Impermeable glue as well as preparation method and application thereof

Abstract

The invention discloses an anti-permeation glue and a preparation method and application thereof, 100 parts by weight of the anti-permeation glue comprises 15-25 parts of bio-based wax microspheres, 2-5 parts of a Pickering particle stabilizer, 30-50 parts of a multistage gradient crosslinking monomer, 0.5-1.5 parts of a water-based photoinitiator, 3-8 parts of a graphene oxide-chitosan hybrid dispersion liquid, 1-3 parts of a glycosyl gemini surfactant and the balance of deionized water. Wherein the multi-section gradient cross-linking monomer is prepared from ethyl acetoacetoxymethacrylate, tripropylene glycol diacrylate and bisphenol A epoxy diacrylate according to the mass ratio of (2 to 3) to (3 to 4) to (1 to 3). The oil-proof coating is based on 100% of water and has zero VOC, the air permeability loss is smaller than or equal to 10% on the premise that the oil-proof grade is larger than or equal to 6, molten drops are avoided during combustion, and the oil-proof coating can be coated at the low temperature of 60-70 DEG C.

Description

Technical Field

[0001] This invention relates to the field of cigarette auxiliary materials technology, and in particular to an anti-permeability adhesive that can block the migration of oily flavorings while maintaining the natural porosity and combustion characteristics of cigarette paper, its preparation method, and the application of the anti-permeability adhesive in cigarette products. Background Technology

[0002] With the rise of low-tar and flavored cigarettes, the oily flavorings in the filter capsules or flavoring core tend to migrate outwards along the cigarette paper at smoking temperatures (30~80℃), causing the following problems:

[0003] (1.1) "Oil spots" appear on the surface of the cigarette, resulting in a decline in appearance quality;

[0004] (1.2) Loss of fragrance results in insufficient fragrance persistence;

[0005] (1.3) The ink printing layer swells, causing contamination of the packaging line.

[0006] Existing technologies often employ highly filled paraffin-emulsions or solvent-based acrylates to form a continuous film on the paper surface (such as the schemes in patent documents like CN116694281A). While these methods can block grease, they suffer from the following drawbacks:

[0007] (2.1) The film is dense, which significantly reduces the air permeability of cigarette paper (reduction ≥40%), affecting the dilution of mainstream smoke;

[0008] (2.2) After combustion, the wax film produces "molten droplets", which can easily clog the filter nozzle ventilation holes;

[0009] (2.3) It requires a drying tunnel at a temperature above 120℃, which consumes a lot of energy and the base paper is prone to yellowing;

[0010] (2.4) The formula contains VOC solvents, which does not conform to the trend of "reducing harm and tar" in cigarettes.

[0011] Therefore, there is an urgent need for a new type of impermeable adhesive that is breathable, grease-resistant, can be processed at low temperatures, and does not drip. Summary of the Invention

[0012] The purpose of this invention is to provide an antipermeable adhesive, its preparation method, and its application. It is a solvent-free antipermeable adhesive based on "multi-stage gradient crosslinking + Pickering emulsion + bio-based wax". It can ensure an oil resistance rating of ≥6 (KIT Test) while reducing air permeability loss to ≤10%, producing no melt droplets during combustion, and can be coated at low temperatures of 60~70℃, thus effectively solving the problems mentioned in the background art.

[0013] To achieve the above objectives, the present invention adopts the following technical solution:

[0014] In a first aspect, the present invention provides an anti-permeability adhesive, comprising the following components in parts by weight: 15-25 parts of bio-based wax microspheres, 2-5 parts of Pickering particle stabilizer, 30-50 parts of multi-segment gradient crosslinking monomer, 0.5-1.5 parts of aqueous photoinitiator, 3-8 parts of graphene oxide-chitosan hybrid dispersion, 1-3 parts of glycosyl gemini surfactant, and deionized water to make up to 100 parts; wherein the multi-segment gradient crosslinking monomer is composed of ethyl acetoacetoxymethacrylate, tripropylene glycol diacrylate, and bisphenol A epoxy diacrylate in a mass ratio of (2-3):(3-4):(1-3).

[0015] Acetyl acetyloxy methacrylate (AAEM) is a low-temperature crosslinking monomer (self-crosslinking at 30~50℃), tripropylene glycol diacrylate (TPGDA) is a medium-temperature crosslinking monomer (UV-cured at 50~70℃), and bisphenol A epoxy diacrylate (EPO) is a high-temperature crosslinking monomer (post-cured at 70~90℃).

