CN113648984A - temperature-pH response molecularly imprinted fiber membrane and preparation method thereof - Google Patents
temperature-pH response molecularly imprinted fiber membrane and preparation method thereof Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 69
- 239000000835 fiber Substances 0.000 title claims abstract description 53
- 230000004044 response Effects 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229920001661 Chitosan Polymers 0.000 claims abstract description 34
- 238000001179 sorption measurement Methods 0.000 claims abstract description 33
- ZXJXZNDDNMQXFV-UHFFFAOYSA-M crystal violet Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1[C+](C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 ZXJXZNDDNMQXFV-UHFFFAOYSA-M 0.000 claims abstract description 19
- 229960001235 gentian violet Drugs 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002121 nanofiber Substances 0.000 claims abstract description 18
- 229920000642 polymer Polymers 0.000 claims abstract description 14
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 7
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 4
- 231100000719 pollutant Toxicity 0.000 claims abstract description 4
- 229920001577 copolymer Polymers 0.000 claims abstract description 3
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims abstract description 3
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract 4
- 150000002500 ions Chemical class 0.000 claims abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 10
- 229920000344 molecularly imprinted polymer Polymers 0.000 claims description 10
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims description 10
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 9
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000009987 spinning Methods 0.000 claims description 8
- XFHJDMUEHUHAJW-UHFFFAOYSA-N n-tert-butylprop-2-enamide Chemical compound CC(C)(C)NC(=O)C=C XFHJDMUEHUHAJW-UHFFFAOYSA-N 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000004800 polyvinyl chloride Substances 0.000 claims description 4
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 claims description 4
- 238000003795 desorption Methods 0.000 claims description 3
- GGXRSUUOWQBVFB-UHFFFAOYSA-N 2,3-dibromo-2-methylpropanoyl bromide Chemical compound BrCC(Br)(C)C(Br)=O GGXRSUUOWQBVFB-UHFFFAOYSA-N 0.000 claims description 2
- 239000005457 ice water Substances 0.000 claims description 2
- 230000010412 perfusion Effects 0.000 claims description 2
- 239000000975 dye Substances 0.000 claims 3
- 230000005587 bubbling Effects 0.000 claims 1
- 150000002191 fatty alcohols Chemical class 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 238000004458 analytical method Methods 0.000 abstract description 3
- 239000008204 material by function Substances 0.000 abstract description 2
- 238000001514 detection method Methods 0.000 abstract 1
- 230000004043 responsiveness Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- BPYKTIZUTYGOLE-IFADSCNNSA-N Bilirubin Chemical compound N1C(=O)C(C)=C(C=C)\C1=C\C1=C(C)C(CCC(O)=O)=C(CC2=C(C(C)=C(\C=C/3C(=C(C=C)C(=O)N\3)C)N2)CCC(O)=O)N1 BPYKTIZUTYGOLE-IFADSCNNSA-N 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- ZRWPUFFVAOMMNM-UHFFFAOYSA-N Patulin Chemical compound OC1OCC=C2OC(=O)C=C12 ZRWPUFFVAOMMNM-UHFFFAOYSA-N 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000011067 equilibration Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 239000004695 Polyether sulfone Substances 0.000 description 3
- 229960003638 dopamine Drugs 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920006393 polyether sulfone Polymers 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- BLHCMGRVFXRYRN-UHFFFAOYSA-N 6-hydroxynicotinic acid Chemical compound OC(=O)C1=CC=C(O)N=C1 BLHCMGRVFXRYRN-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- QNLOWBMKUIXCOW-UHFFFAOYSA-N indol-2-one Chemical compound C1=CC=CC2=NC(=O)C=C21 QNLOWBMKUIXCOW-UHFFFAOYSA-N 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- 241000238557 Decapoda Species 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- -1 Hg)2+ Inorganic materials 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
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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
- B01J20/22—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
- B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
-
- 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
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
- B01J20/28038—Membranes or mats made from fibers or filaments
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- 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
- D06M14/06—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 animal origin, e.g. wool or silk
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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Abstract
