Counter hot melt adhesive material with high viscosity

Abstract

The invention relates to a counter hot melt adhesive material with high viscosity, and belongs to the technical field of hot melt adhesives. The counter hot melt adhesive material with high viscosity provided by the invention is prepared from the following raw materials in parts by weight: 41.5 to 42.5 parts of TPU, 55.5 to 56.5 parts of EVA and 1 to 3 parts of functional aids, and the functional aids comprise POE-g-MAH, a tackifying system, nano boron nitride with the surface grafted with a silane coupling agent, an antioxidant 1076, dibenzoyl peroxide, epoxy-terminated silicone oil and white mineral oil. According to the counter hot melt adhesive material provided by the invention, all the components cooperate with one another, so that the counter hot melt adhesive material can still keep relatively high viscosity in a humid and hot environment, and the requirements of practical application are met.

Description

Technical Field

[0001] This invention belongs to the field of hot melt adhesive technology and relates to a hot melt adhesive material with high viscosity. Background Technology

[0002] Hot melt adhesive is an important shoe-making material, mainly used for bonding the upper and sole of shoes. Its main component is a thermoplastic resin as an extruded adhesive, which is heated and melted and then applied to the substrate. After cooling, it forms a strong bond.

[0003] However, in actual use, insufficient adhesion often occurs, especially in high temperature or high humidity environments, where the adhesive is prone to softening or losing its stickiness, leading to bonding failure. This has become a technical problem that companies urgently need to overcome. Summary of the Invention

[0004] The purpose of this invention is to provide a hot melt adhesive material with high viscosity. The hot melt adhesive material prepared by this invention can maintain high viscosity in a humid and hot environment, thus meeting the needs of practical applications.

[0005] The objective of this invention can be achieved through the following technical solutions: A highly viscous hot melt adhesive material, wherein the raw materials of the hot melt adhesive material, by weight, include 41.5-42.5 parts TPU, 55.5-56.5 parts EVA, and 1-3 parts functional additives; The raw materials of the functional additive, by weight, include 18-22 parts POE-g-MAH, 22-30 parts thickening system, 2.5-3.5 parts nano boron nitride grafted with silane coupling agent, 0.8-1.2 parts antioxidant 1076, 1.6-2 parts terminal epoxy silicone oil, and 2-3 parts white mineral oil.

[0006] Furthermore, the EVA is obtained by modification with polysiloxane, specifically including the following steps: S11. EVA, aminopropyl double-terminated polydimethylsiloxane, maleic anhydride, benzoyl peroxide, and antioxidant 1010 are mixed and stirred evenly at 800-1200 rpm. The mixture is then melt-extruded by a twin-screw extruder, water-cooled and pelletized, and vacuum-dried at 80°C to obtain polysiloxane-modified EVA.

[0007] Further, the mass ratio of EVA, aminopropyl double-terminated polydimethylsiloxane, maleic anhydride, benzoyl peroxide, and antioxidant 1010 in step S11 is 10:0.08-0.12:0.1-0.2:0.01-0.03:0.02-0.04.

[0008] Furthermore, the raw materials of the thickening system, by weight, include 25-31 parts of montmorillonite-grafted C9 petroleum resin and 9-15 parts of hydrogenated rosin glycerol ester.

[0009] Furthermore, the preparation method of the montmorillonite-grafted C9 petroleum resin includes the following steps: S21. Stir montmorillonite and KH-570 at 76-84℃ and 1600-2400rpm for 30-40min to obtain pretreated montmorillonite. S22. After heating the reactor to 120-130℃, add C9 petroleum resin and propylene glycol methyl ether acetate, stir evenly, then add pretreated montmorillonite, and stir at 80-160 rpm for 4-5 hours to obtain a mixture. S23. Wash the mixture with ethanol to remove unreacted reagents, and dry it under vacuum at 80°C to obtain montmorillonite-grafted C9 petroleum resin.

[0010] Further, the mass ratio of montmorillonite and KH-570 in step S21 is 1:0.18-0.22; the mass ratio of C9 petroleum resin, propylene glycol methyl ether acetate, and pretreated montmorillonite in step S22 is 1:0.42-0.46:0.95-1.15.

