CN114907499A - Ultrahigh crosslinked beta-cyclodextrin polymer and preparation method and application thereof - Google Patents
Ultrahigh crosslinked beta-cyclodextrin polymer and preparation method and application thereof Download PDFInfo
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- 229920000858 Cyclodextrin Polymers 0.000 title claims abstract description 151
- 239000001116 FEMA 4028 Substances 0.000 title claims abstract description 151
- 235000011175 beta-cyclodextrine Nutrition 0.000 title claims abstract description 151
- 229960004853 betadex Drugs 0.000 title claims abstract description 151
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 title claims abstract description 143
- 229920000642 polymer Polymers 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 162
- 238000006243 chemical reaction Methods 0.000 claims abstract description 127
- 238000003756 stirring Methods 0.000 claims abstract description 51
- 238000001035 drying Methods 0.000 claims abstract description 44
- 239000000047 product Substances 0.000 claims abstract description 37
- 239000002904 solvent Substances 0.000 claims abstract description 27
- 238000005406 washing Methods 0.000 claims abstract description 27
- -1 hydroxyl deprotonated beta-cyclodextrin Chemical class 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 239000011968 lewis acid catalyst Substances 0.000 claims abstract description 11
- 238000005574 benzylation reaction Methods 0.000 claims abstract description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 7
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 3
- 238000010992 reflux Methods 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 108
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 23
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 19
- 239000000706 filtrate Substances 0.000 claims description 19
- UOSROERWQJTVNU-UHFFFAOYSA-N 9,10-bis(chloromethyl)anthracene Chemical compound C1=CC=C2C(CCl)=C(C=CC=C3)C3=C(CCl)C2=C1 UOSROERWQJTVNU-UHFFFAOYSA-N 0.000 claims description 16
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims description 16
- 229940073608 benzyl chloride Drugs 0.000 claims description 16
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 235000010290 biphenyl Nutrition 0.000 claims description 6
- 239000004305 biphenyl Substances 0.000 claims description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 6
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 claims description 5
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 5
- 229940012189 methyl orange Drugs 0.000 claims description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003431 cross linking reagent Substances 0.000 claims description 4
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical group COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 claims description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 239000002351 wastewater Substances 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims description 2
- YHEMDXGFCREMGG-UHFFFAOYSA-N 9,10-bis(bromomethyl)anthracene Chemical compound C1=CC=C2C(CBr)=C(C=CC=C3)C3=C(CBr)C2=C1 YHEMDXGFCREMGG-UHFFFAOYSA-N 0.000 claims description 2
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 claims description 2
- OIQPTROHQCGFEF-UHFFFAOYSA-L chembl1371409 Chemical compound [Na+].[Na+].OC1=CC=C2C=C(S([O-])(=O)=O)C=CC2=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 OIQPTROHQCGFEF-UHFFFAOYSA-L 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- ZBQZBWKNGDEDOA-UHFFFAOYSA-N eosin B Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC([N+]([O-])=O)=C(O)C(Br)=C1OC1=C2C=C([N+]([O-])=O)C(O)=C1Br ZBQZBWKNGDEDOA-UHFFFAOYSA-N 0.000 claims description 2
- FUKUFMFMCZIRNT-UHFFFAOYSA-N hydron;methanol;chloride Chemical compound Cl.OC FUKUFMFMCZIRNT-UHFFFAOYSA-N 0.000 claims description 2
- 229940107698 malachite green Drugs 0.000 claims description 2
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 claims description 2
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 claims description 2
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 2
- VOFUROIFQGPCGE-UHFFFAOYSA-N nile red Chemical compound C1=CC=C2C3=NC4=CC=C(N(CC)CC)C=C4OC3=CC(=O)C2=C1 VOFUROIFQGPCGE-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 2
- 229940043267 rhodamine b Drugs 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 23
- 238000004132 cross linking Methods 0.000 abstract description 9
- 239000011148 porous material Substances 0.000 abstract description 7
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 abstract description 5
- 239000003344 environmental pollutant Substances 0.000 abstract description 4
- 231100000719 pollutant Toxicity 0.000 abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract 3
- 239000000126 substance Substances 0.000 description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 17
- 239000004677 Nylon Substances 0.000 description 17
- 238000000944 Soxhlet extraction Methods 0.000 description 17
- 239000008367 deionised water Substances 0.000 description 17
- 229910021641 deionized water Inorganic materials 0.000 description 17
- 238000001914 filtration Methods 0.000 description 17
- 238000010438 heat treatment Methods 0.000 description 17
- 239000005457 ice water Substances 0.000 description 17
- 239000003350 kerosene Substances 0.000 description 17
- 239000007788 liquid Substances 0.000 description 17
- 239000012528 membrane Substances 0.000 description 17
- 229920001778 nylon Polymers 0.000 description 17
- 238000002390 rotary evaporation Methods 0.000 description 17
- 239000007787 solid Substances 0.000 description 17
- 239000000203 mixture Substances 0.000 description 16
- 238000001179 sorption measurement Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229920000554 ionomer Polymers 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229920000426 Microplastic Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
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- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002429 nitrogen sorption measurement Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
- C08B37/0012—Cyclodextrin [CD], e.g. cycle with 6 units (alpha), with 7 units (beta) and with 8 units (gamma), large-ring cyclodextrin or cycloamylose with 9 units or more; 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
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
- B01J20/267—Cross-linked polymers
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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
- B01J20/28054—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 surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28059—Surface area, e.g. B.E.T specific surface area being less than 100 m2/g
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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
-
- 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 belongs to the technical field of preparation of functionalized porous materials, and discloses an ultrahigh crosslinked beta-cyclodextrin polymer, and a preparation method and application thereof. The method comprises the following steps: dissolving beta-cyclodextrin in a solvent, adding NaH (sodium hydroxide) and stirring to obtain a hydroxyl deprotonated beta-cyclodextrin solution, adding a benzylation reagent into the solution, reacting for 8-24 h at 20-140 ℃, adding anhydrous methanol to stop the reaction, washing and extracting the reaction solution, collecting and drying a lower layer product to obtain a benzyl substituted beta-cyclodextrin compound, dissolving the benzyl substituted beta-cyclodextrin compound in the solvent, adding an active polyaromatic ring rigid structure compound, adding a Lewis acid catalyst in an inert atmosphere, carrying out reflux reaction for 18-36 h at 60-120 ℃, washing, extracting and drying the reaction product to obtain the ultrahigh crosslinked beta-cyclodextrin polymer. The method has mild conditions and controllable crosslinking degree, and the prepared polymer has good morphology and pore structure and can be used for efficiently removing various pollutants in water.