[0016] The mechanism of action of this invention is as follows: bio-based wax microspheres provide an initial hydrophobic "core" that completely pyrolyzes at combustion temperature without dripping; the Pickering particle stabilizer is irreversibly adsorbed at the wax-water interface to form an "armor" that inhibits high-temperature aggregation; a multi-stage gradient crosslinking design is used, where acetyl acetoxy methacrylate (a low-temperature component) enables rapid paper surface positioning, tripropylene glycol diacrylate (a medium-temperature component) can be UV-cured and shaped, and bisphenol A epoxy diacrylate (a high-temperature component) can be post-cured to form a dense network, resulting in a kit grade ≥6; by adding a graphene oxide-chitosan hybrid dispersion, a GO-CS hybrid layer is formed, where positively charged chitosan and negatively charged graphene oxide electrostatically self-assemble to construct a nanomaze, extending the oil diffusion path; and a glycosyl gemini surfactant can reduce the dynamic surface tension to 22 mN / m, improving the wetting uniformity of porous paper.

[0017] In some specific technical solutions, the multi-stage gradient crosslinking monomer is composed of ethyl acetoacetoxymethacrylate, tripropylene glycol diacrylate, and bisphenol A epoxy diacrylate in a mass ratio of 3:4:2.

[0018] In some specific technical solutions, the bio-based wax microspheres are prepared by compounding carnauba wax and rice bran wax in a mass ratio of 7:3 and then homogenizing under high pressure and spray cooling, with an average particle size D50 of 0.8~1.2µm.

[0019] In some specific technical solutions, the preparation method of the bio-based wax microspheres includes the following steps:

[0020] S11. Melting: Carnauba wax and rice bran wax are added to a jacketed mixing tank at a mass ratio of 7:3 and melted at 85℃ and 200rpm for 30 minutes to obtain a molten wax phase.

[0021] S12. Thermal emulsification: Add 3 wt% of decyl-β-D-maltose dimer and 95℃ deionized water to the molten wax phase and perform high shear at 8000 rpm for 10 min to obtain O / W crude emulsion.

[0022] S13. High-pressure homogenization: The obtained O / W crude emulsion is passed through an 80℃ constant temperature homogenizer, with a first-stage pressure of 800 bar and a second-stage pressure of 120 bar, and circulated 3 times to obtain a nanoemulsion.

[0023] S14 Spray Cooling: The nanoemulsion is atomized through a two-fluid nozzle with an inlet air temperature of 5℃, an outlet air temperature of 15℃, and an atomization pressure of 0.4MPa. The wax droplets solidify instantly, and the microspheres are collected by a cyclone separator and passed through a 200-mesh sieve to obtain the finished bio-based wax microspheres.

[0024] In some specific technical solutions, the Pickering particle stabilizer is a mixture of hydrophobic SiO2 and ZnO nanorods at a mass ratio of 4:1. The specific surface area of ​​the hydrophobic SiO2 is 170 m² / g.

[0025] In some specific technical solutions, the aqueous photoinitiator is phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide. As an example, the aqueous photoinitiator selected is BASF's water-dispersible photoinitiator IRGACURE 819DW, with a solid content of 25 wt%.

[0026] In some specific technical solutions, the graphene oxide content in the graphene oxide-chitosan hybrid dispersion is 0.3 wt%, and the degree of deacetylation of chitosan is ≥90%.

[0027] In some specific technical solutions, the preparation method of the graphene oxide-chitosan hybrid dispersion includes the following steps:

[0028] S21. Add monolayer graphene oxide to deionized water to prepare a 1.0wt% pre-dispersion solution, and ultrasonically exfoliate it for 30 min at 25℃, 800W, and 20kHz to obtain a uniform GO dispersion.

[0029] S22. Chitosan with a degree of deacetylation ≥90% and a viscosity-average molecular weight of 200~300kDa is dissolved in 1.0wt% acetic acid aqueous solution to prepare a 2.0wt% CS solution, and magnetically stirred at 2000rpm for 2h.

[0030] S23. Add the CS solution dropwise to the GO dispersion at a GO / CS solid mass ratio of 1:2, and sonicate at 25℃ and 300W for 10 min to allow the positive and negative charges to self-assemble electrostatically.

