CN109894082A - A kind of preparation method and application of the covalent organic frame composite material of nanometer of flower pattern - Google Patents
A kind of preparation method and application of the covalent organic frame composite material of nanometer of flower pattern Download PDFInfo
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- CN109894082A CN109894082A CN201910132803.5A CN201910132803A CN109894082A CN 109894082 A CN109894082 A CN 109894082A CN 201910132803 A CN201910132803 A CN 201910132803A CN 109894082 A CN109894082 A CN 109894082A
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- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 150000001412 amines Chemical class 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000041 non-steroidal anti-inflammatory agent Substances 0.000 claims abstract description 9
- 229940021182 non-steroidal anti-inflammatory drug Drugs 0.000 claims abstract description 9
- 238000010992 reflux Methods 0.000 claims abstract description 7
- 239000000758 substrate Substances 0.000 claims abstract description 6
- 150000004705 aldimines Chemical class 0.000 claims abstract description 4
- 238000006482 condensation reaction Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 32
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 27
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 235000019441 ethanol Nutrition 0.000 claims description 11
- 239000000725 suspension Substances 0.000 claims description 11
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Natural products CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000000605 extraction Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000005576 amination reaction Methods 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 239000005416 organic matter Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 5
- 229920006125 amorphous polymer Polymers 0.000 abstract description 4
- 125000000524 functional group Chemical group 0.000 abstract description 4
- 238000010899 nucleation Methods 0.000 abstract description 3
- 230000006911 nucleation Effects 0.000 abstract description 3
- 238000001556 precipitation Methods 0.000 abstract description 3
- 230000005611 electricity Effects 0.000 abstract description 2
- 230000009881 electrostatic interaction Effects 0.000 abstract description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 description 9
- 239000000523 sample Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 150000002466 imines Chemical class 0.000 description 5
- NXUBVBMQRSLBHQ-UHFFFAOYSA-N O1OOCC=C1.C1=CC=CC=C1 Chemical compound O1OOCC=C1.C1=CC=CC=C1 NXUBVBMQRSLBHQ-UHFFFAOYSA-N 0.000 description 4
- MQOKYEROIFEEBH-UHFFFAOYSA-N 5-methyl-6-phenylphenanthridin-5-ium-3,8-diamine;bromide Chemical compound [Br-].C12=CC(N)=CC=C2C2=CC=C(N)C=C2[N+](C)=C1C1=CC=CC=C1 MQOKYEROIFEEBH-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229920000344 molecularly imprinted polymer Polymers 0.000 description 3
- 239000002057 nanoflower Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000002262 Schiff base Substances 0.000 description 2
- 150000004753 Schiff bases Chemical class 0.000 description 2
- 239000012491 analyte Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- CWVRJTMFETXNAD-JUHZACGLSA-N chlorogenic acid Chemical compound O[C@@H]1[C@H](O)C[C@@](O)(C(O)=O)C[C@H]1OC(=O)\C=C\C1=CC=C(O)C(O)=C1 CWVRJTMFETXNAD-JUHZACGLSA-N 0.000 description 2
- 239000013310 covalent-organic framework Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- CWVRJTMFETXNAD-FWCWNIRPSA-N 3-O-Caffeoylquinic acid Natural products O[C@H]1[C@@H](O)C[C@@](O)(C(O)=O)C[C@H]1OC(=O)\C=C\C1=CC=C(O)C(O)=C1 CWVRJTMFETXNAD-FWCWNIRPSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- -1 Amino Chemical group 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- PZIRUHCJZBGLDY-UHFFFAOYSA-N Caffeoylquinic acid Natural products CC(CCC(=O)C(C)C1C(=O)CC2C3CC(O)C4CC(O)CCC4(C)C3CCC12C)C(=O)O PZIRUHCJZBGLDY-UHFFFAOYSA-N 0.000 description 1
