CN109364889A - A kind of preparation method and its usage of temperature-sensitive hydrogel - Google Patents
A kind of preparation method and its usage of temperature-sensitive hydrogel Download PDFInfo
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- CN109364889A CN109364889A CN201811214515.6A CN201811214515A CN109364889A CN 109364889 A CN109364889 A CN 109364889A CN 201811214515 A CN201811214515 A CN 201811214515A CN 109364889 A CN109364889 A CN 109364889A
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- hydrogel
- fibrous
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- temperature
- cellulose nano
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- 239000000017 hydrogel Substances 0.000 title claims abstract description 102
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 229920002678 cellulose Polymers 0.000 claims abstract description 56
- 239000001913 cellulose Substances 0.000 claims abstract description 56
- 239000002121 nanofiber Substances 0.000 claims abstract description 37
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims abstract description 28
- 229920002301 cellulose acetate Polymers 0.000 claims abstract description 22
- 239000002131 composite material Substances 0.000 claims abstract description 19
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 71
- 238000006243 chemical reaction Methods 0.000 claims description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 37
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 25
- 239000000377 silicon dioxide Substances 0.000 claims description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 22
- 229910001385 heavy metal Inorganic materials 0.000 claims description 21
- 229920002554 vinyl polymer Polymers 0.000 claims description 19
- 235000019441 ethanol Nutrition 0.000 claims description 18
- -1 vinyl silica Chemical compound 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims description 12
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 11
- 150000002500 ions Chemical class 0.000 claims description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 11
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 10
- 238000010521 absorption reaction Methods 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 8
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 238000000944 Soxhlet extraction Methods 0.000 claims description 6
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 6
- 238000010791 quenching Methods 0.000 claims description 6
- 230000000171 quenching effect Effects 0.000 claims description 6
- 150000008065 acid anhydrides Chemical class 0.000 claims description 5
- 238000005660 chlorination reaction Methods 0.000 claims description 5
- 239000002070 nanowire Substances 0.000 claims description 5
- 229910001431 copper ion Inorganic materials 0.000 claims description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims 1
- 239000011976 maleic acid Substances 0.000 claims 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 12
- 230000008901 benefit Effects 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 description 20
- 239000000835 fiber Substances 0.000 description 12
- 239000010949 copper Substances 0.000 description 8
- 238000004108 freeze drying Methods 0.000 description 8
- 229920006395 saturated elastomer Polymers 0.000 description 7
- 239000003463 adsorbent Substances 0.000 description 6
- 230000008878 coupling Effects 0.000 description 6
- 238000010168 coupling process Methods 0.000 description 6
- 238000005859 coupling reaction Methods 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000008961 swelling Effects 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229920006221 acetate fiber Polymers 0.000 description 4
- 238000005266 casting Methods 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 238000007710 freezing Methods 0.000 description 4
- 230000008014 freezing Effects 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 230000005415 magnetization Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 210000002966 serum Anatomy 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 229920005615 natural polymer Polymers 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000011953 bioanalysis Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000009514 concussion Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229940056319 ferrosoferric oxide Drugs 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229920003213 poly(N-isopropyl acrylamide) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- 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
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0052—Preparation of gels
- B01J13/0065—Preparation of gels containing an organic phase
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/264—Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
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- 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
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- 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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- 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
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- 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
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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- 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
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- 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
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- 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
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- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
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- Environmental & Geological Engineering (AREA)
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Abstract
The invention discloses a kind of preparation methods of temperature-sensitive hydrogel comprising following steps: preparing cellulose acetate nanofiber；The cellulose acetate nanofiber is carried out with lye deacetylated, obtained cellulose nano-fibrous；Cellulose nano-fibrous poly- (n-isopropyl acrylamide-co- maleic anhydride) hydrogel of cellulose nano-fibrous grafting is prepared using described；Cellulose nano-fibrous poly- (n-isopropyl acrylamide-co- maleic anhydride) hydrogel of grafting is immersed in the mixed solution of frerrous chloride and iron chloride, ammonium hydroxide is added to be reacted, cellulose nano-fibrous poly- (n-isopropyl acrylamide-co- the maleic anhydride)/Fe of grafting is obtained3O4Magnetic Nano fiber composite hydrogel, i.e., the described temperature-sensitive hydrogel.Compared with prior art, the present invention has following the utility model has the advantages that the present invention prepare cellulose nano-fibrous by Thermal inactive method, and simple process, yield height are very suitable for industrialized production.