Description
Technical Field
The invention belongs to the field of chemically synthesized functionalized porous materials, and relates to an ultrahigh crosslinked beta-cyclodextrin polymer, and a preparation method and application thereof.
Background
With the rapid advance of the urbanization and industrialization process, the ecological environment is seriously damaged by a large amount of wastewater discharged by industrial and agricultural production and urban life, and the continuous development of the trend of water quality deterioration can greatly threaten human health and human society. The most widely used means for treating actual water samples at present is an adsorption method, the research and development of high-performance and high-efficiency adsorption materials become main research hotspots in the field, and the porous material with good pore-size structure and excellent physical and chemical properties can effectively enhance the adsorption performance through physical action, chemical action or physical and chemical synergistic enhancement.
As a supermolecular compound, the beta-cyclodextrin has special host-guest interaction and other synergistic effects of various weak interactions, and has unique advantages in the aspects of identifying and adsorbing pollutants such as organic dyes, heavy metal ions, antibiotics, micro plastics, polycyclic aromatic hydrocarbons and the like. The beta-cyclodextrin is prepared into the beta-cyclodextrin polymer in a crosslinking or immobilized mode, so that the stability and the recycling performance of the beta-cyclodextrin polymer as an adsorbent can be effectively improved. However, most of the materials are of non-porous structures or contain a small amount of macropores, the integral specific surface area is small, the saturated adsorption capacity of the materials to various pollutants in wastewater is small, and the requirements for real water sample treatment are difficult to meet.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention aims to provide a preparation method of an ultrahigh crosslinked beta-cyclodextrin polymer.
The invention also aims to provide the ultrahigh crosslinking beta-cyclodextrin polymer prepared by the method.
Still another object of the present invention is to provide the use of the above ultra-highly crosslinked beta-cyclodextrin polymer. A method for preparing a porous beta-cyclodextrin polymer adsorbent with a large specific surface area by an ultrahigh crosslinking method comprises the following specific implementation strategies: firstly, introducing a proper amount of active rigid benzene ring structures on hydroxyl groups of beta-cyclodextrin, and then preparing the beta-cyclodextrin polymer with large specific surface area and porous high crosslinking through the internal crosslinking or external crosslinking of the beta-cyclodextrin and one or more aromatic ring rigid structures.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of a super-high cross-linked beta-cyclodextrin polymer comprises the following steps:
(1) dissolving beta-cyclodextrin in a solvent, adding NaH, and reacting under stirring to deprotonate hydroxyl groups of the beta-cyclodextrin to form oxygen anions, thereby obtaining a deprotonated hydroxyl beta-cyclodextrin solution;
(2) adding a benzylation reagent into the solution obtained in the step (1), reacting for 8-24 h at 20-140 ℃, adding anhydrous methanol to stop the reaction, washing and extracting the reaction solution, collecting and drying a lower-layer product to obtain a benzyl-substituted beta-cyclodextrin compound;
(3) dissolving the benzyl-substituted beta-cyclodextrin compound in the step (2) in a solvent, adding an active polyaromatic ring rigid structure compound, adding a Lewis acid catalyst in an inert atmosphere, carrying out reflux reaction at 60-120 ℃ for 18-36 h, washing, extracting and drying a reaction product to obtain the ultrahigh cross-linked beta-cyclodextrin polymer.
Preferably, the benzylation reagent in the step (2) is one or two of benzyl chloride and benzyl bromide;
and (3) the active polyaromatic ring rigid structure compound is one or more than two of p-dichlorobenzyl, biphenyl dichlorobenzyl, 4 '-dichloromethyl terphenyl, 9, 10-bis (chloromethyl) anthracene, p-dibromide benzyl, biphenyl dibromide benzyl, 4-dibromomethyl terphenyl, 9, 10-bis (bromomethyl) anthracene, p-diphenol and 4,4' -dihydroxy biphenyl.
Preferably, the solvent in the step (1) is one or two of DMF and DMSO;
and (3) the solvent is one or more than two of DMF, chlorobenzene, o-dichlorobenzyl, nitrobenzene, dichloromethane and dichloroethane.
Preferably, the mass ratio of the beta-cyclodextrin to the NaH in the step (1) is 1: 1-4: 1, and the reaction temperature is-5 ℃;
the molar mass ratio of the beta-cyclodextrin in the step (1) to the benzylation reagent in the step (2) is 1: 7-1: 21.
Preferably, the Lewis acid catalyst in the step (3) is ZnCl 2 、AlCl 3 、FeCl 3 、SnCl 4 The mass ratio of the benzylated beta-cyclodextrin to the active polyaromatic ring rigid structure compound and the Lewis acid catalyst is (1-3): (0.1-0.5): (1-5);
and (3) adding an external cross-linking agent into the inert atmosphere, wherein the external cross-linking agent is dimethoxymethane, and the mass ratio of the benzylated beta-cyclodextrin to the dimethoxymethane is 1: 1-10: 1.
Preferably, the Lewis acid catalyst in the step (3) is FeCl 3 The mass ratio of the benzylated beta-cyclodextrin to the active polyaromatic ring rigid structure compound to the Lewis acid catalyst is 1:0.2: 2.4.
Preferably, the washing in step (2) is sequentially washing with ethanol-methanol-2M HCl-methanol until the filtrate is clear, and the drying is anhydrous Na 2 SO 4 Standing and drying overnight, wherein the inert atmosphere in the step (3) is N 2 Or He or Ar.
The ultrahigh crosslinked beta-cyclodextrin polymer is prepared by the method.
