Methods for detecting volatile components in cigarette smoke, including smoke adsorption materials, trapping plates, and other components.

Abstract

This invention relates to the field of cigarette component analysis technology, and particularly to smoke adsorption materials, trapping sheets, and methods for detecting volatile components in cigarette smoke. The smoke adsorption material comprises tetraazacalix[2]aromatic[2]triazine supported on a covalent organic framework. It exhibits good trapping effect on various components in cigarette smoke, especially polycyclic aromatic hydrocarbons and aromatic amines in very low concentrations. Furthermore, it has a stable structure, the tetraazacalix[2]aromatic[2]triazine is not easily detached, and it has a long service life. When this material is made into a smoke trapping sheet for the detection of volatile components in cigarette smoke, it can fundamentally reduce the extraction loss of smoke components and improve the final detection range and accuracy.

Description

Technical Field

[0001] This invention relates to the field of cigarette component analysis technology, and in particular to smoke adsorption materials, trapping sheets, and methods for detecting volatile components in cigarette smoke. Background Technology

[0002] Cigarette combustion is a complex chemical system. Besides the gaseous substances produced by the complete combustion and decomposition of organic matter (such as carbon monoxide, water, methane, and other lower hydrocarbons), many complex chemical changes occur under anaerobic conditions due to insufficient oxygen supply in some areas. Volatile substances in tobacco (such as semi-volatile 5- and 6-membered nitrogen-containing heterocyclic compounds) also volatilize into the smoke. Simultaneously, terpenes, sugars, amino acids, cellulose, and many other components in tobacco produce volatile and semi-volatile gases through thermal decomposition, thermal synthesis, dry distillation, polymerization, condensation, and free radical reactions. Harmful substances in these gases can affect smokers' sleep quality and fertility, leading to chronic bronchitis, osteoporosis, and even serious diseases such as coronary heart disease and cancer. With increasing health awareness, people are paying more attention to the harmful substances in cigarette smoke. Therefore, analyzing the composition of cigarette smoke before it leaves the factory is of great significance for improving tobacco quality and promoting the sustainable development of tobacco production.

[0003] In the prior art, methods for detecting cigarette smoke components include GC-MS and headspace solid-phase microextraction-gas chromatography-mass spectrometry (HS-SPME). For example, the patent document with publication number CN113406238A disclosed by the applicant provides a highly efficient method for detecting volatile components in cigarette smoke, which includes the following steps: S1, extraction of smoke components: the cigarette is smoked and the smoke is captured, so that the mainstream smoke of the cigarette to be tested passes through a Cambridge filter; S2, sample pretreatment: the Cambridge filter obtained in step S1 is cut into small fragments, the fragments are placed in a headspace vial, an internal standard solution is added to obtain a sample, and then the sample is stored in a refrigerator for later use; S3, headspace solid-phase microextraction: the sample prepared in step S2 is taken out and placed in a constant temperature incubator for thawing, and then extracted using a fully automated headspace solid-phase microextraction system (HS-SPME); S4, GC-MS detection: the sample to be tested obtained in step S3 is entered into a GC-MS detection system for detection and analysis.

[0004] Current detection methods can detect 533 volatile substances, but they are still difficult to effectively detect some components in very low concentrations in mainstream flue gas, such as polycyclic aromatic hydrocarbons (benzanthracene, benzo[a]pyrene, etc.), aromatic amines and their derivatives (aminonaphthalene, aminobiphenyl, etc.). Although these components are present in very low concentrations in mainstream flue gas, they have relatively high biotoxicity, and their detection is of great significance for exposure risk assessment. Summary of the Invention

[0005] The present invention aims to solve the above problems by providing a smoke adsorption material, a trapping plate, and a method for detecting volatile components in cigarette smoke. The smoke adsorption material effectively improves the enrichment effect of various components in the smoke, thereby improving the detection range and accuracy of the smoke.

[0006] The technical solution to the problem of this invention is: First, a flue gas adsorption material is provided, comprising tetraazacalix[2]aromatic[2]triazine supported on a covalent organic framework.

