WO2023116767A1 - Biodegradable solid material for granular tobacco-type heating cigarettes, and preparation method therefor - Google Patents

Abstract

A biodegradable solid material for granular tobacco-type heating cigarettes, and a preparation method therefor. Bio-based polymer materials such as PLA, PVA, PBAT and PBS, which are used as base materials, and glycerol-modified jute fibers, silane coupling agent-modified bamboo powder or straw powder, carbon fibers or calcium carbonate whiskers and the like, which are used as heat-resistant filling materials, are added to an internal mixer, melted, blended and hot pressed to obtain the solid material. The solid material can play a supporting role when a granular tobacco-type heating cigarette is consumed, has relatively high thermal stability, and is not prone to shrinkage and heat-caused collapse after being heated. The solid material does not add hazardous substances which are released in the mainstream smoke of the heat cigarette, and has no negative influence on the sensory quality of the cigarette.

Description

A biodegradable solid material for granular heating cigarettes and its preparation method technical field

The invention belongs to the technical field of novel tobacco products, and in particular relates to a biodegradable solid material used for granular heating cigarettes and a preparation method thereof.

Background technique

With the improvement of people's economic and cultural level, more and more people pay more attention to their health, so it is imperative to develop new tobacco products. Particulate heated cigarettes are one of the important forms of new tobacco products. Different from the current heat-not-burn cigarette products on the market, particle-type heated cigarettes use tobacco particles as the smoke-releasing substance, with sufficient smoke volume, good continuity of smoke release, excellent sensory quality, and large room for formula optimization and adjustment. However, how to encapsulate the tobacco particles in the cigarette so as not to drop and inhale during the heating and smoking process is a key technical issue in the production of cigarettes.

The solid material used to block tobacco particles is one of the important components of particle-type heating cigarettes. At present, high-temperature-resistant plastic fasteners are used as the middle section barrier material, but the mainstream plastic products on the market are non-degradable materials and the heat resistance is not good enough. They will soften and melt during the heating and suction process, which not only cannot play an effective barrier role. , It will also release peculiar smell, which seriously reduces the quality of smoke and the smoking experience. After use, it is not easy to degrade when discarded in the environment, which will pollute the environment.

Therefore, it is of great significance to study new firmware materials.

Contents of the invention

The purpose of the present invention is to overcome the deficiencies of the prior art, to provide a biodegradable solid material for granular heating cigarettes and its preparation method, aiming to make it have good support and heat resistance in the cigarette Does not affect the sensory quality of cigarettes.

The present invention adopts following technical scheme for realizing the purpose:

The present invention is used for the biodegradable solid material of granular heating cigarettes, and the composition of each raw material according to the mass percentage is:

The base material is 25-50%, and the heat-resistant filling material is 50%-75%.

Further, the base material is PBAT (polybutylene adipate/terephthalate), PBS (polybutylene succinate), PVA (polyvinyl alcohol) and PLA (polylactic acid). at least one of .

Further, the heat-resistant filling material is at least one of glycerin-modified jute fiber, silane coupling agent-modified bamboo powder or straw powder, carbon fiber and calcium carbonate whiskers.

Further, the preparation method of the glycerol-modified jute fiber is as follows: the jute fiber is cut to a length of not more than 3cm, then put into a NaOH solution with a concentration of 10g/L and soaked for 24h at room temperature, take it out and rinse until neutral, Dry at 60°C for 24 hours to obtain the jute fiber after alkali treatment; stir and mix hydrochloric acid, glycerin and deionized water according to the mass fraction of 1.2%: 78.8%: 20% to obtain water-acidified glycerin; jute fiber after alkali treatment according to 10% The mass concentration was added to the water-acidified glycerin, stirred and refluxed at 130°C for 30 minutes, then diluted, dried by suction filtration, and dried in an oven at 80°C for 12 hours to obtain glycerin-modified jute fiber.

Furthermore, the preparation method of the bamboo powder or straw powder modified by the silane coupling agent is as follows: the bamboo powder or straw powder is placed in a _H2SO4 solution with a mass concentration of 0.1%, _soaked at 55°C for 1.5h , washed and dried to obtain the acid-treated material; the acid-treated material was added to a NaOH solution with a mass concentration of 0.5%, soaked at room temperature for 2 hours, removed and rinsed until neutral, and dried at 80°C for 4 hours to obtain the alkali Treated material; mix silane coupling agent (KH550) and absolute ethanol according to the mass percentage of 1.5%:98.5%, then add the alkali-treated material, soak at room temperature for 4 hours, take it out and dry at 60°C for 24 hours to obtain silane Coupling agent modified bamboo powder or straw powder.

