CN118530466A - Octamethyl ureido deep calixarene crosslinked polymer as well as preparation method and application thereof - Google Patents
Octamethyl ureido deep calixarene crosslinked polymer as well as preparation method and application thereof Download PDFInfo
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- calixarene
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- VTJUKNSKBAOEHE-UHFFFAOYSA-N calixarene Chemical compound COC(=O)COC1=C(CC=2C(=C(CC=3C(=C(C4)C=C(C=3)C(C)(C)C)OCC(=O)OC)C=C(C=2)C(C)(C)C)OCC(=O)OC)C=C(C(C)(C)C)C=C1CC1=C(OCC(=O)OC)C4=CC(C(C)(C)C)=C1 VTJUKNSKBAOEHE-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229920006037 cross link polymer Polymers 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- RSPZSDWVQWRAEF-UHFFFAOYSA-N hepta-1,6-diyne Chemical compound C#CCCCC#C RSPZSDWVQWRAEF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000003463 adsorbent Substances 0.000 claims description 9
- 239000000356 contaminant Substances 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000012265 solid product Substances 0.000 claims description 6
- XMTQQYYKAHVGBJ-UHFFFAOYSA-N 3-(3,4-DICHLOROPHENYL)-1,1-DIMETHYLUREA Chemical compound CN(C)C(=O)NC1=CC=C(Cl)C(Cl)=C1 XMTQQYYKAHVGBJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000005510 Diuron Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 239000000575 pesticide Substances 0.000 claims description 3
- 239000011755 sodium-L-ascorbate Substances 0.000 claims description 3
- 235000019187 sodium-L-ascorbate Nutrition 0.000 claims description 3
- 239000004009 herbicide Substances 0.000 claims description 2
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 claims description 2
- 229960005055 sodium ascorbate Drugs 0.000 claims description 2
- PVGBHEUCHKGFQP-UHFFFAOYSA-N sodium;n-[5-amino-2-(4-aminophenyl)sulfonylphenyl]sulfonylacetamide Chemical compound [Na+].CC(=O)NS(=O)(=O)C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 PVGBHEUCHKGFQP-UHFFFAOYSA-N 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 21
- 229920000642 polymer Polymers 0.000 abstract description 18
- 238000011069 regeneration method Methods 0.000 abstract description 5
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 4
- 230000008929 regeneration Effects 0.000 abstract description 4
- 238000012650 click reaction Methods 0.000 abstract description 2
- 238000004132 cross linking Methods 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 150000001540 azides Chemical class 0.000 description 9
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- 239000003344 environmental pollutant Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- 238000003911 water pollution Methods 0.000 description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 239000005574 MCPA Substances 0.000 description 3
- WHKUVVPPKQRRBV-UHFFFAOYSA-N Trasan Chemical compound CC1=CC(Cl)=CC=C1OCC(O)=O WHKUVVPPKQRRBV-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- 238000012565 NMR experiment Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000000463 material Substances 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
- 238000000746 purification Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinyl group Chemical class C1(O)=CC(O)=CC=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- KKVTYAVXTDIPAP-UHFFFAOYSA-M sodium;methanesulfonate Chemical compound [Na+].CS([O-])(=O)=O KKVTYAVXTDIPAP-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000005299 abrasion 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
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 238000004896 high resolution mass spectrometry Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- 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
- B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
-
- 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
- C02F2101/306—Pesticides
-
- 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
- C02F2101/34—Organic compounds containing oxygen
-
- 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
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- 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
- C02F2101/36—Organic compounds containing halogen
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to an octamethyl ureido deep calixarene cross-linked polymer, a preparation method and application thereof, wherein the structural formula of the octamethyl ureido deep calixarene cross-linked polymer is shown as follows: wherein R is The octamethyl ureido deep calixarene cross-linked polymer is prepared by taking octamethyl ureido deep calixarene as a main macrocyclic module and performing cross-linking with 1, 6-heptadiyne through a Click reaction. Compared with the prior art, the polymer prepared by the invention has the capability of efficiently adsorbing organic pollutants in water, the adsorption efficiency of the polymer on the organic pollutants can reach more than 99 percent, the adsorption quantity is larger, and the polymer has the regeneration performance.