[0007] The applicant found that the reason why the existing technology is difficult to detect polycyclic aromatic hydrocarbons and aromatic amines with extremely low content in flue gas is mainly because it is difficult to effectively enrich these components with extremely low content. Therefore, this application first provides a flue gas adsorption material. Among them, tetraazacalix[2]arene[2]triazine (TCT) is a heteroatom calixarene composed of two benzene rings and two triazine rings bridged by nitrogen atoms. Its specific chemical structure endows it with multi-mode molecular recognition function. For example, the aromatic ring of TCT can generate π-π interaction with the adsorbate, the nitrogen heteroatom can generate hydrogen bonding and charge transfer interaction with the adsorbate, the macrocyclic cavity can play the role of inclusion and ion exchange, etc. It can not only further capture the relatively high content of components in flue gas, but also effectively adsorb and enrich polycyclic aromatic hydrocarbons and aromatic amines with extremely low content. Meanwhile, by loading tetraazacalix[2]arene[2]triazine onto a covalent organic framework (COF), on the one hand, the covalent organic framework itself has a large porous structure, an extensible conjugated system, and a large number of benzene rings and abundant bridging nitrogen atoms, which can further capture various components in flue gas, especially aromatic amines, through various intermolecular interactions, including π-π interactions, CH-π interactions, NHO hydrogen bonds, and LP-π interactions, thereby improving the flue gas enrichment effect. On the other hand, as an organic polymer, the covalent organic framework directly binds the loaded tetrazacalix[2]arene[2]triazine through chemical bonds, which makes the entire adsorbent material have good stability, making it difficult for the tetrazacalix[2]arene[2]triazine to fall off, avoiding the tetrazacalix[2]arene[2]triazine from being mixed into the sample and affecting subsequent detection, and facilitating the recovery of the tetrazacalix[2]arene[2]triazine; in comparison, the existing technology uses silica to support tetrazacalix[2]arene[2]triazine, in which silica indirectly binds the tetrazacalix[2]arene[2]triazine through a silane coupling agent, and the tetrazacalix[2]arene[2]triazine is prone to falling off.

[0008] Based on this, this application provides a flue gas adsorption material that has a good capture effect on various components in flue gas, especially polycyclic aromatic hydrocarbons and aromatic amines with extremely low content, and has a stable structure and whose main adsorption component, tetraazacalix[2]aromatic[2]triazine, is not easy to fall off.

[0009] The pore shape of the covalent organic framework varies depending on the building blocks. The pore shape is unrestricted; for example, it can be hexagonal COF, including boron-oxygen hexacyclic linked COF-1, borate ester linked COF-6, COF-8, COF-11, COF-14, COF-16, and COF-18, imine linked TpPa, TpBD, TpPaSO3H, TpPa-Py, EB-COF:X (X = F, Cl, Br, I), TPB-DMTP, TAPB-PDA, and TPB-TP, hydrazone linked COF-42 and COF-43, triazine linked CTF-1, and carbon-carbon double bond linked COF-701. It can also be quadrilateral COF, including Tph-COF, Pc-PBBA, and ZnP-COF. Furthermore, it can be rhombic COF, including ILCOF-1, Py-Azine COF, and sp... 2 c-COF, etc. It can also be a triangular COF, including HPB-COF, HBC-COF, HAT-COF, HFPTP-BPDA-COF, etc. Preferably, the covalent organic framework is a hexagonal COF, which has a relatively large surface area and pore volume, facilitating further adsorption and storage of flue gas components.

[0010] The covalent organic framework should be functionalized to load tetraazacalix[2]arene[2]triazine via chemical bonds, primarily to facilitate nucleophilic substitution with the C=N unsaturated bonds on the tetraazacalix[2]arene[2]triazine ring carbon. Therefore, the functionalization of the covalent organic framework can take the form of amination, hydroxylation, thiolation, etc. Preferably, the covalent organic framework is at least one of amino-functionalized COF, hydroxyl-functionalized COF, and thiol-functionalized COF.

[0011] The preparation methods for these functionalized COFs are not limited. For example, they can be prepared by the following steps: A. synthesizing vinyl COFs; B. grafting functionalized groups onto vinyl COFs.

[0012] As a preferred embodiment of the present invention, in step A, vinyl COF is synthesized from 1,4-dialdehyde-2,5-divinylbenzene (Dva) and 1,3,5-tris(4-aminophenyl)benzene (Tab) at room temperature and in acetonitrile.

[0013] In some embodiments, amino-functionalized COF is used as a preferred embodiment of the present invention. In step B, vinyl COF and 4-aminothiophenol are used as raw materials to synthesize the product at 90-100°C using azobisisobutyronitrile.

[0014] In some embodiments, thiol-functionalized COF is used as a preferred embodiment of the present invention. In step B, vinyl COF and 1,2-ethylenedithiol are used as raw materials to synthesize the COF at 70-90°C using azobisisobutyronitrile.

