High-performance fiber composite material for sports protectors and preparation method of high-performance fiber composite material

Abstract

The invention belongs to the technical field of functional fiber materials, and particularly relates to a high-performance fiber composite material for sports protectors and a preparation method thereof.The high-performance fiber composite material is prepared from, by weight, 40 parts of fiber skeleton base material, 30-45 parts of TPU, 3-8 parts of cross-linking agent, 5-15 parts of nano filler and 2 parts of calcium chloride; the plant microfiber reinforced fiber skeleton network provides a composite material interface anchoring effect, the compatibility contradiction between a rigid filler and an elastic matrix is solved, the nanofiller cooperates with an ion network to improve the energy dissipation efficiency and the wear resistance, and the gel network coating has certain hemostatic performance and structural integrity, so that the composite material has a good application prospect. And a light-weight and functional solution is provided for sports protectors.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of functional fiber materials, and particularly relates to a high-performance fiber composite material for sports protective gear and a preparation method thereof. BACKGROUND

[0002] Currently, mainstream protective gear materials are usually composed of synthetic polymers and reinforcing fibers. Although such materials can provide basic physical protection, they have the problem of single function in practical application, mainly focusing on the optimization of mechanical properties, and lack the ability to actively respond to sports injuries. In particular, in high-intensity and competitive projects, athletes often suffer skin surface damage and bleeding due to collision and friction. However, the existing materials cannot accelerate hemostasis, support wound healing, or even exacerbate the injury due to rough surface or poor air permeability. In addition, conventional composite materials are difficult to balance high density, high strength and flexible cushioning performance. For example, when rigid fibers are introduced to improve puncture resistance, the cushioning and energy absorption efficiency is often sacrificed. On the other hand, the foaming structure that optimizes the cushioning performance easily loses support rigidity due to insufficient density. This imbalance in performance limits the protective effect of the protective gear in complex stress scenarios.

[0003] Therefore, there is an urgent need for a high-performance composite material with a simplified structure that maintains high mechanical strength and wear resistance while imparting the material with rapid hemostasis and biological activity to promote tissue repair, thereby truly upgrading the functionality of sports protective gear. SUMMARY

[0004] In view of the above, the present application provides a high-performance fiber composite material for sports protective gear and a preparation method thereof. Natural proteins and high-molecular-weight biological fibers are used as the skeleton substrate to activate hemostatic factors through their micro-nano structure and surface properties. The interface unification of rigid protection and flexible healing is achieved through gelation design. Finally, through a hot pressing integration process, a functional fiber composite material is constructed in a one-step formed dense structure.

[0005] To achieve the above-mentioned purposes, the technical solutions adopted by the present application are as follows: The present application provides a high-performance fiber composite material for sports protective gear, which comprises the following raw materials by weight: fiber skeleton substrate 40 parts, TPU (thermoplastic polyurethane elastomer) 30-45 parts, crosslinking agent 3-8 parts, nano filler 5-15 parts, and calcium chloride 2 parts.

[0006] Further, the crosslinking agent is selected from any one of sodium alginate, gelatin and carrageenan.

[0007] Further, the nanofiller is selected from any one of shell powder, zeolite powder, montmorillonite powder and diopside powder.