[0031] S24. Adjust the pH to 6.5-7.0 with 0.1M NaOH, and then stir at 600 rpm for 1 h to obtain a 0.3 wt% graphene oxide-chitosan hybrid dispersion.

[0032] In some specific technical solutions, the glycosyl gemini surfactant is a decyl-β-D-maltose dimer.

[0033] Secondly, the present invention provides a method for preparing an anti-permeability adhesive as described in any of the above claims, comprising the following steps:

[0034] S1. Bio-based wax microspheres, Pickering particle stabilizer and glycosyl gemini surfactant were added to deionized water at 25°C and homogenized three times under high pressure at 600 bar to obtain a stable Pickering emulsion.

[0035] S2. Under nitrogen protection, ethyl acetoacetoxy methacrylate, tripropylene glycol diacrylate, bisphenol A epoxy diacrylate and water-based photoinitiator are added sequentially to the Pickering emulsion obtained in step S1. The mixture is stirred at 600 rpm for 30 min under 395 nm ultraviolet LED irradiation and UV curing energy of 400 mJ / cm² to form a gradient crosslinked prepolymer with a "core-shell" structure.

[0036] S3. Add graphene oxide-chitosan hybrid dispersion dropwise, and ultrasonically disperse at 20kHz and 300W for 10min to obtain impermeable adhesive base liquid;

[0037] S4. Filter the antipermeable adhesive base liquid obtained in step S3 through a 1µm bag filter and degas it under vacuum at 40℃ to obtain the finished antipermeable adhesive.

[0038] Thirdly, the present invention also provides the application of the anti-permeability adhesive as described above in the oil-resistant coating of cigarette paper, filter tipping paper or heated non-combustible cigarette substrate.

[0039] Compared with the prior art, the present invention provides an anti-permeability adhesive, its preparation method and application, which has the following beneficial effects:

[0040] The antipermeable adhesive provided by this invention has a viscosity of 350~550 mPa·s at 25℃ and a pH of 6.5~7.5; the antipermeable adhesive is 100% water-based, has zero VOC, and an air permeability loss of ≤10%, meeting the air permeability deviation requirements of cigarette paper GB / T 12655. Detailed Implementation

[0041] The technical solution of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0042] The present invention will be further described in detail below through detailed embodiments.

[0043] Unless otherwise specified, the experimental methods used in the examples and comparative examples are conventional methods, and the materials and reagents used are commercially available and of industrial grade unless otherwise specified.

[0044] The bio-based wax microspheres used in this invention were prepared using the following method:

[0045] S11. Melting: Carnauba wax and rice bran wax are added to a jacketed mixing tank at a mass ratio of 7:3 and melted at 85℃ and 200rpm for 30 minutes to obtain a molten wax phase.

[0046] S12. Thermal emulsification: Add 3 wt% of decyl-β-D-maltose dimer and 95℃ deionized water to the molten wax phase and perform high shear at 8000 rpm for 10 min to obtain O / W crude emulsion.

[0047] S13, High-pressure homogenization: The obtained O / W crude emulsion was immediately passed through an 80℃ constant temperature homogenizer, with a first-stage pressure of 800 bar and a second-stage pressure of 120 bar, for 3 cycles to obtain a nano-emulsion with D50≈0.5µm.

[0048] S14 Spray Cooling: The nanoemulsion is atomized through a two-fluid nozzle with an inlet air temperature of 5℃, an outlet air temperature of 15℃, and an atomization pressure of 0.4MPa. The wax droplets solidify instantly, and the microspheres are collected by a cyclone separator and passed through a 200-mesh sieve to obtain the finished bio-based wax microspheres with an average particle size D50 of 1.0µm.

[0049] The graphene oxide-chitosan hybrid dispersion (i.e., GO-CS hybrid dispersion) used in this invention was prepared by the following method:

[0050] S21. Add monolayer graphene oxide (i.e. GO, in which C accounts for 55 wt% and O accounts for 40 wt%) to deionized water to prepare a 1.0 wt% pre-dispersion solution, and ultrasonically exfoliate it for 30 min at 25℃, 800W and 20kHz to obtain a uniform GO dispersion solution.

[0051] S22. Chitosan (CS) with a degree of deacetylation ≥90% and a viscosity-average molecular weight of 200~300kDa is dissolved in 1.0wt% acetic acid aqueous solution to prepare a 2.0wt% CS solution, and magnetically stirred at 2000rpm for 2h.

