LU501789B1 - Covalent Organic Framework Material Coated Adsorption Device and Preparation Method Thereof - Google Patents

Covalent Organic Framework Material Coated Adsorption Device and Preparation Method Thereof Download PDF

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Publication number
LU501789B1
LU501789B1 LU501789A LU501789A LU501789B1 LU 501789 B1 LU501789 B1 LU 501789B1 LU 501789 A LU501789 A LU 501789A LU 501789 A LU501789 A LU 501789A LU 501789 B1 LU501789 B1 LU 501789B1
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epoxy resin
solid
porous polymer
crystalline porous
phase microextraction
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LU501789A
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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
    • B01J20/30—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
    • B01J20/3272—Polymers obtained by reactions otherwise than 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
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3289—Coatings involving more than one layer of same or different nature
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • 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
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The invention discloses a solid-phase microextraction device and a preparation method thereof, belonging to the cross field of analytical chemistry and environmental chemistry. The solid-phase microextraction device adopts a novel composite coating of crystalline porous polymer and epoxy resin as a functional extraction head, and the solid-phase microextraction efficiency of pyrethroid pesticides is significantly improved by utilizing the synergistic effect of crystalline porous polymer and epoxy resin. The extraction efficiency of various commercial SPME extractors can reach 1.5-150 times. Therefore, the sensitivity of detection of pyrethroid substances is significantly improved, and the qualitative and quantitative detection of pyrethroid pesticides in water is well realized.