Description
Technical field
The present invention relates to a kind of preparation methods of temperature-sensitive hydrogel, belong to porous adsorbing material technical field.
Background technique
Heavy metal refers to that density is greater than 4.5m2The metallic element of/g, such as Cu, Ag, Cr, Pb metal.Heavy metal ion master
It to be discharged into water by Chemical Manufacture, fertilizer and pesticide, sanitary wastewater and mining etc., when the concentration of heavy metal ion in water is super
When crossing the self-purification capacity of water body, heavy metal pollution of water body is resulted in.With the fast development of industry and agricultural, a large amount of heavy metal
Discharge of wastewater, heavy metal pollution have become one of environmental pollution damage maximum.Heavy metal is not easy to be degraded under field conditions (factors), and
It is enriched in human body by food chain, domestic heavy metal water contamination accident takes place frequently nearly ten years, solves heavy metal pollution problem and carves
Do not allow to delay.Chemical method, such as chemical precipitation method, oxidation-reduction method are mainly passed through to the pollution of heavy metal at present；Bioanalysis, such as plant
Weight repairing method, biosorption process and bio-flocculation process；Physical method, such as partition method, ion-exchange and absorption method.Absorption method due to
The advantages that adsorbent abundance, cheap, large amount of adsorption, treatment effeciency are high, simple and easy to operate and without secondary pollution, it is wide
The general processing applied to effluent containing heavy metal ions.Common adsorbent comes with some shortcomings in terms of selectivity and recycling.
The adsorbent studied at present is attempted to combine a variety of adsorbent materials by physical doping or chemical connection process, utilizes each material
Structural advantage, preparation have high-adsorption-capacity, strong adaptability and the adsorbent material convenient for recycling.
Hydrogel is that a kind of hydrophilic polymer is intertwine with each other by being physically or chemically crosslinked, and forms three-dimensional net structure
Solid material, hole of the water as decentralized medium filling whole network structure.Hydrogel has three-dimensional net structure as one kind
High molecular material, had its unique advantages in terms of removing removing heavy metals.Progress in Intelligent Hydrogel to environmental stimuli (such as: temperature,
PH, ionic strength, electric field strength etc.), there is responsiveness, therefore using progress in Intelligent Hydrogel as adsorbent, it can be outer by changing
Boundary's environment regulates and controls hydrogel to the adsorption process of heavy metal ion, or according to the specific response of hydrogel to heavy metal ion
It is identified.
Natural polymer hydrogel has abundance, and inexpensive and good biocompatibility is widely used in hydrogel system
It is standby, but its stability is poor, therefore the modes such as natural polymer and the polymer blended or graft copolymerization of synthesis are often improved water-setting
Glue actual requirement.However most of natural polymer is powdered, blocky or membrane structure, porosity is low, specific surface area is small, connects
Branch is modified, however it remains the problems such as porosity is low, specific surface area is small, therefore it is low to the adsorption capacity of heavy metal ion.Why
The adsorption capacity that sample improves heavy metal ion becomes critical issue urgently to be solved.
Summary of the invention
The object of the present invention is to provide a kind of preparation method and its usages of temperature-sensitive hydrogel.The present invention is by following
What technical solution was realized:
A kind of preparation method of temperature-sensitive hydrogel comprising following steps:
Prepare cellulose acetate nanofiber；
The cellulose acetate nanofiber is carried out with lye deacetylated, obtained cellulose nano-fibrous；
Cellulose nano-fibrous poly- (n-isopropyl acrylamide-co- the horse of cellulose nano-fibrous grafting is prepared using described
Carry out acid anhydrides) hydrogel；
By the cellulose nano-fibrous poly- (N of grafting-N-isopropylacrylamide-co- maleic anhydride) hydrogel is immersed in
In the mixed solution of frerrous chloride and iron chloride, ammonium hydroxide is added and is reacted, obtains cellulose nano-fibrous poly- (the N- isopropyl of grafting
Base acrylamide-co- maleic anhydride)/Fe3O4Magnetic Nano fiber composite hydrogel, i.e., the described temperature-sensitive hydrogel.