The application of the ultrahigh crosslinked beta-cyclodextrin polymer in treating wastewater containing organic dye.
Preferably, the organic dye is one or more of methyl orange, methyl blue, methylene blue, rhodamine B, Nile Red, Crystal Violet, Malachite Green, eosin B, sunset yellow.
The invention has the following advantages and beneficial effects:
the preparation method has mild conditions and controllable crosslinking degree, and the prepared ultrahigh crosslinking polymer has good appearance and pore structure and larger specific surface area and can be used for efficiently removing various pollutants in water.
Drawings
FIG. 1 is a flow chart of a method of preparing a hyper-crosslinked beta-cyclodextrin polymer of the present invention;
FIG. 2 is a nitrogen sorption and desorption curve of the ultra-highly crosslinked beta-cyclodextrin polymer prepared in example 13;
FIG. 3 is a structural view of a reactive aromatic ring rigid structure compound used in step (2) of the present invention;
FIG. 4 is a graph showing the change in absorbance with time when polymer 13 in example 18 adsorbs methyl orange.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto, and may be carried out with reference to conventional techniques for process parameters not particularly noted.
Example 1
1. Preparation of benzylated beta-cyclodextrin:
2g of beta-cyclodextrin was dissolved in 40ml of anhydrous DMF and the solution was placed in an ice water bath to which 0.6g of NaH was added(kerosene storage, content 60 wt%) and stirring was continued for about 15 min. Then, 3g of benzyl chloride was slowly injected into the reaction system, and after stirring for a while, the reaction system was warmed to room temperature to continue the reaction for 12 hours. After the reaction is finished, 5mL of anhydrous methanol is poured to terminate the reaction, the reaction solution is washed by about 100mL of deionized water and poured into a separating funnel, the mixture is extracted 3 times by dichloromethane (about 50mL each time), products in dichloromethane at the lower layer are combined and collected, and anhydrous Na is used for 2 SO 4 And standing and drying overnight. And removing suspended insoluble substances from the dried solution by using a needle filter of a hydrophilic nylon filter membrane, and then removing the solvent by rotary evaporation to obtain colorless transparent liquid, namely the benzylated beta-cyclodextrin.
2. Preparing the ultrahigh crosslinked beta-cyclodextrin polymer:
1g of benzylated beta-cyclodextrin and 0.2g of p-dichlorobenzyl (a) are dissolved in 60mL of anhydrous dichloroethane in N 2 2.4g of anhydrous FeCl was rapidly added in the atmosphere 3 Stirring at room temperature for 30min, heating to 80 ℃, and continuing to react for 18 h. After the reaction is finished, filtering the brown solid, sequentially washing with ethanol-methanol-2M HCl and methanol until the filtrate is clear, performing Soxhlet extraction on the brown yellow product in methanol for 48 hours, and then drying in vacuum to obtain the ultrahigh crosslinked beta-cyclodextrin polymer 1.
Example 2
1. Preparation of benzylated beta-cyclodextrin:
2g of beta-cyclodextrin was dissolved in 40ml of anhydrous DMF. The solution was then placed in an ice-water bath to which 0.6g NaH (kerosene reserve, 60 wt%) was added and stirring was continued for about 15 min. Then, 3g of benzyl bromide was slowly injected into the reaction system, and after stirring for a while, the reaction system was warmed to room temperature to continue the reaction for 12 hours. After the reaction is finished, 5mL of anhydrous methanol is poured to terminate the reaction, the reaction solution is washed by about 100mL of deionized water and poured into a separating funnel, the mixture is extracted 3 times by dichloromethane (about 50mL each time), products in dichloromethane at the lower layer are combined and collected, and anhydrous Na is used for 2 SO 4 And standing and drying overnight. And removing suspended insoluble substances from the dried solution by using a needle filter of a hydrophilic nylon filter membrane, and then removing the solvent by rotary evaporation to obtain colorless transparent liquid, namely the benzylated beta-cyclodextrin.
2. Preparing the ultrahigh crosslinked beta-cyclodextrin polymer:
1g of benzylated beta-cyclodextrin and 0.2g of p-dichlorobenzyl (a) are dissolved in 60mL of anhydrous dichloroethane in N 2 2.4g of anhydrous FeCl was rapidly added in the atmosphere 3 Stirring at room temperature for 30min, heating to 80 ℃, and continuing to react for 18 h. And after the reaction is finished, filtering the brown solid, sequentially washing with ethanol-methanol-2M HCl and methanol until the filtrate is clear, performing Soxhlet extraction on the brown product in methanol for 48 hours, and drying in vacuum to obtain the ultrahigh crosslinked beta-cyclodextrin polymer 2.
Example 3
1. Preparation of benzylated beta-cyclodextrin:
2g of beta-cyclodextrin was dissolved in 40ml of anhydrous DMF. The solution was then placed in an ice-water bath to which 0.6g NaH (kerosene reserve, 60 wt%) was added and stirring was continued for about 15 min. 4.5g of benzyl chloride was then slowly injected into the reaction system, stirred for a while, and then warmed to room temperature to continue the reaction for 12 hours. After the reaction is finished, 5mL of anhydrous methanol is poured to terminate the reaction, the reaction solution is washed by about 100mL of deionized water and poured into a separating funnel, the mixture is extracted 3 times by dichloromethane (about 50mL each time), products in dichloromethane at the lower layer are combined and collected, and anhydrous Na is used for 2 SO 4 And standing and drying overnight. Removing suspended insoluble substances from the dried solution by using a needle filter with a hydrophilic nylon filter membrane, and then removing the solvent by rotary evaporation to obtain colorless transparent liquid, namely the benzylated beta-cyclodextrin.
2. Preparing the ultrahigh crosslinked beta-cyclodextrin polymer:
1g of benzylated beta-cyclodextrin and 0.2g of p-dichlorobenzyl (a) are dissolved in 60mL of anhydrous dichloroethane in N 2 2.4g of anhydrous FeCl was rapidly added in the atmosphere 3 Stirring at room temperature for 30min, heating to 80 ℃, and continuing to react for 18 h. After the reaction is finished, filtering the brown solid, sequentially washing with ethanol-methanol-2M HCl and methanol until the filtrate is clear, performing Soxhlet extraction on the brown yellow product in methanol for 48 hours, and then drying in vacuum to obtain the ultrahigh crosslinked beta-cyclodextrin polymer 3.
