A biomass buffer energy-absorbing panel, its preparation method and application

Abstract

This invention discloses a biomass-based energy-absorbing buffer panel, its preparation method, and its application. The biomass-based energy-absorbing buffer panel comprises an energy-absorbing layer, carbon fiber reinforcement layers located on both sides of the energy-absorbing layer, and an adhesive layer between the energy-absorbing layer and the carbon fiber reinforcement layers; the energy-absorbing layer contains biomass polyurethane, and the carbon fiber reinforcement layers contain carbon fibers and furan-based polyester. This biomass-based energy-absorbing buffer panel exhibits excellent cushioning effect and mechanical properties, and is environmentally friendly.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, and in particular to a biomass buffer energy-absorbing plate, its preparation method, and its application. Background Technology

[0002] With the booming economy, the development of transportation vehicles is increasing daily. While bringing convenience to people, transportation vehicles also consume large amounts of non-renewable resources and generate harmful gases that pollute the environment. Lightweighting of transportation vehicles is not only an essential way to address the energy crisis and environmental pollution, but also helps improve the comfort, power, and operational stability of these vehicles. Steel is the most commonly used material in transportation vehicles, but an all-steel body has disadvantages such as high weight, high fuel consumption, and high emissions, which does not meet current demands for lightweighting. Adopting lightweight materials is the most effective measure to achieve lightweighting of transportation vehicles.

[0003] Aluminum alloys and carbon fiber composites, compared to steel, have lower density and higher strength, making them two excellent lightweight materials that are currently used in various transportation vehicles. However, while achieving lightweight transportation vehicles, it is essential to ensure collision safety. Improving crashworthiness remains the most important and direct way to guarantee collision safety.

[0004] Rigid materials like aluminum alloys and carbon fiber rely on crack propagation or even breakage to cushion impacts. However, this method of impact resistance poses safety risks. When the impact is large enough, the fragments can cause secondary injuries to people or objects on board. For example, when a carbon fiber car body is subjected to a strong impact, the brittle fracture of the carbon fiber composite material causes the body panels in front of the energy-absorbing box to shatter into pieces before the energy-absorbing box can fully absorb the energy. Therefore, relying solely on rigid materials like aluminum alloys and carbon fiber to cushion impacts is insufficient; additional structural elements are needed to supplement the impact resistance.

[0005] Common cushioning structures include honeycomb sandwich structures, corrugated structures, and laminated structures, all of which require significant thickness. However, excessively thick cushioning structures reduce the volume utilization of transportation vehicles, making them unsuitable. Laminated structures, on the other hand, are thinner and have strong impact resistance, and the gel-like elastomer effectively cushions the impact while protecting the rigid structure. However, common materials such as polyurethane and polyester are petroleum-based products with poor environmental friendliness, failing to meet increasingly stringent environmental protection requirements. Furthermore, the bonding between biomass polymers and carbon fibers is poor, hindering effective impact transmission.

[0006] Therefore, there is a need to develop a cushioning energy-absorbing board that uses biomass as raw material and has excellent cushioning performance. Summary of the Invention

[0007] To address the aforementioned technical problems, the present invention aims to provide a biomass buffer energy-absorbing board, its preparation method, and its application; this biomass buffer energy-absorbing board has excellent buffering effect and mechanical properties, and is environmentally friendly.

[0008] To achieve the above-mentioned technical objectives and effects, the present invention is implemented through the following technical solution:

[0009] A biomass cushioning and energy-absorbing panel includes an energy-absorbing layer, carbon fiber reinforcement layers located on both sides of the energy-absorbing layer, and an adhesive layer between the energy-absorbing layer and the carbon fiber reinforcement layers; the energy-absorbing layer contains biomass polyurethane, and the carbon fiber reinforcement layers contain carbon fibers and furan-based polyester.

[0010] The energy-absorbing layer is a structure that can absorb impact energy. Specifically, it absorbs energy through elastic deformation to reduce the vibration caused by the impact.

[0011] The energy-absorbing layer contains biomass polyurethane, which is a type of polyurethane synthesized from biomass. Polyurethane is an organic polymer material produced by the reaction of polyisocyanates and polyols and has multiple urethane segments. The biomass polyurethane contains bio-based polyol segments; bio-based polyol segments are compounds containing two or more hydroxyl groups, with biomass as all or part of the raw material. Preferably, the bio-based polyol is selected from one or more combinations of bio-based polytrimethylene ether glycol, bio-based polyethylene glycol, and bio-based polylactic acid polyol.

