CN112915978A - Nitrogen-rich calix [4] arene cross-linked polymer and preparation method and application thereof - Google Patents
Nitrogen-rich calix [4] arene cross-linked polymer and preparation method and application thereof Download PDFInfo
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- CN112915978A CN112915978A CN202110083304.9A CN202110083304A CN112915978A CN 112915978 A CN112915978 A CN 112915978A CN 202110083304 A CN202110083304 A CN 202110083304A CN 112915978 A CN112915978 A CN 112915978A
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 132
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 68
- 229920006037 cross link polymer Polymers 0.000 title claims abstract description 60
- GQPLZGRPYWLBPW-UHFFFAOYSA-N calix[4]arene Chemical compound C1C(C=2)=CC=CC=2CC(C=2)=CC=CC=2CC(C=2)=CC=CC=2CC2=CC=CC1=C2 GQPLZGRPYWLBPW-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- WHSQATVVMVBGNS-UHFFFAOYSA-N 4-[4,6-bis(4-aminophenyl)-1,3,5-triazin-2-yl]aniline Chemical compound C1=CC(N)=CC=C1C1=NC(C=2C=CC(N)=CC=2)=NC(C=2C=CC(N)=CC=2)=N1 WHSQATVVMVBGNS-UHFFFAOYSA-N 0.000 claims abstract description 21
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical compound C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 26
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000003463 adsorbent Substances 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 12
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000003599 detergent Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 56
- 229920000642 polymer Polymers 0.000 abstract description 11
- 239000002351 wastewater Substances 0.000 abstract description 7
- 238000002336 sorption--desorption measurement Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 62
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 60
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 38
- 229950011260 betanaphthol Drugs 0.000 description 30
- JBIJLHTVPXGSAM-UHFFFAOYSA-N 2-naphthylamine Chemical compound C1=CC=CC2=CC(N)=CC=C21 JBIJLHTVPXGSAM-UHFFFAOYSA-N 0.000 description 18
- PRPINYUDVPFIRX-UHFFFAOYSA-N 1-naphthaleneacetic acid Chemical compound C1=CC=C2C(CC(=O)O)=CC=CC2=C1 PRPINYUDVPFIRX-UHFFFAOYSA-N 0.000 description 14
- 239000005971 1-naphthylacetic acid Substances 0.000 description 12
- VIBOGIYPPWLDTI-UHFFFAOYSA-N 2-naphthylacetic acid Chemical compound C1=CC=CC2=CC(CC(=O)O)=CC=C21 VIBOGIYPPWLDTI-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 125000003118 aryl group Chemical group 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 239000003344 environmental pollutant Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 231100000719 pollutant Toxicity 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 230000008929 regeneration Effects 0.000 description 5
- 238000011069 regeneration method Methods 0.000 description 5
- 239000011550 stock solution Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 229920000858 Cyclodextrin Polymers 0.000 description 3
- 239000001116 FEMA 4028 Substances 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 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 description 3
- 235000011175 beta-cyclodextrine Nutrition 0.000 description 3
- 229960004853 betadex Drugs 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- 125000006414 CCl Chemical group ClC* 0.000 description 2
- 229920001661 Chitosan Polymers 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- -1 amino calixarene Chemical compound 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000005384 cross polarization magic-angle spinning Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
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- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
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- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 230000036962 time dependent Effects 0.000 description 2
- 239000010457 zeolite Substances 0.000 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 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000009303 advanced oxidation process reaction Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 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 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 230000008821 health effect Effects 0.000 description 1
- 230000002489 hematologic effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000010983 kinetics study Methods 0.000 description 1
- 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 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 238000007339 nucleophilic aromatic substitution reaction Methods 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000000241 respiratory effect Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229950003937 tolonium Drugs 0.000 description 1
- HNONEKILPDHFOL-UHFFFAOYSA-M tolonium chloride Chemical compound [Cl-].C1=C(C)C(N)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 HNONEKILPDHFOL-UHFFFAOYSA-M 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000563 toxic property Toxicity 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
- B01J20/267—Cross-linked polymers
-
- 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
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/54—Three nitrogen atoms
- C07D251/70—Other substituted melamines
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/32—Hydrocarbons, e.g. oil
- C02F2101/327—Polyaromatic Hydrocarbons [PAH's]
-
- 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
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- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
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- Water Supply & Treatment (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to a nitrogen-rich calix [4] arene cross-linked polymer, a preparation method and application thereof, wherein the preparation method comprises the steps of reacting 4-amino calix [4] arene with s-triazine under an ice bath condition to obtain an intermediate; carrying out functional polymerization on the intermediate and 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine under an alkaline condition to obtain a nitrogen-rich calix [4] arene cross-linked polymer; the nitrogen-rich calix [4] arene cross-linked polymer can be used for adsorbing and treating polycyclic aromatic hydrocarbon in water. Compared with the prior art, the nitrogen-rich calix [4] arene crosslinked polymer prepared by the invention has the advantages of specific adsorption to polycyclic aromatic hydrocarbon, high adsorption efficiency, large adsorption capacity, good adsorption/desorption circulation effect, good reproducibility, good stability of the polymer and the like, and has a wide application prospect in the aspect of removing the polycyclic aromatic hydrocarbon which is difficult to degrade in wastewater.