[0008] Further, the fiber skeleton substrate comprises the following raw materials by weight: collagen 45-50 parts, chitosan 20-25 parts, flax fiber 15 parts, bamboo fiber 15 parts and genipin 0.3 parts, and specifically comprises the following steps: S1: after mixing flax fiber 15 parts and bamboo fiber 15 parts, boiling in 0.1 M NaOH solution for 30 min, removing non-fiber components, exposing the hydroxyl groups on the surface of flax fiber and bamboo fiber, and then washing with purified water until the pH is neutral, obtaining pretreated fibers, placing the pretreated fibers and 10 times weight of purified water in a high-pressure homogenizer to homogenize, forming nanoscale diameter fibers, and obtaining microfibrillated fibers; S2: collagen 45-50 parts and chitosan 20-25 parts are dissolved in 200 parts by weight of 0.1 M acetic acid solution, self-assembled into a three-dimensional network, and electrospun under a voltage of 25 kV, a receiving distance of 15 cm, and a push-in speed of 0.8 mL / h, to form an adhesion framework based on nanofibers, and collect a wet fiber mat with a thickness of 200±20 μm, to obtain electrospun fibers; S3: genipin 0.3 parts is dissolved in 10 parts by weight of ethanol and mixed with microfibrillated fibers, ultrasonic dispersion is performed, to obtain a crosslinking liquid, the electrospun fibers are immersed in the crosslinking liquid for 30 min, and then ultrasonic dispersion is performed at 40 kHz for 30 min, to form covalent crosslinking sites between the amino groups in the collagen molecules and the hydroxyl groups on the surface of the flax fiber and bamboo fiber in the microfibrillated fibers, improve the chimeric effect of the microfibrillated fibers and enhance the interpenetration ability of the rigid and flexible interfaces, vacuum suction is performed to remove the liquid, to obtain a film material, the film material is washed with purified water and hot air dried at 60℃ until the water content is less than 8%, to obtain a composite fiber mat; S4: the composite fiber mat is cut by a cutting machine, combed by a combing machine, and reinforced by a double-roller hot pressing, to obtain a fiber skeleton substrate.

[0009] The application also provides a preparation method of a high-performance fiber composite material for sports protective gear, specifically comprising the following steps: Step 1: TPU 30-45 parts is dissolved in DMF (N,N-dimethylformamide) at 70℃, then nanofiller 5-15 parts is added, and ultrasonic dispersion is performed at 400 W for 15 min, to form a pre-dispersion system in which TPU molecules wrap the nanofiller to inhibit agglomeration, and to obtain an organic phase; Step 2: The fiber skeleton substrate is weighed and immersed in the organic phase twice, the first time: 2 min, 10 cm / min, slow penetration to fill the pores in the fiber skeleton substrate with the organic phase, form a primary dense structure, 60 DEG C pre-baking 2 min to fix the structure to prevent sedimentation, the second time: 30 s, 30 cm / min, hanging to no liquid drop, further improve the density and induce the directional distribution of TPU molecules, to obtain the impregnated substrate; Step 3: Weighing calcium chloride 2 parts and crosslinking agent 3-8 parts in 100 parts of ultrapure water, the active groups in the crosslinking agent combine with calcium ions to form ionic bonds to achieve hemostatic function, to obtain crosslinking liquid, the impregnated substrate is placed in the crosslinking liquid and shaken for 10 min, then taken out, washed, and vacuum dried at 40 DEG C for 24 h, to obtain a single layer substrate; Step 4: The single layer substrate is laminated and hot pressed at 120 DEG C, 10 MPa for 8 min, cooled to 50 DEG C, demolded, and slowly released the interlayer internal pressure to prevent peeling, to obtain a high-performance fiber composite material.

[0010] The beneficial effects obtained by the present application are as follows: The high-performance fiber composite material for sports protective gear provided by the present application is constructed with collagen-chitosan as the matrix and plant microfibers as the reinforcing phase to form a three-dimensional skeleton network, which retains the biocompatibility and durability of natural materials while the rich active groups on the surface create a microenvironment more conducive to cell infiltration. After the fiber skeleton is gradiently impregnated and combined with the TPU matrix, a deep interpenetrating interface entanglement structure is formed, effectively overcoming the compatibility contradiction between rigid fibers and elastic matrix, so that the material can still maintain stable interlayer bonding force under impact load, thereby having both high strength and anti-deformation ability. The combination of crosslinking agent and calcium chloride has a bonding effect: a dynamic ionic network is constructed in the TPU continuous phase, which improves the energy dissipation efficiency of the material through reversible bonding reorganization; the nano-filler cooperates to strengthen the wear resistance and structural integrity of the matrix through close coupling with the organic / inorganic interface; finally, the components are fused through hot pressing forming process, realizing the synergistic optimization of protection performance, functional durability and processing feasibility on the basis of simple process.

