A composite smoke agent containing porous materials and polyols and its application

Abstract

The present invention relates to a composite system smoke agent containing porous materials and polyols and its application, wherein the composite system smoke agent comprises a composite polyol and a porous material dispersed in the composite polyol, and the composite polyol is loaded in the pores of the porous material. The smoke agent can be well adapted to various types of heated cigarettes, has the characteristics of large smoke release, good smoke release uniformity, stable chemical properties, high release transfer rate, etc., and effectively improves the intrinsic quality and smoking sensory evaluation of heated cigarettes.

Description

Technical Field

[0001] The present invention belongs to the technical field of tobacco materials, and relates to a smoke generator and its application, in particular to a composite system smoke generator containing a porous material and a polyol and its application. Background Art

[0002] Heated tobacco products are a new type of tobacco product with good development prospects and high consumer recognition. It mainly volatilizes flavor substances and nicotine in tobacco sheets by heating and provides them to smokers. Due to the characteristic of heating without combustion, the amount of smoke released by heated tobacco products themselves is smaller than that of traditional cigarettes. Therefore, it is often necessary to additionally add a smoke generator to the tobacco core of heated tobacco products to improve their smoke generation effect.

[0003] The amount of smoke in heated tobacco products is an important index for sensory evaluation, which directly affects the smoking quality of heated tobacco products and has a great impact on promoting the release of aroma and improving the satisfaction of strength. The smoke release amount of heated tobacco products usually cannot be continuously maintained in a stable state, and generally shows a trend of first increasing and then gradually decreasing. This is because the heat source used in heated tobacco devices is usually fixed. When a heated tobacco product is inserted into the device, as the heating time prolongs, the smoke generator around the heat source will gradually decrease, so the smoke release amount of the heated tobacco product will gradually decay.

[0004] Currently, glycerol is often used as the main smoke generator in commercialized heated tobacco products at home and abroad, and the usage amount of glycerol is relatively large, and the usage proportion is generally 14%-22% of the mass of tobacco sheets. Although glycerol is widely used as a common smoke generator and has good application effects, there are still some adverse factors when using glycerol in heated tobacco products. First, glycerol has strong hygroscopicity, which makes heated tobacco products prone to moisture absorption in the air, affecting quality and taste, and is not conducive to production and storage. Second, glycerol has unstable chemical properties at high temperatures and is prone to react with itself, between molecules, and with inherent substances in tobacco to generate reaction products such as glyceraldehyde, diglycerol, and monoacetin, which will also have a certain impact on the smoking quality of heated tobacco products. Finally, due to the high boiling point of glycerol, a relatively high heating temperature is required to volatilize and release it. Therefore, the release and transfer rate of glycerol in heated tobacco products is low, and the residue rate is high, resulting in low effective utilization rate of glycerol.

[0005] In view of the smoke release characteristics of heated tobacco products and some disadvantages of glycerol use, it is necessary to develop a new type of smoke generator for heated tobacco products in order to obtain better smoking quality. Summary of the Invention

[0006] Aiming at the deficiencies of the prior art, the purpose of the present invention is to provide a smoke generator and its application, specifically to provide a composite system smoke generator containing porous materials and polyols and its application. This smoke generator can be better adapted to various heated cigarettes, and has the characteristics of large smoke release amount, good smoke release uniformity, stable chemical properties, high release transfer rate, etc., effectively improving the internal quality and suction sensory evaluation of heated cigarettes.

[0007] To achieve the purpose of this invention, the following technical solutions are adopted:

[0008] In the first aspect, the present invention provides a composite system smoke generator containing porous materials and polyols. The composite system smoke generator includes composite polyols and porous materials dispersed in the composite polyols, and the pores of the porous materials are loaded with composite polyols.

[0009] The main components of the composite system smoke generator involved in the present invention are composite polyols and porous materials dispersed in the composite polyols, and other auxiliary components such as dispersants can also be optionally included.