Preferably, the cellulose acetate nanofiber the preparation method comprises the following steps:
Cellulose acetate is dissolved in tetrahydrofuran and N, the in the mixed solvent of N '-dimethyl formamide obtains quenching liquid,
After the quenching liquid is quenched at -30~-15 DEG C, it is washed with distilled water and removes tetrahydrofuran and N, N '-dimethyl first
Amide, the cellulose acetate nanofiber being freeze-dried.
Preferably, in the quenching liquid, cellulose acetate, tetrahydrofuran and N, the weight of N '-dimethyl formamide
Measuring number is respectively 0.2~0.5 part, 1~3 part, 5~10 parts.
Preferably, the lye is the ethanol solution of NaOH, and wherein the concentration of NaOH is 0.1~0.2mol/L.
Preferably, cellulose nano-fibrous poly- (n-isopropyl acrylamide-co- maleic anhydride) water of grafting
Gel the preparation method comprises the following steps:
By n-isopropyl acrylamide, maleic anhydride, N, N '-methylene-bisacrylamide is dissolved in nitric acid solution, obtains
To reaction solution A；
Ammonium ceric nitrate is dissolved in nitric acid solution, modified by vinyl silica and the cellulose Nanowire is added
Dimension, obtains reaction solution B；
Reaction solution A is added dropwise in reaction solution B by constant pressure funnel, after being reacted at 30~60 DEG C, according to
Secondary adopt is washed with distilled water, and using acetone Soxhlet extraction, filters, and obtains cellulose nano-fibrous poly- (the N- isopropyl propylene of grafting
Amide-co- maleic anhydride) hydrogel.
Preferably, in the reaction solution A: n-isopropyl acrylamide, maleic anhydride, N, N '-di-2-ethylhexylphosphine oxide third
The parts by weight of acrylamide are respectively 5~10 parts, 2~3 parts, 0.05~0.1 part；In the reaction solution B: ammonium ceric nitrate, fiber
Plain nanofiber, modified by vinyl silica parts by weight be respectively 1~3 part, 2~6 parts, 0.2~0.5 part.
Preferably, the modified by vinyl silica the preparation method comprises the following steps: by vinyltriethoxysilane
With silicon dioxde reaction, modified by vinyl silica is obtained.
Preferably, in the mixed solution of the frerrous chloride and iron chloride, mole of frerrous chloride and iron chloride
Than for 1:2；The concentration of the ammonium hydroxide is 1mol/L.
A kind of purposes of the temperature-sensitive hydrogel obtained by aforementioned preparation process in heavy metal ion adsorbed.
Preferably, the heavy metal ion is copper ion.
Mechanism of the invention is:
It is prepared by Thermal inactive method cellulose nano-fibrous.By free radical polymerization, by N- isopropyl third
In acrylamide and maleic anhydride to cellulose chain.It is compound will to have magnetic ferroso-ferric oxide finally by coprecipitation method
Onto hydrogel.
Using in n-isopropyl acrylamide amino and maleic anhydride hydrolysis after the coordination of the carboxyl that generates to copper ion
Chelating plays suction-operated.Using cellulose nano-fibrous high porosity and bigger serface, its adsorption capacity is improved.It utilizes
Fe on hydrogel3O4Magnetism, be conducive to hydrogel absorption after recycling.The addition of modified by vinyl silica
In order to improve the porosity of hydrogel, its swelling ratio and adsorption capacity are improved.
Compared with prior art, the present invention have it is following the utility model has the advantages that
1, n-isopropyl acrylamide and maleic anhydride are grafted on cellulose nano-fibrous with biocompatibility,
The volume size for reducing hydrogel increases specific surface area and porosity, and swelling ratio greatly improves, to improve copper ion
Adsorption capacity；
2, the addition of modified by vinyl silica forms discrete network pore structure, and porosity improves, swelling ratio
It improves, adsorption capacity also increases accordingly；
3, by Thermal inactive method prepare it is cellulose nano-fibrous, simple process, yield height, be very suitable for industry
Metaplasia produces.