[0015] To facilitate the recovery of flue gas adsorption materials, as a preferred embodiment of the present invention, the covalent organic framework is a magnetically modified covalent organic framework, wherein the magnetically modified covalent organic framework has Fe3O4 as the core, a covalent organic framework as the shell, and SiO2 as the core-shell connecting layer.

[0016] This magnetic modification method is unrestricted; for example, it can be modified through the following steps: A. Synthesizing Fe3O4 magnetic nanospheres; B. In-situ synthesis of silicon dioxide on Fe3O4 magnetic nanospheres to obtain Fe3O4@SiO2; C. Amination of Fe3O4@SiO2 to obtain Fe3O4@SiO2-NH2; D. In-situ synthesis of vinyl COF on Fe3O4@SiO2-NH2; E. Functionalization reaction.

[0017] As a preferred embodiment of the present invention, in step D: Fe3O4@SiO2-NH2, 1,4-dialdehyde-2,5-divinylbenzene, acetic acid, and acetonitrile are first mixed, rapidly frozen and evacuated in a liquid nitrogen bath, and then heated at 100-130°C for 10-16 hours; after cooling to room temperature, 1,4-dialdehyde-2,5-divinylbenzene and 1,3,5-tris(4-aminophenyl)benzene are added, frozen and evacuated, and then heated under vacuum at 100-130°C for 2-3 days; finally, the product is collected by an external magnet, washed, and then dried under vacuum.

[0018] Secondly, another objective of this invention is to provide a method for preparing the above-mentioned flue gas adsorption material, comprising the following steps: reacting a covalent organic framework with tetraazacalix[2]arene[2]triazine in a nitrogen atmosphere at 100-120°C for 40-50 hours.

[0019] Secondly, another object of the present invention is to provide a flue gas capture plate, including a filter plate and an adsorption material loaded on the filter plate; the adsorption material is the flue gas adsorption material described above.

[0020] The choice of filter is not limited; for example, it can be at least one of glass fiber filter and polyester fiber filter. Preferably, the filter is a glass fiber filter. The silica in the glass fiber filter can be used to further fix the flue gas adsorption material, reducing the shedding of the flue gas adsorption material from the filter.

[0021] The ratio of filter element to flue gas adsorption material should be limited. Too much flue gas adsorption material may affect the capture effect of the filter element in this application, while too little will not significantly improve the adsorption effect. As a preferred embodiment of the present invention, the mass ratio of the filter element to the flue gas adsorption material is 1:(0.005~0.02), more preferably 1:(0.008~0.015), such as 1:0.008, 1:0.009, 1:0.01, 1:0.011, 1:0.012, 1:0.013, 1:0.014, 1:0.015, with 1:0.01 being the optimal ratio.

[0022] The preparation method of the flue gas capture plate is not limited, and may include the following steps: dispersing the flue gas adsorption material in a solvent to obtain a dispersion, immersing the filter plate in the dispersion, and then taking it out and drying it.

[0023] In some embodiments, the filter is a glass fiber filter, and the preparation method of the flue gas capture sheet includes the following steps: mixing the glass fiber filter and the adsorbent material under a silane coupling agent, reacting at 100-110°C for 8-16 hours in a nitrogen atmosphere, and then drying.

[0024] Finally, another object of the present invention is to provide a method for detecting volatile components in cigarette smoke, comprising the following steps:

[0025] S1. The above-mentioned smoke trapping plate is used to capture cigarette smoke;

[0026] S2. After extracting the flue gas capture plate with a solvent, add an internal standard, remove the flue gas capture plate, and obtain the extract;

[0027] S3. Headspace solid-phase microextraction-gas chromatography-mass spectrometry was used to detect volatile components in the extract.

[0028] As a preferred embodiment of the present invention, the mass ratio of the flue gas capturing plate to the internal standard is 40:(1.3-2.0).

[0029] As a preferred embodiment of the present invention, the internal standard is [2H8]-acetylbenzene with a concentration of 10 μg / mL, which has high accuracy.

[0030] As a preferred embodiment of the present invention, the heating temperature during headspace solid-phase microextraction is 50–80°C.

[0031] As a preferred embodiment of the present invention, the solvent includes at least one selected from ethanol, diethyl ether, xylene, n-hexane, acetonitrile, and dichloromethane.

[0032] As a preferred embodiment of the present invention, in the headspace solid-phase microextraction, the surface of the extraction head is coated with the flue gas adsorption material, which further improves the detection range and detection accuracy.

