CN115947938A - 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
- Publication number
- CN115947938A CN115947938A CN202310063420.3A CN202310063420A CN115947938A CN 115947938 A CN115947938 A CN 115947938A CN 202310063420 A CN202310063420 A CN 202310063420A CN 115947938 A CN115947938 A CN 115947938A
- Authority
- CN
- China
- Prior art keywords
- formula
- ellagic acid
- porous polymer
- organic porous
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 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 71
- 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 71
- 229920002079 Ellagic acid Polymers 0.000 title claims abstract description 71
- 229960002852 ellagic acid Drugs 0.000 title claims abstract description 71
- 235000004132 ellagic acid Nutrition 0.000 title claims abstract description 71
- 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 71
- 229920000642 polymer Polymers 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 125000003118 aryl group Chemical group 0.000 claims abstract description 12
- 229920000768 polyamine Polymers 0.000 claims abstract description 11
- 238000006149 azo coupling reaction Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 44
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 21
- 239000005457 ice water Substances 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 claims description 12
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 239000012954 diazonium Substances 0.000 claims description 11
- 150000001989 diazonium salts Chemical class 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 125000005647 linker group Chemical group 0.000 claims description 8
- 150000002829 nitrogen Chemical class 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 239000012670 alkaline solution Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 235000010288 sodium nitrite Nutrition 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 230000009935 nitrosation Effects 0.000 claims description 5
- 238000007034 nitrosation reaction Methods 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 238000006467 substitution reaction Methods 0.000 claims description 5
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 4
- 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
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- 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 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000004108 freeze drying Methods 0.000 claims description 3
- OWFXIOWLTKNBAP-UHFFFAOYSA-N isoamyl nitrite Chemical compound CC(C)CCON=O OWFXIOWLTKNBAP-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 238000000643 oven drying Methods 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 3
- 239000004304 potassium nitrite Substances 0.000 claims description 3
- 235000010289 potassium nitrite Nutrition 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000002210 supercritical carbon dioxide drying Methods 0.000 claims description 3
- 230000000274 adsorptive effect Effects 0.000 claims description 2
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 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
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 22
- 239000002149 hierarchical pore Substances 0.000 abstract description 3
- 239000003344 environmental pollutant Substances 0.000 abstract description 2
- 125000000524 functional group Chemical group 0.000 abstract description 2
- 229920000620 organic polymer Polymers 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract 1
- 239000010865 sewage Substances 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 description 17
- 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
- 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
- 238000012360 testing method Methods 0.000 description 8
- 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
- 239000000178 monomer Substances 0.000 description 5
- 239000002861 polymer material Substances 0.000 description 5
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 4
- 229940012189 methyl orange Drugs 0.000 description 4
- 239000002738 chelating agent Substances 0.000 description 3
- 238000005388 cross polarization Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- 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
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 238000000944 Soxhlet extraction Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 239000011734 sodium Substances 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
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005004 MAS NMR spectroscopy Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000129 anionic group Chemical group 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
- 230000004071 biological effect Effects 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
- 239000013522 chelant Substances 0.000 description 1
- 239000013310 covalent-organic framework Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000018927 edible plant Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
Images
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides an ellagic acid-based organic porous polymer, and a preparation method and application thereof, wherein the ellagic acid-based organic porous polymer is a structural unit shown as a formula IIIa
And a connecting unit connected with the IIIa structural unit. Wherein the linking unit is a group having 2 to 4 linking sites. The polymer is prepared by the 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, and is resistant to organic micro-pollutants and metal ionsHas good adsorption performance 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 linking organic monomers through covalent bonds. The nano-composite material has the advantages of low density, large specific surface area, easy functional modification, good stability and the like, so that the nano-composite material is widely concerned, and has wide application prospects in the aspects of adsorption, separation, catalysis, sensing, energy storage and the like. In the past decades, efforts have been made to explore new functional organic monomers to build organic porous polymers to meet specific needs. However, due to the complex synthetic route, functional organic monomers obtained from fossil raw materials are still scarce and often expensive. Therefore, the search for new organic monomers with high functionality and low cost is still an urgent need in the field of organic porous polymers.