Detailed description of the invention
Upon reading the detailed description of non-limiting embodiments with reference to the following drawings, other feature of the invention,
Objects and advantages will become more apparent upon:
Poly- (the Malaysia n-isopropyl acrylamide-co- of cellulose nano-fibrous grafting that in Fig. 1 present invention prepared by embodiment 1
Acid anhydrides)/Fe3O4Magnetic coupling hydrogel scanning electron microscope (SEM) photograph；
Poly- (the Malaysia n-isopropyl acrylamide-co- of cellulose nano-fibrous grafting that in Fig. 2 present invention prepared by embodiment 1
Acid anhydrides)/Fe3O4The relationship of magnetic coupling hydrogel temperature and swelling ratio；
Poly- (the Malaysia n-isopropyl acrylamide-co- of cellulose nano-fibrous grafting that in Fig. 3 present invention prepared by embodiment 1
Acid anhydrides)/Fe3O4The curve of adsorption kinetics of magnetic coupling hydrogel.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection scope.
Embodiment 1
1) cellulose nano-fibrous preparation
By 1g tetrahydrofuran and 10g N, N '-dimethyl formamide is added in serum bottle, rear to be added 0.3g acetate fiber
Element, stirring and dissolving form clear transparent solutions.Solution is poured into culture dish, refrigerator freezing handles 3h at -20 DEG C.After
It takes out, is put into mixture of ice and water, every 6h changes primary distilled water, changes 4 times.Finally freeze-drying obtains cellulose acetate Nanowire
Dimension；Cellulose acetate nanofiber is immersed in the NaOH/ ethanol solution of 0.1mol/L for 24 hours, after be washed with distilled water, until
Cleaning solution pH value is 7.Freeze-drying obtains cellulose nano-fibrous.
2) preparation of cellulose nano-fibrous poly- (n-isopropyl acrylamide-co- maleic anhydride) hydrogel of grafting.
1g vinyltriethoxysilane is dissolved in 15mL ethyl alcohol, by 1g silica ultrasonic disperse 10mL second
In alcohol.Vinyltriethoxysilane solution is added in silica mixed solution, 2h is ultrasonically treated, centrifuge separation, ethyl alcohol are washed
It washs, 50 DEG C of vacuum drying obtain modified by vinyl silica.
By 0.6g n-isopropyl acrylamide, 0.2g maleic anhydride, the dissolution of 0.008g N, N '-methylene-bisacrylamide
In 15mL 1mol/L nitric acid solution, reaction solution A is obtained；0.1g ammonium ceric nitrate is dissolved in 15mL 1mol/L nitric acid solution
In, it is added that 0.2g is cellulose nano-fibrous and 0.03g modified by vinyl silica, obtains reaction solution B；It is leaked by constant pressure addition
Bucket reaction solution A is added dropwise in reaction solution B, 50 DEG C of reaction temperature, reaction 4h, distillation water washing, using acetone Soxhlet extraction,
It filters, obtains cellulose nano-fibrous poly- (n-isopropyl acrylamide-co- maleic anhydride) hydrogel of grafting, be abbreviated as Cell-
G-P (NIPAm-co-MA) nanofiber hydrogels.
3)Cell-g-P(NIPAm-co-MA)/Fe3O4The preparation of magnetic Nano fiber composite hydrogel.
0.3g Cell-g-P (NIPAm-co-MA) hydrogel is immersed in 100mL frerrous chloride (0.0852g) and chlorination
In iron (0.2316g) solution, 10mL 1mol/L ammonium hydroxide is added, reacts 9h, obtains Cell-g-P (NIPAm-co-MA)/Fe3O4Magnetic
Property nanofiber composite hydrogel, that is, be used for copper absorption temperature-sensitive hydrogel.
Cell-g-P(NIPAm-co-MA)/Fe3O4Scanning electron microscope (SEM) photograph such as Fig. 1 institute of magnetic Nano fiber composite hydrogel
Show, porous fibrous structure is presented in hydrogel, and fibre diameter is 178 ± 100nm, and the porosity and specific surface area of hydrogel are distinguished
For 93.8% and 24.4m2/ g, intensity of magnetization 0.022emu/g.Fig. 2 is Cell-g-P (NIPAm-co-MA)/Fe3O4Magnetism is received
Rice fiber composite swelling behavior ratio varies with temperature curve, Cell-g-P (NIPAm-co-MA)/Fe3O4Magnetic Nano fiber is multiple
Heshui gel starts quick dehydration at 28 DEG C, and about 40 DEG C reach balance, and it is sensitive special good temperature nearby occur at 36.2 DEG C
Property.