The invention provides a temperature-pH response molecularly imprinted fiber membrane and a preparation method thereof, belonging to the field of high molecular functional materials. The preparation method of the temperature-pH response molecularly imprinted fiber membrane comprises the steps of preparing a nanofiber membrane from chitosan by using an electrostatic spinning technology, then grafting a temperature response polymer poly (isopropyl acrylamide) -co-tert-butyl acrylamide-co-methacrylic acid on the surface of the fiber membrane through a free radical polymerization reaction, wherein the prepared material has a specific recognition capability on dye or heavy metal ions, the maximum adsorption capacity on gentian violet dye reaches 212.0 mg/g, and the adsorption balance time is 7 min. The resolution rate reaches 97 percent. The fiber membrane keeps the shape in a solution with the pH =6.0-14.0, the fiber membrane is dissolved in a solution with the pH =1.0-6.0, the molecular chains are stretched out in a hydrophilic mode when the temperature of the polymer brush is lower than 32.5 ℃, and the molecular chains are coiled and separated out of water when the temperature is higher than 32.5 ℃. After the adsorption is finished, the temperature and pH responsiveness make the pollutants easy to be quickly separated out, so that the effective removal and enrichment of the pollutants are realized. Has good application prospect in the aspects of environmental protection and water quality detection and analysis.
Description
Technical Field
The invention belongs to the field of high molecular functional materials, and particularly relates to a preparation method of a temperature-pH response molecularly imprinted fiber membrane.
Background
With the great development of society, the living standard of people is continuously improved, and the environmental quality and the drinking water health are increasingly paid attention to people. Heavy metals and organic matters in the industrial wastewater have hard degradability and high toxicity, can be accumulated in organisms, and cause harm to human bodies along with the circulation of a food chain. The current common water treatment methods include precipitation, ion exchange, biological treatment, membrane separation, etc., and the adsorption method is widely used due to its low cost, simple equipment, easy operation, and environmental friendliness.
The chitosan is natural alkaline high molecular polysaccharide extracted from shrimp and crab, and is the deacetylated product of chitin. The chitosan molecule has a large amount of-NH2Isofunctional group capable of reacting with many metal ions (such as Hg)2+、Ni2+、Cu2+、Pb2+、Ca2+、Ag+Etc.) to form stable chelates. The chitosan has rich sources, is non-toxic, is easy to biodegrade, is not easy to cause secondary pollution, and is a typical environment-friendly adsorption material. However, the chitosan sold in the market is insoluble in water, has small specific surface area and limited adsorption capacity.
Electrospinning is a production technique that can produce nanomaterials continuously and efficiently at low cost. The electrostatic spinning chitosan fiber membrane has higher specific surface area and ultrahigh porosity. And constructing a molecularly imprinted polymer brush on the surface of the chitosan fiber. The molecularly imprinted polymer can provide a large number of binding sites and selectively adsorb template molecules, thereby improving the adsorption capacity and selectivity.
The functional monomer dopamine is subjected to self-polymerization on the surface of a polyether sulfone (PES) fiber membrane in a weakly alkaline aqueous solution to prepare the molecularly imprinted fiber membrane by the Wu Ke. The preparation process is that PES fiber membrane (100.0 mg) is put into 50.0 mM Tris buffer solution (10.0 mM, pH 8.5) containing 20 mg of template dye bilirubin, and shaken at room temperature for 2 h. After addition of 100 mg dopamine, the solution was incubated for a further 4 hours at room temperature. Subsequently, the resultant product was washed several times with deionized water to remove unreacted dopamine. Thereafter, the sample was washed several times with a methanol/acetic acid solution (9:1, v/v) to remove the intercalated template bilirubin. And (3) after detecting that no bilirubin exists in the solution at the wavelength of 441 nm by using an ultraviolet visible spectrophotometer, thoroughly washing the sample by using deionized water, removing residual methanol and acetic acid, and drying at 40 ℃ for 24 hours to obtain the electrospun polyethersulfone fiber membrane with the molecularly imprinted surface. The adsorption equilibrium time of the molecularly imprinted fiber membrane on bilirubin is 2h, and the maximum adsorption amount is 184.24 mg/g. However, the process of removing the template bilirubin is complex and not beneficial to practical application, and part of the template bilirubin cannot be eluted, so that the acid liquor can also damage the molecular imprinting structure, the binding sites are reduced, the adsorption capacity is reduced, and the subsequent fiber membrane recycling performance is influenced. (Wu K, Yang W, Jian Y, A surface molecular imprinted Polymeric (PES) fiber mat for selective removal of bilirubin [ J ]. Journal of Materials Chemistry B, 2017:10.1039.C7TB 00643H.)
