A smoke generating agent for anti-hygroscopic cigarettes and its preparation method and application

Abstract

The invention discloses an anti-hygroscopic cigarette smoke agent and a preparation method and application thereof. The anti-hygroscopic cigarette smoke agent is composed of a cigarette smoke agent encapsulated inside a hydrophobic microcapsule shell. The preparation process is as follows: dissolving the cigarette smoke agent, an inorganic acid and a surfactant in water to obtain a solution A, and dissolving the surfactant in a non-polar organic solvent to obtain a solution B; under stirring conditions, adding solution A to solution B for emulsification to obtain an emulsion; dropping a microcapsule shell precursor material into the emulsion, stirring the reaction, and subjecting the obtained product to a surface hydrophobic treatment. The preparation method is simple, low in cost, mild in conditions, and conducive to large-scale production. The prepared anti-hygroscopic cigarette smoke agent is added to a heat-not-burn cigarette, and has good anti-hygroscopic performance without affecting normal smoking.

Description

Technical Field

[0001] The invention relates to a smoking material, in particular to a smoking agent for cigarettes with an anti-hygroscopic function, and also to a preparation method and application thereof, belonging to the technical field of new smoking materials. Background Art

[0002] Due to the continuous advancement of global tobacco control, the pressure on traditional cigarettes is increasing, and new tobacco products have gradually become a research hotspot, among which heat-not-burn cigarettes have received particular attention. Heat-not-burn cigarettes are made of tobacco components as the main raw material to make cigarette cartridges, and then the tobacco is heated (300-400℃) to make the tobacco volatilize smoke containing tobacco components in a non-burning state to meet the smoking requirements of consumers. In order to make the cigarette produce enough smoke when smoking, 10-30% of the smoke-generating agent needs to be added during the production process of the cigarette cartridge, and the main component of the smoke-generating agent is glycerol (glycerin). Although glycerol has a good smoking effect and does not have a negative impact on the taste of cigarettes, it has strong hygroscopicity, so it has an adverse effect on the production and storage of heat-not-burn cigarette cartridges. In order to solve this practical problem faced by the production and application of heat-not-burn cigarettes, Chinese patent (CN210043197U) proposed to adjust the moisture content of heat-not-burn cigarettes by a composite filter rod containing tobacco materials, Chinese patent (CN110881684A) proposed to use functional materials to support smoking materials, and Chinese patent (CN108451054A) reported that the hygroscopicity of the cigarette cartridge core material was reduced by coating a hydrophobic material on the tobacco sheet. Although the solution proposed by Chinese patent (CN210043197U) can reduce the moisture content of smoke, it cannot solve the problem of hygroscopicity of the cigarette cartridge, and the use of functional materials to support smoking agents proposed by Chinese patent (CN110881684A) also has the problem of adsorption capacity. As for the coating of hydrophobic materials in the cigarette production process, there are still certain disadvantages. Summary of the invention

[0003] In order to solve the problems that the use of a large amount of smoke-generating agent in heat-not-burn cigarette cartridges leads to strong hygroscopicity of cigarettes and is not conducive to storage, the first purpose of the present invention is to provide a smoke-generating agent for anti-hygroscopic cigarettes. The anti-hygroscopic smoke-generating agent uses a hydrophobic treated inorganic shell capsule to encapsulate the smoke-generating agent, which not only reduces the direct contact of the smoke-generating agent with the solvent and the air, but also does not affect the normal smoking effect, thereby solving the high hygroscopicity problem of heat-not-burn cigarettes caused by the smoke-generating agent.

[0004] The second object of the present invention is to provide a method for preparing the anti-hygroscopic cigarette smoking agent under mild conditions, simple process and low cost.

[0005] The third object of the present invention is to provide an application of a smoke-generating agent for anti-hygroscopic cigarettes in heat-not-burn cigarettes. The use of the smoke-generating agent for anti-hygroscopic cigarettes can effectively solve the technical problem that existing heat-not-burn cigarettes have strong hygroscopicity and are difficult to preserve due to the use of smoke-generating agents.

