Environment-friendly composite material for automobile and preparation method of environment-friendly composite material

Abstract

The invention belongs to the technical field of automobile interior composite materials, and particularly discloses an environment-friendly composite material for an automobile and a preparation method of the environment-friendly composite material. The environment-friendly composite material for the automobile sequentially comprises a bottom layer non-woven fabric, a surface bonding film I, a reinforcing layer I, a bonding layer I, a PET (Polyethylene Terephthalate) foam sheet, a bonding layer II, a reinforcing layer II and a surface bonding film II from bottom to top, the PET foam sheet comprises a PET foam sheet base layer and a coating, and the coating comprises the following raw materials: 20-25 parts of waterborne acrylic acid, 13-16 parts of a composite plant extract, 9-12 parts of silicon dioxide nanoparticles, 5-8 parts of calcium carbonate, 50-55 parts of deionized water, 1-2 parts of sodium dodecyl benzene sulfonate and 2-3 parts of a silane coupling agent. The composite material has multiple functions of high strength, impact resistance, heat insulation, sound insulation and the like, and the tensile strength is improved.

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 development trends.

[0003] Currently, the main composite materials used for automobile 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 environment 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 long-term performance degradation of polyurethane composite materials, the present application provides an environmentally friendly composite material for automobiles and a preparation method thereof.

[0006] The present application provides an environmentally friendly composite material for automobiles, which adopts the following technical solution: An environmentally friendly composite material for automobiles, comprising, from bottom to top: a bottom non-woven fabric, a surface adhesive film, a reinforcement layer, an adhesive layer, a PET bubble sheet, an adhesive layer, a reinforcement layer, and a 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 dodecylbenzene sulfonate, and 2-3 parts of a silane coupling agent.

[0007] By adopting the above technical solution, the bottom non-woven fabric has excellent mechanical properties to provide basic support. The surface adhesive film I and the surface adhesive film II provide good adhesive properties and barrier properties, ensuring the firm adhesion between the bottom non-woven fabric and the first reinforcing layer, and the firm adhesion between the second reinforcing layer and the surface adhesive film II. The first reinforcing layer and the second reinforcing layer improve the mechanical strength and impact resistance of the composite material, and prolong the durability of the composite material. The first adhesive layer and the second adhesive layer firmly bond the first reinforcing layer to the PET foam sheet and firmly bond the PET foam sheet to the second reinforcing layer, ensuring the interfacial bonding strength. The PET foam sheet provides lightweight and high-strength cushioning performance, and at the same time has good heat insulation and sound insulation effects. Through the multi-layer structure design, the weight of the material is reduced, and various functions such as high strength, impact resistance, heat insulation, and sound insulation of the composite material are provided.

[0008] The non-woven fabric base provides basic structural support. The PET foam sheet includes a PET foam sheet base and a coating. In the coating, the water-based acrylic acid has good film-forming properties and adhesiveness, can provide the weather resistance and water resistance of the coating, is environmentally friendly, uses water as a solvent, and does not generate harmful gases and pollutants during use. The composite plant extract has good antibacterial and antioxidant properties, improves the corresponding properties of the coating, and prolongs the durability of the coating. The silica nanospheres have size effects and self-healing properties, can improve the heat resistance and mechanical properties of the coating, and make the coating have good elasticity. In the structure of the calcium carbonate-filled coating system, combined with the silica nanospheres, the hardness and stability of the coating are improved. Sodium dodecylbenzenesulfonate reduces the surface tension of water, makes the silica nanospheres and calcium carbonate disperse evenly, improves the dispersibility and uniformity of the coating, and helps to improve the comprehensive performance of the coating. The silane coupling agent improves the compatibility between the silica nanospheres and calcium carbonate and the water-based acrylic acid, and enhances the overall performance of the coating.

[0009] In this application, water-based acrylic acid and deionized water are used, reducing the use of organic solvents, meeting the 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 agent ensures the uniform dispersion of each component in water, and improves the mechanical properties such as the flexibility, strength and tear resistance of the coating.

[0010] Preferably, both the surface adhesive film I and the surface adhesive film II include a fabric adhesive layer, a penetration barrier layer, and a low-temperature adhesive layer; the fabric adhesive layer is a polypropylene modified material with a melt index (MI) > 50 g / 10min and a thickness of 20 ± 5 µm, the penetration barrier layer is a polypropylene modified material with an MI < 20 g / 10min and a thickness of 20 ± 5 µm, and the low-temperature adhesive layer is a polypropylene modified material with an MI ≥ 20 g / 10min and a thickness of 20 ± 5 µm.

[0011] By adopting the above technical solutions, the fabric adhesive layer firmly bonds the bottom non-woven fabric and the permeation barrier layer together, ensuring the stability and durability of the overall structure. The permeation barrier layer prevents the fabric adhesive layer from permeating into Reinforcement One / Reinforcement Two after melting and failing to achieve a good bonding effect, thereby protecting the performance and integrity of the internal materials. The low-temperature adhesive layer bonds the permeation barrier layer and Reinforcement One / Reinforcement Two together, ensuring the stability and defect-free of the surface adhesive layer, and providing good bonding performance and protection.

