CN115947938B - Ellagic acid-based organic porous polymer and preparation method and application thereof - Google Patents
Ellagic acid-based organic porous polymer and preparation method and application thereof Download PDFInfo
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- CN115947938B CN115947938B CN202310063420.3A CN202310063420A CN115947938B CN 115947938 B CN115947938 B CN 115947938B CN 202310063420 A CN202310063420 A CN 202310063420A CN 115947938 B CN115947938 B CN 115947938B
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- AFSDNFLWKVMVRB-UHFFFAOYSA-N Ellagic acid Chemical compound OC1=C(O)C(OC2=O)=C3C4=C2C=C(O)C(O)=C4OC(=O)C3=C1 AFSDNFLWKVMVRB-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229920000642 polymer Polymers 0.000 title claims abstract description 57
- ATJXMQHAMYVHRX-CPCISQLKSA-N Ellagic acid Natural products OC1=C(O)[C@H]2OC(=O)c3cc(O)c(O)c4OC(=O)C(=C1)[C@H]2c34 ATJXMQHAMYVHRX-CPCISQLKSA-N 0.000 title claims abstract description 50
- 229920002079 Ellagic acid Polymers 0.000 title claims abstract description 50
- 229960002852 ellagic acid Drugs 0.000 title claims abstract description 50
- 235000004132 ellagic acid Nutrition 0.000 title claims abstract description 50
- FAARLWTXUUQFSN-UHFFFAOYSA-N methylellagic acid Natural products O1C(=O)C2=CC(O)=C(O)C3=C2C2=C1C(OC)=C(O)C=C2C(=O)O3 FAARLWTXUUQFSN-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title abstract description 26
- 238000006149 azo coupling reaction Methods 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 238000006467 substitution reaction Methods 0.000 claims description 4
- 230000000274 adsorptive effect Effects 0.000 claims description 2
- PEQHIRFAKIASBK-UHFFFAOYSA-N tetraphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 PEQHIRFAKIASBK-UHFFFAOYSA-N 0.000 claims description 2
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims 2
- 238000001179 sorption measurement Methods 0.000 abstract description 23
- 125000003118 aryl group Chemical group 0.000 abstract description 9
- 229920000768 polyamine Polymers 0.000 abstract description 8
- 239000003344 environmental pollutant Substances 0.000 abstract description 2
- 125000000524 functional group Chemical group 0.000 abstract description 2
- 239000002149 hierarchical pore Substances 0.000 abstract description 2
- 229920000620 organic polymer Polymers 0.000 abstract description 2
- 231100000719 pollutant Toxicity 0.000 abstract description 2
- 229910021645 metal ion Inorganic materials 0.000 abstract 1
- 239000010865 sewage Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 17
- 239000005457 ice water Substances 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 14
- 229960000907 methylthioninium chloride Drugs 0.000 description 14
- 150000002829 nitrogen Chemical class 0.000 description 12
- 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 description 12
- 229940043267 rhodamine b Drugs 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 10
- 239000012954 diazonium Substances 0.000 description 9
- 150000001989 diazonium salts Chemical class 0.000 description 9
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000002861 polymer material Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 239000000178 monomer Substances 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 235000017550 sodium carbonate Nutrition 0.000 description 5
- 235000010288 sodium nitrite Nutrition 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000012670 alkaline solution Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 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 4
- 229940012189 methyl orange Drugs 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000009935 nitrosation Effects 0.000 description 4
- 238000007034 nitrosation reaction Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000005004 MAS NMR spectroscopy Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000005388 cross polarization Methods 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 2
- SYBFZFROLBNDDF-UHFFFAOYSA-N 4-[2,3-bis(4-aminophenyl)phenyl]aniline Chemical compound C1=CC(N)=CC=C1C1=CC=CC(C=2C=CC(N)=CC=2)=C1C1=CC=C(N)C=C1 SYBFZFROLBNDDF-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- SNLFYGIUTYKKOE-UHFFFAOYSA-N 4-n,4-n-bis(4-aminophenyl)benzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1N(C=1C=CC(N)=CC=1)C1=CC=C(N)C=C1 SNLFYGIUTYKKOE-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- AZFNGPAYDKGCRB-XCPIVNJJSA-M [(1s,2s)-2-amino-1,2-diphenylethyl]-(4-methylphenyl)sulfonylazanide;chlororuthenium(1+);1-methyl-4-propan-2-ylbenzene Chemical compound [Ru+]Cl.CC(C)C1=CC=C(C)C=C1.C1=CC(C)=CC=C1S(=O)(=O)[N-][C@@H](C=1C=CC=CC=1)[C@@H](N)C1=CC=CC=C1 AZFNGPAYDKGCRB-XCPIVNJJSA-M 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- OWFXIOWLTKNBAP-UHFFFAOYSA-N isoamyl nitrite Chemical compound CC(C)CCON=O OWFXIOWLTKNBAP-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- 239000004304 potassium nitrite Substances 0.000 description 2
