A composite material based on heteroporous covalent organic framework and its preparation method and application

Abstract

The invention discloses a composite material based on a heteroporous covalent organic framework and its preparation method and application. The invention adopts the method of step-by-step addition of monomers, and first covalently bonds p-phenylene on the surface of polymer microspheres. Amine and 1,3,5-three (4-aminophenyl) benzene, it is easier to control the growth of the covalent organic framework and the morphology of the final product; the present invention adds two kinds of amine compounds in the reaction, respectively for Phenylenediamine and 1,3,5-tri(4-aminophenyl)benzene finally generate heteroporous covalent organic frameworks with different pore sizes, which can realize the extraction of a variety of compounds with different molecular sizes. The composite material prepared by the invention can be used for extraction and elimination, and can be used for liquid chromatography columns to separate various compounds.

Description

technical field

[0001] The invention relates to the field of solid-phase extraction sample pretreatment, in particular to a composite material based on a heteroporous covalent organic framework and a preparation method and application thereof. Background technique

[0002] Non-steroidal anti-inflammatory drugs have antipyretic, anti-inflammatory and analgesic effects, and are commonly used in the treatment of rheumatic diseases, inflammation and soreness. Due to their large annual consumption, NSAIDs are released into the environment in the form of pharmaceutical factory waste, urine, wastewater, and discarded expired drugs. NSAIDs, which are continuously released into the environment, have chronic effects on aquatic and terrestrial inhabitants and endanger human health. The World Health Organization (WHO) considers NSAIDs to be emerging contaminants. Therefore, suitable methods are needed to monitor NSAIDs in environmental samples.

[0003] At present, the sample pretrea...

Examples

Embodiment 1

[0030] Example 1 Preparation of covalent organic framework / polyglycidyl methacrylate-divinylbenzene composite material

[0031] (1) Preparation of polyglycidyl methacrylate-divinylbenzene microspheres

[0032] Polyglycidyl methacrylate-divinylbenzene microspheres are prepared by using existing conventional methods; the specific preparation process is as follows:

[0033]3 g of polyvinylpyrrolidone and 100 mL of a mixture of ethanol and water (volume ratio of ethanol to water 95:5, V / V) were added to a 250 mL four-neck round bottom flask and heated in a water bath at 70°C. Mix 18 g of styrene and 0.8 g of azobisisobutyronitrile and add dropwise to the above flask, control the dropping speed, and complete the dropwise addition in about 30 minutes. After reacting under nitrogen protection for 24 hours, the obtained solids (ie, polymer seeds) were washed with excess water and stored in a 1% aqueous solution of sodium dodecyl sulfonate (m / v). The polymer seeds were dispersed in 1...

Embodiment 2

[0036] Example 2 Morphology study

[0037] like figure 2 As shown in a and 2b, the surface of polyglycidyl methacrylate-divinylbenzene microspheres has a porous structure. like figure 2 As shown in c and 2d, in the whole reaction, p-phenylenediamine, 1,3,5-tris(4-aminophenyl)benzene, 1,3,5-tris(p-formylbenzene)benzene and polymethacrylic acid The mass ratio of glycidyl ester-divinylbenzene microspheres is 1:3:5:12; in the dehydration reaction stage, p-phenylenediamine, 1,3,5-tris(4-aminophenyl)benzene and polymethyl The mass ratio of glycidyl acrylate-divinylbenzene microspheres was 9:20:300; the final reaction product was agglomerated spheres with uneven crystal growth on the surface of the spheres;

[0038] like figure 2 As shown in e and 2f, in the whole reaction, when p-phenylenediamine, 1,3,5-tris(4-aminophenyl)benzene, 1,3,5-tris(p-formylbenzene)benzene and polymethyl The mass ratio of glycidyl acrylate-divinylbenzene microspheres is 1:2:4:12, in the dehydration ...