Description

DESCRIPTION LU501789 Covalent Organic Framework Material Coated Adsorption Device and Preparation Method Thereof
TECHNICAL FIELD The invention relates to a solid-phase microextraction device for SPME-GC/MS, which realizes the detection of pyrethroid pesticides in water, and belongs to the cross field of analytical chemistry and environmental chemistry.
BACKGROUND Pyrethroid pesticide is a broad-spectrum pesticide widely used in the world. Although compared with traditional pesticides such as organochlorine and organophosphorus, pyrethroids have the advantages of short half-life and low toxicity. However, with the rapid development of agriculture and aquaculture, the use scale of pyrethroid pesticides is increasing day by day, and pyrethroids exposed to the environment are likely to cause chronic toxic effects of human and animals. Moreover, the pyrethroid content in the water environment is also increasing through the ways of dry and wet deposition in the atmosphere, precipitation runoff, direct application and discharge from pesticide factories. Pyrethroids have high toxicological activity on aquatic organisms, and a large amount of pyrethroids in water environment will inevitably affect the quality of water environment, endanger the water ecosystem and cause the quality of aquatic products to decline. In addition, through eating, pyrethroids can enter mammals, including humans, which are at the top of the biological chain, and pose a cumulative risk, causing damage to related organs and functions of the human body, such as endocrine system, reproductive system, immune system and central nervous system.
Therefore, the detection of pyrethroid pesticides in water is of great significance for environmental water monitoring, drinking water quality detection, pyrethroid pesticide use and risk assessment. At present, the detection methods of pyrethroid pesticides mainly include gas chromatography and liquid chromatography. The main sample pretreatment methods include liquid-liquid extraction, Soxhlet extraction, microwave-assisted extraction, supercritical fluid extraction, solid-phase extraction, solid-phase microextraction and accelerated solvent extraction. Solid-phase microextraction (SPME) is a sample pretreatment technology that integrates sampling, extraction, concentration and sampling. Stable and efficient extraction head can effectively improve the sensitivity and accuracy of analysis. At present, the research and development of stable and efficient extraction head or extractor is an important way to detects 1789 pyrethroid pesticides in water by solid-phase microextraction.
SUMMARY The invention aims at improving the functional extraction head of solid-phase microextraction, and provides a solid-phase microextraction device with high sensitivity and accuracy, which is used in SPME-GC/MS to detect pyrethroid pesticides in water.
In order to realize the purpose of the invention, the invention adopts the extraction head coated with crystalline porous polymer/epoxy resin composite coating to prepare the solid-phase microextraction device, and then carries out sampling, extraction, concentration and sampling, and adopts the solid-phase microextraction (SPME) technology combined with gas chromatography-mass spectrometry (GC-MS) method to realize the detection of pyrethroid pesticides in water.
The solid-phase microextraction device is a coated fiber made of crystalline porous polymer/epoxy resin, and its preparation method is as follows: one end of the stainless steel fiber substrate with hydroxylated surface is inserted into diluted epoxy resin, slowly taken out, then inserted into the prepared crystalline porous polymer powder for drying, and the above operations are repeated until the required coating thickness is reached. Finally, the above-mentioned fibers are placed in a micro-sampler to obtain the SPME extractor. Before use, age at 230-280°C for 1-5 hours.
The thickness of the coating is 10-100 um.
The preparation method of the crystalline porous polymer comprises the following steps: fully mixing rigid polyamine and benzo [1,2-b:3,4-b":5,6-b'] trithiophene -2,5,8- trialdehyde (molar ratio of 0.5-2: 1), adding into a pressure-resistant glass tube, and sequentially injecting dioxane and mesitylene. Freeze the mixture in liquid nitrogen, vacuumize and backfill with nitrogen. Finally, the glass tube is sealed in vacuum and heated for reaction. After the reaction, the solid product is cleaned and dried, and finally the target product is brown-black solid powder.
The rigid polyamine is tris (4- aminophenyl) amine, 1,3,5- tris (4- aminophenyl) benzene, 1,3,5-triaminobenzene, melamine, p-phenylenediamine, 5,5'- diamino -2,2'- bipyridine.
The epoxy resin is bisphenol A epoxy resin and bisphenol S epoxy resin.
The method for detecting pyrethroid pesticides in water includes the following steps: (1) diluting pyrethroid pesticides with water to the required concentration as a standard solution; LU501789 (2) take the standard solution, test the concentration from low to high in turn, put it in a glass extraction bottle, stir evenly and seal; (3) insert the solid-phase microextraction device based on the crystalline porous polymer/epoxy resin composite coating into the extraction bottle, push out the fiber head, put it all in the sample solution, and enrich it under stirring (50-80°C); (4) after the enrichment, the extraction head is pulled back into the micro sampler, then the micro sampler is pulled out, immediately inserted into the gas chromatography sample inlet, and the extraction head is pushed out again, the temperature of the sample inlet is 240-280°C, and the desorption time is 1-10 min; (5) through GC-MS analysis, the measured peak area (Y) and the mass concentration (X) of the standard solution are linearly regressed to obtain the standard curve equation of each target compound.
(6) take a water sample containing pyrethroid pesticides, dilute it several times, analyze the water sample according to the test method of the standard working solution in step 2-5 above, measure the peak area value of the target, and substitute it into the standard curve equation to find out the contents of various pyrethroid pesticides in the sample.
The concentration of the pyrethroid pesticide standard solution is 1, 10, 50, 100, 500, 1000 ng/L.
The volume of the standard solution in step 2 is 5-50 mL.
The chromatographic conditions are SH-Rtx-5SMS capillary column (30mx0.25mx0.25jum). The flow rate of carrier gas He is 1.5 ml/min; The sampling temperature is 260-280 C; Temperature program of chromatographic column: keep it at 70°C for 1 minute, and increase it to 250°C at 25°C/min for 17 minutes.
