CN109295713B - Preparation method and application of magnetic composite hydrogel based on cellulose nanofibers - Google Patents
Preparation method and application of magnetic composite hydrogel based on cellulose nanofibers Download PDFInfo
- Publication number
- CN109295713B CN109295713B CN201811108173.XA CN201811108173A CN109295713B CN 109295713 B CN109295713 B CN 109295713B CN 201811108173 A CN201811108173 A CN 201811108173A CN 109295713 B CN109295713 B CN 109295713B
- Authority
- CN
- China
- Prior art keywords
- cellulose
- magnetic composite
- composite hydrogel
- isopropylacrylamide
- acrylic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000002121 nanofiber Substances 0.000 title claims abstract description 97
- 229920002678 cellulose Polymers 0.000 title claims abstract description 86
- 239000001913 cellulose Substances 0.000 title claims abstract description 86
- 239000000017 hydrogel Substances 0.000 title claims abstract description 85
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229920002301 cellulose acetate Polymers 0.000 claims abstract description 24
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 21
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 14
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 106
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 45
- 235000019441 ethanol Nutrition 0.000 claims description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 238000010791 quenching Methods 0.000 claims description 25
- 230000000171 quenching effect Effects 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 24
- 238000001179 sorption measurement Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000012295 chemical reaction liquid Substances 0.000 claims description 20
- 239000012153 distilled water Substances 0.000 claims description 20
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 20
- 108091034057 RNA (poly(A)) Proteins 0.000 claims description 18
- -1 vinyl modified silica Chemical class 0.000 claims description 17
- 229920002554 vinyl polymer Polymers 0.000 claims description 17
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 16
- 239000000377 silicon dioxide Substances 0.000 claims description 16
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 15
- 239000012046 mixed solvent Substances 0.000 claims description 15
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims description 12
- 235000012239 silicon dioxide Nutrition 0.000 claims description 12
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 11
- 229960002089 ferrous chloride Drugs 0.000 claims description 11
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 11
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 11
- 239000000835 fiber Substances 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 9
- 229910002651 NO3 Inorganic materials 0.000 claims description 9
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 229910001431 copper ion Inorganic materials 0.000 claims description 8
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 229920000875 Dissolving pulp Polymers 0.000 claims description 3
- 238000000944 Soxhlet extraction Methods 0.000 claims description 2
- 230000000850 deacetylating effect Effects 0.000 claims description 2
- 239000002114 nanocomposite Substances 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 4
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000000975 co-precipitation Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 2
- 229920001504 poly(N-isopropylacrylamide-co-acrylic acid) Polymers 0.000 abstract 2
- 239000010865 sewage Substances 0.000 abstract 1
- 235000010980 cellulose Nutrition 0.000 description 66
- 239000000243 solution Substances 0.000 description 39
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 238000004108 freeze drying Methods 0.000 description 8
- 229920006395 saturated elastomer Polymers 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- 230000005415 magnetization Effects 0.000 description 5
- 229920000578 graft copolymer Polymers 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000005266 casting Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002145 thermally induced phase separation Methods 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229920001222 biopolymer Polymers 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
- D06M14/02—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of natural origin
- D06M14/04—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of natural origin of vegetal origin, e.g. cellulose or derivatives thereof
-
- 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
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- 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
- B01J20/28002—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 physical properties
- B01J20/28009—Magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- 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
-
- 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
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
- D01F2/24—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives
- D01F2/28—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives from organic cellulose esters or ethers, e.g. cellulose acetate
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/49—Oxides or hydroxides of elements of Groups 8, 9,10 or 18 of the Periodic Table; Ferrates; Cobaltates; Nickelates; Ruthenates; Osmates; Rhodates; Iridates; Palladates; Platinates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
- D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
- D06M2101/08—Esters or ethers of cellulose
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Dispersion Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention provides a preparation method of magnetic composite hydrogel based on cellulose nanofibers. The method comprises the steps of selecting a natural high polymer material cellulose acetate with good biocompatibility as a raw material, and grafting N-isopropylacrylamide and acrylic acid with carboxyl and amino onto cellulose acetate nanofibers to prepare the cellulose nanofiber grafted poly (N-isopropylacrylamide-co-acrylic acid) hydrogel. Finally, the cellulose nanofiber grafted poly (N-isopropylacrylamide-co-acrylic acid)/Fe is obtained by a coprecipitation method3O4Magnetic composite hydrogel. The raw materials are reproducible and easily obtained, and the preparation method is simple and suitable for industrial production. The synthesized hydrogel has good biocompatibility and low price, and can strongly adsorb heavy metal ions in sewage.
Description
Technical Field
The invention relates to a preparation method of magnetic composite hydrogel based on cellulose nanofibers, and belongs to the technical field of polymer nanofibers.