[0011] Compared with traditional protective gear materials, the present application provides a more reliable lightweight protection solution for high-intensity sports scenarios under the premise of ensuring biological safety through the design of material components. BRIEF DESCRIPTION OF DRAWINGS

[0012] Figure 1 Scanning electron microscope results of the high-performance fiber composite material prepared in Example 1 at different positions; Figure 2Results of abrasion resistance investigation of high-performance fiber composite material prepared for Examples 1-4 and Comparative Example 1; Figure 3 Results of fibroblast compatibility investigation of high-performance fiber composite material prepared for Examples 1 and Comparative Example 1; Figure 4 Results of tensile strength change with time of high-performance fiber composite material prepared for Examples 1-4 and Comparative Example 1; Figure 5 Results of hemostatic performance investigation of high-performance fiber composite material prepared for Examples 1-4 and Comparative Example 1. DETAILED DESCRIPTION

[0013] The technical solutions in the embodiments of the present application will be clearly and completely described in combination with the drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments of the present application; based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative work fall within the protection scope of the present application.

[0014] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by one of ordinary skill in the art. In addition, any method and material similar or equivalent to those described herein can be used in the present application. The preferred implementation methods and materials described herein are only used for demonstration, but cannot limit the content of the present application.

[0015] In the following examples, unless otherwise specified, the methods are conventional; in the following examples, unless otherwise specified, the materials used are new materials purchased on the market, wherein, in the following examples and comparative examples, the flax fiber length is 10-15 mm, the diameter is 14-18 μm, and the cellulose content is ≥85%; the bamboo fiber length is 8-12 mm, the diameter is 37-45 μm, and the hemicellulose content is ≤12%; the collagen used is type I collagen with a molecular weight of about 300 kDa; the chitosan has a molecular weight of about 500 kDa and a degree of deacetylation of ≥90%; the sodium alginate has a molecular weight of 5-10 kDa; the gelatin has a purity of 95% and a molecular weight of 50-100 kDa; the carrageenan is in the form of K (Kappa) sodium salt; the shell powder, zeolite powder and montmorillonite powder are all in nanoscale, wherein the shell powder and zeolite powder are activated in advance in a 5% mass fraction citric acid solution for 12 h, washed with water until neutral, and then dried; the diopside powder is sieved through a 200 mesh screen.

[0016] Example 1: The present embodiment provides a high-performance fiber composite material for sports protective gear, which comprises the following raw materials by weight: a fiber framework substrate 40 parts, TPU 30 parts, sodium alginate 8 parts, shell powder 15 parts, and calcium chloride 2 parts.

[0017] The fiber skeleton substrate comprises the following raw materials by weight: collagen 45 parts, chitosan 25 parts, flax fiber 15 parts, bamboo fiber 15 parts and genipin 0.3 parts, and specifically comprises the following steps: S1: after mixing flax fiber 15 parts and bamboo fiber 15 parts, the mixture is boiled in 100 parts by weight of 0.1 M NaOH solution for 30 min, then washed with purified water until the pH is neutral, to obtain pretreated fibers, and the pretreated fibers and 300 parts of purified water are placed in a high-pressure homogenizer, and the program is set to 500 bar for 3 cycles, 800 bar for 3 cycles, and 1500 bar for 4 cycles, at a temperature of 38℃, to obtain microfibrillated fibers; S2: collagen 45 parts and chitosan 25 parts are dissolved in 200 parts by weight of 0.1 M acetic acid solution, and electrospinning treatment is carried out at a voltage of 25 kV, a receiving distance of 15 cm, and a push-in speed of 0.8 mL / h, and a wet fiber mat with a thickness of 200±20 μm is collected by an anodized aluminum foil, to obtain electrospun fibers; S3: genipin 0.3 parts is dissolved in 10 parts by weight of ethanol and mixed with microfibrillated fibers, and ultrasonic dispersion is carried out at 300 W, 5 s on / 2 s off, and the temperature is controlled at 10℃, to obtain a crosslinking liquid, the electrospun fibers are immersed in the crosslinking liquid for 30 min, ultrasonicated at 40 kHz for 30 min, and then the liquid is removed by vacuum suction, to obtain a film material, the film material is washed with purified water and dried at 60℃ with hot air until the moisture content is 7.6%, to obtain a composite fiber mat; S4: the composite fiber mat is cut into 3×3 mm pieces by a cutting machine, carded by a carding machine, and reinforced by double-roller hot pressing, with the upper roller at 90℃, the lower roller at 100℃, and the linear pressure at 0.50 MPa, to obtain a fiber skeleton substrate, with a grammage of 180±5 g / m 2 and a thickness of 0.30±0.03 mm.

