A high polymer film composite graphene heating plate and a preparation method thereof

Abstract

The application discloses a high-molecular film composite graphene heating plate and a preparation method thereof, and relates to the technical field of decoration. The heating plate is composed of the following structures from top to bottom: a color aluminum veneer, a high-molecular film, a graphene heating film, a high-molecular film, an aluminum plate, a high-molecular film, a honeycomb core, a high-molecular film and an aluminum plate, and the thickness of each layer has a specific range of values; the high-molecular film is made of modified polyolefin elastomers, modified nano-silica and other raw materials through a multi-step process. The preparation adopts a step-by-step temperature control thermal compounding process, and the product is obtained after flattening, edge trimming, edge sealing and temperature controller installation. The heating plate is prepared by high-temperature compounding of the environment-friendly high-molecular film, is non-toxic and formaldehyde-free, has the functions of heating and decoration, can be adapted to various surface layer styles, has uniform heating, adjustable temperature, firm interlayer combination, no warping and wrinkling problems, and is suitable for wall surfaces, murals and other scenes in houses and offices.

Description

Technical Field

[0001] This invention relates to the field of decorative technology, specifically to a polymer film composite graphene heating plate and its preparation method. Background Technology

[0002] In the field of technology that integrates decoration and indoor heating, wall heating decorative panels have become an important application product for indoor scenarios such as residences and offices because they combine space utilization and heating functions. Traditional indoor heating methods mostly rely on equipment such as air conditioners and radiators, which have problems such as large space occupation, uneven heating, and poor decoration. On the other hand, single decorative panels only have aesthetic effects and no heating function, which makes it difficult to meet the market's demand for multifunctional building materials.

[0003] Currently, graphene heating composite panels have emerged in existing technologies. These panels are mostly made by simply combining aluminum honeycomb panels, graphene heating films, and decorative panels, attempting to combine heating and decoration. However, the composite process of these panels mostly uses conventional adhesives, which have problems such as formaldehyde release and poor environmental performance. In addition, the bonding force between composite layers is weak, making them prone to warping and separation.

[0004] Meanwhile, the heating film of existing products has insufficient protection and is easily corroded by moisture, affecting the heating effect. The surface layer has low adaptability, and the processing is mostly done by on-site cutting, which easily generates decorative waste. In addition, the temperature control accuracy is poor, and there are local overheating and uneven heating. Overall, there are obvious defects in environmental protection, structural stability, processing convenience and safety of use, making it difficult to meet the high-quality requirements of practical applications. Summary of the Invention

[0005] To address the shortcomings of existing technologies, this invention provides a polymer film composite graphene heating plate and its preparation method, which solves the problems of poor environmental performance, easy structural damage, and limited functionality of existing heating decorative panels.

[0006] To achieve the above objectives, the present invention provides the following technical solution: A polymer film composite graphene heating plate is composed of the following structure, from top to bottom: colored aluminum decorative panel, polymer film, graphene heating film, polymer film, aluminum plate, polymer film, honeycomb core, polymer film, and aluminum plate.

[0007] Furthermore, the thickness of the colored aluminum decorative panel is 0.3-0.5mm, the thickness of each layer of polymer film is 0.15-0.25mm, the thickness of the graphene heating film is 0.1-0.2mm, the thickness of each layer of aluminum plate is 0.2-0.3mm, and the thickness of the honeycomb core is 10-13mm.

[0008] Furthermore, the polymer membrane is prepared from the following raw materials in parts by weight: 100 parts modified polyolefin elastomer (POE), 3-5 parts modified nano silica, 5-8 parts ethylene-acrylic acid copolymer (EAA), 10-15 parts ethylene-vinyl acetate copolymer (EVA), 8-12 parts polyethylene glycol 4000, 0.4-0.6 parts zinc stearate, 0.4-0.6 parts antioxidant 1010, 0.2-0.3 parts antioxidant 168, and 2-3 parts epoxidized soybean oil.

[0009] Furthermore, the ethylene-acrylic acid copolymer has an acrylic acid content of 6-10 wt% and a melt index of 5-10 g / 10 min; the ethylene-vinyl acetate copolymer has a vinyl acetate content of 18-28 wt% and a melt index of 3-8 g / 10 min.

[0010] Furthermore, the specific preparation steps of the polymer membrane are as follows: L1. Add 100 parts of dried modified polyolefin elastomer, 10-15 parts of ethylene-vinyl acetate copolymer, 5-8 parts of ethylene-acrylic acid copolymer, and 8-12 parts of polyethylene glycol 4000 to a high-speed mixer at a speed of 800-900 r / min and a temperature of 113-117℃ for 10-13 min. Then add 2-3 parts of epoxidized soybean oil, 0.4-0.6 parts of antioxidant 1010, and 0.2-0.3 parts of antioxidant 168. Mix at a speed of 1000-1100 r / min for 5-7 min. Discharge and cool to room temperature to obtain premix A. L2. Mix 3-5 parts of modified nano-silica with 0.4-0.6 parts of zinc stearate at 1800-2000 r / min for 2-4 min to obtain side feed B; L3. Set the twin-screw extruder to 133-135℃ in zone 1, 153-155℃ in zone 2, 163-165℃ in zone 3, 158-160℃ in zone 4, 160-168℃ at the die head, and 300-320 r / min for screw speed. Add premix A to the main feed port and add side feed B to zone 2 through the side feeder. Control the residence time of the material in the extruder to 2.5-3.5 min. After extrusion, water cooling, and pelleting, obtain high-molecular membrane granules. L4. Add the special granules into the casting film machine, set the barrel temperature to 168-172℃, the die head temperature to 173-177℃, the cooling roller temperature to 23-27℃, the traction speed to 23-27m / min, and the air knife pressure to 0.3-0.5MPa, to prepare a polymer film with a thickness of 0.15-0.25mm. L5. Anneal the cast polymer film in a 60-80℃ hot air circulating oven for 2-4 hours; then cool to room temperature and place in a corona treatment machine with a corona power of 400-500W and a processing speed of 15-20m / min until the surface tension is ≥48mN / m, to obtain the desired polymer film. (Zn in zinc stearate) 2+ The ionic crosslinking clusters are formed with the carboxyl groups of the modified POE side chain. During the medium-temperature annealing process, the ionic clusters undergo ordered recombination and annealing stabilization to construct a three-dimensional reversible physical crosslinking network.

