Environmentally friendly composite material for automobiles and preparation method thereof

Abstract

The present application belongs to the technical field of composite materials for automobile interior decoration, and specifically discloses an environmentally friendly composite material for automobile and its preparation method. The environmentally friendly composite material for automobile, from bottom to top, is as follows: bottom non-woven fabric, surface adhesive film one, reinforcement layer one, adhesive layer one, PET bubble sheet, adhesive layer two, reinforcement layer two, surface adhesive film two; PET bubble sheet includes PET bubble sheet base layer and coating, and the coating includes the following raw materials: 20-25 parts of water-based acrylic acid, 13-16 parts of composite plant extract, 9-12 parts of silica nanospheres, 5-8 parts of calcium carbonate, 50-55 parts of deionized water, 1-2 parts of sodium dodecylbenzene sulfonate, and 2-3 parts of silane coupling agent. The composite material of the present application has multiple functions such as high strength, impact resistance, heat insulation, and sound insulation, and improves tensile strength.

Description

Technical Field

[0001] The present application relates to the technical field of composite materials for automobile interior decoration, and in particular to an environmentally friendly composite material for automobiles and a preparation method thereof. Background Art

[0002] Cars have become a means of transportation for families. Automotive interior composite materials play an increasingly important role in modern automobile manufacturing. They not only improve the comfort and functionality of the interior, but also help achieve the lightweight and environmental protection goals of the car. Automotive interior materials are increasingly tending towards high performance, environmental protection, low carbon and low odor.

[0003] Currently, the main composite materials used in automotive interiors on the market are polyurethane composite materials. The components of polyurethane composite materials mainly include polyisocyanates, polyols, chain extenders, fillers and reinforcing agents. The prepared polyurethane composite materials have the characteristics of low density and high strength, which can effectively reduce the weight of the car, have good heat insulation and sound insulation properties, and can significantly improve the comfort of the car interior.

[0004] However, polyurethane composite materials will experience performance degradation during long-term use. High temperature environments will cause thermal oxidation aging of the ether bonds of polyurethane, resulting in a decrease in tensile strength. Summary of the Invention

[0005] In order to improve the problem of performance degradation of polyurethane composite materials during long-term use, the present application provides an environmentally friendly composite material for automobiles and a preparation method thereof.

[0006] This application provides an environmentally friendly composite material for automobiles, which adopts the following technical solutions:

[0007] An environmentally friendly composite material for automobiles, comprising, from bottom to top: a bottom non-woven fabric, a first surface adhesive film, a first reinforcement layer, a first adhesive layer, a PET bubble sheet, a second adhesive layer, a second reinforcement layer, and a second surface adhesive film; the PET bubble sheet comprises a PET bubble sheet base layer and a coating, and the coating comprises the following raw materials, by weight: 20-25 parts of water-based acrylic acid, 13-16 parts of a composite plant extract, 9-12 parts of silicon dioxide nanospheres, 5-8 parts of calcium carbonate, 50-55 parts of deionized water, 1-2 parts of sodium dodecylbenzenesulfonate, and 2-3 parts of a silane coupling agent.

[0008] By adopting the above technical solution, the bottom non-woven fabric has excellent mechanical properties and provides basic support. The surface adhesive film 1 and the surface adhesive film 2 provide good bonding properties and barrier properties, ensuring a strong bond between the bottom non-woven fabric and the reinforcement layer 1, and a strong bond between the reinforcement layer 2 and the surface adhesive film 2. The reinforcement layer 1 and the reinforcement layer 2 improve the mechanical strength and impact resistance of the composite material and extend the durability of the composite material. The adhesive layer 1 and the adhesive layer 2 firmly bond the reinforcement layer 1 to the PET bubble sheet, and firmly bond the PET bubble sheet to the reinforcement layer 2, ensuring the interlayer bonding strength. The PET bubble sheet provides lightweight, high-strength cushioning performance, and also has good heat insulation and sound insulation effects. Through the multi-layer structural design, the weight of the material is reduced, and the composite material is provided with multiple functions such as high strength, impact resistance, heat insulation, and sound insulation.

[0009] The non-woven fabric base provides basic structural support, and the PET bubble sheet includes a PET bubble sheet base and a coating. In the coating, water-based acrylic acid has good film-forming and adhesive properties, can provide the coating with weather resistance and water resistance, is environmentally friendly, uses water as a solvent, and does not produce harmful gases and pollutants during use. The composite plant extract has good antibacterial and antioxidant properties, which improves the corresponding performance of the coating and extends the durability of the coating. Silica nanoparticles have size effects and self-healing properties, which can improve the heat resistance and mechanical properties of the coating, making the coating have good elasticity. The calcium carbonate-filled coating system is combined with silica nanoparticles to improve the hardness and stability of the coating. Sodium dodecylbenzene sulfonate reduces the surface tension of water, allowing the silica nanoparticles and calcium carbonate to be evenly dispersed, improving the dispersion and uniformity of the coating, and helping to improve the overall performance of the coating. The silane coupling agent improves the compatibility between silica nanoparticles and calcium carbonate and water-based acrylic acid, enhancing the overall performance of the coating.

[0010] In this application, water-based acrylic acid and deionized water are used to reduce the use of organic solvents and meet environmental protection requirements. By adding silica nanospheres, composite plant extracts and calcium carbonate, the heat resistance and hardness of the coating are improved. The use of sodium dodecylbenzenesulfonate and silane coupling agents ensures the uniform dispersion of each component in water, thereby improving the mechanical properties of the coating such as flexibility, strength and tear resistance.