Background
In recent years, due to the rapid development of industry and the random discharge of heavy metal ions, the pollution of water bodies gradually threatens the health of human beings. Copper ions are a common environmental pollution source and widely come from electroplating, papermaking, pesticides, herbicides and the like. It is therefore necessary to remove the copper ions from the wastewater before discharge. The existing methods for removing copper ions include adsorption, electrochemical deposition, precipitation, ion exchange, membrane filtration, electrochemical separation, reverse osmosis, and the like. The adsorption method in the above methods has the advantages of high efficiency, economy, easy operation, no by-product and the like, and gradually becomes an effective method for treating copper ions in industrial wastewater.
The hydrogel is a functional polymer material which can be quickly swelled but not dissolved in water and has a three-dimensional cross-linked network structure. The hydrogel prepared from the biological polymer has good heavy metal adsorption performance due to the fact that the hydrogel contains abundant hydroxyl, carboxyl, amino and other functional groups. Common biological macromolecules such as chitosan, gelatin, cellulose, sodium alginate and the like have the advantages of low cost and biodegradability, and are widely used in the field of environmental water treatment. However, how to increase the adsorption capacity of the biopolymer hydrogel and the subsequent recovery treatment thereof becomes the key of research.
Disclosure of Invention
The invention aims to provide a preparation method of magnetic composite hydrogel based on cellulose nanofibers.
The invention is realized by the following technical scheme:
a preparation method of magnetic composite hydrogel based on cellulose nanofibers comprises the following steps:
dissolving cellulose acetate inN,N-In a mixed solvent of dimethyl formamide and 1, 4-dioxane to obtain quenching liquid;
quenching the quenching liquid at the temperature of minus 40 to minus 10 ℃ for 2 to 3 hours, and then removing the quenching liquid by using distilled waterN,N-a mixed solvent of dimethylformamide/1, 4-dioxane to obtain cellulose acetate nanofibers;
deacetylating the cellulose acetate nano composite fibers by using an ethanol solution of sodium hydroxide to obtain cellulose nano fibers;
will be provided withN-isopropylacrylamide, acrylic acid,N, N’Dissolving methylene bisacrylamide in 1mol/L nitric acid solution to obtain reaction liquid A, dissolving ammonium ceric nitrate in 1mol/L nitric acid solution, adding vinyl modified silica and the cellulose nanofiber to obtain reaction liquid B, dropwise adding the reaction liquid A into the reaction liquid B through a constant-pressure dropping funnel, reacting at 30-60 ℃ for 2-4 hours, and then sequentially carrying out distilled water washing, Soxhlet extraction and suction filtration to obtain cellulose nanofiber graft poly (A)N-isopropylacrylamide-co-acrylic acid) hydrogel;
grafting the cellulose nanofibers with poly (A)N-isopropylacrylamide-coSoaking acrylic acid) hydrogel in a solution containing ferrous chloride and ferric chloride, adding ammonia water, and reacting for 5-10 h to obtain cellulose nanofiber graft poly (A)N-isopropylacrylamide-co-acrylic acid)/Fe3O4The magnetic composite hydrogel is the magnetic composite hydrogel based on the cellulose nano-fiber.
Preferably, in the quenching liquid, the mass fraction of cellulose acetate is 2-5%, in the mixed solvent,N, N-the mass ratio of the dimethylformamide to the 1, 4-dioxane is 6: (1-2).
Preferably, the concentration of the ethanol solution of sodium hydroxide is 0.05-0.2 mol/L.
Preferably, in the reaction solution A,N-isopropylacrylamide, acrylic acid andN, N’-methylenebisacrylamide in a mass ratio of 10: (6-10): 0.2.
preferably, in the reaction solution B, the mass ratio of the ammonium ceric nitrate to the cellulose nanofibers is 4: (1-2).
Preferably, the preparation method of the vinyl modified silica comprises the following steps:
preparing an ethanol solution of vinyl triethoxysilane and an ethanol dispersion of silicon dioxide respectively; and adding the ethanol solution of the vinyl triethoxysilane into the ethanol dispersion liquid of the silicon dioxide, carrying out ultrasonic treatment for 2 hours, and then carrying out centrifugal separation, ethanol washing and vacuum drying at 50 ℃ to obtain the vinyl modified silicon dioxide.
Preferably, the preparation method of the ethanol solution of the vinyltriethoxysilane is as follows:
dissolving vinyl triethoxysilane in anhydrous ethanol;
the preparation method of the ethanol dispersion liquid of the silicon dioxide comprises the following steps:
dispersing silicon dioxide in absolute ethyl alcohol, and uniformly dispersing.
Preferably, the molar ratio of the ferrous chloride to the ferric chloride in the solution containing the ferrous chloride and the ferric chloride is 1: 2.
Preferably, the concentration of the ammonia water is 1 mol/L.
The application of the magnetic composite hydrogel based on the cellulose nanofibers, which is obtained by the preparation method, in copper ion adsorption.