Chinese patent CN110560016A discloses a preparation method of patulin molecular imprinting nano-fiber membrane, which comprises the following steps of according to a molar ratio of 1.0: 1.0-4.0 is dissolved in methanol, then 3-aminopropyltriethoxysilane is added for magnetic stirring to carry out prepolymerization for 10-50min, tetraethoxysilane is added and 1.0-10.0mL of ammonia water is dripped, after magnetic stirring for 15-90min, the reactant is put into a water bath kettle at 30-80 ℃ for incubation reaction for 4-24h to obtain polymer solid, wherein the template molecules are 2-indolone and 6-hydroxynicotinic acid. Washing the polymer solid with methanol for 2-5 times, drying and aging at 40-80 ℃ for 4-24h in vacuum, putting the dried polymer into a 100mL round-bottom flask, adding a primary organic solvent for pre-elution, magnetically stirring for 2-8h, washing with methanol, drying at 40-80 ℃ in vacuum for 4-12h, eluting the polymer solid with a secondary organic solvent for eluting the template until the template molecule can not be detected by an ultraviolet spectrophotometer. Carrying out electrostatic spinning on a polyvinyl alcohol spinning solution containing 4.0-10.0% of molecularly imprinted polymer (wherein the molecularly imprinted polymer accounts for 10.0-40.0% of the mass fraction of the polyvinyl alcohol) under the conditions of spinning voltage of 8-23kV, spinning distance of 8-20cm, flow rate of 10-40 mu L/min and relative humidity of 40-50% to obtain the molecularly imprinted fiber membrane. The process of eluting the template polymer is also complex and takes longer, and the total use of organic solvent for elution increases the waste liquid treatment cost and is contrary to environmental friendliness.
The molecularly imprinted nanofiber membrane obtained by combining the preparation of the molecularly imprinted polymer with the electrostatic spinning technology has good specific adsorption and reutilization property on patulin by using 2-indolone and 6-hydroxynicotinic acid as virtual template molecules and combining the sol-gel technology with the electrostatic spinning technology, and can realize the specific adsorption on the patulin by the application of specific identification, efficient separation and enrichment on the patulin.
The invention relates to a method for adsorbing pollutants by using a molecular imprinting polymer, which has the advantages of large adsorption capacity and specific adsorption capacity, but the bottleneck problems of difficult analysis, low analysis speed and low repeatable utilization rate generally exist. The problems existing in the prior art are well solved.
Disclosure of Invention
Compared with the reference documents, the method for preparing the temperature-pH response molecularly imprinted fiber membrane for water treatment adopts the following technical scheme:
1) the chitosan nanofiber membrane is prepared by taking chitosan, trichloroacetic acid, dichloromethane and fatty alcohol-polyvinyl chloride ether as main raw materials and adopting an electrostatic spinning technology. The method comprises the following specific steps:
1-1) sequentially adding chitosan, trichloroacetic acid, dichloromethane and fatty alcohol-polyvinyl chloride ether into a glass vessel according to a proportion, and continuously stirring for 1-2h to prepare the chitosan spinning solution with the mass concentration of 5.0-7.0%.
1-2) taking the spinning solution as a raw material, adopting an electrostatic spinning technology, under the voltage of 15-20kV, the acceptance distance of 5.0-15.0cm and the perfusion speed of 0.1mLh-1-0.5mLh-1Preparing the chitosan nanofiber membrane.