[0018] The embodiment also provides a preparation method of a high-performance fiber composite material for sports protective gear, specifically comprising the following steps: Step 1: TPU 30 parts is dissolved in 120 parts of DMF at 70℃, then shell powder 15 parts is added, and ultrasonic dispersion is carried out at 400 W for 15 min, with a pulse cycle of 2 s on / 1 s off and a temperature control of 20℃, to obtain an organic phase; Step 2: the fiber skeleton substrate is immersed in the organic phase twice, the first time: for 2 min, at a pulling rate of 10 cm / min, and pre-dried at 60℃ with hot air circulation for 2 min, with an air speed of 1.5 m / s, the second time: for 30 s, at a pulling rate of 30 cm / min, and suspended until no liquid drops, to obtain an impregnated substrate; Step 3: Take calcium chloride 2 parts and sodium alginate 8 parts, and dissolve them in 100 parts by weight of ultrapure water at 50°C to obtain a crosslinking solution with a viscosity of 429 mPa·s. Place the immersed substrate in the crosslinking solution and oscillate at a frequency of 120 Hz for 10 min, then take it out, rinse it, and vacuum dry at 40°C for 24 h to obtain a single-layer substrate; Step 4: Stack the single-layer substrate and hot-press it at 120°C and 10 MPa for 8 min, then cool it to 50°C to demold to obtain a high-performance fiber composite material.

[0019] Example 2: A high-performance fiber composite material for sports protective gear is provided, which includes the following raw materials by weight: fiber skeleton substrate 40 parts, TPU 40 parts, gelatin 5 parts, zeolite powder 8 parts, and calcium chloride 2 parts.

[0020] The fiber skeleton substrate includes the following raw materials by weight: collagen 48 parts, chitosan 22 parts, flax fiber 15 parts, bamboo fiber 15 parts, and genipin 0.3 parts, and specifically includes the following steps: S1: Mix flax fiber 15 parts and bamboo fiber 15 parts, then boil them in 100 parts by weight of 0.1 M NaOH solution for 30 min, and then rinse them with purified water until the pH is neutral to obtain pretreated fibers. Place the pretreated fibers and 300 parts of purified water in a high-pressure homogenizer and homogenize them, with the program set to 500 bar for 3 cycles, 800 bar for 3 cycles, and 1500 bar for 4 cycles at a temperature of 38°C to obtain microfibrillated fibers; S2: Dissolve collagen 48 parts and chitosan 22 parts in 200 parts by weight of 0.1 M acetic acid solution, and perform electrospinning treatment under a voltage of 25 kV, a receiving distance of 15 cm, and a push-in speed of 0.8 mL / h. Collect the electrospun fibers on an anodized aluminum foil to obtain a wet fiber mat with a thickness of 200±20 μm; S3: Dissolve genipin 0.3 parts in 10 parts by weight of ethanol, mix it with the microfibrillated fibers, and perform ultrasonic dispersion at 300 W, with a 5 s on / 2 s off cycle and a temperature control of 10°C to obtain a crosslinking solution. Soak the electrospun fibers in the crosslinking solution for 30 min, then perform ultrasonic treatment at 40 kHz for 30 min. Remove the liquid by vacuum suction to obtain a membrane material. Rinse the membrane material with purified water and dry it with hot air at 60°C until the moisture content is 7.2% to obtain a composite fiber mat; S4: Cut the composite fiber mat into 3×3 mm pieces using a cutting machine, card it using a carding machine, and reinforce it using a double-roller hot press with the upper roller at 90°C, the lower roller at 100°C, and a linear pressure of 0.50 MPa to obtain a fiber skeleton substrate with a grammage of 180±5 g / m 2 and a thickness of 0.30±0.03 mm.