The mechanism of the invention is as follows:
the method is characterized in that natural polymer cellulose acetate with biocompatibility is used as a raw material, cellulose acetate nano-fibers are prepared by a thermally induced phase separation method, and then the cellulose acetate nano-fibers are obtained by hydrolysis. Using ammonium ceric nitrate as initiator, mixing acrylic acid with carboxyl and aminoNGrafting of isopropyl acrylamide onto cellulose acetate nanofibersPreparation of cellulose nanofiber graft poly(s) (ii)N-isopropylacrylamide-co-acrylic acid) hydrogel. Finally obtaining the cellulose nano-fiber graft poly (A) (by a coprecipitation method)N-isopropylacrylamide-co-acrylic acid)/Fe3O4Magnetic composite hydrogel.
By means of carboxyl groups on acrylic acid andNthe amino group on the isopropyl acrylamide plays an adsorption role in coordination chelation of copper ions. The high porosity and large specific surface area of the cellulose nano-fiber are utilized to improve the adsorption capacity of the cellulose nano-fiber. Using Fe on hydrogel3O4The magnetic property of the hydrogel is beneficial to recycling after the hydrogel is adsorbed. The vinyl modified silica is added to improve the porosity of the hydrogel and the swelling rate and adsorption capacity of the hydrogel.
Compared with the prior art, the invention has the following beneficial effects:
1. the cellulose nano-fiber is prepared by a thermally induced phase separation method, the process is simple, the yield is high, and the method is very suitable for industrial production;
2. will be provided withNIsopropyl acrylamide and acrylic acid are grafted to the cellulose nanofiber with biocompatibility, so that the volume size of the hydrogel is reduced, the specific surface area and the porosity are increased, and the swelling rate is greatly improved, so that the adsorption capacity of copper ions is improved;
3. the addition of the vinyl modified silicon dioxide forms a discontinuous network pore structure, so that the porosity is improved, the swelling rate is improved, and the adsorption capacity is also improved.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 cellulose nanofiber graft poly(s) (prepared in example 1 of the present invention)N-isopropylacrylamide-co-acrylic acid)/Fe3O4Scanning electron microscope images of the magnetic composite hydrogel;
FIG. 2 cellulose nanofiber graft poly(s) (prepared in example 1 of the present invention)N-isopropylacrylamide-co-COlefine acid)/Fe3O4Adsorption kinetics curve of magnetic composite hydrogel.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
1) Preparation of cellulose nanofibers
0.35 g of cellulose acetate was added to 6 gN,N-Dissolving dimethylformamide and 1 g of 1, 4-dioxane mixed solvent by magnetic stirring for 10 hours at normal temperature to obtain quenching liquid; introducing the quenching liquid into a culture dish with diameter of 7 cm, quenching the culture dish in a refrigerator precooled to-30 deg.C for 2h, rapidly placing the culture dish into cold distilled water after quenching, and removingN,N-The mixed solvent of dimethylformamide and 1, 4-dioxane was changed with distilled water every 6h for 4 times. Finally, freeze drying to obtain cellulose acetate nano-fibers; soaking the cellulose acetate nano-fiber in 0.08 mol/L NaOH/ethanol solution for 24 h, and then washing with distilled water until the pH value of the washing liquid is 7. And (5) freeze-drying to obtain the cellulose nanofiber.
2) Cellulose nanofiber graft poly(s) (ii)N-isopropylacrylamide-coAcrylic acid) preparation of hydrogels.
1 g of vinyltriethoxysilane was dissolved in 15 mL of ethanol, and 1 g of silica was ultrasonically dispersed in 10 mL of ethanol. Adding the vinyl triethoxysilane solution into the silicon dioxide mixed solution, carrying out ultrasonic treatment for 2h, carrying out centrifugal separation, washing with ethanol, and carrying out vacuum drying at 50 ℃ to obtain the vinyl modified silicon dioxide.
0.25 gNIsopropyl acrylamide, 0.16 g acrylic acid, 0.005 gN, N’Dissolving methylene bisacrylamide in 15 mL of 1mol/L nitric acid solution to obtain reaction liquid A; 0.4 g of ammonium ceric nitrate was dissolved inAdding 0.1 g of cellulose nano-fiber and 0.005 g of vinyl modified silicon dioxide into 15 mL of 1mol/L nitric acid solution to obtain reaction liquid B; dropwise adding the reaction liquid A into the reaction liquid B through a constant-pressure dropping funnel, reacting at 40 ℃ for 4 hours, washing with distilled water, soxhlet extracting with acetone, and filtering to obtain the cellulose nanofiber graft polymer (A)N-isopropylacrylamide-co-acrylic acid) hydrogel.
3) Cellulose nanofiber graft poly(s) (ii)N-isopropylacrylamide-co-acrylic acid)/Fe3O4And (3) preparing the magnetic composite hydrogel.
1 g of cellulose nanofibers was grafted with poly (A)N-isopropylacrylamide-coAcrylic acid) hydrogel is soaked in 100 mL ferrous chloride (0.2981 g) and ferric chloride (0.8106 g) solution, 20 mL 1mol/L ammonia water is added, and reaction is carried out for 6h to obtain cellulose nanofiber graft poly (A)N-isopropylacrylamide-co-acrylic acid)/Fe3O4Magnetic composite hydrogel, namely magnetic composite hydrogel based on cellulose nano-fiber.
