TVOC (Total Volatile Organic Compound) adsorption supramolecular cage as well as preparation method and application thereof
By designing a supramolecular cage structure that matches TVOC molecules, the problems of limited adsorption capacity and catalyst activity in the prior art are solved, and efficient and stable TVOC adsorption and regeneration are achieved, avoiding the generation of by-products. Ensure environmental and human safety.
Patent Information
- Application Number
- CN202411280637.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-12
- Publication Date
- 2024-12-17
AI Technical Summary
In the existing TVOC purification methods, the adsorption capacity of the physical adsorption method is limited and the efficiency is not high, and the catalyst activity of the chemical oxidation method is susceptible to environmental factors and may produce harmful by-products.
A TVOC adsorption supramolecular cage is designed, with its structure matching TVOC molecules, and is prepared by specific chemical synthesis methods to achieve high selectivity and high capacity adsorption, and maintain stability under different environmental conditions to avoid the generation of by-products. .
It achieves efficient and stable TVOC adsorption and regenerative properties, significantly improves adsorption efficiency and capacity, and is harmless to the environment and the human body.
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Figure CN119143772A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of organic synthesis, and in particular relates to a TVOC adsorption supramolecular cage and a preparation method and application thereof. Background Art
[0002] TVOC is a common organic pollutant that poses a serious threat to human health. At present, the commonly used TVOC purification methods are mainly physical adsorption and chemical oxidation. Physical adsorption is a method of separating TVOC from the air by using the pore structure and surface functional groups of the adsorbent to interact with TVOC molecules. Commonly used adsorbents include activated carbon, zeolite, silica gel, etc. Chemical oxidation is a method of using catalysts or photocatalysts to promote the reaction of TVOC molecules with oxygen and convert TVOC molecules into harmless carbon dioxide and water. Commonly used catalysts or photocatalysts include titanium dioxide, manganese oxide, iron oxide, etc.
[0003] The disadvantage of the physical adsorption method is that the adsorption capacity of the adsorbent is limited. After the adsorption equilibrium is reached, TVOC cannot be removed further. The adsorbent needs to be replaced or regenerated regularly, which increases the cost and difficulty of maintenance. Moreover, the pore structure and surface functional groups of the adsorbent often cannot fully match the size and shape of various TVOC molecules, resulting in low adsorption efficiency. The disadvantage of the chemical oxidation method is that the activity of the catalyst or photocatalyst is easily affected by environmental factors such as temperature, humidity, light, etc., and some side reactions may occur to generate other harmful substances, such as ozone, nitrite, etc. Summary of the invention
[0004] In order to solve the problems existing in the prior art, the present invention provides a TVOC adsorption supramolecular cage and its preparation method and application. The TVOC adsorption supramolecular cage provided by the present invention can achieve high selectivity and high capacity TVOC adsorption, and the supramolecular cage has good stability and regeneration, can be used for a long time under different environmental conditions, and will not produce harmful byproducts.
[0005] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:
[0006] The present invention provides a TVOC adsorption supramolecular cage having a structure shown in Formula I:
[0007]
[0008] The present invention also provides a method for preparing the TVOC adsorption supramolecular cage described in the above technical solution, comprising the following steps:
[0009] Mixing 2,6-dimethylphenol, acetic anhydride and pyridine, and performing a first substitution reaction to obtain 2,6-dimethylphenoxyacetate;
[0010] 2,6-dimethylphenoxyacetate, N-bromosuccinimide and azobisisobutyronitrile are dissolved in tetrachloroethylene, and the resulting solution is subjected to a second substitution reaction to obtain intermediate I-1;
[0011]
[0012] The intermediate I-1 is dissolved in tetrahydrofuran, and a sodium hydroxide aqueous solution is added dropwise to the solution of the intermediate I-1, followed by heating under reflux to obtain 2-hydroxy-2,6-benzenedicarbaldehyde;
[0013] The 2-hydroxy-2,6-benzenedicarbaldehyde, toluene and anhydrous ethylene glycol are mixed, and a third substitution reaction is carried out under the catalysis of p-toluenesulfonic acid to obtain an intermediate I-2;
[0014]
[0015] The intermediate I-2, phthalic anhydride and methanesulfonic acid are mixed and subjected to a fourth substitution reaction to obtain the intermediate I-3;
[0016]
[0017] Under a protective atmosphere, the intermediate I-3, anhydrous ethanol and cyclohexanediamine are mixed and subjected to a reflux reaction to obtain the TVOC adsorption supramolecular cage.
