein the molar ratio of SHP Yu BTCA is 4；Graded composite functional membrane is impregnated
In above-mentioned solution, wherein graded composite functional membrane is 1:80 with the mass ratio of BTCA, impregnates at 30 DEG C
33min；Then take out composite nano-fiber membrane, at 110 DEG C, bake 2h, now BTCA upper part carboxylic
Base reacts with the hydroxyl on nano micro crystal cellulose；The most at room temperature use deionized water rinsing three times, remove
Remove the unreacted BTCA in surface, dry, i.e. obtain heavy metal ion adsorbing material；By above-mentioned heavy metal ion
It is the Hg of 10ppm that adsorbing material immerses concentration2+Solution in, after reaching saturated absorption, take out film；Test
Show that heavy metal ion adsorbing material is to Hg2+Adsorption rate be 99.7%.
Embodiment 10
The preparation method of a kind of graded composite functional membrane based on three-dimensional network shape, is 300 μm at thickness
PET nano fibrous membrane surface spraying concentration is the nano micro crystal cellulose suspension of 2.5wt%, wherein suspension
PH value be 10, a length of 80nm of nano micro crystal cellulose, a diameter of 10nm in suspension, spraying
Amount is 0.1g/m2；The technological parameter of spraying is: spraying swath is 100mm, air pressure 0.4MPa, and flow is
4.5mL/min, spraying height is 25cm；Then drying forming at 30 DEG C, forms nano micro crystal cellulose
Each strange land, direction intersperses among nano fiber basis material surface and the graded composite functional membrane on the shallow top layer of nano fiber basis material；
Test shows that the contact angle rate of change of the nano fiber basis material prepared is 65%, and varying aperture rate is 100%, by force
Power rate of change is 30%.
The preparation method of heavy metal ion adsorbing material, BTCA is soluble in water, and its mass fraction is 30wt%；
Adding catalyst SHP, wherein the molar ratio of SHP Yu BTCA is 4；Graded composite functional membrane is impregnated
In above-mentioned solution, wherein graded composite functional membrane is 1:55 with the mass ratio of BTCA, impregnates at 30 DEG C
30min；Then take out composite nano-fiber membrane, at 110 DEG C, bake 2h, now BTCA upper part carboxylic
Base reacts with the hydroxyl on nano micro crystal cellulose；The most at room temperature use deionized water rinsing three times, remove
Remove the unreacted BTCA in surface, dry, i.e. obtain heavy metal ion adsorbing material；By above-mentioned heavy metal ion
It is the Cr of 160ppm that adsorbing material immerses concentration6+Solution in, after reaching saturated absorption, take out film；Test
Show that heavy metal ion adsorbing material is to Cr6+Adsorption rate be 99.35%.
Embodiment 11
The preparation method of a kind of graded composite functional membrane based on three-dimensional network shape, at the PBT that thickness is 400 μm
Nano fibrous membrane surface spraying concentration is the nano micro crystal cellulose suspension of 3wt%, the wherein pH of suspension
Value is 11, and a length of 100nm of nano micro crystal cellulose in suspension, a diameter of 20nm, quantity for spray is
0.2g/m2；The technological parameter of spraying is: spraying swath is 120mm, air pressure 0.2MPa, and flow is 2.5
ML/min, spraying height is 40cm；Then drying forming at 38 DEG C, forms nano micro crystal cellulose side
Nano fiber basis material surface and the graded composite functional membrane on the shallow top layer of nano fiber basis material is interspersed among to each strange land；Survey
The contact angle rate of change of bright prepared nano fiber basis material of taking temperature is 68%, and varying aperture rate is 100%, strongly
Rate of change is 27%.
The preparation method of degradation of organic substances material, by anthraquinone-2-carboxylic acid's molecular solution that concentration is 5mM, solvent
For DMF, at 60 DEG C of 4h that vibrate；It is subsequently adding the graded composite nano fibrous membrane prepared,
Wherein graded composite nano fibrous membrane is 1:5 with the mass ratio of anthraquinone-2-carboxylic acid's molecule, reacts at a temperature of 60 DEG C
6h；Prepare degradation of organic substances material；Above-mentioned prepared degradation of organic substances material is put into concentration is 0.2mM's
In Aldicarb solution, irradiating after 30min the clearance to Aldicarb under ultraviolet light is 99.5%, in ultraviolet
After light irradiation 10min, the bacteriostasis rate to escherichia coli and staphylococcus aureus is 99.9999%.