Further, the PVA is glycerol-modified PVA, and the modification method is to add glycerol accounting for 10% to 50% of the PVA mass into the PVA, and obtain the glycerin-modified PVA after sufficient infiltration.

The preparation method of the biodegradable fastener material of the present invention is as follows: weighing each raw material according to the proportion, adding it to an internal mixer for melting and blending, and then hot pressing to obtain a finished product.

The invention also discloses the application of the above-mentioned firmware material, which is used in particle-type heating cigarettes to support cigarettes and resist heat.

Among the biodegradable firmware materials of the present invention: PLA, PVA, PBAT, and PBS are emerging bio-based polymer materials, which have attracted widespread attention due to their excellent biocompatibility and degradability. Bamboo powder and straw powder are added to the above polymer materials as additive bio-based materials, which can effectively improve the heat resistance of the polymer and prepare degradable high-temperature resistant firmware materials. Due to its large specific surface area and other reasons, fiber materials can promote the crystallization of PLA, PBS and other materials, thereby improving their heat resistance.

Compared with the prior art, the beneficial effects of the present invention are reflected in:

1. The firmware material of the present invention is made of fully biodegradable materials, and it will not cause pollution when discarded in the environment.

2. The firmware material of the present invention can play a supporting role in the use of granular heating cigarettes, and has high thermal stability. After being heated, there is no obvious shrinkage and thermal collapse, and it does not appear in the mainstream smoke of heating cigarettes. Increase the release of harmful substances and have no negative impact on the sensory quality of cigarettes.

3. The firmware material of the present invention has a simple preparation process, readily available raw materials, easy industrial production, and is environmentally friendly.

Description of drawings

Fig. 1 is the DSC curve of sample 11～15 prepared in embodiment 1;

Fig. 2 is the DSC curve of sample 16～20 prepared in embodiment 1;

Fig. 3 is the TG and DTG curve of samples 11-15 prepared in embodiment 1;

Fig. 4 is the TG and DTG curves of samples 16-20 prepared in Example 1.

Detailed ways

The embodiments of the present invention are described in detail below. This embodiment is implemented on the premise of the technical solution of the present invention, and detailed implementation methods and specific operating procedures are provided, but the protection scope of the present invention is not limited to the following implementation example.

In the following examples, the preparation method of the jute fiber modified with glycerol is: the jute fiber is cut to a length of no more than 3cm, then put into a NaOH solution with a concentration of 10g/L and soaked for 24h at room temperature, take out and rinse until neutral , dry at 60°C for 24h to obtain the jute fiber after alkali treatment; stir and mix hydrochloric acid, glycerin and deionized water according to the mass percentage of 1.2%:78.8%:20% to obtain water-acidified glycerin; jute fiber after alkali treatment according to 10% The mass concentration was added to water-acidified glycerin, stirred and refluxed at 130°C for 30 minutes, then diluted, dried by suction filtration, and dried in an oven at 80°C for 12 hours to obtain glycerin-modified jute fiber.

In the following examples, the preparation method of the bamboo powder modified by the silane coupling agent used is as follows: the bamboo powder is placed in a _H2SO4 solution with a mass concentration of 0.1%, soaked at 55°C for 1.5h, washed, _dried Dry to obtain the acid-treated material; add the acid-treated material to a NaOH solution with a mass concentration of 0.5%, soak it at room temperature for 2 hours, take it out and rinse until neutral, and dry it at 80°C for 4 hours to obtain the alkali-treated material; The coupling agent (KH550) and absolute ethanol are mixed uniformly according to the mass percentage of 1.5%:98.5%, then the alkali-treated material is added, soaked at room temperature for 4 hours, taken out and dried at 60°C for 24 hours to obtain the bamboo powder modified by the silane coupling agent.

In the following examples, glycerol-modified PVA is used by adding glycerol, which accounts for 10% to 50% of the PVA mass, into the PVA, and after sufficient infiltration, the glycerin-modified PVA is obtained.