- 235000010289 potassium nitrite Nutrition 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 238000002210 supercritical carbon dioxide drying Methods 0.000 description 2
- 238000002211 ultraviolet spectrum Methods 0.000 description 2
- 239000003403 water pollutant Substances 0.000 description 2
- 238000004482 13C cross polarization magic angle spinning Methods 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 description 1
- LNHGLSRCOBIHNV-UHFFFAOYSA-N 4-[tris(4-aminophenyl)methyl]aniline Chemical compound C1=CC(N)=CC=C1C(C=1C=CC(N)=CC=1)(C=1C=CC(N)=CC=1)C1=CC=C(N)C=C1 LNHGLSRCOBIHNV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000013310 covalent-organic framework Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 235000018927 edible plant Nutrition 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 235000012055 fruits and vegetables Nutrition 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000013102 re-test Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides an ellagic acid group organic porous polymer, a preparation method and application thereof, wherein the ellagic acid group organic porous polymer has a structural unit shown in a formula IIIa belowAnd a linking unit attached to the IIIa structural unit. Wherein the connecting unit is a group with 2-4 connecting sites. The polymer is prepared by azo coupling reaction of ellagic acid and aromatic polyamine. The obtained organic polymer has a hierarchical pore structure, excellent hydrophilicity, rich functional groups and good stability, has good adsorption performance on organic micro pollutants and metal ions, and can be used for sewage treatment.
Description
Technical Field
One or more embodiments of the present disclosure relate to the technical field of organic polymer materials, and in particular, to an ellagic acid-based organic porous polymer, and a preparation method and an application thereof.
Background
Organic porous polymers (POPs) are an emerging class of polymeric porous materials formed by covalent bonding of organic monomers. The modified carbon fiber has the advantages of low density, large specific surface area, easy functional modification, good stability and the like, is widely concerned, and has wide application prospect in the aspects of adsorption, separation, catalysis, sensing, energy storage and the like. Over the past several decades, efforts have been directed to the discovery of new functional organic monomers to construct organic porous polymers to meet specific needs. However, due to the complex synthetic routes, the functional organic monomers obtained from the fossil raw materials are still very few and often expensive. Thus, there remains an urgent need in the art for organic cellular polymers to explore new organic monomers that are highly functional and low cost.
The natural renewable molecule has the characteristics of easy availability, degradability, various structures and the like, and is a potential substitute for fossil-source monomers. Ellagic Acid (EA) is a natural polyphenol molecule with a near-planar dilactone structure, and is widely found in edible plants such as fruits and vegetables. Because of the existence of two adjacent phenol groups in the structure, the polymer has higher bioactivity and can be used as a chelating agent, an organic electrode material and a structural element of a biological material. In recent years, ellagic acid-based metal-phenol chelate network frameworks and covalent organic frameworks have been successfully constructed using ortho-phenols as reactive sites. However, to our knowledge, ellagic acid based organic porous materials with a high degree of functionality have not been reported.
In view of the above, the present application now provides an ellagic acid-based organic porous polymer, and a preparation method and application thereof, which solve the above-mentioned problems.
Disclosure of Invention
The invention aims to solve the problems in the background art, and one or more embodiments of the present specification aim to provide a functional ellagic acid group organic porous polymer, a preparation method and an application thereof.
