A high-capacity phytic acid-based porous moisture-retaining material, preparation method and application thereof
By preparing high-capacity phytic acid-based porous moisture-retaining materials, the problem of moisture loss in cigarettes is solved, stable moisture retention of tobacco and improvement of sensory quality are achieved, and it is suitable for the field of tobacco moisture preservation.
Patent Information
- Application Number
- CN202310694513.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2023-06-13
- Publication Date
- 2025-09-23
- Estimated Expiration
- 2043-06-13
AI Technical Summary
How to effectively prevent moisture loss in stored cigarettes without affecting the intrinsic quality of tobacco, improve the intrinsic quality of cigarettes, and realize industrial production, solve the problem of cigarettes drying out easily in the dry climate in northern my country, and improve the humidity of smoke and storage capacity.
Benzoic acid and phytic acid are mixed and a high-capacity phytic acid-based porous moisturizing material is prepared through carboxylic anhydride copolymerization reaction to form a two-dimensional layered structure, which increases the specific surface area and water vapor adsorption capacity. It is then added to tobacco to maintain a stable moisture content.
It maintains stability above 200°C, significantly improves the balanced moisture content and sensory quality of tobacco, increases water vapor adsorption by more than 3.6 times, and improves smoke humidity and storage capacity.
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Figure CN116769173B_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the application field of tobacco industry, and particularly relates to a high-capacity phytic acid-based porous moisture-retaining material, a preparation method and application thereof. Background Art
[0002] Humectant is an additive added to tobacco during cigarette manufacturing to maintain a stable moisture content. It maintains tobacco's toughness, improves its processing resistance, stabilizes the moisture content of cut tobacco, reduces sensory stimulation during smoking, and maintains a comfortable draw.
[0003] When the moisture content of cigarettes is too high, the air permeability will be reduced when the cigarette is burned, the combustion ability will be poor, the aroma will be weak, the strength will be insufficient, and it will be easy to mold, which is not conducive to long-term preservation and affects its storage capacity and characteristics; when the moisture content is too low, the tobacco will easily become too dry, which will cause it to break and there will be empty heads in the cigarettes.
[0004] Northern my country has low annual rainfall and a perennially dry climate, making tobacco drying out a particularly prominent problem. Cigarette smoke is commonly associated with dryness, acridity, throat irritation, a lack of sweetness, and excessive phlegm production. Developing tobacco humectants that effectively prevent moisture loss during storage, improve the quality of cigarettes, and mitigate health risks without compromising their inherent quality, while also achieving industrialized production, remains a pressing technical challenge. Summary of the Invention
[0005] In order to solve the above technical problems, the present invention provides a high-capacity phytic acid-based porous moisture-retaining material, the preparation method of which comprises the following steps:
[0006] Benzoic acid and phytic acid are mixed in a molar ratio of 1:50 to 10:1, and an organic solvent is added and stirred until uniformly mixed, and then an acidic solution catalyst is added, wherein the concentration of the acidic solution is 3 mol / L to 9 mol / L, and the mixture is kept at 40 to 150° C. for 1 to 7 days, refluxed with water for 5 to 20 hours, and washed with toluene, chloroform, acetone, water and tetrahydrofuran in sequence and vacuum dried to obtain a high-capacity phytic acid-based porous moisturizing material; the organic solvent is a mixture of toluene, dioxane and n-butanol, and the volume ratio of toluene, dioxane and n-butanol is 1:1:0.1 to 0.1:0.1:1; the acidic solution is one of p-toluenesulfonic acid or concentrated sulfuric acid; the structure of the high-capacity phytic acid-based porous moisturizing material is as follows:
[0007] The molecular weight of the high-capacity phytic acid-based porous moisturizing material is 500-5000.
[0008] Furthermore, the particle size of the high-capacity phytic acid-based porous moisturizing material is 80-150 nm, and the specific surface area is 10-200 m 2·g -1 .
