阅读说明：本技术 一种铕稀土配合物改性多孔聚合物及其制备和应用 (Europium rare earth complex modified porous polymer and preparation and application thereof ) 是由 廖耀祖 左宏瑜 李颖 于 2019-09-09 设计创作，主要内容包括：本发明涉及一种铕稀土配合物改性多孔聚合物及其制备和应用,包括多孔聚合物以及后修饰多孔聚合物上的稀土配合物。本发明所得改性多孔聚合物在荧光传感检测有机材料、气体吸附或催化剂等方法的应用。本发明具有材料易得,灵敏度高,稳定性好等优点。(The invention relates to a europium rare earth complex modified porous polymer and a preparation method and application thereof, and the europium rare earth complex modified porous polymer comprises a porous polymer and a rare earth complex on a post-modified porous polymer. The modified porous polymer obtained by the invention is applied to methods of fluorescence sensing detection of organic materials, gas adsorption or catalysts and the like. The invention has the advantages of easily obtained materials, high sensitivity, good stability and the like.)

1. A modified porous polymer having the general formula:

2. The modified porous polymer of claim 1, having the following specific formula:

3. a method of preparing a modified porous polymer comprising: the covalent organic framework porous polymer is used as a carrier and then modified by a rare earth metal complex to prepare the rare earth metal complex.

4. The preparation method according to claim 3, which comprises:

(1)1,3,5- (aminophenyl) benzene and 2, 5-dihydroxy terephthalaldehyde are taken as monomers, and are reacted by Schiff base to prepare a covalent organic framework material porous polymer;

(2) mixing the covalent organic framework material porous polymer, triethylamine bromide ion liquid and potassium carbonate in a reaction bottle filled with DMF, reacting for 24h at 120 ℃, filtering, and drying to obtain a post-modified covalent organic porous polymer;

(3) and mixing the post-modified covalent organic porous polymer with a ligand, rare earth metal salt and sodium hydroxide in alcohol, reacting at 70 ℃ for 12-24h, performing suction filtration, and drying to obtain the modified porous polymer.

5. The method according to claim 4, wherein the molar ratio of 1,3,5 (aminophenyl) benzene-and 2, 5-dihydroxyterephthalaldehyde in the step (1) is 2: 3.

6. The method according to claim 4, wherein the reaction in step (1) is: reacting at 120 ℃ for 48-72 h.

7. The preparation method according to claim 4, wherein the mass ratio of the porous polymer with the covalent organic skeleton, the triethylamine bromide ion solution and the potassium carbonate in the step (2) is 1: 1: 0.6.

8. the preparation method according to claim 4, wherein in the step (3), the ligand is 2-thenoyltrifluoroacetone TTA, and the rare earth metal salt is europium chloride; the alcohol is ethanol.

9. The method according to claim 4, wherein the molar ratio of the ligand, the rare earth metal salt and the sodium hydroxide in the step (3) is 1:4: 4.

10. The use of the modified porous polymer of claim 1 in fluorescence sensing detection of organic materials, gas adsorption or catalysts.

Technical Field

The invention belongs to the field of fluorescent sensing materials and preparation and application thereof, and particularly relates to a europium rare earth complex modified porous polymer and preparation and application thereof.

Background

The fluorescence sensing material is a material which is based on a fluorescence sensor and uses the fluorescence characteristic of the fluorescence sensor to identify and detect molecules. Fluorescence has many characteristics such as high sensitivity, good selectivity, short response time, direct observation and the like, which makes it one of the most powerful conduction mechanisms for chemical detection. The rare earth complex is an important luminescent functional material, and the excellent luminescent property of the rare earth complex enables the rare earth complex to have great application in the aspect of sensing and detection. However, rare earth complexes have the disadvantages of poor light stability and thermal stability. The emerging porous polymer has the advantages of high specific surface area, good stability and the like, so that the porous polymer and the fluorescent sensor are hopeful to be used for fluorescent sensing detection by modifying the porous polymer and the fluorescent sensor. At present, rare earth complex modified porous polymers for organic solvent detection are still lacked.

Currently common techniques, including gas chromatography, GC-MS, and Electrochemiluminescence (ECL) spectroscopy, are used to detect acetone. However, these methods often suffer from problems such as complicated sample handling, use of toxic reagents, high cost and time consuming operations, etc.

Disclosure of Invention

The invention aims to solve the technical problem of providing an europium rare earth complex modified porous polymer and preparation and application thereof, and filling the vacancy of the existing rare earth complex modified porous polymer for organic solvent detection.

A modified porous polymer according to the present invention,

the structural formula is as follows:

wherein R is independently selected from rare earth complex or H, and is not H at the same time.

The specific structural formula is as follows:

the invention provides a preparation method of a modified porous polymer, which comprises the following steps: the covalent organic framework porous polymer is used as a carrier and then modified by a rare earth metal complex to prepare the rare earth metal complex.

Further, the preparation method specifically comprises the following steps:

(1)1,3,5- (aminophenyl) benzene and 2, 5-dihydroxy terephthalaldehyde are taken as monomers, and are reacted by Schiff base to prepare a covalent organic framework material porous polymer;

(2) mixing the covalent organic framework material porous polymer, triethylamine bromide ion liquid and potassium carbonate in a reaction bottle filled with DMF, reacting for 24h at 120 ℃, filtering, and drying to obtain a post-modified covalent organic porous polymer;

(3) and mixing the post-modified covalent organic porous polymer with a ligand, rare earth metal salt and sodium hydroxide in alcohol, reacting at 70 ℃ for 12-24h, performing suction filtration, and drying to obtain the modified porous polymer.