[0011] Preferably, the surface adhesive film 1 and the surface adhesive film 2 both include a fabric adhesive layer, a permeation barrier layer, and a low-temperature adhesive layer; the fabric adhesive layer is a polypropylene modified material with an MI (melt index) greater than 50 g / 10min and a thickness of 20±5µm, the permeation barrier layer is a polypropylene modified material with an MI less than 20 g / 10min and a thickness of 20±5µm, and the low-temperature adhesive layer is a polypropylene modified material with an MI greater than or equal to 20g / 10min and a thickness of 20±5µm.

[0012] By employing this technical solution, the fabric adhesive layer firmly bonds the bottom nonwoven fabric to the permeation barrier layer, ensuring the stability and durability of the overall structure. The permeation barrier layer prevents the fabric adhesive layer from melting and penetrating into the first and second reinforcement layers, preventing effective bonding. This protects the performance and integrity of the internal materials. The low-temperature adhesive layer bonds the permeation barrier layer to the first and second reinforcement layers, ensuring a stable, defect-free surface adhesive layer and providing excellent bonding and protection.

[0013] Preferably, the first adhesive layer and the second adhesive layer are both polypropylene modified hot melt adhesive films;

[0014] The preparation method of the polypropylene modified hot melt adhesive film comprises: uniformly mixing polypropylene, styrene, phenolic terpene resin, quartz powder, compatibilizer, metal organic framework material, benzoyl peroxide, cationic polyacrylamide, and antioxidant 1010, melt blending, extruding and pelletizing, casting, cooling and shaping, and obtaining the polypropylene modified hot melt adhesive film.

[0015] By adopting the above technical solution, the polypropylene modified hot melt adhesive film has good bonding properties, can form strong bonds on the material surface, also has good temperature resistance and weather resistance, can maintain its bonding properties under different environmental conditions, can quickly bond after heating, and quickly solidify after cooling, saving production time and improving production efficiency.

[0016] Polypropylene exhibits excellent flexibility, heat resistance, and chemical stability, enabling the hot-melt adhesive film to melt and flow when heated and rapidly solidify upon cooling, thus achieving rapid bonding. Styrene enhances the hardness and chemical resistance of the hot-melt adhesive film. When blended with polypropylene, styrene improves the surface properties and bonding strength of polypropylene, enhancing the adhesive's adhesion. Phenolic terpene resin enhances the adhesive's bonding and heat resistance, strengthening its adhesion and heat resistance, allowing it to maintain good adhesion even in high-temperature environments. Quartz powder exhibits excellent mechanical properties and heat resistance, and when dispersed within the system, improves the mechanical properties of the hot-melt adhesive film. A compatibilizer ensures uniform dispersion of polypropylene, styrene, the metal-organic framework (MOF), and the quartz powder. The MOF's large surface area and adsorption properties allow it to interact with the quartz powder, further enhancing the system's mechanical properties and thermal stability. Benzoyl peroxide, acting as an initiator, promotes the grafting reaction of polypropylene and the polymerization reaction of styrene, increasing the system's cross-linking and improving the material's thermal stability and mechanical properties.

[0017] Cationic polyacrylamide improves the rheological properties of the system, ensuring uniform mixing of the components and enhancing product quality. Antioxidant 1010 prevents oxidative degradation during processing and use, extending the material's service life. The polypropylene-modified hot-melt adhesive film obtained through melt blending exhibits excellent bonding properties, temperature and weather resistance, and high strength. It is solvent-free and water-free, meeting environmental requirements.

[0018] Preferably, the method for preparing the quartz powder comprises the following steps: grinding the quartz stone, sieving, dispersing in anhydrous ethanol, soaking for 20-25 minutes, calcining at a temperature of 750-770°C for 5-6 hours, then dispersing in a sodium hydroxide solution, soaking for 30-35 minutes, washing with water, and drying to obtain a pretreated powder;

[0019] The pretreated powder is dispersed in deionized water, and pearl powder, polyvinyl alcohol water-based adhesive, silane coupling agent, and N,N'-ethylene bisstearamide are added. The mixture is stirred at a temperature of 70-75°C for 2-3 hours and dried to obtain quartz stone powder.

[0020] By employing the above technical solution, quartz is ground into a fine powder to increase its specific surface area and enhance its reactivity. Anhydrous ethanol is then used to disperse the quartz powder, simultaneously removing surface impurities. Calcination at 1200-1250°C removes organic impurities from the quartz powder, while also increasing its crystallinity and purity. Sodium hydroxide solution further removes impurities from the quartz powder's surface, enhancing its reactivity. This ensures that the resulting pretreated powder has a uniform particle size and exhibits good reactivity, facilitating mixing with other components.

[0021] Pretreated quartz powder is added to deionized water to ensure uniform dispersion. Pearl powder, with its excellent dispersibility and surface activity, adsorbs onto the surface of the quartz powder particles, improving the surface properties of the quartz powder, enhancing its compatibility and adsorption with other ingredients, and improving the mechanical properties of the quartz powder, subsequently enhancing the structural strength of the polypropylene-modified hot-melt adhesive film. Polyvinyl alcohol-based water-based adhesives, with their excellent film-forming and adhesion properties, enhance the bonding between the quartz powder and pearl powder, and strengthen its adhesion within the polypropylene-modified hot-melt adhesive film, allowing the polypropylene-modified hot-melt adhesive film to adhere better to other surfaces. Silane coupling agents improve the compatibility between the quartz powder pearl powder and organic polymers, ensuring uniform mixing of the various components of the polypropylene-modified hot-melt adhesive film and enhancing the mechanical properties and thermal stability of the material. N,N'-ethylene bisstearamide, with its excellent lubricity and dispersibility, improves the processing properties of the quartz powder and pearl powder, prevents particle agglomeration, and allows the pearl powder to adsorb evenly onto the surface of the quartz powder particles, enhancing the performance of the quartz powder.