Example 4
1. Preparation of benzylated beta-cyclodextrin:
2g of beta-cyclodextrin was dissolved in 40ml of anhydrous DMF. Subsequently placing the solution in0.6g NaH (kerosene content: 60% by weight) was added to the ice-water bath and stirring was continued for about 15 min. Then 6g of benzyl chloride is slowly injected into the reaction system, stirred for a while, and then raised to room temperature to continue the reaction for 12 hours. After the reaction is finished, 5mL of anhydrous methanol is poured to terminate the reaction, the reaction solution is washed by about 100mL of deionized water and poured into a separating funnel, the mixture is extracted 3 times by dichloromethane (about 50mL each time), products in dichloromethane at the lower layer are combined and collected, and anhydrous Na is used for 2 SO 4 And standing and drying overnight. Removing suspended insoluble substances from the dried solution by using a needle filter with a hydrophilic nylon filter membrane, and then removing the solvent by rotary evaporation to obtain colorless transparent liquid, namely the benzylated beta-cyclodextrin.
2. Preparing the ultrahigh crosslinked beta-cyclodextrin polymer:
1g of benzylated beta-cyclodextrin and 0.2g of p-dichlorobenzyl (a) are dissolved in 60mL of anhydrous dichloroethane in N 2 2.4g of anhydrous FeCl was rapidly added in the atmosphere 3 Stirring at room temperature for 30min, heating to 80 ℃, and continuing to react for 18 h. After the reaction is finished, filtering the brown solid, sequentially washing with ethanol-methanol-2M HCl and methanol until the filtrate is clear, performing Soxhlet extraction on the brown yellow product in methanol for 48 hours, and then drying in vacuum to obtain the ultrahigh crosslinked beta-cyclodextrin polymer 4.
Example 5
1. Preparation of benzylated beta-cyclodextrin:
2g of beta-cyclodextrin was dissolved in 40ml of anhydrous DMF. The solution was then placed in an ice-water bath to which 0.6g NaH (kerosene reserve, 60 wt%) was added and stirring was continued for about 15 min. Then, 3g of benzyl chloride was slowly injected into the reaction system, and after stirring for a while, the reaction system was warmed to room temperature to continue the reaction for 12 hours. After the reaction is finished, 5mL of anhydrous methanol is poured to terminate the reaction, the reaction solution is washed by about 100mL of deionized water and poured into a separating funnel, the mixture is extracted 3 times by dichloromethane (about 50mL each time), products in dichloromethane at the lower layer are combined and collected, and anhydrous Na is used for 2 SO 4 And standing and drying overnight. And removing suspended insoluble substances from the dried solution by using a needle filter of a hydrophilic nylon filter membrane, and then removing the solvent by rotary evaporation to obtain colorless transparent liquid, namely the benzylated beta-cyclodextrin.
2. Preparing the ultrahigh crosslinked beta-cyclodextrin polymer:
1g of benzylated beta-cyclodextrin and 0.2g of biphenyldichlorobenzyl (c) were dissolved in 60mL of anhydrous dichloroethane in the presence of N 2 2.4g of anhydrous FeCl was rapidly added in the atmosphere 3 Stirring at room temperature for 30min, heating to 80 ℃, and continuing to react for 18 h. After the reaction is finished, filtering the brown solid, sequentially washing with ethanol-methanol-2M HCl and methanol until the filtrate is clear, performing Soxhlet extraction on the brown yellow product in methanol for 48 hours, and then drying in vacuum to obtain the ultrahigh crosslinked beta-cyclodextrin polymer 5.
Example 6
1. Preparation of benzylated beta-cyclodextrin:
2g of beta-cyclodextrin was dissolved in 40ml of anhydrous DMF. The solution was then placed in an ice-water bath to which 0.6g NaH (kerosene reserve, 60 wt%) was added and stirring was continued for about 15 min. Then, 3g of benzyl bromide was slowly injected into the reaction system, and after stirring for a while, the reaction system was warmed to room temperature to continue the reaction for 12 hours. After the reaction is finished, 5mL of anhydrous methanol is poured to terminate the reaction, the reaction solution is washed by about 100mL of deionized water and poured into a separating funnel, the mixture is extracted 3 times by dichloromethane (about 50mL each time), products in dichloromethane at the lower layer are combined and collected, and anhydrous Na is used for 2 SO 4 And standing and drying overnight. And removing suspended insoluble substances from the dried solution by using a needle filter of a hydrophilic nylon filter membrane, and then removing the solvent by rotary evaporation to obtain colorless transparent liquid, namely the benzylated beta-cyclodextrin.
2. Preparing the ultrahigh crosslinked beta-cyclodextrin polymer:
1g of benzylated beta-cyclodextrin and 0.2g of biphenyldibromobenzyl (d) are dissolved in 60mL of anhydrous dichloroethane in N 2 2.4g of anhydrous FeCl was rapidly added in the atmosphere 3 Stirring at room temperature for 30min, heating to 80 ℃, and continuing to react for 18 h. And after the reaction is finished, filtering the brown solid, sequentially washing with ethanol-methanol-2M HCl and methanol until the filtrate is clear, performing Soxhlet extraction on the brown product in methanol for 48 hours, and drying in vacuum to obtain the ultrahigh crosslinked beta-cyclodextrin polymer 6.