- HEFNNWSXXWATRW-UHFFFAOYSA-N Ibuprofen Chemical compound CC(C)CC1=CC=C(C(C)C(O)=O)C=C1 HEFNNWSXXWATRW-UHFFFAOYSA-N 0.000 description 1
- CWVRJTMFETXNAD-KLZCAUPSSA-N Neochlorogenin-saeure Natural products O[C@H]1C[C@@](O)(C[C@@H](OC(=O)C=Cc2ccc(O)c(O)c2)[C@@H]1O)C(=O)O CWVRJTMFETXNAD-KLZCAUPSSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229920004890 Triton X-100 Polymers 0.000 description 1
- 239000013504 Triton X-100 Substances 0.000 description 1
- 239000008351 acetate buffer Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 239000012472 biological sample Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229940074393 chlorogenic acid Drugs 0.000 description 1
- FFQSDFBBSXGVKF-KHSQJDLVSA-N chlorogenic acid Natural products O[C@@H]1C[C@](O)(C[C@@H](CC(=O)C=Cc2ccc(O)c(O)c2)[C@@H]1O)C(=O)O FFQSDFBBSXGVKF-KHSQJDLVSA-N 0.000 description 1
- 235000001368 chlorogenic acid Nutrition 0.000 description 1
- 238000011208 chromatographic data Methods 0.000 description 1
- BMRSEYFENKXDIS-KLZCAUPSSA-N cis-3-O-p-coumaroylquinic acid Natural products O[C@H]1C[C@@](O)(C[C@@H](OC(=O)C=Cc2ccc(O)cc2)[C@@H]1O)C(=O)O BMRSEYFENKXDIS-KLZCAUPSSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000005053 phenanthridines Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- QEVHRUUCFGRFIF-MDEJGZGSSA-N reserpine Chemical compound O([C@H]1[C@@H]([C@H]([C@H]2C[C@@H]3C4=C(C5=CC=C(OC)C=C5N4)CCN3C[C@H]2C1)C(=O)OC)OC)C(=O)C1=CC(OC)=C(OC)C(OC)=C1 QEVHRUUCFGRFIF-MDEJGZGSSA-N 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention discloses the preparation method and application of the covalent organic frame composite material of a kind of nanometer of flower pattern, low concentration reaction monomers are added step by step in the aaerosol solution containing substrate, generate amorphous heterogeneous core, add high concentration reaction monomers and catalyst, aldimine condensation reaction is carried out under heated reflux condition, obtains covalent organic frame composite material.The present invention is prepared for the covalent organic frame composite material of nanometer flower pattern ion using two step heterogeneous nucleation means, the presence of heterogeneous core inhibits the rapid precipitation of early stage amorphous polymer, the crystalline form of covalent organic frame is instructed to grow, compared with hydro-thermal method, generated time is substantially reduced, while the functional group for modifying material surface is more uniform;Present invention employs the amine monomers containing positive charge to prepare covalent organic frame composite material, electrostatic interaction can occur with the negative electricity group of target compound molecule, realize the selective enrichment of non-steroidal anti-inflammatory drug in water sample.
Description
Technical field
The present invention relates to the preparations and application of a kind of covalent organic frame composite material, specifically, being to be related to one kind to receive
The preparation method of the covalent organic frame composite material of popped rice type ion and its application as solid phase extraction material
Background technique
Covalent organic frame (COF) is covalently bound crystalline, porous material, by lightweight element such as C, H, O, N and B composition.
Since 2005 report for the first time, covalent organic frame has caused to pay attention to extensively.These materials have quite charming characteristic,
Including high-specific surface area, excellent thermal stability, high porosity and low-density [1].In addition, covalently organic frame is in water and acidity
It is more more stable than metal organic frame in medium.Due to having these unique properties, covalent organic frame is considered to have good
The promising sorbent material of good capacity.