Cellulose nanofiber graft poly(s) (ii)N-isopropylacrylamide-co-acrylic acid)/Fe3O4The diameter of the fiber in the magnetic composite hydrogel is 150 +/-65 nm, as shown in figure 1. The porosity and the specific surface area were 94.8% and 21.2 m, respectively2(ii)/g, apparent saturation magnetization of 0.021 emu/g.
50 mL of Cu with a concentration of 500 mg/L2+The solution was added to an erlenmeyer flask and pH =7.0 adjusted with NaOH or HCl. Adding 10 mg hydrogel into the above solution, shaking in constant temperature water bath at 25 deg.C for 10, 20, 50, 100, 200, 300, 400, 500, 800, 1200 and 1500 min, and filtering supernatant. Measuring Cu in solution by atomic absorption spectrometer2+Concentration, calculating Cu in the adsorbed solution2+The concentration, adsorption curve is shown in FIG. 2. Within 0-300 min, the adsorption quantity increases rapidly along with the adsorption time, the adsorption quantity gradually slows down in 300-500 min, the adsorption balance is reached after 500 min, and the fiber hydrogel can adsorb Cu2+The saturated adsorption amount of (A) was 327.20 mg/g.
Example 2
1) Preparation of cellulose nanofibers
0.16 g of cellulose acetate was added to 6 gN,N-Dissolving dimethylformamide and 1.5 g of 1, 4-dioxane mixed solvent by magnetic stirring for 10 hours at normal temperature to obtain quenching liquid; introducing the quenching liquid into a culture dish with diameter of 7 cm, quenching the culture dish in a refrigerator precooled to-20 deg.C for 2h, rapidly placing the culture dish in cold distilled water after quenching, and removingN,N-The mixed solvent of dimethylformamide and 1, 4-dioxane was changed with distilled water every 6h for 4 times. Finally, freeze drying to obtain cellulose acetate nano-fibers; soaking the cellulose acetate nano-fiber in 0.1 mol/L NaOH/ethanol solution for 24 h, and then washing with distilled water until the pH value of the washing liquid is 7. And (5) freeze-drying to obtain the cellulose nanofiber.
2) Cellulose nanofiber graft poly(s) (ii)N-isopropylacrylamide-coAcrylic acid) preparation of hydrogels.
1 g of vinyltriethoxysilane was dissolved in 15 mL of ethanol, and 1 g of silica was ultrasonically dispersed in 10 mL of ethanol. Adding the vinyl triethoxysilane solution into the silicon dioxide mixed solution, carrying out ultrasonic treatment for 2h, carrying out centrifugal separation, washing with ethanol, and carrying out vacuum drying at 50 ℃ to obtain the vinyl modified silicon dioxide.
0.25 gNIsopropyl acrylamide, 0.18 g acrylic acid, 0.005 gN, N’Dissolving methylene bisacrylamide in 15 mL of 1mol/L nitric acid solution to obtain reaction liquid A; dissolving 0.4 g of ammonium ceric nitrate in 15 mL of 1mol/L nitric acid solution, and adding 0.1 g of cellulose nanofiber and 0.005 g of vinyl modified silicon dioxide to obtain reaction liquid B; dropwise adding the reaction liquid A into the reaction liquid B through a constant-pressure dropping funnel, reacting at 45 ℃ for 3 hours, washing with distilled water, soxhlet extracting with acetone, and filtering to obtain the cellulose nanofiber graft polymer (A)N-isopropylacrylamide-co-acrylic acid) hydrogel.
3) Cellulose nanofiber graft poly(s) (ii)N-isopropylacrylamide-co-acrylic acid)/Fe3O4And (3) preparing the magnetic composite hydrogel.
1.2 g of cellulose nanofibers was grafted with poly (A)N-isopropylacrylamide-coAcrylic acid) hydrogel is soaked in 100 mL ferrous chloride (0.2981 g) and ferric chloride (0.8106 g) solution, 20 mL 1mol/L ammonia water is added, and reaction is carried out for 8 h to obtain cellulose nanofiber graft poly (A)N-isopropylacrylamide-co-acrylic acid)/Fe3O4Magnetic composite hydrogel, namely magnetic composite hydrogel based on cellulose nano-fiber.
Cellulose nanofiber graft poly(s) (ii)N-isopropylacrylamide-co-acrylic acid)/Fe3O4The diameter of the fiber in the magnetic composite hydrogel is 169 +/-68 nm. The porosity and the specific surface area were 92.8% and 20.1 m, respectively2(ii)/g, apparent saturation magnetization of 0.022 emu/g. Fibrous hydrogel to Cu2+The saturated adsorption amount of (A) was 301.78 mg/g.