[0011] Furthermore, the method for preparing the surface-grafted silane coupling agent-coated boron nitride nanoparticles includes the following steps: S31. Mix KH-550, anhydrous ethanol and deionized water, then add acetic acid dropwise to adjust the pH to 4-5, and stir at 38-42℃ for 30-40 min to obtain silane hydrolysate. S32. Add boron nitride nanoparticles to silane hydrolysate, set the ultrasonic power to 200-400W, ultrasonically disperse for 10-20 min, heat to 68-72℃ and stir for 3.5-4.5 h, centrifuge, wash with ethanol to remove unreacted reagents, and vacuum dry at 80℃ to obtain boron nitride nanoparticles grafted with silane coupling agent.

[0012] Furthermore, the mass ratio of the nano boron nitride, KH-550, anhydrous ethanol, and deionized water is 10:0.5-0.9:28-32:1-1.4.

[0013] Furthermore, the preparation method of the hot melt adhesive for the Hongbao (Hong Kong-style) pipe includes the following steps: S41. Stir TPU, EVA, and POE-g-MAH white mineral oil at 88-92℃ and 500-700rpm for 2-4 minutes to obtain a premix. S42. Add the thickening system and nano boron nitride with surface-grafted silane coupling agent to the premix, and stir at 800-1200 rpm for 4-6 minutes to obtain the mixture. S43. Cool to 68-72℃, add antioxidant 1076 and terminal epoxy silicone oil to the mixture, stir at 700-900 rpm for 3-5 minutes, melt extrude through a twin-screw extruder, and calender to obtain the final product.

[0014] Furthermore, the thickness after calendering in step S43 is 0.45-0.55 mm.

[0015] The beneficial effects of this invention are: (1) This invention provides a hot melt adhesive material with high viscosity. In the polysiloxane-modified EVA, the siloxane segments migrate to the surface to form a waterproof barrier, which prevents the adhesive layer from swelling and causing a decrease in viscosity. At the same time, the Si-O bond is not easy to break at high temperature, thereby improving the heat resistance and hydrophobicity of the material. On this basis, POE-g-MAH is introduced into the functional additives to enhance flexibility and creep resistance, reduce deformation under high temperature stress, and improve the interfacial compatibility and bonding force with the tackifying system, EVA and other materials.

[0016] (2) The present invention provides a hot melt adhesive material with high viscosity, which introduces a thickening system into the functional additives, and achieves grafting of montmorillonite and C9 petroleum resin through coupling agent. The layered structure of montmorillonite blocks the diffusion of water vapor and heat, and at the same time, it is compounded with hydrogenated rosin glycerol ester to improve viscosity.

[0017] (3) The present invention provides a hot melt adhesive material with high viscosity. The nano boron nitride in the functional additives, which has been grafted with silane coupling agent, forms a thermally conductive network by combining the epoxy groups on the surface with the terminal epoxy silicone oil. At the same time, it works synergistically with polysiloxane modified EVA to accelerate heat dispersion, avoid local overheating and softening of the adhesive layer, thereby enhancing the interfacial bonding force between the filler and the substrate and reducing interfacial peeling in humid and hot environments. Detailed Implementation

[0018] To further illustrate the technical means and effects of the present invention in achieving its intended purpose, the following detailed description of the specific implementation methods, structures, features, and effects of the present invention, in conjunction with embodiments, is provided below.

[0019] In all embodiments and comparative examples of this invention, EVA and C9 petroleum resin were purchased from Jinan Shanhai Chemical Technology Co., Ltd.; TPU and POE-g-MAH were purchased from Dongguan Nabaichuan Plastics Co., Ltd.; aminopropyl dimethylsiloxane, antioxidant 1010, hydrogenated rosin glycerol ester, KH-570, KH-550, and antioxidant 1076 were purchased from Hubei Xinyuhong Biomedical Technology Co., Ltd.; maleic anhydride and montmorillonite were purchased from Thermo Fisher Scientific (China) Co., Ltd.; benzoyl peroxide was purchased from Jinan Huijinchuan Trading Co., Ltd.; propylene glycol methyl ether acetate was purchased from Shanghai Maclean Biochemical Technology Co., Ltd.; nano boron nitride was purchased from Qinghe County Chaotai Metal Materials Co., Ltd.; terminal epoxy silicone oil was purchased from Zhongshan Dixing Chemical Co., Ltd.; and white mineral oil was purchased from Sigma-Aldrich (Shanghai) Trading Co., Ltd.