[0010] In the present invention, the composite system smoke generator is prepared by a preparation method including the following steps:

[0011] (1) Heat-activate the porous material, then perform vacuum treatment in a dry environment and introduce an inert gas to obtain a porous material filled with the inert gas;

[0012] (2) Mix the porous material filled with the inert gas with a composite polyol solution, heat and stir, then mix and stir with a dispersant, and cool to obtain the composite system smoke generator containing porous materials and polyols.

[0013] The present invention uses the above specific preparation process to prepare the composite system smoke generator. First, a series of pretreatments need to be performed on the porous material. The purpose of heat activation is to exhaust the moisture in the pores of the porous material. The purpose of further performing vacuum treatment and introducing an inert gas is to ensure a dry environment in the pores. The porous material after this pretreatment can make polyol molecules enter and be loaded in its pores easily and stably, ultimately promoting the stable and long-term release of smoke, and improving the internal quality and suction sensory evaluation of heated cigarettes. Moreover, the composite system smoke generator involved in the present invention can be prepared by the above specific preparation process, and this preparation process is simple in operation and easy for industrial production.

[0014] Preferably, the temperature of the heating activation is 200-400°C, such as 200°C, 220°C, 250°C, 280°C, 300°C, 320°C, 350°C, 380°C, 400°C, etc.; the time is 1-5h, such as 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, etc. Other specific point values ​​within the above numerical ranges can be selected, and they will not be repeated here one by one.

[0015] When the above-mentioned process parameters are selected for the heating activation, the final product has a better effect in improving the intrinsic quality of the heated cigarette and the sensory evaluation of smoking.

[0016] Preferably, the inert gas includes any one of helium, nitrogen, carbon dioxide or argon, or a combination of at least two of them.

[0017] Preferably, the heating and stirring is carried out at 40-120°C (e.g., 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, etc.) for 10-240min (e.g., 10min, 30min, 50min, 70min, 100min, 130min, 150min, 200min, 220min, 240min, etc.). Other specific point values ​​within the above numerical ranges can be selected and will not be described one by one here.

[0018] Preferably, the dispersant includes an inorganic dispersant and / or an organic dispersant.

[0019] The dispersant used in the present invention can be an inorganic dispersant, including silicate and alkali metal phosphate dispersants; it can also be an organic dispersant, including anionic dispersants such as alkyl aryl phosphates and alkyl benzene sulfonates, cationic dispersants such as amine salts, quaternary ammonium salts, pyridinium salts, and non-ionic dispersants such as fatty alcohol polyoxyethylene ethers, polyoxyethylene alkylamines, and polyol alkylates, and it can also be a polymer dispersant such as polycarboxylates and polyacrylic acid derivatives.

[0020] Preferably, the mass ratio of the dispersant to the porous material is 1:100-1:5, for example, 1:100, 1:90, 1:80, 1:70, 1:60, 1:50, 1:40, 1:30, 1:20, 1:10, 1:5, etc.

[0021] Preferably, the complex polyol is selected from any one of diol, triol or polyethylene glycol or a combination of at least two thereof; preferably a combination of diol and triol.

[0022] Preferably, the diol is selected from any one or a combination of at least two of ethylene glycol, propylene glycol, butylene glycol, pentylene glycol or hexylene glycol; the triol is selected from any one or a combination of at least two of glycerol, butanetriol, pentanetriol or hexanetriol; the polyethylene glycol is selected from polyethylene glycols with a molecular weight of 200-1000 (such as PEG200, PEG400, PEG500, PEG600, PEG800, PEG1000, etc.).

[0023] More preferably, the composite polyol includes a combination of glycerol, propylene glycol and butylene glycol.

[0024] The present invention also finds that the composite polyol in the above specific combination mode is better in improving the intrinsic quality of the heated cigarette and the effect of the suction sensory evaluation.

[0025] Preferably, the mass ratio of glycerol, propylene glycol to butylene glycol is 1:(1-2):(2-4), such as 1:1:2, 1:1:3, 1:1:4, 1:2:2, 1:2:3, 1:2:4, etc. Other specific point values within this numerical range can be selected and will not be elaborated one by one here.