[0022] The prepared quartz stone powder has good dispersibility, which helps to disperse evenly in the polypropylene modified hot melt adhesive film. The addition of polyvinyl alcohol water-based adhesive and silane coupling agent improves the bonding performance and compatibility of the quartz stone powder, so that the various components in the polypropylene modified hot melt adhesive film are evenly stirred, thereby improving the mechanical properties, bonding properties and processing properties of the polypropylene modified hot melt adhesive film.

[0023] Preferably, the first and second reinforcing layers are both 200-500 g / m 2 Lightweight GMT felt.

[0024] By adopting the above technical solutions, the lightweight GMT felt has low density and high strength, reducing the weight of the material while maintaining excellent mechanical properties, high impact resistance, good bending and tensile strength, and excellent resistance to chemical corrosion. It can be recycled and reused, meeting environmental protection requirements.

[0025] Preferably, the preparation method of the composite plant extract comprises the following steps: drying camellia petals, soaking them in an ethanol solution, adding propylene glycol fatty acid ester, calcium gluconate and malic acid, heating and refluxing for 3-4 times, each extraction time being 1-1.5 hours, combining the extracts, filtering, and concentrating the filtrate to obtain a dry powder;

[0026] The dry powder is dispersed in deionized water, and porous nano-aluminum nitride powder, carboxymethyl chitosan, and succinic acid are added. The mixture is stirred at a rate of 1000-1200 r / min and at 60-65° C. for 35-40 minutes to obtain a composite plant extract dispersion with a uniform texture. The dispersion is dried and sieved to obtain a composite plant extract.

[0027] By adopting the above technical solution, camellia petals are dried, their moisture removed, and then immersed in an ethanol solution. Propylene glycol fatty acid ester, calcium gluconate, and malic acid are then added. Propylene glycol fatty acid ester has good solubility and stability, preventing the aggregation of active ingredients and facilitating the dissolution and extraction of active ingredients from the camellia. Calcium gluconate adjusts the pH of the extract, promoting the dissolution of active ingredients in the camellia, while also preventing microbial growth and providing certain antioxidant and preservative properties. Calcium gluconate stabilizes the pH of the extract and, in combination with malic acid, protects the active ingredients in the camellia. The extract is then concentrated and dried to remove the solvent, increasing the concentration of the extract and producing a dry powder.

[0028] Porous nano-aluminum nitride powder has a high specific surface area and good mechanical strength, and can be adsorbed on the surface of dry powder particles, improving the thermal stability and mechanical properties of the dry powder. Carboxymethyl chitosan has good water solubility, viscosity, and film-forming properties, allowing the dry powder particles and porous nano-aluminum nitride powder to bond evenly, improving the structural strength of the composite plant extract and subsequently aiding in film formation. Succinic acid adjusts the pH value of the system and has antioxidant and preservative effects. On the one hand, it helps protect the active ingredients in camellia, and on the other hand, it cross-links with carboxymethyl chitosan to form a three-dimensional cross-linked network, increasing the strength of the system and better embedding the dry powder and porous nano-aluminum nitride powder into the three-dimensional network structure, subsequently improving the mechanical properties, antibacterial properties, and tear resistance of the coating.

[0029] Preferably, the mass ratio of the dry powder, porous nano-aluminum nitride powder and carboxymethyl chitosan is 1:0.6-0.7:0.1-0.3.

[0030] By adopting the above technical solution, the mass ratio of dry powder, porous nano-aluminum nitride powder and carboxymethyl chitosan is further limited within a certain range, and the resulting composite plant extract has good antibacterial properties, adhesion and mechanical properties. The porous nano-aluminum nitride powder has excellent adsorption and mechanical properties and can be loaded on the surface of the dry powder particles to improve the mechanical properties of the dry powder. The carboxymethyl chitosan has film-forming properties, adhesion and water solubility, which makes the dry powder and the porous nano-aluminum nitride powder adhere firmly, improving the performance stability of the dry powder. The modified composite plant extract has excellent mechanical properties, antibacterial properties and viscosity, and is subsequently applied to the coating to improve the adhesion of the various components in the coating, improve the mechanical properties of the coating, and reduce the chance of the coating tearing.

[0031] Preferably, the method for preparing the porous nano-aluminum nitride powder comprises the following steps: dispersing the nano-aluminum nitride in a sodium hydroxide solution, stirring at a temperature of 60-65° C. for 45-50 minutes, washing with water, drying, and calcining at a temperature of 700-750° C. under nitrogen conditions for 2-3 hours to obtain a pretreated powder;

[0032] The pretreated powder is dispersed in an ethanol aqueous solution, and silver nanowires, methyl benzoate, polyvinyl alcohol, and cellulose nanofibrils are added. The mixture is stirred at a temperature of 50-55° C. for 2-3 hours and dried to obtain porous nano-aluminum nitride powder.

[0033] By adopting the above technical solution, the nano-aluminum nitride is treated with sodium hydroxide solution, removing impurities from the surface aluminum oxide and etching the aluminum nitride surface, resulting in a porous structure. Calcination further improves the crystallinity and purity of the powder, while removing organic impurities, increasing the specific surface area of ​​the nano-aluminum nitride and enhancing its adsorption capacity.

[0034] The pretreated powder is dispersed in anhydrous ethanol, and silver nanowires, methyl benzoate, polyvinyl alcohol, and cellulose nanofibrils are added. The silver nanowires have excellent flexibility and antibacterial properties and can be adsorbed on the surface and within the pores of the nanoaluminum nitride particles, improving the corresponding properties of the nanoaluminum nitride. The methyl benzoate and cellulose nanofibrils help to evenly disperse the nanoaluminum nitride and silver nanowires, so that the silver nanowires are evenly loaded in the nanoaluminum nitride structure. The polyvinyl alcohol has good film-forming and adhesive properties, allowing the silver nanowires to evenly adhere to the nanoaluminum nitride structure, enhancing the mechanical properties of the porous nanoaluminum nitride powder and subsequently improving the mechanical properties and antibacterial properties of the non-woven fabric coating.

