LU501793B1 - Aromatic polymer adsorption device and preparation method thereof - Google Patents

Aromatic polymer adsorption device and preparation method thereof Download PDF

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LU501793B1
LU501793B1 LU501793A LU501793A LU501793B1 LU 501793 B1 LU501793 B1 LU 501793B1 LU 501793 A LU501793 A LU 501793A LU 501793 A LU501793 A LU 501793A LU 501793 B1 LU501793 B1 LU 501793B1
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fiber
preparation
adsorption device
aromatic polymer
paf
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LU501793A
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German (de)
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Zhongyue Li
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Univ Yantai
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28023—Fibres or filaments
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3204—Inorganic carriers, supports or substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3268—Macromolecular compounds
    • B01J20/327—Polymers obtained by reactions involving only carbon to carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3291—Characterised by the shape of the carrier, the coating or the obtained coated product
    • B01J20/3293—Coatings on a core, the core being particle or fiber shaped, e.g. encapsulated particles, coated fibers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
    • B01D15/12—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to the preparation of the feed
    • B01D15/125—Pre-filtration

Abstract

The invention relates to an aromatic polymer adsorption device and preparation method thereof. The SPME extraction fiber comprises a fiber carrier and a coating attached to its surface, wherein the carrier fiber is the surface hydroxylated base fiber, and one end of the carrier fiber is coated with a coating material which is a mixture of PAF-41 and glue. PAF-41 of the present invention is a porous organic framework material, which has uniform microporous structure, high specific surface area and high aromaticity. Its structural characteristics make it have good affinity for aromatic volatile substances, which can improve the extraction efficiency of SPME, thus improving the sensitivity of target detection.

Description

DESCRIPTION LU501793
AROMATIC POLYMER ADSORPTION DEVICE AND PREPARATION METHOD THEREOF
TECHNICAL FIELD The invention belongs to the technical field of sample analysis pretreatment, is an interdisciplinary subject of analytical chemistry and material chemistry, and specifically relates to an aromatic polymer adsorption device and preparation method thereof.
BACKGROUND Solid-phase microextraction (SPME) is a sample pretreatment technology that integrates sampling, extraction, concentration and injection, and has been widely used in environmental engineering, biological engineering, pharmaceutical engineering and food engineering. The core of SPME technology lies in the extraction fiber (or extraction fiber), and the quality of the extraction fiber depends on the efficiency, selectivity and stability of the extraction coating on the analyte. At present, the commercial SPME fibers are expensive and limited in variety. The main components of the coating are polydimethylsiloxane (PDMS), polyacrylic acid (PA), divinylbenzene (DVB) carbon molecular sieve (CAR) and so on. In order to improve the analysis effect of SPME technology, researchers try to use a variety of materials as the coating of SPME extraction fiber, such as: organic polymer, ionic liquid, carbon nano material, molecular printing polymer, mesoporous material, metal-organic framework material, covalent organic framework material and so on. Among them, metal-organic framework materials and covalent organic framework materials have become the research focus of SPME coatings in recent years because of their diverse and controllable structures, uniform pore size and large specific surface area. Covalent organic framework material is a kind of porous material constructed by connecting organic structural elements through covalent bonds. Compared with metal-organic framework, it usually has better thermal and chemical stability, and can be used under worse conditions, which overcomes the limitations of metal-organic framework materials. Therefore, as the coating material of SPME fiber, covalent organic framework material is the ideal choice. However, there is no aromatic covalent organic framework material in the prior art, so it is of great significance to develop an aromatic covalent organic framework material with strong enrichment ability for aromatic and amino-containing targets.
SUMMARY LU501793 The invention aims to provide an aromatic polymer adsorption device and a preparation method thereof. The SPME extraction fiber has good extraction effect, good stability, long service life and strong enrichment ability for aromatic volatile substances, can be used as the main component of SPME sample pretreatment method and can be combined with analysis methods such as gas chromatography, liquid chromatography and mass spectrometry.
In order to solve the above technical problems, the technical scheme adopted by the invention is as follows: An aromatic polymer adsorption device and its preparation method, comprise a fiber carrier and a coating attached to its surface, wherein one end of the carrier fiber is coated with a coating material, and the coating material is a mixture of PAF-41 and glue.
Preferably, the carrier fiber comprises quartz fiber, glass fiber, stainless steel fiber, quartz capillary with stainless steel inner core or glass capillary with stainless steel inner core.