[0026] Preferably, the porous material is selected from any one or a combination of at least two of metals, metal alloys, metal oxides, metal carbides, metal nitrides, metal borides, metal silicides, metal sulfides, metal silicates or metal phosphates.

[0027] Preferably, the pore size range of the porous material is 0.4-50 nm. The porous material can be a solid powder containing ordered pores and disordered pores.

[0028] The pore size range of the porous material can be adjusted arbitrarily within the range of 0.4-50 nm according to the type of the selected composite polyol, so that the pore size can ensure the entry of the polyol while preventing the entry of other preparation raw materials of the heated cigarette, and ensure the stability of the smoke agent product.

[0029] In a second aspect, the present invention provides a heat-not-burn cigarette, and the preparation raw materials of the heat-not-burn cigarette include the composite system smoke agent containing the porous material and the polyol described in the first aspect.

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

[0031] The present invention creatively loads a composite polyol with a certain molecular diameter on a porous material with matching pores to form a novel composite system smoke generating agent. The present invention utilizes a porous material with a network structure formed by mutually interpenetrating or closed pores as a carrier, which has a large number of irregular pores and a large specific surface area, and can absorb and accommodate polyols. This allows the free polyols to volatilize and release first in the early stage of heating when the tobacco slices are heated, while the polyols adsorbed inside the porous material begin to be gradually released in the middle and late stages. At the same time, the porous material will gradually have more and more vaporization centers and boiling nuclei as the polyols are released, thereby further promoting the stable and long-lasting release of smoke from the smoke generating agent.

[0032] The present invention also utilizes the characteristics of the constant boiling mixture formed by the two-component or multi-component polyol, so that the azeotropic temperature is significantly lower than that of the single component, the total vapor pressure generated is significantly increased, and it is easier to volatilize and release. In addition, the present invention also effectively replaces or reduces the amount of glycerol used, so that the physical properties of the heated cigarette product are stable and not easily affected by moisture absorption, and the chemical properties are relatively stable during heating, and it is not easy to generate reaction products such as glyceraldehyde, diglycerol, and monoacetin, so it can effectively improve the smoking sensory quality of the heated cigarette. DETAILED DESCRIPTION

[0033] In order to further explain the technical means and effects adopted by the present invention, the technical solution of the present invention is further described below in conjunction with the preferred embodiments of the present invention, but the present invention is not limited to the scope of the embodiments.

[0034] The sources of some raw materials involved in the following examples or comparative examples are as follows:

[0035] Polyols: glycerol, 1,2-propylene glycol, 1,3-butylene glycol, analytical grade, all purchased from Sinopharm Chemical Reagent Company;

[0036] Porous materials: Boron nitride porous material, aluminosilicate porous material, and titanium dioxide porous material were all purchased from Xi'an Ruixi Biotechnology Co., Ltd.

[0037] Dispersants: isooctyl alcohol polyoxyethylene ether, sodium dodecylbenzene sulfonate, hexadecyltrimethylammonium chloride, chemically pure, all purchased from Sinopharm Chemical Reagent Company.

[0038] Example 1

[0039] This embodiment provides a composite system smoke agent, and the preparation method thereof is as follows:

[0040] (1) Glycerol, 1,2-propylene glycol and 1,3-butylene glycol are mixed in a mass ratio of 2:3:5 to prepare a composite mother solution.

[0041] (2) Heat the boron nitride porous material (pore size 0.90 nm) in a muffle furnace to 280 °C for activation for 3 hours. After activation, wait for the boron nitride porous material to cool below 180 °C, then put it into a vacuum dryer with a three-way valve for vacuum pumping; after pumping is completed, open the valve to introduce carbon dioxide gas, and cool and place it.

[0042] (3) Immerse the cooled porous material in the mother liquor of the glycerol / 1,2 - propanediol / 1,3 - butanediol system, heat it to 70 °C and stir for 45 min, then add a dodecyl polyoxyethylene ether dispersant (the mass ratio of the dispersant to the porous material is 1:100), stir evenly, and obtain a boron nitride - glycerol / 1,2 - propanediol / 1,3 - butanediol smoke agent after cooling.