[0033] The beneficial effects of this invention are:

[0034] 1. This application provides a flue gas adsorption material that has a good capture effect on various components in flue gas, especially polycyclic aromatic hydrocarbons and aromatic amines with extremely low content. It has a stable structure, and the main adsorbed component, tetraazacalix[2]aromatic[2]triazine, is not easy to fall off, and has a long service life.

[0035] 2. This application provides a flue gas capture plate that captures flue gas using both traditional filter plates and flue gas adsorption materials, and features a wide capture range and good enrichment effect.

[0036] 3. This application provides a method for detecting volatile components in cigarette smoke. During the smoking stage, various components in the smoke are enriched by a smoke trap, which fundamentally reduces the extraction loss of smoke components and can improve the final detection range and detection accuracy. Detailed Implementation

[0037] The following are specific embodiments of the present invention, and the technical solutions of the present invention will be further described, but the present invention is not limited to these embodiments.

[0038] Flue gas adsorption materials

[0039] Example 1

[0040] A flue gas adsorbent material comprising a hexagonal amino-functionalized covalent organic framework and a tetraazacalix[2]arene[2]triazine loaded thereon.

[0041] It is prepared through the following steps:

[0042] (1) Preparation of hexagonal amino-functionalized covalent organic framework:

[0043] 14.3 mg (0.04 mmol) of 1,4-dialdehyde-2,5-divinylbenzene, 11.5 mg (0.06 mmol) of 1,3,5-tris(4-aminophenyl)benzene, and 5 mL of acetonitrile were mixed and sonicated for 1 min. Then, 0.4 mL of 6 mol / L acetic acid was added to the system, and the mixture was vortexed for 10 s and allowed to stand for 3 days to obtain a yellow precipitate. The product was washed three times each with tetrahydrofuran and ethanol, and then vacuum dried in a 60 °C oven to obtain hexagonal vinyl COF.

[0044] 50 mg vinyl COF, 250 mg 4-aminobenzylthiophenol, 5 mg azobisisobutyronitrile and 4 mL trifluorotoluene were mixed and heated at 90 °C for 6 h under a nitrogen atmosphere; then the mixture was restored to room temperature, washed three times with tetrahydrofuran, and vacuum dried in an oven at 60 °C to obtain amino-functionalized COF.

[0045] (2) Hexagonal amino-functionalized covalent organic framework supporting tetraazacalix[2]arene[2]triazine:

[0046] 10 mg of amino-functionalized COF was added to 50 mL of N,N-dimethylformamide and stirred until homogeneous. Then, 5 mg of tetrazacalix[2]arene[2]triazine was added and heated at 110 °C for 48 h under a nitrogen atmosphere. The mixture was then restored to room temperature, and the product was washed three times with N,N-dimethylformamide and acetone. The product was then placed in a 60 °C oven and vacuum dried to obtain the flue gas adsorption material.

[0047] Example 2

[0048] A flue gas adsorbent material comprising a hexagonal thiol-functionalized covalent organic framework and a tetraazacalix[2]arene[2]triazine loaded thereon.

[0049] It is prepared through the following steps:

[0050] (1) Preparation of hexagonal thiol-functionalized covalent organic framework:

[0051] 14.3 mg (0.04 mmol) of 1,4-dialdehyde-2,5-divinylbenzene, 11.5 mg (0.06 mmol) of 1,3,5-tris(4-aminophenyl)benzene, and 5 mL of acetonitrile were mixed and sonicated for 1 min. Then, 0.4 mL of 6 mol / L acetic acid was added to the system, and the mixture was vortexed for 10 s and allowed to stand for 3 days to obtain a yellow precipitate. The product was washed three times each with tetrahydrofuran and ethanol, and then vacuum dried in a 60 °C oven to obtain hexagonal vinyl COF.

[0052] 250 mg vinyl COF, 10 mL 1,2-ethylenedithiol, and 25 mg azobisisobutyronitrile were mixed, rapidly frozen and vacuumed with liquid nitrogen, and then reacted at 80 °C for 48 h. After returning to room temperature, the product was washed three times with acetone and then vacuum dried in a 60 °C oven to obtain thiol-functionalized COF.