The natural renewable molecules have the characteristics of easy obtainment, degradability, various structures and the like, and are potential substitutes of fossil-derived monomers. Ellagic Acid (EA) is a natural polyphenol molecule with a nearly planar dilactone structure, and widely exists in edible plants such as fruits and vegetables. Because the structure of the organic chelating agent has two adjacent phenol groups, the organic chelating agent has higher biological activity 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 reaction sites. However, to the best of our knowledge, ellagic acid-based organic porous materials with high functionality have not been reported.
In summary, the present application now proposes an ellagic acid-based organic porous polymer, a preparation method and applications thereof to 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 specification aim to provide a functional ellagic acid-based 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 by having a structural unit represented by formula IIIa below:
and a linker attached to the structure of formula IIIa, wherein the linker is a group having 2-4 sites and the linker is a group formed by loss of 2-4 hydrogen atoms from a compound selected from the group consisting of: NH3, CH4, substituted or unsubstituted C6-C20 arene;
wherein said substitution means that one or more hydrogen atoms on the group are substituted by a group selected from the group consisting of: C1-C4 alkyl, halogen;
and in the organic porous polymer, the arrangement sequence of the structural unit and the connecting unit in the formula IIIa is as follows: any two of the structural units of formula IIIa are connected through a connecting unit, and any two of the connecting units are connected through the structural units of formula IIIa.
According to the ellagic acid-based organic porous polymer of the embodiment of the present invention, the linking unit has the following structure:
R 1 selected from the group consisting of: NH 3 ，CH 4 Substituted or unsubstituted C6-C20 aromatic hydrocarbons.
The ellagic acid-based organic porous polymer according to an embodiment of the present invention has a structural unit represented by formula IIIa below, and a structural unit represented by formula IIIb, or formula IIIc, or formula IIId:
and in the organic porous polymer, the arrangement mode of the structural units shown in formula IIIa and formula IIIb, formula IIIc or formula IIId is as follows: any two of the formula IIIa structural units are connected through a formula IIIb structural unit or a formula IIIc structural unit or a formula IIId structural unit, and any two of the formula IIIb structural units or the formula IIIc structural units or the formula IIId structural units are connected through the formula IIIa structural unit.
The ellagic acid-based organic porous polymer according to the embodiment of the present invention 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 formula I is as follows:
the second connecting unit is provided with 2-4-NH 2 A molecule of a group, and the organic porous polymer comprises the following repeating units:
according to the ellagic acid-based organic porous polymer of the embodiment of the present invention, the second linking group is formed by-NH having 2 to 4 hydrogen atoms 2 A group-substituted molecule selected from the group consisting of: triphenylamine, tetraphenylmethane, substituted or unsubstituted C6-C20 aromatic hydrocarbons; wherein said substitution means that one or more hydrogen atoms on the group are substituted 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) Carrying out a first reaction by using aromatic polyamine shown in a formula II to prepare a multi-nitrogen salt shown in a formula IV;
(2) Performing azo coupling reaction between ellagic acid shown in formula I and the multiple nitrogen salt through a second reaction under alkaline conditions, and performing post-treatment to obtain ellagic acid-based organic porous polymer shown in formula III
The compound of formula II is of any one of the following structures:
according to the preparation method of the ellagic acid based organic porous polymer, X in the polyammonium salt comprises Cl and SO 4 、BF 4 And OAc.
According to the method for preparing the ellagic acid-based organic porous polymer of the embodiment of the present invention, the first reaction includes:
under the condition of ice-water bath, dissolving the aromatic polyamine in a mixed solution of an acidic medium and a first solvent, and uniformly stirring;
dripping 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 polynitrogen 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 of the embodiment of the present invention, the second reaction includes: under the condition of ice-water bath, regulating the solution of the multiple nitrogen salt to be neutral by using an alkaline solution;
mixing ellagic acid and an alkaline substance, dissolving the mixture in a second solvent, preparing an alkali solution, and placing the alkali solution in an ice water bath for precooling;
dropwise adding the alkali solution into the solution of the multi-nitrogen salt 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;
carrying out post-treatment to obtain the ellagic acid-based organic porous polymer.