[0009] The present invention also provides an application of a high-capacity phytic acid-based porous moisture-retaining material in the field of tobacco moisture retention.
[0010] Compared with the prior art, the advantages of the present invention are:
[0011] The present invention uses benzoic acid as a unit, and makes it undergo carboxylic anhydride copolymerization reaction with phytic acid molecules to prepare a phytic acid-based porous moisturizing material. The moisturizing material obtained by the present invention has high stability and can maintain stability at 200°C and above; the moisturizing material has a two-dimensional layered structure and is composed of 80-150 nanometer particles stacked together; the nitrogen adsorption experiment shows that the specific surface area of the phytic acid-based porous moisturizing material is increased by 19 times or more compared with the original phytic acid molecule; the water vapor adsorption experiment shows that compared with phytic acid, the moisturizing material of the present invention has a significantly reduced stacking structure density, so the water vapor adsorption amount is increased by 3.6 times or more compared with the phytic acid molecule. The tobacco moisturizing experiment shows that under the conditions of 25°C and 30% RH, the moisturizing material of the present invention and propylene glycol are added to the tobacco at a mass of 5 / 1000 respectively. The results show that under the same conditions, the 48-hour equilibrium moisture content of the tobacco with the moisturizing material of the present invention added is significantly higher than that of the traditional propylene glycol moisturizer, achieving the best moisturizing performance currently available. BRIEF DESCRIPTION OF THE DRAWINGS
[0012] The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.
[0013] Figure 1 This is a comparison chart of infrared spectra of the phytic acid-based porous moisturizing material prepared in Example 1 and phytic acid;
[0014] Figure 2 This is the thermogravimetric analysis curve of the phytic acid-based porous moisture-retaining material prepared in Example 1;
[0015] Figure 3 This is an SEM image of the phytic acid-based porous moisture-retaining material prepared in Example 1;
[0016] Figure 4 This is a comparative X-ray diffraction curve of the phytic acid-based porous moisturizing material, phytic acid, and benzoic acid prepared in Example 1;
[0017] Figure 5 This is a comparison chart of the N2 adsorption curves of the phytic acid-based porous moisture-retaining material and phytic acid prepared in Example 1;
[0018] Figure 6 This is a comparison diagram of the pore distribution curves of the phytic acid-based porous moisturizing material prepared in Example 1 and phytic acid;
[0019] Figure 7This is a comparison chart of the water vapor adsorption curves of the phytic acid-based porous moisture retaining material prepared in Example 1 and phytic acid. DETAILED DESCRIPTION
[0020] Example 1
[0021] 1 mol of benzoic acid and 2 mol of phytic acid were added to 1500 ml of a mixed solvent of toluene, dioxane and n-butanol (volume ratio of 5:1:1), stirred for half an hour until uniformly mixed, and then 100 ml of p-toluenesulfonic acid (3 mol / L) catalyst was added. The mixture was first heated at 45° C. for reaction for 6 hours, then heated at 90° C. for reflux for 18 hours, and refluxed with water for 10 hours, then the reaction was stopped, the system was cooled to room temperature, filtered to remove salt, and then dried in a vacuum oven at 60° C. for 24 hours to obtain a phytic acid-based porous moisturizing material 1.
[0022] The phytic acid-based porous moisturizing material 1 was tested for its moisturizing performance. C3F blank tobacco from Qujing, Yunnan was selected. Phytic acid-based porous moisturizing material 1 and propylene glycol were added to the blank tobacco at a mass ratio of 5‰ to prepare tobacco samples. Under the same conditions, a 48-hour equilibrium moisture content test was conducted. The results showed that the moisture content of the tobacco added with phytic acid-based porous moisturizing material 1 was 24.26% higher than that of the tobacco added with propylene glycol.
[0023] The structural formula of the moisturizing material 1 obtained in Example 1 is as follows:
[0024] ,
[0025] The molecular weight is 2200-3000.
