Preparation method and application of acidic post-nasal smoke adsorption material

Abstract

The application provides a preparation method of an acidic postnasal smoke adsorbing material, which comprises two steps of aldehyde-ammonia polycondensation reaction and condensate amination. The application also provides application of the adsorbing material prepared by the preparation method to postnasal smoke analysis and detection. The acidic postnasal smoke adsorbing material prepared by the application has good adsorbing effect, high adsorbing efficiency and good stability, and especially has good adsorbing effect on acidic components in postnasal smoke.

Description

Technical Field

[0001] This invention relates to the field of adsorbent material preparation, specifically to a method for preparing and applying an acidic postnasal smoke adsorbent material. Background Technology

[0002] Aroma is one of the most important sensory qualities of food, determining consumer acceptance. Aroma perception is the sum of chemical stimuli, physiological responses, and psychological effects of aroma compounds, and is the result of the interaction between humans and food. Aroma perception involves two independent pathways: the anterior nasal pathway and the posterior nasal pathway. The anterior nasal pathway refers to the perception of aromas in the environment through the nostrils, providing early warning signals about the external environment and information about the edibility of food. The posterior nasal pathway emphasizes the aroma perceived during the chewing process (oral processing), providing information about food acceptance and sensory enjoyment, and also reflecting human behavioral characteristics.

[0003] For cigarettes, the aroma in the anterior nasal cavity mainly consists of the olfactory aroma and the aroma of the transnasal smoke; the aroma in the posterior nasal cavity is the aroma perceived during cigarette inhalation and is the main aroma affecting the flavor and taste of cigarettes. Therefore, the detection of posterior nasal smoke can accurately reflect the flavor and taste information of cigarettes. Since the polar acidic components in posterior nasal smoke are an important aroma component in cigarettes, especially Chinese flue-cured cigarettes, they are not only related to the pH of the smoke but also improve the flavor, increase comfort and smoothness, reduce irritation, and improve aroma quality. Therefore, developing a material that can efficiently adsorb acidic posterior nasal smoke components has significant practical implications.

[0004] To address the above problems, this invention is proposed. Summary of the Invention

[0005] The objective of this invention is achieved through the following technical solutions.

[0006] The first aspect of this invention provides a method for preparing an acidic postnasal smoke adsorption material, comprising the following steps:

[0007] Step (1): Aldehyde-amine polycondensation reaction

[0008] Take 2,4,6-trihydroxy-1,3,5-tricarboxymethylbenzene, 2,4,6-trihydroxy-benzaldehyde and triaminoguanidine chloride, add them to N-methylacetamide, mix well, slowly add sulfuric acid aqueous solution, react at room temperature for 5-7 days, take out the precipitate by centrifugation, put the precipitate into a dialysis membrane and dialyze it in deionized water for 3 days to remove small molecules, take it out and dry it for 12 hours to obtain the condensate of trihydroxybenzyltrialdehyde and triaminoguanidine chloride;

[0009] Step (2): Amination of condensate

[0010] The trihydroxybenzyltrialdehyde condensate obtained in step (1) and triaminoguanidine chloride condensate were added to a solvent, ultrasonically dispersed, and then diisocyanate and amination reagent were added. The mixture was stirred and reacted at room temperature for 24 hours. The precipitate was removed and centrifuged. The precipitate was placed in a dialysis membrane and dialyzed in deionized water for 3 days. The precipitate was then removed and dried for 12 hours to obtain the amination condensate, which is the acidic postnasal smoke adsorption material.

[0011] Preferably, in step (1), the molar ratio of 2,4,6-trihydroxy-1,3,5-tricarboxyphenyl, 2,4,6-trihydroxy-benzaldehyde and triaminoguanidine chloride is 1:(0.01-0.1):1.

[0012] Preferably, the volume of N-methylacetamide in step (1) is 50-200 mL.

[0013] Preferably, the concentration of the sulfuric acid aqueous solution in step (1) is 1-3 mol / L, and the amount added is 5-10 mL.

[0014] Preferably, the molecular weight cutoff of the dialysis membrane in steps (1) and (2) is 20,000-50,000.

[0015] Preferably, in step (2), the mass-volume concentration of the trihydroxybenzyltrialdehyde and triaminoguanidine chloride condensate solution is 0.01-0.2 g / mL.

[0016] Preferably, the solvent in step (2) is one or more of chloroform, dichloromethane and acetone.

[0017] Preferably, in step (2), the diisocyanate is one or more of isophorone diisocyanate, hexamethylene diisocyanate, and lysine diisocyanate, and the amount added is 5-20% of the mass of the trihydroxybenzenetrialdehyde and triaminoguanidine chloride condensate.

[0018] Preferably, in step (2), the amination agent is one or more of ethylenediamine, butanediamine, and urea, and the amount added is 5-20% of the mass of the trihydroxybenzyltrialdehyde and triaminoguanidine chloride condensate.

[0019] The second aspect of this invention provides an application of the adsorbent material prepared by the method of the first aspect for postnasal smoke analysis and detection.