[0020] Example 1 A highly viscous hot melt adhesive material, wherein the raw materials of the hot melt adhesive material, by weight, include 41.5 parts TPU, 55.5 parts EVA, and 1 part functional additives; The raw materials of the functional additive, by weight, include 18 parts POE-g-MAH, 22 parts thickening system, 2.5 parts nano boron nitride grafted with silane coupling agent, 0.8 parts antioxidant 1076, 1.6 parts terminal epoxy silicone oil, and 2 parts white mineral oil.

[0021] The EVA is obtained by modification with polysiloxane, specifically through the following steps: S11. EVA, aminopropyl double-terminated polydimethylsiloxane, maleic anhydride, benzoyl peroxide, and antioxidant 1010 are mixed and stirred evenly at 800 rpm. The mixture is then melt-extruded by a twin-screw extruder, water-cooled and pelletized, and vacuum-dried at 80°C to obtain polysiloxane-modified EVA.

[0022] The mass ratio of EVA, aminopropyl double-terminated polydimethylsiloxane, maleic anhydride, benzoyl peroxide, and antioxidant 1010 in step S11 is 10:0.08:0.1:0.01:0.02.

[0023] The raw materials of the thickening system, by weight, include 25 parts montmorillonite-grafted C9 petroleum resin and 9 parts hydrogenated rosin glycerol ester.

[0024] The method for preparing montmorillonite-grafted C9 petroleum resin includes the following steps: S21. Montmorillonite and KH-570 are stirred at 76℃ and 1600rpm for 30min to obtain pretreated montmorillonite. S22. After the reactor is heated to 120°C, C9 petroleum resin and propylene glycol methyl ether acetate are added and stirred evenly. Then, pretreated montmorillonite is added and stirred at 80 rpm for 4 hours to obtain a mixture. S23. Wash the mixture with ethanol to remove unreacted reagents, and dry it under vacuum at 80°C to obtain montmorillonite-grafted C9 petroleum resin.

[0025] The mass ratio of montmorillonite and KH-570 in step S21 is 1:0.18; the mass ratio of C9 petroleum resin, propylene glycol methyl ether acetate, and pretreated montmorillonite in step S22 is 1:0.42:0.95.

[0026] The method for preparing the nano-boron nitride with surface-grafted silane coupling agent includes the following steps: S31. Mix KH-550, anhydrous ethanol, and deionized water, then add acetic acid to adjust the pH to 4. Stir at 38°C for 30 min to obtain silane hydrolysate. S32. Add boron nanoparticles to silane hydrolysate, set the ultrasonic power to 200W, ultrasonically disperse for 10 min, heat to 68℃ and stir for 3.5 h, centrifuge, wash with ethanol to remove unreacted reagents, and vacuum dry at 80℃ to obtain boron nanoparticles grafted with silane coupling agent.

[0027] The mass ratio of the nano boron nitride, KH-550, anhydrous ethanol, and deionized water is 10:0.5:28:1.

[0028] The preparation method of the hot melt adhesive for the Hongbao (Hong Kong-style) pipe includes the following steps: S41. TPU, EVA, and POE-g-MAH white mineral oil are stirred at 88℃ and 500rpm for 2 minutes to obtain a premix. S42. Add the thickening system and nano boron nitride with surface-grafted silane coupling agent to the premix, and stir at 800 rpm for 4 min to obtain the mixture. S43. Cool down to 68℃, add antioxidant 1076 and terminal epoxy silicone oil to the mixture, stir at 700 rpm for 3 minutes, melt extrude through a twin-screw extruder, and calender to obtain the final product.

[0029] The thickness after calendering in step S43 is 0.45 mm.

[0030] Example 2 A highly viscous hot melt adhesive material, wherein the raw materials of the hot melt adhesive material, by weight, include 41.8 parts TPU, 55.8 parts EVA, and 1.5 parts functional additives; The raw materials of the functional additive, by weight, include 19 parts POE-g-MAH, 24 parts thickening system, 2.8 parts nano boron nitride grafted with silane coupling agent, 0.9 parts antioxidant 1076, 1.7 parts terminal epoxy silicone oil, and 2.2 parts white mineral oil.