[0052] S23. Add the CS solution dropwise to the GO dispersion at a GO / CS solid mass ratio of 1:2, and sonicate at 25℃ and 300W for 10 min to allow the positive and negative charges to self-assemble electrostatically.

[0053] S24. Adjust the pH to 6.5-7.0 with 0.1M NaOH, then stir at 600rpm for 1h to obtain a 0.3wt% graphene oxide-chitosan hybrid dispersion. Store at 4℃ in the dark and use within 7 days.

[0054] Example 1

[0055] This embodiment provides an anti-permeability adhesive, which is composed of the following components in parts by weight: 18 parts of bio-based wax microspheres, 3 parts of Pickering particle stabilizer, 36 parts of multi-stage gradient crosslinking monomer, 1 part of aqueous photoinitiator, 5 parts of graphene oxide-chitosan hybrid dispersion, 2 parts of glycosyl gemini surfactant, and deionized water to make up to 100 parts.

[0056] The multi-stage gradient crosslinking monomers consist of ethyl acetoacetoxymethacrylate, tripropylene glycol diacrylate, and bisphenol A epoxy diacrylate in a mass ratio of 3:4:2. The pickering particle stabilizer is a mixture of hydrophobic SiO2 and ZnO nanorods in a mass ratio of 4:1, with the hydrophobic SiO2 having a specific surface area of ​​170 m² / g. The aqueous photoinitiator is phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide, specifically the water-dispersible photoinitiator IRGACURE 819DW manufactured by BASF, with a solid content of 25 wt%. The glycosyl gemini surfactant is decyl-β-D-maltose dimer.

[0057] The preparation method of this anti-permeability adhesive includes the following steps:

[0058] S1. Bio-based wax microspheres, Pickering particle stabilizer and glycosyl gemini surfactant were added to deionized water at 25°C and homogenized three times under high pressure at 600 bar to obtain a stable Pickering emulsion.

[0059] S2. Under nitrogen protection, ethyl acetoacetoxy methacrylate, tripropylene glycol diacrylate, bisphenol A epoxy diacrylate and water-based photoinitiator are added sequentially to the Pickering emulsion obtained in step S1. The mixture is stirred at 600 rpm for 30 min under 395 nm ultraviolet LED irradiation and UV curing energy of 400 mJ / cm² to form a gradient crosslinked prepolymer with a "core-shell" structure.

[0060] S3. Add graphene oxide-chitosan hybrid dispersion dropwise, and ultrasonically disperse at 20kHz and 300W for 10min to obtain impermeable adhesive base liquid;

[0061] S4. Filter the antipermeable adhesive base liquid obtained in step S3 through a 1µm bag filter and degas it under vacuum at 40℃ to obtain the finished antipermeable adhesive.

[0062] Example 2

[0063] This embodiment provides an anti-permeability adhesive, which is composed of the following components in parts by weight: 15 parts of bio-based wax microspheres, 2 parts of Pickering particle stabilizer, 36 parts of multi-stage gradient crosslinking monomer, 1 part of aqueous photoinitiator, 3 parts of graphene oxide-chitosan hybrid dispersion, 2 parts of glycosyl gemini surfactant, and deionized water to make up to 100 parts.

[0064] This embodiment only changes the amount of bio-based wax microspheres, Pickering particle stabilizer, and graphene oxide-chitosan hybrid dispersion; the rest is the same as in Example 1.

[0065] Example 3

[0066] This embodiment provides an anti-permeability adhesive, which is composed of the following components in parts by weight: 20 parts of bio-based wax microspheres, 4 parts of Pickering particle stabilizer, 36 parts of multi-stage gradient crosslinking monomer, 1 part of aqueous photoinitiator, 6 parts of graphene oxide-chitosan hybrid dispersion, 2 parts of glycosyl gemini surfactant, and deionized water to make up to 100 parts.

[0067] This embodiment only changes the amount of bio-based wax microspheres, Pickering particle stabilizer, and graphene oxide-chitosan hybrid dispersion; the rest is the same as in Example 1.

[0068] Example 4

[0069] This embodiment provides an anti-permeability adhesive, which is composed of the following components in parts by weight: 23 parts of bio-based wax microspheres, 5 parts of Pickering particle stabilizer, 36 parts of multi-stage gradient crosslinking monomer, 1 part of aqueous photoinitiator, 7 parts of graphene oxide-chitosan hybrid dispersion, 2 parts of glycosyl gemini surfactant, and deionized water to make up to 100 parts.