[0006] In order to achieve the above technical purpose, the present invention provides an anti-hygroscopic smoking agent for cigarettes, which is composed of the smoking agent for cigarettes encapsulated inside a hydrophobic microcapsule shell.

[0007] The existing smoking agents for cigarettes are mainly small molecule polyol compounds, which have strong hygroscopicity and are easy to volatilize during storage. The anti-hygroscopic smoking agent for cigarettes provided by the present invention can not only well prevent the smoking agent from absorbing moisture, but also prevent the volatilization loss of the smoking agent during storage. At the same time, the use of hydrophobic microcapsule shells to encapsulate the smoking agent does not affect its normal smoking effect, which well solves the technical problem that the smoking agent for cigarettes has strong hygroscopicity and is difficult to store.

[0008] As a preferred solution, the hydrophobic microcapsule shell is composed of an inorganic oxide shell and a hydrophobic layer modified on its surface.

[0009] As a preferred solution, the inorganic oxide shell is composed of at least one inorganic material selected from titanium dioxide, silicon dioxide and aluminum oxide. These materials have good stability and safety, meet the requirements of cigarette additives, and are low-cost, pollution-free and easy to obtain.

[0010] As a preferred solution, the hydrophobic layer is composed of at least one hydrophobic material selected from polysulfone, polyarylsulfone and polyethersulfone. These polymer materials have good hydrophobicity and thermal stability, and are modified on the surface of the inorganic oxide material to further improve the hydrophobicity of the microcapsule shell.

[0011] As a preferred solution, the smoke generating agent for cigarettes is at least one of glycerol, propylene glycol, ethylene glycol, butylene glycol, and butanetriol. More preferably, the smoke generating agent for cigarettes is at least one of glycerol, propylene glycol, and butylene glycol.

[0012] As a preferred solution, the mass ratio of the smoking agent to the hydrophobic microcapsule shell is 9:1 to 1:1. The more preferred mass ratio is 9:1 to 7:1.

[0013] The present invention also provides a method for preparing a smoke-generating agent for anti-hygroscopic cigarettes, which comprises the following steps:

[0014] 1) dissolving a smoking agent, an inorganic acid and a surfactant in water to obtain a solution A, and dissolving the surfactant in a non-polar organic solvent to obtain a solution B;

[0015] 2) adding solution A to solution B under stirring to emulsify and obtain an emulsion;

[0016] 3) adding a microcapsule shell precursor material dropwise to the emulsion, stirring for reaction, and subjecting the obtained reaction product to solid-liquid separation, washing, and drying to obtain a solid particle material;

[0017] 4) adding the solid particulate material to the solution containing the hydrophobic material, stirring for reaction, filtering for separation, and drying to obtain the product.

[0018] As a preferred solution, the volume ratio of the smoke generating agent to water and the non-polar organic solvent is 1-10:1:10-50. The preferred ratio is conducive to capsule formation. If the ratio is not well controlled, it is easy to cause low efficiency of smoke generating agent coating or difficulty in forming microcapsule structure.

[0019] As a preferred solution, the non-polar organic solvent is n-hexane and / or cyclohexane. These non-polar solvents are insoluble in water and are conducive to the subsequent formation of an emulsion.

[0020] As a preferred solution, the inorganic acid is at least one of hydrochloric acid, sulfuric acid and nitric acid. The inorganic acid mainly plays a catalytic role, catalyzing the hydrolysis of the precursor to generate silicon dioxide, titanium dioxide and aluminum oxide.

[0021] As a preferred solution, the concentration of the inorganic acid in solution A is 0.1-6.5M.

[0022] As a preferred solution, the surfactant is at least one of sodium dodecyl sulfonate, sodium dodecyl sulfate, Span 80, Tween 80, and hexadecyl trimethyl ammonium bromide. The surfactant mainly promotes the formation of tiny droplets or microemulsion droplets of the smoke-generating agent in the two-phase system, and then deposits the inorganic oxide generated by the hydrolysis of the precursor on the surface of the droplet to coat it to obtain a (micro) capsule.

