A composite material of polyborosiloxane and a fiber fabric, and a method for preparing and use thereof

Abstract

The application provides a composite material composed of polyborosiloxane and fiber fabric and a preparation method and application thereof, and belongs to the field of composite materials. The composite material is a composite material formed by alternately stacking polyborosiloxane plates and fiber fabrics. The composite material has excellent impact resistance and can be used as a novel protective impact-resistant composite material for electronic device protection, sports protection and building protection.

Description

Technical Field

[0001] The present invention belongs to the field of composite materials, and in particular relates to a composite material composed of polyborosiloxane and fiber fabric, and a preparation method and application thereof. Background Art

[0002] Currently, many fields require the use of excellent impact-resistant materials to protect materials and products. For example, (1) electronic devices need protection during transportation; (2) frequent impacts during sports and military activities also require protection; (3) when mining some natural resources, mining cars are generally used to load and unload raw materials. However, due to frequent collisions, the material hoppers of mining cars have no protective layer and are damaged, causing certain economic losses. In response to this situation, there is an urgent need to develop a composite impact-resistant material with functions such as strain rate response, impact hardening, and energy dissipation through material network design.

[0003] Basalt fiber (BF) is a continuous fiber made by rapidly drawing basalt stone through a bushing after melting it at high temperature. Due to its excellent properties, including high strength, electrical insulation, and corrosion resistance, it is widely used in rail transportation, engineering, and construction. Compared with carbon fiber, basalt fiber is less expensive and has a higher failure strain. Unlike glass fiber, basalt fiber contains a more complex composition, such as silica, alumina, and calcium oxide. These components provide a complex cross-linked structure, resulting in excellent chemical resistance in corrosive environments. Compared with synthetic polymer fibers such as high-molecular-weight polyethylene fiber and aramid fiber, basalt fiber is the only environmentally friendly structural material produced using a single natural mineral raw material without any additives. With the continuous advancement of my country's dual carbon goals, the increasing demand for green environmental protection, and the continuous development of basalt fiber production technology, basalt fiber is bound to receive increasing attention in my country's high-tech materials sector. The development and research of high-performance, impact-resistant basalt fiber suitable for dynamic working conditions has been a key development trend in recent years. However, basalt fiber exhibits brittle mechanical properties when subjected to rapid strain, which significantly affects the reliability and safety of basalt fiber materials in actual use. To improve the comprehensive mechanical properties and impact resistance of basalt fiber materials, a current effective approach is to combine it with other polymer materials to prepare high-performance composite materials.

[0004] In recent years, polyborosiloxane (PDBS) has become a leading example of impact-resistant and shock-absorbing materials due to its unique viscoelastic properties. While PDBS exhibits a viscous, fluid state when static and flexible, it exhibits rigid mechanical behavior when subjected to external impact forces, significantly limiting its practical applications. However, its lack of a permanent crosslinked network results in poor mechanical properties, significantly limiting the practical application of PDBS. Therefore, by combining PDBS with other polymers and rationally manipulating their structure at the microscale, it is hoped that the composite's impact resistance and shock-absorbing properties can be optimized simultaneously.

[0005] Therefore, it is of great significance to develop a new protective impact-resistant composite material suitable for use in electronic device protection, sports protection, and building protection. Summary of the Invention

[0006] The purpose of the present invention is to provide a composite material composed of polyborosiloxane and fiber fabric, and a preparation method and application thereof.

[0007] The invention provides a composite material, which is formed by alternately laminating polyborosiloxane plates and fiber fabrics.

[0008] Furthermore, the aforementioned composite material is a composite material of three or more layers formed by alternately stacking polyborosiloxane sheets and fiber fabrics.

[0009] Furthermore, the composite material has a thickness of 0.5 to 100 mm.

[0010] Furthermore, the thickness ratio of each layer of polyborosiloxane sheet to each layer of fiber fabric is 1:10 to 10:1.

[0011] Preferably, the thickness ratio of each layer of polyborosiloxane to each layer of fiber fabric is 1:8 to 3:1.