[0021] The embodiment also provides a preparation method of the high-performance fiber composite material for sports protective equipment, specifically comprising the following steps: Step 1: weigh TPU 40 parts, dissolve in 110 parts of DMF at 70℃, then add zeolite powder 8 parts, 400 W ultrasonic dispersion for 15 min, pulse cycle 2 s on / 1 s off, temperature control 20℃, to obtain an organic phase; Step 2: weigh the fiber skeleton substrate and immerse it in the organic phase twice, the first time: 2 min, pulling rate 10 cm / min, 60℃ hot air circulation pre-drying 2 min, air speed 1.5 m / s, the second time: 30 s, pulling rate 30 cm / min, hanging to no liquid dripping, to obtain the impregnated substrate; Step 3: weigh calcium chloride 2 parts and gelatin 5 parts, dissolve in 50℃ 100 parts by weight of ultrapure water, the viscosity is 48 mPa·s, to obtain a crosslinking liquid, place the impregnated substrate in the crosslinking liquid and oscillate at a frequency of 120 Hz for 10 min, then take it out, rinse and vacuum dry at 40℃ for 24 h, to obtain a single-layer substrate; Step 4: stack the single-layer substrate, hot-press at 120℃ and 10 MPa for 8 min, cool to 50℃ and demold, to obtain the high-performance fiber composite material.

[0022] Embodiment 3: The embodiment provides a high-performance fiber composite material for sports protective equipment, which comprises the following raw materials by weight: fiber skeleton substrate 40 parts, TPU 45 parts, carrageenan 3 parts, montmorillonite powder 5 parts and calcium chloride 2 parts.

[0023] The fiber skeleton substrate comprises the following raw materials by weight: collagen 50 parts, chitosan 20 parts, flax fiber 15 parts, bamboo fiber 15 parts and genipin 0.3 parts, and specifically comprises the following steps: S1: weigh the mixture of flax fiber 15 parts and bamboo fiber 15 parts, boil in 100 parts by weight of 0.1 M NaOH solution for 30 min, then rinse with purified water until the pH is neutral, to obtain pretreated fibers, place the pretreated fibers and 300 parts of purified water in a high-pressure homogenizer, and set the program to 500 bar for 3 cycles, 800 bar for 3 cycles and 1500 bar for 4 cycles, at a temperature of 38℃, to obtain microfibrillated fibers; S2: weigh collagen 50 parts and chitosan 20 parts, dissolve in 200 parts by weight of 0.1 M acetic acid solution, and perform electrospinning treatment under a voltage of 25 kV, a receiving distance of 15 cm and a push injection speed of 0.8 mL / h, to collect the electrospun fibers into a wet fiber mat with a thickness of 200±20 μm through an anodized aluminum foil, to obtain electrospun fibers; S3: Genipin 0.3 parts was dissolved in 10 parts by weight of ethanol and mixed with microfibrillated fibers, ultrasonic dispersion with 300 W probe, 5 s on / 2 s off, temperature control 10℃, to obtain a crosslinking liquid, the electrospun fibers were immersed in the crosslinking liquid for 30 min, ultrasonic treatment at 40 kHz for 30 min, then vacuum suction to remove the liquid, to obtain a membrane material, the membrane material was washed with purified water and hot air dried at 60℃ until the water content was 7.7%, to obtain a composite fiber felt; S4: The composite fiber felt was cut into 3×3 mm pieces by a cutting machine, carded by a carding machine, and reinforced by double-roller hot pressing, with the upper roller at 90℃, the lower roller at 100℃, and the linear pressure at 0.50 MPa, to obtain a fiber skeleton base material with a grammage of 180±5 g / m 2 and a thickness of 0.30±0.03 mm.