[0018] Preferably, the volume ratio of the acetic anhydride to pyridine is 1:1; the volume ratio of the 2,6-dimethylphenol, acetic anhydride and pyridine is 20 g:40 mL.
[0019] Preferably, the molar ratio of the 2,6-dimethylphenoxyacetate, N-bromosuccinimide and azobisisobutyronitrile is 61:270:6.1.
[0020] Preferably, the mass concentration of the sodium hydroxide aqueous solution is 10%; the volume ratio of the solution of the intermediate I-1 to the sodium hydroxide aqueous solution is 200:120;
[0021] The heating reflux time is 12h.
[0022] Preferably, the molar ratio of the 2-hydroxy-2,6-benzenedicarbaldehyde to anhydrous ethylene glycol is 15.2:91.4; the usage ratio of the 2-hydroxy-2,6-benzenedicarbaldehyde to toluene is 2.28 g:80 mL.
[0023] Preferably, the third substitution reaction is to heat the mixture of the 2-hydroxy-2,6-benzenedicarbaldehyde, toluene and anhydrous ethylene glycol to reflux; the reflux time is 23 hours.
[0024] Preferably, the molar ratio of the intermediate I-2 to phthalic anhydride is 13.3:7.4; the usage ratio of the intermediate I-2 to methanesulfonic acid is 2.0 g:15 mL;
[0025] The temperature of the fourth substitution reaction is 90° C. and the insulation time is 5 h.
[0026] Preferably, the molar ratio of the intermediate I-3 to cyclohexanediamine is 1:4; and the reflux reaction time is 12 hours.
[0027] The present invention also provides the use of the TVOC adsorption supramolecular cage described in the above technical solution or the TVOC adsorption supramolecular cage prepared by the above preparation method in adsorbing TVOC.
[0028] The present invention provides a TVOC adsorption supramolecular cage having a structure shown in Formula I. As shown in Formula I, the cavity size and shape of the TVOC adsorption supramolecular cage provided by the present invention perfectly match the size and shape of TVOC molecules, thereby achieving high-selectivity and high-capacity TVOC adsorption. Compared with conventional adsorbents, the adsorption efficiency and adsorption amount are significantly improved; the inner wall of the cavity of the supramolecular cage has functional groups that interact with TVOC molecules, thereby enhancing the interaction between TVOC molecules and the supramolecular cage, so that the TVOC molecules can be firmly adsorbed in the supramolecular cage and are not easy to fall off or leak; the supramolecular cage has good stability and regeneration, can be used for a long time under different environmental conditions, and will not produce harmful by-products, and is harmless to the environment and human body. BRIEF DESCRIPTION OF THE DRAWINGS
[0029] Figure 1 is the H NMR spectrum of intermediate I-3;
[0030] Figure 2 HPLC analysis of TVOC adsorption supramolecular cage prepared in Example 1;
[0031] Figure 3 This is the infrared spectrum of the TVOC adsorption supramolecular cage prepared in Example 1. DETAILED DESCRIPTION
[0032] The present invention provides a TVOC adsorption supramolecular cage having a structure shown in Formula I:
[0033]
[0034] The present invention also provides a method for preparing the TVOC adsorption supramolecular cage described in the above technical solution, comprising the following steps:
[0035] Mixing 2,6-dimethylphenol, acetic anhydride and pyridine, and performing a first substitution reaction to obtain 2,6-dimethylphenoxyacetate;
[0036] 2,6-dimethylphenoxyacetate, N-bromosuccinimide and azobisisobutyronitrile are dissolved in tetrachloroethylene, and the resulting solution is subjected to a second substitution reaction to obtain intermediate I-1;
[0037]
[0038] The intermediate I-1 is dissolved in tetrahydrofuran, and a sodium hydroxide aqueous solution is added dropwise to the solution of the intermediate I-1, followed by heating under reflux to obtain 2-hydroxy-2,6-benzenedicarbaldehyde;
[0039] The 2-hydroxy-2,6-benzenedicarbaldehyde, toluene and anhydrous ethylene glycol are mixed, and a third substitution reaction is carried out under the catalysis of p-toluenesulfonic acid to obtain an intermediate I-2;
[0040]
[0041] Under a protective atmosphere, the intermediate I-2, phthalic anhydride and methanesulfonic acid are mixed to carry out a fourth substitution reaction to obtain the intermediate I-3;
[0042]
[0043] Under a protective atmosphere, the intermediate I-3, anhydrous ethanol and cyclohexanediamine are mixed and subjected to a reflux reaction to obtain the TVOC adsorption supramolecular cage.