Example 3
1) Preparation of cellulose nanofibers
0.25 g of cellulose acetate was added to 6 gN,N-Dissolving dimethylformamide and 1.8 g of 1, 4-dioxane mixed solvent by magnetic stirring for 10 hours at normal temperature to obtain quenching liquid; introducing the quenching liquid into a culture dish with diameter of 7 cm, quenching the culture dish in a refrigerator precooled to-20 deg.C for 2.5 h, rapidly putting the culture dish into cold distilled water after quenching, and removingN,N-The mixed solvent of dimethylformamide and 1, 4-dioxane was changed with distilled water every 6h for 4 times. Finally, freeze drying to obtain cellulose acetate nano-fibers; soaking the cellulose acetate nano-fiber in 0.15 mol/L NaOH/ethanol solution for 24 h, and then washing with distilled water until the pH value of the washing liquid is 7. And (5) freeze-drying to obtain the cellulose nanofiber.
2) Cellulose nanofiber graft poly(s) (ii)N-isopropylacrylamide-coAcrylic acid) preparation of hydrogels.
1 g of vinyltriethoxysilane was dissolved in 15 mL of ethanol, and 1 g of silica was ultrasonically dispersed in 10 mL of ethanol. Adding the vinyl triethoxysilane solution into the silicon dioxide mixed solution, carrying out ultrasonic treatment for 2h, carrying out centrifugal separation, washing with ethanol, and carrying out vacuum drying at 50 ℃ to obtain the vinyl modified silicon dioxide.
0.25 gNIsopropyl acrylamide, 0.2 g acrylic acid, 0.005 gN, N’Dissolving methylene bisacrylamide in 15 mL of 1mol/L nitric acid solution to obtain reaction liquid A; dissolving 0.4 g of ammonium ceric nitrate in 15 mL of 1mol/L nitric acid solution, and adding 0.15 g of cellulose nanofiber and 0.005 g of vinyl modified silicon dioxide to obtain reaction liquid B; dropwise adding the reaction solution A into the reaction solution B through a constant-pressure dropping funnel, reacting at 50 ℃ for 2.5 h, washing with distilled water, soxhlet extracting with acetone, and vacuum-filtering to obtain the cellulose nanofiber graft polymer (A)N-isopropylacrylamide-co-acrylic acid) hydrogel.
3) Cellulose nanofiber graft poly(s) (ii)N-isopropylacrylamide-co-acrylic acid)/Fe3O4And (3) preparing the magnetic composite hydrogel.
1.4 g of cellulose nanofibers was grafted with poly (A)N-isopropylacrylamide-coAcrylic acid) hydrogel is soaked in 100 mL ferrous chloride (0.2981 g) and ferric chloride (0.8106 g) solution, 20 mL 1mol/L ammonia water is added, and reaction is carried out for 8 h to obtain cellulose nanofiber graft poly (A)N-isopropylacrylamide-co-acrylic acid)/Fe3O4Magnetic composite hydrogel, namely magnetic composite hydrogel based on cellulose nano-fiber.
Cellulose nanofiber graft poly(s) (ii)N-isopropylacrylamide-co-acrylic acid)/Fe3O4The diameter of the fiber in the magnetic composite hydrogel is 141 +/-57 nm. The porosity and the specific surface area were 95.5% and 22.1 m, respectively2(ii)/g, apparent saturation magnetization of 0.020 emu/g. Fibrous hydrogel to Cu2+The saturated adsorption amount of (A) was 330.19 mg/g.
Example 4
1) Preparation of cellulose nanofibers
0.4 g of cellulose acetate was added to 6 gN,N-Dissolving dimethylformamide and 2 g of 1, 4-dioxane mixed solvent by magnetic stirring for 10 hours at normal temperature to obtain quenching liquid; introducing the quenching liquid into a culture dish with a diameter of 7 cm, and placing the culture dishPre-cooling to-15 deg.C, quenching in refrigerator for 3 hr, quickly placing the culture dish in cold distilled water, and removingN,N-The mixed solvent of dimethylformamide and 1, 4-dioxane was changed with distilled water every 6h for 4 times. Finally, freeze drying to obtain cellulose acetate nano-fibers; soaking the cellulose acetate nano-fiber in 0.18 mol/L NaOH/ethanol solution for 24 h, and then washing with distilled water until the pH value of the washing liquid is 7. And (5) freeze-drying to obtain the cellulose nanofiber.
2) Cellulose nanofiber graft poly(s) (ii)N-isopropylacrylamide-coAcrylic acid) preparation of hydrogels.
1 g of vinyltriethoxysilane was dissolved in 15 mL of ethanol, and 1 g of silica was ultrasonically dispersed in 10 mL of ethanol. Adding the vinyl triethoxysilane solution into the silicon dioxide mixed solution, carrying out ultrasonic treatment for 2h, carrying out centrifugal separation, washing with ethanol, and carrying out vacuum drying at 50 ℃ to obtain the vinyl modified silicon dioxide.
0.25 gNIsopropyl acrylamide, 0.25 g acrylic acid, 0.005 gN, N’Dissolving methylene bisacrylamide in 15 mL of 1mol/L nitric acid solution to obtain reaction liquid A; dissolving 0.4 g of ammonium ceric nitrate in 15 mL of 1mol/L nitric acid solution, and adding 0.18 g of cellulose nanofiber and 0.005 g of vinyl modified silicon dioxide to obtain reaction liquid B; dropwise adding the reaction solution A into the reaction solution B through a constant-pressure dropping funnel, reacting at 55 ℃ for 2.5 h, washing with distilled water, soxhlet extracting with acetone, and vacuum-filtering to obtain the cellulose nanofiber graft polymer (A)N-isopropylacrylamide-co-acrylic acid) hydrogel.