[0012] Biomass polyurethane has excellent tensile strength, tear strength, impact resistance, abrasion resistance, weather resistance, hydrolysis resistance, and oil resistance. As a component of the energy-absorbing layer of this invention, biomass polyurethane can effectively mitigate impact force and transfer the impact force to the carbon fiber reinforced layer.

[0013] Furthermore, the energy-absorbing layer also contains carbon fiber powder. The carbon fiber powder is an aggregate of carbon fibers with a particle size of less than 1000 μm, which can disperse the impact and prevent excessive localized impact from causing the energy-absorbing layer to break. In this invention, for more effective impact dispersion, carbon fiber powder with a particle size of less than 10-100 μm is preferred. If the particle size is too large, the dispersion effect is poor; if the particle size is too small, the polyurethane composition has excessive viscosity and is difficult to process.

[0014] The carbon fiber reinforcement layer is a high-strength layer containing carbon fibers. It can withstand impact without deformation and can transfer the impact force to the energy-absorbing layer, which can effectively improve the impact resistance of the cushioning board and reduce damage and breakage caused by impact.

[0015] The carbon fibers in the carbon fiber reinforcement layer are high-strength fibers with a carbon content of over 90%. Carbon fibers can be classified according to their morphology into long-bundle carbon fiber filaments, short-bundle carbon fiber filaments, chopped carbon fibers, carbon fiber powder, carbon fiber fabrics, etc. In this invention, carbon fibers play a role in improving the strength and toughness of the carbon fiber reinforcement layer. Preferably, the carbon fibers in the carbon fiber reinforcement layer of this invention are carbon fiber fabrics, which, as the main body bearing impact force, possess high strength.

[0016] The carbon fiber reinforcement layer also contains furan-based polyester. Furan-based polyester is a furan resin whose repeating units in the molecular chain contain ester groups (-COO-), and whose main chain contains rigid furan rings. Specific examples include polyethylene furanate, propylene furanate, butylene furanate, hexanediol furanate, octanediol furanate, and decanediol furanate. The furan-based polyester resin in the carbon fiber reinforcement layer of this invention is at least one of polyethylene furanate, propylene furanate, butylene furanate, hexanediol furanate, octanediol furanate, decanediol furanate, and their copolymers. In this invention, the furan-based polyester plays a role in improving the adhesion between the carbon fiber and the polyurethane (the polyurethane in the adhesive layer) and in protecting the carbon fiber.

[0017] The bonding layer is a structure that bonds the energy-absorbing layer and the carbon fiber reinforcement layer. It can not only effectively bond the carbon fiber reinforcement layer and the energy-absorbing layer, but also effectively transfer the impact force on the carbon fiber reinforcement layer to the energy-absorbing layer.

[0018] The adhesive layer contains a bio-based polyurethane thermoplastic elastomer. Polyurethane thermoplastic elastomer is a type of thermoplastic elastomer obtained from polyurethane; it refers to an elastomer that is elastic at room temperature and malleable at high temperatures. In this invention, the bio-based polyurethane thermoplastic elastomer, as an adhesive layer, can provide effective bonding and impact force transfer.

[0019] Considering the application range, processing cost, and mechanical properties of the energy-absorbing buffer panel, the thickness of the energy-absorbing layer is 4–20 mm, the thickness of the adhesive layer is 0.5–2 mm, and the thickness of the carbon fiber reinforcement layer is 1–4 mm. If the energy-absorbing layer is too thin, it will not effectively provide cushioning; if it is too thick, the cost will increase and the volume will be too large for practical application. If the adhesive layer is too thin, it will not bond the energy-absorbing layer and the carbon fiber reinforcement layer well; if the adhesive layer is too thick, it will reduce the mechanical properties of the panel. If the carbon fiber reinforcement layer is too thin, it will not effectively improve the mechanical properties of the panel; if it is too thick, the volume will be too large for its use.

[0020] This invention also provides a method for preparing a biomass buffer energy-absorbing panel, comprising the following steps:

[0021] S1, respectively prepare the energy-absorbing layer, the bonding layer, and the carbon fiber reinforcement layer;

[0022] S2, the energy-absorbing layer, adhesive layer and carbon fiber reinforcement layer are stacked in the order of carbon fiber reinforcement layer / adhesive layer / energy-absorbing layer / adhesive layer / carbon fiber reinforcement layer and then hot-pressed into shape.