Example 1

The firmware material of this embodiment, the composition of each raw material by mass percentage is as shown in Table 1:

Table 1 The formula of the firmware material based on PVA

The firmware material prepared in this embodiment is used in Vicat thermal deformation testing machine (Meters Industrial Systems (China) Co., Ltd.), DSC8500 (Perkin Elmer, USA), TA Q5000IR thermo-analyzer (TA Instruments Inc., U.S.) , to test its Vicat softening temperature, DSC, TG and DTG, the specific methods and results are as follows:

Vicat softening temperature test method: place the sample in a high-temperature silicone oil heat transfer medium, use a heating rate of 50°C/h to raise the temperature, place a 50N weight, and test the temperature when the sample is pressed into 1mm by a 1mm ² needle. The card softens. The sample size is 10mm×10mm×3mm, and the number of stacked layers is 1.

DSC test method: the sample is ground into powder and tested under a nitrogen atmosphere with a heating rate of 20°C/min.

TG and DTG test methods: Grind the sample into powder and test it in an air atmosphere. The heating rate is 20°C/min, and the temperature is raised to 800°C.

Vicat softening temperature test results: Table 2 shows the Vicat softening temperature of the firmware material with PVA as the main matrix. It can be seen from Table 2 that the greater the amount of glycerin added, the lower the Vicat softening temperature of PVA. Therefore, screening out the effective ratio of glycerin addition is a key step to balance the processing performance and heat resistance of PVA heat-resistant composite materials. Through the Vicat softening point test, it can be seen that when the amount of glycerin added is 10%, the Vicat softening temperatures of the composites prepared with different amounts of jute fiber and bamboo powder are almost above 100°C. The highest Vicat softening temperature is the composite material mixed with 20% glycerin swollen PVA and 60% jute fiber.

Table 2 Vicat softening temperature of firmware materials with PVA as the main matrix

serial number

Vicat softening temperature ℃

serial number

Vicat softening temperature ℃

1	/	14	106.1
2	68.5	15	80.3
3	68.4	16	52.1
4	/	17	89.4
5	88.8	18	88.5
6	/	19	126.3
7	81.0	20	72.1
8	63.7	twenty one	64.1
9	107.4	twenty two	125.1
10	87.1	twenty three	94.5
11	/	twenty four	101.9
12	98.4	25	126.0
13	94.7	the	the

DSC test results: for the barrier firmware material with PVA as the main substrate, the DSC curves of samples No. 11-15 are shown in Figure 1, and the DSC curves of samples No. 16-20 are shown in Figure 2. It can be seen that all samples have no obvious melting peaks and phase transitions, and no obvious chemical reactions have occurred. It shows that the existence of glycerol obviously destroys the crystallization property of PVA, makes its processing temperature drop, thus makes it feasible to fill it with heat-resistant filler. It can be seen from Figure 2 that the PVA composite material with a glycerol content of 20% appears crystallization and melting at 105°C, which shows that there are still some PVAs that are not swollen by glycerin, so there are still crystallized PVAs, which will have a negative impact on the melt processability of PVA. impact, thus resulting in insufficient dispersion of fillers in PVA composites. It can also be seen from the DSC curve that the PVA composite material with a glycerol content of 20% has a certain degree of side group elimination and main chain decomposition at about 160 °C. Therefore, the PVA composite material with a glycerol content of 30% has the best practicability.

TG and DTG test results: for barrier firmware materials with PVA as the main substrate, the thermogravimetric analysis results of samples No. 11-15 are shown in Figure 3, and the thermogravimetric analysis results of samples No. 16-20 are shown in Figure 4. Since samples No. 11-15 are all PVA with 30% glycerin content, the average Vicat softening temperature (94.9°C) is higher in PVA composites with different glycerin content, and the average hardness is lower, and the average thermal conductivity is the lowest. The softening temperature is higher than 80 ℃, and it is the largest proportion of PVA swellable glycerin. Therefore, samples No. 11-15 were selected for thermogravimetric analysis. As can be seen from Figure 3, the thermal decomposition of PVA with a glycerol content of 30% is mainly divided into four stages: dehydration (room temperature-100°C), glycerin overflow (100-261°C), elimination of PVA side groups (261-400°C ℃), the main chain of PVA decomposes (400-600 ℃). The 30% glycerin PVA without filler has a weight loss of 33% in the second stage, and the peak weight loss rate is 0.44%/min. The weight loss in the third stage is 37%, and the peak weight loss rate is 42%/min. The weight loss in the fourth stage is 19%. The weight loss rate was 0.28%/min. It can be seen that with the addition of fillers, the peak weight loss rate temperature of each stage decreases. The second stage weight loss of the filled PVA composite was lower than that of the 30% glycerol content PVA without filler. The peak weight loss rates of the third and fourth stages of PVA composites with fillers were higher than those of PVA with 30% glycerol content without fillers.