The covalent organic frame of most conventional molecular engram mainly contains a large amount of π-π covalent bond, passes through strong hydrophobic effect, π-
π interaction and molecular specificity identification also have some hydrophobic chaff interferents so as to cause it to extract non-steroid anti-inflammatory drug
Certain affinity not can be carried out complete matrix and eliminate [2].Studies have shown that being introduced on molecularly imprinted polymer surface hydrophilic
Property functional group can not only improve the hydrophily of polymer, improve extraction efficiency, moreover it is possible to charge attraction be provided, trace effect is reinforced
Fruit.Puoci et al. introduces polarity parent using the ring-opening reaction of molecularly imprinted polymer surface methyl groups glycidyl acrylate
Water functional group, and it is applied to the extraction of biological sample China acamol, there is preferable selectivity [3].Zhu
Et al. using hydrophilic propyl-triethoxysilicane as monomer, with ethylene glycol dimethacrylate and γ-metering system
Acyl reaction prepares molecularly imprinted polymer, the polymer energy selective extraction chlorogenic acid [4].By the inspiration of these documents, I
Wish to introduce into the hydrophilic covalent organic frame of monomer synthetic molecules trace, improve the selectivity of fiber material.
Covalent organic frame composite material is easy to reunite during preparation, is generally prepared into composite material and carries out benefit
With [5].Conventional silica matrix uses pH range relatively narrow, limits the use scope of composite material.Spherical base simultaneously
The specific surface area of matter is less.In order to solve these problems, we have proposed a kind of new mediums.
Bibliography
[1]Y.B.Zhang,J.Su,H.Furukawa,Y.Yun,F.Gandara,A.Duong,X.Zou,O.M.Yaghi,
Single-crystal structure of a covalent organic framework,J Am Chem Soc,135
(2013)16336-16339.
[2]W.Ji,R.Sun,Y.Geng,W.Liu,X.Wang,Rapid,low temperature synthesis of
molecularly imprinted covalent organic frameworks for the highly selective
extraction of cyano pyrethroids from plant samples,Anal.Chim.Acta,1001(2018)
179-188.
[3]F.Puoci,F.Iemma,G.Cirillo,M.Curcio,O.I.Parisi,U.G.Spizzirri,
N.Picci,New restricted access materials combined to molecularly imprinted
polymers for selective recognition/release in water media,Eur.Polym.J.,45
(2009)1634-1640.
[4]W.Tang,G.Li,K.H.Row,T.Zhu,Preparation of hybrid molecularly
imprinted polymer with double-templates for rapid simultaneous purification
of theophylline and chlorogenic acid in green tea,Talanta,152(2016)1-8.
[5]R.Wang,Z.Chen,A covalent organic framework-based magnetic sorbent
for solid phase extraction of polycyclic aromatic hydrocarbons,and its
hyphenation to HPLC for quantitation,Microchim.Acta,184(2017)3867-3874.
Summary of the invention
It in order to solve the deficiencies in the prior art, is screened by many experiments, the present invention provides a kind of nanometer of flower pattern ions
The preparation method of covalent organic frame composite material.Purpose is to realize the rapid synthesis of covalent organic frame composite material and answers
With.
The present invention is achieved by the following technical solutions:
The invention discloses the preparation methods of the covalent organic frame composite material of a kind of nanometer of flower pattern, outstanding containing substrate
Low concentration reaction monomers are added step by step in floating solution, generates amorphous heterogeneous core, adds high concentration reaction monomers and catalyst,
Aldimine condensation reaction is carried out under heated reflux condition, obtains covalent organic frame composite material.
As a further improvement, specific preparation step of the invention are as follows:
1) a kind of aldehyde monomers are dissolved in NH2-SnO2In dioxane solution, reaction is stirred at room temperature in suspension;
2) the resulting solution of step 1) is added in another amine monomers and catalyst acetic acid, reaction is stirred at room temperature;
3) dilution step 2) resulting solution, and the higher aldehyde monomers of concentration, amine monomers and catalyst acetic acid is added;
4) heating reflux reaction, stannic oxide Surface Creation coating;
5) the resulting solid of step 4) being centrifugated, ethyl alcohol/acetate mixture washs, and it is dry, it is total that nanometer flower pattern can be obtained
Valence organic frame composite material.