[0011] Furthermore, the modified polyolefin elastomer is prepared using the following specific steps: A1. Polyolefin elastomer particles were spread evenly in a plasma treatment chamber, and high-purity argon gas was introduced to replace the air three times at a flow rate of 50-100 mL / min. The power was set to 180 W, the treatment time was 10 min, and the chamber temperature was controlled below 40℃. After treatment, the particles were immediately transferred to a mixer preheated to 160℃. Maleic anhydride, a mixture of benzoyl peroxide and acetone, and N,N-dimethylformamide were added. The mixer speed was 60 r / min, and the reaction time was 9 min. The product was pulled out while hot, cooled to room temperature, washed three times with deionized water, washed twice with acetone, and vacuum dried at 60℃ for 6 h. Granulation was then performed to obtain the first modified polyolefin elastomer. An anhydride ring was introduced into the POE main chain to provide reaction sites for subsequent aminolysis, while a small amount of ring-opening generated initial carboxyl groups.

[0012] A2. The first modified polyolefin elastomer was added to a reaction vessel, along with toluene that had been deoxygenated by bubbling under nitrogen. The mixture was heated to 85°C and stirred to swell for 30 min. Allylamine was slowly added dropwise through a dropping funnel over 1 h. After the addition was complete, the reaction continued for 2.5 h. The entire reaction was carried out under nitrogen protection, and the system pressure was maintained at 0.4 MPa. After the reaction was completed, toluene and excess allylamine were removed by vacuum distillation at 60°C and -0.09 MPa. The product was washed three times with acetone and dried under vacuum at 60°C for 4 h to obtain the second modified polyolefin elastomer. Allyl double bonds and carboxyl groups were introduced. The double bonds were used for site-specific grafting, and the carboxyl groups participated in subsequent ionic crosslinking.

[0013] A3. The second modified polyolefin elastomer was added to a reaction flask, along with toluene that had been deoxygenated by bubbling under nitrogen. The mixture was stirred and swollen at room temperature for 30 min. A mixture of mercaptopropionic acid, 2,2-dimethoxy-2-phenylacetophenone, and toluene was then added. Nitrogen gas was continuously introduced into the reaction system, and a 365 nm, 100 W high-pressure mercury lamp ultraviolet light source was turned on, with the light source 10 cm above the liquid surface. The reaction was carried out at room temperature for 1.5 h. After the reaction, toluene was removed by vacuum distillation. The product was washed three times with methanol and dried under vacuum at 60 °C for 4 h to obtain the modified polyolefin elastomer. This method efficiently introduces additional carboxyl groups by stabilizing thioether bonds, avoiding chain breakage side reactions associated with traditional free radical grafting, and maintaining the integrity of the POE main chain. The click reaction exhibits high selectivity, eliminates the risk of POE main chain crosslinking, and maintains thermoplasticity.

[0014] Furthermore, the ratio of polyolefin elastomer particles, maleic anhydride, benzoyl peroxide, acetone, and N,N-dimethylformamide in A1 is 100g: 6-10g: 0.3-0.5g: 10mL: 0.5-1.0mL.

[0015] Furthermore, the ratio of the first modified polyolefin elastomer, toluene, and allylamine in A2 is 100g:120mL:3-5mL.

[0016] Furthermore, the ratio of the amount of the second modified polyolefin elastomer, toluene for swelling the elastomer, mercaptopropionic acid, 2,2-dimethoxy-2-phenylacetophenone, and toluene for dissolving 2,2-dimethoxy-2-phenylacetophenone in A3 is 100g:150mL:4-6mL:0.2-0.4g:5mL.

[0017] Furthermore, the modified nano-silica is prepared using the following specific steps: B1. Place nano-silica in a high-speed mixer, add silane coupling agent KH-570, anhydrous ethanol, and deionized water, and stir at 600-700 r / min for 1.5-2 h at 75℃. After the reaction is completed, vacuum dry at 80℃ for 6 h to obtain the first modified nano-silica. Polymerizable double bonds are introduced on the surface of silica to achieve inorganic-organic interface transition, while giving the particles dispersion stability in toluene.

[0018] B2. The first-stage modified nano-silica was ultrasonically dispersed in toluene, then transferred to a three-necked flask. Methyl methacrylate, n-dodecyl mercaptan, and azobisisobutyronitrile were added. Under nitrogen protection at 85°C, methyl methacrylate was added dropwise over a semi-continuous period of 2 hours. After the addition was complete, the reaction continued for another 3 hours. After the reaction was completed, the precipitate was centrifuged, washed three times with toluene, and dried under vacuum at 65°C for 8 hours to obtain modified nano-silica. This forms a polymethyl methacrylate shell, shielding the surface of the inorganic silica and making the particles compatible with the POE / EVA organic matrix.