Description
Technical Field
The invention relates to the technical field of organic supermolecular polymer preparation, in particular to a nitrogen-rich calix [4] arene cross-linked polymer, and a preparation method and application thereof.
Background
Polycyclic Aromatic Hydrocarbons (PAHs) contaminate surface and ground water, which is one of the most serious environmental problems facing mankind today, and their presence in aquatic environments is of increasing concern. One of the PAHs often found in nature is naphthalene. Its toxic properties cause respiratory or hematological and ocular health effects, and its derivatives 2-naphthol and 1-naphthol are typical pollutants in many chemical plant wastewaters and are the most important substructures of potential carcinogenic pollutants emitted by the pharmaceutical, dye, photographic and agrochemical industries. Thus, efficient removal of PAHs from wastewater has become an increasingly important environmental concern.
Various technologies have been developed to remediate organic contaminants such as PAHs in wastewater, such as advanced oxidation processes, photocatalysis, adsorption, volatilization, biological treatment, and membrane technologies. Among these methods, adsorption techniques are effective in removing PAHs due to their low cost and ease of operation. However, the difficulty is that effective corresponding adsorbents with high adsorption capacities must be found. In the last two decades, the PAHs in the water body can be effectively removed by using various traditional adsorbents such as activated carbon, zeolite, chitosan, clay and the like, but the problems of low treatment capacity, low adsorption speed, non-regeneration and the like still exist. Therefore, there is a need to develop a polymeric adsorbent having a stable structure, multi-functionalization, easy regeneration, and higher surface area and porosity, which has been used as a substitute for industrial applications to effectively remove PAHs from wastewater.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a nitrogen-rich calix [4] arene cross-linked polymer, a preparation method and application thereof, and solves the problems of low processing capacity, low adsorption speed, difficult regeneration process and the like of the conventional adsorbent for adsorbing polycyclic aromatic hydrocarbons in water.
The purpose of the invention can be realized by the following technical scheme:
the first purpose of the invention is to protect a preparation method of a nitrogen-rich calix [4] arene crosslinked polymer, which comprises the following steps:
s1: reacting 4-aminocalix [4] arene with s-triazine in an organic solvent under an ice bath condition to obtain an intermediate;
s2: and (3) carrying out functional polymerization on the intermediate obtained in the S1 and 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine under an alkaline condition to obtain the nitrogen-rich calix [4] arene crosslinked polymer.
Further, the organic solvent in S1 is tetrahydrofuran, the reaction process is a stirring reaction for 6-12h, and the solvent is removed after the reaction is completed to obtain an intermediate.
Further, S2 includes:
s2-1: dissolving the intermediate obtained in S1 and 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine in dioxane containing potassium carbonate to obtain a mixed reaction liquid in an alkaline polymerization environment;
s2-2: and (3) reacting the mixed reaction liquid under a heating condition, and after the reaction is finished, sequentially carrying out cooling, centrifugal separation, washing and vacuum drying processes to obtain the nitrogen-enriched calix [4] arene cross-linked polymer.