[0035] Preferably, the PET material, chain extender, nucleating agent, flame retardant and foaming agent are dried at 100-180° C. for 5-10 h;

[0036] Add PET material, chain extender, nucleating agent and flame retardant and mix them, react for 5-10 minutes to prepare a mixture;

[0037] The mixed material and the foaming agent are mixed, extruded, cooled and shaped to obtain a primary foaming material, which is then heated and foamed twice to obtain a PET foam sheet base layer;

[0038] The raw materials in the coating are mixed evenly, coated on both sides of the PET bubble sheet base layer, and dried to obtain the PET bubble sheet.

[0039] By adopting the above technical solution, after the PET material, chain extender, nucleating agent and flame retardant are uniformly mixed with each other, a foaming agent is added to prepare a primary foam material. The foaming process is extrusion foaming, which is relatively simple and has low difficulty. In the prepared primary foam material, the PET material, chain extender and nucleating agent are cross-linked to form a network structure, so that the pores in the primary foam material are mostly closed cells, creating conditions for secondary foaming. After the primary foam material is heated, the primary foam material softens and undergoes secondary foaming. The primary foam material further expands and the pores grow. The prepared PET foam sheet base layer has a high porosity, an increased volume and a reduced density, thereby achieving lightweight PET foam material. The PET foam sheet base layer prepared by secondary foaming is easy to process. When the PET foam sheet base layer is used to process automotive interiors, no cutting, welding or other operations are required, thereby reducing the generation of waste. In addition, the secondary foaming process facilitates the control of the density of the PET foam sheet base layer, making it easy to prepare a PET foam sheet base layer of a desired density. The process is more controllable and precise, and is suitable for preparing automotive interiors with relatively complex shapes. Finally, a film is coated on the surface of the PET bubble sheet base layer to obtain a PET bubble sheet with good heat resistance, wear resistance and mechanical properties, thereby enhancing the overall performance of the PET bubble sheet.

[0040] Preferably, the chain extender is one or more of diols, triols, and tetraols; and the nucleating agent is one or more of talc, calcium carbonate, and nanocrystals of organic materials.

[0041] Secondly, the present application also provides a method for preparing an environmentally friendly composite material for automobiles, comprising the following steps: stacking the bottom non-woven fabric, surface adhesive film one, reinforcement layer one, adhesive layer one, PET foam sheet, adhesive layer two, reinforcement layer two, and surface adhesive film two in sequence, heating and compounding them, and obtaining the environmentally friendly composite material for automobiles after cooling.

[0042] By adopting the above technical solution and the above preparation method, the operation is simple and the process time is short, the production efficiency of preparing environmentally friendly composite materials for automobiles is improved, and the obtained environmentally friendly composite materials for automobiles have good mechanical properties and antibacterial properties.

[0043] Preferably, the composite temperature is 200-230° C., the composite roller gap is 5-7 mm, and the composite conveyor belt speed is 5-7 m / min.

[0044] In summary, this application has the following beneficial effects:

[0045] 1. In this application, the weight of the material is reduced through the multi-layer structure design, and multiple functions such as high strength, impact resistance, heat insulation, and sound insulation of the composite material are provided.

[0046] 2. The PET foam sheet in this application is a closed-cell thermoplastic renewable polymer foam with excellent temperature resistance, plasticity and strength, and is an ideal molding material for automotive interior parts.

[0047] 3. The non-woven fabric coating in this application has excellent flexibility and adhesion, which improves the durability of the composite material. DETAILED DESCRIPTION

[0048] The present application is further described in detail below with reference to the embodiments.

[0049] The raw materials used in the examples and comparative examples can all be obtained commercially.

[0050] Preparation Example 1

[0051] The preparation method of the composite plant extract comprises the following steps: drying 100 kg of camellia petals, soaking them in 300 L of 95% ethanol solution, adding 20 kg of propylene glycol fatty acid ester, 8 kg of calcium gluconate, and 10 kg of malic acid, heating and refluxing for extraction three times, each extraction time being 1.5 hours, combining the extracts, filtering, and concentrating the filtrate to obtain a dry powder;

[0052] 20 kg of dry powder was dispersed in 70 L of deionized water, and porous nano-aluminum nitride powder, carboxymethyl chitosan, and 2 kg of succinic acid were added. The mixture was stirred at 63 ° C at a rate of 1100 r / min for 38 min to obtain a composite plant extract dispersion with uniform texture. The dispersion was dried and passed through a 100 mesh sieve to obtain a composite plant extract.

[0053] The mass ratio of dry powder, porous nano-aluminum nitride powder and carboxymethyl chitosan is 1:0.6:0.3.

[0054] The method for preparing porous nano-aluminum nitride powder comprises the following steps: dispersing 25 kg of nano-aluminum nitride in 60 L of a 1 mol / L sodium hydroxide solution, stirring at 62° C. for 48 minutes, washing with water, drying, and calcining at 720° C. under nitrogen for 2.5 hours to obtain a pretreated powder;

[0055] The pretreated powder was dispersed in 90 L of ethanol aqueous solution (water-ethanol volume ratio 1:1), and 6 kg of silver nanowires, 1 kg of methyl benzoate, 3 kg of polyvinyl alcohol, and 2 kg of cellulose nanofibrils were added. The mixture was stirred at 53 ° C for 2.6 h and dried to obtain porous nano-aluminum nitride powder.

[0056] Cellulose nanofibrils were purchased from Nanjing Tianlu Nanotechnology Co., Ltd.