As a further improvement, in step 1) of the present invention, concentration of the aldehyde monomers in suspension is
0.04mol L-1, the reaction time is 1 hour.
As a further improvement, in step 2) of the present invention, concentration of the amine monomers in suspension is
0.06mol L-1, the reaction time is 10 minutes.
As a further improvement, aldehydes and amine monomers are in dioxane solution in step 3) of the present invention
Concentration be respectively 0.05mol L-1With 0.75mol L-1, concentration of the catalyst in dioxane solution is 3mol L-1。
As a further improvement, the reaction time is 3 hours in step 4) of the present invention, reaction temperature is
120 degrees Celsius.
As a further improvement, in step 5) of the present invention, ethyl alcohol/acetate mixture volumetric concentration ratio is
98/2。
As a further improvement, the substrate of the present invention that use for preparing is amination stannic oxide.
As a further improvement, the monomer of the present invention that use for preparing is the amine organic matter containing cation.
The invention has the advantages that and effect:
1, the present invention is prepared for the covalent organic frame composite material of nanometer flower pattern ion using two step heterogeneous nucleation means, heterogeneous
The presence of core inhibits the rapid precipitation of early stage amorphous polymer, instructs the crystalline form of covalent organic frame to grow, with hydro-thermal method
It compares, substantially reduces generated time, while the functional group for modifying material surface is more uniform;
2、NH2-SnO2Amino reacted with the aldehyde radical of equal benzene trioxin by schiff base reaction, the bromine first of low concentration is added
After phenanthridines solution, schiff base reaction occurs between equal benzene trioxin and trypadine, therefore, on the surface of silica dioxide granule
The upper polymer for forming thin amorphous imines connection will be single by using the polymer of amorphous imines connection as seed
Body is added to synthesize the covalent organic frame of ionic state on the surface of the seed in seed solution, and the benefit grown in this way is mainly by three
Point: 1) growth of the covalent organic frame of imine usually first generates amorphous polymer, then slowly conversion is in crystalline form, this mistake
Journey is veryer long.In this experiment, the presence of heterogeneous core inhibits the rapid precipitation of early stage amorphous polymer.2) amorphous imines
The composition of the polymer of connection is consistent with monomer, this makes monomer be easy to be attracted to the surface of heterogeneous core, and promotes and covalently have
The crystallization of machine frame during the growth process.3) and the polymer seeds remained on surface aldehyde of amorphous imines connection and amino can be with
The crystalline form of covalent organic frame is instructed to grow.
3, present invention employs nanometer flower pattern stannic oxides as matrix prepares composite material, makes it have bigger ratio table
Area.
4, present invention employs the amine monomers containing positive charge to prepare covalent organic frame composite material, energy and targeted
Electrostatic interaction occurs for the negative electricity group of adduct molecule, realizes the selective enrichment of non-steroidal anti-inflammatory drug in water sample.
Detailed description of the invention
Fig. 1 is to make nanometer flower pattern ion covalent organic frame composite material by oneself to prepare schematic diagram;
Fig. 2 is to extract non-steroidal anti-inflammatory drug in water sample using the covalent organic frame composite material of novel nano flower pattern ion
And isolated schematic device.
Specific embodiment
The invention discloses the preparation methods of the covalent organic frame composite material of a kind of nanometer of flower pattern, outstanding containing substrate
Low concentration reaction monomers are added step by step in floating solution, generates amorphous heterogeneous core, adds high concentration reaction monomers and catalyst,
Aldimine condensation reaction is carried out under heated reflux condition, obtains covalent organic frame composite material.