[0026] Example 2
[0027] 1 mol of benzoic acid and 3 mol of phytic acid were added to a 2000 ml mixture of toluene, dioxane, and n-butanol (volume ratio 5:1:1). The mixture was stirred for half an hour until uniformly mixed. Subsequently, 100 ml of concentrated sulfuric acid (4 mol / L) was slowly added to the mixture. The mixed solution in the single-necked flask was heated to 55°C for 8 hours, then heated to 100°C and refluxed for 16 hours. After reflux with water for 8 hours, the reaction was stopped, the system was cooled to room temperature, and filtered to remove salt. The resulting product was dried in a vacuum oven at 65°C for 25 hours to obtain phytic acid-based porous moisture-retaining material 2.
[0028] The moisture retention test measurement method is the same as that in Example 1 and is not described in detail here. The 48-hour equilibrium moisture content of tobacco cuts containing phytic acid porous moisture retention material 2 at a mass ratio of 5‰ increased by 20.09% compared to conventional moisture retention agents. The moisture retention material 2 has the following structural formula:
[0029] ,
[0030] The molecular weight is 1700-2500.
[0031] Example 3
[0032] 1 mol of benzoic acid and 4 mol of phytic acid were added to a 2500 ml mixture of toluene, dioxane, and n-butanol (volume ratio 5:1:1). The mixture was stirred for half an hour until uniformly mixed. Subsequently, 100 ml of p-toluenesulfonic acid (5 mol / L) catalyst was slowly added to the mixture. The mixed solution in the single-necked flask was heated to 60°C for 9 hours, then heated to 95°C and refluxed for 18 hours. After reflux with water for 10 hours, the reaction was stopped, the system was cooled to room temperature, and filtered to remove salt. The resulting product was dried in a vacuum oven at 70°C for 24 hours to obtain phytic acid-based porous moisture-retaining material 3.
[0033] The moisture retention test measurement method is the same as that in Example 1 and is not described in detail here. The 48-hour equilibrium moisture content of tobacco cuts containing phytic acid porous moisture retention material 3 at a mass ratio of 5‰ was 15.33% higher than that of conventional moisture retention agents. The moisture retention material 3 has the following structural formula:
[0034] ,
[0035] The molecular weight is 2000-2900.
[0036] Example 4
[0037] 1 mol of benzoic acid and 5 mol of phytic acid were added to a 3000 ml mixture of toluene, dioxane, and n-butanol (volume ratio 5:1:1). The mixture was stirred for half an hour until uniformly mixed. Subsequently, 100 ml of p-toluenesulfonic acid (6 mol / L) catalyst was slowly added to the mixture. The mixed solution in the single-necked flask was heated to 65°C for 12 hours, then heated to 120°C and refluxed for 18 hours. After reflux with water for 10 hours, the reaction was stopped, the system was cooled to room temperature, and filtered to remove salt. The resulting product was dried in a vacuum oven at 60°C for 24 hours to obtain phytic acid-based porous moisture-retaining material 4.
[0038] The moisture retention test measurement method is the same as that in Example 1 and is not described in detail here. The 48-hour equilibrium moisture content of tobacco cuts containing phytic acid porous moisture retention material 4 at a mass ratio of 5‰ was 12.80% higher than that of conventional moisture retention agents. The moisture retention material 4 has the following structural formula:
[0039] ,
[0040] The molecular weight is 3200-4100.
[0041] Example 5
[0042] 1 mol of benzoic acid and 8 mol of phytic acid were added to a 4500 ml mixture of toluene, dioxane, and n-butanol (volume ratio 5:1:1). The mixture was stirred for half an hour until uniformly mixed. Subsequently, 100 ml of p-toluenesulfonic acid (9 mol / L) catalyst was slowly added to the mixture. The mixed solution in the single-necked flask was heated to 65°C for 12 hours, then heated to 140°C and refluxed for 18 hours. After reflux with water for 10 hours, the reaction was stopped, the system was cooled to room temperature, and filtered to remove salt. The resulting product was dried in a vacuum oven at 60°C for 24 hours to obtain phytic acid-based porous moisture-retaining material 5.