[0053] (2) Hexagonal thiol-functionalized covalent organic framework supported on tetraazacalix[2]arene[2]triazine:

[0054] 10 mg of thiol-functionalized COF was added to 50 mL of N,N-dimethylformamide and stirred until homogeneous. Then, 5 mg of tetraazacalix[2]arene[2]triazine was added. The mixture was heated at 110 °C for 48 h under a nitrogen atmosphere. The mixture was then restored to room temperature. The product was washed three times with N,N-dimethylformamide and acetone and then vacuum dried in a 60 °C oven to obtain the flue gas adsorption material.

[0055] Example 3

[0056] A flue gas adsorbent material comprising a hexagonal amino-functionalized magnetically modified covalent organic framework and a tetraazacalix[2]arene[2]triazine loaded thereon.

[0057] It is prepared through the following steps:

[0058] (1) Preparation of hexagonal amino-functionalized magnetically modified covalent organic framework:

[0059] 5 mmol of ferric chloride hexahydrate was dissolved in 50 mL of ethylene glycol and stirred until clear. Then, 3.6 g of NaAc and 1.0 g of polyethylene glycol were added. The mixture was stirred vigorously for 30 min and then reacted at 200 °C for 12 h under sealed conditions. The product was separated by a magnet and washed three times with ethanol and water to obtain Fe3O4 magnetic nanospheres.

[0060] 2 g of wet Fe3O4 was mixed with 200 mL of 0.5 M citric acid and activated by mechanical stirring at 40 °C for 12 h. The activated Fe3O4 was separated using an external magnet, washed with ethanol and water, and then dispersed in 160 mL of 80% (v / v) ethanol-water solution while sonicating with 4 mL of ammonia solution. The mixture was then placed in a 45 °C water bath, and 2 mL of tetraethyl silicate was added dropwise while mechanically stirring for 12 h. The resulting product was separated using an external magnet, washed sequentially with ethanol, acetone, and water, and then vacuum dried at 40 °C for 12 h to obtain Fe3O4@SiO2.

[0061] 2 g of Fe3O4@SiO2 was dispersed in 120 mL of anhydrous toluene and sonicated for 20 min. Then, under nitrogen protection, 4 mL of 3-aminopropyltriethoxysilane was added dropwise while stirring. The mixture was then stirred at 115 °C for 12 h. The resulting product was separated using an external magnet, washed sequentially with toluene, acetone, water, and ethanol, and dried under vacuum at 40 °C for 12 h to obtain Fe3O4@SiO2-NH2.

[0062] 109 mg Fe3O4@SiO2-NH2, 7 mg 1,4-dialdehyde-2,5-divinylbenzene, 0.4 mL 6 mol / L acetic acid, and 5 mL acetonitrile were mixed. The mixture was rapidly frozen and evacuated in a liquid nitrogen bath, and then heated at 120 °C for 12 h. After cooling to room temperature, 7 mg 1,4-dialdehyde-2,5-divinylbenzene and 11.5 mg 1,3,5-tris(4-aminophenyl)benzene were added. The mixture was frozen and evacuated, and then heated under vacuum at 120 °C for 3 days. Finally, the product was collected using an external magnet, washed three times with acetonitrile, and vacuum dried in a 60 °C oven to obtain magnetically modified vinyl COF.

[0063] 50 mg vinyl COF, 250 mg 4-aminobenzylthiophenol, 5 mg azobisisobutyronitrile and 4 mL trifluorotoluene were mixed and heated at 90 °C for 6 h under a nitrogen atmosphere; then the mixture was restored to room temperature, washed three times with tetrahydrofuran, and vacuum dried in an oven at 60 °C to obtain amino-functionalized magnetic modified COF.

[0064] (2) Hexagonal amino-functionalized magnetically modified covalent organic framework supported on tetraazacalix[2]arene[2]triazine:

[0065] 10 mg of amino-functionalized magnetically modified COF was added to 50 mL of N,N-dimethylformamide and stirred until homogeneous. Then, 5 mg of tetrazacalix[2]arene[2]triazine was added and heated at 110 °C for 48 h under a nitrogen atmosphere. The mixture was then restored to room temperature, and the product was washed three times with N,N-dimethylformamide and acetone. It was then placed in a 60 °C oven and vacuum dried to obtain the flue gas adsorption material.

[0066] Smoke capture plate

[0067] Example 4

[0068] A flue gas capture sheet includes a glass fiber filter sheet and a flue gas adsorption material loaded on it.

[0069] The flue gas adsorbent material prepared in Example 1 was prepared by adding 10 mg of the flue gas adsorbent material to 100 mL of acetonitrile solution to obtain a mixture. Then, 1 g of glass fiber filter was soaked in the mixture and soaked at room temperature for 12 h. After soaking, the filter was removed and placed in a 60 °C oven for vacuum drying to obtain the flue gas trapping sheet.