[0044] The present invention mixes 2,6-dimethylphenol, acetic anhydride and pyridine, and performs a first substitution reaction to obtain 2,6-dimethylphenoxyacetic acid ester.
[0045] As an embodiment, the mixing is to add 2,6-dimethylphenol to a mixed solvent of acetic anhydride and pyridine under ice bath conditions. As an embodiment, the volume ratio of acetic anhydride to pyridine is 1:1; the mass of 2,6-dimethylphenol, the volume of acetic anhydride and pyridine and the usage ratio are 20g:40mL.
[0046] As an embodiment, the temperature of the first substitution reaction is room temperature and the time is 10 hours; the first substitution reaction is carried out under stirring conditions.
[0047] As an embodiment, after the first substitution reaction, the system obtained by the first substitution reaction is diluted with ethyl acetate, washed with a sodium chloride aqueous solution, washed with a sodium carbonate aqueous solution, and dried with anhydrous sodium sulfate, and the obtained organic phase is concentrated under reduced pressure and distilled under vacuum. As an embodiment, the mass concentration of the sodium chloride aqueous solution is 10%.
[0048] As another embodiment, after the first substitution reaction, the method further comprises diluting the system obtained from the first substitution reaction with ethyl acetate, washing with a sodium chloride aqueous solution, washing with a sodium carbonate aqueous solution, and drying with anhydrous sodium sulfate, and then subjecting the obtained organic phase to silica gel column chromatography.
[0049] After obtaining 2,6-dimethylphenoxyacetic acid ester, the present invention dissolves 2,6-dimethylphenoxyacetic acid ester, N-bromosuccinimide and azobisisobutyronitrile in tetrachloroethylene, and the obtained solution is subjected to a second substitution reaction to obtain intermediate I-1.
[0050] As another embodiment, the molar ratio of the 2,6-dimethylphenoxyacetic acid ester, N-bromosuccinimide and azobisisobutyronitrile is 61:270:6.1. As another embodiment, the mass ratio of the 2,6-dimethylphenoxyacetic acid ester to the volume ratio of tetrachloroethylene is 10.0 g:200 mL.
[0051] As another embodiment, the second substitution reaction is to heat the obtained solution to reflux; the reflux time is 10 hours.
[0052] As another embodiment, after the second substitution reaction, the process further includes cooling to room temperature, filtering, and concentrating the filtrate under reduced pressure.
[0053] After obtaining the intermediate I-1, the present invention dissolves the intermediate I-1 in tetrahydrofuran, drops a sodium hydroxide aqueous solution into the obtained solution of the intermediate I-1, and heats under reflux to obtain 2-hydroxy-2,6-benzenedicarbaldehyde.
[0054] As another embodiment, the mass concentration of the sodium hydroxide aqueous solution is 10%. As another embodiment, the volume ratio of the solution of the intermediate I-1 to the sodium hydroxide aqueous solution is 200:120.
[0055] As another embodiment, the heating reflux time is 12 hours.
[0056] As an embodiment, after the heating and reflux, the product obtained by heating and reflux is cooled to room temperature, distilled under reduced pressure and acidified with hydrochloric acid in sequence; the water layer obtained by acidification is extracted with ethyl acetate, and the obtained organic phase is washed, dried, concentrated under reduced pressure and recrystallized in sequence. As another embodiment, the concentration of hydrochloric acid is 10wt%; the acidification is carried out to a pH of 5; as another embodiment, the washing is sequentially washed with water and washed with a saturated sodium chloride aqueous solution.
[0057] After obtaining 2-hydroxy-2,6-benzenedicarbaldehyde, the present invention mixes the 2-hydroxy-2,6-benzenedicarbaldehyde, toluene and anhydrous ethylene glycol, and performs a third substitution reaction under the catalysis of p-toluenesulfonic acid to obtain intermediate I-2.
[0058] As an embodiment, the third substitution reaction is carried out under a protective atmosphere; the molar ratio of the 2-hydroxy-2,6-benzenedicarbaldehyde to anhydrous ethylene glycol is 15.2:91.4; the amount ratio of the 2-hydroxy-2,6-benzenedicarbaldehyde to toluene is 2.28g:80mL.