[0019] Furthermore, the ratio of nano-silica, silane coupling agent KH-570, anhydrous ethanol, and deionized water in B1 is 10g:3-4mL:40-50mL:2-3mL.

[0020] Furthermore, in B2, the ratio of the first modified nano-silica, toluene, methyl methacrylate, n-dodecyl mercaptan, and azobisisobutyronitrile is 10g:50mL:5-6mL:0.05-0.07g:0.15-0.2g; wherein the ratio of the two uses of methyl methacrylate is 2.5-3mL:2.5-3mL.

[0021] A method for preparing a polymer film composite graphene heating plate specifically includes the following steps: S1. Lay all clean and dry materials on the lower hot plate of the high-temperature thermal laminating machine in the following order from bottom to top: aluminum plate, polymer film, honeycomb core, polymer film, aluminum plate, polymer film, graphene heating film, polymer film, colored aluminum decorative panel; strictly align the centers of each layer during the laying process, and leave a margin for the polymer film to adhere to the edges of each board. S2. A step-by-step temperature-controlled composite process is adopted, with nitrogen protection throughout to prevent metal oxidation. The parameters of the hot composite machine are set as follows: the temperature around the graphene heating film in the first stage is 100-110℃, the pressure is 3MPa, and the hot pressing time is 7-9min; the temperature of the entire board in the second stage is 120-130℃, the pressure is 4-5MPa, and the hot pressing time is 13-17min. The hot-melt adhesive properties of the self-made polymer film are used to tightly composite the 9 layers into one. S3. After the thermal bonding is completed, the composite board is quickly transferred to the flattening machine and flattened at room temperature and 2-3MPa pressure for 40 minutes to eliminate the internal stress of the board and prevent the board from warping, the film layer from wrinkling, and the interlayer from separating. S4. Remove the polymer film from the edges of the board to leave enough for edge pressing, ensuring accurate finished dimensions; use an edge banding machine to apply aluminum alloy edge banding to the four sides of the board to match the style of the colored aluminum decorative panel, preventing moisture from entering the board and damaging the graphene heating film and honeycomb core. S5. Install a thermostat and power connector at the temperature control interface of the graphene heating film. After standardizing the wiring, power on and debug to ensure that the thermostat can achieve temperature control and adjustment. After the heating film is powered on, the temperature rises evenly without local overheating or heat interruption, thus obtaining a polymer film composite graphene heating plate.

[0022] This invention provides a polymer film composite graphene heating plate and its preparation method, which has the following beneficial effects: 1. Using a self-made environmentally friendly polymer film as the composite adhesive layer, the entire process is free of formaldehyde and other toxic and harmful substances. The high-temperature composite process replaces the traditional adhesive bonding method. The finished product meets the environmental protection standards for indoor decoration and there is no harmful gas volatilization during use, ensuring the safety of the indoor environment.

[0023] 2. By using a step-by-step temperature-controlled thermal composite process combined with room temperature pressure flattening, along with a highly adhesive polymer film, the nine-layer board is tightly bonded between layers, effectively eliminating internal stress and avoiding problems such as warping, film wrinkling, and layer separation. In addition, the aluminum alloy edge sealing can isolate moisture, protect the graphene heating film and honeycomb core, and improve the overall durability of the board.

[0024] 3. The surface layer of colored aluminum decorative panel can achieve various styles such as imitation fabric texture and imitation stone texture, which can be matched with different decorative scenes such as walls, murals, and cabinet surfaces. At the same time, the graphene heating film heats up evenly and the temperature is adjustable. It can be used immediately after plugging in and is dust-free and noiseless, without taking up indoor space, thus balancing the practicality of heating and the aesthetics of decoration. Attached Figure Description

[0025] Figure 1 This is a schematic diagram of the structure of the polymer film composite graphene heating plate of the present invention.

[0026] In the picture: 1. Colored aluminum decorative panel; 2. Polymer film; 3. Graphene heating film; 4. Polymer film; 5. Aluminum plate; 6. Polymer film; 7. Honeycomb core; 8. Polymer film; 9. Aluminum plate. Detailed Implementation

[0027] The technical solutions in the embodiments 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.

[0028] Example 1: Preparation of a polymer film composite graphene heating plate. The specific preparation steps are as follows: S1. Lay all clean and dry materials on the lower hot plate of the high-temperature thermal laminating machine in the following order from bottom to top: aluminum plate, polymer film, honeycomb core, polymer film, aluminum plate, polymer film, graphene heating film, polymer film, colored aluminum decorative panel; strictly align the centers of each layer during the laying process, and leave a margin for the polymer film to adhere to the edges of each board. S2. A step-by-step temperature-controlled composite process is adopted, with nitrogen protection throughout to prevent metal oxidation. The parameters of the thermal composite machine are set as follows: the temperature around the graphene heating film in the first stage is 100℃, the pressure is 3MPa, and the hot pressing time is 7min; the temperature of the entire board in the second stage is 120℃, the pressure is 4MPa, and the hot pressing time is 13min. The hot-melt adhesiveness of the self-made polymer film is used to tightly composite the 9 layers into one. S3. After the thermal bonding is completed, the composite board is quickly transferred to the flattening machine and flattened at room temperature and 2MPa pressure for 40 minutes to eliminate the internal stress of the board and prevent the board from warping, the film layer from wrinkling, and the interlayer from separating. S4. Remove the polymer film from the edges of the board to leave enough for edge pressing, ensuring accurate finished dimensions; use an edge banding machine to apply aluminum alloy edge banding to the four sides of the board to match the style of the colored aluminum decorative panel, preventing moisture from entering the board and damaging the graphene heating film and honeycomb core. S5. Install a thermostat and power connector at the temperature control interface of the graphene heating film. After standardizing the wiring, power on and debug to ensure that the thermostat can achieve temperature control and adjustment. After the heating film is powered on, the temperature rises evenly without local overheating or heat interruption, thus obtaining a polymer film composite graphene heating plate.