In view of the above, one or more embodiments of the present disclosure provide an ellagic acid-based organic porous polymer characterized in that the organic porous polymer has a structural unit represented by the following formula IIIa:
And a linking unit attached to the structure of formula IIIa, wherein the linking unit is a group having a 2-4 linkage site and the linking unit is a group formed by a compound losing 2-4 hydrogen atoms selected from the group consisting of: NH3, CH4, substituted or unsubstituted C6-C20 aromatic hydrocarbons;
Wherein said substitution means that one or more hydrogen atoms on the group are replaced by a group selected from the group consisting of: C1-C4 alkyl, halogen;
in the organic porous polymer, the arrangement sequence of the structural unit of the formula IIIa and the connecting unit is as follows: any two structural units of the formula IIIa are connected through connecting units, and any two connecting units are connected through the structural units of the formula IIIa.
According to the ellagic acid-based organic porous polymer disclosed by the embodiment of the invention, the linking unit has the following structure:
Wherein n=2-4;
R 1 is selected from the group consisting of: NH 3,CH4, substituted or unsubstituted C6-C20 aromatic hydrocarbon.
According to an embodiment of the invention, the ellagic acid-based organic porous polymer has a structural unit represented by the following formula IIIa, and a structural unit represented by the following formula IIIb, IIIc or IIId:
wherein, in the structure shown in formula IIId: x is selected from C or N;
In the organic porous polymer, the structural units of the formula IIIa and the structural units of the formula IIIb, the formula IIIc or the formula IIId are arranged in the following manner: any two structural units of the formula IIIa are connected through structural units of the formula IIIb or structural units of the formula IIIc or structural units of the formula IIId, and any two structural units of the formula IIIb or structural units of the formula IIIc or structural units of the formula IIId are connected through structural units of the formula IIIa.
An ellagic acid-based organic porous polymer according to an embodiment of the present invention is characterized in that the organic porous polymer is formed by azo coupling of a compound of formula I (ellagic acid) with a second linking unit;
Wherein the structure of the compound of the formula I is as follows:
The second connecting unit is a molecule with 2-4-NH 2 groups, and the organic porous polymer comprises the following repeating units:
according to the ellagic acid based organic porous polymer disclosed by the embodiment of the invention, the second connecting group is a molecule with 2-4 hydrogen atoms replaced by-NH 2 groups, wherein the molecule is selected from the following groups: triphenylamine, tetraphenylmethane, substituted or unsubstituted C6-C20 aromatic hydrocarbons; wherein said substitution means that one or more hydrogen atoms on the group are replaced by a group selected from the group consisting of: C1-C4 alkyl, halogen.
The preparation method of the ellagic acid-based organic porous polymer comprises the following steps:
(1) Performing a first reaction by using aromatic polyamine shown in a formula II to prepare a multi-nitrogen salt shown in a formula IV;
(2) Under alkaline condition, azo coupling reaction is carried out on ellagic acid shown in formula I and the multiple nitrogen salt through a second reaction, and aftertreatment is carried out to obtain the ellagic acid group organic porous polymer shown in formula III
The compound of the formula II has any one of the following structures:
According to the preparation method of the ellagic acid-based organic porous polymer, X in the multi-nitrogen salt comprises any one of Cl, SO 4、BF4 and OAc.
According to the preparation method of the ellagic acid-based organic porous polymer, the first reaction comprises:
Under the ice water bath condition, the aromatic polyamine is dissolved in the mixed solution of the acid medium and the first solvent and stirred uniformly;
dropwise adding a nitrosation reagent precooled in an ice water bath into the mixed solution of the aromatic polyamine at a preset speed, and reacting for a first preset time to obtain the multiple nitrogen salt; the preset speed is 0.2-1 drop/second; the first preset time is 20-60min.
According to the preparation method of the ellagic acid based organic porous polymer, the nitrosation reagent comprises any one of sodium nitrite, potassium nitrite and isoamyl nitrite.
According to the preparation method of the ellagic acid-based organic porous polymer, the acidic medium comprises any one of hydrochloric acid, sulfuric acid, fluoroboric acid and acetic acid.
According to the preparation method of the ellagic acid-based organic porous polymer, the solvent of the first reaction is any one of water, water/N, N-dimethylformamide, methanol and ethanol.
According to the preparation method of the ellagic acid-based organic porous polymer, the second reaction comprises: under the ice water bath condition, an alkaline solution is used for adjusting the solution of the multiple nitrogen salts to be neutral;
mixing ellagic acid and alkaline substances, dissolving in a second solvent, preparing an alkali solution, and pre-cooling in an ice-water bath;
Dropwise adding the alkali solution into the solution of the multiple nitrogen salts at a preset speed, and reacting for a second preset time; the preset speed is 0.5-2 drops/second; the first preset time is 6-24 hours;
and (3) performing aftertreatment to obtain the ellagic acid group organic porous polymer.