The Cu for being 500mg/L by 50mL concentration2+Solution is added in conical flask, adjusts pH=7.0 with NaOH or HCl.It will
10mg hydrogel is added in above-mentioned solution, 25 DEG C, respectively water bath with thermostatic control concussion 10,20,50,100,200,300,400,500,
800, after 1200 and 1500min, supernatant liquor is taken to filter.Using Cu in Atomic Absorption Spectrometer measurement solution2+Concentration is calculated and is inhaled
Cu in attached solution2+Concentration, adsorption curve are as shown in Figure 3.In 0-300min, adsorbance is sharply increased with adsorption time,
300-500min adsorbance gradually eases up, and adsorption equilibrium is reached after 500min, fiber hydrogel is to Cu2+Saturated extent of adsorption reach
390.2mg/g。
Embodiment 2
1) cellulose nano-fibrous preparation
By 2g tetrahydrofuran and 8g N, N '-dimethyl formamide is added in serum bottle, rear to be added 0.2g acetate fiber
Element, stirring and dissolving form clear transparent solutions.Solution is poured into culture dish, refrigerator freezing handles 2.5h at -25 DEG C.Terminate
After take out, be put into mixture of ice and water, every 6h changes primary distilled water, changes 4 times.Finally freeze-drying obtains cellulose acetate nanometer
Fiber；Cellulose acetate nanofiber is immersed in the NaOH/ ethanol solution of 0.15mol/L for 24 hours, after be washed with distilled water,
Until cleaning solution pH value is 7.Freeze-drying obtains cellulose nano-fibrous.
2) preparation of cellulose nano-fibrous poly- (n-isopropyl acrylamide-co- maleic anhydride) hydrogel of grafting.
1g vinyltriethoxysilane is dissolved in 15mL ethyl alcohol, by 1g silica ultrasonic disperse 10mL second
In alcohol.Vinyltriethoxysilane solution is added in silica mixed solution, 2h is ultrasonically treated, centrifuge separation, ethyl alcohol are washed
It washs, 50 DEG C of vacuum drying obtain modified by vinyl silica.
By 0.4g n-isopropyl acrylamide, 0.28g maleic anhydride, the dissolution of 0.01g N, N '-methylene-bisacrylamide
In 15mL 1mol/L nitric acid solution, reaction solution A is obtained；0.3g ammonium ceric nitrate is dissolved in 15mL 1mol/L nitric acid solution
In, it is added that 0.3g is cellulose nano-fibrous and 0.04g modified by vinyl silica, obtains reaction solution B；It is leaked by constant pressure addition
Bucket reaction solution A is added dropwise in reaction solution B, 45 DEG C of reaction temperature, reaction 3h, distillation water washing, using acetone Soxhlet extraction,
It filters, obtains cellulose nano-fibrous poly- (n-isopropyl acrylamide-co- maleic anhydride) hydrogel of grafting, be abbreviated as Cell-
G-P (NIPAm-co-MA) nanofiber hydrogels.
3)Cell-g-P(NIPAm-co-MA)/Fe3O4The preparation of magnetic Nano fiber composite hydrogel.
0.3g Cell-g-P (NIPAm-co-MA) hydrogel is immersed in 100mL frerrous chloride (0.0852g) and chlorination
In iron (0.2316g) solution, 10mL 1mol/L ammonium hydroxide is added, reacts 6h, obtains Cell-g-P (NIPAm-co-MA)/Fe3O4Magnetic
Property nanofiber composite hydrogel, that is, be used for copper absorption temperature-sensitive hydrogel.
Cell-g-P(NIPAm-co-MA)/Fe3O4In magnetic Nano fiber composite hydrogel fibre diameter be 170 ±
70nm, the porosity and specific surface area of hydrogel are respectively 91.8% and 26.1m2/ g, intensity of magnetization 0.024emu/g.