[0012] Preferably, both Adhesive Layer One and Adhesive Layer Two are polypropylene-modified hot melt adhesive films; The preparation method of the polypropylene-modified hot melt adhesive film includes: 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, and then through casting and cooling and shaping to obtain the polypropylene-modified hot melt adhesive film.

[0013] By adopting the above technical solutions, the polypropylene-modified hot melt adhesive film has good bonding performance, can form a strong bond on the material surface, and also has good heat resistance and weather resistance, can maintain its bonding performance under different environmental conditions, can quickly bond after heating, and quickly solidify after cooling, saving production time and improving production efficiency.

[0014] Polypropylene has good flexibility, heat resistance and chemical stability, enabling the hot melt adhesive film to melt and flow when heated and quickly solidify after cooling, thus achieving rapid bonding. Styrene improves the hardness and chemical resistance of the hot melt adhesive film. After blending with polypropylene, it can improve the surface performance and bonding performance of polypropylene and enhance the adhesion of the hot melt adhesive film. Phenolic terpene resin improves the bonding performance and heat resistance of the hot melt adhesive film, enhances the adhesion and heat resistance of the hot melt adhesive film, and enables it to maintain good bonding effect under high-temperature environment. 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 compatibilizer makes polypropylene, styrene, metal-organic framework material and quartz powder disperse evenly. The metal-organic framework material has a large specific surface area and adsorption property, can cooperate with quartz powder to further improve the mechanical properties and thermal stability of the system. Benzoyl peroxide is used as an initiator to promote the grafting reaction of polypropylene and the polymerization reaction of styrene, improve the crosslinking degree of the system, and improve the thermal stability and mechanical properties of the material.

[0015] Cationic polyacrylamide improves the rheological properties of the system, making each component mix evenly and enhancing the product quality. Antioxidant 1010 prevents the oxidative degradation of materials during processing and use, extending the service life of the materials. The hot-melt adhesive film modified by polypropylene obtained through melt blending has good adhesion, heat resistance, and weather resistance, as well as relatively high strength. It is solvent-free and water-free in use, meeting the environmental protection requirements.

[0016] Preferably, the preparation method of the quartz powder comprises the following steps: grinding the quartz stone, sieving it, dispersing it in absolute ethanol, soaking for 20 - 25 min, calcining at a temperature of 750 - 770 °C for 5 - 6 h, then dispersing it in a sodium hydroxide solution, soaking for 30 - 35 min, washing with water, and drying to obtain a pretreated powder. Disperse the pretreated powder in deionized water, add pearl powder, polyvinyl alcohol-based waterborne adhesive, silane coupling agent, and N,N'-ethylenebisstearamide, stir at a temperature of 70 - 75 °C for 2 - 3 h, and dry to obtain the quartz powder.

[0017] By adopting the above technical scheme, the quartz stone is ground into fine powder, increasing its specific surface area and improving the reaction activity. The quartz powder is dispersed in absolute ethanol, while removing surface impurities. Calcining at a temperature of 1200 - 1250 °C removes the organic impurities in the quartz powder, while improving the crystallinity and purity of the powder. The sodium hydroxide solution further removes the impurities on the surface of the quartz powder, improves the reaction activity of the powder, ensures that the particle size of the subsequent obtained pretreated powder is uniform, has good reaction activity, and helps to mix with other components.

[0018] Add the pretreated quartz powder into deionized water to ensure uniform dispersion of the powder. Pearl powder has good dispersibility and surface activity, adsorbs on the surface of the quartz powder particles, improves the surface properties of the quartz powder, enhances its compatibility and adsorption with other components, improves the mechanical properties of the quartz powder, and subsequently improves the structural strength of the hot-melt adhesive film modified by polypropylene. The polyvinyl alcohol-based waterborne adhesive has good film-forming and bonding properties, improves the bonding performance between the quartz powder and the pearl powder, enhances its bonding in the hot-melt adhesive film modified by polypropylene, and enables the hot-melt adhesive film modified by polypropylene to better adhere to the surface of other materials. The silane coupling agent improves the compatibility between the quartz powder, pearl powder and the organic polymer, makes the components of the hot-melt adhesive film modified by polypropylene mix evenly, and enhances the mechanical properties and thermal stability of the material. N,N'-ethylenebisstearamide has good lubricity and dispersibility, improves the processing performance of the quartz powder and the pearl powder, prevents particle agglomeration, makes the pearl powder evenly adsorbed on the surface of the quartz powder particles, and improves the performance improvement of the quartz powder.

[0019] The prepared quartz powder has good dispersibility, which helps to disperse evenly in the hot-melt adhesive film modified with polypropylene. The addition of polyvinyl alcohol-based waterborne adhesives and silane coupling agents improves the bonding performance and compatibility of the quartz powder, making the components in the hot-melt adhesive film modified with polypropylene stirred evenly, and improving the mechanical properties, bonding performance and processing performance of the hot-melt adhesive film modified with polypropylene.

[0020] Preferably, both the first reinforcing layer and the second reinforcing layer are lightweight GMT felts with a weight of 200-500 g / m 2 ².

[0021] By adopting the above technical solution, the lightweight GMT felt has low density and high strength, reduces the weight of the material, while maintaining excellent mechanical properties, having high impact resistance, good bending and tensile strength, and excellent chemical corrosion resistance, and can be recycled, meeting the environmental protection requirements.