Preferably, the carrier fiber is a substrate fiber with hydroxylated surface; the preparation method comprises: soaking one end of the fiber in sodium hydroxide solution, then neutralizing excess hydroxide ions with hydrochloric acid solution, and finally cleaning the fiber with deionized water and drying in the air.
Preferably, the concentration of sodium hydroxide solution is 0.5-2 mol-L! and the concentration of hydrochloric acid solution is 0.5-2 mol-L*!.
Preferably, the preparation method of PAF-41 is as follows: (1) under the protection of nitrogen, adding bis-(1,5-cyclooctadiene) nickel and 2,2-bipyridine in equal molar ratio into a reactor, then injecting anhydrous 1,5-cyclooctadiene and anhydrous N,N-dimethylacetamide in a volume ratio of 1:10-1:100, wherein the concentration of bis-(1,5-cyclooctadiene) nickel is 0.01-0.5 mol-L™!, and the mixture is heated and stirred at 80-95°C for 0.5-5 hours to activate the catalyst; (2) similarly, under the protection of nitrogen, dissolving tris (4-bromobenzene) amine in anhydrous N,N-dimethylacetamide with the concentration of 0.01-0.1 mol: L-', and stirring at 80-95°C for 0.5-5 hours; (3) subsequently, mixing the two solutions, and heating and stirring the whole reaction system at 80-95°C for 72-120 hours;
(4) after reducing the temperature of the reaction system to room temperature, addidg)501793 concentrated hydrochloric acid until the color becomes emerald green and filtering to obtain a crude product; (5) washing with a large amount of distilled water until the solution is neutral, then washing the crude product with ethanol and chloroform for 3-10 times to remove unreacted raw materials and catalysts, and finally vacuumizing at 80-200°C to obtain PAF-41.
Preferably, the preparation method of PAF-41 is as follows: (1) under the protection of nitrogen, adding anhydrous Lewis acid catalyst into a reactor, injecting anhydrous CHCIs, and stirring at 60-90°C for 2-6 hours; (2) dissolving 1,3,5-triphenylamine in anhydrous CHCls; (3) injecting that solution of step (2) into the system of step (1), reacting at 60-90°C for 1-5 day with the mol ratio of catalyst to 1, 3, 5-triphenylamine of 0.4-3:5; (4) After the reaction is finished and the temperature is reduced to room temperature, filtering, washing the product with hydrochloric acid, methanol and acetone respectively, and then sequentially soxhlet extracting the product with ethanol, tetrahydrofuran and chloroform for 1-3 days; (5) dinally, vacuumizing at 80-200°C to obtain PAF-41.
Preferably, the Lewis catalyst is AlCl3, FeCl; or CuCl.
An aromatic polymer adsorption device and preparation method thereof, comprising the following steps: (1) inserting one end of carrier fiber into auxiliary glue, slowly pulling out, then inserting into prepared PAF-41 powder, drying at 50-90°C for 2-60 minutes, and repeating the above operations until the required thickness is reached, (2) finally, aging at 200-250°C for 1-5 hours to obtain SPME extraction fiber.
Preferably, the auxiliary adhesive is polydimethylsiloxane, polyimide prepolymer or ethylene oxide adhesive.
Preferably, the thickness of the coating is 20-100 pm.
Effect of Invention (1) The coating functional component of SPME fiber is a covalent organic framework material, PAF-41, which has uniform microporous structure, high specific surface area and high aromaticity. PAF-41 has a good affinity for aromatic volatile substances due to its structural501793 characteristics. Compared with commercial SPME fiber, the extraction efficiency can be increased by 20%-2000%.
The aromatic volatile substances here include nonpolar benzene, toluene, xylene, ethylbenzene, styrene, etc., and polar aniline, toluidine, dimethylaniline, methoxyaniline, chloroaniline, naphthylamine, aminobenzene, etc.
(2) The powder+glue layer preparation method adopted in the invention can well help the granular PAF-41 to form a film on quartz or stainless steel fiber substrate, and ensure the stability and service life of SPME fiber.
BRIEF DESCRIPTION OF THE FIGURES Fig. 1 is a scanning electron microscope picture of SPME fiber prepared in Example 1 of the present invention; Fig. 2 shows the SPME extraction fiber prepared in Example 1 of the present invention combined with GC for the detection of ethylbenzene, xylene and styrene, and the comparison of extraction efficiency with commercial fibers (PDMS/DVB and CAR/PDMS).