Cell-g-P(NIPAm-co-MA)/Fe3O4Magnetic Nano fiber composite hydrogel is to Cu2+Saturated extent of adsorption reach
410.1mg/g。
Embodiment 3
1) cellulose nano-fibrous preparation
By 3g tetrahydrofuran and 7g N, N '-dimethyl formamide is added in serum bottle, rear to be added 0.3g acetate fiber
Element, stirring and dissolving form clear transparent solutions.Solution is poured into culture dish, refrigerator freezing handles 3h at -20 DEG C.After
It takes out, is put into mixture of ice and water, every 6h changes primary distilled water, changes 4 times.Finally freeze-drying obtains cellulose acetate Nanowire
Dimension；Cellulose acetate nanofiber is immersed in the NaOH/ ethanol solution of 0.15mol/L for 24 hours, after be washed with distilled water, directly
It is 7 to cleaning solution pH value.Freeze-drying obtains cellulose nano-fibrous.
2) preparation of cellulose nano-fibrous poly- (n-isopropyl acrylamide-co- maleic anhydride) hydrogel of grafting.
1g vinyltriethoxysilane is dissolved in 15mL ethyl alcohol, by 1g silica ultrasonic disperse 10mL second
In alcohol.Vinyltriethoxysilane solution is added in silica mixed solution, 2h is ultrasonically treated, centrifuge separation, ethyl alcohol are washed
It washs, 50 DEG C of vacuum drying obtain modified by vinyl silica.
0.5g n-isopropyl acrylamide, 0.25g maleic anhydride, 0.008g N, N '-methylene-bisacrylamide is molten
Solution obtains reaction solution A in 15mL 1mol/L nitric acid solution；0.2g ammonium ceric nitrate is dissolved in 15mL 1mol/L nitric acid solution
In, it is added that 0.5g is cellulose nano-fibrous and 0.05g modified by vinyl silica, obtains reaction solution B；It is leaked by constant pressure addition
Bucket reaction solution A is added dropwise in reaction solution B, 40 DEG C of reaction temperature, reaction 3h, distillation water washing, using acetone Soxhlet extraction,
It filters, obtains cellulose nano-fibrous poly- (n-isopropyl acrylamide-co- maleic anhydride) hydrogel of grafting, be abbreviated as Cell-
G-P (NIPAm-co-MA) nanofiber hydrogels.
3)Cell-g-P(NIPAm-co-MA)/Fe3O4The preparation of magnetic Nano fiber composite hydrogel.
0.4g Cell-g-P (NIPAm-co-MA) hydrogel is immersed in 100mL frerrous chloride (0.0852g) and chlorination
In iron (0.2316g) solution, 10mL 1mol/L ammonium hydroxide is added, reacts 6h, obtains Cell-g-P (NIPAm-co-MA)/Fe3O4Magnetic
Property nanofiber composite hydrogel, that is, be used for copper absorption temperature-sensitive hydrogel.
Cell-g-P(NIPAm-co-MA)/Fe3O4In magnetic Nano fiber composite hydrogel fibre diameter be 189 ±
90nm, the porosity and specific surface area of hydrogel are respectively 92.1% and 23.1m2/ g, intensity of magnetization 0.020emu/g.
Cell-g-P(NIPAm-co-MA)/Fe3O4Magnetic Nano fiber composite hydrogel is to Cu2+Saturated extent of adsorption reach
380.1mg/g。
Embodiment 4
1) cellulose nano-fibrous preparation
By 2g tetrahydrofuran and 8g N, N '-dimethyl formamide is added in serum bottle, rear to be added 0.45g acetate fiber
Element, stirring and dissolving form clear transparent solutions.Solution is poured into culture dish, refrigerator freezing handles 3h at -15 DEG C.After
It takes out, is put into mixture of ice and water, every 6h changes primary distilled water, changes 4 times.Finally freeze-drying obtains cellulose acetate Nanowire
Dimension；Cellulose acetate nanofiber is immersed in the NaOH/ ethanol solution of 0.2mol/L for 24 hours, after be washed with distilled water, until
Cleaning solution pH value is 7.Freeze-drying obtains cellulose nano-fibrous.
2) preparation of cellulose nano-fibrous poly- (n-isopropyl acrylamide-co- maleic anhydride) hydrogel of grafting.
1g vinyltriethoxysilane is dissolved in 15mL ethyl alcohol, by 1g silica ultrasonic disperse 10mL second
In alcohol.Vinyltriethoxysilane solution is added in silica mixed solution, 2h is ultrasonically treated, centrifuge separation, ethyl alcohol are washed
It washs, 50 DEG C of vacuum drying obtain modified by vinyl silica.