[0022] Preferably, the preparation method of the composite plant extract comprises the following steps: drying the camellia petals, soaking them in an ethanol solution, adding propylene glycol fatty acid ester, calcium gluconate and malic acid, heating under reflux for extraction 3-4 times, with each extraction time being 1-1.5 h, combining the extraction solutions, filtering, and after concentrating and drying the filtrate, obtaining a dry powder; Dispersing the dry powder in deionized water, adding porous nano-aluminum nitride powder, carboxymethyl chitosan and succinic acid, and stirring at a rate of 1000-1200 r / min at 60-65 °C for 35-40 min to obtain a uniformly textured composite plant extract dispersion, drying, and sieving to obtain the composite plant extract.

[0023] By adopting the above technical solution, drying the camellia petals to remove the moisture in the petals, soaking them in an ethanol solution, adding propylene glycol fatty acid ester, calcium gluconate and malic acid, propylene glycol fatty acid ester has good solubility and stability, preventing the agglomeration of active ingredients, and helping the dissolution and extraction of active ingredients in camellia. Calcium gluconate adjusts the pH value of the extraction solution, promotes the dissolution of active ingredients in camellia, while preventing the growth of microorganisms, and has certain antioxidant and anti-corrosion effects. Calcium gluconate can stabilize the pH value of the extraction solution and cooperate with malic acid to protect the active ingredients in camellia. Concentrating and drying to remove the solvent and increase the concentration of the extract to obtain a dry powder.

[0024] The porous nano aluminum nitride powder has a high specific surface area and good mechanical strength, can adsorb on the surface of dry powder particles, and improve the thermal stability and mechanical properties of the dry powder. Carboxymethyl chitosan has good water solubility, viscosity and film-forming property, making the dry powder particles and the porous nano aluminum nitride powder adhere evenly, improving the structural strength of the composite plant extract, and facilitating film formation subsequently. Succinic acid adjusts the pH value of the system and has antioxidant and anti-corrosion effects. On the one hand, it helps to protect the active ingredients in camellia, and on the other hand, it crosslinks with carboxymethyl chitosan to form a three-dimensional crosslinked network, improving the strength of the system, enabling the dry powder and the porous nano aluminum nitride powder to better embed in the three-dimensional network structure, and subsequently improving the mechanical properties, antibacterial property and tear resistance of the coating.

[0025] Preferably, the mass ratio of the dry powder, the porous nano aluminum nitride powder and carboxymethyl chitosan is 1:0.6 - 0.7:0.1 - 0.3.

[0026] By adopting the above technical solution, further limiting the mass ratio of the dry powder, the porous nano aluminum nitride powder and carboxymethyl chitosan within a certain range, the obtained composite plant extract has good antibacterial property, adhesiveness and mechanical properties. The porous nano aluminum nitride powder has excellent adsorption property and mechanical properties, can be loaded on the surface of dry powder particles, and improve the mechanical properties of the dry powder. Carboxymethyl chitosan has film-forming property, adhesiveness and water solubility, making 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 property and viscosity, and is subsequently applied to the coating, improving the adhesion of each component in the coating, and moreover, improving the mechanical properties of the coating and reducing the probability of coating tearing.

[0027] Preferably, the preparation method of the porous nano aluminum nitride powder includes the following steps: dispersing nano aluminum nitride in sodium hydroxide solution, stirring at a temperature of 60 - 65 °C for 45 - 50 min, washing with water, drying, and calcining under nitrogen conditions at a temperature of 700 - 750 °C for 2 - 3 h to obtain a pretreated powder; Dispersing the pretreated powder in an ethanol aqueous solution, adding silver nanowires, methyl benzoate, polyvinyl alcohol, and cellulose nanofibrils, stirring at a temperature of 50 - 55 °C for 2 - 3 h, and drying to obtain the porous nano aluminum nitride powder.

[0028] By adopting the above technical solution, treating nano aluminum nitride with sodium hydroxide solution removes the impurities of surface alumina and etches the surface of aluminum nitride, making the surface have a porous structure. Calcination further improves the crystallinity and purity of the powder, simultaneously removes organic impurities, increases the specific surface area of nano aluminum nitride, and enhances the adsorption property.

[0029] Disperse the pretreated powder in anhydrous ethanol, and add silver nanowires, methyl benzoate, polyvinyl alcohol, and cellulose nanofibrils. The silver nanowires have good flexibility and antibacterial properties and can adsorb on the surface and within the pores of aluminum nitride nanoparticles, improving the corresponding properties of aluminum nitride nanoparticles. The combination of methyl benzoate and cellulose nanofibrils helps to uniformly disperse aluminum nitride nanoparticles and silver nanowires, enabling the silver nanowires to be uniformly loaded in the aluminum nitride nanostructure. Polyvinyl alcohol has good film-forming and adhesive properties, enabling the silver nanowires to be uniformly adhered to the aluminum nitride nanostructure, enhancing the mechanical properties of the porous aluminum nitride powder, and subsequently improving the mechanical properties and antibacterial properties of the non-woven fabric coating.

