Solid efficient deodorizing aromatic as well as preparation method and application thereof

Abstract

The invention relates to the field of air purification aromatics, in particular to a solid efficient deodorizing aromatic as well as a preparation method and application thereof. The deodorant is used for solving the problem that an existing deodorant is low in peculiar smell removal rate. The odor-removing aromatic is prepared by adding triptycene-adamantane COFs and cucurbit [7] uril, triptycene is nitrated firstly, nitryl is reduced into amino, aldehyde groups are introduced into adamantane to synthesize the triptycene-adamantane COFs, and the triptycene-adamantane COFs have higher specific surface area and narrower pore structure, can accommodate odor molecules with different molecular sizes, and can be used for preparing the odor-removing aromatic. The cucurbituril is a supramolecular compound, a hydrophobic cavity in the cucurbituril can adsorb more oily fragrance components and quickly and effectively adsorb various peculiar smell molecules, harmful molecules and peculiar smell in air are continuously adsorbed and decomposed, and meanwhile, the emitted natural plant essential oil fragrance reacts with the peculiar smell molecules, so that the peculiar smell is effectively neutralized, and the air quality is improved. And a fresh use environment is provided.

Description

Technical Field

[0001] This invention relates to the field of air-purifying fragrances, specifically to a solid, high-efficiency deodorizing fragrance, its preparation method, and its application. Background Technology

[0002] In daily life, removing odors and maintaining fresh air are important concerns. Various odor removal methods exist, including the use of activated charcoal, natural plant extracts, and chemically synthesized deodorizers. Traditional solid deodorizing products, such as activated charcoal, while capable of adsorbing odor molecules, are not ideal in eliminating certain stubborn odors. This invention provides a solid, highly efficient deodorizing fragrance agent, its preparation method, and its application, significantly improving both the odor removal effect and stability. Summary of the Invention

[0003] In order to overcome the above-mentioned technical problems, the present invention aims to provide a solid high-efficiency deodorizing fragrance agent, its preparation method and application, which solves the problem of low odor removal rate of existing deodorizing fragrance agents.

[0004] The objective of this invention can be achieved through the following technical solutions: In a first aspect, this application provides a solid, highly efficient deodorizing fragrance agent, comprising the following parts by weight: 5-15 parts of cucurbit[7]urea, 55-70 parts of fragrance and essential oil, 20-35 parts of mesoporous silica, 5-20 parts of attapulgite, 40-50 parts of α-gypsum powder, 0.05-0.3 parts of sodium tetraborate, 0.01-0.05 parts of anhydrous citric acid, 1-2 parts of glyceryl monostearate, 0.2-0.5 parts of polydimethylsiloxane, 0.05-0.2 parts of antioxidant 264, 15-25 parts of deionized water, 3-10 parts of triterpenoid-adamantane COFs, and 0.1-0.2 parts of hydroxyethyl cellulose.

[0005] The tripterene-adamantane COFs are prepared by the following steps: Step A1: Add fuming nitric acid to a double-necked flask, transfer to a low-temperature reactor, stir at -40℃ for 10-20 min, add triterpenes, heat to -5℃ and stir for 2 h, add acetic anhydride-glacial acetic acid solution and react for 1 h, add glacial acetic acid, filter and wash with anhydrous methanol and deionized water in sequence, dry under vacuum at 100℃ for 1 h to obtain the first intermediate; Step A2: Add the first intermediate and tetrahydrofuran to a single-necked flask equipped with a thermometer, sonicate for 10-20 min, add Raney nickel, ensuring the amount added each time is the same, add hydrazine hydrate in four portions, heat to 75℃ and react for 12 h, filter with a sintered funnel, add the filter cake to N,N-dimethylformamide, filter with diatomaceous earth, add the filtrate to deionized water, filter, sonicate the filter cake with anhydrous ethanol, filter by suction, place in a drying oven and vacuum dry at 70℃ for 2-3 h to obtain the second intermediate; Step A3: Add 1-bromoadamantane and benzene to a three-necked flask equipped with a stirrer, thermometer and reflux condenser, stir for 15 min, add tert-butane chloride and aluminum chloride, heat to 80-90℃ and reflux for 7-8 h, cool and add deionized water, let stand for 30 min, add diethyl ether and stir for 10-20 min, filter, wash the filter cake with chloroform 5-7 times, extract the filter cake with chloroform Soxhlet extract for 8-10 h, place in a drying oven and dry at 75℃ for 8-10 h to obtain the third intermediate; Step A4: Add the third intermediate and dichloromethane to a three-necked flask equipped with a stirrer, stir for 10 min, transfer to a low-temperature reactor, add aluminum trichloride, N,N-dimethylformamide and phosphorus oxychloride at -15°C, stir for 30 min, raise the temperature to -10°C and react for 3 h, raise the temperature to 24-26°C and react for 8-10 h, add ice and hydrochloric acid and stir for 1.5-2 h, extract the organic phase by liquid-liquid extraction, wash with deionized water, saturated sodium bicarbonate solution and saturated brine 5-7 times, dry with anhydrous magnesium sulfate, filter, distill under reduced pressure, recrystallize with 1,4-dioxane heated to 110°C, filter to obtain the fourth intermediate; Step A5: Add the second and fourth intermediates to a mortar and mix for 10-20 min. Transfer to a Pyrex tube and add mesitylene, 1,4-dioxane, and acetic acid solution. Freeze the solvent portion at the bottom of the Pyrex tube with liquid nitrogen, seal with a vacuum flame, and place in a constant temperature oven at 120°C for 72 h. After removal, wash three times with tetrahydrofuran, stand in acetone for 24 h, and dry in a vacuum drying oven at 65°C for 12 h to obtain triptene-adamantane COFs.

[0006] As a further aspect of the present invention: the ratio of fuming nitric acid, the first intermediate, the acetic anhydride-glacial acetic acid mixed solution and glacial acetic acid in step A1 is 8-16 mL: 2-4 g: 30-60 mL: 80-160 mL.

[0007] As a further aspect of the present invention: the ratio of acetic anhydride to glacial acetic acid in the acetic anhydride-glacial acetic acid mixed solution in step A1 is 10-20 mL: 20-40 mL.