2) The method for grafting the molecularly imprinted polymer brush on the surface of the chitosan nanofiber membrane comprises the following specific steps:
2-1) adding triethylamine and dibromo isobutyryl bromide into tetrahydrofuran in sequence according to the proportion, wherein m is triethylamine: m-dibromo-isobutyryl bromide is 20.0: 90.0-110.0.
2-2) placing the chitosan nano fiber membrane in tetrahydrofuran solution, and stirring for 1-2h in ice-water bath.
2-3) after the reaction is finished, washing the nanofiber membrane with ethanol for 3-6 times, and drying in a drying oven in vacuum.
2-4) adding the fiber membrane, isopropyl acrylamide, tert-butyl acrylamide, methacrylic acid, cuprous bromide and pentamethyl diethylenetriamine into deionized water in sequence according to the proportion, wherein m is isopropyl acrylamide: m cuprous bromide: m pentamethyldiethylenetriamine: m-tert-butylacrylamide: m methacrylic acid =100.0:2.0-3.0:2.0-3.0:10.0-20.0:50.0-80.0, and the amount of template molecules is 20.0-30.0% of the mass of the functional monomer.
2-5) placing the chitosan nano fiber membrane in the water solution, continuously stirring and introducing nitrogen to bubble for 2-3 h.
2-6) after the reaction is finished, washing the nanofiber membrane with ethanol for 3-6 times, and drying in a drying oven in vacuum.
The invention has the beneficial effects.
(1) The invention adopts chitosan nano fiber membrane as substrate to graft temperature response polymer for the first time to prepare the temperature and pH dual-response molecular imprinting material. The chitosan has rich sources, is non-toxic and easy to biodegrade, and is a typical environment-friendly adsorption material; the preparation of the polymer adopts an atom transfer radical polymerization method, the polymerization condition is mild, the polymerization method is simple, and the polymerization time is short.
(2) The chitosan fiber membrane prepared by the invention is used as a substrate, is grafted with temperature response polymer, contains N-isopropyl acrylamide, tert-butyl acrylamide and methacrylic acid, and has a three-dimensional structure matched with the volume of a target molecule through a template molecule structure. Along with the change of the environmental temperature and the pH value, the molecularly imprinted polymer shows reversible change of a contraction-swelling state, and can realize selective adsorption and desorption of adsorbed molecules.
(3) The fiber membrane prepared by the method has uniform fiber diameter and good stability, has specific recognition capability on the template dye, has the maximum adsorption capacity of 212 mg/g on gentian violet, and has adsorption equilibrium time of only 7 min; the rapid separation of the template dye is realized under the action of temperature and pH, the resolution rate is up to 97 percent, and the resolution is obviously superior to the resolution performance of the dye imprinted polymer reported in the prior literature.
Drawings
FIG. 1 is a scanning electron microscope photograph of chitosan nanofiber membrane, which shows that the fiber diameter of the fiber membrane prepared by the method is in nano level, the fiber diameter is uniformly distributed, and the three-dimensional structure obtained by overlapping the fibers in a staggered way has huge specific surface area and ultrahigh porosity.
FIG. 2 is FT-IR spectrum of chitosan nanofiber membrane and subsequent modification. Proves that the chitosan is successfully subjected to atom transfer radical polymerization and grafted with poly (isopropyl acrylamide) -co-tert-butyl acrylamide-co-methacrylic acid polymer.
Detailed Description
In order to make the technical solutions and advantages of the present invention clearer, the following will clearly and completely describe the technical solutions of the present invention with reference to the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
1.01 g of chitosan fiber membrane, 1.14 g of isopropyl acrylamide, 0.26 g of tert-butyl acrylamide, 0.61 g of methacrylic acid, 0.02 g of cuprous bromide and 0.02 g of pentamethyldiethylenetriamine are dissolved in 20.0 mL of deionized water, 0.2 g of gentian violet containing a template dye is dissolved, and nitrogen is bubbled for 60 min to remove oxygen in the environment. Reacting at 40.0 deg.C for 90min, washing the fiber membrane with ethanol for 3-6 times, and vacuum drying.