[0043] Example 2

[0044] This example provides a composite - system smoke agent, and its preparation method is as follows:

[0045] (1) Mix glycerol and 1,3 - butanediol with a mass ratio of 1:1 to prepare a composite mother liquor.

[0046] (2) Heat the aluminosilicate porous material (pore size 0.75 nm) in a muffle furnace to 300 °C for activation for 2 hours. After activation, wait for the aluminosilicate porous material to cool below 200 °C, then put it into a vacuum dryer with a three - way valve for vacuum pumping; after pumping is completed, open the valve to introduce nitrogen gas, and cool and place it.

[0047] (3) Immerse the cooled porous material in the mother liquor of the glycerol / 1,3 - butanediol system, heat it to 60 °C and stir for 60 min, then add a sodium dodecylbenzenesulfonate dispersant (the mass ratio of the dispersant to the porous material is 1:50), stir evenly, and obtain an aluminosilicate - glycerol / 1,3 - butanediol smoke agent after cooling.

[0048] Example 3

[0049] This example provides a composite - system smoke agent, and its preparation method is as follows:

[0050] (1) Mix 1,2 - propanediol and 1,3 - butanediol with a mass ratio of 2:3 to prepare a composite mother liquor.

[0051] (2) Heat the titanium dioxide porous material (pore size 0.65 nm) in a muffle furnace to 350 °C for activation for 2.5 hours. After activation, wait for the titanium dioxide porous material to cool below 200 °C, then put it into a vacuum dryer with a three - way valve for vacuum pumping; after pumping is completed, open the valve to introduce helium gas, and cool and place it.

[0052] (3) Immerse the cooled porous material into the mother liquor of the 1,2 - propanediol / 1,3 - butanediol system, heat it to 80 °C and stir for 40 min, then add cetyltrimethylammonium chloride dispersant (the mass ratio of the dispersant to the porous material is 1:30), stir evenly, and obtain titanium dioxide - 1,2 - propanediol / 1,3 - butanediol smoke agent after cooling.

[0053] Application Examples 1 - 3

[0054] Adopt the thick slurry method manufacturing process. Respectively mix 4.92 g of the smoke agent prepared in Examples 1 - 3 with 15.6 g of tobacco powder (mellowed tobacco leaves from Fujian region), 94 g of water, 0.7 g of wood fiber (Wuxi Simude Company), and 0.12 g of sodium carboxymethylcellulose (chemically pure, from Sinopharm Chemical Reagent Co., Ltd.) and stir evenly. Use a coater to evenly coat it on a flat plate, dry it and peel it off to obtain a tobacco sheet with a smoke agent mass fraction of 18%. Take 1.5 g of the tobacco sheet, cut the tobacco sheet into cut tobacco and fill it into the empty heated cigarette sticks to make three kinds of heated cigarettes (denoted as Samples 1 - 3 respectively).

[0055] Application Examples 4 - 6

[0056] Refer to the method for preparing heated cigarettes in Application Examples 1 - 3, the difference is only that the smoke agents prepared in Examples 1 - 3 are respectively replaced with smoke agents containing only composite polyols without porous materials, and the reduced mass of the porous material is made up by the composite polyols, and three kinds of heated cigarettes are prepared (denoted as Samples 4 - 6).

[0057] Application Examples 7 - 9

[0058] Refer to the method for preparing heated cigarettes in Application Examples 1 - 3, the difference is only that the smoke agents prepared in Examples 1 - 3 are respectively replaced with smoke agents containing only single polyols (glycerol, 1,2 - propanediol, 1,3 - butanediol) without porous materials, and the reduced mass of the porous material is made up by the single polyols, and three kinds of heated cigarettes are prepared (denoted as Samples 7 - 9).