Further, the molar ratio of the 4-aminocalix [4] arene to the S-triazine in S1 is (1-2) to (2-4).
Further, the intermediate obtained in S1 was first washed with hexane before S2-1.
Furthermore, the molar ratio of the intermediate, 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine and potassium carbonate in S2-1 is 1 (2-3.5) to (5-15).
Further, the heating reaction temperature in S2-2 is 105-115 ℃, and the heating reaction time is 60-84 h.
Further, in the washing process in S2-2, water and an organic solvent detergent are adopted for washing in sequence.
Further, the organic solvent includes methanol, DMF.
A second object of the present invention is to protect a nitrogen-rich calix [4] arene crosslinked polymer prepared by the above process.
The third purpose of the invention is to protect the application of the nitrogen-rich calix [4] arene crosslinked polymer in the adsorbent, and the nitrogen-rich calix [4] arene crosslinked polymer is used as the adsorbent for adsorbing and treating the polycyclic aromatic hydrocarbon in the water body.
Further, the temperature in the adsorption treatment is room temperature or normal temperature.
The invention firstly utilizes s-triazine to modify 4-amino calix [4] arene to form an intermediate, then 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine with a three-dimensional structure reacts with the intermediate to form C-N bonds to complete grafting, and a nitrogen-rich calix [4] arene cross-linked polymer is obtained. The invention specifically relates to a method for modifying and polymerizing amino calixarene by using s-triazine to generate a strong covalent bond, thereby improving the thermal stability of the material and improving the nitrogen content in the polymer.
Compared with the prior art, the invention has the following technical advantages:
1) the invention prepares a nitrogen-rich cup [4]]The aromatic crosslinked polymer shows better stability, can be used as PAHs adsorbent in adsorption wastewater, selects 1-naphthylamine (1-NA), 2-naphthylamine (2-NA), 1-naphthol (1-NO), 2-naphthol (2-NO), 1-naphthylacetic acid (1-NAA) and 2-naphthylacetic acid (2-NAA) as target pollutants, has high adsorption efficiency (the adsorption efficiency on 1-naphthol and 2-naphthol can reach 97.65 percent and 92.45 percent) and large unit mass adsorption capacity (the maximum adsorption capacity on 1-naphthol and 2-naphthol respectively reaches 487.8mg g.g.g)-1、628.93mg·g-1) Good desorption effect, long cycle service life (namely, the polymer still keeps higher adsorption capacity after being recycled for a plurality of times), good heat resistance (the decomposition temperature is about 368 ℃) of the polymer and the like, better replaces the traditional adsorbent, and in addition, the good pollutant removal capacity also proves that the nitrogen-enriched cup [4]]The aromatic crosslinked polymer has a wide application prospect in the aspect of rapidly treating wastewater.
2) The nitrogen-rich calix [4] arene cross-linked polymer prepared by the invention belongs to an organic microporous polymer, and compared with adsorbents such as activated carbon, zeolite, chitosan, clay and the like, the organic microporous polymer is a novel porous material with high specific surface area, porous structure, high thermal stability and light weight, has a large number of open sites and wider pore size distribution after construction is completed, and compared with traditional microporous materials such as organic framework compound Materials (MOFs), the organic microporous polymer-based adsorbent not only has the flexible and targeted pore size design capability consistent with the MOFs, but also can solve the disadvantage that the MOFs cannot maintain a spatial structure in environments such as high temperature, acid and alkali and the like, and shows good adsorption performance and high selectivity.
3) Compared with an adsorbent taking beta-cyclodextrin (beta-CD) as a main component, the adsorbent is widely concerned because of the advantages of strong affinity, low cost and simple design of the beta-CD, but the application range of the adsorbent is limited because of the defect of poor water solubility, and the water solubility of the calixarene polymer material is enhanced by improving the content of nitrogen atoms, so that the problem of limited application range caused by poor water solubility is avoided, and the adsorption capacity of the material on organic micro-pollutants in water is further improved.