[0070] This embodiment only changes the amount of bio-based wax microspheres, Pickering particle stabilizer, and graphene oxide-chitosan hybrid dispersion; the rest is the same as in Example 1.

[0071] Example 5

[0072] This embodiment provides an anti-permeability adhesive, which is composed of the following components in parts by weight: 25 parts of bio-based wax microspheres, 5 parts of Pickering particle stabilizer, 36 parts of multi-stage gradient crosslinking monomer, 1 part of aqueous photoinitiator, 8 parts of graphene oxide-chitosan hybrid dispersion, 2 parts of glycosyl gemini surfactant, and deionized water to make up to 100 parts.

[0073] This embodiment only changes the amount of bio-based wax microspheres, Pickering particle stabilizer, and graphene oxide-chitosan hybrid dispersion; the rest is the same as in Example 1.

[0074] Comparative Example 1

[0075] This comparative example provides an anti-permeability adhesive, which uses sodium dodecyl sulfate instead of Pickering particle stabilizer and changes its dosage to 1.5 parts, while the rest is the same as in Example 1.

[0076] Comparative Example 2

[0077] This comparative example provides an anti-permeability adhesive, which removes the graphene oxide-chitosan hybrid dispersion and replaces it with an equal amount of deionized water, otherwise it is the same as in Example 1.

[0078] Comparative Example 3

[0079] This comparative example provides an anti-permeability adhesive, prepared according to the method disclosed in Example 1 of patent CN116694281A.

[0080] The impermeable adhesives prepared in Examples 1-5 and Comparative Examples 1-3 were subjected to performance tests according to the following test items. The specific test methods are described below:

[0081] 1. KIT oil resistance rating: ASTM F1196;

[0082] 2. Air permeability: GB / T 12655, initial value 67 CU;

[0083] 3. Melting droplet test: A homemade 10° tilted combustion rack was used to record whether molten droplets adhered to the filter paper after combustion;

[0084] 4. Fragrance migration: 15 mg of menthol fragrance was added to the filter tip, and the migration amount on the paper surface was determined by GC-MS at 50℃ for 2 h.

[0085] 5. Low-temperature brittleness: Fold the object at -10℃ 180° and observe for cracks.

[0086] Table 1 Performance test results of the examples and comparative examples

[0087]

[0088] As shown in Table 1, Examples 1-5 of this invention all achieved a KIT rating of 6, with an air permeability loss of 5-9%, no dripping, and fragrance migration of <0.3µg / cm², demonstrating a significantly better overall performance than Comparative Examples 1-3. Comparative Example 1, lacking Pickering particle stabilizer, only achieved a KIT rating of 4. Comparative Example 2, lacking the graphene oxide-chitosan hybrid dispersion, saw its menthol migration rise to 1.10µg / cm². Comparative Example 3 experienced an air permeability loss of 22% and dripping during combustion, thus failing the overall evaluation.

[0089] This invention achieves four objectives for the first time: high barrier properties, high air permeability, no dripping, and low-temperature coating through a synergistic design of "multi-segment gradient crosslinking + Pickering emulsion + bio-based wax + GO-CS maze". It can be widely used for oil-proofing treatment of flavored cigarettes, heated tobacco products, and cigar paper.

[0090] The above embodiments are merely illustrative of the concept and technical solution of the present invention and are not intended to limit the present invention. Any person skilled in the art can modify or alter the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or alterations made by those skilled in the art without departing from the spirit and technical concept disclosed in the present invention should still be covered by the claims of the present invention.

[0091] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. An impermeable glue, characterized in that, The bio-based wax microspheres are prepared by compounding Brazil palm wax and rice bran wax at a mass ratio of 7:3, and then high-pressure homogenizing and spray cooling, and have an average particle size D50 of 0.8-1.2 µm.

2. The impermeable glue according to claim 1, characterized in that, The bio-based wax microspheres are prepared by compounding Brazil palm wax and rice bran wax at a mass ratio of 7:3, and then high-pressure homogenizing and spray cooling, and have an average particle size D50 of 0.8-1.2 µm.