[0057] Preparation Example 2

[0058] The difference from Preparation Example 1 is that no porous nano-aluminum nitride powder is added.

[0059] Preparation Example 3

[0060] The difference from Preparation Example 1 is that carboxymethyl chitosan is not added.

[0061] Preparation Example 4

[0062] The difference from Preparation Example 1 is that the mass ratio of dry powder, porous nano-aluminum nitride powder and carboxymethyl chitosan is 1:0.7:0.1.

[0063] Preparation Example 5

[0064] The difference from Preparation Example 1 is that the mass ratio of dry powder, porous nano-aluminum nitride powder and carboxymethyl chitosan is 1:0.1:0.6.

[0065] Preparation Example 6

[0066] The difference from Preparation Example 1 is that no silver nanowires are added in the preparation method of the porous nano-aluminum nitride powder.

[0067] Preparation Example 7

[0068] The difference from Preparation Example 1 is that polyvinyl alcohol is not added in the preparation method of the porous nano-aluminum nitride powder.

[0069] Example 1 An environmentally friendly composite material for automobiles, comprising, from bottom to top: a bottom non-woven fabric, a first surface adhesive film, a first reinforcing layer, a first adhesive layer, a PET bubble sheet, a second adhesive layer, a second reinforcing layer, and a second surface adhesive film; the PET bubble sheet comprises a PET bubble sheet and a coating, the coating comprising the following raw materials by weight: 20 kg of water-based acrylic acid, 13 kg of a composite plant extract, 9 kg of silica nanospheres, 8 kg of calcium carbonate, 50 kg of deionized water, 1 kg of sodium dodecylbenzenesulfonate, and 2 kg of a silane coupling agent KH550;

[0070] The thickness of the bottom non-woven fabric was 0.5 mm, and the silica nanospheres were purchased from Qinghe Chaotai Metal Materials Co., Ltd.

[0071] Both surface adhesive films 1 and 2 consist of a fabric adhesive layer, a permeation barrier layer, and a low-temperature adhesive layer. The fabric adhesive layer is 20µm thick, using Yanshan Petrochemical's K7100; the permeation barrier layer is 20µm thick, using Singapore's FL7632L; and the low-temperature adhesive layer is 20µm thick, using Basel's EP6051. The thickness of the reinforcement layer 1 / 2 is 1.5mm, and the thickness of the adhesive layer 1 / 2 is 0.6mm.

[0072] The first adhesive layer and the second adhesive layer are both polypropylene-modified hot-melt adhesive films; the polypropylene-modified hot-melt adhesive films are purchased from Hangzhou Zhihe New Materials Co., Ltd.

[0073] Reinforcement layer 1 and reinforcement layer 2 are both 200 g / m 2 The lightweight GMT felt was purchased from Zhejiang Huajiang Technology Co., Ltd.

[0074] The composite plant extract was prepared according to Preparation Example 1.

[0075] The preparation method of PET bubble sheet comprises the following steps: drying PET particles, a chain extender, a nucleating agent, a flame retardant, and a foaming agent, melt-extruding, and cooling to obtain a PET sheet; thermally expanding the PET sheet to obtain a PET bubble sheet base layer; uniformly mixing the raw materials in the coating at a temperature of 85°C, coating the coating on both sides of the PET bubble sheet base layer, and drying to obtain a PET bubble sheet.

[0076] Specifically, 60 kg of PET material, 1 kg of chain extender, 1 kg of nucleating agent, 1 kg of flame retardant and 0.5 kg of foaming agent were dried at 120° C. for 8 hours, wherein the PET material was polyethylene terephthalate, the chain extender was pentaerythritol, the nucleating agent was nanocrystals of talc, the flame retardant was aluminum hydroxide, and the foaming agent was carbon dioxide.

[0077] Mixing: Add PET material, chain extender, nucleating agent and flame retardant into a twin-screw extruder for mixing. The screw temperature is 200°C, the die temperature is 240°C, the die pressure is 10 MPa, and the reaction is carried out for 10 minutes to obtain a mixture.

[0078] The mixed material is transferred to a single-screw extruder through a pressure stabilizer, with a screw temperature of 200°C, a die temperature of 240°C, and a die pressure of 15 MPa. A foaming agent is added, and the mixed material is extruded through a ring die. After cooling and shaping by an air ring, a primary foaming material is obtained.

[0079] The PET foam material is heated and then foamed twice. The heating temperature of the secondary foaming is 150° C. and the heating time is 5 minutes to obtain a PET foam sheet base layer.

[0080] A method for preparing an environmentally friendly composite material for automobiles comprises the following steps: sequentially stacking a bottom non-woven fabric, a first surface adhesive film, a first reinforcing layer, a first adhesive layer, a PET foam sheet, a second adhesive layer, a second reinforcing layer, and a second surface adhesive film, heating and compounding the stacked layers, and cooling the stacked layers to obtain the environmentally friendly composite material for automobiles.

[0081] The laminating temperature was 200°C, the gap between the laminating rollers was 7 mm, and the laminating speed was 5 m / min.

[0082] Example 2 An environmentally friendly composite material for automobiles, which differs from Example 1 in that the coating comprises the following raw materials by weight: 25 kg of aqueous acrylic acid, 16 kg of composite plant extract, 12 kg of silica nanospheres, 5 kg of calcium carbonate, 55 kg of deionized water, 2 kg of sodium dodecylbenzenesulfonate, and 3 kg of silane coupling agent.

[0083] Reinforcement layer 1 and reinforcement layer 2 are both 500 g / m 2 Lightweight GMT felt, reinforcement layer 1 / reinforcement layer 2 thickness is 1mm.