Drawings
FIG. 1 is a FT-IR spectrum of intermediate (e), 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine, nitrogen-rich calix [4] arene crosspolymer (CaCOP) in example 1;
FIG. 2 is an SEM image of a nitrogen-rich calix [4] arene cross-linked polymer of example 1;
FIG. 3 is a TEM image of a nitrogen-rich calix [4] arene cross-linked polymer of example 1;
FIG. 4 is a thermogravimetric plot of a nitrogen-rich calix [4] arene cross-linked polymer of example 1;
FIG. 5 shows nitrogen-rich cup [4] in example 1]N of aromatic crosslinked polymer2Adsorption and desorption isotherm diagram;
FIG. 6 shows nitrogen-rich cup [4] in example 1]CPMAS of aromatic crosslinked polymers (CaCOP)13C NMR spectrum chart;
FIG. 7 shows the CaCOP (1.00 mgmL) in example 2-1) Time-dependent adsorption process profiles for each PAHs (0.200 mM);
FIG. 8 is a graph comparing the removal rates of CaCOP to different PAHs after 30min contact in example 2;
FIG. 9 is a diagram of a device for testing the flow adsorption capacity of CaCOP in example 3;
FIG. 10 is a diagram of an experimental apparatus for the regeneration of CaCOP in example 4.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
Example 1
The method is used for preparing the nitrogen-enriched calix [4] arene cross-linked polymer (CaCOP), the reaction flow is as follows, examples 7 to 9 are all adjusted based on the following flow, but the performance is obviously reduced when the feeding range or the operation parameter range in the examples 7 to 9 is exceeded.
The preparation method comprises the following steps:
1) adding 4-aminocalix [4] arene and s-triazine into tetrahydrofuran in a molar ratio of 1:2, stirring and reacting for 8 hours under an ice bath condition, stopping the reaction, sequentially removing the solvent, washing for several times by using n-hexane, and drying to obtain an intermediate (e) with the yield of 80%;
2) dissolving the intermediate (e) and 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine in dioxane containing potassium carbonate, reacting at 110 ℃ for 72h, and after the reaction is finished, sequentially cooling to room temperature, centrifugally separating, washing with water and an organic solvent (methanol and DMF), and drying in vacuum to obtain the nitrogen-rich calix [4] arene cross-linked polymer (CaCOS), wherein the molar ratio of the intermediate (e) to the 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine to the potassium carbonate is 1:2.7:10, and 600mg of the nitrogen-rich calix [4] arene cross-linked polymer is obtained, and the yield is 40%. The organic solvent is a mixture of water, methanol and DMF.
The characterization of the reactants and products is as follows:
shown in figure 1 are intermediate (e), 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine and nitrogen-rich calix [4]]FT-IR spectrum of aromatic crosslinked polymer (CaCON) showing intermediate (e) and-CH of CaCON2The tensile vibration absorption peak is from 2960cm-1To 2850cm-1And disappearance of the C-Cl peak on the CaCOP (750-700 cm)-1)；
As shown in FIG. 2 and FIG. 3, which are SEM and TEM images of the nitrogen-rich calix [4] arene crosslinked polymer, respectively, the nitrogen-rich calix [4] arene crosslinked polymer can be seen as a three-dimensional structure from the TEM image;
as shown in FIG. 4, which is a thermogravimetric plot of a nitrogen-rich calix [4] arene crosslinked polymer, it can be seen that the decomposition temperature of the nitrogen-rich calix [4] arene crosslinked polymer is about 368 ℃, which indicates that the nitrogen-rich calix [4] arene crosslinked polymer has better stability;
as shown in figure 5, is a nitrogen-rich cup [4]]N of aromatic crosslinked polymer2Adsorption and desorption isotherm diagram with a surface area of 24m2·g-1；
As shown in figure 6, is a nitrogen-rich cup [4]]CPMAS of aromatic crosslinked polymers (CaCOP)13C NMR spectrum shows that e, 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine and CaCOS respectively have obvious absorption peaks at 170.3, 169.5 and 169.5ppm, the functional groups sequentially represented are-C-Cl, -C-N and-C-N, and the C-Cl peak on the CaCOS (170.3ppm) is supposed to obviously disappear, which indicates that the intermediate (e) and the 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine have nucleophilic aromatic substitution reaction.