[0012] Furthermore, the aforementioned composite material is a three-layer composite material formed by alternating layers of polyborosiloxane sheets and fiber fabrics; the upper and lower layers of the three-layer composite material are polyborosiloxane sheets, and the middle layer is fiber fabric, or the upper and lower layers are fiber fabrics, and the middle layer is polyborosiloxane sheets.

[0013] Furthermore, the fiber fabric is one or more of basalt fiber, glass fiber, carbon fiber, polyamide fiber or polyester fiber fabric;

[0014] Preferably, the fiber fabric is basalt fiber.

[0015] Furthermore, the fiber fabric is a treated fiber fabric; and the method for treating the fiber fabric comprises the following steps:

[0016] 1) dispersing the polyborosiloxane material in an alcohol solution to obtain a PDBS suspension;

[0017] 2) soaking the fiber fabric in the PDBS suspension, drying it after soaking, to obtain a treated fiber fabric;

[0018] The fiber fabric in step 2) is coated or not coated with a silane coupling agent; preferably, the coating of the silane coupling agent is to coat the silane coupling agent on the surface of the fiber fabric and then naturally dry it for 2-5 hours;

[0019] Alternatively, the fiber fabric treatment method comprises the following steps: directly pressing PDBS onto the fiber fabric using a press to obtain a treated fiber fabric;

[0020] Preferably,

[0021] In step 1), the alcohol solution is anhydrous ethanol;

[0022] And / or, in step 1), the concentration of the PDBS suspension is 100 mg / ml-400 mg / ml;

[0023] And / or, in step 2), the soaking time is 0.1 to 10 hours;

[0024] And / or, the silane coupling agent is KH540, KH550, KH560, KH570 or KH792 silane coupling agent;

[0025] And / or, the fiber fabric is coated with a silane coupling agent, dried, and then immersed in a PDBS suspension.

[0026] Furthermore, the polyborosiloxane sheet is a sheet obtained by cold-pressing and vulcanizing polyborosiloxane.

[0027] The present invention also provides a method for preparing the aforementioned composite material, which comprises the following steps:

[0028] The polyborosiloxane sheets and fiber fabrics are alternately stacked and then placed in a mold for vulcanization to obtain the product;

[0029] Preferably, the vulcanization pressure is 1 to 20 MPa, and / or the vulcanization time is 1 to 30 minutes.

[0030] The present invention also provides the use of the aforementioned composite material in preparing impact-resistant and / or shock-absorbing protective materials;

[0031] Preferably, the protective material is a protective material used for electronic device protection, sports protection, and building protection.

[0032] Compared with the prior art, the present invention has the following beneficial effects:

[0033] The present invention provides a composite material composed of polyborosiloxane and a fiber fabric, as well as its preparation method and use. The fiber fabric is preferably a basalt fiber fabric. The composite material has excellent impact resistance and can be used as a new protective impact-resistant composite material for electronic device protection, sports protection, and building protection.

[0034] Obviously, based on the above contents of the present invention, according to common technical knowledge and customary means in this field, without departing from the above basic technical ideas of the present invention, other various forms of modifications, replacements or changes can be made.

[0035] The following further describes the above content of the present invention in detail through specific embodiments in the form of examples. However, this should not be construed as limiting the scope of the above subject matter of the present invention to the following examples. All technologies implemented based on the above content of the present invention fall within the scope of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 is the PDBS content in BPB-0.5, BPB-1, BPB-2, PBK-0.5, PBK-1, and PBK-2.

[0037] Figure 2 The peak impact force of various materials at a thickness of 0.5 mm. Reference refers to the peak force of the sensor after a blank ball falls freely.

[0038] Figure 3 The peak impact force of various materials at 1mm thickness. Reference refers to the peak force of the sensor after a blank ball falls freely.

[0039] Figure 4 The peak impact force of various materials at a thickness of 2 mm. Reference refers to the peak force of the sensor after a blank ball falls freely.

[0040] Figure 5 It is the buffer time of BF-1 and PBK-1 materials at heights of 50, 60, 70 and 80 cm.