[0008] As a further aspect of the present invention: in step A2, the ratio of the first intermediate, tetrahydrofuran, Raney nickel, hydrazine hydrate, N,N-dimethylformamide and deionized water is 0.8156-1.6312g: 180-360mL: 5.9964-11.9928g: 8-16mL: 50-100mL: 50-100mL.

[0009] As a further aspect of the present invention: the ratio of 1-bromoadamantane, benzene, tert-butane chloride, aluminum chloride, deionized water and diethyl ether in step A3 is 6-8g: 60-80mL: 7-9g: 1-3g: 100-300mL: 100-300mL.

[0010] As a further embodiment of the present invention: the ratio of the third intermediate, dichloromethane, aluminum trichloride, N,N-dimethylformamide, phosphorus oxychloride, ice, hydrochloric acid and 1,4-dioxane in step A4 is 2-4g: 50-100mL: 1.3-2.6g: 0.5-1g: 0.65-1.3g: 150-300mL: 50-100mL: 10-20mL.

[0011] As a further aspect of the present invention: the molar concentration of hydrochloric acid in step A4 is 1 mol / L.

[0012] As a further embodiment of the present invention: in step A5, the second intermediate, the fourth intermediate, mesitylene, 1,4-dioxane and acetic acid solution are prepared in the following proportions: 0.05 mmol: 0.025 mmol: 0.7 mL: 0.3 mL: 0.1 mL.

[0013] As a further aspect of the present invention: the molar concentration of the acetic acid solution in step A5 is 6 mol / L.

[0014] Secondly, this application provides a method for preparing a solid high-efficiency deodorizing fragrance agent, comprising the following steps: Step 1: Weigh out 5-15 parts of cucurbit[7]urea, 55-70 parts of fragrance oil, 20-35 parts of mesoporous silica, 5-20 parts of attapulgite, 40-50 parts of α-gypsum powder, 0.05-0.3 parts of sodium tetraborate, 0.01-0.05 parts of anhydrous citric acid, 1-2 parts of glyceryl monostearate, 0.2-0.5 parts of polydimethylsiloxane, 0.05-0.2 parts of antioxidant 264, 15-25 parts of deionized water, 3-10 parts of tripterene-adamantane COFs, and 0.1-0.2 parts of hydroxyethyl cellulose according to the following weight proportions: the oil absorption value of the mesoporous silica is 1.5-3 mL / g, and the specific surface area is 150-450 μm. 2 / g, particle size 3-20 micrometers; the attapulgite has a particle size of 10-33 micrometers and a specific surface area of ​​80-120 m². 2 / g; The CAS number of the polydimethylsiloxane is 9016-00-6; Step 2: Add cucurbit[7]urea to a horizontal powder mixing device and start stirring. The stirring speed is 10-30 r / min, and the temperature is controlled at 25-35℃. Under sealed conditions, spray the liquid fragrance through the liquid spraying device on the cover of the mixing device. The interval between each spray is 10-20 min. The ratio of cucurbit[7]urea powder to fragrance is 1:0.5-1, and the mixing time is 1-2 h. Step 3: Add mesoporous silica to the horizontal powder mixing equipment, and spray the added liquid fragrance while mixing and stirring. The interval between each spray is 5-10 minutes. The stirring speed is controlled at 10-30 r / min, the temperature is controlled at 25-35℃, the ratio of powder to essential oil is 1:1.2-2, and the mixing time is 0.5-1.5h. Step 4: Add attapulgite powder to a horizontal powder mixing equipment and stir at a speed of 10-30 r / min. Control the temperature at 25-35℃ and mix for 0.5-1 h. At the same time, spray liquid fragrance. The ratio of powder to essential oil is 1:0.5-0.8 and the mixing time is 0.5 h. Seal and package, and age at room temperature for 24-48 h to obtain solid fragrance. Step 5: Mix solid fragrance, α-gypsum powder, sodium tetraborate, anhydrous citric acid, glyceryl monostearate, polydimethylsiloxane, antioxidant 264, deionized water, tripterene-adamantane COFs, and hydroxyethyl cellulose evenly, pour into a mold, and after curing, obtain a solid high-efficiency deodorizing fragrance.

[0015] Thirdly, the present invention provides a method for preparing a solid high-efficiency deodorizing fragrance and the application of the prepared solid high-efficiency deodorizing fragrance in the field of air purification fragrance.

[0016] Beneficial effects: The present invention provides a solid high-efficiency deodorizing fragrance agent, which uses cucurbita[7]urea, mesoporous silica and attapulgite as carriers for loading fragrance molecules. Triptene-adamantane COFs adsorb odor molecules in the air onto its surface, reducing the concentration of odor molecules in the air, achieving a comprehensive and effective deodorizing effect, and providing a fresh and pleasant environment.

[0017] A solid, highly efficient deodorizing and fragrance agent was prepared. First, tripterene-adamantane COFs were prepared. A nitro group was introduced into tripterene using fuming nitric acid, and then the nitro group was reduced to an amino group by hydrazine hydrate to obtain a second intermediate. 1-Bromoadamantane underwent Friedel-Crafts alkylation with benzene under aluminum trichloride catalysis, introducing four phenyl groups onto the adamantane skeleton to generate a third intermediate. This third intermediate underwent Vilsmeier-Haack formylation in an aluminum trichloride, N,N-dimethylformamide, and phosphorus oxychloride system, directionally introducing an aldehyde group at the para-position of the phenyl groups to generate a fourth intermediate. The second and fourth intermediates formed a dynamic covalent bond through an imine condensation reaction in a mesitylene / 1,4-dioxane / acetic acid system to obtain tripterene-adamantane COFs. The three-dimensional rigid structure of tripterene can induce local charge distribution, enhancing its interaction with polar / nonpolar molecules. The interaction between the two, the cage-like skeleton of adamantane provides a hydrophobic microenvironment, promotes the adsorption of hydrophobic odor molecules, the regular microporous / mesoporous structure of tripterene-adamantane COFs has a high specific surface area and a narrow pore structure, which can accommodate odor molecules of different molecular sizes, and achieve physical adsorption through van der Waals forces. The porous structure promotes the diffusion and condensation of gas molecules in the pores. Especially under high pressure or low temperature conditions, the capillary effect enhances the adsorption capacity. Cucurbita[7]urea is a macrocyclic supramolecular acceptor. The hydrophobic cavity selectively wraps oily fragrance molecules through van der Waals forces or hydrogen bonds. Its dynamic replacement mechanism can achieve the synergistic effect of "adsorbing odors and releasing fragrance", realize the competitive combination of odor molecules and fragrance molecules in the environment, complete the efficient deodorization and fragrance retention, ensure that the product can release fragrance and deodorization effect evenly during use, and finally achieve continuous air purification and provide a comfortable environmental experience. Detailed Implementation