Example 2
This example is intended to examine the static adsorption capacity of nitrogen-rich calix [4] arene cross-linked polymers (CaCOP) prepared in example 1 for PAHs.
The specific experimental process is as follows:
at the experimental ambient temperature of 25 ℃, the cacos (50.00mg) were first washed with 8mL of deionized water for 5.00min and then filtered through a PTFE membrane filter (0.45 μm), after which the cacos, PAHs stock solutions (0.200mM, 50.00mL) were added sequentially to a 100.0mL round bottom flask and the mixture was stirred immediately after the addition of the PAHs stock solution and the suspension in the flask (2.00mL) was removed by syringe at intervals and then immediately filtered using a PTFE membrane filter (0.45 μm) and the residual concentration of PAHs in each filtrate sample was determined by uv-vis spectroscopy. The detection wavelengths of the characteristic absorption peaks of the PAHs are as follows: 1-naphthylamine (1-NA 305.5nm), 2-naphthylamine (2-NA 278.5nm), 1-naphthol (1-NO 293.5nm), 2-naphthol (2-NO 327.5nm), 1-naphthylacetic acid (1-NAA 281nm) and 2-naphthylacetic acid (2-NAA 269nm) are selected.
The experimental results are as follows:
shown in FIG. 7 is CaCOP (1.00 mg. mL)-1) For each PAHs (0.200mM) time-dependent adsorption process diagram, 1-naphthylamine (1-NA), 2-naphthylamine (2-NA), 1-naphthol (1-NO), 2-naphthol (2-NO), 1-naphthylacetic acid (1-NAA) and 2-naphthylacetic acid (2-NAA) are mainly adsorbed, and the removal efficiency of the selected polycyclic aromatic hydrocarbon solution within 30 minutes is calculated according to the following formula.
Wherein C is0、CtThe concentration of the polycyclic aromatic hydrocarbon solution to be detected before adsorption and the concentration of the polycyclic aromatic hydrocarbon solution after 30min of adsorption are respectively.
As shown in FIG. 8, which is a comparison graph of the removal rate of the CaCOP to different PAHs after 30min of contact (data are shown in Table 1), it can be seen from FIG. 8 and Table 1 that the CaCOP shows excellent adsorption capacity to 1-naphthol (1-NO) and 2-naphthol (2-NO), and the removal efficiency reaches 92.45% and 97.65%, respectively, which are higher than that of naphthylamine and naphthylacetic acid. Possible reasons are: firstly, in the adsorption process, an amino group in the CaCOP can form a hydrogen bond with a naphthol hydroxyl group, and secondly, an electron-donating substituent on an aromatic ring in the CaCOP can enhance the interaction between the naphthol and the pi-pi. In addition, the smaller radius of the oxygen atom than the nitrogen atom makes the hydroxylated aromatic hydrocarbon molecule more easily adsorbed into the cavity of the material. Therefore, we speculate that the CaCOP material has super-strong adsorption capacity for hydroxylated aromatic hydrocarbon pollutants in water.
TABLE 1
Example 3
This example is intended to examine the flow adsorption capacity of nitrogen-rich calix [4] arene cross-linked polymers (CaCOP) prepared in example 1 for PAHs.
Specifically, a flow-through adsorption separation experiment was performed using a 5mL syringe (inner diameter of 1cm, total length of 5cm, and a layer of cotton wool was filled at the inner outlet of the syringe to prevent mass loss), and the experimental procedure was as follows:
as shown in fig. 9, at an experimental environment temperature of 25 ℃, cacos (100.00mg) were first washed with 15mL of deionized water for 5.00min, and then filtered through a PTFE membrane filter (0.45 μm), after which the cacos were transferred into a 5mL syringe (filling height of 2mm), after which 2mL of a stock solution of ahs (solution properties same as in example 2) was added into the syringe, and the PAHs stock solution was filtered through a cacos adsorption layer by pushing a piston for 30s (flow rate of 3-4 mL/min), and filtrates were collected, and the residual concentration of PAHs in each filtrate sample was determined using the method of example 2, thereby determining the removal efficiency of various PAHs contaminants, wherein each PAHs was repeated 3 times.