[0030] Preferably, dry the PET material, chain extender, nucleating agent, flame retardant, and foaming agent at 100 - 180 °C for 5 - 10 h; Add the PET material, chain extender, nucleating agent, and flame retardant and mix them for 5 - 10 min to obtain a mixed material; Mix the mixed material and the foaming agent, extrude, and after cooling and shaping, obtain a primary foamed material. After heating, perform secondary foaming to obtain the PET foam sheet base layer; Mix the raw materials in the coating evenly, coat them on both sides of the PET foam sheet base layer, and dry to obtain the PET foam sheet.

[0031] By adopting the above technical solution, after the PET material, chain extender, nucleating agent, and flame retardant are mixed evenly with each other, a foaming agent is added to obtain a primary foamed material. The foaming process is extrusion foaming, the process is relatively simple, the difficulty is low. In the obtained primary foamed material, the PET material, chain extender, and nucleating agent crosslink with each other to form a network structure, making most of the pores in the primary foamed material closed pores, creating conditions for secondary foaming. After heating the primary foamed material, the primary foamed material softens and undergoes secondary foaming, the primary foamed material further expands, the pores grow, and the obtained PET foam sheet base layer has a higher porosity, an increased volume, and a reduced density, realizing the lightweight of the PET foamed material. Moreover, the PET foam sheet base layer obtained by secondary foaming is easy to process. When using the PET foam sheet base layer to process automotive interiors, operations such as cutting and welding are not required, reducing the generation of waste. Also, during the secondary foaming process, it is convenient to control the density of the PET foam sheet base layer, and it is easy to obtain the PET foam sheet base layer with the required density. The process is more controllable and precise, and is suitable for preparing automotive interiors with relatively complex shapes. Finally, coat the surface of the PET foam sheet base layer to obtain the PET foam sheet, which has good heat resistance, wear resistance, and mechanical properties, enhancing the overall performance of the PET foam sheet.

[0032] Preferably, the chain extender is one or more of diols, triols, and tetrols; the nucleating agent is one or more of talcum powder, calcium carbonate, and nanocrystals of organic materials.

[0033] In a second aspect, the present application also provides a method for preparing an environment-friendly composite material for automobiles, comprising the following steps: successively stacking a bottom non-woven fabric, a first surface bonding film, a first reinforcing layer, a first bonding layer, a PET foam sheet, a second bonding layer, a second reinforcing layer, and a second surface bonding film, then performing heat compounding, and cooling to obtain the environment-friendly composite material for automobiles.

[0034] By adopting the above technical solution and the above preparation method, the operation is simple, the process time is short, the production efficiency of preparing the environment-friendly composite material for automobiles is improved, and the obtained environment-friendly composite material for automobiles has good mechanical properties and antibacterial properties.

[0035] Preferably, the compounding temperature is 200 - 230 °C, the compounding roll gap is 5 - 7 mm, and the compounding conveyor belt speed is 5 - 7 m / min.

[0036] In summary, the present application has the following beneficial effects: 1. In the present application, through the multi-layer structure design, the weight of the material is reduced, and multiple functions such as high strength, impact resistance, heat insulation, and sound insulation of the composite material are provided.

[0037] 2. In the present application, the PET foam sheet is a closed-cell thermoplastic renewable polymer foam, which has excellent temperature resistance, plasticity, and strength, and is an ideal molding material for automotive interior parts.

[0038] 3. In the present application, the non-woven fabric coating has excellent flexibility and adhesion, improving the durability of the composite material. Specific Embodiments

[0039] The following further elaborates on the present application with reference to embodiments.

[0040] The raw materials used in the examples and comparative examples can all be obtained commercially.

[0041] Preparation Example 1 A method for preparing a composite plant extract, comprising the following steps: drying 100 kg of camellia petals, soaking them in 300 L of an ethanol solution with a mass concentration of 95%, adding 20 kg of propylene glycol fatty acid ester, 8 kg of calcium gluconate, and 10 kg of malic acid, performing heat reflux extraction 3 times, with each extraction time being 1.5 h, combining the extraction liquids, filtering, and after concentrating and drying the filtrate, obtaining a dry powder; Taking 20 kg of the dry powder, dispersing it in 70 L of deionized water, adding porous nano-aluminum nitride powder, carboxymethyl chitosan, and 2 kg of succinic acid, stirring at a rate of 1100 r / min at 63 °C for 38 min to obtain a uniformly textured composite plant extract dispersion liquid, drying, and passing through a 100-mesh sieve to obtain the composite plant extract.

[0042] The mass ratio of the dry powder, porous nano-aluminum nitride powder, and carboxymethyl chitosan is 1:0.6:0.3.

[0043] A preparation method of porous nano-aluminum nitride powder, comprising the following steps: dispersing 25 kg of nano-aluminum nitride in 60 L of a sodium hydroxide solution with a concentration of 1 mol / L, stirring at a temperature of 62 °C for 48 min, washing with water, drying, and calcining under nitrogen conditions at a temperature of 720 °C for 2.5 h to obtain a pretreated powder; Disperse the pretreated powder in 90 L of an ethanol aqueous solution (volume ratio of water to ethanol is 1:1), add 6 kg of silver nanowires, 1 kg of methyl benzoate, 3 kg of polyvinyl alcohol, and 2 kg of cellulose nanofibrils, stir at a temperature of 53 °C for 2.6 h, and dry to obtain porous nano-aluminum nitride powder.

[0044] The cellulose nanofibrils are purchased from Nanjing Tianlu Nano Technology Co., Ltd.