Example 7
1. Preparation of benzylated beta-cyclodextrin:
2g of beta-cyclodextrin are dissolved in40ml of anhydrous DMF. The solution was then placed in an ice-water bath with 0.6g NaH (kerosene stock, content 60 wt%) added and stirring continued for about 15 min. Then, 3g of benzyl chloride was slowly injected into the reaction system, and after stirring for a while, the reaction system was warmed to room temperature to continue the reaction for 12 hours. After the reaction is finished, 5mL of anhydrous methanol is poured to terminate the reaction, the reaction solution is washed by about 100mL of deionized water and poured into a separating funnel, the mixture is extracted 3 times by dichloromethane (about 50mL each time), products in dichloromethane at the lower layer are combined and collected, and anhydrous Na is used for 2 SO 4 And standing and drying overnight. And removing suspended insoluble substances from the dried solution by using a needle filter of a hydrophilic nylon filter membrane, and then removing the solvent by rotary evaporation to obtain colorless transparent liquid, namely the benzylated beta-cyclodextrin.
2. Preparing the ultrahigh crosslinked beta-cyclodextrin polymer:
1g of benzylated beta-cyclodextrin, 0.2g of 9, 10-bis (chloromethyl) anthracene (g) were dissolved in 60mL of anhydrous dichloroethane in N 2 2.4g of anhydrous FeCl was rapidly added in the atmosphere 3 Stirring at room temperature for 30min, heating to 80 ℃, and continuing to react for 18 h. After the reaction is finished, filtering the brown solid, sequentially washing with ethanol-methanol-2M HCl and methanol until the filtrate is clear, performing Soxhlet extraction on the brown yellow product in methanol for 48 hours, and then drying in vacuum to obtain the ultrahigh crosslinked beta-cyclodextrin polymer 7.
Example 8
1. Preparation of benzylated beta-cyclodextrin:
2g of beta-cyclodextrin was dissolved in 40ml of anhydrous DMF. The solution was then placed in an ice-water bath to which 0.6g NaH (kerosene reserve, 60 wt%) was added and stirring was continued for about 15 min. Then, 3g of benzyl bromide was slowly injected into the reaction system, and after stirring for a while, the reaction system was warmed to room temperature to continue the reaction for 12 hours. After the reaction is finished, 5mL of anhydrous methanol is poured to terminate the reaction, the reaction solution is washed by about 100mL of deionized water and poured into a separating funnel, the mixture is extracted 3 times by dichloromethane (about 50mL each time), products in dichloromethane at the lower layer are combined and collected, and anhydrous Na is used for 2 SO 4 And standing and drying overnight. Removing suspended insoluble substances from the dried solution by using a needle filter with a hydrophilic nylon filter membrane, and then removing the solvent by rotary evaporation to obtain colorless transparent liquid, namely the benzylated beta-cyclodextrin.
2. Preparing the ultrahigh crosslinked beta-cyclodextrin polymer:
1g of benzylated beta-cyclodextrin, 0.2g of p-dibromide benzyl (b) were dissolved in 60mL of anhydrous dichloroethane in N 2 2.4g of anhydrous FeCl was rapidly added in the atmosphere 3 Stirring at room temperature for 30min, heating to 80 ℃, and continuing to react for 18 h. After the reaction is finished, filtering the brown solid, sequentially washing with ethanol-methanol-2M HCl and methanol until the filtrate is clear, performing Soxhlet extraction on the brown yellow product in methanol for 48 hours, and then drying in vacuum to obtain the ultrahigh crosslinked beta-cyclodextrin polymer 8.
Example 9
1. Preparation of benzylated beta-cyclodextrin:
2g of beta-cyclodextrin was dissolved in 40ml of anhydrous DMF. The solution was then placed in an ice-water bath to which 0.6g NaH (kerosene reserve, 60 wt%) was added and stirring was continued for about 15 min. Then, 3g of benzyl chloride was slowly injected into the reaction system, and after stirring for a while, the reaction system was warmed to room temperature to continue the reaction for 12 hours. After the reaction is finished, 5mL of anhydrous methanol is poured to terminate the reaction, the reaction solution is washed by about 100mL of deionized water and poured into a separating funnel, the mixture is extracted 3 times by dichloromethane (about 50mL each time), products in dichloromethane at the lower layer are combined and collected, and anhydrous Na is used for 2 SO 4 And standing and drying overnight. And removing suspended insoluble substances from the dried solution by using a needle filter of a hydrophilic nylon filter membrane, and then removing the solvent by rotary evaporation to obtain colorless transparent liquid, namely the benzylated beta-cyclodextrin.
2. Preparing the ultrahigh crosslinked beta-cyclodextrin polymer:
1g of benzylated beta-cyclodextrin, 0.2g of p-dibromide benzyl (b) were dissolved in 60mL of anhydrous dichloroethane in N 2 2.4g of anhydrous FeCl was rapidly added in the atmosphere 3 Stirring at room temperature for 30min, heating to 80 ℃, and continuing to react for 18 h. After the reaction is finished, filtering the brown solid, sequentially washing with ethanol-methanol-2M HCl and methanol until the filtrate is clear, performing Soxhlet extraction on the brown yellow product in methanol for 48 hours, and then drying in vacuum to obtain the ultrahigh crosslinked beta-cyclodextrin polymer 9.
Example 10
1. Preparation of benzylated beta-cyclodextrin:
2g of beta-cyclodextrin was dissolved in 40ml of anhydrous DMF. The solution was then placed in an ice-water bath to which 0.6g NaH (kerosene reserve, 60 wt%) was added and stirring was continued for about 15 min. Then, 3g of benzyl chloride was slowly injected into the reaction system, and after stirring for a while, the reaction system was warmed to room temperature to continue the reaction for 12 hours. After the reaction is finished, 5mL of anhydrous methanol is poured to terminate the reaction, the reaction solution is washed by about 100mL of deionized water and poured into a separating funnel, the mixture is extracted 3 times by dichloromethane (about 50mL each time), products in dichloromethane at the lower layer are combined and collected, and anhydrous Na is used for 2 SO 4 And standing and drying overnight. Removing suspended insoluble substances from the dried solution by using a needle filter with a hydrophilic nylon filter membrane, and then removing the solvent by rotary evaporation to obtain colorless transparent liquid, namely the benzylated beta-cyclodextrin.