[0084] Specifically, 60 kg of PET particles, 3 kg of chain extender, 1 kg of nucleating agent, 1 kg of flame retardant, and 0.5 kg of foaming agent were dried and extruded through a twin-screw-single-screw extruder through an annular die, cooled, and wound to obtain a film with a surface density of 160 kg / m 3 , 3mm thick PET sheet; after the PET sheet is rolled by upper and lower needle rollers, it is heated and expanded in a heating furnace at 150℃ to produce a 4mm thick PET foam sheet; the PET particles are recycled bottle-grade PET particles; the PET foam sheet is 6mm thick and has a density of 80 kg / m 3 ; The extrusion temperature is 240℃.

[0085] A method for preparing an environmentally friendly composite material for automobiles comprises the following steps: sequentially stacking a bottom non-woven fabric, a first surface adhesive film, a first reinforcing layer, a first adhesive layer, a PET foam sheet, a second adhesive layer, a second reinforcing layer, and a second surface adhesive film, heating and compounding the stacked layers, and cooling the stacked layers to obtain the environmentally friendly composite material for automobiles.

[0086] The laminating temperature was 230°C, the gap between the laminating rollers was 5 mm, and the laminating speed was 7 m / min.

[0087] Example 3 An environmentally friendly composite material for automobiles, which differs from Example 1 in that a method for preparing a polypropylene-modified hot-melt adhesive film comprises: uniformly mixing 80 kg of polypropylene, 10 kg of styrene, 13 kg of phenolic terpene resin, 18 kg of quartz powder, 7 kg of a compatibilizer, 8 kg of a metal-organic framework material, 1 kg of benzoyl peroxide, 0.5 kg of cationic polyacrylamide, and 0.2 kg of an antioxidant 1010, melt-blending in a twin-screw extruder, extruding and pelletizing, adding the mixture to an extrusion casting machine, casting, cooling and shaping, and obtaining a polypropylene-modified hot-melt adhesive film.

[0088] The metal organic framework material is ZIF-67, purchased from Suzhou Kaifa New Material Technology Co., Ltd., the compatibilizer is maleic anhydride grafted polyethylene, the melting temperature is 180°C, and the casting temperature is 170°C.

[0089] The preparation method of quartz stone powder comprises the following steps: grinding 30 kg of quartz stone, passing through a 40-mesh sieve, dispersing in 80 L of anhydrous ethanol, soaking for 23 minutes, calcining at a temperature of 760° C. for 5.5 hours, and then dispersing in 70 L of a 10% by mass sodium hydroxide solution, soaking for 32 minutes, washing with water, and drying to obtain a pretreated powder;

[0090] The pretreated powder was dispersed in 100 L of deionized water, and 6 kg of pearl powder, 3 kg of polyvinyl alcohol water-based adhesive, 1 kg of silane coupling agent KH550, and 0.5 kg of N,N'-ethylenebisstearamide were added. The mixture was stirred at 73 °C for 2.5 h and dried to obtain quartz powder.

[0091] The polyvinyl alcohol water-based adhesive was purchased from Jinan Guocheng Chemical Co., Ltd.

[0092] Example 4 An environmentally friendly composite material for automobiles, which differs from Example 3 in that the preparation method of the polypropylene modified hot melt adhesive film comprises: uniformly mixing 85 kg of polypropylene, 15 kg of styrene, 16 kg of phenolic terpene resin, 22 kg of quartz stone powder, 5 kg of compatibilizer, 11 kg of metal organic framework material, 2 kg of benzoyl peroxide, 0.9 kg of cationic polyacrylamide, and 0.5 kg of antioxidant 1010, melt blending in a twin-screw extruder, extruding and pelletizing, adding the mixture to an extrusion casting machine, casting, cooling and shaping, to obtain a polypropylene modified hot melt adhesive film.

[0093] Example 5 An environmentally friendly composite material for automobiles is different from Example 3 in that quartz stone powder is not added in the preparation method of the polypropylene modified hot melt adhesive film.

[0094] Example 6 An environmentally friendly composite material for automobiles is different from Example 3 in that no metal organic framework material is added in the preparation method of the polypropylene modified hot melt adhesive film.

[0095] Example 7 An environmentally friendly composite material for automobiles is different from Example 3 in that pearl powder is not added in the preparation method of the quartz stone powder.

[0096] Example 8 An environmentally friendly composite material for automobiles is different from Example 3 in that no polyvinyl alcohol-based water-based adhesive is added in the preparation method of the quartz stone powder.

[0097] Example 9 An environmentally friendly composite material for automobiles, which differs from Example 1 in that the composite plant extract is prepared using Preparation Example 2.

[0098] Example 10 An environmentally friendly composite material for automobiles, which differs from Example 1 in that the composite plant extract is prepared using Preparation Example 3.

[0099] Example 11 An environmentally friendly composite material for automobiles, which differs from Example 1 in that the composite plant extract is prepared using Preparation Example 4.

[0100] Example 12 An environmentally friendly composite material for automobiles, which differs from Example 1 in that the composite plant extract is prepared using Preparation Example 5.

[0101] Example 14 is an environmentally friendly composite material for automobiles. The difference from Example 1 is that the composite plant extract is prepared using Preparation Example 6.

[0102] Example 14 An environmentally friendly composite material for automobiles, which differs from Example 1 in that the composite plant extract is prepared using Preparation Example 7.

[0103] Comparative Example 1

[0104] An environmentally friendly composite material for automobiles, which differs from Example 1 in that no composite plant extract is added.

[0105] Comparative Example 2

[0106] An environmentally friendly composite material for automobiles, which differs from Example 1 in that the composite plant extract is replaced by an equal amount of camellia pollen.

[0107] Performance Testing The environmentally friendly composite materials for automobiles prepared in Examples 1-14 and Comparative Examples 1-2 were subjected to performance testing;

[0108] The flexural strength and flexural modulus of environmentally friendly composite materials for automobiles are tested with reference to GB / T 9341-2008; the tensile properties of environmentally friendly composite materials for automobiles are tested with reference to GB / T10404-2006 Test standard for tensile properties of plastics.