[0059] As an embodiment, the third substitution reaction is to heat the mixture of the 2-hydroxy-2,6-benzenedicarbaldehyde, toluene and anhydrous ethylene glycol to reflux; the reflux time is 23 hours.
[0060] As an embodiment, after the third substitution reaction, the reaction product is diluted with ethyl acetate, and then washed and chromatographed on a silica gel column in sequence. As an embodiment, the washing is washed with a NaHCO3 solution, H2O and brine in sequence; as an embodiment, during the silica gel column chromatography, the eluent is n-hexane and ethyl acetate in a volume ratio of 2:1.
[0061] After obtaining the intermediate I-2, the intermediate I-2, phthalic anhydride and methanesulfonic acid are mixed under the protective atmosphere of the present invention to carry out a fourth substitution reaction to obtain the intermediate I-3.
[0062] As an implementation manner, the protective atmosphere is preferably nitrogen.
[0063] As an embodiment, the molar ratio of the intermediate I-2 to phthalic anhydride is 13.3:7.4; the usage ratio of the intermediate I-2 to methanesulfonic acid is 2.0 g:15 mL.
[0064] As an embodiment, the temperature of the fourth substitution reaction is 90° C. and the insulation time is 5 hours.
[0065] As an embodiment, after the fourth substitution reaction, the reaction liquid obtained by the fourth substitution reaction is cooled to room temperature, slowly introduced into ice water, the product is filtered, and the product is washed with water and dried; the obtained crude product is recrystallized and decolorized with activated carbon in sequence.
[0066] After obtaining the intermediate I-3, the present invention mixes the intermediate I-3, anhydrous ethanol and cyclohexanediamine under a protective atmosphere, and performs a reflux reaction to obtain the TVOC adsorption supramolecular cage.
[0067] In the present invention, before the intermediate I-3, anhydrous ethanol and cyclohexanediamine are mixed, the anhydrous ethanol is preferably dried by a magnesium drying method before use. The specific method is: adding magnesium sticks and iodine to anhydrous ethanol, first heating and refluxing until the reaction is complete, and then distilling to obtain anhydrous ethanol.
[0068] As an implementation manner, the protective atmosphere is preferably nitrogen.
[0069] As an embodiment, the molar ratio of the intermediate I-3 to cyclohexanediamine is 1: 4. As an embodiment, the mass ratio of the intermediate I-3 to the volume ratio of anhydrous ethanol is 200 mg: 10 mL.
[0070] As an embodiment, the reflux reaction time is 12 hours.
[0071] As an embodiment, after the reflux reaction, the reflux reaction system is cooled to room temperature, allowed to stand, and filtered. As an embodiment, during the standing, the ambient temperature is 4° C., and the standing time is 24 hours.
[0072] In the present invention, the synthesis method of the supramolecular cage is simple, rapid and low-cost, does not require the use of high temperature, high pressure, toxic or harmful reagents or solvents, and can obtain high-purity, high-crystallinity and uniform-sized supramolecular cage crystals, which are convenient for subsequent processing and application.
[0073] The present invention also provides the use of the TVOC adsorption supramolecular cage described in the above technical solution or the TVOC adsorption supramolecular cage prepared by the above preparation method in adsorbing TVOC.
[0074] The technical solutions provided by the present invention are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the protection scope of the present invention.
[0075] Example 1
[0076] Under ice bath, 2,6-dimethylphenol (20g, 164mmol) was added to 40mL of acetic anhydride and pyridine 1:1 (v / v) mixed solvent. After the obtained light yellow solution was stirred overnight (10 hours) at room temperature, 150mL of ethyl acetate was added to the reaction solution for dilution, and the diluent was washed with 10wt% sodium chloride aqueous solution 3 times (150mL each time), and the organic phase was collected; then the organic phase was washed with 10wt% sodium carbonate aqueous solution 3 times (150mL each time), and the organic phase was dried with anhydrous sodium sulfate. After the dried organic phase was concentrated under reduced pressure, it was distilled under vacuum (bp 87℃, 0.05mmHg) to obtain 2,6-dimethylphenoxyacetate with a yield of 75%.
[0077] The hydrogen spectrum information of 2,6-dimethylphenoxyacetate is: 1 H NMR(CDCl3): δ7.1(m,3H,phenyl-H),2.43(s,3H,CH3CO),2.15(s,6H,CH3).