According to the preparation method of the ellagic acid-based organic porous polymer, the alkaline solution comprises any one of a sodium carbonate solution, a potassium carbonate solution, a sodium hydroxide solution, a potassium hydroxide solution and a 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, the mole ratio of the ellagic acid to the multiple nitrogen salt in the second reaction is (0.5-2): 1.
according to the preparation method of the ellagic acid-based organic porous polymer, the second solvent includes any one of water, water/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-based organic porous polymer, the specific surface area of the prepared ellagic acid-based organic porous polymer is 20-800 m 2 Per gram, pore volume of 0.2-1.5 cm 3 /g。
Use of an ellagic acid-based organic porous polymer according to the preceding description in adsorptive separations.
According to the above, the present invention includes the following advantageous effects:
1. the preparation method of the ellagic acid-based organic porous polymer has the characteristics of simplicity, easiness in implementation, environmental friendliness, mild reaction conditions and the like.
2. The ellagic acid-based organic porous polymer disclosed by the invention has a hierarchical 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
In order to more clearly illustrate one or more embodiments or prior art solutions of the present specification, the drawings that are needed in the description of the embodiments or prior art will be briefly described below, it is obvious that the drawings in the description below are only one or more embodiments of the present specification, and that other drawings may be obtained by those skilled in the art without inventive effort.
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 spectrogram of EA-POP-1 in example 1 of the present invention;
FIG. 3 is a thermogravimetric analysis spectrum of EA-POP-1 in example 1 of the present invention;
FIG. 4 is a nitrogen adsorption/desorption isotherm diagram of EA-POP-1 at 77K in example 1 of the present invention;
FIG. 5 is a UV spectrum of EA-POP-1 versus the adsorption of MB, rhB and MO in an 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 an 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
To make the objects, technical solutions and advantages of the present disclosure more apparent, the present disclosure is further described in detail below with reference to specific embodiments.
Referring to fig. 1, which shows a flow chart of an embodiment of the 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 a diazonium salt shown in a formula IV;
step S2, under an alkaline condition, the ellagic acid shown in the formula I and the multiple nitrogen salt are subjected to azo coupling reaction through a second reaction, and the ellagic acid-based organic porous polymer shown in the formula III is obtained through post-treatment;
in the embodiment of the invention, X in the multi-nitrogen salt comprises Cl and SO 4 、BF 4 And OAc.
In the embodiment of the present invention, the aromatic polyamine represented by the structural formula II includes any one of tris (4-aminophenyl) amine, tetrakis (4-aminophenyl) methane, tris (4-aminophenyl) benzene, tris (4-aminophenyl) -1,3,5-triazine and 4,4' -diaminobiphenyl.
In an embodiment of the present invention, the step S1 includes:
under the condition of ice-water bath, dissolving the aromatic polyamine in a mixed solution of an acidic medium and a first solvent, and uniformly stirring;
dripping 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 polynitrogen 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 an embodiment of the present invention, the acidic medium includes any one of hydrochloric acid, sulfuric acid, fluoroboric acid, and acetic acid.
In the embodiment of the present 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, step S2 includes:
under the condition of ice-water bath, regulating the solution of the multiple nitrogen salt to be neutral by using an alkaline solution;
mixing ellagic acid and an alkaline substance, dissolving the mixture in a second solvent, preparing an alkali solution, and placing the alkali solution in an ice water bath for precooling;
dropwise adding the alkali solution into the solution of the multi-nitrogen salt 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;
carrying out post-treatment to obtain the ellagic acid-based organic porous polymer.
In the embodiment of the invention, the alkaline solution comprises any one of a sodium carbonate solution, a potassium carbonate solution, a sodium hydroxide solution, a potassium hydroxide solution and a sodium acetate solution; the alkaline substance comprises any one of sodium carbonate solution, sodium hydroxide solution and potassium hydroxide solution.
In the embodiment of the present invention, the molar ratio of the ellagic acid to the polynitrogen salt in the second reaction is (0.5 to 2): 1.
in an 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 present invention, the post-treatment includes any one of freeze drying, vacuum oven drying and supercritical carbon dioxide drying.
The embodiment of the invention also provides an ellagic acid based organic porous polymer material, which is prepared by the preparation method.
In order to make the present invention more understandable to those skilled in the art, the ellagic acid-based organic porous polymeric material of the present invention and the method for preparing the same are illustrated below by a plurality of specific examples.