[0045] Preparation Example 2 The difference from Preparation Example 1 is that no porous nano-aluminum nitride powder is added.

[0046] Preparation Example 3 The difference from Preparation Example 1 is that no carboxymethyl chitosan is added.

[0047] Preparation Example 4 The difference from Preparation Example 1 is that the mass ratio of the dry powder, porous nano-aluminum nitride powder, and carboxymethyl chitosan is 1:0.7:0.1.

[0048] Preparation Example 5 The difference from Preparation Example 1 is that the mass ratio of the dry powder, porous nano-aluminum nitride powder, and carboxymethyl chitosan is 1:0.1:0.6.

[0049] Preparation Example 6 The difference from Preparation Example 1 is that in the preparation method of the porous nano-aluminum nitride powder, no silver nanowires are added.

[0050] Preparation Example 7 The difference from Preparation Example 1 is that in the preparation method of the porous nano-aluminum nitride powder, no polyvinyl alcohol is added.

[0051] Example 1 An environmentally friendly composite material for automobiles, which from bottom to top is successively: 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, a surface adhesive film 2; the PET foam sheet includes a PET foam sheet and a coating, and the coating, by weight, comprises the following raw materials: 20 kg of waterborne acrylic acid, 13 kg of composite plant extracts, 9 kg of silicon dioxide nano-microspheres, 8 kg of calcium carbonate, 50 kg of deionized water, 1 kg of sodium dodecylbenzenesulfonate, and 2 kg of silane coupling agent kh550; The thickness of the bottom non-woven fabric is 0.5 mm, and the silica nano-microspheres are purchased from Qinghe Chaotai Metal Materials Co., Ltd.

[0052] Both the surface bonding film 1 and the surface bonding film 2 include a fabric bonding layer, a penetration barrier layer, and a low-temperature bonding layer; the fabric bonding layer is K7100 from Yanshan Petrochemical with a thickness of 20 µm, the penetration barrier layer is FL7632L from Singapore with a thickness of 20 µm, and the low-temperature bonding layer is EP6051 from Basel with a thickness of 20 µm. The thickness of the reinforcement layer 1 / reinforcement layer 2 is 1.5 mm, and the thickness of the bonding layer 1 / bonding layer 2 is 0.6 mm; Both the bonding layer 1 and the bonding layer 2 are polypropylene-modified hot-melt adhesive films; the polypropylene-modified hot-melt adhesive films are purchased from Hangzhou Zhihe New Materials Co., Ltd.

[0053] Both the reinforcement layer 1 and the reinforcement layer 2 are lightweight GMT felts with a weight of 200 g / m 2 and are purchased from Zhejiang Huajiang Technology Co., Ltd.

[0054] The composite plant extract adopts Preparation Example 1.

[0055] The preparation method of the PET foam sheet includes the following steps: drying PET particles, chain extender, nucleating agent, flame retardant, and foaming agent, melt-extruding and cooling to obtain a PET sheet; thermally expanding the PET sheet to obtain a PET foam sheet base layer, mixing the raw materials in the coating evenly at a temperature of 85 °C, coating both sides of the PET foam sheet base layer, and drying to obtain the PET foam sheet.

[0056] 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 are dried at 120 °C for 8 h, where the PET material is polyethylene terephthalate, the chain extender is pentaerythritol, the nucleating agent is nanocrystalline talc powder, the flame retardant is aluminum hydroxide, and the foaming agent is carbon dioxide.

[0057] Mixing: adding the PET material, chain extender, nucleating agent, and flame retardant into a twin-screw device for mixing, the screw temperature is 200 °C, the head temperature is 240 °C, the head pressure is 10 MPa, reacting for 10 min to obtain a mixed material; Transferring the mixed material through a voltage stabilizer to a single-screw device, the screw temperature is 200 °C, the head temperature is 240 °C, the head pressure is 15 MPa, adding the foaming agent, extruding through an annular die head, and cooling and shaping with an air ring to obtain a primary foamed material; Subjecting the PET foamed material to secondary foaming after heating, the heating temperature for secondary foaming is 150 °C, and the heating time is 5 min to obtain the PET foam sheet base layer.

[0058] A preparation method of an environment-friendly composite material for automobiles includes the following steps: successively stack a bottom non-woven fabric, a surface bonding film 1, a reinforcing layer 1, a bonding layer 1, a PET foam sheet, a bonding layer 2, a reinforcing layer 2, and a surface bonding film 2, and then perform heat composite, and obtain the environment-friendly composite material for automobiles after cooling.

[0059] The composite temperature is 200 °C, the gap of the composite roller is 7 mm, and the composite speed is 5 m / min.

[0060] Example 2: An environment-friendly composite material for automobiles, different from that in Example 1, the coating includes the following raw materials by weight: 25 kg of waterborne acrylic acid, 16 kg of composite plant extract, 12 kg of silicon dioxide nano microspheres, 5 kg of calcium carbonate, 55 kg of deionized water, 2 kg of sodium dodecyl benzene sulfonate, and 3 kg of silane coupling agent.

[0061] Both the reinforcing layer 1 and the reinforcing layer 2 are lightweight GMT felts of 500 g / m 2 , and the thickness of the reinforcing layer 1 / the reinforcing layer 2 is 1 mm.