According to the preparation method of the ellagic acid-based organic porous polymer, the alkaline solution comprises any one of sodium carbonate solution, potassium carbonate solution, sodium hydroxide solution, potassium hydroxide solution and sodium acetate solution; the alkaline substance comprises any one of sodium carbonate solution, sodium hydroxide solution and potassium hydroxide solution.
According to the preparation method of the ellagic acid-based organic porous polymer, in the second reaction, the molar ratio of the ellagic acid to the multiple nitrogen salt is (0.5-2): 1.
According to the preparation method of the ellagic acid-based organic porous polymer, the second solvent comprises any one of water, water/N, N-dimethylformamide, N, N-dimethylformamide and N-methylpyrrolidone.
According to the preparation method of the ellagic acid-based organic porous polymer, the post-treatment comprises any one of freeze drying, vacuum oven drying and supercritical carbon dioxide drying.
According to the preparation method of the ellagic acid group organic porous polymer, the specific surface area of the prepared ellagic acid group organic porous polymer is 20-800 m 2/g, and the pore volume is 0.2-1.5 cm 3/g.
Use of an ellagic acid based organic porous polymer according to the foregoing for adsorptive separation.
According to the above, the invention comprises the following beneficial effects:
1. The preparation method of the ellagic acid group organic porous polymer has the characteristics of simplicity, easiness, environment friendliness, mild reaction conditions and the like.
2. The ellagic acid-based organic porous polymer has a multi-level pore structure, excellent hydrophilicity, rich functional groups and good stability, has strong affinity to specific molecules and certain water pollutants, and can be widely applied to the fields of adsorption separation and the like as a solid adsorbent.
Drawings
For a clearer description of one or more embodiments of the present description or of the solutions of the prior art, the drawings that are necessary for the description of the embodiments or of the prior art will be briefly described, it being apparent that the drawings in the description below are only one or more embodiments of the present description, from which other drawings can be obtained, without inventive effort, for a person skilled in the art.
FIG. 1 is a flow chart of a method for preparing an ellagic acid-based organic porous polymer according to an embodiment of the present invention;
FIG. 2 is a cross polarization/magic angle spinning 13C nuclear magnetic resonance spectrum of EA-POP-1 in example 1 of the present invention;
FIG. 3 is a thermogram of the EA-POP-1 of example 1 of the present invention;
FIG. 4 is a graph showing the isothermal adsorption and desorption of nitrogen at 77K for EA-POP-1 in example 1 of the present invention;
FIG. 5 is a UV spectrum of adsorption of EA-POP-1 to MB, rhB and MO in aqueous solution over time in example 1 of the present invention;
FIG. 6 is a pseudo-second order adsorption kinetics fit curve of EA-POP-1 to MB and RhB in aqueous solution in example 1 of the present invention;
FIG. 7 is a Langmuir isothermal adsorption fit curve of EA-POP-1 to MB and RhB in aqueous solution in example 1 of the present invention.
Detailed Description
For the purposes of promoting an understanding of the principles and advantages of the disclosure, reference will now be made in detail to the following specific examples.
Referring to fig. 1, which shows a flowchart of an embodiment of a method for preparing an ellagic acid-based organic porous polymer of the present invention, specifically may include:
Step S1, performing a first reaction by using aromatic polyamine shown in a formula II to prepare multiple nitrogen salts shown in a formula IV;
Step S2, under alkaline conditions, azo coupling reaction is carried out on ellagic acid shown in the formula I and the multiple nitrogen salt through a second reaction, and aftertreatment is carried out to obtain an ellagic acid group organic porous polymer shown in the formula III;
In the embodiment of the invention, X in the multiple nitrogen salt comprises any one of Cl, SO 4、BF4 and OAc.
In the embodiment of the invention, the aromatic polyamine shown in the structural formula II comprises any one of tri (4-aminophenyl) amine, tetra (4-aminophenyl) methane, tri (4-aminophenyl) benzene, tri (4-aminophenyl) -1,3, 5-triazine and 4,4' -diaminobiphenyl.