The experimental results are as follows: by utilizing a flow adsorption experiment, 99.9 percent of 1-naphthylamine (1-NA), 2-naphthylamine (2-NA), 1-naphthol (1-NO) and 2-naphthol (2-NO) are respectively adsorbed by the CaCOP, and the adsorption efficiency of 1-naphthylacetic acid (1-NAA) and 2-naphthylacetic acid (2-NAA) is 90 percent.
Example 4
This example is intended to examine the cycle life of the nitrogen-rich calix [4] arene cross-linked polymer (CaCOP) prepared in example 1.
The specific experimental process is as follows:
as shown in fig. 10, a syringe filled with capos (filling height of 2mm) was obtained by the same method as in example 3, 10mL of PAHs stock solution was filtered through the syringe at a flow rate of 3-4mL/min (1-naphthylacetic acid (1-NAA) and 2-naphthylacetic acid (2-NAA) in example 2 were used as the solutions, respectively), and then the capos were removed and subjected to methanol washing, centrifugation, and drying in sequence, and then repeatedly used, so that adsorption/desorption cycles were performed, and the removal efficiency during each cycle was examined by the same method as in example 2, and it was found that the removal efficiency of the capos during 5 adsorption/desorption cycles was equivalent to and substantially maintained as in example 3, indicating that the capos had excellent regeneration ability.
Example 5
This example was conducted to conduct a batch adsorption kinetics study of nitrogen-enriched calix [4] arene cross-linked polymer (CaCOP) prepared in example 1 on 1-naphthylamine (1-NA), 2-naphthylamine (2-NA), 1-naphthol (1-NO), 2-naphthol (2-NO).
The specific experimental procedures can be found in the literature (Shi, B.et al. A pilar [5] arene-based 3D network polymer for Rapid removal of organic micropollutants from water.J. Mater. chem.A. 5, 24217-.
The relevant balance parameters can be determined by a corresponding linear fit (as shown in table 2). The adsorption kinetics can be quantitatively described through a quasi-first-order kinetic model and a quasi-second-order kinetic model, so that an apparent rate constant K is obtained1And K2And a correlation number R2By comparison, the pseudo-secondary kinetic model was found to be more suitable for describing the adsorption process than the quasi-primary kinetic model, indicating that the adsorption behavior between the nitrogen-rich atoms of CaCOS and 1-naphthylamine (1-NA), 2-naphthylamine (2-NA), 1-naphthol (1-NO), 2-naphthol (2-NO) is mainly due to chemical interactions.
TABLE 2
Example 6
This example was conducted to conduct a batch adsorption thermodynamic study of nitrogen-rich calix [4] arene cross-linked polymer (CaCOP) prepared in example 1 on 1-naphthylamine (1-NA), 2-naphthylamine (2-NA), 1-naphthol (1-NO), 2-naphthol (2-NO).
The specific experimental procedures can be found in the literature (Shi, B.et al. A pilar [5] arene-based 3D network polymer for Rapid removal of organic micropollutants from water.J. Mater. chem.A. 5, 24217-.
Equilibrium isotherm data were composed of two well-known Langmuir and FAnd (3) describing a reandlich isotherm model. The relevant balance parameters can be determined by a corresponding linear fit (as shown in table 3). And (3) obtaining the maximum adsorption quantity of the adsorbent in the equilibrium state of methylene blue, toluidine blue and methyl orange by utilizing a Langmuir adsorption equation. Higher correlation coefficient (R) of Langmuir isothermal model2) It is shown that the adsorption data more closely matches the Langmuir isothermal model, indicating that the adsorption process is predominantly a relatively uniform monolayer adsorption. The maximum adsorption capacities (qm) of the nitrogen-atom-rich CaCOs to 1-naphthylamine (1-NA), 2-naphthylamine (2-NA), 1-naphthol (1-NO) and 2-naphthol (2-NO) are 390.625mg/g543.47mg/g, 487.8mg/g and 628.93mg/g respectively, which are higher than that of the existing Calixane polymer. The higher adsorption capacity may be attributed to the formation of a mesoporous structure and multiple adsorption sites, allowing PAHs molecules to rapidly enter the cavities within the nitrogen-rich atoms of the capos to form guest-guest complexes.