[0070] Example 5

[0071] A flue gas capture sheet includes a glass fiber filter sheet and a flue gas adsorption material loaded on it.

[0072] The gas was prepared by the following steps: 1 g of glass fiber filter and 0.1 g of 3-aminopropyltriethoxysilane were added to 100 mL of toluene to obtain a mixture. The mixture was reacted at 115 °C for 12 h under nitrogen protection. The resulting product was washed with ethanol and acetone and then vacuum dried at 40 °C for 12 h. The dried product was then added to 10 mg of the flue gas adsorbent material prepared in Example 1 in 100 mL of N,N-dimethylamide and reacted at 110 °C for 12 h under a nitrogen atmosphere. The resulting product was washed three times with N,N-dimethylformamide and acetone and then vacuum dried in a 60 °C oven to obtain the flue gas trapping sheet.

[0073] Example 6

[0074] A flue gas capture sheet includes a glass fiber filter sheet and a flue gas adsorption material loaded on it.

[0075] The flue gas adsorption material prepared in Example 1 was prepared by adding 5 mg of the flue gas adsorption material to 100 mL of acetonitrile solution to obtain a mixture. Then, 1 g of glass fiber filter was soaked in the mixture and soaked at room temperature for 12 h. After soaking, the filter was removed and placed in a 60 °C oven for vacuum drying to obtain the flue gas capture sheet.

[0076] Example 7

[0077] A flue gas capture sheet includes a glass fiber filter sheet and a flue gas adsorption material loaded on it.

[0078] The flue gas adsorbent material prepared in Example 1 was prepared by adding 20 mg of the flue gas adsorbent material to 100 mL of acetonitrile solution to obtain a mixture. Then, 1 g of glass fiber filter was soaked in the mixture and soaked at room temperature for 12 h. After soaking, the filter was removed and placed in a 60 °C oven for vacuum drying to obtain the flue gas trapping sheet.

[0079] Example 8

[0080] A flue gas capture sheet includes a polyester fiber filter sheet and a flue gas adsorption material loaded thereon.

[0081] The flue gas adsorbent material prepared in Example 2 was prepared by adding 10 mg of the flue gas adsorbent material to 100 mL of acetonitrile solution to obtain a mixture. Then, 1 g of polyester fiber filter was soaked in the mixture and removed after soaking at room temperature for 12 h. The filter was then placed in a 60 °C oven for vacuum drying to obtain the flue gas capture sheet.

[0082] Example 9

[0083] A flue gas capture sheet includes a glass fiber filter sheet and a flue gas adsorption material loaded on it.

[0084] The gas was prepared by the following steps: 1 g of glass fiber filter and 0.1 g of 3-aminopropyltriethoxysilane were added to 100 mL of toluene to obtain a mixture. The mixture was reacted at 115 °C for 12 h under nitrogen protection. The resulting product was washed with ethanol and acetone and then vacuum dried at 40 °C for 12 h. The dried product was then added to 10 mg of the flue gas adsorbent material prepared in Example 3 in 100 mL of N,N-dimethylamide and reacted at 110 °C for 12 h under a nitrogen atmosphere. The resulting product was washed three times with N,N-dimethylformamide and acetone and then vacuum dried in a 60 °C oven to obtain the flue gas trapping sheet.

[0085] Methods for detecting volatile components in cigarette smoke

[0086] Examples 10-15

[0087] A method for detecting volatile components in cigarette smoke, comprising the following steps:

[0088] S1. The balanced and screened cigarettes are smoked using a rotary smoking machine under the standard conditions specified in GB / T 19609-2004, and the cigarette smoke is captured using the smoke capturing plates prepared in Examples 4 to 9 respectively.

[0089] S2. Add the flue gas capture plate to a sealed bottle, add 3 mL of extraction solvent (dichloromethane and diethyl ether in a volume ratio of 1:1), 25 μL of [2H8]-acetylbenzene with a concentration of 10 μg / mL, and sonicate for 20 min. After extraction, remove the flue gas capture plate to obtain the extract.