[0029] Example 2: Preparation of a polymer film composite graphene heating plate. The specific preparation steps are as follows: S1. Lay all clean and dry materials on the lower hot plate of the high-temperature thermal laminating machine in the following order from bottom to top: aluminum plate, polymer film, honeycomb core, polymer film, aluminum plate, polymer film, graphene heating film, polymer film, colored aluminum decorative panel; strictly align the centers of each layer during the laying process, and leave a margin for the polymer film to adhere to the edges of each board. S2. A step-by-step temperature-controlled composite process is adopted, with nitrogen protection throughout to prevent metal oxidation. The parameters of the hot composite machine are set as follows: the temperature around the graphene heating film in the first stage is 110℃, the pressure is 3MPa, and the hot pressing time is 9min; the temperature of the whole board in the second stage is 130℃, the pressure is 5MPa, and the hot pressing time is 17min. The hot melt adhesiveness of the self-made polymer film is used to tightly composite the 9 layers into one. S3. After the thermal bonding is completed, the composite board is quickly transferred to the flattening machine and flattened at room temperature and 3MPa pressure for 40 minutes to eliminate the internal stress of the board and prevent the board from warping, the film layer from wrinkling, and the interlayer from separating. S4. Remove the polymer film from the edges of the board to leave enough for edge pressing, ensuring accurate finished dimensions; use an edge banding machine to apply aluminum alloy edge banding to the four sides of the board to match the style of the colored aluminum decorative panel, preventing moisture from entering the board and damaging the graphene heating film and honeycomb core. S5. Install a thermostat and power connector at the temperature control interface of the graphene heating film. After standardizing the wiring, power on and debug to ensure that the thermostat can achieve temperature control and adjustment. After the heating film is powered on, the temperature rises evenly without local overheating or heat interruption, thus obtaining a polymer film composite graphene heating plate.

[0030] Example 3: Preparation of a polymer film composite graphene heating plate. The specific preparation steps are as follows: S1. Lay all clean and dry materials on the lower hot plate of the high-temperature thermal laminating machine in the following order from bottom to top: aluminum plate, polymer film, honeycomb core, polymer film, aluminum plate, polymer film, graphene heating film, polymer film, colored aluminum decorative panel; strictly align the centers of each layer during the laying process, and leave a margin for the polymer film to adhere to the edges of each board. S2. A step-by-step temperature-controlled composite process is adopted, with nitrogen protection throughout to prevent metal oxidation. The parameters of the hot composite machine are set as follows: the temperature around the graphene heating film in the first stage is 105℃, the pressure is 3MPa, and the hot pressing time is 8min; the temperature of the whole board in the second stage is 125℃, the pressure is 4MPa, and the hot pressing time is 15min. The hot melt adhesiveness of the self-made polymer film is used to tightly composite the 9 layers into one. S3. After the thermal bonding is completed, the composite board is quickly transferred to the flattening machine and flattened at room temperature and 2MPa pressure for 40 minutes to eliminate the internal stress of the board and prevent the board from warping, the film layer from wrinkling, and the interlayer from separating. S4. Remove the polymer film from the edges of the board to leave enough for edge pressing, ensuring accurate finished dimensions; use an edge banding machine to apply aluminum alloy edge banding to the four sides of the board to match the style of the colored aluminum decorative panel, preventing moisture from entering the board and damaging the graphene heating film and honeycomb core. S5. Install a thermostat and power connector at the temperature control interface of the graphene heating film. After standardizing the wiring, power on and debug to ensure that the thermostat can achieve temperature control and adjustment. After the heating film is powered on, the temperature rises evenly without local overheating or heat interruption, thus obtaining a polymer film composite graphene heating plate.

[0031] Example 4: Preparation of a polymer membrane. The specific preparation steps are as follows: L1. Add 100 parts of dried modified polyolefin elastomer, 10 parts of ethylene-vinyl acetate copolymer, 5 parts of ethylene-acrylic acid copolymer, and 8 parts of polyethylene glycol 4000 to a high-speed mixer at 800 r / min and 113℃ for 10 min. Then add 2 parts of epoxidized soybean oil, 0.4 parts of antioxidant 1010, and 0.2 parts of antioxidant 168, mix at 1000 r / min for 5 min, and discharge and cool to room temperature to obtain premix A. L2. Mix 3 parts of modified nano-silica with 0.4 parts of zinc stearate at 1800 r / min for 2 min to obtain side feed B; L3. Set the twin-screw extruder to 133℃ in zone 1, 153℃ in zone 2, 163℃ in zone 3, 158℃ in zone 4, 160℃ at the die head, and 300r / min for screw speed. Add premix A to the main feed port and add side feed B to zone 2 through the side feeder. Control the residence time of the material in the extruder to 2.5min. After extrusion, water cooling, and pelleting, obtain high-molecular membrane special granules. L4. Add the special granules into the casting film machine, set the barrel temperature to 168℃, the die head temperature to 173℃, the cooling roller temperature to 23℃, the traction speed to 23m / min, and the air knife pressure to 0.3MPa, to prepare a polymer film with a thickness of 0.15mm. L5. Anneal the cast polymer film in a 60℃ hot air circulating oven for 2 hours; then cool it to room temperature and place it in a corona treatment machine with a corona power of 400W and a processing speed of 15m / min to make the surface tension ≥48mN / m, and obtain the desired polymer film.