The preferred mode of the above preparation method is as follows:

the Schiff base reaction in the step (1) is specifically as follows: placing two monomers of 1,3,5 (aminophenyl) benzene-and 2, 5-dihydroxy terephthalaldehyde into a reaction device at normal temperature and normal pressure, adding o-dichlorobenzene and n-butanol, dropwise adding an acetic acid aqueous solution, performing ultrasonic treatment until complete reaction, performing suction filtration and Soxhlet extraction after reaction for 48-72h at 120 ℃, and drying in a vacuum oven to obtain the covalent organic framework polymer.

The volume ratio of the n-butanol to the o-dichlorobenzene to the acetic acid aqueous solution is 7.5:7.5: 1.5.

The volume of the n-butanol and the o-dichlorobenzene is 7.5mL, the volume of the acetic acid aqueous solution is 1.5, and the concentration of the acetic acid aqueous solution is 6M.

The dropwise adding of the acetic acid aqueous solution is carried out until complete reaction specifically comprises the following steps: and (4) carrying out ultrasonic treatment for 10min under the nitrogen atmosphere of the acetic acid aqueous solution until the reaction is completed.

The suction filtration needs to be carried out in a sand core funnel, and acetone is used for washing in the suction filtration process; the solvent used in the Soxhlet extraction is tetrahydrofuran, and the extraction is carried out for 24 hours; the drying is carried out by putting the mixture into a vacuum oven for drying at the temperature of 50-60 ℃ for 24 hours.

In the step (1), the molar ratio of 1,3,5 (aminophenyl) benzene-to 2, 5-dihydroxy terephthalaldehyde is 2: 3.

The reaction in the step (1) is as follows: the reaction is carried out for 48 to 72 hours at 120 ℃, and the reaction time is further preferably 72 hours.

The mass ratio of the divalent organic framework porous polymer, the triethylamine bromide ion liquid and the potassium carbonate in the step (2) is 1: 1: 0.6.

the solvent in the step (2) is DMF.

The drying in the step (2) comprises the following steps: the drying temperature of the vacuum oven is 100 ℃, and the drying time is 24 hours.

In the step (3), the ligand is TTA, and the rare earth metal salt is europium chloride;

the solvent in the step (3) is ethanol;

the molar ratio of the ligand, the rare earth metal salt and the sodium hydroxide in the step (3) is 1:4: 4.

The suction filtration in the step (3) is as follows: and (4) carrying out suction filtration by using a sand core funnel, and washing by using water and ethanol during suction filtration.

The drying in the step (3) is as follows: the drying temperature of the vacuum oven is 60 ℃, and the drying time is 24 h.

The invention provides application of the modified porous polymer in fluorescence sensing detection of an organic solvent.

Specifically, the europium rare earth complex modified porous polymer is dispersed in different organic solvents to test fluorescence intensity, wherein the organic solvents are acetone, DMF, tetrahydrofuran, acetonitrile, ethanol, methanol, dichloromethane and diethyl ether.

Further, the mass-volume ratio of the europium rare earth complex modified porous polymer to the organic solvent is 1 mg: 10 mL.

Such as: the mass of the europium rare earth complex modified porous polymer is 2mg, and the volume of the organic solvent is 20 mL.

The obtained modified polymer has the fluorescence detection function with high selectivity and high sensitivity to acetone.

Advantageous effects

The invention relates to a europium rare earth complex modified porous polymer for organic solvent detection and a preparation method thereof.

Drawings

FIG. 1 is a Fourier transform infrared spectrum of the product obtained in example 1;

FIG. 2 shows the product obtained in example 1¹³C-NMR；

FIG. 3 is an X-ray diffraction chart of the product obtained in example 1;

FIG. 4 is a thermogravimetric analysis of the product obtained in example 1;

FIG. 5 shows N in the product obtained in example 1₂Adsorption-desorption curve;

FIG. 6 is a graph of a theoretical pore size distribution of a delocalized density function;

FIG. 7 is a graph showing fluorescence spectra of excitation at 300nm in examples 2 to 9.

FIG. 8 is a graph comparing the fluorescence spectra of different amounts of acetone in example 10.

Detailed Description

The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.

The following examples are examples of raw material sources: 2, 5-dihydroxy-terephthalaldehyde (Dha, 1g 95%), 1,3, 5-tris (4-aminophenyl) benzene (Tab, 5g 93%), n-butanol (n-BuOH, 500ml 99%), o-dichlorobenzene (o-DCB, 100ml 98%), europium chloride (EuCl)₃·6H₂O, 5g 99.9%) and dithientrifluoroacetylacetone (TTA, 98%) were purchased from adadin Chemistry, shanghai, china. Potassium carbonate (K)₂CO₃500g 99%), N, N' -dimethylformamide (DMF, 500ml 99%), acetonitrile (500ml 99%) and 1, 2-dibromoethane (250ml 98%) were purchased from Chinese medicine (Shanghai, China).