13 mg of the fibrous membrane was immersed in 43 mL of a gentian violet solution having an initial concentration of 20 mg/L, pH was 7.0, and after adsorption equilibration for 7 min, the adsorption capacity was 212.0 mg/g. The fiber membrane adsorbed with gentian violet was transferred to an aqueous hydrochloric acid solution (20 mL, 36.5 g/L) at pH 3.0 and temperature 25 ℃. Then rapidly heating to 60 deg.C, maintaining for 30 min, and rapidly cooling to 25 deg.C. 97% of the adsorbed gentian violet was determined to be resolved.
Example 2
1.01 g of chitosan fiber membrane, 1.14 g of isopropyl acrylamide, 0.26 g of tert-butyl acrylamide, 0.61 g of methacrylic acid, 0.02 g of cuprous bromide and 0.02 g of pentamethyldiethylenetriamine are dissolved in 20.0 mL of deionized water, 0.2 g of gentian violet containing a template dye is dissolved, and nitrogen is bubbled for 60 min to remove oxygen in the environment. Reacting at 40.0 deg.C for 90min, washing the fiber membrane with ethanol for 3-6 times, and vacuum drying.
13 mg of the fibrous membrane was immersed in 43 mL of a gentian violet solution having an initial concentration of 20 mg/L, pH 7.0, and after adsorption equilibration for 7 min, the adsorption capacity was 196.0 mg/g. The fiber membrane loaded with gentian violet by adsorption was transferred to an aqueous hydrochloric acid solution (20 mL, 36.5 g/L) at pH 3.0 and temperature 25 ℃. Then rapidly heating to 60 deg.C, maintaining for 30 min, and rapidly cooling to 25 deg.C. 93% of the adsorbed gentian violet is resolved.
Example 3
1.01 g of chitosan fiber membrane, 1.14 g of isopropyl acrylamide, 0.26 g of tert-butyl acrylamide, 0.61 g of methacrylic acid, 0.02 g of cuprous bromide and 0.02 g of pentamethyldiethylenetriamine are dissolved in 20.0 mL of deionized water, 0.2 g of gentian violet containing a template dye is dissolved, and nitrogen is bubbled for 60 min to remove oxygen in the environment. Reacting at 40.0 deg.C for 90min, washing the fiber membrane with ethanol for 3-6 times, and vacuum drying. The electron microscope test result shows that the fiber is uniform and the porosity is high.
13 mg of the fibrous membrane was immersed in 43 mL of a gentian violet solution having an initial concentration of 20 mg/L, pH 7.0, and after adsorption equilibration for 7 min, the adsorption capacity was found to be 177.0 mg/g. The fiber membrane loaded with gentian violet by adsorption was transferred to an aqueous hydrochloric acid solution (20 mL, 36.5 g/L) at pH 3.0 and temperature 25 ℃. Then rapidly heating to 60 deg.C, maintaining for 30 min, and rapidly cooling to 25 deg.C. 89% of the adsorbed gentian violet is resolved out.
Example 4
1.01 g of chitosan fiber membrane, 1.14 g of isopropyl acrylamide, 0.26 g of tert-butyl acrylamide, 0.61 g of methacrylic acid, 0.02 g of cuprous bromide and 0.02 g of pentamethyldiethylenetriamine are dissolved in 20.0 mL of deionized water, 0.2 g of gentian violet containing a template dye is dissolved, and nitrogen is bubbled for 60 min to remove oxygen in the environment. Reacting at 40.0 deg.C for 90min, washing the fiber membrane with ethanol for 3-6 times, and vacuum drying. The electron microscope test result shows that the fiber is uniform and the porosity is high.
13 mg of the fibrous membrane was immersed in 43 mL of a gentian violet solution having an initial concentration of 20 mg/L, pH was 7.0, and after adsorption equilibration for 7 min, the adsorption capacity was 168.0 mg/g. The fiber membrane loaded with gentian violet by adsorption was transferred to an aqueous hydrochloric acid solution (20 mL, 36.5 g/L) at pH 3.0 and temperature 25 ℃. Then rapidly heating to 60 deg.C, maintaining for 30 min, and rapidly cooling to 25 deg.C. 85% of the adsorbed gentian violet is resolved.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (6)
1. A preparation method of a temperature-pH response molecularly imprinted fiber membrane is characterized in that the membrane is a material formed by grafting chitosan fiber with poly (isopropyl acrylamide) -co-tert-butyl acrylamide-co-methacrylic acid polymer; has selective adsorption capacity to dye.