Description
Technical Field
The invention relates to the technical field of organic materials, in particular to an octamethyl ureido deep calixarene cross-linked polymer as well as a preparation method and application thereof.
Background
In recent years, social economy has rapidly developed, and environmental problems face a number of challenges. Major environmental problems include water pollution, atmospheric pollution, land desertification and nuclear pollution. The ocean occupies 70% of land area, but the fresh water resource available for human use is only 2.5%, and the reliable data shows that the available water source is very small. The water pollution is more and more serious, and pollution sources include wastewater, domestic sewage, special wastewater and the like generated in the industrial production and manufacturing process. The pollution species are various, including dyes, perfluorinated compounds, iodine, heavy metal ions, antibiotics, pesticides and the like. These substances are generally difficult to degrade and carcinogenic. Thus, the discharge and treatment of wastewater is of paramount relevance to our life safety lives.
There is a great deal of interest in how to efficiently and quickly remove contaminants from water. The adsorption method is one of the water pollution removal methods that are currently widely used. However, conventional adsorbents such as zeolite and activated carbon have disadvantages of low selectivity, limited adsorption performance for polar compounds, and need of a severe desorption regeneration procedure. These factors severely limit their further development and use in practical applications.
Macrocyclic host crosslinked polymers are widely developed as a novel advanced organic adsorbent for the removal of organic micropollutants in water. The material constructed by the macrocyclic main body through the covalent bond has the characteristics of structural diversity, modifiable property, stability and the like, and has wide application in the fields of pollutant removal, storage, separation and the like. In particular, macrocyclic host crosslinked polymers are of great concern in the adsorption of contaminants in water. The calixarene structure endows an electron-rich framework, an easily-modified upper port and a lower port and good host-guest recognition performance, and is one of hot spots for research.
Disclosure of Invention
The invention aims to provide an octamethyl ureido deep hole calixarene cross-linked polymer, and a preparation method and application thereof, wherein the existing adsorbent has the defects of low selectivity, limited adsorption performance, difficult regeneration and the like.
The aim of the invention can be achieved by the following technical scheme:
one of the technical schemes of the invention is to provide an octamethyl ureido deep hole calixarene cross-linked polymer, the structural formula of which is shown as follows:
wherein R is
The second technical scheme of the invention is to provide a preparation method of the octamethyl ureido deep hole calixarene crosslinked polymer according to the first technical scheme, which comprises the following steps:
S1, under inert atmosphere, mixing an octamethylureido molecular cup compound and N, N-Dimethylformamide (DMF), adding sodium azide, and heating for reaction to separate out a solid product;
s2, mixing the solid product obtained in the step S1 with CuSO 4, L-sodium ascorbate, dimethyl sulfoxide (DMSO) and 1, 6-heptadiyne in an inert atmosphere, and heating for reaction to obtain the octamethyl ureido deep hole calixarene crosslinked polymer.
In some embodiments, in step S1, the octamethylureido molecular cup compound, sodium azide, has an equivalent ratio of 1:20.
The octamethyl ureido molecule calix is a calixarene with deep holes, and the calix macrocyclic molecules formed by constructing an aromatic wall through aromatic nucleophilic substitution of resorcinol calixarene can be endowed with different functions through adjusting the upper edge structure of the calixarene, so that the octamethyl ureido molecule calix is applied to the fields of molecular recognition, self-assembly, organic reaction regulation and control, reaction intermediate capturing, isomer separation and the like.
In some embodiments, in step S1, the heating reaction is performed at a temperature of 80-85℃for a period of at least 24 hours.
In some embodiments, in step S1, the washing is performed after heating, and the washing process is to sequentially wash with methanol and dichloromethane.
In some embodiments, in step S2, the equivalent ratio of solid product to CuSO 4, sodium L-ascorbate, 1, 6-heptadiyne is 1:0.6:0.6:2.