[0031] The EVA is obtained by modification with polysiloxane, specifically through the following steps: S11. EVA, aminopropyl double-terminated polydimethylsiloxane, maleic anhydride, benzoyl peroxide, and antioxidant 1010 are mixed and stirred evenly at 800 rpm. The mixture is then melt-extruded by a twin-screw extruder, water-cooled and pelletized, and vacuum-dried at 80°C to obtain polysiloxane-modified EVA.

[0032] The mass ratio of EVA, aminopropyl double-terminated polydimethylsiloxane, maleic anhydride, benzoyl peroxide, and antioxidant 1010 in step S11 is 10:0.09:0.12:0.01:0.02.

[0033] The raw materials of the thickening system, by weight, include 27 parts montmorillonite-grafted C9 petroleum resin and 11 parts hydrogenated rosin glycerol ester.

[0034] The method for preparing montmorillonite-grafted C9 petroleum resin includes the following steps: S21. Montmorillonite and KH-570 are stirred at 78℃ and 1800 rpm for 30 minutes to obtain pretreated montmorillonite. S22. After the reactor is heated to 120°C, C9 petroleum resin and propylene glycol methyl ether acetate are added and stirred evenly. Then, pretreated montmorillonite is added and stirred at 100 rpm for 4.3 hours to obtain a mixture. S23. Wash the mixture with ethanol to remove unreacted reagents, and dry it under vacuum at 80°C to obtain montmorillonite-grafted C9 petroleum resin.

[0035] The mass ratio of montmorillonite and KH-570 in step S21 is 1:0.19; the mass ratio of C9 petroleum resin, propylene glycol methyl ether acetate, and pretreated montmorillonite in step S22 is 1:0.43:0.98.

[0036] The method for preparing the nano-boron nitride with surface-grafted silane coupling agent includes the following steps: S31. Mix KH-550, anhydrous ethanol, and deionized water, then add acetic acid to adjust the pH to 4. Stir at 38°C for 30 min to obtain silane hydrolysate. S32. Add boron nanoparticles to silane hydrolysate, set the ultrasonic power to 200W, ultrasonically disperse for 10 min, heat to 68℃ and stir for 3.8 h, centrifuge, wash with ethanol to remove unreacted reagents, and vacuum dry at 80℃ to obtain boron nanoparticles grafted with silane coupling agent.

[0037] The mass ratio of the nano boron nitride, KH-550, anhydrous ethanol, and deionized water is 10:0.6:29:1.1.

[0038] The preparation method of the hot melt adhesive for the Hongbao (Hong Kong-style) pipe includes the following steps: S41. TPU, EVA, and POE-g-MAH white mineral oil are stirred at 88℃ and 500rpm for 2 minutes to obtain a premix. S42. Add the thickening system and nano boron nitride with surface-grafted silane coupling agent to the premix, and stir at 800 rpm for 4 min to obtain the mixture. S43. Cool down to 68℃, add antioxidant 1076 and terminal epoxy silicone oil to the mixture, stir at 700 rpm for 3 minutes, melt extrude through a twin-screw extruder, and calender to obtain the final product.

[0039] The thickness after calendering in step S43 is 0.45 mm.

[0040] Example 3 A high-viscosity hot melt adhesive material for Hongbao (a type of plastic seal), wherein the raw materials of the hot melt adhesive material, by weight, include 42 parts TPU, 56 parts EVA, and 2 parts functional additives; The raw materials of the functional additive, by weight, include 20 parts POE-g-MAH, 26 parts thickening system, 3 parts cumene, 1.8 parts terminal epoxy silicone oil, and 2.5 parts white mineral oil.

[0041] The EVA is obtained by modification with polysiloxane, specifically through the following steps: S11. EVA, aminopropyl double-terminated polydimethylsiloxane, maleic anhydride, benzoyl peroxide, and antioxidant 1010 are mixed and stirred evenly at 1000 rpm. The mixture is then melt-extruded by a twin-screw extruder, water-cooled and pelletized, and vacuum-dried at 80°C to obtain polysiloxane-modified EVA.