TABLE 3
Example 7
The preparation method of the three-dimensional covalent nitrogen-rich calix [4] arene cross-linked polymer comprises the following steps:
1) adding 4-aminocalix [4] arene and s-triazine into tetrahydrofuran in a molar ratio of 1:2, stirring and reacting for 8 hours under an ice bath condition, stopping the reaction, standing overnight at room temperature, filtering, drying, and washing with n-hexane to obtain an intermediate with a yield of 80%;
2) dissolving the intermediate and 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine in dioxane containing potassium carbonate, reacting at 110 ℃ for 72h, and after the reaction is finished, sequentially cooling to room temperature, centrifugally separating, washing with water and an organic solvent, and drying in vacuum to obtain the nitrogen-rich calix [4] arene cross-linked polymer (CaCOS), wherein the molar ratio of the intermediate to the 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine to the potassium carbonate is 1:2:5, so that 600mg of the nitrogen-rich calix [4] arene cross-linked polymer is obtained, and the yield is 40%.
As can be seen from Table 4, the removal efficiency of 1-naphthol (1-NO) and 2-naphthol (2-NO) by the CaCOP prepared in the example reaches 91.71% and 96.93%, and the excellent adsorption capacity is shown.
TABLE 4
Example 8
The preparation method of the three-dimensional covalent nitrogen-rich calix [4] arene cross-linked polymer comprises the following steps:
1) adding 4-aminocalix [4] arene and s-triazine into tetrahydrofuran in a molar ratio of 3:5, stirring and reacting for 8 hours under an ice bath condition, stopping the reaction, standing overnight at room temperature, filtering, drying, and washing with n-hexane to obtain an intermediate with a yield of 80%;
2) dissolving the intermediate and 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine in dioxane containing potassium carbonate, reacting at 110 ℃ for 72h, and after the reaction is finished, sequentially cooling to room temperature, centrifugally separating, washing with water and an organic solvent, and drying in vacuum to obtain the nitrogen-enriched calix [4] arene cross-linked polymer (CaCOS), wherein the molar ratio of the intermediate to the 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine to the potassium carbonate is 1:2.7:10, and 600mg of the nitrogen-enriched calix [4] arene cross-linked polymer is obtained, and the yield is 40%.
As can be seen from Table 5, the CaCOP prepared in this example showed excellent adsorption ability to 1-naphthol (1-NO) and 2-naphthol (2-NO).
TABLE 5
Example 9
The preparation method of the three-dimensional covalent nitrogen-rich calix [4] arene cross-linked polymer comprises the following steps:
1) adding 4-aminocalix [4] arene and s-triazine into tetrahydrofuran in a molar ratio of 1:4, stirring and reacting for 8 hours under an ice bath condition, stopping the reaction, standing overnight at room temperature, filtering, drying, and washing with n-hexane to obtain an intermediate with a yield of 80%;
2) dissolving the intermediate and 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine in dioxane containing potassium carbonate, reacting at 110 ℃ for 72h, and after the reaction is finished, sequentially cooling to room temperature, centrifugally separating, washing with water and an organic solvent, and drying in vacuum to obtain the nitrogen-enriched calix [4] arene cross-linked polymer (CaCOS), wherein the molar ratio of the intermediate to the 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine to the potassium carbonate is 1:3.5:15, and 600mg of the nitrogen-enriched calix [4] arene cross-linked polymer is obtained, and the yield is 40%.
As can be seen from Table 6, the CaCOP prepared in this example showed excellent adsorption ability to 1-naphthol (1-NO) and 2-naphthol (2-NO).
TABLE 6
Comparative example 1
Chinese patent CN111363160A discloses a three-dimensional covalent triazine-based calix [4] arene polymer and a preparation method and application thereof, the patent firstly utilizes s-triazine to modify amino calix [4] arene to form an intermediate, then the intermediate reacts with three-dimensional 1,3,5- (4-aminophenyl) benzene to form C-N bonds to complete grafting, and finally the triazine-based calix [4] arene polymer (1) with higher thermal stability is obtained.