In some embodiments, in step S2, the heating reaction is performed at a temperature of 80-85℃for a period of at least 48 hours.
In some embodiments, in step S2, the washing is performed after heating, and the washing process is performed by washing with water, a saturated aqueous solution of ethylenediamine tetraacetic acid (EDTA), water, ethanol, and dichloromethane in this order.
In some embodiments, in step S2, after heating the reaction, dichloromethane is further added to the reaction system and stirred under reflux for at least 24 hours.
Preferably, the methylene chloride is refluxed and stirred in the reaction system after washing for at least 24 hours.
The third technical scheme of the invention is to provide the application of the octamethyl ureido deep calixarene cross-linked polymer in one of the technical schemes, wherein the octamethyl ureido deep calixarene cross-linked polymer is used for preparing an adsorbent.
In some embodiments, the adsorbent is used to adsorb contaminants in water.
In some embodiments, the contaminant includes a pesticide, a herbicide.
In some embodiments, the contaminant comprises dimethyltetrachloro, diuron, bisphenol a.
Compared with the prior art, the invention has the following beneficial effects:
(1) Compared with a polymer based on calixarene, the calixarene is mainly used as a node for constructing a porous polymer network, the formed polymer is used for adsorption by the specific surface area, and the octamethylureido deep hole calixarene crosslinked polymer prepared by the method is of a non-porous structure, takes the deep hole calixarene as a framework, reserves inherent cavities of the deep hole calixarene, highlights the independent function of a macrocyclic cavity, provides selectivity for the electron-rich cavity through weak interaction, has complete host-guest identification function, and accelerates the removal efficiency of pollutants. In addition, it has abrasion resistance, heat resistance, corrosion resistance and solvent resistance.
(2) The octamethyl ureido deep hole calixarene cross-linked polymer prepared by the invention can be expanded and swelled in water, the space between the main body modules is opened to form a certain adsorption space, the capability of efficiently adsorbing organic micro pollutants is shown, the adsorption efficiency of the octamethyl ureido deep hole calixarene cross-linked polymer on the organic pollutants can reach more than 99%, and the adsorption capacity is larger. After a number of cycles, the adsorption performance is not obviously reduced by simply using methanol or ethanol for regeneration. In addition, the method can be used for simulating the purification of an actual water sample, and the removal efficiency is not obviously reduced after the method is repeatedly used for more than 5 times. These properties impart value to the octamethylureido deep calixarene crosslinked polymers of the present invention for potential environmental remediation and water pollution treatments.
(3) The octamethyl ureido deep calixarene cross-linked polymer synthesized by the method has the advantages of simple and convenient path, easily obtained raw materials, mild reaction conditions, high yield and good reproducibility.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum (600 MHz, DMSO-d 6, 298K) of octamethylureido molecular cup S2 azide in example 1 of the present invention.
FIG. 2 is a nuclear magnetic resonance spectrum (600 MHz, DMSO-d 6, 298K) of octamethylureido molecular cup S2 azide in example 1 of the present invention.
FIG. 3 is a high resolution mass spectrum of octamethylureido molecular cup S2 azide in example 1 of the present invention.
FIG. 4 is an infrared spectrum of octamethylureido molecular cup S2 azide in example 1 of the present invention.
FIG. 5 is a solid 13 C NMR chart of polymer P1 in example 1 of the invention.
FIG. 6 is an infrared spectrum of the polymer P1 in example 1 of the present invention.
FIG. 7 shows nuclear magnetic resonance hydrogen spectra of the polymer P1 prepared in example 1 of the present invention before and after adsorption of MCPA, with an adsorption time of 10h (600 MHz, D 2 O, 298K).
FIG. 8 shows nuclear magnetic resonance hydrogen spectra of the polymer P1 prepared in example 1 of the present invention before and after diuron adsorption, and adsorption time of 10h (600 MHz, D 2 O, 298K).