Embodiment 3

[0040] Example 3 Thermal Stability Study

[0041] Thermogravimetric analysis of polyglycidyl methacrylate-divinylbenzene microspheres and covalent organic framework / polyglycidyl methacrylate-divinylbenzene composites was performed using DSCQ1000 differential scanning calorimetry, respectively. The result is as image 3 As shown, according to the results, the covalent organic framework / polyglycidyl methacrylate-divinylbenzene composite material begins to thermally decompose at 150 degrees Celsius, indicating that it can meet the daily extraction needs.

technical field

[0001] The invention relates to the field of solid-phase extraction sample pretreatment, in particular to a composite material based on a heteroporous covalent organic framework and a preparation method and application thereof. Background technique

[0002] Non-steroidal anti-inflammatory drugs have antipyretic, anti-inflammatory and analgesic effects, and are commonly used in the treatment of rheumatic diseases, inflammation and soreness. Due to their large annual consumption, NSAIDs are released into the environment in the form of pharmaceutical factory waste, urine, wastewater, and discarded expired drugs. NSAIDs, which are continuously released into the environment, have chronic effects on aquatic and terrestrial inhabitants and endanger human health. The World Health Organization (WHO) considers NSAIDs to be emerging contaminants. Therefore, suitable methods are needed to monitor NSAIDs in environmental samples.

[0003] At present, the sample pretrea...

Examples

Embodiment 1

[0030] Example 1 Preparation of covalent organic framework / polyglycidyl methacrylate-divinylbenzene composite material

[0031] (1) Preparation of polyglycidyl methacrylate-divinylbenzene microspheres

[0032] Polyglycidyl methacrylate-divinylbenzene microspheres are prepared by using existing conventional methods; the specific preparation process is as follows:

[0033]3 g of polyvinylpyrrolidone and 100 mL of a mixture of ethanol and water (volume ratio of ethanol to water 95:5, V / V) were added to a 250 mL four-neck round bottom flask and heated in a water bath at 70°C. Mix 18 g of styrene and 0.8 g of azobisisobutyronitrile and add dropwise to the above flask, control the dropping speed, and complete the dropwise addition in about 30 minutes. After reacting under nitrogen protection for 24 hours, the obtained solids (ie, polymer seeds) were washed with excess water and stored in a 1% aqueous solution of sodium dodecyl sulfonate (m / v). The polymer seeds were dispersed in 1...

Embodiment 2

[0036] Example 2 Morphology study

[0037] like figure 2 As shown in a and 2b, the surface of polyglycidyl methacrylate-divinylbenzene microspheres has a porous structure. like figure 2 As shown in c and 2d, in the whole reaction, p-phenylenediamine, 1,3,5-tris(4-aminophenyl)benzene, 1,3,5-tris(p-formylbenzene)benzene and polymethacrylic acid The mass ratio of glycidyl ester-divinylbenzene microspheres is 1:3:5:12; in the dehydration reaction stage, p-phenylenediamine, 1,3,5-tris(4-aminophenyl)benzene and polymethyl The mass ratio of glycidyl acrylate-divinylbenzene microspheres was 9:20:300; the final reaction product was agglomerated spheres with uneven crystal growth on the surface of the spheres;

[0038] like figure 2 As shown in e and 2f, in the whole reaction, when p-phenylenediamine, 1,3,5-tris(4-aminophenyl)benzene, 1,3,5-tris(p-formylbenzene)benzene and polymethyl The mass ratio of glycidyl acrylate-divinylbenzene microspheres is 1:2:4:12, in the dehydration ...

Embodiment 3

[0040] Example 3 Thermal Stability Study

[0041] Thermogravimetric analysis of polyglycidyl methacrylate-divinylbenzene microspheres and covalent organic framework / polyglycidyl methacrylate-divinylbenzene composites was performed using DSCQ1000 differential scanning calorimetry, respectively. The result is as image 3 As shown, according to the results, the covalent organic framework / polyglycidyl methacrylate-divinylbenzene composite material begins to thermally decompose at 150 degrees Celsius, indicating that it can meet the daily extraction needs.

Images