[0041] Figure 6 It is the peak force of PBK-1 after multiple impacts at a height of 70 cm.

[0042] Figure 7 Demonstration of hammer tapping experiment on a 10ml test tube coated with PBK-1 material and an uncoated blank test tube. DETAILED DESCRIPTION

[0043] The raw materials and equipment used in the specific embodiments of the present invention are all known products and are obtained by purchasing commercial products.

[0044] The basalt fiber (BF) fabric in the present invention is a commercially available basalt fiber (BF) cloth (manufacturer: Ningguo Zhongdian New Materials Co., Ltd., batch number: 10065746144238).

[0045] The polyborosiloxane (PDBS) in the present invention is a commercially available product purchased from Chengdu Magic Technology Co., Ltd. with the brand name ANTIPAC-I.

[0046] Example 1: Preparation of the impact-resistant composite material PBK of the present invention

[0047] 10.5 g of polyborosiloxane was placed in a flat-plate vulcanizer and cold-pressed for 3 minutes to obtain a 1 mm thick PDBS sheet. The above experiment was repeated to obtain two 1 mm thick PDBS sheets.

[0048] 9g of 0.4mm thick BF cloth was coated with 2g of KH540 silane coupling agent (C6H 17 The modified BF fabric was then coated on both sides with NO₃Si and dried naturally for 1 hour to obtain the modified BF fabric. The PDBS material was then dispersed in anhydrous ethanol by stirring to obtain a 400 mg / ml PDBS suspension to facilitate penetration. The modified BF fabric was then immersed in the PDBS suspension for 5 hours and then ultrasonically treated for 30 minutes to ensure thorough infiltration. Finally, the ethanol was removed by drying in a vacuum oven at 60°C, resulting in a BF / KH540 composite material with a pre-treatment thickness of 0.4 mm, designated BK. The BK fabric was then stacked with a PDBS sheet, with the PDBS sheets as the top and bottom layers and the BK as the middle layer. The composite was placed in a 1 mm thick mold and vulcanized at room temperature in a flat-bed vulcanizer (10 MPa) for 3 minutes to obtain a composite material with an overall thickness of 1 mm, designated PBK-1. Similarly, different mold thicknesses (0.5 mm and 2 mm) were used to prepare composite materials designated PBK-0.5 and PBK-2. The thickness of each PDBS layer in PBK-0.5 is 0.05mm, and the thickness of BK is 0.4mm; the thickness of each PDBS layer in PBK-1 is 0.3mm, and the thickness of BK is 0.4mm; the thickness of each PDBS layer in PBK-2 is 0.8mm, and the thickness of BK is 0.4mm.

[0049] In addition, 9g of pristine BF cloth (0.4mm thick) was immersed in the PDBS suspension for 5h, then sonicated for 30min to ensure full infiltration. Finally, the cloth was dried in a vacuum oven at 60°C to remove the ethanol, yielding a BF composite. This composite was then laminated with PDBS sheets according to the above method (with the PDBS sheets as the top and bottom layers and the BF cloth as the middle layer). The resulting materials were named PBW-0.5, PBW-1, and PBW-2, depending on their thickness. For example, the 0.5mm thick composite was named PBW-0.5. In PBW-1, each PDBS layer had a thickness of 0.3mm, and the BF layer had a thickness of 0.4mm; in PBW-0.5, each PDBS layer had a thickness of 0.05mm, and the BF layer had a thickness of 0.4mm; and in PBW-2, each PDBS layer had a thickness of 0.8mm, and the BF layer had a thickness of 0.4mm.

[0050] The PDBS sheet is used as the middle layer, and BK is used as the upper and lower layers. Composite materials of different thicknesses are prepared by pressing according to the above method and are named BPB-0.5, BPB-1, and BPB-2. For example, a composite material with a thickness of 0.5 mm is named BPB-0.5. The thickness of PDBS in BPB-1 is 0.2 mm, and the thickness of each BK layer is 0.4 mm; the thickness of PDBS in BPB-0.5 is 0.1 mm, and the thickness of each BK layer is 0.2 mm (BK is first pressed into a thickness of 0.2 mm using a press, and then the composite material is prepared); the thickness of PDBS in BPB-2 is 1.2 mm (PDBS material is deformable, and the thickness of the material can be changed after vulcanization), and the thickness of each BK layer is 0.4 mm.