[0023] The method for preparing the energy-absorbing layer can be compression molding, injection molding, etc., and the preferred temperature is 140-160℃.

[0024] The adhesive layer can be prepared by compression molding, injection molding, etc., and the preferred temperature is 160-200℃.

[0025] The carbon fiber reinforcement layer can be prepared by impregnation molding, compression molding, or vacuum injection molding, with the preferred temperature being 220–260°C.

[0026] Compression molding is a molding process in which powdered, granular, or fibrous raw materials are first placed into a mold cavity at a molding temperature, and then the mold is closed and pressure is applied to shape and solidify them.

[0027] Injection molding refers to a molding process in which raw materials are melted and injected into a mold, and the product is obtained after cooling and demolding.

[0028] The impregnation molding refers to a molding process in which carbon fiber fabric is immersed in molten resin, and a certain pressure is applied to completely immerse the carbon fiber in the molten resin. After cooling and demolding, the product is obtained.

[0029] Vacuum infusion molding refers to a molding process in which carbon fibers are placed in a sealed environment and a vacuum is drawn, then molten resin is poured in to completely encapsulate the carbon fibers, and the product is obtained after cooling and demolding.

[0030] Hot pressing is a molding process that involves heating materials and applying pressure with a hydraulic press to bind them together in a slightly molten state, and then cooling them to obtain the final product.

[0031] In step S2 of the preparation method of the biomass buffer energy-absorbing board of the present invention, the hot pressing temperature is 160-200℃, the pressure is 3-10MPa, and the time is 3-15min.

[0032] The preparation method of the biomass buffer energy-absorbing board of the present invention has the following more specific steps:

[0033] Step 1: Add biomass polyurethane and carbon fiber powder to an extruder, and granulate the mixture by screw extrusion at 140-160℃ and 30-60 r / min to obtain polyurethane / carbon fiber powder mixed granules.

[0034] Step 2: Add the polyurethane / carbon fiber powder mixture to the injection molding machine, melt it at 140-160℃ and 30-60r / min, and inject it into the closed mold through the screw. After cooling, the energy-absorbing layer is obtained.

[0035] Step 3: Add bio-based polyurethane thermoplastic elastomer to the extruder, and inject it into the mold through screw extrusion at 160-200℃ and 30-60r / min. After cooling, the adhesive layer is obtained.

[0036] Step 4: Place the furan-based polyester into a mold and melt it at 220-260°C. Then, immerse the carbon fiber cloth in the furan-based polyester for 5 hours, cool it down, demold it, and take out the carbon fiber reinforced layer.

[0037] Step 5: Stack and hot-press the layers according to the structure of carbon fiber reinforcement layer / bonding layer / energy-absorbing layer / bonding layer / carbon fiber reinforcement layer. The hot-pressing temperature is 160-200℃, the pressure is 3-10MPa, and the time is 3-15min.

[0038] The energy-absorbing buffer sheet of the present invention can be applied to vehicles, ships, and sports equipment. More specifically, it can be applied to the fabrication of transportation vehicle structures including car bumpers, car bodies, car pedals, ship hulls, ship cabins, anchoring devices, and aircraft landing gear.

[0039] It should be understood that terms such as “having,” “containing,” and “including” as used herein do not exclude the presence or addition of one or more other substances, ingredients, properties, states, elements, or combinations thereof.

[0040] The beneficial effects of this invention are:

[0041] The biomass-based energy-absorbing cushioning panel of this invention is composed of an energy-absorbing layer, an adhesive layer, and a carbon fiber reinforcement layer. The energy-absorbing layer can absorb energy through elastic deformation to mitigate impact forces. The biomass polyurethane in the energy-absorbing layer not only endows it with good tensile strength, tear strength, impact resistance, abrasion resistance, weather resistance, hydrolysis resistance, and oil resistance, but also effectively mitigates impact forces and transfers the impact force received by one carbon fiber reinforcement layer to the other. The carbon fiber reinforcement layer can withstand impact forces without deformation and can transfer the impact force to the energy-absorbing layer, effectively improving the impact resistance of the cushioning panel and reducing damage and breakage caused by impacts. The furanyl polyester in the carbon fiber reinforcement layer can improve the adhesion between the carbon fibers and the polyurethane and protect the carbon fibers. The adhesive layer not only effectively bonds the carbon fiber reinforcement layer and the energy-absorbing layer, but also effectively transfers the impact force received by the carbon fiber reinforcement layer to the energy-absorbing layer. This biomass-based energy-absorbing cushioning panel uses biomass as a raw material, thus having the advantage of being environmentally friendly. Detailed Implementation

[0042] The technical solutions of the present invention will be clearly and completely described below with reference to specific embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0043] The raw materials used in the examples and comparative examples are as follows:

[0044] Biomass polyurethane

[0045] raw material:

[0046] Polytrimethylene ether glycol, ECOPROL H1000, manufactured by SK CHEMICAL, South Korea.