3) Cellulose nanofiber graft poly(s) (ii)N-isopropylacrylamide-co-acrylic acid)/Fe3O4And (3) preparing the magnetic composite hydrogel.
1.5 g of cellulose nanofibers was grafted with poly (A)N-isopropylacrylamide-coAcrylic acid) hydrogel is soaked in 100 mL ferrous chloride (0.2981 g) and ferric chloride (0.8106 g) solution, 20 mL 1mol/L ammonia water is added, and reaction is carried out for 10 h to obtain cellulose nanofiber graft poly (A)N-isopropylacrylamide-co-propyleneacid)/Fe3O4Magnetic composite hydrogel, namely magnetic composite hydrogel based on cellulose nano-fiber.
Cellulose nanofiber graft poly(s) (ii)N-isopropylacrylamide-co-acrylic acid)/Fe3O4The diameter of the fiber in the magnetic composite hydrogel is 151 +/-43 nm. The porosity and the specific surface area were 91.3% and 19.6 m, respectively2(ii)/g, apparent saturation magnetization of 0.024 emu/g. Fibrous hydrogel to Cu2+The saturated adsorption amount of (A) was 310.18 mg/g.
Comparative example 1
The difference from the embodiment 1 is that: step 1) dissolving cellulose acetate inN,N-In a mixed solvent of dimethyl formamide and 1, 4-dioxane, preparing a cellulose casting film by adopting a casting film forming method.
The subsequent steps are the same as example 1, and finally the cellulose casting film graft poly (A)N-isopropylacrylamide-co-acrylic acid)/Fe3O4Magnetic composite hydrogel. The hydrogel had a porosity and a specific surface area of 65.89% and 4.89 m, respectively2(ii) in terms of/g. Compared with fiber membrane hydrogel, the porosity and specific surface area are greatly reduced. Mainly because the porous structure cannot be formed like a fiber membrane hydrogel. Cast film hydrogel to Cu2+The saturated adsorption amount of (3) was 72.71.
Comparative example 2
The difference from the embodiment 1 is that: the addition amount of the vinyl-modified silica in the step 2) is 0. Finally obtaining the cellulose nano-fiber graft poly (A)N-isopropylacrylamide-co-acrylic acid)/Fe3O4Magnetic composite hydrogel.
Cellulose nanofiber graft poly(s) (ii)N-isopropylacrylamide-co-acrylic acid)/Fe3O4The diameter of the fiber in the magnetic composite hydrogel is 131 +/-31 nm. The porosity and the specific surface area were 85.12% and 15.78 m, respectively2(ii) in terms of/g. Fibrous hydrogel to Cu2+The saturated adsorption amount of (A) was 265.12 mg/g. The main purpose of adding the vinyl modified silica into the reaction system is to improve the porosity and the specific surface area of the hydrogel,thereby further improving the heavy metal adsorption capacity.
Comparative example 3
The difference from the embodiment 1 is that: the addition amount of the ferrous chloride and the ferric chloride in the step 3) is 0. Finally obtaining the cellulose nano-fiber graft poly (A)N-isopropylacrylamide-co-acrylic acid) hydrogel. The apparent saturation magnetization of this hydrogel was 0 emu/g.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (9)
1. A preparation method of magnetic composite hydrogel based on cellulose nanofibers is characterized by comprising the following steps:
dissolving cellulose acetate inN,N-In a mixed solvent of dimethyl formamide and 1, 4-dioxane to obtain quenching liquid;
quenching the quenching liquid at the temperature of minus 40 to minus 10 ℃ for 2 to 3 hours, and then removing the quenching liquid by using distilled waterN,N-A mixed solvent of dimethyl formamide and 1, 4-dioxane is adopted to obtain cellulose acetate nano-fibers;
deacetylating the cellulose acetate nano composite fibers by using an ethanol solution of sodium hydroxide to obtain cellulose nano fibers;
will be provided withN-isopropylacrylamide, acrylic acid,N, N’Dissolving methylene bisacrylamide in 1mol/L nitric acid solution to obtain reaction liquid A, dissolving ammonium ceric nitrate in 1mol/L nitric acid solution, adding vinyl modified silica and the cellulose nanofiber to obtain reaction liquid B, dropwise adding the reaction liquid A into the reaction liquid B through a constant-pressure dropping funnel, reacting at 30-60 ℃ for 2-4 hours, and then sequentially carrying out distilled water washing, Soxhlet extraction and suction filtration to obtain cellulose nanofiber graft poly (A)N-isopropylacrylamide-co-acrylic acid) hydrogel;
grafting the cellulose nanofibers with poly (A)N-isopropylacrylamide-coSoaking acrylic acid) hydrogel in a solution containing ferrous chloride and ferric chloride, adding ammonia water, and reacting for 5-10 h to obtain cellulose nanofiber graft poly (A)N-isopropylacrylamide-co-acrylic acid)/Fe3O4Magnetic composite hydrogel, namely the magnetic composite hydrogel based on the cellulose nano-fiber;
the preparation method of the vinyl modified silicon dioxide comprises the following steps:
preparing an ethanol solution of vinyl triethoxysilane and an ethanol dispersion of silicon dioxide respectively; and adding the ethanol solution of the vinyl triethoxysilane into the ethanol dispersion liquid of the silicon dioxide, carrying out ultrasonic treatment for 2 hours, and then carrying out centrifugal separation, ethanol washing and vacuum drying at 50 ℃ to obtain the vinyl modified silicon dioxide.
