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 PDF

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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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composite material
organic frame
covalent organic
nanometer
frame composite
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CN109894082B (en
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李巍霞
朱岩
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Zhejiang University ZJU
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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

A kind of preparation method and application of the covalent organic frame composite material of nanometer of flower pattern
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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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

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Cited By (4)

* Cited by examiner, † Cited by third party
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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