2. A preparation method of a temperature-pH response molecularly imprinted fiber membrane comprises the following steps: preparing chitosan spinning solution from chitosan, trichloroacetic acid, dichloromethane and fatty alcohol-polyvinyl chloride ether; preparing chitosan nano fiber membrane from chitosan spinning solution through electrostatic spinning, and then grafting a temperature response molecularly imprinted polymer on the surface of the fiber membrane through free radical polymerization reaction.
3. The preparation method of the temperature-pH response molecularly imprinted fiber membrane for water treatment as claimed in claim 1, characterized in that: the mass ratio of the dichloromethane to the trichloroacetic acid is 1.0: 1.0-3.0; the dosage of the chitosan is 5.0-7.0% of the total mass of the monomers; the dosage of the fatty alcohol polyvinyl chloride ether is 2.0-4.0% of the total mass of the monomers; the mass concentration of the chitosan spinning solution is 5.0-8.0%.
4. The preparation method of the temperature-pH response molecularly imprinted fiber membrane for water treatment as claimed in claim 1, characterized in that: in the electrostatic spinning process, the voltage of a high-voltage power supply is 15.0 kV-20.0 kV, the distance of a receiving screen is 5.0 cm-15.0 cm, and the perfusion speed is 0.1mLh-1-0.5 mLh-1。
5. The preparation method of the temperature-pH response molecularly imprinted fiber membrane for water treatment as claimed in claim 1, wherein the fiber membrane surface is grafted with the temperature response molecularly imprinted polymer through free radical polymerization, and the preparation method comprises the following specific steps: adding triethylamine and dibromo isobutyryl bromide into tetrahydrofuran in sequence according to a proportion, wherein triethylamine: m-dibromo-isobutyryl bromide is 20.0: 90.0-110.0; placing the chitosan nanofiber membrane in a tetrahydrofuran solution, and stirring in an ice-water bath for 1.0-2.0 h;
after the reaction is finished, washing the nanofiber membrane with ethanol for 3-6 times, and drying in a vacuum oven;
sequentially adding isopropyl acrylamide, tert-butyl acrylamide, methacrylic acid, cuprous bromide and pentamethyl diethylenetriamine into deionized water according to a proportion, wherein m is isopropyl acrylamide: m cuprous bromide: m pentamethyldiethylenetriamine: m-tert-butylacrylamide: m methacrylic acid =1.0: 2.0-3.0: 20.0-30.0: 20.0-30.0: 10.0 to 20.0 percent, wherein the dosage of the template dye gentian violet is 20.0 to 30.0 percent of the mass of the functional monomer;
placing the chitosan nano fiber membrane in the solution, continuously stirring and introducing nitrogen for bubbling for 2-3 h;
after the reaction is finished, washing the nanofiber membrane with ethanol for 3-6 times, and drying in vacuum for later use;
the preparation method of the temperature-pH response molecularly imprinted fiber membrane according to claim 1, wherein the temperature response molecularly imprinted polymer is grafted on the surface of the fiber membrane through free radical polymerization reaction, and the preparation method is characterized in that: m isopropyl acrylamide: m cuprous bromide: m pentamethyldiethylenetriamine: m-tert-butylacrylamide: m methacrylic acid =1.0: 2.0-3.0: 20.0-30.0: 20.0-30.0: 10.0-20.0 percent, and the dosage of the template molecule is 20.0-30.0 percent of the mass of the functional monomer.
6. The preparation method of the temperature-pH response molecularly imprinted fiber membrane according to claim 2, wherein the prepared membrane material is suitable for removing dyes and heavy metal ion pollutants in water;
the advantages are large adsorption capacity, short adsorption time, and the temperature-pH response characteristic of the fiber membrane is that the desorption process is convenient and easy after adsorption, and the desorption rate is fast.
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