[0024] The embodiment also provides a preparation method of a high-performance fiber composite material for sports protective gear, specifically including the following steps: Step 1: TPU 45 parts was dissolved in 105 parts of DMF at 70℃, then 5 parts of montmorillonite powder was added, ultrasonic dispersion at 400 W for 15 min, pulse cycle 2 s on / 1 s off, temperature control 20℃, to obtain an organic phase; Step 2: The fiber skeleton base material was immersed in the organic phase twice, the first time: time 2 min, pulling rate 10 cm / min, 60℃ hot air circulation pre-drying 2 min, air speed 1.5 m / s, the second time: time 30 s, pulling rate 30 cm / min, hanging to no liquid dripping, to obtain an impregnated base material; Step 3: Calcium chloride 2 parts and carrageenan 3 parts were dissolved in 100 parts by weight of ultrapure water at 50℃, with a viscosity of 27 mPa·s, to obtain a crosslinking liquid, the impregnated base material was placed in the crosslinking liquid and oscillated at a frequency of 120 Hz for 10 min, then taken out, washed, and vacuum dried at 40℃ for 24 h, to obtain a single-layer base material; Step 4: The single-layer base material was laminated and hot-pressed at 120℃ and 10 MPa for 8 min, then cooled to 50℃ and demolded, to obtain a high-performance fiber composite material.

[0025] Example 4: The embodiment provides a high-performance fiber composite material for sports protective gear, which includes the following raw materials by weight: fiber skeleton base material 40 parts, TPU 40 parts, sodium alginate 4 parts, diopside powder 9 parts, and calcium chloride 2 parts.

[0026] The fiber skeleton base material includes the following raw materials by weight: collagen 50 parts, chitosan 20 parts, flax fiber 15 parts, bamboo fiber 15 parts, and genipin 0.3 parts, specifically including the following steps: S1: 15 parts of flax fibers and 15 parts of bamboo fibers were mixed and then boiled in 100 parts by weight of 0.1 M NaOH solution for 30 min, and then washed with purified water until the pH was neutral to obtain pretreated fibers. The pretreated fibers and 300 parts of purified water were placed in a high-pressure homogenizer, and the program was set to 500 bar for 3 cycles, 800 bar for 3 cycles, and 1500 bar for 4 cycles at a temperature of 38°C to obtain microfibrillated fibers; S2: 50 parts of collagen and 20 parts of chitosan were dissolved in 200 parts by weight of 0.1 M acetic acid solution, and electrospinning treatment was performed at a voltage of 25 kV, a receiving distance of 15 cm, and a push-in speed of 0.8 mL / h. The wet fiber mat with a thickness of 200±20 μm was collected by an anodic aluminum foil to obtain electrospun fibers; S3: 0.3 parts of genipin were dissolved in 10 parts by weight of ethanol and mixed with the microfibrillated fibers, and ultrasonic dispersion was performed at a power of 300 W, an on / off ratio of 5 s on / 2 s off, and a temperature control of 10°C to obtain a crosslinking liquid. The electrospun fibers were immersed in the crosslinking liquid for 30 min, ultrasonicated at 40 kHz for 30 min, and then the liquid was removed by vacuum suction to obtain a film material. The film material was washed with purified water and dried by hot air at 60°C until the water content was 7.3% to obtain a composite fiber mat. S4: The composite fiber mat was cut into 3×3 mm pieces by a cutting machine, carded by a carding machine, and reinforced by double-roller hot pressing at an upper roller temperature of 90°C, a lower roller temperature of 100°C, and a linear pressure of 0.50 MPa to obtain a fiber skeleton base material with a grammage of 180±5 g / m 2 and a thickness of 0.30±0.03 mm.