Specific preparation step are as follows:
6) a kind of aldehyde monomers are dissolved in NH2-SnO2In dioxane solution, reaction, aldehydes is stirred at room temperature in suspension
Concentration of the monomer in suspension is 0.04mol L-1, the reaction time is 1 hour.
7) the resulting solution of step 1) is added in another amine monomers and catalyst acetic acid, reaction is stirred at room temperature;Amine
Concentration of the monomer in suspension is 0.06mol L-1, the reaction time is 10 minutes.
8) dilution step 2) resulting solution, and the higher aldehyde monomers of concentration, amine monomers and catalyst acetic acid is added;
The concentration of aldehydes and amine monomers in dioxane solution is respectively 0.05mol L-1With 0.75mol L-1, catalyst is two
Concentration in six ring solution of oxygen is 3mol L-1。
9) heating reflux reaction, stannic oxide Surface Creation coating, reaction time are 3 hours, and reaction temperature is 120 Celsius
Degree.
10) the resulting solid of step 4) being centrifugated, ethyl alcohol/acetate mixture washs, and it is dry, nanometer flower pattern can be obtained
Covalent organic frame composite material, ethyl alcohol/acetate mixture volumetric concentration ratio are 98/2.
Technical solution of the present invention is described further with reference to the accompanying drawings of the specification:
The present invention prepares the covalent organic frame composite material of a kind of nanometer of flower pattern ion, is reacted, is obtained by heterogeneous nucleation
A kind of novel extraction material has very high by the non-steroidal anti-inflammatory drug in simple Solid Phase Extraction selective enrichment water sample
Bioaccumulation efficiency.The sample introduction in high performance liquid chromatography again separate while being analyzed with UV detector.
Fig. 1 is to make nanometer flower pattern ion covalent organic frame composite material by oneself to prepare schematic diagram, specific preparation process
Are as follows:
1g Triton X-100 is dissolved in 30mL deionized water, 10min is stirred, obtains uniform solution.Take another burning
30mL deionized water, 0.564g stannous chloride hydrate and 0.838g sodium citrate dehydrate is added in cup, stirs 10min, obtains
Clear solution.Then two solution of mixing continue after stirring 5min, 0.4mL tetrapropylammonium hydroxide are added.Above-mentioned solution exists
After stirring 10min, 27mL is taken to be transferred in 50mL reaction kettle, and react 5h at 180 DEG C.It is clear with ethyl alcohol and deionized water difference
Deposit 3 times for washing reactor bottom.Finally obtained stannic oxide product is dried in 60 DEG C of baking ovens.Pass through ultrasonic treatment
By 1g SnO2It is dispersed in 180mL ethyl alcohol.By the propyl-triethoxysilicane of 300 μ L and 20mL ethyl alcohol under ultrasound condition
Mixture is slowly added into SnO2In solution.Then, it flows back again at 70 DEG C 4 hours, so that aminofunctional stannic oxide
(NH2-SnO2) surface.Three times with ethanol washing by the modified particle in surface, and it is dry under atmosphere.
In step 1, equal benzene trioxin (TFB, 83.98mg) is dissolved in 13mLNH2-SnO2Suspension (100mgmL-1
Dioxane solution) in and be stirred at room temperature 1 hour.Then, by trypadine (DB, 197.70mg) and 200 μ L acetic acid
(3mol L-1) be added in mixture.Reaction after ten minutes, forms heterogeneous core, is diluted to 50mgmL with dioxane-1.For step
Rapid 2, equal benzene trioxin (210.6mg) and trypadine (494.3mg) are dissolved in heterogeneous core solution (the 50mg mL of 13mL respectively-1) in.Both solution are mixed, 1.17mL acetic acid and 268.2mg brufen is added.Reaction mixture is transferred to 50mL circle
In the flask of bottom, and 3 hours are maintained the reflux at 120 DEG C.It is removed by being washed for several times with ethyl alcohol/acetate mixture (98/2, v/v)
Remove the template molecule in gained nanocomposite.Finally, by covalent organic frame composite material (the MI-IC-COF@of molecular engram
SnO2) dry in an atmosphere.