2. Preparing the ultrahigh crosslinked beta-cyclodextrin polymer:
1g of benzylated beta-cyclodextrin, 0.1g of p-dichlorobenzyl (a) and 0.1g of biphenyldichlorobenzyl (c) were dissolved in 60mL of anhydrous dichloroethane in the presence of N 2 2.4g of anhydrous FeCl was rapidly added in the atmosphere 3 Stirring at room temperature for 30min, heating to 80 ℃, and continuing to react for 18 h. After the reaction is finished, filtering the brown solid, sequentially washing with ethanol-methanol-2M HCl and methanol until the filtrate is clear, performing Soxhlet extraction on the brown yellow product in methanol for 48 hours, and then drying in vacuum to obtain the ultrahigh crosslinked beta-cyclodextrin polymer 10. The specific surface area of the ultra-high crosslinked beta-cyclodextrin polymer 10 was determined to be 15.8003m by nitrogen desorption curve 2 The nitrogen adsorption and desorption curve shows that the polymer structure contains a certain amount of pore structures, and the adsorption material is an adsorption material with good pore performance.
Example 11
1. Preparation of benzylated beta-cyclodextrin:
2g of beta-cyclodextrin was dissolved in 40ml of anhydrous DMF. The solution was then placed in an ice-water bath with 0.6g NaH (kerosene stock, content 60 wt%) added and stirring continued for about 15 min. Then, 3g of benzyl chloride was slowly injected into the reaction system, and after stirring for a while, the reaction system was warmed to room temperature to continue the reaction for 12 hours. After the reaction, 5mL of anhydrous methanol was added to terminate the reaction, the reaction mixture was washed with about 100mL of deionized water, poured into a separatory funnel, and extracted with dichloromethane 3 times (About 50mL each), the product in the lower methylene chloride layer was collected in combination and dried over anhydrous Na 2 SO 4 And standing and drying overnight. And removing suspended insoluble substances from the dried solution by using a needle filter of a hydrophilic nylon filter membrane, and then removing the solvent by rotary evaporation to obtain colorless transparent liquid, namely the benzylated beta-cyclodextrin.
2. Preparing the ultrahigh crosslinked beta-cyclodextrin polymer:
1g of benzylated beta-cyclodextrin, 0.1g of p-dichlorobenzyl (a) and 0.1g of 9, 10-bis (chloromethyl) anthracene (g) were dissolved in 60mL of anhydrous dichloroethane in N 2 2.4g of anhydrous FeCl was rapidly added in the atmosphere 3 Stirring at room temperature for 30min, heating to 80 ℃, and continuing to react for 18 h. And after the reaction is finished, filtering the brown solid, sequentially washing with ethanol-methanol-2M HCl and methanol until the filtrate is clear, performing Soxhlet extraction on the brown product in methanol for 48 hours, and drying in vacuum to obtain the ultrahigh crosslinked beta-cyclodextrin polymer 11.
Example 12
1. Preparation of benzylated beta-cyclodextrin:
2g of beta-cyclodextrin was dissolved in 40ml of anhydrous DMF. The solution was then placed in an ice-water bath to which 0.6g NaH (kerosene reserve, 60 wt%) was added and stirring was continued for about 15 min. Then, 3g of benzyl chloride was slowly injected into the reaction system, and after stirring for a while, the reaction system was warmed to room temperature to continue the reaction for 12 hours. After the reaction is finished, 5mL of anhydrous methanol is poured to terminate the reaction, the reaction solution is washed by about 100mL of deionized water and poured into a separating funnel, the mixture is extracted 3 times by dichloromethane (about 50mL each time), products in dichloromethane at the lower layer are combined and collected, and anhydrous Na is used for 2 SO 4 And standing and drying overnight. Removing suspended insoluble substances from the dried solution by using a needle filter with a hydrophilic nylon filter membrane, and then removing the solvent by rotary evaporation to obtain colorless transparent liquid, namely the benzylated beta-cyclodextrin.
2. Preparing the ultrahigh crosslinked beta-cyclodextrin polymer:
1g of benzylated beta-cyclodextrin, 0.1g of biphenyldichlorobenzyl (c) and 0.1g of 9, 10-bis (chloromethyl) anthracene (g) were dissolved in 60mL of anhydrous dichloroethane in N 2 Rapidly adding 2.4g of anhydrous FeCl into the atmosphere 3 Stirring at room temperature for 30min, heating to 80 deg.C, and continuing reaction for 18h. After the reaction is finished, filtering the brown solid, sequentially washing with ethanol-methanol-2M HCl and methanol until the filtrate is clear, performing Soxhlet extraction on the brown yellow product in methanol for 48 hours, and then drying in vacuum to obtain the ultrahigh crosslinked beta-cyclodextrin polymer 12.
Example 13
1. Preparation of benzylated beta-cyclodextrin:
2g of beta-cyclodextrin was dissolved in 40ml of anhydrous DMF. The solution was then placed in an ice-water bath to which 0.6g NaH (kerosene reserve, 60 wt%) was added and stirring was continued for about 15 min. Then, 3g of benzyl chloride was slowly injected into the reaction system, and after stirring for a while, the reaction system was warmed to room temperature to continue the reaction for 12 hours. After the reaction is finished, 5mL of anhydrous methanol is poured to terminate the reaction, the reaction solution is washed by about 100mL of deionized water and poured into a separating funnel, the mixture is extracted 3 times by dichloromethane (about 50mL each time), products in dichloromethane at the lower layer are combined and collected, and anhydrous Na is used for 2 SO 4 And standing and drying overnight. And removing suspended insoluble substances from the dried solution by using a needle filter of a hydrophilic nylon filter membrane, and then removing the solvent by rotary evaporation to obtain colorless transparent liquid, namely the benzylated beta-cyclodextrin.
2. Preparing the ultrahigh crosslinked beta-cyclodextrin polymer:
1g of benzylated β -cyclodextrin, 0.067g of p-dichlorobenzyl (a), 0.067g of biphenyl dichlorobenzyl (c) and 0.067g of 9, 10-bis (chloromethyl) anthracene (g) were dissolved in 60mL of anhydrous dichloroethane in N 2 2.4g of anhydrous FeCl was rapidly added in the atmosphere 3 Stirring at room temperature for 30min, heating to 80 ℃, and continuing to react for 18 h. After the reaction is finished, filtering the brown solid, sequentially washing with ethanol-methanol-2M HCl and methanol until the filtrate is clear, performing Soxhlet extraction on the brown yellow product in methanol for 48 hours, and then drying in vacuum to obtain the ultrahigh crosslinked beta-cyclodextrin polymer 13.