[0023] As a preferred solution, the concentration of the surfactant in solution A is 0.01-0.1 g / mL; the concentration of the surfactant in solution B is 0.005-0.05 g / mL.

[0024] As a preferred solution, the microcapsule shell precursor material comprises at least one of n-butyl titanate, titanium tetrachloride, tetramethoxysilane, tetraethoxysilane, aluminum tert-butoxide, and aluminum sec-butoxide. The microcapsule shell precursor material can be added in the form of a stock solution, or dissolved in a non-polar organic solvent for addition.

[0025] As a preferred solution, under the temperature condition of 25-35° C., the microcapsule shell precursor material is added dropwise to the emulsion and stirred for reaction. After the addition is completed, the stirring reaction is continued for 18-30 hours.

[0026] As a preferred solution, the concentration of the hydrophobic material in the solution containing the hydrophobic material is 0.1-0.5 g / mL. The solution containing the hydrophobic material is obtained by dissolving at least one hydrophobic material selected from polysulfone, polyarylsulfone and polyethersulfone in dichloromethane and / or DMF.

[0027] As a preferred solution, in step 4), the stirring reaction time is 0.5 to 3 hours.

[0028] The specific preparation method of the anti-hygroscopic smoking agent for cigarettes provided by the present invention is as follows: dissolving the smoking agent for cigarettes in water containing a certain amount of inorganic acid and surfactant at 25-70°C, and then cooling to 15-30°C to obtain solution A; then dissolving a certain amount of surfactant in a non-polar solvent to obtain solution B; then adding solution A to solution B, stirring and emulsifying at room temperature and a certain speed to obtain a stable emulsion; dropping a microcapsule shell precursor material into the emulsion at 25-35°C; after the addition, stirring and reacting for 24 hours continuously, filtering, washing solid particles with corresponding non-polar solvents and ethanol, drying, and then adding the obtained solid particles to dichloromethane and / or dimethylformamide dissolved with a hydrophobic polymer material, stirring for 0.5-3 hours, filtering and separating, and finally drying to obtain the anti-hygroscopic smoking agent for cigarettes.

[0029] The present invention also provides an application of a smoke generating agent for anti-hygroscopic cigarettes, which is applied to heat-not-burn cigarettes.

[0030] Compared with the prior art, the technical solution of the present invention has the following beneficial effects:

[0031] 1) Adding the anti-hygroscopic cigarette smoke agent capsule to the main material (sheet or tobacco) of the heat-not-burn cigarette bomb, and exposing it to a 60% humidity environment, the water absorption of the anti-hygroscopic cigarette smoke agent does not exceed 3% of the amount of the anti-hygroscopic cigarette smoke agent, and the anti-hygroscopic cigarette smoke agent capsule can extend the storage time compared with the general cigarette smoke agent, and can smoke normally at high temperature without affecting the atomization effect of the smoke agent.

[0032] 2) The preparation process of the smoke-generating agent for anti-hygroscopic cigarettes of the present invention is simple, the raw materials are readily available, the conditions are mild, and it is conducive to industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 SEM image of smoke generator used to prevent hygroscopic smoke;

[0034] Figure 2 This is a comparison chart of thermogravimetric analysis of smoke agents for anti-hygroscopic cigarettes and smoke agents for ordinary cigarettes. DETAILED DESCRIPTION

[0035] The present invention is further described below by way of examples, the purpose of which is to provide a better understanding of the research content of the present invention rather than to limit the protection scope of the present invention.