[0109] The interlayer adhesion of environmentally friendly composite materials for automotive applications was tested according to PV 2034-2020. The interlayer adhesion between the first and second reinforcement layers and the PET foam sheet was tested. The test results are shown in Table 1.

[0110] Table 1 Test data of embodiments and comparative examples

[0111]

[0112] As can be seen from Table 1, the environmentally friendly composite materials for automobiles prepared in Examples 1-2 of the present application have good mechanical properties and mechanical strength. Among them, the tensile strength of Example 1 is 20.6 MPa, the flexural strength is 15.7 MPa, the flexural strength modulus is 973 MPa, and the interlayer adhesion is 10.8 N / 5 cm. It can be seen that the materials prepared in the present application have good strength and elasticity. The components cooperate with each other to improve the adhesion of the environmentally friendly composite materials for automobiles and extend the durability of the composite materials.

[0113] Examples 3-4 prepared polypropylene-modified hot melt adhesive films. As can be seen from Table 1, the test results of tensile strength, flexural strength, flexural strength modulus, and interlayer adhesion of Examples 3-4 are significantly better than those of Examples 1-2, indicating that the modified hot melt adhesive film of the present application has good bonding performance and strength, and the various components work together to subsequently improve the thermal stability, adhesion, and mechanical properties of the composite material.

[0114] In the preparation method of the polypropylene-modified hot melt adhesive film of Examples 5-6, quartz powder and metal-organic framework materials are not added respectively. As can be seen from Table 1, the test results of tensile strength, flexural strength, flexural strength modulus, and interlayer adhesion of Examples 5-6 are significantly worse than those of Examples 3-4, but better than those of Examples 1-2, indicating that quartz powder has good mechanical properties and heat resistance, is dispersed in the structure of the system, and improves the mechanical properties of the hot melt adhesive film; the metal-organic framework material has a large specific surface area and adsorption capacity, and can be combined with quartz powder to further improve the mechanical properties and thermal stability of the system, and subsequently improve the corresponding properties of the composite material.

[0115] In the preparation methods of the quartz powder in Examples 7-8, pearl powder and polyvinyl alcohol-based water-based adhesives were not added. As can be seen from Table 1, the test results of tensile strength, flexural strength, flexural modulus, and interlayer adhesion of Example 7 were significantly worse than those of Examples 3-4 and Example 6, but better than those of Example 5. The test results of tensile strength, flexural strength, flexural modulus, and interlayer adhesion of Example 8 were significantly worse than those of Examples 3-4, but better than those of Examples 5-7. This shows that pearl powder has good dispersibility and surface activity, is adsorbed on the surface of quartz powder particles, enhances its compatibility and adsorption with other components, and improves the mechanical properties of quartz powder; polyvinyl alcohol-based water-based adhesives have good film-forming properties and adhesion, improves the adhesion between quartz powder and pearl powder, enhances its adhesion in the polypropylene-modified hot-melt adhesive film, enables the polypropylene-modified hot-melt adhesive film to better adhere to the surface of other materials, and subsequently enhances the mechanical properties, adhesion, and thermal stability of the composite material.

[0116] In the preparation method of the composite plant extract of Examples 9-10, porous nano-aluminum nitride powder and carboxymethyl chitosan are not added respectively. The mass ratio of dry powder, porous nano-aluminum nitride powder and carboxymethyl chitosan is changed in Examples 11-12. It can be seen from Table 1 that the test results of tensile strength, flexural strength, flexural strength modulus and interlayer adhesion of Examples 9-10 are significantly worse than those of Examples 1-2 and Example 11. The corresponding performance test results of Example 12 are better than those of Examples 9-10, but worse than those of Examples 1-2, indicating that the composite plant extract prepared in this application has excellent mechanical properties, and the porous nano-aluminum nitride powder has a high specific surface area and good mechanical strength, can be adsorbed on the surface of the dry powder particles, and improves the thermal stability and mechanical properties of the dry powder; carboxymethyl chitosan has good water solubility, viscosity and film-forming properties, so that the dry powder particles and the porous nano-aluminum nitride powder are evenly bonded, thereby improving the structural strength of the composite plant extract, subsequently contributing to film formation, and improving the comprehensive performance of the composite material.

[0117] In the preparation methods of the porous nano-aluminum nitride powders of Examples 13-14, silver nanowires and polyvinyl alcohol are not added respectively. As can be seen from Table 1, the test results of tensile strength, flexural strength, flexural strength modulus, and interlayer adhesion of Examples 13-14 are significantly better than those of Example 9, indicating that the silver nanowires have good flexibility and antibacterial properties, can be adsorbed on the surface and pores of nano-aluminum nitride particles, and improve the mechanical properties of nano-aluminum nitride; polyvinyl alcohol has good film-forming and adhesive properties, so that the silver nanowires are uniformly adhered to the nano-aluminum nitride structure, enhancing the mechanical properties of the porous nano-aluminum nitride powder, and subsequently improving the mechanical properties and antibacterial properties of the non-woven fabric coating.

[0118] Comparative Example 1 does not add the composite plant extract. As can be seen from Table 1, the test results of tensile strength, flexural strength, flexural strength modulus, and interlayer adhesion of Comparative Example 1 are significantly worse than those of Examples 1-2, indicating that the composite plant extract prepared in this application has excellent comprehensive properties and is used in environmentally friendly composite materials for automobiles to improve the corresponding properties of the composite materials.