Embodiment 12
The preparation method of a kind of graded composite functional membrane based on three-dimensional network shape, is 400 μm at thickness
PCT nano fibrous membrane surface spraying concentration is the nano micro crystal cellulose suspension of 2.5wt%, wherein suspension
PH value be 10.5, a length of 80nm of nano micro crystal cellulose, a diameter of 12nm in suspension, spray
Painting amount is 0.4g/m2；The technological parameter of spraying is: spraying swath is 100mm, air pressure 0.4MPa, flow
For 4.5mL/min, spraying height is 30cm；Then drying forming at 30 DEG C, forms nano microcrystalline fiber
Element each strange land, direction intersperses among nano fiber basis material surface and the graded composite function on the shallow top layer of nano fiber basis material
Film；Test shows that the contact angle rate of change of the nano fiber basis material prepared is 65%, and varying aperture rate is 130%,
Strongly rate of change is 30%.
The preparation method of heavy metal ion adsorbing material, BTCA is soluble in water, and its mass fraction is 30wt%；
Adding catalyst SHP, wherein the molar ratio of SHP Yu BTCA is 4；Graded composite functional membrane is impregnated
In above-mentioned solution, wherein graded composite functional membrane is 1:75 with the mass ratio of BTCA, impregnates at 30 DEG C
30min；Then take out composite nano-fiber membrane, at 110 DEG C, bake 2h, now BTCA upper part carboxylic
Base reacts with the hydroxyl on nano micro crystal cellulose；The most at room temperature use deionized water rinsing three times, remove
Remove the unreacted BTCA in surface, dry, i.e. obtain heavy metal ion adsorbing material；By above-mentioned heavy metal ion
It is the Cr of 150ppm that adsorbing material immerses concentration6+Solution in, after reaching saturated absorption, take out film；Test
Show that heavy metal ion adsorbing material is to Cr6+Adsorption rate be 99.4%.
Embodiment 13
The preparation method of a kind of graded composite functional membrane based on three-dimensional network shape, is 300 μm at thickness
HDPE nano fibrous membrane surface spraying concentration is the nano micro crystal cellulose suspension of 3wt%, wherein suspension
PH value be 9, a length of 120nm of nano micro crystal cellulose, a diameter of 12nm in suspension, spraying
Amount is 0.2g/m2；The technological parameter of spraying is: spraying swath is 90mm, air pressure 0.3MPa, and flow is 4
ML/min, spraying height is 42cm；Then drying forming at 36 DEG C, forms nano micro crystal cellulose side
Nano fiber basis material surface and the graded composite functional membrane on the shallow top layer of nano fiber basis material is interspersed among to each strange land；Survey
Bright prepared nano fiber basis material contact angle rate of change of taking temperature is 50%, and varying aperture rate is 90%, and strength becomes
Rate is 37%.
The preparation method of degradation of organic substances material, by anthraquinone-2-carboxylic acid's molecular solution that concentration is 10mM, molten
Agent is dioxane, at 65 DEG C of 5h that vibrate；It is subsequently adding the graded composite nano fibrous membrane prepared, wherein
Graded composite nano fibrous membrane is 1:10 with the mass ratio of anthraquinone-2-carboxylic acid's molecule, reacts 7h at a temperature of 62 DEG C；
Prepare degradation of organic substances material；Above-mentioned prepared degradation of organic substances material is put into the tears that concentration is 0.2mM go out
In prestige solution, irradiating after 30min the clearance to Aldicarb under ultraviolet light is 99.1%, at ultraviolet lighting
After penetrating 10min, the bacteriostasis rate to escherichia coli and staphylococcus aureus is 99.9999%.
Embodiment 14
The preparation method of a kind of graded composite functional membrane based on three-dimensional network shape, is 380 μm at thickness
PE-co-AA nano fibrous membrane surface spraying concentration is 4wt% nano micro crystal cellulose suspension, wherein suspends
The pH value of liquid is 11, a length of 180nm of nano micro crystal cellulose, a diameter of 17nm in suspension, spray
Painting amount is 0.4g/m2；The technological parameter of spraying is: spraying swath is 150mm, air pressure 0.5MPa, flow
For 3mL/min, spraying height is 47cm；Then drying forming at 32 DEG C, forms nano microcrystalline fiber
Element each strange land, direction intersperses among nano fiber basis material surface and the graded composite function on the shallow top layer of nano fiber basis material
Film；Test shows that the contact angle rate of change of the nano fiber basis material prepared is 70%, and varying aperture rate is 150%,
Strongly rate of change is 30%.