[0047] Polyethylene glycol, PEG-6000, produced by China National Pharmaceutical Group.

[0048] Polylactic acid polyol, produced by Fengyuan Biotechnology.

[0049] Isocyanate, Aquolin 161, produced by Wanhua Chemical Group Co., Ltd.

[0050] Manufacturing Example 1: Polytrimethylene ether glycol was heated to 30°C and mixed with isocyanate at a weight ratio of 100:2 and stirred at 100 r / min for 10 min to obtain A1.

[0051] Manufacturing Example 2: Polyethylene glycol was heated to 60°C and mixed with isocyanate at a weight ratio of 100:2 and stirred at 100 r / min for 10 min to obtain A2.

[0052] Manufacturing Example 3: Polylactic acid polyol was heated to 200°C and mixed with isocyanate at a weight ratio of 100:2 and stirred at 100 r / min for 10 min to obtain A3.

[0053] Carbon fiber

[0054] B1: MLD-30, fiber length 30μm, manufactured by Toray Industries, Inc.

[0055] B2: Carbon fiber fabric, TB01, produced by Lofis (Shanghai) Industrial Co., Ltd.

[0056] Furan-based polyester

[0057] C1: Polyethylene furanate, produced by Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences.

[0058] C2: Polypropylene furanate, produced by Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences.

[0059] C3: Polybutylene furanate, produced by Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences.

[0060] The preparation methods of Examples 1-13 are as follows:

[0061] Step 1: Add biomass polyurethane and carbon fiber powder to an extruder, and granulate the mixture by screw extrusion at 160℃ and 30r / min to obtain polyurethane / carbon fiber powder mixed granules.

[0062] Step 2: Add the polyurethane / carbon fiber powder mixture to the injection molding machine, melt it at 160℃ and 30r / min, and inject it into a closed mold through a screw. After cooling, the energy-absorbing layer is obtained.

[0063] Step 3: Add the bio-based polyurethane elastomer to the extruder, and inject it into the mold through the screw extrusion at 160℃ and 30r / min. After cooling, the adhesive layer is obtained.

[0064] Step 4: Place the furan-based polyester into a mold and melt it at 260°C. Then, immerse the carbon fiber cloth in the furan-based polyester for 5 hours, cool it down, demold it, and take out the carbon fiber reinforced layer.

[0065] Step 5: Stack and hot-press the layers according to the structure of carbon fiber reinforcement layer / bonding layer / energy-absorbing layer / bonding layer / carbon fiber reinforcement layer. The hot-pressing temperature is 160℃, the pressure is 5MPa, and the time is 10min.

[0066] The preparation method of Comparative Example 1 is as follows:

[0067] Step 1: Add biomass polyurethane and carbon fiber powder to an extruder, and granulate the mixture by screw extrusion at 160℃ and 30r / min to obtain polyurethane / carbon fiber powder mixed granules.

[0068] Step 2: Add the polyurethane / carbon fiber powder mixture to the injection molding machine, melt it at 160℃ and 30r / min, and inject it into a closed mold through a screw. After cooling, the energy-absorbing layer is obtained.

[0069] Step 3: Place the furan-based polyester into a mold and melt it at 260°C. Then, immerse the carbon fiber cloth in the furan-based polyester for 5 hours, cool it down, demold it, and take out the carbon fiber reinforced layer.

[0070] Step 4: Stack and hot-press the layers according to the structure of carbon fiber reinforcement layer / energy absorption layer / carbon fiber reinforcement layer. The hot-pressing temperature is 160℃, the pressure is 5MPa, and the time is 10min.

[0071] The preparation method of Comparative Example 2 is as follows:

[0072] Step 1: Add biomass polyurethane and carbon fiber powder to an extruder, and granulate the mixture by screw extrusion at 160℃ and 30r / min to obtain polyurethane / carbon fiber powder mixed granules.

[0073] Step 2: Add the polyurethane / carbon fiber powder mixture to the injection molding machine, melt it at 160℃ and 30r / min, and inject it into a closed mold through a screw. After cooling, the energy-absorbing layer is obtained.