[0032] Example 5: Preparation of a polymer membrane. The specific preparation steps are as follows: L1. Add 100 parts of dried modified polyolefin elastomer, 15 parts of ethylene-vinyl acetate copolymer, 8 parts of ethylene-acrylic acid copolymer, and 12 parts of polyethylene glycol 4000 to a high-speed mixer at 900 r / min and 117℃ for 13 min. Then add 3 parts of epoxidized soybean oil, 0.6 parts of antioxidant 1010, and 0.3 parts of antioxidant 168, mix at 1100 r / min for 7 min, and discharge and cool to room temperature to obtain premix A. L2. Mix 5 parts of modified nano-silica with 0.6 parts of zinc stearate at 2000 r / min for 4 min to obtain side feed B; L3. Set the twin-screw extruder to 135℃ in zone 1, 155℃ in zone 2, 165℃ in zone 3, 160℃ in zone 4, 168℃ at the die head, and 320r / min for screw speed. Add premix A to the main feed port and add side feed B through the side feeder in zone 2. Control the residence time of the material in the extruder to 3.5min. After extrusion, water cooling, and pelleting, obtain high-molecular membrane granules. L4. Add the special granules into the casting film machine, set the barrel temperature to 172℃, the die head temperature to 177℃, the cooling roller temperature to 27℃, the traction speed to 27m / min, and the air knife pressure to 0.5MPa, to prepare a polymer film with a thickness of 0.25mm. L5. Place the cast polymer film in an 80℃ hot air circulating oven for annealing for 4 hours; then cool it to room temperature and place it in a corona treatment machine with a corona power of 500W and a processing speed of 20m / min to make the surface tension ≥48mN / m, and obtain the desired polymer film.

[0033] Example 6: Preparation of a polymer membrane. The specific preparation steps are as follows: L1. Add 100 parts of dried modified polyolefin elastomer, 12 parts of ethylene-vinyl acetate copolymer, 6 parts of ethylene-acrylic acid copolymer, and 10 parts of polyethylene glycol 4000 to a high-speed mixer at 850 r / min and 115℃ for 11 min. Then add 2 parts of epoxidized soybean oil, 0.5 parts of antioxidant 1010, and 0.2 parts of antioxidant 168, mix at 1050 r / min for 6 min, and discharge and cool to room temperature to obtain premix A. L2. Mix 4 parts of modified nano-silica with 0.5 parts of zinc stearate at 1900 r / min for 3 min to obtain side feed B; L3. Set the twin-screw extruder to 134℃ in zone 1, 154℃ in zone 2, 164℃ in zone 3, 159℃ in zone 4, 164℃ at the die head, and 310r / min for screw speed. Add premix A to the main feed port and add side feed B through the side feeder in zone 2. Control the residence time of the material in the extruder to 3 minutes. After extrusion, water cooling, and pelleting, obtain high-molecular membrane special granules. L4. Add the special granules into the casting film machine, set the barrel temperature to 170℃, the die head temperature to 175℃, the cooling roller temperature to 25℃, the traction speed to 25m / min, and the air knife pressure to 0.4MPa, to prepare a polymer film with a thickness of 0.20mm. L5. Place the cast polymer film in a 70℃ hot air circulating oven for annealing for 3 hours; then cool it to room temperature and place it in a corona treatment machine with a corona power of 450W and a processing speed of 17m / min to make the surface tension ≥48mN / m, and obtain the desired polymer film.

[0034] Example 7: Preparation of modified polyolefin elastomer. The specific preparation steps are as follows: A1. Take 100g of polyolefin elastomer particles and spread them evenly in a plasma treatment chamber. Purge the air three times with high-purity argon gas at a flow rate of 50mL / min, set the power to 180W, and treat for 10min. Control the chamber temperature below 40℃. Immediately after treatment, transfer the particles to a mixer preheated to 160℃. Add 6g of maleic anhydride, 0.3g of benzoyl peroxide and 10mL of acetone mixture, and 0.5mL of N,N-dimethylformamide. Mix the mixer at 60r / min and react for 9min. Pull out the product while it is hot, cool it to room temperature, wash it three times with deionized water and twice with acetone, and vacuum dry it at 60℃ for 6h. Granulate the product to obtain the first modified polyolefin elastomer. A2. 100g of the first-modified polyolefin elastomer was added to a reaction vessel, along with 120mL of toluene that had been deoxygenated by bubbling under nitrogen. The mixture was heated to 85℃ and stirred to swell for 30min. 3mL of allylamine was slowly added dropwise through a dropping funnel over 1h. After the addition was complete, the reaction continued for 2.5h. The entire reaction was carried out under nitrogen protection, and the system pressure was maintained at 0.4MPa. After the reaction was completed, toluene and excess allylamine were removed by vacuum distillation at 60℃ and -0.09MPa. The product was washed three times with acetone and dried under vacuum at 60℃ for 4h to obtain the second-modified polyolefin elastomer. A3. Add 100g of the second modified polyolefin elastomer to a reaction flask, add 150mL of toluene that has been deoxygenated by bubbling under nitrogen, and stir and swell at room temperature for 30min; add 4mL of mercaptopropionic acid, 0.2g of 2,2-dimethoxy-2-phenylacetophenone and 5mL of toluene mixture, continuously purge the reaction system with nitrogen, turn on a 365nm, 100W high-pressure mercury lamp ultraviolet light source, with the light source 10cm above the liquid surface, and react at room temperature for 1.5h; after the reaction is completed, remove the toluene by vacuum distillation, wash the product three times with methanol, and dry it under vacuum at 60℃ for 4h to obtain the modified polyolefin elastomer.