[0018] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0019] Example 1: This embodiment describes a method for preparing a solid, highly efficient deodorizing and fragrance agent, comprising the following steps: Step A1: Add 8 mL of fuming nitric acid to a double-necked flask, transfer to a low-temperature reactor, stir at -40°C for 10 min, add 2 g of triptene, heat to -5°C and stir for 2 h, add 30 mL of acetic anhydride-glacial acetic acid solution and react for 1 h, add 80 mL of glacial acetic acid, filter and wash successively with anhydrous methanol and deionized water, dry under vacuum at 100°C for 1 h to obtain the first intermediate; Step A2: Add 0.8156g of the first intermediate and 180mL of tetrahydrofuran to a single-necked flask equipped with a thermometer, sonicate for 10min, add 5.9964g of Raney nickel, ensuring the amount added each time is the same, add 8mL of hydrazine hydrate in four portions, heat to 75℃ and react for 12h, filter with a sintered glass funnel, add the filter cake to 50mL of N,N-dimethylformamide, filter with diatomaceous earth, add the filtrate to 50mL of deionized water, filter, sonicate the filter cake with anhydrous ethanol, filter by suction, place in a drying oven and vacuum dry at 70℃ for 2h to obtain the second intermediate; Step A3: Add 6g of 1-bromoadamantane and 60mL of benzene to a three-necked flask equipped with a stirrer, thermometer and reflux condenser, stir for 15min, add 7g of tert-butane chloride and 1g of aluminum chloride, heat to 80℃ and reflux for 7h, cool and add 100mL of deionized water, let stand for 30min, add 100mL of diethyl ether and stir for 10min, filter, wash the filter cake 5 times with chloroform, extract the filter cake with chloroform Soxhlet for 8h, place in a drying oven and dry at 75℃ for 8h to obtain the third intermediate; Step A4: Add 2g of the third intermediate and 50mL of dichloromethane to a three-necked flask equipped with a stirrer, stir for 10min, transfer to a low-temperature reactor, add 1.3g of aluminum trichloride, 0.5g of N,N-dimethylformamide and 0.65g of phosphorus oxychloride at -15℃, stir for 30min, raise the temperature to -10℃ and react for 3h, raise the temperature to 24℃ and react for 8h, add 150mL of ice and 50mL of hydrochloric acid and stir for 1.5h, extract the organic phase by liquid-liquid extraction, wash 5 times with deionized water, saturated sodium bicarbonate solution and saturated brine, dry with anhydrous magnesium sulfate, filter, distill under reduced pressure, recrystallize with 10mL of 1,4-dioxane heated to 110°C, filter to obtain the fourth intermediate; Step A5: Add 0.05 mmol of the second intermediate and 0.025 mmol of the fourth intermediate to a mortar and mix for 10 min. Transfer to a Pyrex tube and add 0.7 mL of mesitylene, 0.3 mL of 1,4-dioxane and 0.1 mL of acetic acid solution. Freeze the solvent portion at the bottom of the Pyrex tube with liquid nitrogen, seal with a vacuum flame, and place in a constant temperature oven at 120 °C for 72 h. After removal, wash three times with tetrahydrofuran, stand in acetone for 24 h, and dry in a vacuum drying oven at 65 °C for 12 h to obtain triptene-adamantane COFs. Step A6: Weigh out 5 parts of cucurbita[7]urea, 55 parts of fragrance oil, 20 parts of mesoporous silica, 5 parts of attapulgite, 40 parts of α-gypsum powder, 0.05 parts of sodium tetraborate, 0.01 parts of anhydrous citric acid, 1 part of glyceryl monostearate, 0.2 parts of polydimethylsiloxane, 0.05 parts of antioxidant 264, 15 parts of deionized water, 3 parts of tripterene-adamantane COFs, and 0.1 parts of hydroxyethyl cellulose according to the following weight proportions, and set aside for later use; wherein, the oil absorption value of the mesoporous silica is 1.5-3 mL / g, and the specific surface area is 150-450 μm. 2 / g, particle size 3-20 micrometers; the attapulgite has a particle size of 10-33 micrometers and a specific surface area of ​​80-120 m². 2 / g; The CAS number of the polydimethylsiloxane is 9016-00-6; Step A7: Add cucurbit[7]urea to the horizontal powder mixing equipment and start stirring. The stirring speed is 10r / min, and the temperature is controlled at 25℃. Under the sealed state, the liquid fragrance is sprayed through the liquid spraying device on the cover of the mixing equipment. The interval between each spray is 10min. The ratio of cucurbit[7]urea powder to fragrance is 1:0.5, and the mixing time is 1h. Step A8: Add mesoporous silica to the horizontal powder mixing equipment, and spray the added liquid fragrance while mixing and stirring. Spray each time at a 5-minute interval, control the stirring speed at 10 r / min, control the temperature at 25℃, the ratio of powder to essential oil is 1:1.2, and the mixing time is 0.5 h. Step A9: Add attapulgite powder to a horizontal powder mixing device and stir at a stirring speed of 10 r / min and a temperature of 25℃ for 0.5 h. At the same time, spray liquid fragrance. The ratio of powder to essential oil is 1:0.5 and the mixing time is 0.5 h. Seal and package, and age at room temperature for 24 h to obtain solid fragrance. Step A10: Mix solid fragrance, α-gypsum powder, sodium tetraborate, anhydrous citric acid, glyceryl monostearate, polydimethylsiloxane, antioxidant 264, deionized water, tripterene-adamantane COFs, and hydroxyethyl cellulose evenly, pour into a mold, and after curing, obtain a solid high-efficiency deodorizing fragrance.