[0042] The mass ratio of EVA, aminopropyl double-terminated polydimethylsiloxane, maleic anhydride, benzoyl peroxide, and antioxidant 1010 in step S11 is 10:0.1:0.15:0.02:0.03.

[0043] The raw materials of the thickening system, by weight, include 28 parts montmorillonite-grafted C9 petroleum resin and 12 parts hydrogenated rosin glycerol ester.

[0044] The method for preparing montmorillonite-grafted C9 petroleum resin includes the following steps: S21. Montmorillonite and KH-570 are stirred at 2000 rpm for 35 minutes at 80℃ to obtain pretreated montmorillonite. S22. After the reactor is heated to 125°C, C9 petroleum resin and propylene glycol methyl ether acetate are added and stirred evenly. Then, pretreated montmorillonite is added and stirred at 120 rpm for 4.5 hours to obtain a mixture. S23. Wash the mixture with ethanol to remove unreacted reagents, and dry it under vacuum at 80°C to obtain montmorillonite-grafted C9 petroleum resin.

[0045] The mass ratio of montmorillonite and KH-570 in step S21 is 1:0.2; the mass ratio of C9 petroleum resin, propylene glycol methyl ether acetate, and pretreated montmorillonite in step S22 is 1:0.44:1.05.

[0046] The method for preparing the nano-boron nitride with surface-grafted silane coupling agent includes the following steps: S31. Mix KH-550, anhydrous ethanol, and deionized water, then add acetic acid to adjust the pH to 4.5. Stir at 40°C for 35 minutes to obtain a silane hydrolysate. S32. Add boron nanoparticles to silane hydrolysate, set the ultrasonic power to 300W, ultrasonically disperse for 15 min, heat to 70℃ and stir for 4 h, centrifuge, wash with ethanol to remove unreacted reagents, and vacuum dry at 80℃ to obtain boron nanoparticles grafted with silane coupling agent.

[0047] The mass ratio of the nano boron nitride, KH-550, anhydrous ethanol, and deionized water is 10:0.7:30:1.2.

[0048] The preparation method of the hot melt adhesive for the Hongbao (Hong Kong-style) pipe includes the following steps: S41. TPU, EVA, and POE-g-MAH white mineral oil are stirred at 90℃ and 600rpm for 3 minutes to obtain a premix. S42. Add the thickening system and nano boron nitride with surface-grafted silane coupling agent to the premix, and stir at 1000 rpm for 5 min to obtain the mixture. S43. Cool down to 70℃, add antioxidant 1076 and terminal epoxy silicone oil to the mixture, stir at 800 rpm for 4 minutes, melt extrude through a twin-screw extruder, and calender to obtain the final product.

[0049] The thickness after calendering in step S43 is 0.5 mm.

[0050] Example 4 A highly viscous hot melt adhesive material, wherein the raw materials of the hot melt adhesive material, by weight, include 42.3 parts TPU, 56.2 parts EVA, and 2.5 parts functional additives; The raw materials of the functional additive, by weight, include 21 parts POE-g-MAH, 28 parts thickening system, 3.1 parts nano boron nitride grafted with silane coupling agent, 1.1 parts antioxidant 1076, 1.9 parts terminal epoxy silicone oil, and 2.6 parts white mineral oil.

[0051] The EVA is obtained by modification with polysiloxane, specifically through the following steps: S11. EVA, aminopropyl double-terminated polydimethylsiloxane, maleic anhydride, benzoyl peroxide, and antioxidant 1010 are mixed and stirred evenly at 1200 rpm. The mixture is then melt-extruded by a twin-screw extruder, water-cooled and pelletized, and vacuum-dried at 80°C to obtain polysiloxane-modified EVA.

[0052] The mass ratio of EVA, aminopropyl double-terminated polydimethylsiloxane, maleic anhydride, benzoyl peroxide, and antioxidant 1010 in step S11 is 10:0.11:0.17:0.0.03:0.04.

[0053] The raw materials of the thickening system, by weight, include 30 parts montmorillonite-grafted C9 petroleum resin and 14 parts hydrogenated rosin glycerol ester.