No. 16-20 samples are all PVA with 20% glycerol content, and the average Vicat softening temperature is 94.1°C (removing the No. 16 sample without filler), which is lower than the composite material average Vicat softening temperature (94.9 ℃). As can be seen from Figure 4, the decomposition of the composite material with a glycerol content of 20% PVA is mainly divided into two parts: the side group elimination of PVA and the decomposition of most of the main chain (280-400 ° C), and the decomposition of the remaining part of the main chain (450 ° C). -600°C). It can be seen that the thermal stability of the PVA composite material with 20% glycerin addition is poorer than that of the PVA composite material with 30% addition. The PVA material with an amount of 30% still has 19% undecomposed at 400°C.

Through the analysis of DSC, it can be proved that the PVA modified by glycerol has a relatively lower temperature processing performance, and then the heat resistance performance is significantly improved by adding heat-resistant fillers. The increase in Vicat softening point means that The prepared material can play a supporting role after being heated without collapsing. The analysis of TG and DTG can prove that the thermal stability of the material is good. For PVA swollen with 20% glycerin, only glycerol volatilization overflows below 280°C, while for PVA swollen with 30% glycerin, only glycerol volatilization overflows below 261°C. .

The above are only preferred embodiments of the present invention, and are not intended to limit the present invention. Any modifications, equivalent replacements and improvements made within the spirit and principles of the present invention should be included in the protection scope of the present invention. Inside.

Claims (8)

1. A biodegradable solid material for granular heating cigarettes, characterized in that: the composition of each raw material of the biodegradable solid material in terms of mass percentage is:

   The base material is 25-50%, and the heat-resistant filling material is 50%-75%.
2. The biodegradable firmware material according to claim 1, wherein the base material is at least one of PBAT, PBS, PVA and PLA.
3. The biodegradable solid material according to claim 1, characterized in that: the heat-resistant filling material is glycerin modified jute fiber, silane coupling agent modified bamboo powder or straw powder, carbon fiber and calcium carbonate crystal at least one of the whiskers.
4. biodegradable solid material as claimed in claim 3, is characterized in that, the preparation method of the jute fiber of described glycerol modification is:

   Cut the jute fiber to a length of no more than 3cm, then put it into a NaOH solution with a concentration of 10g/L and soak it at room temperature for 24 hours, take it out, wash it until neutral, dry it at 60°C for 24 hours, and obtain the jute fiber after alkali treatment;

   Stir and mix hydrochloric acid, glycerin and deionized water according to the mass percentage of 1.2%: 78.8%: 20%, to obtain water-acidified glycerin;

   Add the alkali-treated jute fiber to the water-acidified glycerin at a mass concentration of 10%, stir and reflux at 130°C for 30 minutes, then dilute, filter and dry, and dry in an oven at 80°C for 12 hours to obtain glycerin-modified jute fiber.
5. The biodegradable solid material according to claim 3, characterized in that: the preparation method of the bamboo powder or straw powder modified by the silane coupling agent is:

   Bamboo powder or straw powder was placed in _{a H2SO4} solution with a mass concentration of 0.1%, soaked at 55°C for 1.5h, washed and dried to obtain the acid-treated material;

   The acid-treated material was added to a NaOH solution with a mass concentration of 0.5%, soaked at room temperature for 2 hours, then taken out and rinsed until neutral, and dried at 80°C for 4 hours to obtain the alkali-treated material;

   Mix the silane coupling agent and absolute ethanol uniformly according to the mass percentage of 1.5%:98.5%, then add the alkali-treated material, soak it at room temperature for 4 hours, take it out and dry it at 60°C for 24 hours, and obtain the bamboo modified by the silane coupling agent. powder or straw powder.
6. The biodegradable firmware material according to claim 2, characterized in that: the PVA is glycerin modified PVA, and the modification method is to add glycerin accounting for 10% to 50% of the PVA mass into the PVA, and after fully infiltrating, A glycerol-modified PVA is obtained.
7. A method for preparing a biodegradable solid material according to any one of claims 1 to 6, characterized in that: each raw material is weighed according to the proportion, added to an internal mixer for melting and blending, and then hot-pressed to obtain a finished product .
8. An application of the biodegradable solid material according to any one of claims 1 to 6, characterized in that it is used in granular heating cigarettes to support cigarettes and resist heat.

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