Example 14
1. Preparation of benzylated beta-cyclodextrin:
2g of beta-cyclodextrin was dissolved in 40ml of anhydrous DMF. The solution was then placed in an ice-water bath with 0.6g NaH (kerosene stock, content 60 wt%) added and stirring continued for about 15 min. Then, 3g of benzyl chloride was slowly injected into the reaction system, stirred for a while, and then warmed to room temperature, followed byThe reaction is continued for 12 h. After the reaction is finished, 5mL of anhydrous methanol is poured to terminate the reaction, the reaction solution is washed by about 100mL of deionized water and poured into a separating funnel, the mixture is extracted 3 times by dichloromethane (about 50mL each time), products in dichloromethane at the lower layer are combined and collected, and anhydrous Na is used for 2 SO 4 And standing and drying overnight. And removing suspended insoluble substances from the dried solution by using a needle filter of a hydrophilic nylon filter membrane, and then removing the solvent by rotary evaporation to obtain colorless transparent liquid, namely the benzylated beta-cyclodextrin.
2. Preparing the ultrahigh crosslinked beta-cyclodextrin polymer:
1g of benzylated β -cyclodextrin, 0.05g of p-dichlorobenzyl (a), 0.05g of biphenyl dichlorobenzyl (c) and 0.1g of 9, 10-bis (chloromethyl) anthracene (g) were dissolved in 60mL of anhydrous dichloroethane in the presence of N 2 2.4g of anhydrous FeCl was rapidly added in the atmosphere 3 Stirring at room temperature for 30min, heating to 80 ℃, and continuing to react for 18 h. After the reaction is finished, filtering the brown solid, sequentially washing with ethanol-methanol-2M HCl and methanol until the filtrate is clear, performing Soxhlet extraction on the brown yellow product in methanol for 48 hours, and then drying in vacuum to obtain the ultrahigh crosslinked beta-cyclodextrin polymer 14.
Example 15
1. Preparation of benzylated beta-cyclodextrin:
2g of beta-cyclodextrin was dissolved in 40ml of anhydrous DMF. The solution was then placed in an ice-water bath to which 0.6g NaH (kerosene reserve, 60 wt%) was added and stirring was continued for about 15 min. Then, 3g of benzyl chloride was slowly injected into the reaction system, and after stirring for a while, the reaction system was warmed to room temperature to continue the reaction for 12 hours. After the reaction is finished, 5mL of anhydrous methanol is poured to terminate the reaction, the reaction solution is washed by about 100mL of deionized water and poured into a separating funnel, the mixture is extracted 3 times by dichloromethane (about 50mL each time), products in dichloromethane at the lower layer are combined and collected, and anhydrous Na is used for 2 SO 4 And standing and drying overnight. And removing suspended insoluble substances from the dried solution by using a needle filter of a hydrophilic nylon filter membrane, and then removing the solvent by rotary evaporation to obtain colorless transparent liquid, namely the benzylated beta-cyclodextrin.
2. Preparing the ultrahigh crosslinked beta-cyclodextrin polymer:
1g of benzylated beta-cyclodextrin, 0.1g of p-bisBenzyl chloride (a), 0.05g Biphenyldichlorobenzyl (c), 0.05g 9, 10-bis (chloromethyl) anthracene (g) dissolved in 60mL anhydrous dichloroethane in N 2 2.4g of anhydrous FeCl was rapidly added in the atmosphere 3 Stirring at room temperature for 30min, heating to 80 ℃, and continuing to react for 18 h. After the reaction is finished, filtering the brown solid, sequentially washing with ethanol-methanol-2M HCl and methanol until the filtrate is clear, performing Soxhlet extraction on the brown yellow product in methanol for 48 hours, and then drying in vacuum to obtain the ultrahigh crosslinked beta-cyclodextrin polymer 15.
Example 16
1. Preparation of benzylated beta-cyclodextrin:
2g of beta-cyclodextrin was dissolved in 40ml of anhydrous DMF. The solution was then placed in an ice-water bath to which 0.6g NaH (kerosene reserve, 60 wt%) was added and stirring was continued for about 15 min. Then, 3g of benzyl chloride was slowly injected into the reaction system, and after stirring for a while, the reaction system was warmed to room temperature to continue the reaction for 12 hours. After the reaction is finished, 5mL of anhydrous methanol is poured to terminate the reaction, the reaction solution is washed by about 100mL of deionized water and poured into a separating funnel, the mixture is extracted 3 times by dichloromethane (about 50mL each time), products in dichloromethane at the lower layer are combined and collected, and anhydrous Na is used for 2 SO 4 And standing and drying overnight. And removing suspended insoluble substances from the dried solution by using a needle filter of a hydrophilic nylon filter membrane, and then removing the solvent by rotary evaporation to obtain colorless transparent liquid, namely the benzylated beta-cyclodextrin.
2. Preparing the ultrahigh crosslinked beta-cyclodextrin polymer:
1g of benzylated β -cyclodextrin, 0.05g of p-dichlorobenzyl (a), 0.1g of biphenyl dichlorobenzyl (c) and 0.05g of 9, 10-bis (chloromethyl) anthracene (g) were dissolved in 60mL of anhydrous dichloroethane in the presence of N 2 2.4g of anhydrous FeCl was rapidly added in the atmosphere 3 Stirring at room temperature for 30min, heating to 80 ℃, and continuing to react for 18 h. After the reaction is finished, filtering the brown solid, sequentially washing with ethanol-methanol-2M HCl and methanol until the filtrate is clear, performing Soxhlet extraction on the brown yellow product in methanol for 48 hours, and then drying in vacuum to obtain the ultrahigh crosslinked beta-cyclodextrin polymer 16.