[0036] Example 1

[0037] 5mL of glycerol and 0.05g of sodium dodecyl sulfate were added to 2.2mL of an aqueous solution with a hydrochloric acid concentration of 2.5M, stirred and dissolved at 60°C, and cooled to 25°C to obtain liquid A. 0.3g of Span 80 was dissolved in 30mL of cyclohexane to obtain liquid B. Liquid A was added to liquid B, emulsified at 3000RPM for 1 minute to obtain an oil-in-water emulsion, heated to 35°C, and 5mL of ethyl orthosilicate stock solution was slowly added to the emulsion. After the addition, the reaction was stirred continuously at 35°C for 24 hours, filtered, and the filter residue was washed twice with cyclohexane, washed once with ethanol, and dried at 40°C for 12 hours. The obtained solid particles were added to a polysulfone dimethylformamide solution with a concentration of 0.5g / mL, stirred for 1.5 hours, filtered, washed twice with water, and dried at 80°C for 12 hours to obtain the anti-hygroscopic smoke-generating agent.

[0038] The morphology of the smoke-generating agent for anti-hygroscopic cigarettes is shown in Figure 1 As shown in the figure, it can be seen that it is a micron-sized spherical particle with a relatively uniform size.

[0039] Thermogravimetric analysis of smoke-generating agent and glycerol for anti-hygroscopic cigarettes Figure 2 As shown, from Figure 2 It can be seen that there is no significant difference in the atomization temperature between the microcapsule smoke agent and the pure smoke agent substance, so the means of encapsulating the effective ingredients of the smoke agent will not affect the atomization effect of the smoke agent itself.

[0040] Example 2

[0041] 4 mL of glycerol, 1 mL of propylene glycol and 0.01 g of sodium dodecyl sulfate were added to 1 mL of an aqueous solution with a hydrochloric acid concentration of 0.5 M, stirred and dissolved at 70 ° C, and then cooled to 15 ° C to obtain liquid A. 0.1 g of Tween 80 was dissolved in 10 mL of cyclohexane to obtain liquid B. Liquid A was added to liquid B and cooled to 15 ° C, emulsified at 1000 RPM for 5 minutes to obtain an oil-in-water emulsion, heated to 25 ° C, and 3.75 mL of methyl orthosilicate stock solution was slowly added to the emulsion. After the addition, the reaction was stirred continuously at 25 ° C for 24 hours, filtered, and the filter residue was washed twice with cyclohexane, washed once with ethanol, and dried at 40 ° C for 12 hours. The obtained solid particles were added to a polysulfone dimethylformamide solution with a concentration of 0.3 g / mL, stirred for 2 hours, filtered, washed twice with water, and dried at 80 ° C for 12 hours to obtain the anti-hygroscopic smoke-generating agent.

[0042] Example 3

[0043] 8mL of glycerol, 2mL of butanediol and 1g of sodium dodecyl sulfate were added to 1mL of an aqueous solution with a hydrochloric acid concentration of 1M, and the solution A was obtained after stirring and dissolving at 25°C. 2.5g of sodium dodecyl sulfonate was dissolved in 50mL of cyclohexane to obtain solution B. Solution A was added to solution B, and emulsified at 10000RPM for 1 minute at room temperature to obtain an oil-in-water emulsion, which was heated to 30°C and 3.75mL of ethyl orthosilicate stock solution was slowly added to the emulsion. After the addition, the reaction was stirred continuously at 25°C for 24 hours, filtered, and the filter residue was washed twice with cyclohexane, washed once with ethanol, and dried at 40°C for 12 hours. The obtained solid particles were added to a polysulfone dimethylformamide solution with a concentration of 0.5g / mL, stirred for 1 hour, filtered, washed twice with water, and dried at 80°C for 12 hours to obtain the anti-hygroscopic smoke-generating agent.

[0044] The smoke-generating agent for anti-hygroscopic cigarette prepared in the above embodiment was mixed with tobacco flakes at a ratio of 20%, and then exposed to air in a 60% humidity environment for 15 days. The hygroscopic performance of the smoke-generating agent was evaluated by weighing the sample mass. The experimental results are shown in the following table:

[0045]