[0062] 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 are dried and then extruded through a twin-screw - single-screw extruder through an annular die head, cooled, and wound to obtain a PET sheet with a surface density of 160 kg / m 3 , a thickness of 3 mm; after the PET sheet is roll-pressed by upper and lower needle rollers, it is heated and expanded in a heating furnace at 150 °C to obtain a PET foam sheet with a thickness of 4 mm; among them, the PET particles are recycled bottle-grade PET particles; the thickness of the PET foam sheet is 6 mm and the density is 80 kg / m 3 ; the extrusion temperature is 240 °C.

[0063] A preparation method of an environment-friendly composite material for automobiles includes the following steps: successively stack a bottom non-woven fabric, a surface bonding film 1, a reinforcing layer 1, a bonding layer 1, a PET foam sheet, a bonding layer 2, a reinforcing layer 2, and a surface bonding film 2, and then perform heat composite, and obtain the environment-friendly composite material for automobiles after cooling.

[0064] The composite temperature is 230 °C, the gap of the composite roller is 5 mm, and the composite speed is 7 m / min.

[0065] Example 3 An environment-friendly composite material for automobiles, which is different from Example 1 in that the preparation method of the polypropylene-modified hot melt adhesive film includes: mixing 80 kg of polypropylene, 10 kg of styrene, 13 kg of phenolic terpene resin, 18 kg of quartz powder, 7 kg of compatibilizer, 8 kg of metal-organic framework material, 1 kg of benzoyl peroxide, 0.5 kg of cationic polyacrylamide, and 0.2 kg of antioxidant 1010 evenly, melt-blending in a twin-screw extruder, extruding and pelletizing, adding to an extrusion casting machine, and after casting and cooling and shaping, obtaining the polypropylene-modified hot melt adhesive film.

[0066] 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.

[0067] The preparation method of the quartz powder includes 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 min, calcining at a temperature of 760 °C for 5.5 h, then dispersing in 70 L of a 10% sodium hydroxide solution by mass, soaking for 32 min, washing with water, and drying to obtain the pretreated powder; Disperse the pretreated powder in 100 L of deionized water, add 6 kg of pearl powder, 3 kg of polyvinyl alcohol-based water-based adhesive, 1 kg of silane coupling agent KH550, and 0.5 kg of N,N'-ethylenebisstearamide, stir at a temperature of 73 °C for 2.5 h, and dry to obtain the quartz powder.

[0068] The polyvinyl alcohol-based water-based adhesive is a polyvinyl alcohol adhesive, purchased from Jinan Guocheng Chemical Co., Ltd.

[0069] Example 4 An environment-friendly composite material for automobiles, which is different from Example 3 in that the preparation method of the polypropylene-modified hot melt adhesive film includes: mixing 85 kg of polypropylene, 15 kg of styrene, 16 kg of phenolic terpene resin, 22 kg of quartz 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 evenly, melt-blending in a twin-screw extruder, extruding and pelletizing, adding to an extrusion casting machine, and after casting and cooling and shaping, obtaining the polypropylene-modified hot melt adhesive film.

[0070] Example 5 An environment-friendly composite material for automobiles, which is different from Example 3 in that in the preparation method of the polypropylene-modified hot melt adhesive film, no quartz powder is added.

[0071] Example 6 An environment-friendly composite material for automobiles, which is different from Example 3 in that in the preparation method of the polypropylene-modified hot melt adhesive film, no metal-organic framework material is added.

[0072] Example 7: An environment-friendly composite material for automobiles, which is different from Example 3 in that no pearl powder is added in the preparation method of quartz powder.

[0073] Example 8: An environment-friendly composite material for automobiles, which is different from Example 3 in that no polyvinyl alcohol-based waterborne adhesive is added in the preparation method of quartz powder.

[0074] Example 9: An environment-friendly composite material for automobiles, which is different from Example 1 in that the composite plant extract is prepared according to Preparation Example 2.

[0075] Example 10: An environment-friendly composite material for automobiles, which is different from Example 1 in that the composite plant extract is prepared according to Preparation Example 3.

[0076] Example 11: An environment-friendly composite material for automobiles, which is different from Example 1 in that the composite plant extract is prepared according to Preparation Example 4.

[0077] Example 12: An environment-friendly composite material for automobiles, which is different from Example 1 in that the composite plant extract is prepared according to Preparation Example 5.

[0078] Example 14: An environment-friendly composite material for automobiles, which is different from Example 1 in that the composite plant extract is prepared according to Preparation Example 6.

[0079] Example 14: An environment-friendly composite material for automobiles, which is different from Example 1 in that the composite plant extract is prepared according to Preparation Example 7.

[0080] Comparative Example 1 An environment-friendly composite material for automobiles, which is different from Example 1 in that no composite plant extract is added.

[0081] Comparative Example 2 An environment-friendly composite material for automobiles, which is different from Example 1 in that the composite plant extract is replaced by an equal amount of camellia pollen.

[0082] Performance detection test: The environment-friendly composite materials for automobiles prepared in Examples 1-14 and Comparative Examples 1-2 were subjected to performance tests; Referring to GB / T 9341-2008, the flexural strength and flexural modulus of the environment-friendly composite material for automobiles were tested; referring to the test standard of GB / T10404-2006 for the tensile properties of plastics, the tensile properties of the environment-friendly composite material for automobiles were tested.