Example 1
Step 1: and (3) preparing a diazonium salt.
Tris (4-aminophenyl) benzene (141mg, 0.4mmol, 1eq) was dissolved in 0.53mL of a hydrochloric acid aqueous solution of concentrated hydrochloric acid (12M, 0.5mL,6.0mmol, 15eq) and 20mL of deionized water in an ice-water bath, and the mixture was stirred at 0 to 5 ℃ for 20 minutes. Then, 10mL of an aqueous solution of sodium nitrite (92mg, 1.33mmol, 3.3eq) precooled in an ice-water bath was added dropwise to the reaction system at a rate of 1 second/drop, and after a reaction for 30 minutes, a diazonium salt solution was obtained.
Step 2: and (3) preparing an ellagic acid-based organic porous polymer EA-POP-1.
In an ice-water bath, the diazonium salt solution was neutralized with a 1.0mol/L aqueous solution of Na2CO 3. A pre-cooled solution of ellagic acid (0.6 mmol,181mg, 1eq) and sodium hydroxide (400mg, 10mmol, 16.7eq) in deionized water (50 mL) was then added dropwise at a rate of 2 sec/drop. After reacting for 12 hours, the solid product was collected by filtration, washed with water, 0.1mol/L dilute hydrochloric acid, water and methanol in this order, subjected to soxhlet extraction with ethanol for one day, and then freeze-dried to obtain an ellagic acid-based organic porous polymer material EA-POP-1 (250 mg, yield 75%).
In this example, the prepared EA-POP-1 was subjected to cross-polarization/magic angle spin 13C nuclear magnetic resonance test, and the test results are shown in FIG. 2. Cross-polarization/magic angle spin 13C NMR spectral data for EA-POP-1 were as follows:
13 C-CP/MAS NMR(400MHz)δ(ppm):169.57,140.98,127.72。
in FIG. 2, 169.57ppm are the carbons on the carbonyl groups in the polymer backbone, 140.98 and 127.72ppm are the carbons on the aromatic rings in the polymer backbone.
In this example, elemental analysis was performed on the prepared EA-POP-1, and the analysis result showed that the prepared EA-POP-1 had a carbon content of 62.72%, a nitrogen content of 3.73%, and a hydrogen content of 4.48%.
In this example, the prepared EA-POP-1 was subjected to thermogravimetric testing, and the test results are shown in FIG. 3. In FIG. 3, no significant decomposition occurred below 200 ℃ indicating 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 isotherm, indicating that the prepared EA-POP-1 has a microporous-mesoporous hierarchical pore structure.
In this example, the prepared EA-POP-1 was subjected to specific surface area and pore volume tests, and the test data are as follows: the BET specific surface area of EA-POP-1 is 445m 2 g -1 Total pore volume of 0.63cm 3 g -1 。
In this 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 EA-POP-1 on the adsorption of MB, rhB and MO in an aqueous solution over time. It can be seen from fig. 5 that EA-POP-1 can rapidly adsorb the cationic dyes MB and RhB, while hardly adsorbing the anionic dyes.
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 is 2 (g·mg -1 ·min -1 ) Is the adsorption rate constant of the pseudo-second order kinetic model; qe is the equilibrium adsorption capacity; qt is the amount of adsorption at time t.
Based on R 2 The values show that the adsorption of the EA-POP-1 on the MB and the RhB in the aqueous solution accords with a pseudo second-order kinetic model, and the pseudo second-order kinetic adsorption constants of the EA-POP-1 on the MB and the RhB in the aqueous solution are 47.314g mg respectively through calculation -1 ·min -1 And 12.300g mg -1 ·min -1 The EA-POP-1 can adsorb and remove MB and RhB in the aqueous solution very quickly.
FIG. 7 shows Langmuir isothermal adsorption fit curves for EA-POP-1 to MB and RhB in aqueous solution, the Langmuir equation being as follows:
wherein Q is e (mg·g -1 ) To balance the adsorption capacity; c e (mg·L -1 ) Is the equilibrium concentration; q m (mg·g -1 ) Is the maximum adsorption capacity; k L (L·mg -1 ) Langmuir isothermal model constants.