[0054] The method for preparing montmorillonite-grafted C9 petroleum resin includes the following steps: S21. Montmorillonite and KH-570 were stirred at 82℃ and 2200 rpm for 40 min to obtain pretreated montmorillonite. S22. After the reactor is heated to 130°C, C9 petroleum resin and propylene glycol methyl ether acetate are added. After stirring evenly, pretreated montmorillonite is added and stirred at 140 rpm for 4.8 hours to obtain a mixture. S23. Wash the mixture with ethanol to remove unreacted reagents, and dry it under vacuum at 80°C to obtain montmorillonite-grafted C9 petroleum resin.

[0055] The mass ratio of montmorillonite and KH-570 in step S21 is 1:0.21; the mass ratio of C9 petroleum resin, propylene glycol methyl ether acetate, and pretreated montmorillonite in step S22 is 1:0.45:1.12.

[0056] The method for preparing the nano-boron nitride with surface-grafted silane coupling agent includes the following steps: S31. Mix KH-550, anhydrous ethanol, and deionized water, then add acetic acid dropwise to adjust the pH to 5, and stir at 42°C for 40 min to obtain silane hydrolysate. S32. Add boron nitride nanoparticles to silane hydrolysate, set the ultrasonic power to 400W, ultrasonically disperse for 20 min, heat to 72℃ and stir for 4.2 h, centrifuge, wash with ethanol to remove unreacted reagents, and vacuum dry at 80℃ to obtain boron nitride nanoparticles grafted with silane coupling agent.

[0057] The mass ratio of the nano boron nitride, KH-550, anhydrous ethanol, and deionized water is 10:0.8:31:1.3.

[0058] The preparation method of the hot melt adhesive for the Hongbao (Hong Kong-style) pipe includes the following steps: S41. TPU, EVA, and POE-g-MAH white mineral oil are stirred at 92℃ and 700rpm for 4 minutes to obtain a premix. S42. Add the thickening system and nano boron nitride with surface-grafted silane coupling agent to the premix, and stir at 1200 rpm for 6 min to obtain the mixture. S43. Cool down to 72℃, add antioxidant 1076 and terminal epoxy silicone oil to the mixture, stir at 900 rpm for 5 minutes, melt extrude through a twin-screw extruder, and calender to obtain the final product.

[0059] The thickness after calendering in step S43 is 0.55 mm.

[0060] Example 5 A highly viscous hot melt adhesive material, wherein the raw materials of the hot melt adhesive material, by weight, include 42.5 parts TPU, 56.5 parts EVA, and 3 parts functional additives; The raw materials of the functional additive, by weight, include 22 parts POE-g-MAH, 30 parts thickening system, 3.5 parts nano boron nitride grafted with silane coupling agent, 1.2 parts antioxidant 1076, 2 parts terminal epoxy silicone oil, and 3 parts white mineral oil.

[0061] The EVA is obtained by modification with polysiloxane, specifically through the following steps: S11. EVA, aminopropyl double-terminated polydimethylsiloxane, maleic anhydride, benzoyl peroxide, and antioxidant 1010 are mixed and stirred evenly at 1200 rpm. The mixture is then melt-extruded by a twin-screw extruder, water-cooled and pelletized, and vacuum-dried at 80°C to obtain polysiloxane-modified EVA.

[0062] The mass ratio of EVA, aminopropyl double-terminated polydimethylsiloxane, maleic anhydride, benzoyl peroxide, and antioxidant 1010 in step S11 is 10:0.12:0.2:0.03:0.04.

[0063] The raw materials of the thickening system, by weight, include 31 parts montmorillonite-grafted C9 petroleum resin and 15 parts hydrogenated rosin glycerol ester.

[0064] The method for preparing montmorillonite-grafted C9 petroleum resin includes the following steps: S21. Montmorillonite and KH-570 were stirred at 84℃ and 2400 rpm for 40 min to obtain pretreated montmorillonite. S22. After the reactor is heated to 130°C, C9 petroleum resin and propylene glycol methyl ether acetate are added and stirred evenly. Then, pretreated montmorillonite is added and stirred at 160 rpm for 5 hours to obtain a mixture. S23. Wash the mixture with ethanol to remove unreacted reagents, and dry it under vacuum at 80°C to obtain montmorillonite-grafted C9 petroleum resin.