[0090] S3. Headspace solid-phase microextraction-gas chromatography-mass spectrometry (SPME-GC-MS) was used to detect volatile components in the extract. The extraction temperature was 50℃. The GC-MS conditions were as follows: SPME injection parameters: aging temperature: 250℃; aging time: 5 min; heating temperature: 60℃; heating time: 10 min; adsorption time: 20 min; elution time: 5 min; post-injection aging time: 5 min. The chromatographic acquisition conditions were: splitless mode; carrier gas: He; column: DB-5MS (30 m x 0.25 mm x 0.25 μm); column flow rate: 1.0 mL / min; column oven temperature program: 40℃ for 5 min, then increased to 280℃ (6℃ / min) and held for 5 min. The mass spectrometry acquisition conditions were as follows: sample inlet temperature: 250℃; transfer line temperature: 280℃; ion source temperature: 230℃; quadrupole temperature: 150℃; ionization voltage: 70eV; solvent delay: 5min.

[0091] Example 16

[0092] A method for detecting volatile components in cigarette smoke, comprising the following steps:

[0093] S1. The balanced and screened cigarettes are smoked using a rotary smoking machine under the standard conditions specified in GB / T 19609-2004, and the cigarette smoke is captured using the smoke capturing plate prepared in Example 4.

[0094] S2. Add the flue gas capture plate to a sealed bottle, add 3 mL of extraction solvent (dichloromethane and diethyl ether in a volume ratio of 1:1), 25 μL of [2H8]-acetylbenzene with a concentration of 10 μg / mL, and sonicate for 20 min. After extraction, remove the flue gas capture plate to obtain the extract.

[0095] S3. Headspace solid-phase microextraction-gas chromatography-mass spectrometry (SSP-GC-MS) was used to detect volatile components in the extract. In SSP, the extraction head was coated with the flue gas adsorbent material prepared in Example 1. 10 mg (g) of the flue gas adsorbent material prepared in Example 1 was added to 100 mL of acetonitrile solution to obtain a mixture. The extraction head was then immersed in the mixture for 12 hours at room temperature, and then removed and vacuum-dried in a 60°C oven. The extraction temperature was 50°C, and the GC-MS conditions were the same as in Examples 10-14.

[0096] Comparative Example 1

[0097] A flue gas adsorbent material comprising silica and a tetraazacalix[2]arene[2]triazine loaded thereon.

[0098] It is prepared through the following steps:

[0099] 10g of silica nanoparticles and 10mL of 3-aminopropyltriethoxysilane were added to 100mL of toluene. The mixture was reacted at 105℃ for 12h under stirring and nitrogen protection. The product was washed three times with ethanol and acetone and then dried under vacuum at 50℃ for 12h to obtain aminated silica.

[0100] 10 mg of aminated silica was added to 50 mL of N,N-dimethylformamide and stirred until homogeneous. Then, 5 mg of tetrazacalix[2]arene[2]triazine was added and heated at 110 °C for 48 h under a nitrogen atmosphere. The mixture was then cooled to room temperature. The product was washed three times with N,N-dimethylformamide and acetone and then dried under vacuum in a 60 °C oven to obtain the flue gas adsorption material.

[0101] Comparative Example 2

[0102] A flue gas capture plate, which is a glass fiber filter.

[0103] The process involves the following steps: 1 g of glass fiber filter is soaked in 100 mL of acetonitrile solution at room temperature for 12 h, then removed and vacuum dried in a 60 °C oven to obtain the flue gas capture sheet.

[0104] Performance testing of flue gas adsorption materials and flue gas capture plates

[0105] Preparation of the adsorption solution: The adsorption solution contains 30 μg / mL isoprene and 10 × 10⁻⁶ ppm. -3 μg / mL 2-aminonaphthalene, 10×10 -3 μg / mL benzo(a)anthracene.

[0106] Take 10 mg of the flue gas adsorption material prepared in Examples 1-3 and Comparative Example 1 respectively, add it to the above-mentioned adsorption solution, stir and adsorb for 2 hours, filter and magnetically separate, retain the filtrate, and calculate the adsorption efficiency by the change of solute concentration. The test results are shown in Table 1 below.

[0107] Take 10 mg of the flue gas adsorbent material prepared in Examples 1-3 and Comparative Example 1 respectively, and repeatedly perform the following operations: add the flue gas adsorbent material to the solution to be adsorbed, stir and adsorb for 2 hours, filter and separate magnetically, and elute the separated flue gas adsorbent material with n-hexane. Repeat the above adsorption, separation and elution operations for 30 times, take the filtrate obtained in the last time, and detect whether the filtrate contains tetraazacalix[2]aromatic[2]triazine. The detection results are shown in Table 1 below.

[0108] Table 1.