[0043] The moisture retention test measurement method is the same as that in Example 1 and is not described in detail here. The 48-hour equilibrium moisture content of tobacco cuts containing the phytic acid porous moisture retention material 5 at a mass ratio of 5‰ is 8.92% higher than that of the traditional moisture retention agent. The moisture retention material 5 has the following structural formula:
[0044] ,
[0045] The molecular weight is 3000-4300.
[0046] Example 6
[0047] 1 mol of benzoic acid and 0.8 mol of phytic acid were added to a mixture of 900 ml of toluene, dioxane, and n-butanol (volume ratio 5:1:1). The mixture was stirred for half an hour until uniformly mixed. Subsequently, 36 ml of p-toluenesulfonic acid (5 mol / L) catalyst was slowly added to the mixture. The mixed solution in the single-necked flask was heated to 75°C for 24 hours, then heated to 140°C and refluxed for 36 hours. After reflux with water for 10 hours, the reaction was stopped, the system was cooled to room temperature, and filtered to remove salt. The resulting product was dried in a vacuum oven at 60°C for 24 hours. The resulting sample was phytic acid-based porous moisturizing material 6.
[0048] The moisture retention test measurement method is the same as that in Example 1 and is not described in detail here. The 48-hour equilibrium moisture content of tobacco cuts containing phytic acid porous moisture retention material 6 at a mass ratio of 5‰ increased by 4.62% compared to conventional moisture retention agents. The moisture retention material 6 has the following structure:
[0049] ,
[0050] The molecular weight is 1300-1800.
[0051] Structural characterization and performance analysis
[0052] Figure 1 This is a comparison of the infrared spectra of the phytic acid-based porous moisturizing material and phytic acid prepared in Example 1; at 1556 and 814 cm -1 The characteristic peaks of C=C skeleton vibration and CH out-of-plane bending vibration of benzene ring appeared.-1 The -OH stretching vibration corresponding to the position is significantly reduced, 1515cm -1 The C=O stretching absorption in the carboxylic acid dimer corresponding to the position is significantly enhanced. The appearance of the above characteristic peaks clearly proves the occurrence of the anhydride reaction, indicating that the preparation of the phytic acid-based porous moisturizing material is successful.
[0053] Figure 2 This is the thermogravimetric analysis curve of the phytic acid-based porous moisturizing material prepared in Example 1. Thermogravimetric analysis (TGA) shows that the first weight loss occurs above 200°C, when the oligomeric components in the material begin to decompose slightly. After heating to 800°C, almost no residue remains, indicating that the phytic acid-based porous moisturizing material is free of any inorganic substances or catalyst residues. This heating weight loss process demonstrates that the phytic acid-based porous moisturizing material has excellent thermal stability and is free of harmful substances and impurities.
[0054] Figure 3 The SEM image of the phytic acid-based porous moisturizing material prepared in Example 1; The phytic acid-based porous moisturizing material is composed of phytic acid and benzoic acid, and rigid benzoic acid is built into the main skeleton structure of the phytic acid-based porous moisturizing material, which weakens the interlayer hydrogen bond interaction of phytic acid and forms a porous phytic acid-based moisturizing material through phenyl support. The porous phytic acid-based moisturizing material has a bulk morphology of irregular particle accumulation, and the particle size is between 80 and 150 nanometers, so that the molecules are converted from a stacked structure to a dispersed state and can be evenly dispersed, while forming a large number of uniform and open voids, so that the surface area is significantly improved. The phytic acid material has a crystalline bulk structure, and its particle size is between 1 and 5 microns. Therefore, compared with the phytic acid molecule, a large number of pores are formed inside the moisturizing material 1, which is conducive to the flow of particles, and the particle size is much smaller than the phytic acid material. Since the particle size is significantly reduced, the material specific surface area is greatly increased.