In the embodiment of the present invention, the step S1 includes:
Under the ice water bath condition, the aromatic polyamine is dissolved in the mixed solution of the acid medium and the first solvent and stirred uniformly;
dropwise adding a nitrosation reagent precooled in an ice water bath into the mixed solution of the aromatic polyamine at a preset speed, and reacting for a first preset time to obtain the multiple nitrogen salt; the preset speed is 0.2-1 drop/second; the first preset time is 20-60 minutes.
In the embodiment of the invention, the nitrosation reagent comprises any one of sodium nitrite, potassium nitrite and isoamyl nitrite.
In the embodiment of the invention, the acidic medium comprises any one of hydrochloric acid, sulfuric acid, fluoboric acid and acetic acid.
In the embodiment of the invention, the solvent of the first reaction is any one of water, water/N, N-dimethylformamide, methanol and ethanol.
In the embodiment of the present invention, the step S2 includes:
Under the ice water bath condition, an alkaline solution is used for adjusting the solution of the multiple nitrogen salts to be neutral;
mixing ellagic acid and alkaline substances, dissolving in a second solvent, preparing an alkali solution, and pre-cooling in an ice-water bath;
Dropwise adding the alkali solution into the solution of the multiple nitrogen salts at a preset speed, and reacting for a second preset time; the preset speed is 0.5-2 drops/second; the first preset time is 6-24 hours;
and (3) performing aftertreatment to obtain the ellagic acid group organic porous polymer.
In the embodiment of the invention, the alkaline solution comprises any one of sodium carbonate solution, potassium carbonate solution, sodium hydroxide solution, potassium hydroxide solution and sodium acetate solution; the alkaline substance comprises any one of sodium carbonate solution, sodium hydroxide solution and potassium hydroxide solution.
In an embodiment of the present invention, the molar ratio of the ellagic acid to the multiple nitrogen salt in the second reaction is (0.5 to 2): 1.
In the embodiment of the present invention, the second solvent includes any one of water, water/N, N-dimethylformamide, and N-methylpyrrolidone.
In the embodiment of the invention, the post-treatment comprises any one of freeze drying, vacuum oven drying and supercritical carbon dioxide drying.
The embodiment of the invention also provides an ellagic acid group organic porous polymer material, which is prepared by the preparation method.
In order to better understand the present invention, the ellagic acid-based organic porous polymer material of the present invention and the method for preparing the same are described below with reference to a number of specific examples.
Example 1
Step 1: preparation of diazonium salts.
In an ice water bath, tris (4-aminophenyl) benzene (141 mg,0.4mmol,1 eq) was dissolved in an aqueous hydrochloric acid solution of 0.53mL concentrated hydrochloric acid (12M, 0.5mL,6.0mmol,15 eq) and 20mL deionized water, and stirred at 0-5℃for 20min. Then, 10mL of an aqueous sodium nitrite solution (92 mg,1.33mmol,3.3 eq) precooled in an ice-water bath was added dropwise to the reaction system at a rate of 1 second/drop, and after a reaction time of 30 minutes, a diazonium salt solution was obtained.
Step 2: preparation of ellagic acid-based organic porous polymer EA-POP-1.
In an ice-water bath, the diazonium salt solution was neutralized with 1.0mol/L aqueous Na2CO3 solution. A solution of precooled ellagic acid (0.6 mmol,181mg,1 eq) and sodium hydroxide (400 mg,10mmol,16.7 eq) in deionized water (50 mL) was then added dropwise at a rate of 2 seconds/drop. After 12h of reaction, the solid product was collected by filtration and washed with water, 0.1mol/L of dilute hydrochloric acid, water and methanol in this order, soxhlet extracted with ethanol for one day, and then freeze-dried to obtain ellagic acid-based organic porous polymer material EA-POP-1 (250 mg, yield 75%).
The prepared EA-POP-1 is subjected to cross polarization/magic angle spinning 13C nuclear magnetic resonance test in the embodiment, and the test result is shown in figure 2. Cross polarization/magic angle spinning 13C Nuclear magnetic resonance Spectrometry data for EA-POP-1 are as follows:
13C-CP/MAS NMR(400MHz)δ(ppm):169.57,140.98,127.72。
In FIG. 2 169.57ppm is carbon on carbonyl in the polymer backbone, 140.98 and 127.72ppm are carbon on aromatic rings in the polymer backbone.