DESCRIPTION OF THE INVENTION Next, the technical scheme in the embodiment of the invention will be clearly and completely described with reference to the drawings in the embodiment of the invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments in the present invention, all other embodiments obtained by ordinary technicians in the field without creative work are within the scope of the present invention.
Example 1 An aromatic polymer adsorption device and preparation method thereof, comprising the following steps: (1) Under nitrogen protection, adding aluminium trichloride (3.5 mmol) into a 100 mL round-bottomed flask, then injecting 40 mL of anhydrous CHCI; and stirring at 60°C for 3 hours.
(2) Dissolving 1,3,5-triphenylamine (1.5 mmol) in 20 mL anhydrous CHCl.
(3) Injecting the solution of step 2 into the system of step 1, and reacting with stirring at 60/601793 for 24 hours.
(4) After finishing the reaction, reducing the temperature of the system to room temperature, filtering the product, and washing with hydrochloric acid (1 mol-L™), methanol and acetone for three times; then, sequentially using ethanol, tetrahydrofuran and chloroform for soxhlet extraction of the product, and the extraction time is 2 days.
(5) Vacuumizing at 80°C for 12 hours to obtain PAF-41.
(6) Soaking one end of quartz capillary tube with stainless steel inner core in 1 mol-L! sodium hydroxide solution, then neutralize excess hydroxide ions with 1 mol-L™ hydrochloric acid solution, and finally, cleaning the fiber with deionized water and dry it in the air.
(7) Adding 300 pL of methyl trimethoxysilane, 180 mg of polydimethylsiloxane with hydroxyl end and 30 mg of polydimethylsiloxane into the centrifugal tube, and vortexing and shaking for 5 minutes; then, adding 150 pL trifluoroacetic acid (95%), and performing vortex shaking again for 5 minutes.
(8) Inserting one end of quartz fiber with surface hydroxylation and stainless steel inner core into the mixture obtained in step 7 for 5 minutes, then slowly taking it out, then inserting it into PAF-41 powder obtained in step 5, and drying it at 60°C for 2 minutes, repeating for 3 times until the required coating thickness is about 60 um.
(9) Aging the fiber obtained in step 8 at 240°C for 1 hour, the scanning electron microscope picture of SPME extracted fiber is shown in Figure 1, and the granular PAF-41 forms a film on the stone fiber substrate and combines well, which provides a prerequisite for the stability and service life of SPME fiber.
Example 2 An aromatic polymer adsorption device and preparation method thereof, comprising the following steps: (1) Under nitrogen protection, adding FeCl; (4.5 mmol) into a 100 mL round-bottomed flask, then injecting 40 mL of anhydrous CHCI; and stirring at 60°C for 3 hours.
(2) Dissolving 1,3,5-triphenylamine (1.5 mmol) in 20 mL anhydrous CHCl.
(3) Injecting the solution of step 2 into the system of step 1, and reacting with stirring at 60°C for 24 hours.
(4) After finishing the reaction, reducing the temperature of the system to room temperaturei501793 filtering the product, and washing with hydrochloric acid (1 mol-L™), methanol and acetone for three times; then, sequentially using ethanol, tetrahydrofuran and chloroform for soxhlet extraction of the product, and the extraction time is 2 days.
(5) Vacuumizing at 80°C for 12 hours to obtain PAF-41.
(6) Immersing one end (3cm) of quartz capillary tube with stainless steel inner core in 2 mol-L! sodium hydroxide solution, then neutralize excess hydroxide ions with 2 mol-L* hydrochloric acid solution, and finally, cleaning the fiber with deionized water and dry it in the air, obtaining a quartz capillary with hydroxylated surface; (7) Adding 300 pL of methyl trimethoxysilane, 180 mg of polydimethylsiloxane with hydroxyl end and 30 mg of polydimethylsiloxane into the centrifugal tube, and vortexing and shaking for 5 minutes; then, adding 150 pL trifluoroacetic acid (95%), and performing vortex shaking again for 5 minutes.
(8) After inserting the hydroxylated end of the surface of the quartz capillary obtained in step 6 into the mixture obtained in step 7 for 5 minutes, then slowly taking it out, then inserting it into PAF-41 powder obtained in step 5, and drying it at 60°C for 2 minutes, repeating for 3 times until the required coating thickness is about 60 um.