FIG. 9 shows the cyclic adsorption test of the polymer P1 prepared in example 1 of the present invention.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples. The present embodiment is implemented on the premise of the technical scheme of the present invention, and a detailed implementation manner and a specific operation process are given, but the protection scope of the present invention is not limited to the following examples.
In the following examples, unless otherwise indicated, the starting materials or processing techniques are all those conventionally commercially available in the art.
Octamethylureido molecular cup S1: prepared by reference j.am.chem.soc.2014,136,5264.
Example 1:
The embodiment provides an octamethyl ureido deep hole calixarene cross-linked polymer and a preparation method thereof, wherein octamethyl ureido and the lower end edge are subjected to azide, and the octamethyl ureido deep hole calixarene cross-linked polymer and 1, 6-heptadiyne are successfully used as a connecting unit through a Click reaction, so that a supermolecule macrocyclic polymer P1 is formed.
The method comprises the following specific steps:
(1) NaN 3 (0.33 g,10mmol,20 eq) was added to 25mL DMF in a 50mL round bottom flask containing octamethylureido molecular cup S1 (0.72 g,1.0eq,0.5 mmol). Under nitrogen, the resulting suspension was then vigorously stirred at 80℃for 24h, cooled to room temperature, poured into 100mL of water, filtered and thoroughly rinsed with water. The residue was removed by washing with a small amount of methanol, followed by washing with Dichloromethane (DCM). After drying in vacuo, a white solid was obtained as octamethylureido azide, molecular cup S2 (96% yield) which was used in the next step without further purification.
(2) The octamethylureido molecule azide synthesized in the previous step was taken up in a molecular cup S2 (0.623 g,1.0eq,0.4 mmol), cuSO 4·5H2 O (60.0 mg,0.6eq,0.24 mmol), sodium L-ascorbate (42.3 mg,0.6eq,0.24 mmol) and 10mL DMSO. These materials were added to a 25mL round bottom bottle and 1, 6-heptadiyne (100.93 mg,2eq,0.8 mmol) was added under nitrogen and stirred vigorously at 80℃for 48h. The resulting suspension was cooled to room temperature, then poured into 50mL of water and filtered. The filter cake was filtered and thoroughly washed sequentially with water, saturated aqueous EDTA, water, ethanol and dichloromethane. The solid was stirred under reflux in methylene chloride for 24 hours to polymerize and disperse and remove the oligomer, and then filtered and dried under high vacuum to obtain pale yellow powder (0.65 g, yield 90%) as an octamethylureido deep calixarene crosslinked polymer P1.
The synthesis reaction is as follows:
In this example, nuclear magnetic, infrared and mass spectrometry characterization was performed on octamethylureido azide molecular cup S2 as shown in fig. 1-4:
1H NMR(600MHz,DMSO-d6)δ7.86(s,4H),7.75(s,4H),7.72(s,8H),5.68(t,J＝8.2Hz,4H),3.47(t,J＝6.9Hz,8H),3.15(s,24H),2.47-2.40(m,8H),1.57(t,J＝7.3Hz,8H).
13C NMR(151MHz,DMSO)δ155.2,154.3,146.3,135.2,127.0,124.7,116.3,104.1,50.5,48.6,33.0,28.7,27.2.
HR-MS(ESI):Calcd.for C84H77Cl4N8O12[M+H]+:1453.5404,Found:1453.5404.
structural analysis of crosslinked Polymer P1:
Referring to FIGS. 5-6, the structure of polymer P1 was characterized by Fourier transform infrared spectroscopy (FT-IR), solid 13 C NMR. First, the successful synthesis of this polymer P1 was determined by FT-IR and results of solid 13 C NMR data, i.e., the characteristic peak of octamethylureido molecular cup S2 azide disappeared at 2100cm -1, while the characteristic peaks of the other subjects remained unchanged. Characteristic signals near 145ppm and 125ppm of the solid 13 C NMR chemical shift values represent the 3-and 4-positions of triazole, respectively. These characterization results successfully confirm the successful synthesis of the crosslinked polymer P1, while also confirming that the crosslinked polymer P1 retains the backbone structure of its monomers.