[0035] Example 8: Preparation of modified polyolefin elastomer. The specific preparation steps are as follows: A1. Take 100g of polyolefin elastomer particles and spread them evenly in a plasma treatment chamber. Purge the air three times with high-purity argon gas at a flow rate of 100mL / min, set the power to 180W, and treat for 10min. Control the chamber temperature below 40℃. Immediately after treatment, transfer the particles to a mixer preheated to 160℃. Add 10g of maleic anhydride, 0.5g of benzoyl peroxide and 10mL of acetone mixture, and 1.0mL of N,N-dimethylformamide. Mix the mixer at 60r / min and react for 9min. Pull out the product while it is hot, cool it to room temperature, wash it three times with deionized water and twice with acetone, and vacuum dry it at 60℃ for 6h. Granulate the product to obtain the first modified polyolefin elastomer. A2. 100g of the first-modified polyolefin elastomer was added to a reaction vessel, along with 120mL of toluene that had been deoxygenated by bubbling under nitrogen. The mixture was heated to 85℃ and stirred to swell for 30min. 5mL of allylamine was slowly added dropwise through a dropping funnel over 1h. After the addition was complete, the reaction continued for 2.5h. The entire reaction was carried out under nitrogen protection, and the system pressure was maintained at 0.4MPa. After the reaction was completed, toluene and excess allylamine were removed by vacuum distillation at 60℃ and -0.09MPa. The product was washed three times with acetone and dried under vacuum at 60℃ for 4h to obtain the second-modified polyolefin elastomer. A3. Add 100g of the second modified polyolefin elastomer to a reaction flask, add 150mL of toluene that has been deoxygenated by bubbling under nitrogen, and stir and swell at room temperature for 30min; add 6mL of mercaptopropionic acid, 0.4g of 2,2-dimethoxy-2-phenylacetophenone and 5mL of toluene mixture, continuously purging the reaction system with nitrogen, turn on a 365nm, 100W high-pressure mercury lamp ultraviolet light source, with the light source 10cm above the liquid surface, and react at room temperature for 1.5h; after the reaction is completed, remove the toluene by vacuum distillation, wash the product three times with methanol, and dry it under vacuum at 60℃ for 4h to obtain the modified polyolefin elastomer.

[0036] Example 9: Preparation of modified nano-silica. The specific preparation steps are as follows: B1. Place 10g of nano-silica in a high-speed mixer, add 3mL of silane coupling agent KH-570, 40mL of anhydrous ethanol and 2mL of deionized water, and stir at 600r / min for 1.5h at 75℃. After the reaction is completed, vacuum dry at 80℃ for 6h to obtain the first modified nano-silica. B2. 10g of the first-modified nano-silica was ultrasonically dispersed in 50mL of toluene, then transferred to a three-necked flask. 2.5mL of methyl methacrylate, 0.05g of n-dodecyl mercaptan, and 0.15g of azobisisobutyronitrile were added. Under nitrogen protection at 85℃, 2.5mL of methyl methacrylate was added dropwise over a period of 2 hours. After the addition was complete, the reaction was continued for 3 hours. After the reaction was completed, the precipitate was separated by centrifugation, washed three times with toluene, and dried under vacuum at 65℃ for 8 hours to obtain the modified nano-silica.

[0037] Example 10: Preparation of modified nano-silica. The specific preparation steps are as follows: B1. Place 10g of nano-silica in a high-speed mixer, add 4mL of silane coupling agent KH-570, 50mL of anhydrous ethanol and 3mL of deionized water, and stir at 700r / min for 2h at 75℃. After the reaction is completed, vacuum dry at 80℃ for 6h to obtain the first modified nano-silica. B2. 10g of the first-modified nano-silica was ultrasonically dispersed in 50mL of toluene, then transferred to a three-necked flask. 3mL of methyl methacrylate, 0.07g of n-dodecyl mercaptan, and 0.2g of azobisisobutyronitrile were added. Under nitrogen protection at 85℃, 3mL of methyl methacrylate was added dropwise over a period of 2 hours. After the addition was complete, the reaction was continued for another 3 hours. After the reaction was completed, the precipitate was separated by centrifugation, washed three times with toluene, and dried under vacuum at 65℃ for 8 hours to obtain the modified nano-silica.

[0038] Comparative Example 1: A polymer film composite graphene heating plate was prepared. The specific preparation steps are as follows: The remaining steps remain unchanged, except that the modified polyolefin elastomer in the polymer film of Example 6 used in Example 3 is replaced with an unmodified polyolefin elastomer to prepare a polymer film composite graphene heating plate.

[0039] Comparative Example 2: A polymer film composite graphene heating plate was prepared. The specific preparation steps are as follows: The remaining steps remain unchanged, except that the modified nano-silica in the polymer film of Example 6 used in Example 3 is replaced with unmodified nano-silica to prepare a polymer film composite graphene heating plate.

[0040] Comparative Example 3: A polymer film composite graphene heating plate was prepared. The specific preparation steps are as follows: The remaining steps remain unchanged, except that the modified polyolefin elastomer and modified nano-silica in the polymer film of Example 6 used in Example 3 are replaced with unmodified materials to prepare a polymer film composite graphene heating plate.