The maximum adsorption amounts of EA-POP-1 to MB and RhB in the aqueous solution were 498mg g, respectively -1 And 2185 mg. G -1 . The EA-POP-1 has excellent adsorption performance on MB and RhB pollutants in an aqueous solution.
Example 2
Step 1: and (3) preparing a diazonium salt.
In an ice-water bath, tris (4-aminophenyl) -1,3,5-triazine (142mg, 0.4mmol, 1eq) was dissolved in 0.53mL of concentrated hydrochloric acid (12M, 0.5mL,6.0mmol, 15eq) and 20mL of an aqueous hydrochloric acid solution of deionized water, and stirred at 0-5 ℃ for 20min. Then, 10mL of an aqueous solution of sodium nitrite (92mg, 1.33mmol, 3.3eq) precooled in an ice-water bath was added dropwise to the reaction system at a rate of 1 second/drop, and after a reaction for 30 minutes, a diazonium salt solution was obtained.
Step 2: and (3) preparing an ellagic acid-based organic porous polymer EA-POP-2.
In an ice-water bath, the diazonium salt solution is mixed with 1.0mol/L Na 2 CO 3 Neutralizing with water solution. A pre-cooled solution of ellagic acid (0.6 mmol,181mg, 1eq) and sodium hydroxide (400mg, 10mmol, 16.7eq) in deionized water (50 mL) was then added dropwise at a rate of 2 seconds/drop. After reacting for 12 hours, the solid product was collected by filtration, and washed with water, 0.1mol/L dilute hydrochloric acid, water and methanol in this order, subjected to soxhlet extraction with ethanol for one day, and then freeze-dried to obtain an ellagic acid-based organic porous polymer material EA-POP-2 (243 mg, yield 72%).
Example 3
Step 1: and (3) preparing a diazonium salt.
Tris (4-aminophenyl) amine (116mg, 0.4mmol, 1eq) was dissolved in 0.53mL of a hydrochloric acid aqueous solution of concentrated hydrochloric acid (12M, 0.5mL,6.0mmol, 15eq) and 20mL of deionized water in an ice-water bath, and the mixture was stirred at 0 to 5 ℃ for 20 minutes. Then 10mL of an aqueous solution of sodium nitrite (92mg, 1.33mmol, 3.3eq) precooled in an ice-water bath was added dropwise to the reaction system at a rate of 1 second/drop, and after a reaction for 30 minutes, a diazonium salt solution was obtained.
And 2, step: and (3) preparing an ellagic acid-based organic porous polymer EA-POP-3.
In an ice-water bath, the diazonium salt solution is mixed with 1.0mol/L Na 2 CO 3 Neutralizing with water solution. A pre-cooled solution of ellagic acid (0.6 mmol,181mg, 1eq) and sodium hydroxide (400mg, 10mmol, 16.7eq) in deionized water (50 mL) was then added dropwise at a rate of 2 seconds/drop. After the reaction for 12 hours, the solid product was collected by filtration, washed with water, 0.1mol/L dilute hydrochloric acid, water and methanol in this order, soxhlet-extracted with ethanol for one day, and then freeze-dried to obtain an ellagic acid-based organic porous polymer material EA-POP-3 (208 mg, yield 85%).
It is intended that the one or more embodiments of the present specification embrace all such alternatives, modifications and variations as fall within the broad scope of the appended claims. Therefore, any omissions, modifications, substitutions, improvements, and the like that may be made without departing from the spirit and principles of one or more embodiments of the present disclosure are intended to be included within the scope of the present disclosure.
Claims (18)
1. An ellagic acid-based organic porous polymer having structural units represented by formula ilia:
and a linker attached to the structure of formula IIIa, wherein the linker is a group having 2-4 sites and the linker is a group formed by loss of 2-4 hydrogen atoms from a compound selected from the group consisting of: NH3, CH4, substituted or unsubstituted C6-C20 arene;
wherein said substitution means that one or more hydrogen atoms on the group are substituted by a group selected from the group consisting of: C1-C4 alkyl, halogen;
and in the organic porous polymer, the arrangement sequence of the structural unit with the formula IIIa and the connecting unit is as follows: and any two of the formula IIIa structural units are connected through a connecting unit, and any two of the connecting units are connected through the formula IIIa structural units.