[0065] The mass ratio of montmorillonite and KH-570 in step S21 is 1:0.22; the mass ratio of C9 petroleum resin, propylene glycol methyl ether acetate, and pretreated montmorillonite in step S22 is 1:0.46:1.15.

[0066] The method for preparing the nano-boron nitride with surface-grafted silane coupling agent includes the following steps: S31. Mix KH-550, anhydrous ethanol, and deionized water, then add acetic acid to adjust the pH to 5. Stir at 42°C for 40 min to obtain silane hydrolysate. S32. Add boron nitride nanoparticles to silane hydrolysate, set the ultrasonic power to 400W, ultrasonically disperse for 20 min, heat to 72℃ and stir for 4.5 h, centrifuge, wash with ethanol to remove unreacted reagents, and vacuum dry at 80℃ to obtain boron nitride nanoparticles grafted with silane coupling agent.

[0067] The mass ratio of the nano boron nitride, KH-550, anhydrous ethanol, and deionized water is 10:0.9:32:1.4.

[0068] The preparation method of the hot melt adhesive for the Hongbao (Hong Kong-style) pipe includes the following steps: S41. TPU, EVA, and POE-g-MAH white mineral oil are stirred at 92℃ and 700rpm for 4 minutes to obtain a premix. S42. Add the thickening system and nano boron nitride with surface-grafted silane coupling agent to the premix, and stir at 1200 rpm for 6 min to obtain the mixture. S43. Cool down to 72℃, add antioxidant 1076 and terminal epoxy silicone oil to the mixture, stir at 900 rpm for 5 minutes, melt extrude through a twin-screw extruder, and calender to obtain the final product.

[0069] The thickness after calendering in step S43 is 0.55 mm.

[0070] Example 6 Based on Example 3, no modification was performed on EVA, and other conditions remained the same as in Example 3.

[0071] Example 7 Based on Example 3, POE-g-MAH was removed and replaced with an equal weight of POE, which was purchased from Dongguan Nabaichuan Plastics Co., Ltd., and other conditions remained the same as in Example 3.

[0072] Example 8 Based on Example 3, the C9 petroleum resin was not subjected to montmorillonite grafting treatment, and other conditions remained the same as in Example 3.

[0073] Example 9 Based on Example 3, the montmorillonite-grafted C9 petroleum resin in the thickening system was removed and replaced with an equal weight of hydrogenated rosin glycerol ester, while other conditions remained the same as in Example 3.

[0074] Example 10 Based on Example 3, the hydrogenated rosin glycerol ester in the thickening system was removed and replaced with an equal weight of montmorillonite-grafted C9 petroleum resin, while other conditions remained the same as in Example 3.

[0075] Example 11 Based on Example 3, no surface grafting treatment was performed on the nano-boron nitride, and other conditions remained the same as in Example 3.

[0076] Example 12 Based on Example 3, the terminal epoxy silicone oil was removed and replaced with an equal weight of white mineral oil, while other conditions remained the same as in Example 3.

[0077] Using the hot melt adhesive prepared in Examples 1-12 as samples, the peel strength retention rate of the samples was tested by immersing them in water at 70°C for 7 days through a patch hydrolysis test. The higher the retention rate, the better the adhesion of the sample. The specific results are recorded in Table 1 below.

[0078] As shown in Table 1, the hot melt adhesive material prepared by this invention can maintain high viscosity in a humid and hot environment, meeting the needs of practical applications.

[0079] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some modifications or alterations to the above-disclosed technical content to create equivalent embodiments without departing from the scope of the present invention. Any indirect modifications, equivalent changes, and alterations made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the scope of the present invention.

Claims

1. A high-viscosity hot melt adhesive material for totems, characterized in that: The raw materials of the Hongbao hot melt adhesive material, by weight, include 41.5-42.5 parts TPU, 55.5-56.5 parts EVA, and 1-3 parts functional additives; The raw materials of the functional additive, by weight, include 18-22 parts POE-g-MAH, 22-30 parts thickening system, 2.5-3.5 parts nano boron nitride grafted with silane coupling agent, 0.8-1.2 parts antioxidant 1076, 1.6-2 parts terminal epoxy silicone oil, and 2-3 parts white mineral oil.