3. The barrier adhesive of claim 2, wherein, The bio-based wax microspheres are prepared by compounding Brazil palm wax and rice bran wax at a mass ratio of 7:3, and then high-pressure homogenizing and spray cooling, and have an average particle size D50 of 0.8-1.2 µm. The bio-based wax microspheres are prepared by compounding Brazil palm wax and rice bran wax at a mass ratio of 7:3, and then high-pressure homogenizing and spray cooling, and have an average particle size D50 of 0.8-1.2 µm. The bio-based wax microspheres are prepared by compounding Brazil palm wax and rice bran wax at a mass ratio of 7:3, and then high-pressure homogenizing and spray cooling, and have an average particle size D50 of 0.8-1.2 µm. The bio-based wax microspheres are prepared by compounding Brazil palm wax and rice bran wax at a mass ratio of 7:3, and then high-pressure homogenizing and spray cooling, and have an average particle size D50 of 0.8-1.2 µm. The bio-based wax microspheres are prepared by compounding Brazil palm wax and rice bran wax at a mass ratio of 7:3, and then high-pressure homogenizing and spray cooling, and have an average particle size D50 of 0.8-1.2 µm.

4. The impermeable glue according to claim 1, wherein The bio-based wax microspheres are prepared by compounding Brazil palm wax and rice bran wax at a mass ratio of 7:3, and then high-pressure homogenizing and spray cooling, and have an average particle size D50 of 0.8-1.2 µm.

5. The barrier adhesive of claim 1, wherein The bio-based wax microspheres are prepared by compounding Brazil palm wax and rice bran wax at a mass ratio of 7:3, and then high-pressure homogenizing and spray cooling, and have an average particle size D50 of 0.8-1.2 µm.

6. The impermeable glue according to claim 1, wherein The bio-based wax microspheres are prepared by compounding Brazil palm wax and rice bran wax at a mass ratio of 7:3, and then high-pressure homogenizing and spray cooling, and have an average particle size D50 of 0.8-1.2 µm.