[0020] Example 2: This embodiment describes a method for preparing a solid, highly efficient deodorizing and fragrance agent, comprising the following steps: Step A1: Add 12 mL of fuming nitric acid to a double-necked flask, transfer to a low-temperature reactor, stir at -40 °C for 15 min, add 3 g of triptene, heat to -5 °C and stir for 2 h, add 45 mL of acetic anhydride-glacial acetic acid solution and react for 1 h, add 120 mL of glacial acetic acid, filter and wash with anhydrous methanol and deionized water successively, dry under vacuum at 100 °C for 1 h to obtain the first intermediate; Step A2: Add 1.2234g of the first intermediate and 270mL of tetrahydrofuran to a single-necked flask equipped with a thermometer, sonicate for 15min, add 8.9946g of Raney nickel, ensuring the amount added each time is the same, add 12mL of hydrazine hydrate in four portions, heat to 75℃ and react for 12h, filter with a sintered glass funnel, add the filter cake to 75mL of N,N-dimethylformamide, filter with diatomaceous earth, add the filtrate to 75mL of deionized water, filter, sonicate the filter cake with anhydrous ethanol, filter by suction, place in a drying oven and vacuum dry at 70℃ for 2.5h to obtain the second intermediate; Step A3: Add 7g of 1-bromoadamantane and 70mL of benzene to a three-necked flask equipped with a stirrer, thermometer and reflux condenser, stir for 15min, add 8g of tert-butane chloride and 2g of aluminum chloride, heat to 85℃ and reflux for 7.5h, cool and add 200mL of deionized water, let stand for 30min, add 200mL of diethyl ether and stir for 15min, filter, wash the filter cake with chloroform 6 times, extract the filter cake with chloroform Soxhlet for 9h, place in a drying oven and dry at 75℃ for 9h to obtain the third intermediate; Step A4: Add 3g of the third intermediate and 75mL of dichloromethane to a three-necked flask equipped with a stirrer, stir for 10min, transfer to a low-temperature reactor, add 1.95g of aluminum trichloride, 0.75g of N,N-dimethylformamide and 0.975g of phosphorus oxychloride at -15℃, stir for 30min, raise the temperature to -10℃ and react for 3h, raise the temperature to 25℃ and react for 9h, add 230mL of ice and 75mL of hydrochloric acid and stir for 1.75h, extract the organic phase by liquid-liquid extraction, wash 6 times with deionized water, saturated sodium bicarbonate solution and saturated brine, dry with anhydrous magnesium sulfate, filter, distill under reduced pressure, recrystallize with 15mL of 1,4-dioxane heated to 110°C, filter to obtain the fourth intermediate; Step A5: Add 0.05 mmol of the second intermediate and 0.025 mmol of the fourth intermediate to a mortar and mix for 15 min. Transfer to a Pyrex tube and add 0.7 mL of mesitylene, 0.3 mL of 1,4-dioxane and 0.1 mL of acetic acid solution. Freeze the solvent portion at the bottom of the Pyrex tube with liquid nitrogen, seal with a vacuum flame, and place in a constant temperature oven at 120 °C for 72 h. After removal, wash three times with tetrahydrofuran, stand in acetone for 24 h, and dry in a vacuum drying oven at 65 °C for 12 h to obtain triptene-adamantane COFs. Step A6: Weigh out 7.5 parts of cucurbita[7]urea, 62.5 parts of fragrance oil, 27.5 parts of mesoporous silica, 12.5 parts of attapulgite, 45 parts of α-gypsum powder, 0.175 parts of sodium tetraborate, 0.03 parts of anhydrous citric acid, 1.5 parts of glyceryl monostearate, 0.35 parts of polydimethylsiloxane, 0.125 parts of antioxidant 264, 20 parts of deionized water, 6.5 parts of tripterene-adamantane COFs, and 0.15 parts of hydroxyethyl cellulose according to the following weight proportions, and set aside for later use; wherein, the oil absorption value of the mesoporous silica is 1.5-3 mL / g, and the specific surface area is 150-450 μm. 2 / g, particle size 3-20 micrometers; the attapulgite has a particle size of 10-33 micrometers and a specific surface area of ​​80-120 m². 2 / g; The CAS number of the polydimethylsiloxane is 9016-00-6; Step A7: Add cucurbit[7]urea to the horizontal powder mixing equipment and start stirring. The stirring speed is 20r / min, and the temperature is controlled at 30℃. Under the sealed state, the liquid fragrance is sprayed through the liquid spraying device on the cover of the mixing equipment. The interval between each spray is 15min. The ratio of cucurbit[7]urea powder to fragrance is 1:0.75, and the mixing time is 1.5h. Step A8: Add mesoporous silica to the horizontal powder mixing equipment, and spray the added liquid fragrance while mixing and stirring. Spray each time at a 7-minute interval, control the stirring speed at 20 r / min, control the temperature at 30℃, the ratio of powder to essential oil is 1:1.6, and the mixing time is 1 hour. Step A9: Add attapulgite powder to a horizontal powder mixing device and stir at a stirring speed of 20 r / min and a temperature of 30℃ for 0.75 h. At the same time, spray liquid fragrance. The ratio of powder to essential oil is 1:0.65 and the mixing time is 0.5 h. Seal and package, and age at room temperature for 36 h to obtain solid fragrance. Step A10: Mix solid fragrance, α-gypsum powder, sodium tetraborate, anhydrous citric acid, glyceryl monostearate, polydimethylsiloxane, antioxidant 264, deionized water, tripterene-adamantane COFs, and hydroxyethyl cellulose evenly, pour into a mold, and after curing, obtain a solid high-efficiency deodorizing fragrance.