(9) Aging the fiber obtained in step 8 at 240°C for 1 hour to obtain SPME extraction fiber, scanning electron microscope images of SPME extracted fibers are similar to those in Figure 1 and will not be provided.
Example 3 An aromatic polymer adsorption device and preparation method thereof, comprising the following steps: (1) Under nitrogen protection, adding a CuCl, (0.8 mmol) into a 200 mL round-bottomed flask, then injecting 40 mL of anhydrous CHCI; and stirring at 75°C for 3 hours.
(2) Dissolving 1,3,5-triphenylamine (10 mmol) in 50 mL anhydrous CHCl.
(3) Injecting the solution of step 2 into the system of step 1, and reacting with stirring at 70°C for 72 hours.
(4) After finishing the reaction, reducing the temperature of the system to room temperature, filtering the product, and washing with hydrochloric acid (3 mol-L™), methanol and acetone for three times; then, sequentially using ethanol, tetrahydrofuran and chloroform for soxhlet/501793 extraction of the product, and the extraction time is 1 day.
(5) Vacuumizing at 80°C for 12 hours to obtain PAF-41.
(6) Soaking one end (1 cm) of quartz capillary tube with stainless steel inner core in 1.5 mol-L! sodium hydroxide solution, then neutralize excess hydroxide ions with 1.5 mol-L* hydrochloric acid solution, and finally, cleaning the fiber with deionized water and dry it in the air.
(7) Completely dissolving 4 mmol of 4,4-diaminodiphenyl ether in 15 mL of anhydrous N, N-dimethylformamide, under the condition of ice-water bath, slowly adding 4 mmol pyromellitic dianhydride to the above solution while stirring to obtain auxiliary glue, that is, prepolymer of polyimide.
(8) Inserting one end of the hydroxylated surface of the glass fiber obtained in step 6 into the auxiliary glue obtained in step 7 for 0.5 minutes, then slowly taking out, then inserting into the PAF-41 powder obtained in step 5, drying at 50°C for 2 minutes, and repeating twice until the required coating thickness is about 20 um.
(9) Aging the fiber obtained in step 8 at 200°C for 5 hours to obtain SPME extraction fiber, scanning electron microscope images of SPME extracted fibers are similar to those in Figure 1 and will not be provided.
Example 4 An aromatic polymer adsorption device and preparation method thereof, comprising the following steps: (1) Under nitrogen protection, adding aluminium trichloride (6 mmol) into a 100 mL round-bottomed flask, then injecting 30 mL of anhydrous CHCI; and stirring at 90°C for 3 hours.
(2) Dissolving 1,3,5-triphenylamine (10 mmol) in 500 mL anhydrous CHCIs.
(3) Injecting the solution of step 2 into the system of step 1, and reacting with stirring at 60°C for 24 hours.
(4) After finishing the reaction, reducing the temperature of the system to room temperature, filtering the product, and washing with hydrochloric acid (5 mol-L™), methanol and acetone for three times; then, sequentially using ethanol, tetrahydrofuran and chloroform for soxhlet/501793 extraction of the product, and the extraction time is 3 days.
(5) Vacuumizing at 80°C for 12 hours to obtain PAF-41.
(6) Soaking one end (1 cm) of quartz capillary tube with stainless steel inner core in 0.5 mol-L! sodium hydroxide solution, then neutralize excess hydroxide ions with 0.5 mol-L* hydrochloric acid solution, and finally, cleaning the fiber with deionized water and dry it in the air, obtaining quartz fiber with hydroxylated surface; (7) Dissolving polydimethylsiloxane in toluene until the viscosity is moderate, and obtain the auxiliary glue.
(8) Inserting one end of the hydroxylated surface of the quartz fiber obtained in step 6 into the auxiliary glue obtained in step 7 for 30 minutes, then slowly taking out, then inserting into the PAF-41 powder obtained in step 5, and drying at 90°C for 2 minutes, repeating several times until the required coating thickness is about 100 um.
(9) Aging the fiber obtained in step 8 at 230°C for 3 hours to obtain SPME extraction fiber, scanning electron microscope images of SPME extracted fibers are similar to those in Figure 1 and will not be provided.
Example 5 An aromatic polymer adsorption device and preparation method thereof comprise the following steps: (1) under the protection of nitrogen, adding bis-(1,5-cyclooctadiene) nickel and 2,2-bipyridine in equal molar ratio into a reactor, and then injecting anhydrous 1,5-cyclooctadiene and anhydrous N,N-dimethylacetamide (the volume ratio is 1:50), wherein the concentration of bis-(1,5-cyclooctadiene) nickel is 0.16mol-L!, stirring the mixture at 80°C for 1 hour to activate the catalyst.