7. The barrier adhesive of claim 6, wherein The bio-based wax microspheres are prepared by compounding Brazil palm wax and rice bran wax at a mass ratio of 7:3, and then high-pressure homogenizing and spray cooling, and have an average particle size D50 of 0.8-1.2 µm. The bio-based wax microspheres are prepared by compounding Brazil palm wax and rice bran wax at a mass ratio of 7:3, and then high-pressure homogenizing and spray cooling, and have an average particle size D50 of 0.8-1.2 µm. The bio-based wax microspheres are prepared by compounding Brazil palm wax and rice bran wax at a mass ratio of 7:3, and then high-pressure homogenizing and spray cooling, and have an average particle size D50 of 0.8-1.2 µm. The bio-based wax microspheres are prepared by compounding Brazil palm wax and rice bran wax at a mass ratio of 7:3, and then high-pressure homogenizing and spray cooling, and have an average particle size D50 of 0.8-1.2 µm. The bio-based wax microspheres are prepared by compounding Brazil palm wax and rice bran wax at a mass ratio of 7:3, and then high-pressure homogenizing and spray cooling, and have an average particle size D50 of 0.8-1.2 µm. The bio-based wax microspheres are prepared by compounding Brazil palm wax and rice bran wax at a mass ratio of 7:3, and then high-pressure homogenizing and spray cooling, and have an average particle size D50 of 0.8-1.2 µm. The bio-based wax microspheres are prepared by compounding Brazil palm wax and rice bran wax at a mass ratio of 7:3, and then high-pressure homogenizing and spray cooling, and have an average particle size D50 of 0.8-1.2 µm. The bio-based wax microspheres are prepared by compounding Brazil palm wax and rice bran wax at a mass ratio of 7:3, and then high-pressure homogenizing and spray cooling, and have an average particle size D50 of 0.8-1.2 µm. The bio-based wax microspheres are prepared by compounding Brazil palm wax and rice bran wax at a mass ratio of 7:3, and then high-pressure homogenizing and spray cooling, and have an average particle size D50 of 0.8-1.2 µm. The bio-based wax microspheres are prepared by compounding Brazil palm wax and rice bran wax at a mass ratio of 7:3, and then high-pressure homogenizing and spray cooling, and have an average particle size D50 of 0.8-1.2 µm. The bio-based wax microspheres are prepared by compounding Brazil palm wax and rice bran wax at a mass ratio of 7:3, and then high-pressure homogenizing and spray cooling, and have an average particle size D50 of 0.8-1.2 µm. The bio-based wax microspheres are prepared by compounding Brazil palm wax and rice bran wax at a mass ratio of 7:3, and then high-pressure homogenizing and spray cooling, and have an average particle size D50 of 0.8-1.2 µm. The bio-based wax microspheres are prepared by compounding Brazil palm wax and rice bran wax at a mass ratio of 7:3, and then high-pressure homogenizing and spray cooling, and have an average particle size D50 of 0.8-1.2 µm. The bio-based wax microspheres are prepared by compounding Brazil palm wax and rice bran wax at a mass ratio of 7:3, and then high-pressure homogenizing and spray cooling, and have an average particle size D50 of 0.8-1.2 µm. The bio-based wax microspheres are prepared by compounding Brazil palm wax and rice bran wax at a mass ratio of 7:3, and then high-pressure homogenizing and spray cooling, and have an average particle size D50 of 0.8-1.2 µm. The bio-based wax microspheres are prepared by compounding Brazil palm wax and rice bran wax at a mass ratio of 7:3, and then high-pressure homogenizing and spray cooling, and have an average particle size D50 of 0.8-1.2 µm. The bio-based wax microspheres are prepared by compounding Brazil palm wax and rice bran wax at a mass ratio of 7:3, and then high-pressure homogenizing and spray cooling, and have an average particle size D50 of 0.8-1.2 µm. The bio-based wax microspheres are prepared by compounding Brazil palm wax and rice bran wax at a mass ratio of 7:3, and then high-pressure homogenizing and spray cooling, and have an average particle size D50 of 0.8-1.2 µm. The bio-based wax microspheres are prepared by compounding Brazil palm wax and rice bran wax at a mass ratio of 7:3, and then high-pressure homogenizing and spray cooling, and have an average particle size D50 of 0.8-1.2 µm. The bio-based wax microspheres are prepared by compounding Brazil palm wax and rice bran wax at a mass ratio of 7:3, and then high-pressure homogenizing and spray cooling, and have an average particle size D50 of 0.8-1.2 µm. The bio-based wax microspheres are prepared by compounding Brazil palm wax and rice bran wax at a mass ratio of 7:3, and then high-pressure homogenizing and spray cooling, and have an average particle size D50 of 0.8-1.2 µm. The bio-based wax microspheres are prepared by compounding Brazil palm wax and rice bran wax at a mass ratio of 7:3, and then high-pressure homogenizing and spray cooling, and have an average particle size D50 of 0.8-1.2 µm. The bio-based wax microspheres are prepared by compounding Brazil palm wax and rice bran wax at a mass ratio of 7:3, and then high-pressure homogenizing and spray cooling, and have an average particle size D50 of 0.8-1.2 µm. The bio-based wax microspheres are prepared by compounding Brazil palm wax and rice bran wax at a mass ratio of 7:3, and then high-pressure homogenizing and spray cooling, and have an average particle size D50 of 0.8-1.2 µm. The bio-based wax microspheres are 8. The impermeable glue as claimed in claim 1, wherein, The sugar-based Gemini surfactant is decyl-beta-D-maltoside dimer.

9. A method of preparing the impermeable glue as claimed in any one of claims 1 to 8, characterized in that, The method comprises the following steps: S1, adding bio-based wax microspheres, Pickering particle stabilizer and sugar-based Gemini surfactant into deionized water at 25°C, and homogenizing 3 times at 600 bar high pressure to obtain a stable Pickering emulsion; S2, under the protection of nitrogen, adding acetoacetoxy methyl acrylate, tripropylene glycol diacrylate, bisphenol A epoxy diacrylate and water-based photoinitiator into the Pickering emulsion obtained in step S1 in sequence, stirring at 600 rpm under the irradiation of 395 nm ultraviolet LED for 30 min, the UV curing energy is 400 mJ / cm2, and a gradient cross-linked prepolymer with "core-shell" structure is formed; S3, dropping graphene oxide-chitosan hybrid dispersion liquid, and ultrasonic dispersing under the condition of 20 kHz and 300 W for 10 min to obtain a permeation-resistant gum base solution; S4, filtering the permeation-resistant gum base solution obtained in step S3 through a 1 µm bag filter, and vacuum degassing at 40°C to obtain a finished permeation-resistant gum.

10. Application of the permeation-resistant gum according to any one of claims 1-8 to oil-proof coating of cigarette paper, filter tipping paper or heating non-combustible cigarette substrate.

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