The preparation method of heavy metal ion adsorbing material, CA is soluble in water, and its mass fraction is 30wt%；
Adding catalyst SHP, wherein the molar ratio of SHP Yu CA is 3；Graded composite functional membrane be impregnated in
Stating in solution, wherein graded composite functional membrane is 1:70 with the mass ratio of CA, impregnates 30min at 35 DEG C,
Then take out composite nano-fiber membrane, at 120 DEG C, bake 1h, now CA upper part carboxyl and nano microcrystalline
Hydroxyl on cellulose reacts；The most at room temperature use deionized water rinsing three times, remove surface unreacted
CA, dry, i.e. obtain heavy metal ion adsorbing material；Above-mentioned heavy metal ion adsorbing material is immersed dense
Degree is the Mn of 50ppm2+Solution in, after reaching saturated absorption, take out film；Test shows heavy metal ion
Adsorbing material is to Mn2+Adsorption rate be 99.6%.
Claims (10)
1. the preparation method of graded composite functional membrane based on three-dimensional network shape, is characterized in that: at nano fiber basis material
Surface carries out spraying nano micro crystal cellulose suspension, drying forming, forms graded composite functional membrane.
The preparation method of graded composite functional membrane based on three-dimensional network shape the most according to claim 1, it is special
Levying and be, the thickness of described nano fiber basis material is 1-500 μm；Described nano fiber basis material is thermoplasticity
Polymer nanofiber-based material, specially polyester, polyamide, polyolefin or polyolefin copolymer nanometer
Fibrous membrane；
Described polyester is PET, PBT, PCT or PTT；Described polyamide is nylon6, nylon66
Or nylon1212；Described polyolefin is LDPE, iPP or HDPE；Described polyolefin copolymer is
PVA-co-PE, PE-co-GMA, PE-co-MMA or PE-co-AA.
The preparation method of graded composite functional membrane based on three-dimensional network shape the most according to claim 1, it is special
Levying and be, the quantity for spray of described spraying nano micro crystal cellulose suspension is 0.01-0.5g/m2Receive described in,
The concentration of rice microcrystalline Cellulose suspension is 0.01wt%-4wt%.
The preparation method of graded composite functional membrane based on three-dimensional network shape the most according to claim 1, it is special
Levying and be, described nano micro crystal cellulose suspension is through ultrasonic disperse nano micro crystal cellulose in water
Suspension, the pH value of suspension is 8-12.
The preparation method of graded composite functional membrane based on three-dimensional network shape the most according to claim 1, it is special
Levy and be, a length of 1-200nm of described nano micro crystal cellulose, a diameter of 0.5-20nm.
The preparation method of graded composite functional membrane based on three-dimensional network shape the most according to claim 1, it is special
Levying and be, the technological parameter of described spraying is: spraying swath is 50-150mm, air pressure 0.1-0.5MPa,
Flow is 1-5mL/min, and spraying height is 10-50cm；The temperature of described drying is 10-50 DEG C.
7. the graded composite functional membrane that any one preparation method as described in claim 1～6 prepares, is characterized in that:
In described graded composite functional membrane, each strange land, nano micro crystal cellulose direction intersperses among nano fiber basis material table
Face and the shallow top layer of nano fiber basis material；Described graded composite functional membrane contact angle rate of change is 50-80%,
Described graded composite functional membrane varying aperture rate is 30-200%, and strongly rate of change is 5-50%.
8. use the heavy metal ion adsorbing material that the graded composite functional membrane described in claim 7 prepares, its
Feature is: described heavy metal ion adsorbing material is for carry out described graded composite functional membrane with polybasic carboxylic acid
Surface grafting reaction and obtain；Described heavy metal ion adsorbing material heavy metal ionic adsorption rate >=99%；
Described polybasic carboxylic acid is BTCA or citric acid；Described heavy metal ion is Pb2+、Cr3+、Cr6+、
Cd2+、Mn2+Or Hg2+。
9. use the degradation of organic substances material that the graded composite functional membrane described in claim 7 prepares, its feature
It is: described degradation of organic substances material is for carrying out surface by described graded composite nano fibrous membrane and photocatalyst
Graft reaction and obtain, described degradation of organic substances material irradiates after 30min organic removal at ultraviolet light
Rate >=99%, after ultraviolet light irradiates 10min, antibiotic rate is 99.9999%.
Degradation of organic substances material the most according to claim 9, it is characterised in that described photocatalyst is anthraquinone
-2-carboxylic acid；Described Organic substance is Aldicarb；Described antibiotic rate refers to escherichia coli and Staphylococcus aureus
The bacteriostasis rate of bacterium.
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| CN110586042A (en) * | 2019-08-13 | 2019-12-20 | 武汉轻工大学 | Method for treating waste water and method for preparing hexavalent chromium ion adsorbent |
| CN110894312A (en) * | 2019-11-11 | 2020-03-20 | 上海大学 | Nano-cellulose reinforced calcium sulfate whisker composite film and preparation method and application thereof |
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| CN107337802A (en) * | 2017-05-18 | 2017-11-10 | 武汉纺织大学 | Air-sensitive film sensitive to ethanol and acetone and preparation method thereof |
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