2. The ellagic acid-based organic porous polymer of claim 1, wherein the linking unit has the following structure:
R 1 selected from the group consisting of: NH 3 ，CH 4 Substituted or unsubstituted C6-C20 aromatic hydrocarbons.
3. The ellagic acid-based organic porous polymer of claim 1, having structural units of formula ilia, and structural units of formula IIIb, or of formula IIIc, or of formula IIId:
and in the organic porous polymer, the arrangement mode of the structural unit shown in formula IIIa and the structural unit shown in formula IIIb, formula IIIc or formula IIId is as follows: any two of the formula IIIa structural units are connected through a formula IIIb structural unit or a formula IIIc structural unit or a formula IIId structural unit, and any two of the formula IIIb structural units or the formula IIIc structural units or the formula IIId structural units are connected through the formula IIIa structural unit.
4. An ellagic acid-based organic porous polymer formed by azo coupling of a compound of formula I (ellagic acid) with a second linking unit;
wherein, the structure of the compound of formula I is as follows:
the second connecting unit is provided with 2-4-NH 2 A molecule of a group, and the organic porous polymer comprises the following repeating units:
5. the ellagic acid-based organic porous polymer of claim 4, wherein the second linking group is a group of 2-4 hydrogen atoms substituted with-NH 2 A group-substituted molecule selected from the group consisting of: triphenylamine, tetraphenylmethane, substituted or unsubstituted C6-C20 aromatic hydrocarbons; wherein said substitution means that one or more hydrogen atoms on the group are substituted by a group selected from the group consisting of: C1-C4 alkyl, halogen.
6. A production method for producing the ellagic acid-based organic porous polymer of any one of claims 1 or 4, comprising the steps of:
(1) Carrying out 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 the alkaline condition, the ellagic acid shown in the formula I and the multiple nitrogen salt are subjected to azo coupling reaction through a second reaction, and the ellagic acid-based organic porous polymer shown in the formula III is obtained through post-treatment;
the compound of formula II is of any one of the following structures:
7. the method according to claim 6, wherein X in the diazonium salt comprises Cl or SO 4 、BF 4 And OAc.
8. The method of claim 6, wherein the first reaction comprises:
under the condition of ice-water bath, dissolving the aromatic polyamine in a mixed solution of an acidic medium and a first solvent, and uniformly stirring;
dripping 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 multi-nitrogen salt; the preset speed is 0.2-1 drop/second; the first preset time is 20-60min.
9. The method according to claim 8, wherein the nitrosating agent comprises any one of sodium nitrite, potassium nitrite and isoamyl nitrite.
10. The production method according to claim 8, wherein the acidic medium includes any one of hydrochloric acid, sulfuric acid, fluoroboric acid, and acetic acid.
11. The method according to claim 8, wherein the solvent of the first reaction is any one of water, water/N, N-dimethylformamide, methanol and ethanol.
12. The method of claim 8, wherein the second reaction comprises: under the condition of ice-water bath, regulating the solution of the multiple nitrogen salt to be neutral by using an alkaline solution;
mixing the ellagic acid and an alkaline substance, dissolving the mixture in a second solvent, preparing an alkali solution, and placing the alkali solution in an ice water bath for precooling;
dropwise adding the alkali solution into the solution of the multi-nitrogen salt 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;
carrying out post-treatment to obtain the ellagic acid-based organic porous polymer.
13. The method according to claim 12, wherein the alkaline solution comprises any one of a sodium carbonate solution, a potassium carbonate solution, a sodium hydroxide solution, a potassium hydroxide solution, and a sodium acetate solution; the alkaline substance comprises any one of sodium carbonate solution, sodium hydroxide solution and potassium hydroxide solution.
14. The method according to claim 12, wherein the molar ratio of ellagic acid to the polynitrogen salt in the second reaction is (0.5 to 2): 1.
15. the method according to claim 12, wherein the second solvent comprises any one of water, water/N, N-dimethylformamide, and N-methylpyrrolidone.
16. The method of claim 12, wherein the post-treatment includes any one of freeze-drying, vacuum oven-drying and supercritical carbon dioxide-drying.