2. The high-viscosity hot melt adhesive material for tote bags according to claim 1, characterized in that: The EVA is obtained by modification with polysiloxane, specifically through the following steps: S11. EVA, aminopropyl double-terminated polydimethylsiloxane, maleic anhydride, benzoyl peroxide, and antioxidant 1010 are mixed and stirred evenly at 800-1200 rpm. The mixture is then melt-extruded by a twin-screw extruder, water-cooled and pelletized, and vacuum-dried at 80°C to obtain polysiloxane-modified EVA.

3. The high-viscosity hot melt adhesive material for tote bags according to claim 2, characterized in that: The mass ratio of EVA, aminopropyl double-terminated polydimethylsiloxane, maleic anhydride, benzoyl peroxide, and antioxidant 1010 in step S11 is 10:0.08-0.12:0.1-0.2:0.01-0.03:0.02-0.

04.

4. The high-viscosity hot melt adhesive material for tote bags according to claim 1, characterized in that: The raw materials of the thickening system, by weight, include 25-31 parts of montmorillonite-grafted C9 petroleum resin and 9-15 parts of hydrogenated rosin glycerol ester.

5. The high-viscosity hot melt adhesive material for tote bags according to claim 4, characterized in that: The method for preparing montmorillonite-grafted C9 petroleum resin includes the following steps: S21. Stir montmorillonite and KH-570 at 76-84℃ and 1600-2400rpm for 30-40min to obtain pretreated montmorillonite. S22. After the reactor is heated to 120-130℃, C9 petroleum resin and propylene glycol methyl ether acetate are added. After stirring evenly, pretreated montmorillonite is added and stirred at 80-160 rpm for 4-5 hours to obtain a mixture. S23. Wash the mixture with ethanol to remove unreacted reagents, and dry it under vacuum at 80°C to obtain montmorillonite-grafted C9 petroleum resin.

6. The high-viscosity hot melt adhesive material for tote bags according to claim 5, characterized in that: The mass ratio of montmorillonite and KH-570 in step S21 is 1:0.18-0.22; the mass ratio of C9 petroleum resin, propylene glycol methyl ether acetate, and pretreated montmorillonite in step S22 is 1:0.42-0.46:0.95-1.

15.

7. The high-viscosity hot melt adhesive material for tote bags according to claim 1, characterized in that: The method for preparing the nano-boron nitride with surface-grafted silane coupling agent includes the following steps: S31. Mix KH-550, anhydrous ethanol and deionized water, then add acetic acid dropwise to adjust the pH to 4-5, and stir at 38-42℃ for 30-40 min to obtain silane hydrolysate. S32. Add boron nitride nanoparticles to silane hydrolysate, set the ultrasonic power to 200-400W, ultrasonically disperse for 10-20 min, heat to 68-72℃ and stir for 3.5-4.5 h, centrifuge, wash with ethanol to remove unreacted reagents, and vacuum dry at 80℃ to obtain boron nitride nanoparticles grafted with silane coupling agent.

8. The high-viscosity hot melt adhesive material for totems according to claim 7, characterized in that: The mass ratio of the nano boron nitride, KH-550, anhydrous ethanol, and deionized water is 10:0.5-0.9:28-32:1-1.

4.

9. A hot melt adhesive for a toggle switch prepared from a high-viscosity hot melt adhesive material as described in any one of claims 1-8, characterized in that: The preparation method of the hot melt adhesive for the Hongbao (Hong Kong-style) pipe includes the following steps: S41. Stir TPU, EVA, and POE-g-MAH white mineral oil at 88-92℃ and 500-700rpm for 2-4 minutes to obtain a premix. S42. Add the thickening system and nano boron nitride with surface-grafted silane coupling agent to the premix, and stir at 800-1200 rpm for 4-6 minutes to obtain the mixture. S43. Cool to 68-72℃, add antioxidant 1076 and terminal epoxy silicone oil to the mixture, stir at 700-900 rpm for 3-5 minutes, melt extrude through a twin-screw extruder, and calender to obtain the final product.

10. The hot melt adhesive for preparing a high-viscosity toggle stick according to claim 9, characterized in that: The thickness after calendering in step S43 is 0.45-0.55 mm.

Images