Adsorption study of crosslinked Polymer P1 on organic pollutants
Dimethyl tetrachloro (MCPA) and diuron are respectively selected as the sources of the organic micro pollutants. Mixed solutions of organic micropollutants at a final concentration of 0.5mM and sodium methanesulfonate (internal standard) at a final concentration of 0.5mM were prepared separately and subjected to 1 H NMR experiments. To 0.6mL of the above mixed solution was added 3.0mg of the polymer adsorbent P1. The suspension was sonicated for 10 hours. The resulting mixture was then subjected to 298K nuclear magnetic resonance hydrogen spectrometry on a Bruker AVANCE III HD 600M machine. And 64 scans were performed.
Fig. 7-8 show nuclear magnetic hydrogen spectra of the crosslinked polymer P1 before and after adsorption of MCPA and diuron, respectively, with an adsorption time of 10h. The result shows that the signal of the micro-pollutants completely disappears, and the removal rate of the micro-pollutants is more than 99% after the micro-pollutants are quantitatively adsorbed. Since the polymer is non-porous, it is possible that the octamethylurea group of the polymer plays an important role in the adsorption process.
And finally, adding ethanol into the adsorbed cross-linked polymer P1, stirring for 2-3 hours at normal temperature, filtering, collecting solids, and drying in vacuum. A mixed solution of an organic micropollutant having a final concentration of 0.5mM and sodium methanesulfonate (internal standard) having a final concentration of 0.5mM was prepared using bisphenol A (BPA) as a contaminant, and 1 H NMR experiments were performed. To 0.6mL of the above mixed solution was added 3.0mg of the polymer adsorbent P1. The crosslinked polymer P1 was subjected to EtOH simple treatment to achieve complete regeneration and repeated use 6 times, while its removal efficiency remained unchanged, exhibiting excellent stability and recyclability, as shown in fig. 9.
In conclusion, the octamethyl ureido deep calixarene cross-linked polymer synthesized by the invention can be applied to the efficient adsorption of various organic micro pollutants in aqueous solution, and has a certain practical application potential in the field of environmental pollution treatment.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (10)
1. An octamethyl ureido deep calixarene cross-linked polymer is characterized in that, the structural formula of the octamethyl ureido deep hole calixarene cross-linked polymer is shown as follows:
wherein R is
2. A method for preparing the octamethyl ureido deep calixarene cross-linked polymer according to claim 1, comprising the steps of:
s1, under inert atmosphere, mixing an octamethylureido molecular cup compound and N, N-dimethylformamide, adding sodium azide, heating for reaction, and separating out a solid product;
S2, mixing the solid product obtained in the step S1 with CuSO 4, L-sodium ascorbate, dimethyl sulfoxide and 1, 6-heptadiyne under an inert atmosphere, and heating for reaction to obtain the octamethyl ureido deep hole calixarene crosslinked polymer.
3. The preparation method according to claim 2, wherein in step S1, the equivalent ratio of octamethylureido molecular cup compound to sodium azide is 1:20.
4. The process according to claim 2, wherein in step S1, the heating reaction is carried out at a temperature of 80-85 ℃ for a period of at least 24 hours.
5. The process according to claim 2, wherein in step S2, the equivalent ratio of solid product to CuSO 4, sodium L-ascorbate, 1, 6-heptadiyne is 1:0.6:0.6:2.
6. The process according to claim 2, wherein in step S2, the heating reaction is carried out at a temperature of 80-85 ℃ for a period of at least 48 hours.
7. The use of the octamethyl ureido deep calixarene cross-linked polymer according to claim 1, the method is characterized in that the octamethyl ureido deep calixarene cross-linked polymer is used for preparing an adsorbent.
8. The use according to claim 7, wherein the adsorbent is used for adsorbing contaminants in water.
9. The use of claim 8, wherein the contaminants comprise pesticides, herbicides.
10. The use according to claim 9, wherein the contaminants comprise dimethyltetrachloro, diuron, bisphenol a.
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