The material in the technical scheme only shows stronger adsorption capacity to dye molecules with plane configuration with positive charges, the adsorption capacity of the material is possibly related to the configuration of the dye molecules, pi-pi interaction with TAB is facilitated, and the adsorption efficiency of MB and TB molecules is improved.
Compared with the prior art, the technical scheme realizes remarkable progress, and the intermediate reacts with the stereo 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine with high nitrogen content to form the nitrogen-enriched cup [4]]The aromatic crosslinked polymer (2) is noteworthy in that (2) an N atom is introduced, and since the electronegativity of the N atom is larger than that of the C atom, the N atom is presumed to exert an electron-withdrawing action, resulting in(2) In an electron-deficient state, therefore, the selected target pollutants are electron-rich polycyclic aromatic hydrocarbons (1-naphthylamine (1-NA), 2-naphthylamine (2-NA), 1-naphthol (1-NO), 2-naphthol (2-NO), 1-naphthylacetic acid (1-NAA) and 2-naphthylacetic acid (2-NAA) are target pollutants), and the adsorption experiment result shows that (2) has excellent affinity to 2-naphthol and 1-naphthol. Since BET of (2) is 24m2(2) adsorption efficiency to naphthol is higher than naphthylamine, probably due to small radius of O atom. And (2) the adsorption efficiency of the naphthylacetic acid is not ideal and is a normal phenomenon, because the carbonyl is an electron-deficient functional group and can not be beneficial to adsorption.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, 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 embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A preparation method of a nitrogen-enriched calix [4] arene crosslinked polymer is characterized by comprising the following steps:
s1: reacting 4-aminocalix [4] arene with s-triazine in an organic solvent under an ice bath condition to obtain an intermediate;
s2: and (3) carrying out functional polymerization on the intermediate obtained in the S1 and 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine under an alkaline condition to obtain the nitrogen-rich calix [4] arene crosslinked polymer.
2. The method for preparing nitrogen-enriched calix [4] arene crosslinked polymer according to claim 1, wherein the organic solvent S1 is tetrahydrofuran, the reaction process is a stirring reaction for 6-12 hours, and the solvent is removed after the reaction is completed to obtain an intermediate.
3. The method for preparing nitrogen-enriched calix [4] arene crosslinked polymer according to claim 1, wherein S2 comprises:
s2-1: dissolving the intermediate obtained in S1 and 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine in dioxane containing potassium carbonate to obtain a mixed reaction liquid in an alkaline polymerization environment;
s2-2: and (3) reacting the mixed reaction liquid under a heating condition, and after the reaction is finished, sequentially carrying out cooling, centrifugal separation, washing and vacuum drying processes to obtain the nitrogen-enriched calix [4] arene cross-linked polymer.
4. The method for preparing nitrogen-enriched calix [4] arene crosslinked polymer according to claim 1, wherein the molar ratio of the 4-aminocalix [4] arene to the S-triazine in S1 is (1-2) to (2-4).
5. The method of claim 3, wherein the intermediate obtained in S1 is first washed with hexane before S2-1.
6. The method for preparing nitrogen-enriched calix [4] arene crosslinked polymer according to claim 3, wherein the molar ratio of the intermediate, 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine and potassium carbonate in S2-1 is 1 (2-3.5) to (5-15).
7. The method for preparing nitrogen-enriched calix [4] arene crosslinked polymer according to claim 3, wherein the heating reaction temperature in S2-2 is 105 ℃ and 115 ℃, and the heating reaction time is 60-84 h.
8. The method for preparing nitrogen-enriched calix [4] arene crosslinked polymer according to claim 3, wherein water and an organic solvent detergent are sequentially adopted for washing in the washing process in S2-2.
9. A nitrogen-rich calix [4] arene crosslinked polymer prepared from any one of claims 1 to 8.
10. Use of the nitrogen-rich calix [4] arene crosslinked polymer of claim 9 in an adsorbent, wherein the nitrogen-rich calix [4] arene crosslinked polymer is used as an adsorbent for adsorbing polycyclic aromatic hydrocarbons in a treated water body.
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