[0021] Example 3: This embodiment describes a method for preparing a solid, highly efficient deodorizing and fragrance agent, comprising the following steps: Step A1: Add 16 mL of fuming nitric acid to a double-necked flask, transfer it to a low-temperature reactor, stir at -40 °C for 20 min, add 4 g of triptene, heat to -5 °C and stir for 2 h, add 60 mL of acetic anhydride-glacial acetic acid solution and react for 1 h, add 160 mL of glacial acetic acid, filter and wash with anhydrous methanol and deionized water successively, dry under vacuum at 100 °C for 1 h to obtain the first intermediate; Step A2: Add 1.6312g of the first intermediate and 360mL of tetrahydrofuran to a single-necked flask equipped with a thermometer, sonicate for 20min, add 11.9928g of Raney nickel, ensuring the amount added each time is the same, add 16mL of hydrazine hydrate in four portions, heat to 75℃ and react for 12h, filter with a sintered glass funnel, add the filter cake to 100mL of N,N-dimethylformamide, filter with diatomaceous earth, add the filtrate to 100mL of deionized water, filter, sonicate the filter cake with anhydrous ethanol, filter by suction, place in a drying oven and vacuum dry at 70℃ for 3h to obtain the second intermediate; Step A3: Add 8g of 1-bromoadamantane and 80mL of benzene to a three-necked flask equipped with a stirrer, thermometer and reflux condenser, stir for 15min, add 9g of tert-butane chloride and 3g of aluminum chloride, heat to 90℃ and reflux for 8h, cool and add 300mL of deionized water, let stand for 30min, add 300mL of diethyl ether and stir for 20min, filter, wash the filter cake with chloroform 7 times, extract the filter cake with chloroform Soxhlet for 10h, place in a drying oven and dry at 75℃ for 10h to obtain the third intermediate; Step A4: Add 4g of the third intermediate and 100mL of dichloromethane to a three-necked flask equipped with a stirrer, stir for 10min, transfer to a low-temperature reactor, add 2.6g of aluminum trichloride, 1g of N,N-dimethylformamide and 1.3g of phosphorus oxychloride at -15℃, stir for 30min, raise the temperature to -10℃ and react for 3h, raise the temperature to 26℃ and react for 10h, add 300mL of ice and 100mL of hydrochloric acid and stir for 2h, extract the organic phase by liquid-liquid extraction, wash 7 times with deionized water, saturated sodium bicarbonate solution and saturated brine, dry with anhydrous magnesium sulfate, filter, distill under reduced pressure, recrystallize with 20mL of 1,4-dioxane heated to 110°C, filter to obtain the fourth intermediate; Step A5: Add 0.05 mmol of the second intermediate and 0.025 mmol of the fourth intermediate to a mortar and mix for 20 min. Transfer to a Pyrex tube and add 0.7 mL of mesitylene, 0.3 mL of 1,4-dioxane and 0.1 mL of acetic acid solution. Freeze the solvent portion at the bottom of the Pyrex tube with liquid nitrogen, seal with a vacuum flame, and place in a constant temperature oven at 120 °C for 72 h. After removal, wash three times with tetrahydrofuran, stand in acetone for 24 h, and dry in a vacuum drying oven at 65 °C for 12 h to obtain triptene-adamantane COFs. Step A6: Weigh out 15 parts of cucurbita[7]urea, 70 parts of fragrance oil, 35 parts of mesoporous silica, 20 parts of attapulgite, 50 parts of α-gypsum powder, 0.3 parts of sodium tetraborate, 0.05 parts of anhydrous citric acid, 2 parts of glyceryl monostearate, 0.5 parts of polydimethylsiloxane, 0.2 parts of antioxidant 264, 25 parts of deionized water, 10 parts of tripterene-adamantane COFs, and 0.2 parts of hydroxyethyl cellulose according to the following weight proportions, and set aside for later use; wherein, the oil absorption value of the mesoporous silica is 1.5-3 mL / g, and the specific surface area is 150-450 μm. 2 / g, particle size 3-20 micrometers; the attapulgite has a particle size of 10-33 micrometers and a specific surface area of ​​80-120 m². 2 / g; The CAS number of the polydimethylsiloxane is 9016-00-6; Step A7: Add cucurbit[7]urea to the horizontal powder mixing equipment and start stirring. The stirring speed is 30r / min, and the temperature is controlled at 35℃. Under the sealed state, the liquid fragrance is sprayed through the liquid spraying device on the cover of the mixing equipment. The interval between each spray is 20min. The ratio of cucurbit[7]urea powder to fragrance is 1:1, and the mixing time is 1h. Step A8: Add mesoporous silica to the horizontal powder mixing equipment, and spray the added liquid fragrance while mixing and stirring. Spray each time at a 10-minute interval, control the stirring speed at 30 r / min, control the temperature at 35℃, the ratio of powder to essential oil is 1:2, and the mixing time is 1.5h. Step A9: Add attapulgite powder to a horizontal powder mixing equipment and stir at a stirring speed of 30 r / min and a temperature of 35℃ for 1 hour. At the same time, spray liquid fragrance. The ratio of powder to essential oil is 1:0.8 and the mixing time is 0.5 hours. Seal and package the product and age it at room temperature for 48 hours to obtain solid fragrance. Step A10: Mix solid fragrance, α-gypsum powder, sodium tetraborate, anhydrous citric acid, glyceryl monostearate, polydimethylsiloxane, antioxidant 264, deionized water, tripterene-adamantane COFs, and hydroxyethyl cellulose evenly, pour into a mold, and after curing, obtain a solid high-efficiency deodorizing fragrance.