(2) under the protection of nitrogen, dissolving tris (4-bromobenzene) amine in anhydrous N,N-dimethylacetamide with a concentration of 0.014 mol-L™! and stirring at 80°C for 1 hour.
(3) Injecting the solution of step 2 into the system of step 1, and reacting with stirring at 80°C for 72 hours.
(4) After the reaction is over, and the system temperature drops to room temperature, addidg)501793 concentrated hydrochloric acid (12 mol-L"!) until the color becomes emerald green, and filtering to obtain the crude product.
(5) Washing the crude product with a large amount of distilled water until the solution is neutral, and then washing the crude product with ethanol and chloroform for 5 times in order to remove the raw materials and catalysts that have not fully reacted, and finally, vacuumizing at 80°C for 12 hours to obtain the PAF-41.
(6) Soaking one end (3 cm) of stainless steel fiber (diameter 0.1 mm, length 6 cm) in 0.5-2 mol-L sodium hydroxide solution, then neutralize excess hydroxide ions with 0.5-2 mol-L"! hydrochloric acid solution, finally, cleaning the fiber with deionized water and drying it in the air to obtain the surface hydroxylated stainless steel fiber; (7) Adding 300 pL of methyl trimethoxysilane, 180 mg of polydimethylsiloxane with hydroxyl end and 30 mg of polydimethylsiloxane into the centrifugal tube, and vortexing and shaking for 5 minutes; then, adding 150 pL trifluoroacetic acid (95%), and performing vortex shaking again for 5 minutes.
(8) Inserting the hydroxylated end of the surface hydroxylated stainless steel fiber into the mixture obtained in step 7 for 5 minutes, then slowly taking it out, then inserting it into the PAF-41 powder obtained in step 5, and then drying it at 60°C for 2 minutes; repeating several times until the required coating thickness is about 60 um.
(9) Aging the fiber obtained in step 8 at 240°C for 2 hours to obtain SPME extraction fiber.
Example 6 An aromatic polymer adsorption device and a preparation method thereof comprise the following steps: (1) under the protection of nitrogen, adding bis-(1,5-cyclooctadiene) nickel and 2,2-bipyridine in equal molar ratio into a reactor, and then injecting anhydrous 1,5-cyclooctadiene and anhydrous N,N-dimethylacetamide (the volume ratio is 1:10), wherein the concentration of bis-(1,5-cyclooctadiene) nickel is 0.01mol-L*, stirring the mixture at 90°C for 0.5 hour to activate the catalyst.
(2) under the protection of nitrogen, dissolving tris (4-bromobenzene) amine in anhydrous N,N-dimethylacetamide with a concentration of 0.01 mol-L“ and stirring at 90°C for 0.5 hour.
(3) Injecting the solution of step 2 into the system of step 1, and reacting with stirring at 9Q/601793 for 100 hours.
(4) After the reaction is over, and the system temperature drops to room temperature, adding concentrated hydrochloric acid (12 mol-L"!) until the color becomes emerald green, and filtering to obtain the crude product.
(5) Washing the crude product with a large amount of distilled water until the solution is neutral, and then washing the crude product with ethanol and chloroform for 3 times in order to remove the raw materials and catalysts that have not fully reacted, and finally, vacuumizing at 120°C for 10 hours to obtain the PAF-41.
(6) Soaking one end (1 cm) of stainless steel fiber (diameter 0.1 mm, length 6 cm) in 1 mol-L! sodium hydroxide solution, then neutralize excess hydroxide ions with 1 mol-L* hydrochloric acid solution, finally, cleaning the fiber with deionized water and drying it in the air to obtain the surface hydroxylated stainless steel fiber; (7) Adding 300 pL of methyl trimethoxysilane, 180 mg of polydimethylsiloxane with hydroxyl end and 30 mg of polydimethylsiloxane into the centrifugal tube, and vortexing and shaking for 5 minutes; then, adding 150 pL trifluoroacetic acid (95%), and performing vortex shaking again for 5 minutes.
(8) Inserting the hydroxylated end of the surface hydroxylated stainless steel fiber into the mixture obtained in step 7 for 0.5 minutes, then slowly taking it out, then inserting it into the PAF-41 powder obtained in step 5, and then drying it at 50°C for 2 minutes; repeating 2 times until the required coating thickness is about 20 um.