[0078] 2,6-Dimethylphenoxyacetate (10.0 g, 61 mmol), N-bromosuccinimide (49.4 g, 270 mmol) and azobisisobutyronitrile (1.0 g, 6.1 mmol) were dissolved in 200 mL of tetrachloroethylene. After refluxing overnight (10 hours), the reaction solution was cooled to room temperature, and then the insoluble N-bromosuccinimide was removed by filtration. The filtrate was concentrated under reduced pressure to obtain 22.8 g of intermediate I-1 with a yield of 78%.
[0079] The intermediate I-1 was redissolved in 200 mL of tetrahydrofuran and heated to reflux. Then, 120 mL of 10 wt% sodium hydroxide aqueous solution was added dropwise within 2 h. After heating and stirring for another 12 h, the obtained brown mixture was cooled to room temperature, tetrahydrofuran was removed by vacuum distillation, and the solution was acidified to a pH of 5 with 10 wt% hydrochloric acid, and the aqueous layer was collected. The aqueous layer was extracted with ethyl acetate (3 × 100 mL), the organic phases were combined, and then washed with water (100 mL) and saturated sodium chloride aqueous solution (100 mL), dried with Na2SO4, and concentrated under reduced pressure to obtain a crude product, which was recrystallized in water to obtain 5.5 g of a colorless needle-shaped product, 2-hydroxy-2,6-benzenedicarbaldehyde, with a yield of 69%.
[0080] The hydrogen spectrum information of 2-hydroxy-2,6-benzenedicarbaldehyde is: 1 H NMR (DMSO-d6, 400MHz) d 11.60 (s, 1H), 10.21 (s, 2H), 8.03 (d, J = 7.66Hz, 2H), 7.18 (t, J = 7.66Hz, 1H) ppm; 13 CNMR(DMSO-d6,100MHz)d 192.9,162.3,137.2,123.4,120.7ppm.
[0081] Under argon environment, 2-hydroxy-2,6-benzenedicarbaldehyde (15.2mmol, 2.28g) was added to a 250mL three-necked flask (the reaction vessel was equipped with a Dean-Stark water separator and a condenser), and then the flask was evacuated and backfilled with high-purity nitrogen, and the operation was repeated three times. Then, 80mL toluene and anhydrous ethylene glycol (91.4mmol, 5.67g) were added by a syringe under argon environment, and then the catalyst TsOH (0.167mmol, 0.032g) was added to reflux for about 23h. After the reaction solution was diluted with ethyl acetate (300mL), it was washed with 1mol / LNaHCO3 solution (50mL), H2O (50mL) and brine (50mL) in sequence. Then, the organic phase obtained by washing was purified by silica gel column chromatography (eluent was n-hexane and ethyl acetate with a volume ratio of 2:1) to obtain intermediate I-2.
[0082] Intermediate I-2 (2.0 g, 13.3 mmol) and phthalic anhydride (1.1 g, 7.4 mmol) were added to 15 mL of methanesulfonic acid, and stirred at 90 ° C for 5 h under nitrogen protection. The reaction solution was then cooled to room temperature and slowly introduced into ice water, the product was filtered, washed with water and dried, and the obtained crude product was purified by recrystallization and decolorized with activated carbon to obtain intermediate I-3.
[0083] 200 mg of intermediate I-3 was dissolved in 10 mL of anhydrous ethanol dried over iodine / magnesium, and 4 equivalents of cyclohexanediamine were added under nitrogen atmosphere. The mixture was refluxed for 12 h, cooled to room temperature, and allowed to stand in a refrigerator overnight. 220 mg of yellow solid powder was obtained by suction filtration.
[0084] The H NMR spectrum of intermediate I-3 is as follows Figure 1 As shown, the hydrogen spectrum information is: the hydrogen spectrum detected 4 peaks of the target product, and the sum of their integral ratios is 14, which is consistent with the 14 H (C 24 H 14 O8). The first 1.763 is the two hydrogens on the phenolic hydroxyl group, the second 4.000 is the four symmetrical aldehyde hydrogens, and the third and fourth are the eight benzene ring hydrogens. Since the four symmetrical hydrogens are together, there is a peak. The other four hydrogens are asymmetric, so there will be t peaks and multiple peaks. Therefore, the structure analyzed by the hydrogen spectrum is consistent with the structure of the target product.