[0055] Figure 4 The X-ray diffraction comparison curves of phytic acid, benzoic acid and phytic acid-based porous moisturizing material prepared in Example 1; the components and crystal structures of phytic acid, benzoic acid and phytic acid-based porous moisturizing material 1 were characterized by X-ray diffraction (XRD) experiments. The phytic acid molecule itself is an amorphous material, and the benzoic acid molecule shows a series of characteristic signal peaks between 7 and 40°. After the phytic acid and benzoic acid molecules undergo glycoside polycondensation reaction, the phytic acid-based porous moisturizing material 1 shows diffraction peaks at 8°, 16°, and 24° respectively. This equidistant and periodic characteristic diffraction peak proves that the phytic acid-based porous moisturizing material 1 is a two-dimensional layered material, which will facilitate the flow of particles inside the material and help improve the performance of the material itself. The disappearance of the benzoic acid characteristic peak proves that the benzoic acid molecules have reacted, further indicating the successful preparation of the phytic acid-based porous moisturizing material.
[0056] Figure 5Comparison of the N2 adsorption curves of the phytic acid-based porous moisturizing material 1 and phytic acid prepared in Example 1; N2 adsorption-desorption experiments were conducted at 77K, and the BET specific surface area of the phytic acid sample was only 2m 2 g -1 The BET specific surface area of the phytic acid-based porous moisturizing material 1 is 39m 2 g -1 This is because the polymerization of benzoic acid and phytic acid molecules disrupts the previously tightly packed structure of the phytic acid molecules. This creates a large number of open voids, and the particle size of Humectant 1 is smaller than that of phytic acid particles. This significantly increases the surface area of Humectant 1 and the nitrogen adsorption capacity of phytic acid. Compared to the nitrogen adsorption capacity of phytic acid at 2 cubic centimeters per gram, Humectant 1 has a nitrogen adsorption capacity of 180 cubic centimeters per gram.
[0057] Figure 6 This is a comparison chart of the pore distribution curves of the phytic acid-based porous moisturizing material 1 and phytic acid prepared in Example 1; the pore distribution curves of the samples were calculated by the DFT method. The pore size of the phytic acid molecules used in the present invention is mainly distributed in the range of ~2.5nm, and the pore size is relatively uniform, mainly due to the close stacking of phytic acid molecules. Phytic acid-based porous moisturizing material 1 has holes in the range of 5-35nm, and the pore size range is 5-35nm. This increased pore volume and pore size fully proves that the moisturizing material has produced a large number of pores and is supported, forming a larger pore volume and a wide pore size range, which can increase the contact area and accommodation volume between the phytic acid-based porous moisturizing material and water molecules.
[0058] Figure 7 This is a comparison of the water vapor adsorption curves of phytic acid-based porous moisturizing material 1 and phytic acid prepared in Example 1. The phytic acid sample, due to the dense molecular packing formed by hydrogen bonding between molecules, has a water vapor adsorption capacity of 5 cubic centimeters per gram. However, after the anhydride polymerization reaction, the water vapor adsorption capacity of phytic acid-based porous moisturizing material 1 increases to 18 cubic centimeters per gram.
[0059] Table 1 shows the moisture retention performance test results of the phytic acid-based porous moisturizing material 1 prepared in Example 1 added to blank C3F tobacco from Qujing, Yunnan. Under constant temperature of 25°C and humidity of 30% RH, the equilibrium moisture content of the tobacco changed over time. Tobacco samples were prepared by adding the phytic acid-based porous moisturizing material 1 to the blank tobacco at a mass ratio of 5‰. Under the same conditions, equilibrium moisture content testing showed that the equilibrium moisture content of the tobacco added with the phytic acid-based porous moisturizing material 1 was higher than that of the tobacco added with propylene glycol, demonstrating that the phytic acid-based porous moisturizing material significantly outperforms traditional moisturizing agents in terms of moisture retention.