[0041] Performance testing Test Project Test Standards Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Interlayer peel strength (N / cm) GB / T2790-1995 18.2 18.5 18.8 12.5 13.1 11.5 Temperature at which no deformation occurs (°C) under 1.8 MPa GB / T1634.2-2019 112 118 125 100 115 90 Water resistance (immersion in water for 72 hours, interlayer condition) GB / T17657-2022 No layering, no wrinkles No layering, no wrinkles No layering, no wrinkles Slight wrinkling, localized micro-layering Slight wrinkles Slight wrinkling, localized micro-layering Performance test results of the polymer film composite graphene heating plate showed that Examples 1-3, which used modified polyolefin elastomers and modified nano-silica to prepare polymer films, exhibited excellent performance in interlayer peel strength (18.2-18.8 N / cm), no-deformation temperature at 1.8 MPa (112-125℃), and water resistance (no delamination or wrinkling after immersion in water for 72 hours), with Example 3 being the best. In contrast, Comparative Examples 1-3, which replaced the modified polyolefin elastomers and modified nano-silica with unmodified materials, showed a significant decrease in all performance aspects. Among them, Comparative Example 3, which used neither modified material nor modified material, had the worst performance, with an interlayer peel strength of only 11.5 N / cm and a no-deformation temperature at 1.8 MPa of 90℃. It also showed slight wrinkling and local micro-delamination after immersion in water, fully demonstrating the key role of raw material modification in improving the overall performance of the heating plate.

[0042] The above description is merely an example and illustration of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described, or use similar methods to replace them, as long as they do not deviate from the invention or exceed the scope defined in the claims, all of which should fall within the protection scope of the present invention.

Claims

1. A polymer film composite graphene heating plate, characterized in that: The polymer film composite graphene heating plate is composed of the following structure, from top to bottom: colored aluminum decorative panel (1), polymer film (2), graphene heating film (3), polymer film (4), aluminum plate (5), polymer film (6), honeycomb core (7), polymer film (8), and aluminum plate (9).

2. The polymer film composite graphene heating plate according to claim 1, characterized in that: The thickness of the colored aluminum decorative panel is 0.3-0.5mm, the thickness of each layer of polymer film is 0.15-0.25mm, the thickness of the graphene heating film is 0.1-0.2mm, the thickness of each layer of aluminum plate is 0.2-0.3mm, and the thickness of the honeycomb core is 10-13mm.

3. The polymer film composite graphene heating plate according to claim 1, characterized in that: The polymer membrane is prepared from the following raw materials in parts by weight: 100 parts modified polyolefin elastomer, 3-5 parts modified nano silica, 5-8 parts ethylene-acrylic acid copolymer, 10-15 parts ethylene-vinyl acetate copolymer, 8-12 parts polyethylene glycol 4000, 0.4-0.6 parts zinc stearate, 0.4-0.6 parts antioxidant 1010, 0.2-0.3 parts antioxidant 168, and 2-3 parts epoxidized soybean oil.

4. The polymer film composite graphene heating plate according to claim 3, characterized in that: The ethylene-acrylic acid copolymer has an acrylic acid content of 6-10 wt% and a melt index of 5-10 g / 10 min; the ethylene-vinyl acetate copolymer has a vinyl acetate content of 18-28 wt% and a melt index of 3-8 g / 10 min.

5. The polymer film composite graphene heating plate according to claim 3, characterized in that: The specific preparation steps of the polymer membrane are as follows: L1. Add 100 parts of dried modified polyolefin elastomer, 10-15 parts of ethylene-vinyl acetate copolymer, 5-8 parts of ethylene-acrylic acid copolymer, and 8-12 parts of polyethylene glycol 4000 to a high-speed mixer at a speed of 800-900 r / min and a temperature of 113-117℃ for 10-13 min. Then add 2-3 parts of epoxidized soybean oil, 0.4-0.6 parts of antioxidant 1010, and 0.2-0.3 parts of antioxidant 168. Mix at a speed of 1000-1100 r / min for 5-7 min. Discharge and cool to room temperature to obtain premix A. L2. Mix 3-5 parts of modified nano-silica with 0.4-0.6 parts of zinc stearate at 1800-2000 r / min for 2-4 min to obtain side feed B; L3. Set the twin-screw extruder to 133-135℃ in zone 1, 153-155℃ in zone 2, 163-165℃ in zone 3, 158-160℃ in zone 4, 160-168℃ at the die head, and 300-320 r / min for screw speed. Add premix A to the main feed port and add side feed B to zone 2 through the side feeder. Control the residence time of the material in the extruder to 2.5-3.5 min. After extrusion, water cooling, and pelleting, obtain high-molecular membrane granules. L4. Add the special granules into the casting film machine, set the barrel temperature to 168-172℃, the die head temperature to 173-177℃, the cooling roller temperature to 23-27℃, the traction speed to 23-27m / min, and the air knife pressure to 0.3-0.5MPa, to prepare a polymer film with a thickness of 0.15-0.25mm. L5. Anneal the cast polymer film in a hot air circulating oven at 60-80℃ for 2-4 hours; then cool it to room temperature and place it in a corona treatment machine with a corona power of 400-500W and a processing speed of 15-20m / min to make the surface tension ≥48mN / m, and obtain the desired polymer film.