(9) Aging the fiber obtained in step 8 at 200°C for 5 hours to obtain SPME extraction fiber. Scanning electron microscope images of SPME extracted fibers are similar to those in Figure 1 and will not be provided.
Example 7 An aromatic polymer adsorption device and preparation method thereof comprise the following steps: (1) under the protection of nitrogen, adding bis-(1,5-cyclooctadiene) nickel and 2,2-bipyridine in equal molar ratio into a reactor, and then injecting anhydrous 1,5-cyclooctadiene and anhydrous N,N-dimethylacetamide (the volume ratio is 1:50), wherein the concentration of bis-(1,5-cyclooctadiene) nickel is 0.5 mol-L!, stirring the mixture at 951501793 for 5 hour to activate the catalyst.
(2) under the protection of nitrogen, dissolving tris (4-bromobenzene) amine in anhydrous N,N-dimethylacetamide with a concentration of 0.1 mol:L and stirring at 95°C for 0.5 hour.
(3) Injecting the solution of step 2 into the system of step 1, and reacting with stirring at 95°C for 120 hours.
(4) After the reaction is over, and the system temperature drops to room temperature, adding concentrated hydrochloric acid (12 mol-L"!) until the color becomes emerald green, and filtering to obtain the crude product.
(5) Washing the crude product with a large amount of distilled water until the solution is neutral, and then washing the crude product with ethanol and chloroform for 10 times in order to remove the raw materials and catalysts that have not fully reacted, and finally, vacuumizing at 200°C for 3 hours to obtain the PAF-41.
(6) Soaking one end (2 cm) of stainless steel fiber in 2 mol-L™" sodium hydroxide solution, then neutralize excess hydroxide ions with 2 mol L-! hydrochloric acid solution, finally, cleaning the fiber with deionized water and drying it in the air to obtain the surface hydroxylated stainless steel fiber; (7) Completely dissolving 5 mmol of 4,4-diaminodiphenyl ether in 20 mL of anhydrous N, N-dimethylformamide, under the condition of ice-water bath, slowly adding 5 mmol pyromellitic dianhydride to the above solution while stirring to obtain auxiliary glue, that is, prepolymer of polyimide.
(8) Inserting the hydroxylated end of the surface hydroxylated stainless steel fiber into the mixture obtained in step 7, then slowly taking it out, then inserting it into the PAF-41 powder obtained in step 5, and then drying it at 90°C for 2 minutes; repeating several times until the required coating thickness is about 80 um.
(9) Aging the fiber obtained in step 8 at 250°C for 1 hours to obtain SPME extraction fiber.
Effect experiment: The PAF-41 coated SPME extraction fiber prepared in Example 1 was combined with GC to detect ethylbenzene, xylene and styrene, and compared with commercial fibers (PDMS/DVB and CAR/PDMS) in extraction efficiency.
The specific steps are as follows: LU501793 (1) Taking 5 mL of standard solution containing ethylbenzene, xylene and styrene (100 ug-l") and putting it into 20 mL headspace bottle, add magnetic stirrer and seal the headspace bottle.
(2) Connecting the prepared SPME extraction fiber (or PDMS/DVB or CAR/PDMS) to a 5 ul micro-injection needle as a solid-phase microextraction fiber.
(3) Inserting the solid-phase microextraction fiber mentioned in (2) into the top empty bottle, pushing out the solid-phase microextraction fiber head, placing it in the headspace of the sample solution, and keeping it at 40°C for 30 min with a stirring speed of 400 r/min.
(5) Withdrawing the extraction fiber head into the solid-phase microextraction device, then pulling out the micro sampler, immediately inserting it into the gas chromatography sample inlet, and pushing out the extraction head, with the sample inlet temperature of 230°C and the interpretation time of 0.5 min.
(6) Separation by gas chromatography, detection by FID detector and quantification by external standard method.
As shown in Figure 2, compared with commercial fibers (PDMS/DVB and CAR/PDMS), PAF-41 coated fiber has obvious advantages in the extraction efficiency of ethylbenzene, xylene and styrene. The SPME extraction fiber of the invention has uniform micropores, high specific surface area, high aromaticity, good enrichment ability for aromatic volatile substances, and can improve the extraction efficiency of SPME, thereby improving the sensitivity of target detection.
The above description is only the preferred embodiment of the present invention, and it is not intended to limit the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the scope of protection of the present invention.