[0020] Preferably, the obtained adsorbent material is added to, for example... Figure 2 In the purge collection tube of the portable postnasal smoke collection device shown, add 1-5 cm of material for postnasal smoke adsorption. After adsorption is complete, remove the material and perform purge collection-GCMS analysis directly at 100-300℃, or elute with acetonitrile, acetone or tetrahydrofuran before analysis.

[0021] Preferably, the portable retronasal smoke collection device includes the following components:

[0022] Nasal mask (1), drying tube (2), trap (3), buffer bottle (4), pump (5);

[0023] The trap (3) includes: a condenser tube (31), a purge trap tube (32), a connecting tube III (34), a fixed rubber plug I (37), and a fixed rubber plug II (38).

[0024] Preferably, the nasal mask (1) and the drying tube (2) are connected by a connecting tube I (11).

[0025] Preferably, the inner diameter of the drying tube (2) is 0.3cm-2cm and the height is 3cm-6cm.

[0026] Preferably, a drying tube additive (21) is added inside the drying tube (2), and the addition height of the drying tube additive (21) inside the drying tube (2) is 2cm-5cm.

[0027] Preferably, the bottom of the drying tube (2) is provided with a drying tube partition (22), which is a 2mm thick sand core partition with a micropore diameter of 80-120 micrometers.

[0028] Preferably, the drying tube (2) and the trap (3) are connected by a connecting tube II (23).

[0029] Preferably, the condenser tube (31) can be a reflux condenser tube or a straight condenser tube, with a length of 15cm-30cm and an inner diameter greater than 0.5cm.

[0030] Preferably, the purge collection tube (32) is filled with 1-5 cm of adsorbent material.

[0031] Preferably, the buffer bottle (4) has two openings. One opening is sealed to the connecting pipe III (34) through a sealing plug (42), and the other opening is connected to the pump through the connecting pipe IV (41).

[0032] Preferably, the pump (5) can generate a negative pressure of 500-10 kPa at the nasal mask (1) after being connected and turned on.

[0033] Compared with the prior art, the present invention has the following beneficial effects:

[0034] 1. This invention is the first to prepare an adsorbent material for acidic postnasal smoke and apply it to the analysis and detection of postnasal smoke.

[0035] 2. The acidic postnasal smoke adsorption material obtained by the present invention has a good adsorption effect, high adsorption efficiency, and good stability, especially for acidic components in postnasal smoke. Attached Figure Description

[0036] Figure 1 This is a schematic diagram of the synthesis in Example 1;

[0037] Figure 2 A portable retronasal smoke collection device;

[0038] (1) Nasal mask; (11) Connecting tube I; (2) Drying tube; (21) Drying tube additive; (22) Drying tube partition; (23) Connecting tube II; (31) Condenser tube; (32) Purge and trap tube; (34) Connecting tube III; (37) Fixing rubber stopper I; (38) Fixing rubber stopper II; (42) Sealing stopper; (4) Buffer bottle; (41) Connecting tube IV; (5) Pump connection. Detailed Implementation

[0039] The present invention will be described below with reference to specific embodiments, but the implementation of the present invention is not limited thereto. Experimental methods not specifically described in the embodiments generally use conventional conditions and conditions described in manuals, or conditions recommended by the manufacturer. The general equipment, materials, reagents, etc., used are all commercially available unless otherwise specified.

[0040] Example 1

[0041] Step (1): Aldehyde-amine polycondensation reaction

[0042] 1 mmol of 2,4,6-trihydroxy-1,3,5-tricarboxymethylbenzene, 0.05 mmol of 2,4,6-trihydroxy-benzaldehyde, and 1 mmol of triaminoguanidine chloride were added to 100 mL of N-methylacetamide. The mixture was sonicated for 20 min until the monomers were completely mixed. 5 mL of 2 mol / L sulfuric acid aqueous solution was slowly added dropwise. The reaction was carried out at room temperature for 7 days. The precipitate was collected by centrifugation and placed in a dialysis membrane with a molecular weight cutoff of 30,000. Dialysis was performed in deionized water for 3 days to remove small molecules. The precipitate was then dried for 12 h to obtain the condensate TG-THTCB. Figure 1 As shown.

[0043] Step (2): Amination of condensate

[0044] 1 g of the above condensate was added to 30 ml of chloroform and ultrasonically dispersed. 100 mg of lysine diisocyanate and 100 mg of urea were added and stirred at room temperature for 24 h. The precipitate was removed and centrifuged. The precipitate was placed in a dialysis membrane with a molecular weight cutoff of 30,000 and dialyzed in deionized water for 3 days. The precipitate was removed and dried for 12 h to obtain the aminated condensate TG-THTCB-NH2, which is the required adsorbent material 1.

[0045] Controlled Experiment 1

[0046] In Example 1, 2,4,6-trihydroxybenzaldehyde was not added, and all other conditions were exactly the same as in Example 1, resulting in adsorbent material 2.

[0047] Controlled Experiment 2

[0048] In Example 1, the condensate amination step was not performed, and all other conditions were exactly the same as in Example 1, resulting in adsorbent material 3.