[0022] Comparative Example 1: This comparative example illustrates a method for preparing a solid, highly efficient deodorizing and fragrance agent, comprising the following steps: Step A1: Add 16 mL of fuming nitric acid to a double-necked flask, transfer it to a low-temperature reactor, stir at -40 °C for 20 min, add 4 g of triptene, heat to -5 °C and stir for 2 h, add 60 mL of acetic anhydride-glacial acetic acid solution and react for 1 h, add 160 mL of glacial acetic acid, filter and wash with anhydrous methanol and deionized water successively, dry under vacuum at 100 °C for 1 h to obtain the first intermediate; Step A2: Add 1.6312g of the first intermediate and 360mL of tetrahydrofuran to a single-necked flask equipped with a thermometer, sonicate for 20min, add 11.9928g of Raney nickel, ensuring the amount added each time is the same, add 16mL of hydrazine hydrate in four portions, heat to 75℃ and react for 12h, filter with a sintered glass funnel, add the filter cake to 100mL of N,N-dimethylformamide, filter with diatomaceous earth, add the filtrate to 100mL of deionized water, filter, sonicate the filter cake with anhydrous ethanol, filter by suction, place in a drying oven and vacuum dry at 70℃ for 3h to obtain the second intermediate; Step A3: Add 0.05 mmol of the second intermediate and 0.025 mmol of terephthalaldehyde to a mortar and mix for 20 min. Transfer to a Pyrex tube, add 0.7 mL of mesitylene, 0.3 mL of 1,4-dioxane and 0.1 mL of acetic acid solution. Freeze the solvent portion at the bottom of the Pyrex tube with liquid nitrogen, seal with a vacuum flame, and place in a constant temperature oven at 120 °C for 72 h. After removal, wash three times with tetrahydrofuran, stand in acetone for 24 h, and dry in a vacuum drying oven at 65 °C for 12 h to obtain triptene COFs. Step A4: Weigh out 15 parts of cucurbita[7]urea, 70 parts of fragrance oil, 35 parts of mesoporous silica, 20 parts of attapulgite, 50 parts of α-gypsum powder, 0.3 parts of sodium tetraborate, 0.05 parts of anhydrous citric acid, 2 parts of glyceryl monostearate, 0.5 parts of polydimethylsiloxane, 0.2 parts of antioxidant 264, 25 parts of deionized water, 10 parts of triterpenes COFs, and 0.2 parts of hydroxyethyl cellulose according to the following weight proportions, and set aside; wherein, the oil absorption value of the mesoporous silica is 1.5-3 mL / g, and the specific surface area is 150-450 μm. 2 / g, particle size 3-20 micrometers; the attapulgite has a particle size of 10-33 micrometers and a specific surface area of ​​80-120 m². 2 / g; The CAS number of the polydimethylsiloxane is 9016-00-6; Step A5: Add cucurbit[7]urea to the horizontal powder mixing equipment and start stirring. The stirring speed is 30r / min, and the temperature is controlled at 35℃. Under the sealed state, the liquid fragrance is sprayed through the liquid spraying device on the cover of the mixing equipment. The interval between each spray is 20min. The ratio of cucurbit[7]urea powder to fragrance is 1:1, and the mixing time is 1h. Step A6: Add mesoporous silica to the horizontal powder mixing equipment, and spray the added liquid fragrance while mixing and stirring. Spray each time at 10-minute intervals, control the stirring speed at 30 r / min, control the temperature at 35℃, the ratio of powder to essential oil is 1:2, and the mixing time is 1.5 hours. Step A7: Add attapulgite powder to a horizontal powder mixing device and stir at a stirring speed of 30 r / min and a temperature of 35℃ for 1 hour. At the same time, spray liquid fragrance. The ratio of powder to essential oil is 1:0.8 and the mixing time is 0.5 hours. Seal and package the product and age it at room temperature for 48 hours to obtain solid fragrance. Step A8: Mix solid fragrance, α-gypsum powder, sodium tetraborate, anhydrous citric acid, glyceryl monostearate, polydimethylsiloxane, antioxidant 264, deionized water, triterpenes COFs, and hydroxyethyl cellulose evenly, pour into a mold, and after curing, obtain a solid high-efficiency deodorizing fragrance.

[0023] Comparative Example 2: This comparative example illustrates a method for preparing a solid, highly efficient deodorizing and fragrance agent, comprising the following steps: Step A1: Add 8g of 1-bromoadamantane and 80mL of benzene to a three-necked flask equipped with a stirrer, thermometer and reflux condenser, stir for 15min, add 9g of tert-butane chloride and 3g of aluminum chloride, heat to 90℃ and reflux for 8h, cool and add 300mL of deionized water, let stand for 30min, add 300mL of diethyl ether and stir for 20min, filter, wash the filter cake with chloroform 7 times, extract the filter cake with chloroform Soxhlet for 10h, place in a drying oven and dry at 75℃ for 10h to obtain the first intermediate; Step A2: Add 4g of the third intermediate and 100mL of dichloromethane to a three-necked flask equipped with a stirrer, stir for 10min, transfer to a low-temperature reactor, add 2.6g of aluminum trichloride, 1g of N,N-dimethylformamide and 1.3g of phosphorus oxychloride at -15℃, stir for 30min, raise the temperature to -10℃ and react for 3h, raise the temperature to 26℃ and react for 10h, add 300mL of ice and 100mL of hydrochloric acid and stir for 2h, extract the organic phase by liquid-liquid extraction, wash 7 times with deionized water, saturated sodium bicarbonate solution and saturated brine, dry with anhydrous magnesium sulfate, filter, distill under reduced pressure, recrystallize with 20mL of 1,4-dioxane heated to 110°C, filter to obtain the second intermediate; Step A3: Add 0.05 mmol of p-phenylenediamine and 0.025 mmol of the second intermediate to a mortar and mix for 20 min. Transfer to a Pyrex tube and add 0.7 mL of mesitylene, 0.3 mL of 1,4-dioxane and 0.1 mL of acetic acid solution. Freeze the solvent portion at the bottom of the Pyrex tube with liquid nitrogen, seal with a vacuum flame, and place in a constant temperature oven at 120 °C for 72 h. After removal, wash three times with tetrahydrofuran, stand in acetone for 24 h, and dry in a vacuum drying oven at 65 °C for 12 h to obtain adamantane COFs. Step A4: Weigh out 15 parts of cucurbita[7]urea, 70 parts of fragrance oil, 35 parts of mesoporous silica, 20 parts of attapulgite, 50 parts of α-gypsum powder, 0.3 parts of sodium tetraborate, 0.05 parts of anhydrous citric acid, 2 parts of glyceryl monostearate, 0.5 parts of polydimethylsiloxane, 0.2 parts of antioxidant 264, 25 parts of deionized water, 10 parts of adamantane COFs, and 0.2 parts of hydroxyethyl cellulose according to the following weight proportions, and set aside for later use; wherein, the oil absorption value of the mesoporous silica is 1.5-3 mL / g, and the specific surface area is 150-450 μm. 2 / g, particle size 3-20 micrometers; the attapulgite has a particle size of 10-33 micrometers and a specific surface area of ​​80-120 m². 2 / g; The CAS number of the polydimethylsiloxane is 9016-00-6; Step A5: Add cucurbit[7]urea to the horizontal powder mixing equipment and start stirring. The stirring speed is 30r / min, and the temperature is controlled at 35℃. Under the sealed state, the liquid fragrance is sprayed through the liquid spraying device on the cover of the mixing equipment. The interval between each spray is 20min. The ratio of cucurbit[7]urea powder to fragrance is 1:1, and the mixing time is 1h. Step A6: Add mesoporous silica to the horizontal powder mixing equipment, and spray the added liquid fragrance while mixing and stirring. Spray each time at 10-minute intervals, control the stirring speed at 30 r / min, control the temperature at 35℃, the ratio of powder to essential oil is 1:2, and the mixing time is 1.5 hours. Step A7: Add attapulgite powder to a horizontal powder mixing device and stir at a stirring speed of 30 r / min and a temperature of 35℃ for 1 hour. At the same time, spray liquid fragrance. The ratio of powder to essential oil is 1:0.8 and the mixing time is 0.5 hours. Seal and package the product and age it at room temperature for 48 hours to obtain solid fragrance. Step A8: Mix solid fragrance, α-gypsum powder, sodium tetraborate, anhydrous citric acid, glyceryl monostearate, polydimethylsiloxane, antioxidant 264, deionized water, adamantane COFs, and hydroxyethyl cellulose evenly, pour into a mold, and after curing, obtain a solid high-efficiency deodorizing fragrance.