2. The method for preparing the magnetic composite hydrogel based on the cellulose nanofibers according to claim 1, wherein in the quenching liquid, the mass fraction of cellulose acetate is 2-5%, and in the mixed solvent,N,N-the mass ratio of the dimethylformamide to the 1, 4-dioxane is 6: (1-2).
3. The method for preparing the cellulose nanofiber-based magnetic composite hydrogel according to claim 1, wherein the concentration of the ethanol solution of sodium hydroxide is 0.05-0.2 mol/L.
4. The method for preparing magnetic composite hydrogel based on cellulose nanofibers according to claim 1, wherein in the reaction solution A,N-isopropylacrylamide, acrylic acid andN, N’-methylenebisacrylamide in a mass ratio of 10: (6-10): 0.2.
5. the method for preparing the magnetic composite hydrogel based on the cellulose nanofibers according to claim 1, wherein the mass ratio of ammonium ceric nitrate to the cellulose nanofibers in the reaction solution B is 4: (1-2).
6. The method for preparing the magnetic composite hydrogel based on the cellulose nanofibers according to claim 1, wherein the method for preparing the ethanol solution of vinyltriethoxysilane is as follows:
dissolving vinyl triethoxysilane in anhydrous ethanol;
the preparation method of the ethanol dispersion liquid of the silicon dioxide comprises the following steps:
dispersing silicon dioxide in absolute ethyl alcohol, and uniformly dispersing.
7. The method for preparing the magnetic composite hydrogel based on the cellulose nanofibers according to claim 1, wherein the molar ratio of the ferrous chloride to the ferric chloride in the solution containing the ferrous chloride and the ferric chloride is 1: 2.
8. The method for preparing the magnetic composite hydrogel based on the cellulose nanofibers according to claim 1, wherein the concentration of the aqueous ammonia is 1 mol/L.
9. Use of the magnetic composite hydrogel based on cellulose nanofibers obtained by the preparation method of any one of claims 1-8 in copper ion adsorption.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811108173.XA CN109295713B (en) | 2018-09-21 | 2018-09-21 | Preparation method and application of magnetic composite hydrogel based on cellulose nanofibers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811108173.XA CN109295713B (en) | 2018-09-21 | 2018-09-21 | Preparation method and application of magnetic composite hydrogel based on cellulose nanofibers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109295713A CN109295713A (en) | 2019-02-01 |
| CN109295713B true CN109295713B (en) | 2020-12-15 |
Family
ID=65163745
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811108173.XA Expired - Fee Related CN109295713B (en) | 2018-09-21 | 2018-09-21 | Preparation method and application of magnetic composite hydrogel based on cellulose nanofibers |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109295713B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110117380B (en) * | 2019-04-28 | 2021-10-12 | 晋江瑞碧科技有限公司 | preparation method and application of pH-responsive magnetic polystyrene porous microspheres |
| CN110229383B (en) * | 2019-06-19 | 2021-10-22 | 安徽农业大学 | Magnetic aerogel based on bisamidoxime cellulose/sodium alginate and preparation and application thereof |
| CN110560015A (en) * | 2019-08-23 | 2019-12-13 | 魏旭榕 | nano hydrated oxidized metal composite hydrogel and application of nano hydrated oxidized metal composite hydrogel in sewage treatment |
| CN110423363B (en) * | 2019-09-17 | 2022-02-08 | 安徽农业大学 | Preparation method and application of high-strength ultrahigh-elasticity hydrogel |
| CN110903432B (en) * | 2019-11-08 | 2021-05-18 | 上海交通大学 | Preparation of photo-thermal response drug sustained-release hydrogel based on magnetic cellulose nanocrystal |
| CN111841502B (en) * | 2020-07-10 | 2022-10-28 | 天津市武清区疾病预防控制中心 | Cellulose composite adsorption material and preparation method and application thereof |
| CN111877019B (en) * | 2020-08-06 | 2022-11-18 | 晋江瑞碧科技有限公司 | Preparation method of conductive hydrogel |
| CN112142993B (en) * | 2020-09-27 | 2022-04-01 | 中国林业科学研究院林产化学工业研究所 | Preparation method of high-toughness low-swelling cellulose-based magnetic double-network hydrogel |
| CN114747714A (en) * | 2021-01-11 | 2022-07-15 | 天津科技大学 | Preparation method of novel plant-derived slow-release antibacterial magnetic aerogel |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101935070A (en) * | 2010-09-17 | 2011-01-05 | 东华大学 | Method for synthesizing superparamagnetic ferroferric oxide nano particle in situ by induction of acrylic acid polymer nano hydrogel |