In the embodiment, element analysis is performed on the prepared EA-POP-1, and analysis results show that the content of carbon element in the prepared EA-POP-1 is 62.72%, the content of nitrogen element is 3.73%, and the content of hydrogen element is 4.48%.
The prepared EA-POP-1 was subjected to thermal re-testing in this example, and the test results are shown in FIG. 3. In FIG. 3, no obvious decomposition below 200deg.C indicates that EA-POP-1 has good thermal stability.
In this example, the prepared EA-POP-1 was subjected to a nitrogen adsorption and desorption test at 77K, and the test results are shown in FIG. 4. In FIG. 4, the adsorption and desorption isotherms of the prepared EA-POP-1 conform to the type IV isotherms, indicating that the prepared EA-POP-1 has a micropore-mesopore hierarchical pore structure.
Specific surface area and pore volume tests were performed on prepared EA-POP-1 in this example, and the test data are as follows: the BET specific surface area of EA-POP-1 was 445m 2 g-1 and the total pore volume was 0.63cm 3 g-1.
In the embodiment, the prepared EA-POP-1 is subjected to water pollutant adsorption performance research, and specifically Methylene Blue (MB), rhodamine B (RhB) and Methyl Orange (MO) adsorption performance research is performed.
FIG. 5 shows the UV spectrum of the adsorption of EA-POP-1 to MB, rhB and MO in aqueous solution over time. From FIG. 5 it can be seen that EA-POP-1 can adsorb cationic dyes MB and RhB rapidly, while adsorbing anionic dyes hardly.
FIG. 6 shows a pseudo-second order kinetic adsorption fit curve of EA-POP-1 to MB and RhB in aqueous solution, the pseudo-second order kinetic equation being as follows:
Wherein k 2(g·mg-1·min-1) is the adsorption rate constant of the pseudo-secondary kinetic model; qe is the equilibrium adsorption quantity; qt is the adsorption amount at time t.
Based on the R 2 value, the adsorption of EA-POP-1 to MB and RhB in the aqueous solution accords with a pseudo-secondary kinetic model, and through calculation, the pseudo-secondary kinetic adsorption constants of EA-POP-1 to MB and RhB in the aqueous solution are 47.314 g.mg -1·min-1 and 12.300 g.mg -1·min-1 respectively, which indicates that EA-POP-1 can adsorb and remove MB and RhB in the aqueous solution very rapidly.
FIG. 7 shows a Langmuir isothermal adsorption fit curve of EA-POP-1 to MB and RhB in aqueous solution, the Langmuir equation being as follows:
Wherein, Q e(mg·g-1) is the equilibrium adsorption quantity; c e(mg·L-1) is the equilibrium concentration; q m(mg·g-1) is the maximum adsorption amount; k L(L·mg-1) is Langmuir isothermal model constant.
By calculation, the maximum adsorption amounts of MB and RhB in the aqueous solution of EA-POP-1 were 498 mg.g -1 and 2185 mg.g -1, respectively. The EA-POP-1 has excellent adsorption performance on MB and RhB pollutants in the aqueous solution.
Example 2
Step 1: preparation of diazonium salts.
Tris (4-aminophenyl) -1,3, 5-triazine (142 mg,0.4mmol,1 eq) was dissolved in 0.53mL of concentrated hydrochloric acid (12M, 0.5mL,6.0mmol,15 eq) and 20mL of deionized water in aqueous hydrochloric acid in an ice-water bath and stirred at 0-5℃for 20min. Then, 10mL of an aqueous sodium nitrite solution (92 mg,1.33mmol,3.3 eq) precooled in an ice-water bath was added dropwise to the reaction system at a rate of 1 second/drop, and after a reaction time of 30 minutes, a diazonium salt solution was obtained.
Step 2: preparation of ellagic acid-based organic porous polymer EA-POP-2.
In an ice water bath, the diazonium salt solution was neutralized with 1.0mol/L aqueous Na 2CO3 solution. A solution of precooled ellagic acid (0.6 mmol,181mg,1 eq) and sodium hydroxide (400 mg,10mmol,16.7 eq) in deionized water (50 mL) was then added dropwise at a rate of 2 seconds/drop. After 12h of reaction, the solid product was collected by filtration and washed with water, 0.1mol/L of dilute hydrochloric acid, water and methanol in this order, soxhlet extracted with ethanol for one day, and then freeze-dried to obtain ellagic acid-based organic porous polymer material EA-POP-2 (243 mg, yield 72%).