[0060] Table 2 shows the comparison of the moisture retention performance of the phytic acid-based porous moisture retention materials prepared in Examples 1 to 6, which were added to Yunnan Qujing C3F blank tobacco at a mass ratio of 5‰ for 48 hours. Among them, the moisture retention material obtained in Example 1 has the best performance.
[0061] Table 3 is a smoking comparison table of the phytic acid-based porous moisturizing materials prepared in Examples 1 to 6 and propylene glycol added to blank C3F tobacco from Qujing, Yunnan at a mass ratio of 2‰. The smoking results were scored based on aroma quality, aroma quantity, concentration, strength, miscellaneous gases, irritation, and aftertaste. It can be seen that Example 1 has the best sensory quality, with an elegant and penetrating aroma, a distinct sweet fragrance, a rich and sufficient aroma, moderate concentration and strength, flowing, smooth and delicate smoke, better taste characteristics, less irritation to the oral and nasal cavity, and a clean and comfortable aftertaste. The comprehensive smoking performance indicators of the moisturizing material obtained in Example 1 of the present invention are better than those of the traditional propylene glycol moisturizing agent material, and a significant improvement has been made compared with the prior art.
[0062] In summary, the phytic acid-based porous moisturizing material provided by the present invention has a clear structure, good stability, excellent adsorption performance, and good recyclability. The reaction raw materials, proportions, and processes of all embodiments of the present invention are different. Among them, Example 1 obtains the best moisturizing properties such as nitrogen and water vapor adsorption, and achieves significantly improved technical effects compared with existing propylene glycol. This shows that the optimal performance of the moisturizing agent obtained by the present invention is achieved by the synergistic effect of raw materials, proportions, and processes.
[0063] Table 1 Comparison of the equilibrium moisture content of the moisturizing material obtained in Example 1 and propylene glycol in tobacco over time
[0064]
[0065] Table 2 Comparison of the 48h moisturizing performance of the phytic acid-based porous moisturizing materials prepared in Examples 1 to 6
[0066]
[0067] Table 3 Comparison of smoking results of tobacco cuts with equal proportions of the phytic acid-based porous moisturizing materials prepared in Examples 1 to 6 and propylene glycol (the following values represent scores; the higher the value, the better the smoking result)
[0068]
Claims
1. A high-capacity phytic acid-based porous moisture-retaining material, characterized in that: Its preparation method comprises the following steps: Benzoic acid and phytic acid are mixed in a molar ratio of 1:50 to 10:1, and an organic solvent is added and stirred until uniformly mixed, and then an acidic solution catalyst is added, wherein the concentration of the acidic solution is 3 mol / L to 9 mol / L, and the mixture is kept at 40 to 150° C. for 1 to 7 days, refluxed with water for 5 to 20 hours, and washed with toluene, chloroform, acetone, water and tetrahydrofuran in sequence and vacuum dried to obtain a high-capacity phytic acid-based porous moisturizing material; the organic solvent is a mixture of toluene, dioxane and n-butanol, and the volume ratio of toluene, dioxane and n-butanol is 1:1:0.1 to 0.1:0.1:1; the acidic solution is one of p-toluenesulfonic acid or concentrated sulfuric acid; the structure of the high-capacity phytic acid-based porous moisturizing material is as follows:
2. A high-capacity phytic acid-based porous moisturizing material according to claim 1, characterized in that: The particle size of the high-capacity phytic acid-based porous moisturizing material is 80-150nm, and the specific surface area is 10-200m 2 / g.
3. Use of the high-capacity phytic acid-based porous moisture-retaining material according to claim 1 or 2 in the field of tobacco moisture retention.