Claims

1. A smoke-generating agent for anti-hygroscopic cigarettes, characterized in that: The invention is composed of a smoke generating agent encapsulated in a hydrophobic microcapsule shell; the hydrophobic microcapsule shell is composed of an inorganic oxide shell and a hydrophobic layer modified on its surface; the inorganic oxide shell is composed of at least one inorganic material selected from titanium dioxide, silicon dioxide and aluminum oxide; the hydrophobic layer is composed of at least one hydrophobic material selected from polysulfone, polyarylsulfone and polyethersulfone; The anti-hygroscopic cigarette smoke generating agent is obtained by the following preparation method: comprising the following steps: 1) dissolving a smoking agent, an inorganic acid and a surfactant in water to obtain a solution A, and dissolving the surfactant in a non-polar organic solvent to obtain a solution B; 2) Under stirring conditions, adding solution A to solution B for emulsification to obtain an emulsion; 3) adding a microcapsule shell precursor material dropwise to the emulsion, stirring for reaction, and subjecting the obtained reaction product to solid-liquid separation, washing, and drying to obtain a solid particle material; 4) Add the solid particulate material to the solution containing the hydrophobic material, stir to react, filter to separate, and dry to obtain.

2. The smoke-generating agent for preventing hygroscopic cigarettes according to claim 1, characterized in that: The smoke generating agent for cigarette is at least one of glycerol, propylene glycol, ethylene glycol, butylene glycol and butanetriol.

3. The smoke-generating agent for preventing hygroscopic cigarettes according to any one of claims 1 to 2, characterized in that: The mass ratio of the smoke generating agent for cigarettes to the hydrophobic microcapsule shell is 9:1 to 1:

1.

4. The smoke-generating agent for preventing hygroscopic cigarettes according to claim 1, characterized in that: The volume ratio of the smoke generating agent to water and the non-polar organic solvent is 1-10:1:10-50.

5. The smoke-generating agent for preventing hygroscopic cigarettes according to claim 4, characterized in that: The non-polar organic solvent is n-hexane and / or cyclohexane.

6. The smoke-generating agent for preventing hygroscopic cigarettes according to claim 1, characterized in that: The inorganic acid is at least one of hydrochloric acid, sulfuric acid and nitric acid.

7. The smoke-generating agent for preventing hygroscopic cigarettes according to claim 1 or 6, characterized in that: The concentration of the inorganic acid in solution A is 0.1-6.5M.

8. The smoke-generating agent for preventing hygroscopic cigarettes according to claim 1, characterized in that: The surfactant is at least one of sodium dodecyl sulfonate, sodium dodecyl sulfate, Span 80, Tween 80, and hexadecyltrimethylammonium bromide.

9. The smoke-generating agent for preventing hygroscopic cigarettes according to claim 1 or 8, characterized in that: The concentration of the surfactant in solution A is 0.01-0.1 g / mL; the concentration of the surfactant in solution B is 0.005-0.05 g / mL.

10. The smoke-generating agent for preventing hygroscopic cigarettes according to claim 1, characterized in that: The microcapsule shell precursor material comprises at least one of n-butyl titanate, titanium tetrachloride, tetramethoxysilane, tetraethoxysilane, aluminum tert-butoxide, and aluminum sec-butoxide.

11. The smoke-generating agent for preventing hygroscopic cigarettes according to claim 1, characterized in that: Under the temperature condition of 25-35°C, the microcapsule shell precursor material is added dropwise to the emulsion and stirred for reaction. After the addition is completed, the stirring reaction is continued for 18-30 hours.

12. The anti-hygroscopic smoke generating agent according to claim 1, characterized in that: The concentration of the hydrophobic material in the solution containing the hydrophobic material is 0.1-0.5 g / mL.

13. The smoke-generating agent for preventing hygroscopic cigarettes according to claim 12, characterized in that: The solution containing the hydrophobic material is obtained by dissolving at least one hydrophobic material selected from polysulfone, polyarylsulfone and polyethersulfone in dichloromethane and / or DMF.

14. The smoke-generating agent for preventing hygroscopic cigarettes according to claim 1, characterized in that: In step 4), the stirring reaction time is 0.5 to 3 hours.

15. The use of a smoke generating agent for anti-hygroscopic cigarettes according to any one of claims 1 to 14, characterized in that: Applied to heat-not-burn cigarettes.

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