| CN103724633A (en) * | 2012-10-15 | 2014-04-16 | 中国科学院兰州化学物理研究所 | Granular hydrogel |
| CN104941610A (en) * | 2015-06-09 | 2015-09-30 | 西安交通大学 | Preparation and application of magnetic hydrogel loaded with one-dimensional Fe3O4 nanocrystals |
-
2018
- 2018-09-21 CN CN201811108173.XA patent/CN109295713B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101935070A (en) * | 2010-09-17 | 2011-01-05 | 东华大学 | Method for synthesizing superparamagnetic ferroferric oxide nano particle in situ by induction of acrylic acid polymer nano hydrogel |
| CN103724633A (en) * | 2012-10-15 | 2014-04-16 | 中国科学院兰州化学物理研究所 | Granular hydrogel |
| CN104941610A (en) * | 2015-06-09 | 2015-09-30 | 西安交通大学 | Preparation and application of magnetic hydrogel loaded with one-dimensional Fe3O4 nanocrystals |
Non-Patent Citations (3)
| Title |
|---|
| 单一热致相分离法制备聚乳酸纳米纤维大孔支架;郑雄飞等;《功能材料》;20100620;第184-188页 * |
| 热致相分离制备聚乳酸纳米纤维支架;刘淑琼等;《高等学校化学学报》;20110210(第02期);第372-378页 * |
| 热致相分离法制备聚乳酸/聚己内酯多孔支架材料;李凯娜等;《福建师范大学学报(自然科学版)》;20121120(第06期);第76-80页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109295713A (en) | 2019-02-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109295713B (en) | Preparation method and application of magnetic composite hydrogel based on cellulose nanofibers | |
| Liu et al. | Rapid and efficient removal of heavy metal and cationic dye by carboxylate-rich magnetic chitosan flocculants: role of ionic groups | |
| CN109364889B (en) | Preparation method and application of temperature-sensitive hydrogel | |
| Urbina et al. | Design of reusable novel membranes based on bacterial cellulose and chitosan for the filtration of copper in wastewaters | |
| Ngah et al. | Removal of copper (II) ions from aqueous solution onto chitosan and cross-linked chitosan beads | |
| Wu et al. | Facile preparation of magnetic sodium alginate/carboxymethyl cellulose composite hydrogel for removal of heavy metal ions from aqueous solution | |
| Wang et al. | Collagen/cellulose hydrogel beads reconstituted from ionic liquid solution for Cu (II) adsorption | |
| Kwak et al. | Preparation of bead-type biosorbent from water-soluble Spirulina platensis extracts for chromium (VI) removal | |
| Türkmen et al. | Heavy metal ions removal from wastewater using cryogels: A review | |
| Zhou et al. | Mechanisms of lead biosorption on cellulose/chitin beads | |
| CN108993452B (en) | Preparation method of magnetic composite hydrogel for copper ion adsorption | |
| CN109295716B (en) | Preparation method of magnetic and thermal synergistic stimulation response hydrogel | |
| Zhang et al. | A novel Cu (II) ion-imprinted alginate–chitosan complex adsorbent for selective separation of Cu (II) from aqueous solution | |
| CN109261138A (en) | It is a kind of for heavy metal ion adsorbed ultrabranching polyamide modified sodium alginate microballoon and preparation method thereof | |
| Rostamian et al. | Preparation and neutralization of forcespun chitosan nanofibers from shrimp shell waste and study on its uranium adsorption in aqueous media | |
| Romal et al. | Marine polysaccharide-based hydrogels for critical materials selective removal and recovery: A review | |
| CN108658193A (en) | A kind of preparation method of novel magnetic flocculant | |
| Li et al. | Preparation of green magnetic hydrogel from cellulose nanofibril (CNF) originated from soybean residue for effective and rapid removal of copper ions from waste water | |
| CN113908815A (en) | High-molecular modified adsorbent and preparation method and application thereof | |
| Yuan et al. | Facile preparation of EDTA-functionalized magnetic chitosan for removal of co (II) from aqueous solutions | |
| Gao et al. | Preparation of PSSS‐grafted polysulfone microfiltration membrane and its rejection and removal properties towards heavy metal ions | |
| Jia et al. | Synthesis and investigation of the imprinting efficiency of ion imprinted nanoparticles for recognizing copper | |
| KR102118413B1 (en) | Polyethyleneimine-grafted nanocellulose shaped body, preparation thereof, andselective adsorbent using the same for platinum group metals | |
| CN113209942A (en) | Cellulose-based heavy metal composite adsorption material and preparation method thereof | |
| CN110115985B (en) | Cyclodextrin-based cross-linked polymer adsorption material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20201215 |