Example 17
1. Preparation of benzylated beta-cyclodextrin:
2g of beta-cyclodextrinDissolved in 40ml dry DMF. The solution was then placed in an ice-water bath with 0.6g NaH (kerosene stock, content 60 wt%) added and stirring continued for about 15 min. Then, 3g of benzyl chloride was slowly injected into the reaction system, and after stirring for a while, the reaction system was warmed to room temperature to continue the reaction for 12 hours. After the reaction is finished, 5mL of anhydrous methanol is poured to terminate the reaction, the reaction solution is washed by about 100mL of deionized water and poured into a separating funnel, the mixture is extracted 3 times by dichloromethane (about 50mL each time), products in dichloromethane at the lower layer are combined and collected, and anhydrous Na is used for 2 SO 4 And standing and drying overnight. And removing suspended insoluble substances from the dried solution by using a needle filter of a hydrophilic nylon filter membrane, and then removing the solvent by rotary evaporation to obtain colorless transparent liquid, namely the benzylated beta-cyclodextrin.
2. Preparing the ultrahigh crosslinked beta-cyclodextrin polymer:
1g of benzylated beta-cyclodextrin and 0.2g of hydroquinone are dissolved in 60mL of anhydrous dichloroethane in N 2 1g FDA and 2.4g anhydrous FeCl were added rapidly to the atmosphere 3 Stirring at room temperature for 30min, heating to 80 ℃, and continuing to react for 18 h. After the reaction is finished, filtering the brown solid, sequentially washing with ethanol-methanol-2M HCl and methanol until the filtrate is clear, performing Soxhlet extraction on the brown yellow product in methanol for 48 hours, and then drying in vacuum to obtain the ultrahigh crosslinked beta-cyclodextrin polymer 17.
Example 18
20mg of the ionomer 13 prepared according to the best protocol of example 13 was taken and placed in a container containing 50mL of ionomer 13 with a concentration of 50 mg. L -1 The solution is shaken in a water bath constant temperature shaker at room temperature for 4 hours, a solution sample is taken after adsorption balance, and the change condition of the absorbance of the methyl orange after adsorption is finished is measured by an ultraviolet-visible spectrophotometer. As shown in fig. 4, in the adsorption process of methyl orange, as shown in the figure, the absorbance decreases with the increase of time, and when the adsorption time is 180min, the adsorption is almost completely finished.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of a super-high cross-linked beta-cyclodextrin polymer is characterized by comprising the following steps:
(1) dissolving beta-cyclodextrin in a solvent, adding NaH, and reacting under stirring to deprotonate hydroxyl groups of the beta-cyclodextrin to form oxygen anions, thereby obtaining a deprotonated hydroxyl beta-cyclodextrin solution;
(2) adding a benzylation reagent into the solution obtained in the step (1), reacting for 8-24 h at 20-140 ℃, adding anhydrous methanol to stop the reaction, washing and extracting the reaction solution, collecting and drying a lower-layer product to obtain a benzyl-substituted beta-cyclodextrin compound;
(3) dissolving the benzyl-substituted beta-cyclodextrin compound in the step (2) in a solvent, adding an active polyaromatic ring rigid structure compound, adding a Lewis acid catalyst in an inert atmosphere, carrying out reflux reaction at 60-120 ℃ for 18-36 h, washing, extracting and drying a reaction product to obtain the ultrahigh cross-linked beta-cyclodextrin polymer.
2. The preparation method according to claim 1, wherein the benzylation reagent in step (2) is one or both of benzyl chloride and benzyl bromide;
and (4) the active multi-aromatic ring rigid structure compound in the step (3) is one or more than two of p-dichlorobenzyl, biphenyl dichlorobenzyl, 4 '-dichloromethyl terphenyl, 9, 10-bis (chloromethyl) anthracene, p-dibromobenzyl, biphenyl dibromobenzyl, 4-dibromomethyl terphenyl, 9, 10-bis (bromomethyl) anthracene, p-diphenol and 4,4' -dihydroxybiphenyl.
3. The method according to claim 1, wherein the solvent in step (1) is one or both of DMF and DMSO;
and (3) the solvent is one or more than two of DMF, chlorobenzene, o-dichlorobenzyl, nitrobenzene, dichloromethane and dichloroethane.
4. The preparation method according to claim 1, 2 or 3, wherein the mass ratio of the beta-cyclodextrin to NaH in the step (1) is 1: 1-4: 1, and the reaction temperature is-5 ℃;
the molar mass ratio of the beta-cyclodextrin in the step (1) to the benzylation reagent in the step (2) is 1: 7-1: 21.
5. The process according to claim 4, wherein the Lewis acid catalyst of step (3) is ZnCl 2 、AlCl 3 、FeCl 3 、SnCl 4 The mass ratio of the benzylated beta-cyclodextrin to the active polyaromatic ring rigid structure compound and the Lewis acid catalyst is (1-3): (0.1-0.5): (1-5);
and (3) adding an external cross-linking agent into the inert atmosphere, wherein the external cross-linking agent is dimethoxymethane, and the mass ratio of the benzylated beta-cyclodextrin to the dimethoxymethane is 1: 1-10: 1.
6. The method according to claim 5, wherein the Lewis acid catalyst in the step (3) is FeCl 3 The mass ratio of the benzylated beta-cyclodextrin to the active polyaromatic ring rigid structure compound to the Lewis acid catalyst is 1:0.2: 2.4.
7. The method according to claim 1, wherein the washing in step (2) is sequentially washing with ethanol-methanol-2M HCl-methanol until the filtrate is clear, and the drying is anhydrous Na 2 SO 4 Standing and drying overnight, wherein the inert atmosphere in the step (3) is N 2 Or He or Ar.
8. An ultra-high cross-linked beta-cyclodextrin polymer, characterized in that it is prepared by the method of any of claims 1-7.
9. Use of the ultra-highly crosslinked β -cyclodextrin polymer of claim 8 for treating organic dye-containing wastewater.
10. The use according to claim 9, wherein the organic dye is one or more of methyl orange, methyl blue, methylene blue, rhodamine B, nile red, crystal violet, malachite green, eosin B, sunset yellow.
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