[0083] Refer to PV 2034-2020 to test the interlaminar adhesion of the environmentally friendly composite material for automobiles, and test the interlaminar adhesion between the first / second reinforcing layers and the PET foam sheet; the test results are shown in Table 1.

[0084] Table 1 Test data of examples and comparative examples

[0085] As can be seen from Table 1, the environmentally friendly composite materials for automobiles prepared in Examples 1-2 of this 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 interlaminar adhesion is 10.8 N / 5 cm. It can be seen that the materials prepared in this application have good strength and elasticity, and each component cooperates with each other, improving the adhesion of the environmentally friendly composite material for automobiles and extending the durability of the composite material.

[0086] Examples 3-4 prepared a polypropylene-modified hot melt adhesive film. As can be seen from Table 1, the test results of the tensile strength, flexural strength, flexural strength modulus, and interlaminar adhesion of Examples 3-4 are significantly better than those of Examples 1-2, indicating that the modified hot melt adhesive film of this application has good bonding performance and strength, and each component cooperates synergistically, subsequently improving the thermal stability, adhesiveness, and mechanical properties of the composite material.

[0087] In the preparation methods of the polypropylene-modified hot melt adhesive films in Examples 5-6, quartz powder and metal-organic framework materials were not added respectively. As can be seen from Table 1, the test results of the tensile strength, flexural strength, flexural strength modulus, and interlaminar 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 property, can cooperate with the quartz powder, further improve the mechanical properties and thermal stability of the system, and subsequently improve the corresponding properties of the composite material.

[0088] In the preparation methods of quartz powder in Examples 7 - 8, pearl powder and polyvinyl alcohol - based water - borne adhesives are not added respectively. It can be seen from Table 1 that the test results of tensile strength, flexural strength, flexural strength modulus, and interlayer adhesion in Example 7 are significantly worse than those in Examples 3 - 4 and Example 6, but better than those in Example 5. The test results of tensile strength, flexural strength, flexural strength modulus, and interlayer adhesion in Example 8 are significantly worse than those in Examples 3 - 4, but better than those in Examples 5 - 7. This shows that pearl powder has good dispersibility and surface activity, adsorbs 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 - borne adhesives have good film - forming properties and adhesiveness, improve the bonding performance between quartz powder and pearl powder, enhance its adhesiveness in the polypropylene - modified hot - melt adhesive film, and enable the polypropylene - modified hot - melt adhesive film to better adhere to the surface of other materials, and subsequently enhance the mechanical properties, adhesiveness, and thermal stability of the composite material.

[0089] In the preparation methods of composite plant extracts in Examples 9 - 10, porous nano - aluminum nitride powder and carboxymethyl chitosan are not added respectively. In Examples 11 - 12, the mass ratios of dry powder, porous nano - aluminum nitride powder, and carboxymethyl chitosan are changed. It can be seen from Table 1 that the test results of tensile strength, flexural strength, flexural strength modulus, and interlayer adhesion in Examples 9 - 10 are significantly worse than those in Examples 1 - 2 and Example 11. The corresponding performance test results in Example 12 are better than those in Examples 9 - 10, but worse than those in Examples 1 - 2. This shows that the composite plant extract prepared in this application has excellent mechanical properties. Porous nano - aluminum nitride powder has a high specific surface area and good mechanical strength, can adsorb on the surface of dry powder particles, and improve the thermal stability and mechanical properties of dry powder; carboxymethyl chitosan has good water - solubility, viscosity, and film - forming properties, makes the dry powder particles and porous nano - aluminum nitride powder adhere evenly, improves the structural strength of the composite plant extract, and subsequently helps to form a film and improve the comprehensive performance of the composite material.

[0090] In the preparation methods of porous nano - aluminum nitride powder in Examples 13 - 14, silver nanowires and polyvinyl alcohol are not added respectively. It can be seen from Table 1 that the test results of tensile strength, flexural strength, flexural strength modulus, and interlayer adhesion in Examples 13 - 14 are significantly better than those in Example 9. This shows that silver nanowires have good flexibility and antibacterial properties, can adsorb 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 properties and adhesiveness, makes the silver nanowires evenly adhere to the nano - aluminum nitride structure, enhances the mechanical properties of porous nano - aluminum nitride powder, and subsequently improves the mechanical properties and antibacterial properties of the non - woven fabric coating.

[0091] In Comparative Example 1, the composite plant extract was not added. As can be seen from Table 1, the test results of the tensile strength, flexural strength, flexural strength modulus, and interlaminar adhesion of Comparative Example 1 were significantly worse than those of Examples 1-2, indicating that the composite plant extract prepared in this application has excellent comprehensive properties. When applied to the environmentally friendly composite material for automobiles, it can improve the corresponding properties of the composite material.

[0092] In Comparative Example 2, the composite plant extract was replaced by an equal amount of camellia pollen. As can be seen from Table 1, the test results of the tensile strength, flexural strength, flexural strength modulus, and interlaminar adhesion of Comparative Example 2 were significantly worse than those of Examples 1-2, but better than those of Comparative Example 1, indicating that the composite plant extract prepared in this application has relatively excellent mechanical properties. When applied to the composite material, it can improve the mechanical properties and adhesiveness of the composite material.