6. The polymer film composite graphene heating plate according to claim 5, characterized in that: The modified polyolefin elastomer is prepared using the following specific steps: A1. Take polyolefin elastomer particles and spread them evenly in a plasma treatment chamber. Purge the air three times with high-purity argon gas at a flow rate of 50-100 mL / min, set the power to 180 W, and treat for 10 min. Control the chamber temperature below 40℃. Immediately after treatment, transfer the particles to a mixer preheated to 160℃. Add maleic anhydride, a mixture of benzoyl peroxide and acetone, and N,N-dimethylformamide. Mix the mixer at 60 r / min and react for 9 min. Pull out the product while it is hot, cool it to room temperature, wash it three times with deionized water and twice with acetone, and vacuum dry it at 60℃ for 6 h. Granulate the product to obtain the first modified polyolefin elastomer. A2. The first modified polyolefin elastomer was added to a reaction vessel, along with toluene that had been deoxygenated by bubbling under nitrogen. The mixture was heated to 85°C and stirred to swell for 30 min. Allylamine was slowly added dropwise through a dropping funnel over 1 h. After the addition was complete, the reaction continued for 2.5 h. The entire reaction was carried out under nitrogen protection, and the system pressure was maintained at 0.4 MPa. After the reaction was completed, toluene and excess allylamine were removed by vacuum distillation at 60°C and -0.09 MPa. The product was washed three times with acetone and dried under vacuum at 60°C for 4 h to obtain the second modified polyolefin elastomer. A3. The second modified polyolefin elastomer was added to a reaction flask, and toluene that had been deoxygenated by bubbling with nitrogen was added. The mixture was stirred and swollen at room temperature for 30 min. A mixture of mercaptopropionic acid, 2,2-dimethoxy-2-phenylacetophenone and toluene was added. Nitrogen was continuously introduced into the reaction system. A 365 nm, 100 W high-pressure mercury lamp ultraviolet light source was turned on, with the light source 10 cm above the liquid surface. The reaction was carried out at room temperature for 1.5 h. After the reaction was completed, toluene was removed by vacuum distillation. The product was washed three times with methanol and dried under vacuum at 60 °C for 4 h to obtain the modified polyolefin elastomer.

7. The polymer film composite graphene heating plate according to claim 6, characterized in that: The ratio of polyolefin elastomer particles, maleic anhydride, benzoyl peroxide, acetone, and N,N-dimethylformamide in A1 is 100g: 6-10g: 0.3-0.5g: 10mL: 0.5-1.0mL; The ratio of the first modified polyolefin elastomer, toluene, and allylamine in A2 is 100g:120mL:3-5mL; The ratio of the amount of the second modified polyolefin elastomer, toluene for swelling the elastomer, mercaptopropionic acid, 2,2-dimethoxy-2-phenylacetophenone, and toluene for dissolving 2,2-dimethoxy-2-phenylacetophenone in A3 is 100g:150mL:4-6mL:0.2-0.4g:5mL.

8. The polymer film composite graphene heating plate according to claim 5, characterized in that: The modified nano-silica is prepared using the following specific steps: B1. Place nano-silica in a high-speed mixer, add silane coupling agent KH-570, anhydrous ethanol, and deionized water, and stir at 600-700 r / min for 1.5-2 h at 75 °C; after the reaction is completed, vacuum dry at 80 °C for 6 h to obtain the first modified nano-silica. B2. The modified nano-silica was ultrasonically dispersed in toluene and then transferred to a three-necked flask. Methyl methacrylate, n-dodecyl mercaptan, and azobisisobutyronitrile were added. Under nitrogen protection at 85°C, methyl methacrylate was added dropwise in a semi-continuous manner for 2 hours. After the addition was completed, the reaction was continued for 3 hours. After the reaction was completed, the precipitate was separated by centrifugation, washed three times with toluene, and dried under vacuum at 65°C for 8 hours to obtain modified nano-silica.

9. The polymer film composite graphene heating plate according to claim 8, characterized in that: The ratio of nano-silica, silane coupling agent KH-570, anhydrous ethanol, and deionized water in B1 is 10g: 3-4mL: 40-50mL: 2-3mL. The ratio of the first modified nano-silica, toluene, methyl methacrylate, n-dodecyl mercaptan, and azobisisobutyronitrile in B2 is 10g:50mL:5-6mL:0.05-0.07g:0.15-0.2g; wherein the ratio of the two uses of methyl methacrylate is 2.5-3mL:2.5-3mL.

10. A method for preparing a polymer film composite graphene heating plate, characterized in that: Specifically, it includes the following steps: S1. Lay all clean and dry materials on the lower hot plate of the high-temperature thermal laminating machine in the following order from bottom to top: aluminum plate, polymer film, honeycomb core, polymer film, aluminum plate, polymer film, graphene heating film, polymer film, colored aluminum decorative panel; strictly align the centers of each layer during the laying process, and leave a margin for the polymer film to adhere to the edges of each board. S2. A step-by-step temperature-controlled composite process is adopted, with nitrogen protection throughout to prevent metal oxidation. The parameters of the hot composite machine are set as follows: the temperature around the graphene heating film in the first stage is 100-110℃, the pressure is 3MPa, and the hot pressing time is 7-9min; the temperature of the entire board in the second stage is 120-130℃, the pressure is 4-5MPa, and the hot pressing time is 13-17min. The hot-melt adhesive properties of the self-made polymer film are used to tightly composite the 9 layers into one. S3. After the thermal bonding is completed, the composite board is quickly transferred to the flattening machine and flattened at room temperature and 2-3MPa pressure for 40 minutes to eliminate the internal stress of the board and prevent the board from warping, the film layer from wrinkling, and the interlayer from separating. S4. Remove the polymer film from the edges of the board to leave enough for edge pressing, ensuring accurate finished dimensions; use an edge banding machine to apply aluminum alloy edge banding to the four sides of the board to match the style of the colored aluminum decorative panel, preventing moisture from entering the board and damaging the graphene heating film and honeycomb core. S5. Install a thermostat and power connector at the temperature control interface of the graphene heating film. After standardizing the wiring, power on and debug to ensure that the thermostat can achieve temperature control and adjustment. After the heating film is powered on, the temperature rises evenly without local overheating or heat interruption, thus obtaining a polymer film composite graphene heating plate.

Images