[0049] Specific surface area and pore size testing

[0050] The surface data of the samples were determined using a physical adsorption instrument via nitrogen adsorption at 77 K. The specific surface area was calculated using the BET model, and the pore size distribution was obtained using the BJH model. The data are shown in Table 1. Table 1 shows that, compared to material 1 obtained in Example 1, material 2 obtained without the addition of 2,4,6-trihydroxybenzaldehyde has a significantly lower specific surface area and a significantly higher pore size; while material 3, without amination, has a slightly higher specific surface area and a slightly lower pore size. This is because the amination process leads to a slight decrease in specific surface area.

[0051] Table 1. BET specific surface area and pore size data of the adsorbent materials

[0052]

[0053] Postnasal smoke detection

[0054] Brand A cigarettes were selected as the test cigarettes. After lighting the cigarette and taking a puff, the tester quickly covered their nose with the retronasal trap. After exhaling the smoke through the nose, they took a second puff, and so on. Each cigarette was smoked evenly for 7 puffs, and a set of 4 cigarettes was completed. After adsorption was complete, the cigarettes were removed and directly analyzed by purge-trap-GCMS at 300℃. The results are shown in Table 2.

[0055] Table 2 GC-MS data of different adsorbents

[0056]

[0057]

[0058]

[0059] Note: "N" indicates that no detection was detected.

[0060] As shown in Table 2, the adsorbent material prepared in Example 1 of this invention detected 64 postnasal smoke components with a total detection concentration of 1854 μg / cigarette, of which all 45 acidic components were detected, with a total detection concentration of 1664 μg / cigarette. In contrast, the adsorbent material prepared in Control Example 1 detected 47 postnasal smoke components with a total detection concentration of 588 μg / cigarette, of which 28 acidic components were detected, with a total detection concentration of 397 μg / cigarette. Furthermore, the adsorbent material prepared in Control Example 2 detected 44 postnasal smoke components with a total detection concentration of 1036 μg / cigarette, of which 21 acidic components were detected, with a total detection concentration of 701 μg / cigarette. The results indicate that this invention has good adsorption capacity and adsorption strength, especially for acidic postnasal smoke, further confirming the superiority of the method of this invention.

Claims

1. A method of preparing an acidic postnasal smoke adsorbing material, characterized by, The method comprises the following steps: Step (1): aldehyde amino polycondensation reaction 2,4,6-trihydroxy-1,3,5-triformylbenzene, 2,4,6-trihydroxy-benzaldehyde and triamino guanidine chloride are taken and added into N-methyl acetamide, mixed uniformly, slowly dripped into aqueous sulfuric acid solution, reacted at room temperature for 5-7 days, taken out and centrifuged to precipitate, the precipitate is put into dialysis membrane and dialyzed in deionized water for 3 days to remove small molecules, taken out and dried for 12 hours to obtain a trihydroxybenzene tricarboxaldehyde and triamino guanidine chloride condensate; Step (2): aminoization of the condensate The trihydroxybenzene tricarboxaldehyde and triamino guanidine chloride condensate obtained in step (1) is added into a solvent, ultrasonically dispersed, then diisocyanate and an aminoization reagent are added, stirred and reacted at room temperature for 24 hours, taken out and centrifuged to precipitate, the precipitate is put into dialysis membrane and dialyzed in deionized water for 3 days, taken out and dried for 12 hours to obtain an aminoized condensate, i.e. an acidic postnasal smoke adsorption material is prepared; The molar ratio of 2,4,6-trihydroxy-1,3,5-triformylbenzene, 2,4,6-trihydroxy-benzaldehyde and triamino guanidine chloride in step (1) is 1:(0.01-0.1):1; The diisocyanate in step (2) is one or more of isophorone diisocyanate, hexamethylene diisocyanate and lysine diisocyanate.

2. The production method according to claim 1, characterized by, The volume of N-methyl acetamide in step (1) is 50-200 mL.

3. The preparation method according to claim 1, characterized in that, The concentration of the aqueous sulfuric acid solution in step (1) is 1-3 mol / L, and the amount added is 5-10 mL.

4. The production method according to claim 1, characterized by, The molecular weight cut-off of the dialysis membrane in step (1) and step (2) is 20,000-50,000.

5. The method of claim 1, wherein, The mass / volume concentration of the trihydroxybenzene tricarboxaldehyde and triamino guanidine chloride condensate solution in step (2) is 0.01-0.2 g / mL.

6. The method of claim 1, wherein, The solvent in step (2) is one or more of chloroform, dichloromethane and acetone.

7. The preparation method according to claim 1, characterized in that, The amount of diisocyanate in step (2) is 5-20% of the mass of the trihydroxybenzene tricarboxaldehyde and triamino guanidine chloride condensate, and the diisocyanate is one or more of isophorone diisocyanate, hexamethylene diisocyanate and lysine diisocyanate.

8. The method of claim 1, wherein, The amount of the aminoization reagent in step (2) is 5-20% of the mass of the trihydroxybenzene tricarboxaldehyde and triamino guanidine chloride condensate, and the aminoization reagent is one or more of ethylenediamine, butanediamine and urea.

9. Use of the adsorption material prepared by the preparation method of claim 1 for postnasal smoke analysis and detection.

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