[0051] PDBS (9 g) and pristine BF fabric (1 g) were mechanically blended on a two-roll mill to produce randomly distributed PDBS / BF composites. The composites were then placed into molds of varying thicknesses and cold-cured on a flat-plate vulcanizer for 3 minutes. These composites were named PBR-0.5, PBR-1, and PBR-2, depending on their thickness. For example, a 0.5 mm thick composite was named PBR-0.5.

[0052] In addition, pure BF cloth and pure PDBS are named BF-0.5, BF-1, BF-2, PDBS-0.5, PDBS-1, and PDBS-2 according to their thickness.

[0053] PDBS detection method: Soak 1g of BPB-0.5, BPB-1, BPB-2, PBK-0.5, PBK-1, or PBK-2 in anhydrous ethanol and sonicate for 2 hours to remove the PDBS. Dry the remaining BF material in a 60°C vacuum oven for 1 hour. Remove the BF material from the oven, cool it to room temperature, and weigh it to determine the PDBS content.

[0054] Figure 1 is the PDBS content in BPB-0.5, BPB-1, BPB-2, PBK-0.5, PBK-1, and PBK-2 composite materials. Figure 1 The PDBS content in BPB-0.5, BPB-1, and BPB-2 is 23.5%, 28.9%, and 53.5%, respectively. The PDBS content in PBK-0.5, PBK-1, and PBK-2 is 65.1%, 70%, and 86.3%, respectively. This indicates that the PDBS content increases with increasing thickness.

[0055] The beneficial effects of the present invention are demonstrated below through specific test examples.

[0056] Test Example 1: Study on the impact resistance of the composite material of the present invention

[0057] 1. Experimental Methods

[0058] The various materials prepared in Example 1 were formed into 25mm diameter discs with thicknesses of 0.5mm, 1mm, and 2mm. These discs were placed at the center of a force sensor and a 5g iron ball was dropped from a specified height (H) to investigate the impact resistance of the composite materials with different structures. The change in peak force on the sensor as the ball dropped was recorded to evaluate the impact resistance of the materials. The drop ball impact tests were conducted at different heights of 50, 60, 70, and 80cm. A reference sample, designated as a blank group without any material, was also used.

[0059] 2. Experimental Results

[0060] Figures 2-4 They are the peak impact forces of various materials at 0.5mm, 1mm, and 2mm thicknesses, and Reference represents the peak force of the sensor after a blank ball falls freely. Figure 2-4 The results show that as the height increases from 50cm to 80cm, the peak force of the reference group increases significantly from 439.6N to 1600.9N. As the height increases from 50cm to 80cm, PDBS exhibits effective cushioning properties. Taking PDBS-1 as an example, the peak force decays to 54.2N and 226.6N. For PBK-1, the peak force decays to 23.6 and 63.5N, and the decayed peak force is significantly higher than that of other samples, showing excellent impact resistance. In addition, taking a height of 60cm as an example, compared with PDBS-1, the impact resistance of PBK-1 is improved by 466%, and compared with the reference group, the impact force is attenuated by 97.4%. Compared with PDBS-0.5 and PDBS-2, PBK-0.5 and PBK-2 increased by 236% and 148% respectively. This also shows that the densified structure of PBK-1 and its excellent structural synergy enable the composite material to achieve optimal impact resistance.