Fig. 2 is to extract non-steroidal anti-inflammatory drug in water sample using the covalent organic frame composite material of novel nano flower pattern ion
And isolated schematic device, use fragrance in the covalent organic frame composite material extraction water sample of novel nano flower pattern ion
The process of amine is as follows:
The first step, enrichment: by 10mg MI-IC-COF@SnO2It is dispersed directly into 10mL water sample.Mixture solution is surpassed
Sonication 5 minutes, 4 minutes then were centrifuged to separate two-phase with the speed of 6400rpm.After removing supernatant, 0.5mL is added and contains
The methanol of 1% acetic acid is simultaneously ultrasonically treated 5 minutes to desorb non-steroid anti-inflammatory drug from isolated adsorbent.Finally, by 25 μ L
Acquired solution injects HPLC-UV system.
Second step, analysis: the analysis of non-steroid anti-inflammatory drug carries out in Ultimate 3000HPLC system.At 40 DEG C
It is lower to separate analyte using Hypersil GOLD C18 column (250mm × 4.6mm, i.d.5.0 μm).It will be molten by 1% acetate buffer
The mobile phase of liquid (A) and methanol (B) composition is with 1.0mLmin-1Pumping.Gradient program selection is as follows: 0 minute, 20%B;0-4 points
Clock, 20-80%B;4-12 minutes, 80%B;12-20 minutes, 80-20%B.The chromatographic data of analyte in 225nm, 255nm and
It is collected under 277nm.
The above enumerated are only specific embodiments of the present invention for finally, it should also be noted that.Obviously, the present invention is unlimited
It, can also be there are many deforming in above embodiments, those skilled in the art can directly lead from present disclosure
Out or all deformations for associating, it is considered as protection scope of the present invention.
Claims (10)
1. the preparation method of the covalent organic frame composite material of a kind of nanometer of flower pattern, which is characterized in that in the suspension containing substrate
Low concentration reaction monomers are added in solution step by step, generates amorphous heterogeneous core, adds high concentration reaction monomers and catalyst, add
Aldimine condensation reaction is carried out under hot counterflow condition, obtains covalent organic frame composite material.
2. the preparation method of the covalent organic frame composite material of according to claim 1 nanometer of flower pattern, which is characterized in that tool
Preparation step are as follows:
1) a kind of aldehyde monomers are dissolved in NH2-SnO2In dioxane solution, reaction is stirred at room temperature in suspension;
2) the resulting solution of step 1) is added in another amine monomers and catalyst acetic acid, reaction is stirred at room temperature;
3) dilution step 2) resulting solution, and the higher aldehyde monomers of concentration, amine monomers and catalyst acetic acid is added;
4) heating reflux reaction, stannic oxide Surface Creation coating;
5) the resulting solid of step 4) is centrifugated, ethyl alcohol/acetate mixture washs, and dry, can obtain nanometer flower pattern covalently has
Machine frame composite material.
3. the preparation method of the covalent organic frame composite material of according to claim 2 nanometer of flower pattern, which is characterized in that institute
In the step 1) stated, concentration of the aldehyde monomers in suspension is 0.04mol L-1, the reaction time is 1 hour.
4. the preparation method of the covalent organic frame composite material of according to claim 2 nanometer of flower pattern, which is characterized in that institute
In the step 2) stated, concentration of the amine monomers in suspension is 0.06mol L-1, the reaction time is 10 minutes.
5. the preparation method of the covalent organic frame composite material of according to claim 2 nanometer of flower pattern, which is characterized in that institute
In the step 3) stated, the concentration of aldehydes and amine monomers in dioxane solution is respectively 0.05mol L-1With 0.75mol L-1, concentration of the catalyst in dioxane solution is 3mol L-1。
6. the preparation method of the covalent organic frame composite material of according to claim 2 nanometer of flower pattern, which is characterized in that institute
In the step 4) stated, the reaction time is 3 hours, and reaction temperature is 120 degrees Celsius.