[0109]

[0110] As shown in Table 1, comparing Examples 1-3 and Comparative Example 1, it can be seen that loading tetraazacalix[2]arene[2]triazine onto COF not only improves the adsorption rate of common components in flue gas such as isoprene, 2-aminonaphthalene, and benzo(a)anthracene, but also has the characteristics of structural stability and the tetraazacalix[2]arene[2]triazine not easily falling off after multiple uses.

[0111] The flue gas capture plates prepared in Examples 4-7 and Comparative Example 2 were respectively added to the above-mentioned adsorption solution. After stirring and adsorption for 2 hours, they were filtered, magnetically separated, and the filtrate was retained. The adsorption efficiency was calculated by the change in solute concentration. The test results are shown in Table 2 below.

[0112] Table 2.

[0113]

[0114] As shown in Table 2, comparing Example 4 and Comparative Example 2, it can be seen that loading the flue gas adsorption material onto the filter can further improve the adsorption rate of components in the flue gas. Meanwhile, comparing Examples 4-7, it can be seen that the loading method of the filter and the flue gas adsorption material has little effect on the adsorption rate, but the ratio of the amount of filter to the amount of flue gas adsorption material does affect the adsorption rate. When the amount of flue gas adsorption material is small, the adsorption rate decreases significantly; when the amount of flue gas adsorption material is large, the adsorption rate also decreases slightly. This may be because excessive flue gas adsorption material affects the adsorption capacity of the filter itself.

[0115] The specific embodiments described herein are merely illustrative of the spirit of the invention. Those skilled in the art to which this invention pertains may make various modifications or additions to the described specific embodiments or use similar methods to substitute them, without departing from the spirit of the invention or exceeding the scope defined by the appended claims.

Claims

1. A smoke capturing sheet, characterized by: The filter sheet and the flue gas adsorbing material loaded on the filter sheet; The flue gas adsorbing material comprises a covalent organic framework loaded tetraazacalix[2]arene[2]triazine; The covalent organic framework is a magnetic modified covalent organic framework, which takes Fe3O4 as a core, takes a covalent organic framework as a shell, and takes SiO2 as a shell-core connecting layer; The magnetic modified covalent organic framework is modified through the following steps: A. Synthesizing Fe3O4 magnetic nanospheres; B. Synthesizing silica in situ on the Fe3O4 magnetic nanospheres to obtain Fe3O4@SiO2; C. Aminating Fe3O4@SiO2 to obtain Fe3O4@SiO2-NH2; D. Synthesizing vinyl COF in situ on Fe3O4@SiO2-NH2; E. Functionalization reaction; In step D: first, mix Fe3O4@SiO2-NH2, 1,4-dialdehyde-2,5-divinylbenzene, acetic acid, and acetonitrile, quickly freeze in a liquid nitrogen bath, and vacuumize, then heat at 100-130℃ for 10-16h; after cooling to room temperature, continue to add 1,4-dialdehyde-2,5-divinylbenzene, and add 1,3,5-tris(4-aminophenyl)benzene, freeze and vacuumize, then heat at 100-130℃ under vacuum for 2-3d; finally, collect the product by an external magnet, wash, and vacuum dry; In step E: the direction of functionalization is at least one of amination and mercaptanization; The flue gas adsorbing material is prepared through the following steps: React the magnetic modified covalent organic framework and tetraazacalix[2]arene[2]triazine at 100-120℃ for 40-50h under a nitrogen atmosphere.

2. A flue gas capture sheet according to claim 1, characterised in that: The filter sheet is a glass fiber filter sheet.

3. A flue gas capture sheet according to claim 1, wherein: The mass ratio of the filter sheet to the flue gas adsorbing material is 1: (0.005-0.02).

4. A method for detecting volatile components of cigarette smoke, characterized by: The method comprises the following steps: S1. Trapping cigarette flue gas by using the flue gas trapping sheet as claimed in any one of claims 1-3; S2. After extracting the flue gas trapping sheet with a solvent, adding an internal standard, removing the flue gas trapping sheet, and obtaining an extract; S3. Detecting volatile components in the extract by using headspace solid-phase microextraction-gas chromatography-mass spectrometry.

5. The method for detecting volatile components of cigarette smoke according to claim 4, characterized in that: The solvent comprises at least one of ethanol, diethyl ether, dimethylbenzene, n-hexane, acetonitrile, and dichloromethane.

6. The method for detecting volatile components of cigarette smoke according to claim 4, characterized in that: In the headspace solid-phase microextraction, the extraction head is coated with the flue gas adsorbing material.

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