[0061] Figure 5 This is the cushioning time of the PBK-1 and BF-1 at a drop height of 50-80cm. Cushioning time is a crucial criterion for evaluating protective performance. For example, at a drop height of 70cm, the BF-1 material's cushioning time is 0.11ms, posing a serious risk of impact damage. Due to its superior structural design, the PBK-1's cushioning time is increased to 0.65ms, a 491% improvement over the BF-1, significantly enhancing its protective performance. Figure 6 It represents the peak force of PBK-1 after multiple impacts at a height of 70cm. Figure 6 It can be seen that the peak force after three cycles of impact is constant at around 48N, indicating that the impact resistance of PBK-1 remains stable during multiple impacts.

[0062] Test Example 2: Study on the protective properties of the composite material of the present invention

[0063] 1. Experimental Methods

[0064] A 10ml test tube (20cm x 15cm) was coated with the PBK-1 composite material prepared in Example 1 to form a protective layer. The tube was then struck with a hammer, ensuring each strike was below 10cm. A reference test was performed using an uncoated 10ml test tube.

[0065] 2. Experimental Results

[0066] Figure 7 Photos showing the test tubes wrapped with PBK-1 and blank test tubes before, during, and after tapping. Figure 7 The results show that the test tube coated with PBK-1 material can still withstand hammer blows well after experiencing multiple impacts, demonstrating the excellent protective performance of PBK-1 material. It can be used as a new type of high-efficiency impact-resistant flexible polymer material to protect flexible or brittle objects under impact.

[0067] In summary, the present invention provides a composite material composed of polyborosiloxane and fiber fabric, as well as its preparation method and use. The composite material of the present invention has excellent impact resistance and can be used as a new protective impact-resistant composite material for electronic device protection, sports protection, and building protection.

Claims

1. A composite material, characterized in that: It is a composite material of three or more layers formed by alternately stacking polyborosiloxane sheets and fiber fabrics; the upper and lower layers of the composite material are polyborosiloxane sheets; The polyborosiloxane sheet is a sheet obtained by cold-pressing and vulcanizing polyborosiloxane; The fiber fabric is a treated fiber fabric; the method for treating the fiber fabric comprises the following steps: 1) Dispersing polyborosiloxane material in an alcohol solution to obtain a PDBS suspension; 2) Soaking the fiber fabric in the PDBS suspension, drying it after soaking, to obtain the treated fiber fabric; The fiber fabric in step 2) is obtained by coating the silane coupling agent on the surface of the fiber fabric and then naturally drying it for 2-5 hours.

2. The composite material according to claim 1, characterized in that: The thickness of the composite material is 0.5-100 mm.

3. The composite material according to claim 2, characterized in that: The thickness ratio of each layer of polyborosiloxane sheet to each layer of fiber fabric is 1:10~10:

1.

4. The composite material according to claim 3, characterized in that: The invention relates to a three-layer composite material formed by alternately stacking polyborosiloxane sheets and fiber fabrics. Among the three layers of the composite material, the upper and lower layers are polyborosiloxane sheets, and the middle layer is fiber fabric.

5. The composite material according to any one of claims 1 to 4, characterized in that: The fiber fabric is one or more of basalt fiber, glass fiber, carbon fiber, polyamide fiber or polyester fiber fabric.

6. The composite material according to claim 5, characterized in that: The fiber fabric is basalt fiber.

7. The composite material according to claim 5, characterized in that: In step 1), the alcohol solution is anhydrous ethanol; And / or, in step 1), the concentration of the PDBS suspension is 100 mg / ml-400 mg / ml; And / or, in step 2), the soaking time is 0.1 to 10 hours; And / or, the silane coupling agent is KH540, KH550, KH560, KH570 or KH792 silane coupling agent.

8. The method for preparing the composite material according to any one of claims 1 to 7, characterized in that: The method comprises the following steps: alternately stacking polyborosiloxane sheets and fiber fabrics, and then placing them in a mold for vulcanization to obtain the product.

9. The preparation method according to claim 8, characterized in that: The vulcanization pressure is 1-20 MPa, and / or the vulcanization time is 1-30 min.

10. Use of the composite material according to any one of claims 1 to 7 in the preparation of impact-resistant and / or shock-absorbing protective materials.

11. The use according to claim 10, characterized in that: The protective material is a protective material used for electronic device protection, sports protection, and building protection.

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