[0024] Comparative Example 3: This comparative example illustrates a method for preparing a solid, highly efficient deodorizing and fragrance agent, comprising the following steps: Step A1: Weigh out 15 parts of cucurbita[7]urea, 70 parts of fragrance oil, 35 parts of mesoporous silica, 20 parts of attapulgite, 50 parts of α-gypsum powder, 0.3 parts of sodium tetraborate, 0.05 parts of anhydrous citric acid, 2 parts of glyceryl monostearate, 0.5 parts of polydimethylsiloxane, 0.2 parts of antioxidant 264, 25 parts of deionized water, and 0.2 parts of hydroxyethyl cellulose according to the following weight proportions: the oil absorption value of the mesoporous silica is 1.5-3 mL / g, and the specific surface area is 150-450 μm. 2 / g, particle size 3-20 micrometers; the attapulgite has a particle size of 10-33 micrometers and a specific surface area of ​​80-120 m². 2 / g; The CAS number of the polydimethylsiloxane is 9016-00-6; Step A2: Add cucurbit[7]urea to the horizontal powder mixing equipment and start stirring. The stirring speed is 30r / min, and the temperature is controlled at 35℃. Under the sealed state, the liquid fragrance is sprayed through the liquid spraying device on the cover of the mixing equipment. The interval between each spray is 20min. The ratio of cucurbit[7]urea powder to fragrance is 1:1, and the mixing time is 1h. Step A3: Add mesoporous silica to the horizontal powder mixing equipment, and spray the added liquid fragrance while mixing and stirring. Spray each time at a 10-minute interval, control the stirring speed at 30 r / min, control the temperature at 35℃, the ratio of powder to essential oil is 1:2, and the mixing time is 1.5h. Step A4: Add attapulgite powder to a horizontal powder mixing device and stir at a stirring speed of 30 r / min and a temperature of 35℃ for 1 hour. At the same time, spray liquid fragrance. The ratio of powder to essential oil is 1:0.8 and the mixing time is 0.5 hours. Seal and package the product and age it at room temperature for 48 hours to obtain solid fragrance. Step A5: Mix solid fragrance, α-gypsum powder, sodium tetraborate, anhydrous citric acid, glyceryl monostearate, polydimethylsiloxane, antioxidant 264, deionized water, and hydroxyethyl cellulose evenly, pour into a mold, and after curing, obtain a solid high-efficiency deodorizing fragrance.

[0025] Performance testing The solid high-efficiency deodorizing fragrances of Examples 1-3 and Comparative Examples 1-3 were tested according to the "QB / T 2761-2006 Method for Determining the Purification Effect of Indoor Air Purification Products" to obtain the odor removal rate.

[0026] Referring to the table above, based on the comparison between Examples 1-3 and Comparative Examples 1-3, it can be seen that the solid high-efficiency deodorizing fragrance prepared by adding triterpenoid-adamantane COFs and cucurbit[7]urea has excellent odor removal ability; Based on the comparison between Example 3 and Comparative Example 1, it can be seen that the hydrogen sulfide removal rate of the solid high-efficiency deodorizing fragrance prepared by adding tripterene-adamantane COFs and cucurbit[7]urea is greater than that of the solid high-efficiency deodorizing fragrance prepared by adding tripterene COFs and cucurbit[7]urea. This indicates that the solid high-efficiency deodorizing fragrance prepared by adding tripterene-adamantane COFs and cucurbit[7]urea has excellent odor removal ability. Based on the comparison between Example 3 and Comparative Example 2, it can be seen that the hydrogen sulfide removal rate of the solid high-efficiency deodorizing fragrance prepared by adding tripterene-adamantane COFs and cucurbit[7]urea is greater than that of the solid high-efficiency deodorizing fragrance prepared by adding adamantane COFs and cucurbit[7]urea. This indicates that the solid high-efficiency deodorizing fragrance prepared by adding tripterene-adamantane COFs and cucurbit[7]urea has excellent odor removal ability. Based on the comparison between Example 3 and Comparative Example 3, it can be seen that the hydrogen sulfide removal rate of the solid high-efficiency deodorizing fragrance prepared by adding tripterene-adamantane COFs and cucurbit[7]urea is greater than that of the solid high-efficiency deodorizing fragrance prepared by adding cucurbit[7]urea. This indicates that the solid high-efficiency deodorizing fragrance prepared by adding tripterene-adamantane COFs and cucurbit[7]urea has excellent odor removal ability.

[0027] In the description of this specification, references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0028] The above description is merely an example and illustration of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described or use similar methods to replace them, as long as they do not deviate from the invention or exceed the scope defined in this application, they should all fall within the protection scope of the present invention.