The mass spectrometry conditions are as follows: the ion source temperature is 230°C; Interface temperature; 200°C » Compared with the prior art, the invention has the following advantages: The SPME extractor used in this invention is a coating fiber based on a novel crystalline porous polymer/epoxy resin composite material. Firstly, epoxy resin not only helps crystalline porous polymer to form film on fiber, but also has certain enrichment ability for pyrethroid pesticides (as shown in Figure 1, taking cypermethrin as an example). The synergistic effect of the two makes the SPME extractor have good extraction performance for pyrethroid substances, 59 1789 Therefore, compared with other composite materials of resin materials and crystalline porous materials, the SPME extractor coated with crystalline porous polymer/epoxy resin composite material has remarkable advantages in extraction efficiency, as shown in Figure 2. Secondly, the crystalline porous polymer is a novel porous adsorbent, and its microscopic skeleton contains a large number of N, S heterocyclic structures, regular pore channels with adjustable size, large specific surface area and good enrichment and adsorption capacity for pyrethroids. The functional extraction head suitable for solid-phase microextraction prepared by combining the two technologies can effectively improve the extraction efficiency of SPME, and the extraction efficiency can reach 1.5-150 times that of various commercial SPME extractors, as shown in Figure 3. Therefore, the sensitivity of detection of pyrethroid substances is significantly improved, and the qualitative and quantitative detection of pyrethroid pesticides in water is well realized.
BRIEF DESCRIPTION OF THE FIGURES Fig. 1 is a column comparison diagram of the extraction performance of cypermethrin by SPME extractor with epoxy resin coating and crystalline porous polymer/epoxy resin composite coating obtained in Example 1.
Fig. 2 is a column comparison diagram of the extraction performance of six pyrethroid pesticides by the crystalline porous polymer/silicone resin composite coating and the crystalline porous polymer/epoxy resin composite coating obtained in Example 1.
Fig. 3 is a comparison of the extraction performance of cypermethrin by the SPME extractor with crystalline porous polymer/epoxy resin composite coating obtained in Example 1 and five commercial extractors.
Fig. 4 is a scanning electron microscope photograph of the SPME extractor obtained in Example 1.
DESCRIPTION OF THE INVENTION To better illustrate the present invention, the following examples are given: Example 1 The solid-phase microextraction device is a coated fiber made of crystalline porous polymer/epoxy resin, and its preparation method is as follows: one end of the stainless steel fiber substrate with hydroxylated surface is inserted into diluted epoxy resin, slowly taken out, then inserted into the prepared crystalline porous polymer powder, dried at 80°C for 10 minutes, and = 1789 the above operations are repeated until the required coating thickness is reached. Finally, the above fibers were placed in a 5 u L micro-sampler. Get SPME extractor. Before use, age at 250°C for 2 hours.
The thickness of the coating is 60 um.
The preparation method of the crystalline porous polymer comprises the following steps: fully mixing tris (4- aminophenyl) amine and benzo [1,2-b:3,4-b":5,6-b"] trithiophene -2,5,8- trialdehyde (the molar ratio is 0.5-2: 1), adding into a pressure-resistant glass tube, and sequentially The mixture was frozen in liquid nitrogen for 30 minutes, evacuated for 30 minutes, backfilled with nitrogen, and repeated for 5 times. Finally, the glass tube was sealed in vacuum and reacted at 120°C for 5 days. After the reaction, the solid product was washed with N,N- dimethylformamide and tetrahydrofuran for three times in turn. Drying at 100°C for 24 hours.
The method for detecting pyrethroid pesticides in water comprises the following steps: Dilute cypermethrin with water to the required concentration as the standard solution with the concentration of 1, 10, 50, 100 ug/L; Take 10mL of standard solution, test the concentration from low to high in turn, put it in a glass extraction bottle, stir well and seal; The solid-phase microextraction device based on the crystalline porous polymer/epoxy resin composite coating is inserted into the extraction bottle, the fiber head is pushed out, placed in the sample solution, enriched at 80°C for 30 minutes, and the stirring speed is 600 rpm; Immediately after enrichment, insert the gas chromatographic inlet and push out the extraction head again, with the inlet temperature of 270°C and desorption time of 1 min.
By GC/MS analysis, the measured peak area (Y) and the mass concentration (X) of the standard solution were analyzed by linear regression, and the standard curve equation of each target compound was obtained.
ImL of water sample containing cypermethrin pesticide was diluted to SmL. According to the above test method, the water sample was analyzed, and the peak area value of the target was measured. By substituting it into the standard curve equation, the content of cypermethrin in the sample was 89.23 ug/L.
Example 2 Deltamethrin was diluted with water to the required concentration as the standard solution,
with the concentration of 1, 10, 50, 100 pg/L; LU501789 Take 10mL of standard solution, test the concentration from low to high in turn, put it in a glass extraction bottle, stir well and seal; The solid-phase microextraction device based on the crystalline porous polymer/epoxy resin composite coating 1s inserted into the extraction bottle, the fiber head is pushed out, all of which are placed in the sample solution, enriched at 80°C for 30 minutes, and the stirring speed is 600 rpm; After enrichment, the extraction head is pulled back into the micro-sampler, then the micro-sampler is pulled out, immediately inserted into the gas chromatography sample inlet, and the extraction head is pushed out again, the sample inlet temperature is 270°C, and the desorption time is 1 min; By GC/MS analysis, the measured peak area (y) and the mass concentration (x) of the standard solution were analyzed by linear regression, and the standard curve equation of each target compound was obtained.
ImL of water sample containing deltamethrin pesticide was diluted to SmL. According to the above test method, the water sample was analyzed, and the peak area value of the target was measured. By substituting it into the standard curve equation, the content of deltamethrin in the sample was found to be 102.23 ng/L.
The preparation method of the solid-phase microextraction device of the crystalline porous polymer/epoxy resin composite coating includes inserting one end of the surface hydroxylated stainless steel fiber substrate into diluted epoxy resin, slowly taking it out, then inserting it into the prepared crystalline porous polymer powder, drying at 60°C for 20 minutes, and repeating the above operations until the required coating thickness is reached. Finally, the above fibers were placed in a 5 BL micro-sampler. Get SPME extractor. Before use, age at 260°C for 5 hours.
The thickness of the coating is 100 um.
The preparation method of the crystalline porous polymer comprises the following steps: fully mixing 1,3,5-tris (4- aminophenyl) benzene and benzo [1,2-b:3,4-b":5,6-b"] trithiophene -2,5,8- trialdehyde (molar ratio of 0.5-2), and adding The mixture was frozen in liquid nitrogen for 30 minutes, evacuated for 30 minutes, backfilled with nitrogen, and repeated for 5 times. Finally, the glass tube was sealed in vacuum and reacted at 120°C for 5 days. After the reaction,
the solid product was washed with N, N- dimethylformamide and tetrahydrofuran for three times, 501789 in turn.
Drying at 150°C for 12 hours.