[0027] The embodiment also provides a preparation method of a high-performance fiber composite material for sports protective gear, which specifically comprises the following steps: Step 1: 40 parts of TPU were dissolved in 110 parts of DMF at 70°C, and then 9 parts of diopside powder were added and ultrasonically dispersed at a power of 400 W for 15 min, with a pulse cycle of 2 s on / 1 s off and a temperature control of 20°C to obtain an organic phase; Step 2: The fiber skeleton base material was immersed in the organic phase twice. The first immersion was performed at a time of 2 min, a pull-up rate of 10 cm / min, and a hot air circulation pre-drying at 60°C for 2 min at an air speed of 1.5 m / s. The second immersion was performed at a time of 30 s, a pull-up rate of 30 cm / min, and a suspension until no liquid droplets fell to obtain an impregnated base material; Step 3: 2 parts of calcium chloride and 4 parts of sodium alginate were dissolved in 100 parts by weight of ultrapure water at 50°C to obtain a crosslinking liquid with a viscosity of 173 mPa·s. The impregnated base material was placed in the crosslinking liquid, oscillated at a frequency of 120 Hz for 10 min, taken out, washed, and vacuum dried at 40°C for 24 h to obtain a single-layer base material; Step 4: The single-layer substrate was laminated and hot-pressed at 120℃, 10 MPa for 8 min, and demoulded at 50℃ to obtain the high-performance fiber composite material.

[0028] Comparative Example 1 differs from Example 1 in that the same weight of chitosan is used to replace the fiber skeleton substrate for the preparation of the fiber composite material, and the rest is the same as Example 1.

[0029] Morphology characterization After the high-performance fiber composite material prepared in Example 1 was frozen and broken in liquid nitrogen, the cross-section and the plane were placed on a copper mesh, gold was sprayed, and the microstructure was observed by scanning electron microscopy SEM, and the results are shown in Figure 1 .

[0030] Multi-directional impact test The high-performance fiber composite materials prepared in Examples 1-4 and Comparative Example 1 were taken to investigate the impact resistance of the materials in the impact tester, the impact energy was 30 J, the diameter of the hemispherical punch was 20 mm, and it was fixed in a ring-shaped clamp with an inner diameter of 40 mm. The deformation process was recorded, and the indentation depth was detected. The results are shown in Table 1.

[0031] Accelerated wear test The high-performance fiber composite materials prepared in Examples 1-4 and Comparative Example 1 were taken to investigate the wear resistance of the materials by using a wear tester. The wheel type was CS-10, the load was 500 g / wheel, and the rotation speed was 60 rpm. The mass loss was recorded every 500 rotations, and a total of 3000 rotations were tested. The weight loss and wear rate results are shown in Figure 2 .

[0032] Biocompatibility investigation A 24-well plate was taken and seeded with L929 fibroblasts at a cell density of 2×10 5 cells / well, and cultured with DMEM medium containing 10% FBS. After the cells adhered, the high-performance fiber composite materials prepared in Example 1 and Comparative Example 1 were sterilized by high-temperature steam and ultraviolet, and then placed in the adherent cell well plate for incubation for 20 min. The live and dead cell detection kit was used to investigate the cell growth, and the results are shown in Figure 3 .

[0033] Humidity stability investigation The high-performance fiber composite materials prepared in Examples 1-4 and Comparative Example 1 were placed in a constant temperature and humidity accelerated box at 70℃ / 85% RH to investigate the change of tensile strength with time. The test was performed once a week, and the results are shown in Figure 4 .

[0034] Hemostatic effect investigation Healthy BALB / c mice were taken, after soaking the tail in warm water for 3 min, cutting at the tail tip 2-3 mm, wrapping the high-performance fiber composite material prepared in Examples 1-4 and Comparative Example 1, respectively, and the control group was wrapped with a nylon fabric material, and the hemostatic time of each group was recorded, and the results are shown in Table 1 Figure 5 .

[0035] Table 1 Multidirectional impact test results

[0036] Figure 1 The results show that the fiber composite material prepared in Example 1 has uniform diameter, and the surface is covered with a continuous gel protective layer, which is uniformly wrapped and can play a role in buffering and wear resistance.

[0037] The impact test results in Table 1 show that the fiber composite materials prepared in Examples 1-4 have good impact resistance, and the gel protective layer effectively disperses the impact stress, verifying the key role of biodegradable fibers in maintaining the integrity of the layer.

[0038] Figure 2 The results show that the fiber composite material prepared in Example 1 has low weight loss after 3000 revolutions, and can resist external wear and tear, thanks to the wear-resistant network formed by the high-hardness calcium carbonate crystals in the TPU and the shear resistance of the plant fiber skeleton.