By 0.7g n-isopropyl acrylamide, 0.2g maleic anhydride, the dissolution of 0.005g N, N '-methylene-bisacrylamide
In 15mL 1mol/L nitric acid solution, reaction solution A is obtained；0.2g ammonium ceric nitrate is dissolved in 15mL1mol/L nitric acid solution,
It is added that 0.4g is cellulose nano-fibrous and 0.02g modified by vinyl silica, obtains reaction solution B；Pass through constant pressure funnel
Reaction solution A is added dropwise in reaction solution B, 40 DEG C of reaction temperature, reaction 4h distill water washing, using acetone Soxhlet extraction, pumping
Filter obtains cellulose nano-fibrous poly- (n-isopropyl acrylamide-co- maleic anhydride) hydrogel of grafting, is abbreviated as Cell-g-
P (NIPAm-co-MA) nanofiber hydrogels.
3)Cell-g-P(NIPAm-co-MA)/Fe3O4The preparation of magnetic Nano fiber composite hydrogel.
0.2g Cell-g-P (NIPAm-co-MA) hydrogel is immersed in 100mL frerrous chloride (0.0852g) and chlorination
In iron (0.2316g) solution, 10mL 1mol/L ammonium hydroxide is added, reacts 8h, obtains Cell-g-P (NIPAm-co-MA)/Fe3O4Magnetic
Property nanofiber composite hydrogel, that is, be used for copper absorption temperature-sensitive hydrogel.
Cell-g-P(NIPAm-co-MA)/Fe3O4In magnetic Nano fiber composite hydrogel fibre diameter be 169 ±
80nm, the porosity and specific surface area of hydrogel are respectively 93.2% and 22.1m2/ g, intensity of magnetization 0.025emu/g.
Cell-g-P(NIPAm-co-MA)/Fe3O4Magnetic Nano fiber composite hydrogel is to Cu2+Saturated extent of adsorption reach
397.1mg/g。
Comparative example 1
Difference from Example 1 is: cellulose acetate is dissolved in tetrahydrofuran and N, N '-dimethyl first by step 1)
Amide in the mixed solvent prepares cellulose casting films using casting film-forming method afterwards.
Subsequent step is same as Example 1, finally obtains cellulose casting films and is grafted poly- (n-isopropyl acrylamide-co-
Maleic anhydride)/Fe3O4Magnetic coupling hydrogel.The porosity and specific surface area of the hydrogel are respectively 60.3% and 1.19m2/
g.It is compared to tunica fibrosa hydrogel, porosity and specific surface area reduce significantly.It is primarily due to no image of Buddha tunica fibrosa hydrogel one
Sample forms porous structure.Casting films hydrogel is to Cu2+Saturated extent of adsorption be 120.1m2/g。
Comparative example 2
Difference from Example 1 is: the additive amount that step 2) medium vinyl modifies silica is 0.It finally obtains
Cellulose nano-fibrous poly- (n-isopropyl acrylamide-co- the maleic anhydride)/Fe of grafting3O4Magnetic coupling hydrogel.
Cellulose nano-fibrous poly- (n-isopropyl acrylamide-co- the maleic anhydride)/Fe of grafting3O4Magnetic coupling hydrogel
Middle fibre diameter is 161 ± 55nm.Porosity and specific surface area are respectively 81.1% and 15.12m2/g.Fiber hydrogel is to Cu2+
Saturated extent of adsorption reach 267.78mg/g.It is to mention that the main purpose of modified by vinyl silica is added in reaction system
The porosity and specific surface area of high hydrogel, and further increase its heavy metal adsorption capacity.
Comparative example 3
Difference from Example 1 is: the additive amount of maleic anhydride is 0 in step 2).Finally obtain cellulose nanometer
Fibre grafting poly(N-isopropylacrylamide) hydrogel.Fibre diameter is 151 ± 78nm, the hole of hydrogel in the hydrogel
Rate and specific surface area are respectively 67.2% and 0.45m2/g.The hydrogel is to Cu2+Saturated extent of adsorption reach 110.6mg/g.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited to above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring substantive content of the invention.