Claims (2)

CLAIMS LU501789
1. A solid-phase microextraction device, which is a coated adsorption device, is characterized in that is made of crystalline porous polymer and epoxy resin by composite coating, and is prepared by the following methods: (1) inserting one end of a stainless steel fiber substrate with hydroxylated surface into diluted epoxy resin, slowly taking it out, and then inserting it into crystalline porous polymer powder for drying; (2) repeating the operation in step (1) until the required coating thickness is reached; finally, putting the fiber into a micro sampler to obtain a solid-phase micro extractor; the crystalline porous polymer is prepared by the following method: mixing rigid polyamine and benzo [1,2-b:3,4-b":5,6-b'] trithiophene -2,5,8- trialdehyde, adding into a pressure-resistant glass tube, and sequentially injecting dioxane, mesitylene and acetic acid; freezing the mixture in liquid nitrogen, vacuumizing, and backfilling with nitrogen; finally, the glass tube is fused and sealed in vacuum, and heated for reaction; after the reaction, the solid product is cleaned and dried to finally obtain the target; the rigid polyamine is tris (4- aminophenyl) amine, 1,3,5- tris (4- aminophenyl) benzene, 1,3,5-triaminobenzene, melamine, p-phenylenediamine, 5,5'- diamino -2,2'- bipyridine; the epoxy resin is bisphenol A epoxy resin and bisphenol S epoxy resin.
2. The solid-phase microextraction device according to claim 1, which is characterized in that the thickness of the coating is 10-100 um.
LU501789A 2022-04-04 2022-04-04 Covalent Organic Framework Material Coated Adsorption Device and Preparation Method Thereof LU501789B1 (en)

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