Claims (10)

CLAIMS LU501793
1. An aromatic polymer adsorption device and preparation method thereof, comprising a carrier fiber and a coating attached to its surface, characterized in that one end of the carrier fiber is coated with a coating material, and the coating material is a mixture of PAF-41 and glue.
2. The aromatic polymer adsorption device and preparation method thereof according to claim 1, characterized in that the carrier fiber comprises quartz fiber, glass fiber, stainless steel fiber, quartz capillary with stainless steel inner core or glass capillary with stainless steel inner core.
3. The aromatic polymer adsorption device and preparation method thereof according to claim 2, characterized in that the carrier fiber is a substrate fiber with hydroxylated surface; the preparation method comprises: soaking one end of the fiber in sodium hydroxide solution, then neutralizing excess hydroxide ions with hydrochloric acid solution, and finally cleaning the fiber with deionized water and drying in the air.
4. The aromatic polymer adsorption device and preparation method thereof according to claim 3, characterized in that the concentration of sodium hydroxide solution is 0.5-2 mol -L™ and the concentration of hydrochloric acid solution is 0.5-2 mol-L.
5. The aromatic polymer adsorption device and preparation method thereof according to any one of claims 1-4, characterized in that the preparation method of PAF-41 is as follows: (1) under the protection of nitrogen, adding bis-(1,5-cyclooctadiene) nickel and 2,2-bipyridine in equal molar ratio into a reactor, then injecting anhydrous 1,5-cyclooctadiene and anhydrous N,N-dimethylacetamide in a volume ratio of 1:10-1:100, wherein the concentration of bis-(1,5-cyclooctadiene) nickel is 0.01-0.5 mol-L"!, and heating and stirring the mixture at 80-95°C for 0.5-5 hours to activate the catalyst; (2) under the protection of nitrogen, dissolving tris (4-bromobenzene) amine in anhydrous N,N-dimethylacetamide with the concentration of 0.01-0.1 mol-L*, and stirring at 80-95°C for
0.5-5 hours; (3) subsequently, mixing the two solutions, and heating and stirring the whole reaction system at 80-95°C for 72-120 hours;
(4) after reducing the temperature of the reaction system to room temperature, addidg)501793 concentrated hydrochloric acid until the color becomes emerald green, and filtering to obtain a crude product; (5) washing the solution with a large amount of distilled water to neutrality, then washing the crude product with ethanol and chloroform for 3-10 times to remove unreacted raw materials and catalysts, and finally vacuumizing at 80-200°C to obtain PAF-41.
6. The aromatic polymer adsorption device and preparation method thereof according to any one of claims 1-4, characterized in that the preparation method of PAF-41 is as follows: (1) under the protection of nitrogen, adding anhydrous Lewis acid catalyst into a reactor, injecting anhydrous CHCIs, and stirring at 60-90°C for 2-6 hours; (2) dissolving 1,3,5-triphenylamine in anhydrous CHCI3; (3) injecting that solution in step (2) into the system of step (1), reacting at 60-90°C for 1-5 day with the mol ratio of catalyst to 1, 3, 5-triphenylamine of 0.4-3:5; (4) after the reaction is finished and the temperature is reduced to room temperature, filtering, washing the product with hydrochloric acid, methanol and acetone respectively, and then sequentially soxhlet extracting the product with ethanol, tetrahydrofuran and chloroform for 1-3 days; (5) finally, vacuumizing at 80-200°C to obtain PAF-41.
7. The aromatic polymer adsorption device and preparation method thereof according to claim 6, characterized in that the Lewis catalyst is AlCls, FeCls or CuCl.
8. The aromatic polymer adsorption device and preparation method thereof according to any one of claims 1-7, characterized by comprising the following steps: (1) inserting one end of carrier fiber into auxiliary glue, slowly pulling out, then inserting into prepared PAF-41 powder, drying at 50-90°C for 2-60 minutes, and repeating the above operations until the required thickness is reached, (2) finally, aging at 200-250°C for 1-5 hours to obtain SPME extraction fiber.
9. The aromatic polymer adsorption device and preparation method thereof according to claim 8, characterized in that the auxiliary adhesive is polydimethylsiloxane, polyimide prepolymer or ethylene oxide adhesive.
10. The aromatic polymer adsorption device and preparation method thereof according t&J501793 claim 8, characterized in that the thickness of the coating is 20-100 um.
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