Example 3
Step 1: preparation of diazonium salts.
In an ice water bath, tris (4-aminophenyl) amine (116 mg,0.4mmol,1 eq) was dissolved in an aqueous hydrochloric acid solution of 0.53mL concentrated hydrochloric acid (12M, 0.5mL,6.0mmol,15 eq) and 20mL deionized water and stirred at 0-5℃for 20min. Then, 10mL of an aqueous sodium nitrite solution (92 mg,1.33mmol,3.3 eq) precooled in an ice-water bath was added dropwise to the reaction system at a rate of 1 second/drop, and after a reaction time of 30 minutes, a diazonium salt solution was obtained.
Step 2: preparation of ellagic acid-based organic porous polymer EA-POP-3.
In an ice water bath, the diazonium salt solution was neutralized with 1.0mol/L aqueous Na 2CO3 solution. A solution of precooled ellagic acid (0.6 mmol,181mg,1 eq) and sodium hydroxide (400 mg,10mmol,16.7 eq) in deionized water (50 mL) was then added dropwise at a rate of 2 seconds/drop. After 12h of reaction, the solid product was collected by filtration and washed successively with water, 0.1mol/L dilute hydrochloric acid, water and methanol, soxhlet extracted with ethanol for one day, and then freeze-dried to obtain ellagic acid-based organic porous polymer material EA-POP-3 (208 mg, yield 85%).
The present disclosure is intended to embrace all such alternatives, modifications and variances which fall within the broad scope of the appended claims. Any omissions, modifications, equivalents, improvements, and the like, which are within the spirit and principles of the one or more embodiments of the disclosure, are therefore intended to be included within the scope of the disclosure.
Claims (4)
1. An ellagic acid based organic porous polymer characterized in that the organic porous polymer has a structural unit represented by the following formula IIIa:
And a linking unit attached to the structure of formula IIIa, wherein the linking unit is a group having a 2-4 linkage site and the linking unit is a group formed by a compound losing 2-4 hydrogen atoms selected from the group consisting of: NH 3,CH4, substituted or unsubstituted C 6-C20 aromatic hydrocarbons;
Wherein said substitution means that one or more hydrogen atoms on the group are replaced by a group selected from the group consisting of: c 1-C4 alkyl, halogen;
in the organic porous polymer, the arrangement sequence of the structural unit of the formula IIIa and the connecting unit is as follows: any two structural units of the formula IIIa are connected through connecting units, and any two connecting units are connected through the structural units of the formula IIIa.
2. An ellagic acid based organic porous polymer, characterized in that said organic porous polymer is formed by azo coupling a compound of formula I with a second linking unit;
Wherein the structure of the compound of the formula I is as follows:
The second connecting unit is a molecule with 2-4-NH 2 groups, and the organic porous polymer comprises the following repeating units:
3. The ellagic acid based organic porous polymer of claim 2, wherein said second linking unit is a molecule having 2 to 4 hydrogen atoms replaced with a-NH 2 group selected from the group consisting of: triphenylamine, tetraphenylmethane, substituted or unsubstituted C 6-C20 aromatic hydrocarbons; wherein said substitution means that one or more hydrogen atoms on the group are replaced by a group selected from the group consisting of: c 1-C4 alkyl, halogen.
4. Use of an ellagic acid-based organic porous polymer according to claim 3 for adsorptive separation.
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| CN108409961A (en) * | 2018-02-11 | 2018-08-17 | 北京理工大学 | A kind of amino azo functionalization organic porous polymer material and preparation method thereof |
| CN110016135A (en) * | 2019-02-27 | 2019-07-16 | 北京理工大学 | A kind of organic porous polymer material and preparation method thereof of ketone-hydrazone skeleton structure |
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| CN108409961A (en) * | 2018-02-11 | 2018-08-17 | 北京理工大学 | A kind of amino azo functionalization organic porous polymer material and preparation method thereof |
| CN110016135A (en) * | 2019-02-27 | 2019-07-16 | 北京理工大学 | A kind of organic porous polymer material and preparation method thereof of ketone-hydrazone skeleton structure |
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