Claims

1. A solid, highly efficient deodorizing and fragrance agent, characterized in that, Includes the following components by weight: 5-15 parts of cucurbit[7]urea, 55-70 parts of fragrance and essential oil, 20-35 parts of mesoporous silica, 5-20 parts of attapulgite, 40-50 parts of α-gypsum powder, 0.05-0.3 parts of sodium tetraborate, 0.01-0.05 parts of anhydrous citric acid, 1-2 parts of glyceryl monostearate, 0.2-0.5 parts of polydimethylsiloxane, 0.05-0.2 parts of antioxidant 264, 15-25 parts of deionized water, 3-10 parts of triterpenoid-adamantane COFs, and 0.1-0.2 parts of hydroxyethyl cellulose; The tripterene-adamantane COFs are prepared by the following steps: Step A1: Stir the fuming nitric acid, add triterpenes and stir, add acetic anhydride-glacial acetic acid solution to react, add glacial acetic acid, dry, and obtain the first intermediate; Step A2: The first intermediate and tetrahydrofuran are sonicated, reacted with Raney nickel and hydrazine hydrate, and dried to obtain the second intermediate; Step A3: Stir 1-bromoadamantane and benzene, add tert-butane chloride and aluminum chloride and reflux, add diethyl ether and stir, dry to obtain the third intermediate; Step A4: Stir the third intermediate and dichloromethane, add aluminum trichloride, N,N-dimethylformamide and phosphorus oxychloride, stir, react, add ice and hydrochloric acid and stir to obtain the fourth intermediate; Step A5: Mix the second and fourth intermediates, add mesitylene, 1,4-dioxane and acetic acid solution, freeze, seal, stand, wash, stand, and dry to obtain triterpenoid-adamantane COFs.

2. The solid high-efficiency deodorizing and fragrance agent according to claim 1, characterized in that, In step A1, the ratio of fuming nitric acid, the first intermediate, the acetic anhydride-glacial acetic acid mixed solution, and glacial acetic acid is 8-16 mL: 2-4 g: 30-60 mL: 80-160 mL; the ratio of acetic anhydride to glacial acetic acid in the acetic anhydride-glacial acetic acid mixed solution is 10-20 mL: 20-40 mL.

3. The solid high-efficiency deodorizing and fragrance agent according to claim 1, characterized in that, In step A2, the ratio of the first intermediate, tetrahydrofuran, Raney nickel, hydrazine hydrate, N,N-dimethylformamide, and deionized water is 0.8156-1.6312g: 180-360mL: 5.9964-11.9928g: 8-16mL: 50-100mL: 50-100mL.

4. The solid high-efficiency deodorizing and fragrance agent according to claim 1, characterized in that, The ratio of 1-bromoadamantane, benzene, tert-butane chloride, aluminum chloride, deionized water, and diethyl ether in step A3 is 6-8g: 60-80mL: 7-9g: 1-3g: 100-300mL: 100-300mL.

5. The solid high-efficiency deodorizing and fragrance agent according to claim 1, characterized in that, In step A4, the ratio of the third intermediate, dichloromethane, aluminum trichloride, N,N-dimethylformamide, phosphorus oxychloride, ice, hydrochloric acid, and 1,4-dioxane is 2-4g: 50-100mL: 1.3-2.6g: 0.5-1g: 0.65-1.3g: 150-300mL: 50-100mL: 10-20mL; the molar concentration of the hydrochloric acid is 1mol / L.

6. The solid high-efficiency deodorizing and fragrance agent according to claim 1, characterized in that, In step A5, the second intermediate, the fourth intermediate, mesitylene, 1,4-dioxane, and acetic acid solution are prepared in the following proportions: 0.05 mmol: 0.025 mmol: 0.7 mL: 0.3 mL: 0.1 mL; the molar concentration of the acetic acid solution is 6 mol / L.

7. A method for preparing a solid, highly efficient deodorizing fragrance, characterized in that, The preparation of the solid high-efficiency deodorizing fragrance as described in any one of claims 1-6 includes the following steps: Step 1: Weigh out 5-15 parts of cucurbit[7]urea, 55-70 parts of fragrance oil, 20-35 parts of mesoporous silica, 5-20 parts of attapulgite, 40-50 parts of α-gypsum powder, 0.05-0.3 parts of sodium tetraborate, 0.01-0.05 parts of anhydrous citric acid, 1-2 parts of glyceryl monostearate, 0.2-0.5 parts of polydimethylsiloxane, 0.05-0.2 parts of antioxidant 264, 15-25 parts of deionized water, 3-10 parts of tripterene-adamantane COFs, and 0.1-0.2 parts of hydroxyethyl cellulose according to the following weight proportions, and set aside. Step 2: Add cucurbit[7]urea to a horizontal powder mixing device and start stirring. The stirring speed is 10-30 r / min, and the temperature is controlled at 25-35℃. Under sealed conditions, spray the liquid fragrance through the liquid spraying device on the cover of the mixing device. The interval between each spray is 10-20 min. The ratio of cucurbit[7]urea powder to fragrance is 1:0.5-1, and the mixing time is 1-2 h. Step 3: Add mesoporous silica to the horizontal powder mixing equipment, and spray the added liquid fragrance while mixing and stirring. The interval between each spray is 5-10 minutes. The stirring speed is controlled at 10-30 r / min, the temperature is controlled at 25-35℃, the ratio of powder to essential oil is 1:1.2-2, and the mixing time is 0.5-1.5h. Step 4: Add attapulgite powder to a horizontal powder mixing equipment and stir at a speed of 10-30 r / min. Control the temperature at 25-35℃ and mix for 0.5-1 h. At the same time, spray liquid fragrance. The ratio of powder to essential oil is 1:0.5-0.8 and the mixing time is 0.5 h. Seal and package, and age at room temperature for 24-48 h to obtain solid fragrance. Step 5: Mix solid fragrance, α-gypsum powder, sodium tetraborate, anhydrous citric acid, glyceryl monostearate, polydimethylsiloxane, antioxidant 264, deionized water, tripterene-adamantane COFs, and hydroxyethyl cellulose evenly, pour into a mold, and after curing, obtain a solid high-efficiency deodorizing fragrance.

8. The method for preparing a solid high-efficiency deodorizing and fragrance agent according to claim 7, characterized in that, The mesoporous silica has an oil absorption value of 1.5-3 mL / g and a specific surface area of ​​150-450 m². 2 / g, particle size 3-20 micrometers; the attapulgite has a particle size of 10-33 micrometers and a specific surface area of ​​80-120 m². 2 / g; the CAS number of the polydimethylsiloxane is 9016-00-6.

9. The application of a solid high-efficiency deodorizing fragrance according to any one of claims 1-6 or a solid high-efficiency deodorizing fragrance prepared by the preparation method of the solid high-efficiency deodorizing fragrance according to claim 7, characterized in that, The solid high-efficiency deodorizing fragrance is used in the field of air purification fragrance.

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