[0093] This specific embodiment is only an interpretation of this application and does not limit this application. After reading this specification, those skilled in the art can make modifications to this embodiment without creative contributions according to needs, but as long as it is within the scope of the claims of this application, it is protected by the patent law.

Claims

1. An environmentally friendly composite material for automobiles, characterized in that, From bottom to top, they are: bottom non-woven fabric, surface adhesive film 1, reinforcement layer 1, adhesive layer 1, PET foam sheet, adhesive layer 2, reinforcement layer 2, surface adhesive film 2; the PET foam sheet includes a PET foam sheet base layer and a coating, and the coating, by weight, includes the following raw materials: 20-25 parts of waterborne 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 dodecylbenzenesulfonate, and 2-3 parts of silane coupling agent.

2. The environmentally friendly composite material for automobiles according to claim 1, characterized in that, Both the surface adhesive film 1 and the surface adhesive film 2 include a fabric adhesive layer, a penetration barrier layer, and a low-temperature adhesive layer; the fabric adhesive layer is a polypropylene modified material with MI > 50 g / 10min and a thickness of 20 ± 5 µm, the penetration barrier layer is a polypropylene modified material with MI < 20 g / 10min and a thickness of 20 ± 5 µm, and the low-temperature adhesive layer is a polypropylene modified material with MI ≥ 20 g / 10min and a thickness of 20 ± 5 µm.

3. An environment-friendly composite material for automobiles according to claim 1, characterized in that, Both the adhesive layer 1 and the adhesive layer 2 are polypropylene-modified hot melt adhesive films; The preparation method of the polypropylene-modified hot melt adhesive film includes: mixing polypropylene, styrene, phenolic terpene resin, quartz powder, compatibilizer, metal-organic framework material, benzoyl peroxide, cationic polyacrylamide, and antioxidant 1010 evenly, melt-blending, extruding and pelletizing, and then through casting and cooling and shaping to obtain the polypropylene-modified hot melt adhesive film.

4. An environment-friendly composite material for automobiles according to claim 3, characterized in that, The preparation method of the quartz powder includes the following steps: grinding quartz stone, sieving, dispersing in absolute ethanol, soaking for 20-25 min, roasting at a temperature of 750-770 °C for 5-6 h, then dispersing in sodium hydroxide solution, soaking for 30-35 min, washing with water, and drying to obtain the pretreated powder; Disperse the pretreated powder in deionized water, add pearl powder, polyvinyl alcohol-based waterborne adhesive, silane coupling agent, and N,N'-ethylenebisstearamide, stir at a temperature of 70-75 °C for 2-3 h, and dry to obtain the quartz powder.

5. An environment-friendly composite material for automobiles according to claim 1, characterized in that, Both the first reinforcement layer and the second reinforcement layer are lightweight GMT felts with a weight of 200-500 g / m 2 .

6. An environment-friendly composite material for automobiles according to claim 1, characterized in that, The preparation method of the composite plant extract includes the following steps: drying camellia petals, soaking in an ethanol solution, adding propylene glycol fatty acid ester, calcium gluconate, and malic acid, heating under reflux for extraction 3-4 times, with each extraction time being 1-1.5 h, combining the extraction solutions, filtering, and concentrating and drying the filtrate to obtain a dry powder; Disperse the dry powder in deionized water, add porous nano-aluminum nitride powder, carboxymethyl chitosan, and succinic acid, stir at a rate of 1000-1200 r / min at 60-65 °C for 35-40 min to obtain a uniformly textured composite plant extract dispersion, dry, and sieve to obtain the composite plant extract.

7. An environmentally friendly composite material for automobiles according to claim 6, 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.

8. An environmentally friendly composite material for automobiles according to claim 6, characterized in that, The preparation method of the 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 min, washing with water, drying, and calcining under nitrogen conditions at a temperature of 700 - 750 °C for 2 - 3 h to obtain a pretreated powder; Dispersing the pretreated powder in an ethanol aqueous solution, adding silver nanowires, methyl benzoate, polyvinyl alcohol, and cellulose nanofibrils, stirring at a temperature of 50 - 55 °C for 2 - 3 h, and drying to obtain the porous nano aluminum nitride powder.

9. An environment-friendly composite material for automobiles according to claim 1, characterized in that, The preparation method of the PET foam sheet comprises the following steps: Drying PET material, chain extender, nucleating agent, flame retardant, and foaming agent at 100 - 180 °C for 5 - 10 h; Adding and mixing PET material, chain extender, nucleating agent, and flame retardant, reacting for 5 - 10 min to obtain a mixed material; Mixing the mixed material and the foaming agent, extruding, and after cooling and shaping, obtaining a primary foamed material, and performing secondary foaming after heating to obtain a PET foam sheet base layer; Mixing the raw materials in the coating evenly, coating both sides of the PET foam sheet base layer, and drying to obtain the PET foam sheet.

10. The preparation method of an environment-friendly composite material for automobiles according to claim 1, characterized in that, Comprising the following steps: sequentially stacking a bottom non-woven fabric, a surface adhesive film I, a reinforcing layer I, an adhesive layer I, a PET foam sheet, an adhesive layer II, a reinforcing layer II, and a surface adhesive film II, heating and laminating, and cooling to obtain an environment-friendly composite material for automobiles.

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