[0085] Figure 2 HPLC analysis of TVOC adsorption on supramolecular cages. Figure 2 It can be seen that the peak with a retention time of 1.888 min is the highest, which is the peak of the product, and the other peaks are very low, indicating that the product has high purity.
[0086] Figure 3 The infrared spectrum of TVOC adsorbed supramolecular cage is shown in Figure 2. Figure 3 It can be seen that the present invention successfully prepared the TVOC adsorption supramolecular cage with the structure shown in Formula I.
[0087] The present invention tests the adsorption performance of the TVOC adsorption supramolecular cage prepared in Example 1. The test method refers to GB / T 35565-2017 "Test method for wood activated carbon - Determination of formaldehyde absorption rate". The test result is: each gram of TVOC adsorption supramolecular cage can absorb 148 mg of formaldehyde.
[0088] Although the above embodiment describes the present invention in detail, it is only a part of the embodiments of the present invention, not all of the embodiments. Other embodiments can be obtained based on this embodiment without creativity, and these embodiments all fall within the protection scope of the present invention.
Claims
1. A TVOC adsorption supramolecular cage, characterized in that: It has the structure shown in formula I:
2. The method for preparing the TVOC adsorption supramolecular cage according to claim 1, characterized in that: The following steps are involved: Mixing 2,6-dimethylphenol, acetic anhydride and pyridine, and performing a first substitution reaction to obtain 2,6-dimethylphenoxyacetate; 2,6-dimethylphenoxyacetate, N-bromosuccinimide and azobisisobutyronitrile are dissolved in tetrachloroethylene, and the resulting solution is subjected to a second substitution reaction to obtain intermediate I-1; The intermediate I-1 is dissolved in tetrahydrofuran, and a sodium hydroxide aqueous solution is added dropwise to the solution of the intermediate I-1, followed by heating under reflux to obtain 2-hydroxy-2,6-benzenedicarbaldehyde; The 2-hydroxy-2,6-benzenedicarbaldehyde, toluene and anhydrous ethylene glycol are mixed, and a third substitution reaction is carried out under the catalysis of p-toluenesulfonic acid to obtain an intermediate I-2; Under a protective atmosphere, the intermediate I-2, phthalic anhydride and methanesulfonic acid are mixed to carry out a fourth substitution reaction to obtain the intermediate I-3; Under a protective atmosphere, the intermediate I-3, anhydrous ethanol and cyclohexanediamine are mixed and subjected to a reflux reaction to obtain the TVOC adsorption supramolecular cage.
3. The preparation method according to claim 2, characterized in that: The volume ratio of the acetic anhydride to pyridine is 1:1; the volume ratio of the 2,6-dimethylphenol, acetic anhydride and pyridine is 20 g:40 mL.
4. The preparation method according to claim 2, characterized in that: The molar ratio of the 2,6-dimethylphenoxyacetate, N-bromosuccinimide and azobisisobutyronitrile is 61:270:6.
1.
5. The preparation method according to claim 2, characterized in that: The mass concentration of the sodium hydroxide aqueous solution is 10%; the volume ratio of the intermediate I-1 solution to the sodium hydroxide aqueous solution is 200:120; The heating reflux time is 12h.
6. The preparation method according to claim 2, characterized in that: The molar ratio of the 2-hydroxy-2,6-benzenedicarbaldehyde to anhydrous ethylene glycol is 15.2:91.4; the usage ratio of the 2-hydroxy-2,6-benzenedicarbaldehyde to toluene is 2.28 g:80 mL.
7. The preparation method according to claim 6, characterized in that: The third substitution reaction is to heat the mixture of the 2-hydroxy-2,6-benzenedicarbaldehyde, toluene and anhydrous ethylene glycol to reflux; the reflux time is 23 hours.
8. The preparation method according to claim 2, characterized in that: The molar ratio of the intermediate I-2 to phthalic anhydride is 13.3:7.4; the usage ratio of the intermediate I-2 to methanesulfonic acid is 2.0 g:15 mL; The temperature of the fourth substitution reaction is 90° C. and the insulation time is 5 h.
9. The preparation method according to claim 8, characterized in that: The molar ratio of the intermediate I-3 to cyclohexanediamine is 1:4; and the reflux reaction time is 12 hours.
10. Use of the TVOC adsorption supramolecular cage according to claim 1 or the TVOC adsorption supramolecular cage prepared by the preparation method of any one of claims 2 to 9 in adsorbing TVOC.