[0059] Test Example 1

[0060] Use a core - needle type heating smoking device (Jiangsu Zhongyan, iROD X1 type) to heat the above nine kinds of heated cigarettes, use a linear heated cigarette smoking machine with a smoke collector (Hefei Zhongwo, SML600 type) for suction, use a smoke physical property detection instrument (Hefei Zhongwo, SHT100 type) to detect the smoke volume per puff of the heated cigarettes, the suction mode is the HCI mode (55 mL, interval 30 s), and the number of suction puffs is 10. The relevant data of the heated sample smoke volume are shown in Table 1.

[0061] Table 1 Smoke volume per puff of different types of smoke agents in heated cigarettes

[0062]

[0063] As can be seen from Table 1, when different types of smoke agents are applied to heated cigarettes, the order of the mean values of the smoke volume is as follows: the polyol composite smoke agent containing porous materials > the polyol composite smoke agent > the single polyol smoke agent. Among them, the smoke volume of the polyol composite smoke agent is significantly greater than that of the single polyol smoke agent.

[0064] When different types of smoke agents are applied to heated cigarettes, for the heated cigarettes with the polyol composite smoke agent containing porous materials, the attenuation degree of the smoke volume in the later stage of puffing is relatively low, and its release uniformity and consistency are significantly higher than those of the polyol composite smoke agent and the single polyol smoke agent.

[0065] Application Examples 10 - 12

[0066] Referring to the method for preparing heated cigarettes in Application Examples 1 - 3, the difference is only that the porous materials in the smoke agents prepared in Examples 1 - 3 are not subjected to thermal activation, gas replacement, and heating and stirring treatments, but the porous materials are directly immersed in the corresponding polyol system mother liquor and stirred at room temperature. Other preparation processes are respectively consistent with those in Examples 1 - 3, and three kinds of heated cigarettes (denoted as Samples 10 - 12) are prepared.

[0067] Test Example 2

[0068] The smoke volume of the heated cigarettes was measured using the same detection method as in Test Example 1, and the results are shown in Table 2 below.

[0069] Table 2 Influence of Pretreatment of Porous Materials on the Per-Puff Smoke Volume of Heated Cigarettes

[0070]

[0071] As can be seen from Table 2, the mean value of the smoke volume of the heated cigarette samples 10 - 12 with the polyol composite smoke agent of untreated porous materials decreased to a certain extent compared with Samples 1 - 3, and the decrease in the later stage of the smoke volume was also relatively obvious, indicating that the thermal activation, gas replacement, and stirring and heating treatments of the porous materials have a greater impact on the smoke release amount of the smoke agent, and also have an obvious impact on the release uniformity and consistency of the smoke.

[0072] Test Example 3

[0073] Sampling was carried out according to the sampling method of the national standard "Cigarettes - Part 4: Sensory Technical Requirements" (GB5606.4 - 2005). Ten top-level sensory evaluation panelists were organized, and each person was given a sensory evaluation form for heated cigarettes. According to the evaluation content and judgment criteria in Tables 3 - 4, Samples 1 - 9 were scored for sensory evaluation from six dimensions respectively, and the scoring of the sensory quality indicators was all in a hundred-point system.

[0074] Table 3

[0075] Sensory quality evaluation indicators Definition Smoke volume Degree of smoke size or concentration Smoke uniformity Situation of smoke volume delivery stability during puffing Aroma and flavor Pleasant aroma and taste felt during puffing Strength Physiological satisfaction brought by cigarette nicotine Irritation Uncomfortable feelings brought by cigarette smoke to the senses, such as nasal cavity and oral cavity irritation, etc. Aftertaste Feeling generated after cigarette smoke leaves the oral cavity and nasal cavity, mainly described by the degree of comfort and cleanliness

[0076] Table 4

[0077]

[0078] Note: The higher the score of irritation, the smaller the irritation; the higher the score of aftertaste, the smaller the aftertaste residue.