Claims (10)
1. a kind of preparation method of temperature-sensitive hydrogel, which comprises the steps of:
Prepare cellulose acetate nanofiber；
The cellulose acetate nanofiber is carried out with lye deacetylated, obtained cellulose nano-fibrous；
Cellulose nano-fibrous poly- (n-isopropyl acrylamide-co- the maleic acid of cellulose nano-fibrous grafting is prepared using described
Acid anhydride) hydrogel；
Cellulose nano-fibrous poly- (n-isopropyl acrylamide-co- maleic anhydride) hydrogel of grafting is immersed in chlorination
In ferrous and iron chloride mixed solution, ammonium hydroxide is added and is reacted, obtains cellulose nano-fibrous poly- (the N- isopropyl third of grafting
Acrylamide-co- maleic anhydride)/Fe3O4Magnetic Nano fiber composite hydrogel, i.e., the described temperature-sensitive hydrogel.
2. the preparation method of temperature-sensitive hydrogel as described in claim 1, which is characterized in that the cellulose acetate Nanowire
Dimension the preparation method comprises the following steps:
Cellulose acetate is dissolved in tetrahydrofuran and N, the in the mixed solvent of N '-dimethyl formamide obtains quenching liquid, by institute
It states after quenching liquid quenched at -30~-15 DEG C, is washed with distilled water and removes tetrahydrofuran and N, N '-dimethyl formamide,
It is freeze-dried obtained cellulose acetate nanofiber.
3. the preparation method of temperature-sensitive hydrogel as claimed in claim 2, which is characterized in that in the quenching liquid, acetic acid is fine
Dimension element, tetrahydrofuran and N, the parts by weight of N '-dimethyl formamide are respectively 0.2~0.5 part, 1~3 part, 5~10 parts.
4. the preparation method of temperature-sensitive hydrogel as described in claim 1, which is characterized in that the lye is the ethyl alcohol of NaOH
Solution, wherein the concentration of NaOH is 0.1~0.2mol/L.
5. the preparation method of temperature-sensitive hydrogel as described in claim 1, which is characterized in that described cellulose nano-fibrous to connect
Poly- (n-isopropyl acrylamide-co- maleic anhydride) hydrogel of branch the preparation method comprises the following steps:
By n-isopropyl acrylamide, maleic anhydride, N, N '-methylene-bisacrylamide is dissolved in nitric acid solution, is obtained anti-
Answer liquid A；
Ammonium ceric nitrate is dissolved in nitric acid solution, modified by vinyl silica and described cellulose nano-fibrous is added, obtains
To reaction solution B；
Reaction solution A is added dropwise in reaction solution B by constant pressure funnel, after being reacted at 30~60 DEG C, is successively adopted
It is washed with distilled water, using acetone Soxhlet extraction, filters, obtain the cellulose nano-fibrous poly- (n-isopropyl acrylamide-of grafting
Co- maleic anhydride) hydrogel.
6. the preparation method of temperature-sensitive hydrogel as claimed in claim 5, which is characterized in that in the reaction solution A: N- isopropyl
Base acrylamide, maleic anhydride, N, the parts by weight of N '-methylene-bisacrylamide are respectively 5~10 parts, 2~3 parts, 0.05
~0.1 part；In the reaction solution B: ammonium ceric nitrate, cellulose nano-fibrous, modified by vinyl silica parts by weight point
It Wei not be 1~3 part, 2~6 parts, 0.2~0.5 part.
7. the preparation method of temperature-sensitive hydrogel as claimed in claim 5, which is characterized in that the modified by vinyl titanium dioxide
Silicon the preparation method comprises the following steps: by vinyltriethoxysilane and silicon dioxde reaction, obtain modified by vinyl silica.
8. the preparation method of temperature-sensitive hydrogel as described in claim 1, which is characterized in that the frerrous chloride and iron chloride
Mixed solution in, the molar ratio of frerrous chloride and iron chloride is 1:2；The concentration of the ammonium hydroxide is 1mol/L.
9. a kind of temperature-sensitive hydrogel that the preparation method as described in any one of claim 1~8 obtains is in heavy metal ion
Purposes in absorption.
10. purposes as claimed in claim 9, which is characterized in that the heavy metal ion is copper ion.
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