[0074] Step 3: Add the bio-based polyurethane elastomer to the extruder, and inject it into the mold through the screw extrusion at 160℃ and 30r / min. After cooling, the adhesive layer is obtained.

[0075] Step 4: Place the biomass polyurethane into a mold and melt it at 160°C. Then, immerse the carbon fiber cloth in the biomass polyurethane for 5 hours, cool it down, demold it, and remove it to obtain the carbon fiber reinforced layer.

[0076] Step 5: Stack and hot-press the layers according to the structure of carbon fiber reinforcement layer / bonding layer / energy-absorbing layer / bonding layer / carbon fiber reinforcement layer. The hot-pressing temperature is 160℃, the pressure is 5MPa, and the time is 10min.

[0077] The performance testing methods are as follows:

[0078] 1. Destructive Impact Strength: Cut the sample into 10×10cm specimens and place them on a horizontal steel plate. Cover the specimen with a 12×12cm steel plate. Suspend a 10000g weight with a bottom diameter of 10cm directly above the specimen at a height of 1m, and then lower the weight. Observe whether the specimen is damaged. If it is not damaged, raise the weight by 0.1m and continue the experiment. If it is damaged, repeat the experiment. After two consecutive failures at the same height, record the height H at which the specimen was not damaged in the previous test. Damage refers to the appearance of cracks or breakage in any one or more layers of the specimen.

[0079] 2. Interlaminar shear performance testing standard: The interlaminar shear failure stress shall be tested according to the test method of GB / T28889-2012.

[0080] The material selection, thickness design, and test performance results of each layer in the examples and comparative examples are shown in Table 1.

[0081] Table 1

[0082]

[0083]

[0084] As shown in Table 1, compared with Comparative Example 1, the presence of the adhesive layer in Examples 1 and 2 significantly improved the bonding effect of the energy-absorbing buffer sheet and increased the interlaminar shear failure stress. Compared with Comparative Example 2, furan-based polyester as the material for coating carbon fibers in Examples 1 and 2 significantly improved the impact resistance of the energy-absorbing buffer sheet.

[0085] The above description is merely an embodiment of the present invention and does not limit the patent scope of the present invention. Any modifications or equivalent transformations made based on the content of the present invention specification, or direct or indirect applications in other related technical fields, are similarly included within the patent protection scope of the present invention.

Claims

1. A biomass cushioning energy-absorbing panel, characterized by, It comprises an energy-absorbing layer, carbon fiber reinforcement layers located on both sides of the energy-absorbing layer, and an adhesive layer between the energy-absorbing layer and the carbon fiber reinforcement layers; the energy-absorbing layer contains biomass polyurethane, and the carbon fiber reinforcement layers contain carbon fibers and furan-based polyester; The energy-absorbing layer also contains carbon fiber powder; The furan-based polyester is selected from at least one of polyethylene furanate, propylene furanate, butylene furanate, hexane furanate, octyl furanate, sebaccharide furanate, and copolymers thereof. The adhesive layer contains a bio-based polyurethane thermoplastic elastomer.

2. The biomass cushioning energy-absorbing panel of claim 1, wherein, The biomass polyurethane contains bio-based polyol segments.

3. The biomass cushioning energy-absorbing panel of claim 2, wherein, The bio-based polyol is at least one of bio-based polytrimethylene ether glycol, bio-based polyethylene glycol, and bio-based polylactic acid polyol.

4. The biomass cushioning energy absorbing panel of claim 1, wherein, The thickness of the energy-absorbing layer is 4~20mm, the thickness of the adhesive layer is 0.5~2mm, and the thickness of the carbon fiber reinforcement layer is 1~4mm.

5. A method for producing the biomass cushioning energy-absorbing panel according to any one of claims 1 to 4, characterized by, Includes the following steps: S1, respectively prepare the energy-absorbing layer, the bonding layer, and the carbon fiber reinforcement layer; S2, the energy-absorbing layer, adhesive layer and carbon fiber reinforcement layer are stacked in the order of carbon fiber reinforcement layer / adhesive layer / energy-absorbing layer / adhesive layer / carbon fiber reinforcement layer and then hot-pressed into shape.

6. The method for preparing the biomass buffer energy-absorbing plate according to claim 5, characterized in that, The hot pressing temperature is 160~200℃ and the pressure is 3~10MPa.

7. The application of the biomass cushioning and energy-absorbing panels according to any one of claims 1 to 4 in vehicles, ships, and sports equipment.

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