7. the preparation method of the covalent organic frame composite material of according to claim 2 nanometer of flower pattern, which is characterized in that institute
In the step 5) stated, ethyl alcohol/acetate mixture volumetric concentration ratio is 98/2.
8. the preparation of the covalent organic frame composite material of nanometer flower pattern described according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7
Method, which is characterized in that preparing the substrate used is amination stannic oxide.
9. the preparation of the covalent organic frame composite material of nanometer flower pattern described according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7
Method, which is characterized in that preparing the monomer used is the amine organic matter containing cation.
10. a kind of system of the covalent organic frame composite material of nanometer flower pattern described in claims 1 or 2 or 3 or 4 or 5 or 6 or 7
Non-steroidal anti-inflammatory drug and isolated application in the extraction water sample of composite material made of standby.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110684203A (en) * | 2019-10-25 | 2020-01-14 | 南京大学 | Two-dimensional bromine-containing covalent organic framework compound and preparation method thereof |
CN110975840A (en) * | 2019-12-16 | 2020-04-10 | 中国计量大学 | Composite material based on heteroporous covalent organic framework and preparation method and application thereof |
CN112430327A (en) * | 2020-11-25 | 2021-03-02 | 南开大学 | Reticular magnetic molecular imprinting covalent organic framework material and preparation method and application thereof |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20140037944A1 (en) * | 2010-09-13 | 2014-02-06 | Cornell University | Covalent organic framework films, and methods of making and uses of same |
CN106083909A (en) * | 2016-06-24 | 2016-11-09 | 兰州大学 | A kind of preparation method of covalent organic frame material monocrystalline |
CN106390765A (en) * | 2015-07-27 | 2017-02-15 | 北京工业大学 | Covalent organic skeleton material-doped alcohol perm-selective membrane and preparation method thereof |
CN109232884A (en) * | 2018-07-07 | 2019-01-18 | 盐城师范学院 | A kind of interface preparation method of two dimension organic framework materials |
-
2019
- 2019-02-21 CN CN201910132803.5A patent/CN109894082B/en not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20140037944A1 (en) * | 2010-09-13 | 2014-02-06 | Cornell University | Covalent organic framework films, and methods of making and uses of same |
CN106390765A (en) * | 2015-07-27 | 2017-02-15 | 北京工业大学 | Covalent organic skeleton material-doped alcohol perm-selective membrane and preparation method thereof |
CN106083909A (en) * | 2016-06-24 | 2016-11-09 | 兰州大学 | A kind of preparation method of covalent organic frame material monocrystalline |
CN109232884A (en) * | 2018-07-07 | 2019-01-18 | 盐城师范学院 | A kind of interface preparation method of two dimension organic framework materials |
Non-Patent Citations (2)
Title |
---|
XIANG ZHU ET AL.: "Efficient Removal of Organic Dye Pollutants Using Covalent Organic Frameworks", 《AICHE JOURNAL》 * |
孙兵 等: "二维共价有机框架的设计、合成与应用", 《中国科学:化学》 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110684203A (en) * | 2019-10-25 | 2020-01-14 | 南京大学 | Two-dimensional bromine-containing covalent organic framework compound and preparation method thereof |
CN110975840A (en) * | 2019-12-16 | 2020-04-10 | 中国计量大学 | Composite material based on heteroporous covalent organic framework and preparation method and application thereof |
CN110975840B (en) * | 2019-12-16 | 2022-06-21 | 中国计量大学 | Composite material based on heteroporous covalent organic framework and preparation method and application thereof |
CN112430327A (en) * | 2020-11-25 | 2021-03-02 | 南开大学 | Reticular magnetic molecular imprinting covalent organic framework material and preparation method and application thereof |
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