[0079] The statistical table of the sensory quality evaluation results of each group of samples is shown in Table 5 (presented by the average score value of 10 top-grade smokers):

[0080] Table 5 Sensory Evaluation of Heat-not-burn Cigarettes with Different Kinds of Smoking Agents

[0081] Sample Smoke volume Uniformity Aroma Strength Irritation Aftertaste Total score 1 19 19 18 17 9 10 92 2 18 19 17 18 10 9 91 3 16 18 16 17 9 9 85 4 18 17 17 16 8 9 85 5 17 16 16 16 9 8 82 6 15 16 16 15 8 8 78 7 15 14 16 17 7 7 76 8 13 15 14 13 8 7 70 9 14 14 15 14 8 8 73

[0082] It can be seen from the evaluation results in Table 5 that the order of the total evaluation scores of heat-not-burn cigarettes with different smoking agents is as follows: polyol composite smoking agent containing porous materials > polyol composite smoking agent > single polyol smoking agent. Compared with glycerol sample 7, the smoke volume of polyol composite samples 4-6 has been greatly improved, the uniformity has been slightly improved, and the irritation and aftertaste have both been improved. For polyol composite samples 1-3 containing porous materials, compared with glycerol sample 7, their smoke volume and uniformity have been significantly improved, and the irritation and aftertaste have also been greatly improved. When smoking heat-not-burn cigarette samples 1-3, the smoke volume is large, the uniformity is good, the aroma is sufficient, the strength is appropriate, and the irritation and aftertaste residue are small.

[0083] The applicant declares that the present invention uses the above embodiments to illustrate a composite system smoking agent containing porous materials and polyols and its application, but the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must rely on the above embodiments to be implemented. Those skilled in the art should understand that any improvement of the present invention, the equivalent replacement of each raw material of the product of the present invention, the addition of auxiliary components, and the selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

[0084] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, and these simple modifications all belong to the protection scope of the present invention.

[0085] In addition, it should be noted that, in the case of no conflict, the various specific technical features described in the above specific embodiments can be combined in any suitable way. In order to avoid unnecessary repetition, the present invention will not separately describe various possible combination methods.

Claims

1. A composite smoke agent containing a porous material and a polyol, characterized in that, The composite smoke agent includes composite polyols and a porous material dispersed in the composite polyols, and the pores of the porous material are loaded with composite polyols; The composite polyols are composed of glycerol, propylene glycol and butylene glycol; The composite smoke agent is prepared by a preparation method including the following steps: (1) Heat-activate the porous material, then perform vacuum treatment and introduce an inert gas in a dry environment to obtain a porous material filled with the inert gas; (2) Mix the porous material filled with the inert gas with a composite polyol solution, heat and stir, then mix and stir with a dispersant, and obtain the composite smoke agent containing the porous material and polyols after cooling.

2. The smoke agent of the composite system containing a porous material and a polyol according to claim 1, wherein, The temperature of the heat activation is 200-400 °C, and the time is 1-5 h.

3. The smoke agent of the composite system containing porous material and polyol according to claim 1, characterized in that, The inert gas includes any one or a combination of at least two of helium, nitrogen, carbon dioxide or argon.

4. The smoke agent of the composite system containing a porous material and a polyol according to claim 1, characterized in that, The heat stirring is carried out at 40-120 °C for 10-240 min.

5. The smoke agent of the composite system containing a porous material and a polyol according to claim 1, wherein The dispersant includes an inorganic dispersant and / or an organic dispersant.

6. The smoke agent of the composite system containing a porous material and a polyol according to claim 1, characterized in that, The mass ratio of the dispersant to the porous material is 1:100-1:

5.

7. The smoke agent of the composite system containing a porous material and a polyol according to claim 1, characterized in that, The mass ratio of the glycerol, propylene glycol and butylene glycol is 1:(1-2):(2-4).

8. The smoke agent of the composite system containing porous material and polyol according to claim 1, characterized in that, The porous material is selected from any one or a combination of at least two of metals, metal alloys, metal oxides, metal carbides, metal nitrides, metal borides, metal silicides, metal sulfides, metal silicates or metal phosphates.

9. The smoke agent of the composite system containing a porous material and a polyol according to claim 1, characterized in that, The pore size range of the porous material is 0.4-50 nm.

10. A heat-not-burn cigarette, characterized in that, The preparation raw material of the heat non-combustible cigarette includes the composite smoke agent containing the porous material and polyols according to any one of claims 1-9.

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