[0119] In Comparative Example 2, the composite plant extract is replaced by an equal amount of camellia pollen. As can be seen from Table 1, the test results of tensile strength, flexural strength, flexural strength modulus, and interlayer adhesion of Comparative Example 2 are significantly worse than those of Examples 1-2, but better than Comparative Example 1, indicating that the composite plant extract prepared in this application has better mechanical properties and is used in composite materials to improve the mechanical properties and adhesion of the composite materials.

[0120] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make non-creative modifications to the present embodiment as needed, but as long as they are within the scope of the claims of the present application, they are protected by the patent law.

Claims

1. An environmentally friendly composite material for automobiles, characterized in that: From bottom to top, the following are: bottom non-woven fabric, surface adhesive film 1, reinforcement layer 1, adhesive layer 1, PET bubble sheet, adhesive layer 2, reinforcement layer 2, surface adhesive film 2; the PET bubble sheet includes a PET bubble sheet base layer and a coating, and the coating comprises the following raw materials, in parts by weight: 20-25 parts of water-based acrylic acid, 13-16 parts of a composite plant extract, 9-12 parts of silica nanospheres, 5-8 parts of calcium carbonate, 50-55 parts of deionized water, 1-2 parts of sodium dodecylbenzenesulfonate, and 2-3 parts of a silane coupling agent; The preparation method of the composite plant extract comprises the following steps: drying camellia petals, soaking them in an ethanol solution, adding propylene glycol fatty acid ester, calcium gluconate and malic acid, heating and refluxing for 3-4 times, each extraction time being 1-1.5 hours, combining the extracts, filtering, and concentrating and drying the filtrate to obtain a dry powder; Dispersing the dry powder in deionized water, adding porous nano-aluminum nitride powder, carboxymethyl chitosan, and succinic acid, stirring at a rate of 1000-1200 r / min at 60-65° C. for 35-40 minutes to obtain a composite plant extract dispersion with a uniform texture, drying, and sieving to obtain a composite plant extract; The preparation method of the PET foam sheet comprises the following steps: Dry the PET material, chain extender, nucleating agent, flame retardant and foaming agent at 100-180°C for 5-10 hours; Add PET material, chain extender, nucleating agent and flame retardant and mix them, react for 5-10 minutes to prepare a mixture; The mixed material and the foaming agent are mixed, extruded, cooled and shaped to obtain a primary foaming material, which is then heated and foamed twice to obtain a PET foam sheet base layer; The raw materials in the coating are mixed evenly, coated on both sides of the PET bubble sheet base layer, and dried to obtain the PET bubble sheet.

2. The environmentally friendly composite material for automobiles according to claim 1, characterized in that: The surface adhesive film 1 and the surface adhesive film 2 both include a fabric adhesive layer, a permeation barrier layer, and a low-temperature adhesive layer; the fabric adhesive layer is a polypropylene modified material with an MI greater than 50 g / 10min and a thickness of 20±5µm, the permeation barrier layer is a polypropylene modified material with an MI less than 20 g / 10min and a thickness of 20±5µm, and the low-temperature adhesive layer is a polypropylene modified material with an MI greater than or equal to 20 g / 10min and a thickness of 20±5µm.

3. The environmentally friendly composite material for automobiles according to claim 1, characterized in that: The first and second adhesive layers are both polypropylene modified hot melt adhesive films; The preparation method of the polypropylene modified hot melt adhesive film comprises: uniformly mixing polypropylene, styrene, phenolic terpene resin, quartz powder, compatibilizer, metal organic framework material, benzoyl peroxide, cationic polyacrylamide, and antioxidant 1010, melt blending, extruding and pelletizing, casting, cooling and shaping, and obtaining the polypropylene modified hot melt adhesive film.

4. The environmentally friendly composite material for automobiles according to claim 3, characterized in that: The method for preparing quartz powder comprises the following steps: grinding quartz stone, sieving, dispersing in anhydrous ethanol, soaking for 20-25 minutes, roasting at a temperature of 750-770°C for 5-6 hours, then dispersing in a sodium hydroxide solution, soaking for 30-35 minutes, washing with water, and drying to obtain pretreated powder; The pretreated powder is dispersed in deionized water, and pearl powder, polyvinyl alcohol water-based adhesive, silane coupling agent, and N,N'-ethylene bisstearamide are added. The mixture is stirred at a temperature of 70-75°C for 2-3 hours and dried to obtain quartz stone powder.

5. The environmentally friendly composite material for automobiles according to claim 1, characterized in that: The reinforcement layer 1 and the reinforcement layer 2 are both 200-500g / m 2 Lightweight GMT felt.

6. The environmentally friendly composite material for automobiles according to claim 1, characterized in that: The mass ratio of the dry powder, porous nano-aluminum nitride powder and carboxymethyl chitosan is 1:0.6-0.7:0.1-0.

3.

7. The environmentally friendly composite material for automobiles according to claim 1, characterized in that: The method for preparing porous nano-aluminum nitride powder comprises the following steps: dispersing nano-aluminum nitride in a sodium hydroxide solution, stirring at a temperature of 60-65°C for 45-50 minutes, washing with water, drying, and calcining at a temperature of 700-750°C under nitrogen conditions for 2-3 hours to obtain a pretreated powder; The pretreated powder is dispersed in an ethanol aqueous solution, and silver nanowires, methyl benzoate, polyvinyl alcohol, and cellulose nanofibrils are added. The mixture is stirred at a temperature of 50-55° C. for 2-3 hours and dried to obtain porous nano-aluminum nitride powder.

8. The method for preparing an environmentally friendly composite material for automobiles according to claim 1, characterized in that: The method comprises the following steps: sequentially stacking a bottom non-woven fabric, a surface adhesive film 1, a reinforcing layer 1, an adhesive layer 1, a PET foam sheet, an adhesive layer 2, a reinforcing layer 2 and a surface adhesive film 2, heating and compounding the stacked ...

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