[0039] Figure 3 The results show that compared with Comparative Example 1, the fiber composite material prepared in Example 1 has better biocompatibility, and the cells survive well, which is conducive to the wound contact during sports injuries.

[0040] Figure 4 The results show that after 4 weeks of acceleration, the tensile strength retention rate of the fiber composite material prepared in Example 1 is still 86.2%, showing that the gel network and nanofiller improve the performance of the fiber material.

[0041] Figure 5 The hemostatic effect test shows that the fiber composite materials of Examples 1-4 activate platelets based on collagen to promote blood clotting, form a physical barrier with sodium alginate-calcium chloride, and continuously release calcium ions with shell powder to accelerate the conversion of fibrinogen, which has better hemostatic effect.

[0042] Although embodiments of the present application have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the application, and the scope of the present application is defined by the appended claims and their equivalents.

[0043] The above describes the present application and its embodiments, which are not limited, and the drawings only show one of the embodiments of the present application, and the actual application is not limited thereto. In general, if a person skilled in the art is inspired by it, without departing from the purpose of the present application, without creative design, similar ways and embodiments of the technical solution should belong to the protection scope of the present application.

Claims

1. A high performance fiber composite material for sports protectors, characterized in that, The high-performance fiber composite material comprises the following raw materials by weight: 40 parts of a fiber skeleton base material, 30-45 parts of TPU, 3-8 parts of a cross-linking agent, 5-15 parts of a nano filler, and 2 parts of calcium chloride; The fiber skeleton base material comprises the following raw materials: collagen, chitosan, flax fiber, bamboo fiber, and genipin, and the fiber skeleton base material is prepared in the following manner: S1: boiling and homogenizing the flax fiber and the bamboo fiber in an alkaline solution to obtain microfibrillated fiber; S2: dissolving the collagen and the chitosan and then performing electrospinning treatment to obtain electrospun fiber; S3: weighing and dissolving the genipin and mixing the microfibrillated fiber to obtain a cross-linking solution, immersing the electrospun fiber in the cross-linking solution, and then rinsing and drying to obtain a composite fiber felt; S4: cutting, carding, and hot-pressing the composite fiber felt to obtain the fiber skeleton base material.

2. A high performance fiber composite material for sports protectors according to claim 1, characterized in that, The weight parts of the collagen, the chitosan, the flax fiber, the bamboo fiber, and the genipin are 45-50 parts, 20-25 parts, 15 parts, 15 parts, and 0.3 parts, respectively; In step S2, the solvent used in the dissolving process of the collagen and the chitosan is 0.1 M acetic acid solution; In step S3, the water content of the composite fiber felt is <8%.

3. A high performance fiber composite material for sports protectors according to claim 1, characterized in that, The cross-linking agent is selected from any one of sodium alginate, gelatin, and carrageenan.

4. A high performance fiber composite material for sports protectors according to claim 1, characterized in that, The nano filler is selected from any one of shell powder, zeolite powder, montmorillonite powder, and diopside powder.

5. A process for the production of a high performance fiber composite material for sports protectors according to any one of claims 1-4, characterized in that, Specifically comprises the following steps: Step 1: dissolving the TPU and then adding the nano filler to disperse in the organic phase; Step 2: immersing the fiber skeleton base material twice in the organic phase to obtain an impregnated base material; Step 3: weighing and dissolving the calcium chloride and the cross-linking agent to obtain a cross-linking solution, placing the impregnated base material in the cross-linking solution, oscillating, and drying to obtain a single-layer base material; Step 4: laminating and hot-pressing the single-layer base material to obtain the high-performance fiber composite material.

6. A method of manufacturing a high performance fiber composite material for sports protectors according to claim 5, characterized in that, In step 2, the process of immersing the fiber skeleton base material twice in the organic phase is as follows: First immersion: time 2 min, pulling rate 10 cm / min, 60℃ pre-drying 2 min, second immersion: time 30 s, pulling rate 30 cm / min, hanging to no liquid dripping.

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