17. The preparation method of claim 6, wherein the specific surface area of the prepared ellagic acid-based organic porous polymer is 20 to 800m 2 Per g, pore volume of 0.2-1.5 cm 3 /g。
18. Use of the ellagic acid-based organic porous polymer of claim 17 in adsorptive separations.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310063420.3A CN115947938B (en) | 2023-02-05 | 2023-02-05 | Ellagic acid-based organic porous polymer and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310063420.3A CN115947938B (en) | 2023-02-05 | 2023-02-05 | Ellagic acid-based organic porous polymer and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115947938A true CN115947938A (en) | 2023-04-11 |
| CN115947938B CN115947938B (en) | 2024-05-17 |
Family
ID=87290844
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310063420.3A Active CN115947938B (en) | 2023-02-05 | 2023-02-05 | Ellagic acid-based organic porous polymer and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115947938B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011086284A1 (en) * | 2009-12-23 | 2011-07-21 | L'oreal | Composition for dyeing keratin fibers, including at least one ortho-diphenol derivative, one chemical oxidizing agent, and one alkalinizing agent |
| 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 |
-
2023
- 2023-02-05 CN CN202310063420.3A patent/CN115947938B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011086284A1 (en) * | 2009-12-23 | 2011-07-21 | L'oreal | Composition for dyeing keratin fibers, including at least one ortho-diphenol derivative, one chemical oxidizing agent, and one alkalinizing agent |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115947938B (en) | 2024-05-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Garibay et al. | Accessing functionalized porous aromatic frameworks (PAFs) through a de novo approach | |
| Klumpen et al. | Microporous organic polyimides for CO2 and H2O capture and separation from CH4 and N2 mixtures: interplay between porosity and chemical function | |
| US10982014B2 (en) | Cyclodextrin polymer with ultra-fast adsorption performance | |
| Shen et al. | Tetraphenyladamantane-based microporous polyimide and its nitro-functionalization for highly efficient CO2 capture | |
| US8470900B2 (en) | Porous polymer and synthetic method thereof | |
| US10889678B2 (en) | Amine-based porous polymer for selective carbon dioxide capture | |
| Zhang et al. | Pillararene-based conjugated porous polymers | |
| CN109806851B (en) | Cyclodextrin porous material and preparation method thereof | |
| CN106700005B (en) | Organic microporous polymer and its preparation method and application based on three phosphonitrile of ring for gas absorption | |
| Ding et al. | Mannitol-based acetal-linked porous organic polymers for selective capture of carbon dioxide over methane | |
| US20200165189A1 (en) | Pseudo tröger's base amines and microporous polymers derived from pseudo tröger's base amines | |
| Rong et al. | Tetraphenyladamantane-based microporous polyaminals for efficient adsorption of CO2, H2 and organic vapors | |
| CN113083257A (en) | Preparation method and application of multiple-interlocking functional organic polymer material | |
| Li et al. | A defects-free ZIF-90/6FDA-Durene membrane based on the hydrogen bonding/covalent bonding interaction for gas separation | |
| US11235306B2 (en) | Phenothiazine based crosslinked polymer and methods thereof | |
| CN109400874B (en) | Main chain azobenzene type organic porous polymer material and preparation method thereof | |
| CN115947938A (en) | Ellagic acid-based organic porous polymer and preparation method and application thereof | |
| CN108409961A (en) | A kind of amino azo functionalization organic porous polymer material and preparation method thereof | |
| KR101546888B1 (en) | Covalent Organic Polymers with Troeger's Base Functionalities and Adsorbent of Carbon Dioxide Comprising the Same | |
| CN111019145B (en) | Organic covalent polymer material and preparation method and application thereof | |
| CN110016135B (en) | Organic porous polymer material with ketone-hydrazone framework structure and preparation method thereof | |
| Zhang et al. | Facile synthesis of mesoporous poly (melamine–formaldehyde) solid adsorbent in ethylene glycol | |
| Ben et al. | Porous aromatic frameworks for carbon dioxide capture | |
| CN110975838B (en) | Imino diacetic acid functionalized super-crosslinked polymer, and preparation and application thereof | |
| Chang et al. | Synthesis of a pyridine-based covalent organic framework as an efficient adsorbent for rhodamine B removal |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |