High-strength corrosion-resistant inflatable boat material and preparation method thereof

Abstract

The invention discloses a high-strength corrosion-resistant inflatable boat material and a preparation method thereof, and relates to the technical field of inflatable boat material processing. The method comprises the following steps: preparing 90-100 parts of TPU particles, 20-30 parts of aramid fibers, 15-20 parts of polyester fibers, 5-8 parts of nano silicon dioxide, 10-15 parts of an epoxy resin modifier, 2-3 parts of an anti-ultraviolet agent, 3-5 parts of nano zirconium phosphate, 8-10 parts of a flame retardant, 1-2 parts of a silane coupling agent, 0.5-1 part of an antioxidant and 8-13 parts of an antibacterial intermediate; wherein the antibacterial intermediate is prepared by the following steps: step 1, adding triclosan, nano silicon dioxide and polyethylene wax into a mixing machine; the antibacterial intermediate is added into the raw materials, the nano silicon dioxide is subjected to silanization treatment, and the synergistic effect of the antibacterial intermediate and the silanized nano silicon dioxide is utilized, so that double optimization of the surface performance and the internal structure of the material is realized.

Description

Technical Field

[0001] The present invention relates to the technical field of inflatable boat material processing. Specifically, it relates to a high-strength and corrosion-resistant inflatable boat material and a preparation method thereof. Background Art

[0002] An inflatable boat is a type of boat that mainly relies on air filling to maintain its shape and buoyancy. As an inflatable boat, with its lightweight and multi-functional characteristics, it is widely used in various water operations such as water leisure, entertainment, fishing, and fishing. Compared with traditional boats, it has higher safety and can adapt to various water environments; However, when an inflatable boat is used on the sea surface for a long time, due to the high salt content in seawater, its surface material is in long-term contact with seawater, and erosion is extremely likely to occur. This not only affects the service life of the inflatable boat but also may pose a potential threat to its safety during water operations. Currently, existing inflatable boat materials on the market such as PVC, etc., have obvious deficiencies in dealing with seawater erosion. The salts in seawater will damage the stability of the external material of the inflatable boat, and the salt solution will penetrate into the interior of the material, weakening the intermolecular forces of the inflatable boat material. Moreover, during the long-term use in seawater, the metabolic activities of microorganisms in seawater will cause erosion and damage to the inflatable boat material, making it difficult to meet the requirements of stable use in the sea surface environment for a long time.

[0003] Regarding the problems in the related art, no effective solution has been proposed yet. Summary of the Invention

[0004] Regarding the problems in the related art, the present invention proposes a high-strength and corrosion-resistant inflatable boat material and a preparation method thereof to overcome the above-mentioned technical problems existing in the existing related technologies.

[0005] For this purpose, the specific technical solutions adopted by the present invention are as follows: A high-strength and corrosion-resistant inflatable boat material, comprising the following raw materials in parts by mass: 90 - 100 parts of TPU particles, 20 - 30 parts of aramid fiber, 15 - 20 parts of polyester fiber, 5 - 8 parts of nano-silica, 10 - 15 parts of epoxy resin modifier, 2 - 3 parts of ultraviolet absorber, 3 - 5 parts of nano-zirconium phosphate, 8 - 10 parts of flame retardant, 1 - 2 parts of silane coupling agent, 0.5 - 1 part of antioxidant, 8 - 13 parts of antibacterial intermediate; Among them, the antibacterial intermediate is prepared by the following steps: Step 1: Add triclosan, nano-silica, and polyethylene wax to a mixer, heat up to 50 °C, and stir until the powder is uniform and without agglomeration to obtain premix A; Step 2: Add premix A to a twin-screw extruder, melt and extrude, then cool and pelletize with water, and dry at 60 °C for 2 hours to obtain the antibacterial intermediate.

[0006] As a preferred embodiment, the mass ratio of triclosan, nano-silica, and polyethylene wax used in step 1 is 1:90:0.1, the rotation speed of the mixer is 950 rpm, and the time is 18 minutes.

[0007] As a preferred embodiment, the screw rotation speed of the twin-screw extruder used in step 2 is 140 rpm, the die hole diameter of the pelletizer is 2 mm, the pellet length is 2.5 mm, and the temperatures of the first, second, third, and fourth zones of the twin-screw extruder are 150 °C, 160 °C, 165 °C, and 170 °C, respectively.

[0008] As a preferred embodiment, the mass ratio of polyvinyl alcohol, ethylene glycol, and sodium hydroxide used is 1:0.6:0.005.

[0009] A high-strength and corrosion-resistant inflatable boat material and its preparation method, including the following preparation steps: S1. Weigh the following raw materials by mass parts: 90 - 100 parts of TPU particles, 20 - 30 parts of aramid fiber, 15 - 20 parts of polyester fiber, 5 - 8 parts of nano-silica, 10 - 15 parts of epoxy resin modifier, 2 - 3 parts of ultraviolet absorber, 3 - 5 parts of nano-zirconium phosphate, 8 - 10 parts of flame retardant, 1 - 2 parts of silane coupling agent, 0.5 - 1 part of antioxidant, and 8 - 13 parts of antibacterial intermediate; S2. Dry the aramid fiber and polyester fiber in a vacuum drying oven for 4 hours to make the humidity ≤ 0.1%. Weave them through a fiber loom with aramid fiber in the warp direction and polyester fiber in the weft direction. After weaving, immerse them in the impregnating solution for 5 minutes, and cure at 80 °C for 30 minutes to obtain a fiber cloth; S3. Mix the silane coupling agent and absolute ethanol in a ratio of 1:9, stir for 10 minutes to prepare a treatment solution. Add nano-silica to the treatment solution, ultrasonically disperse for 30 minutes, then dry in an oven for 2 hours, and sieve to obtain silanized nano-silica; S4. Mix the TPU particles, epoxy resin modifier, ultraviolet absorber, flame retardant, and antibacterial intermediate in a high-speed mixer for 10 minutes. Add nano-zirconium phosphate and silanized nano-silica, heat up to 120 °C, and conduct vacuum degassing for 15 minutes. Then, melt and blend through a twin-screw extruder to obtain a modified TPU masterbatch; S5. Add the modified TPU masterbatch and nano-zirconium phosphate to a three-layer co-extrusion blown film machine to blow and obtain an outer corrosion-resistant film. Add the modified TPU masterbatch and silanized nano-silica to a three-layer co-extrusion blown film machine to blow and obtain an inner airtight film; S6. Press the outer corrosion-resistant film, fiber cloth, and inner airtight film in sequence through a flat vulcanizing machine. Spray the silane coupling agent between layers, preheat at 170 °C for 5 minutes, apply pressure at 175 °C for 20 minutes, and cool down gradually to obtain a high-strength and corrosion-resistant inflatable boat material.

[0010] As a preferred embodiment, the step of determining the dosage of the flame retardant intermediate is included in S2: The step of jointly preparing the antibacterial intermediate is included in S3: Step 1: Mix the silane coupling agent and absolute ethanol at a ratio of 1:9, stir at room temperature for 10 minutes to obtain a treatment solution, add triclosan to the treatment solution and stir until there are no visible suspended particles. The mass ratio of the treatment solution to triclosan is 100:1.2 to obtain an antibacterial treatment solution. Add nano-silica to the antibacterial treatment solution, with a solid-liquid ratio of 1:5, ultrasonically disperse at 60 °C for 30 minutes, and dry in an oven at 120 °C for 2 hours and pass through a 200-mesh sieve to obtain silanized antibacterial nano-silica; Step 2: Calculate the effective load retention rate of the silanized antibacterial nano-silica. The specific steps are as follows: Based on the specific surface area of nano-silica , Avogadro's constant , the cross-sectional area of a single triclosan molecule , and the molar mass of triclosan , calculate the theoretical maximum load : ; Based on the total mass of the modified silanized antibacterial nano-silica and the mass of the unmodified original nano-silica , calculate the actual load : ; Based on the actual load and the theoretical maximum load , calculate the effective load retention rate in Step 1: ; Among them, are respectively the highest process temperature in Step 1 and the decomposition temperature of triclosan, respectively represent the ideal dispersion particle size and the measured particle size by dynamic light scattering DLS; Step 3: Calculate the melt load retention rate after correction by the melt process based on the effective load retention rate : ; Among them, is the melt temperature in S4, is the decomposition activation energy of triclosan, is the gas constant, are respectively the time in the melting stage and the reference decomposition time; Step 4: According to the target value of the payload retention rate in the current inflatable boat preparation requirements , determine the molten payload retention rate : When ≥ , execute Step 1 to replace S3 and do not add antibacterial intermediates in S4; When < , execute S1 - S6 to prepare a high-strength and corrosion-resistant inflatable boat material.

[0011] As a preferred embodiment, the temperature of the vacuum drying oven in S2 is set at 80°C, the vacuum degree is -0.1 MPa, the weaving parameter is 18×18 threads / cm², the impregnating solution is bisphenol A epoxy resin E - 51 and curing agent T31, and the mass ratio of bisphenol A epoxy resin E - 51 to curing agent T31 is 1:0.3.

[0012] As a preferred embodiment, the solid-liquid ratio of nano-silica to the treatment liquid in S3 is 1:5, the ultrasonic dispersion temperature is set at 60°C, the oven temperature is set at 120°C, and the sieving parameter is set at 200 mesh.

[0013] As a preferred embodiment, the mixing parameters of TPU particles, epoxy resin, ultraviolet absorber, flame retardant, and antibacterial intermediate in the high-speed mixer in S4 are 500 rpm, the vacuum degassing vacuum degree is -0.08 MPa, the temperature of the first zone of the twin-screw extruder is 160°C, the second zone is 175°C, the third zone is 185°C, the fourth zone is 190°C, the screw speed is 200 rpm, and the pelletizing length is 3 mm.

[0014] As a preferred embodiment, when blowing the outer corrosion-resistant film in S5, the die head temperature is set at 190°C, the melt temperature is set at 185°C, the blow-up ratio is 2.5:1, and the traction speed is 10 m / min. When blowing the inner airtight film, the die head temperature is 185°C, the melt temperature is set at 180°C, the blow-up ratio is 2:1, and the traction speed is 8 m / min. In S6, the spraying amount of silane coupling agent for interlayer spraying is 0.1 g / m², the pressurization is segmented pressurization, the parameter settings are 0 to 10 MPa / 2 min to 25 MPa / 5 min, and the gradient cooling parameter settings are 5°C / min to room temperature.

[0015] As a preferred embodiment, the ultraviolet absorber is UV - 531, the flame retardant is aluminum hydroxide, the silane coupling agent is KH - 550, the antioxidant is antioxidant - 1010, and the epoxy resin modifier is bisphenol A epoxy resin E - 51.

[0016] The beneficial effects of the present invention are: 1. The present invention realizes the dual optimization of the surface properties and internal structure of the material by adding an antibacterial intermediate to the raw materials and performing silanization treatment on nano-silica. The introduction of the antibacterial intermediate endows the material with excellent antibacterial properties, which can effectively inhibit the attachment and reproduction of marine microorganisms. The nano-silica after silanization treatment can enhance the interfacial bonding force with the TPU matrix and improve the filler dispersion. The combination of the two not only improves the antibacterial effect of the material but also enhances the hydrophobicity and seawater erosion resistance of the material by forming a dense surface structure, which is beneficial to solving the problem of performance degradation of inflatable boat materials caused by microbial erosion and seawater corrosion in the marine environment; 2. The present invention uses TPU particles, aramid fibers, and polyester fibers as matrix materials, compounding functional fillers such as nano-silica, nano-zirconium phosphate, and epoxy resin modifiers, and prepares a high-strength and corrosion-resistant inflatable boat material through fiber braiding reinforcement, multi-layer co-extrusion blow molding, and hot pressing composite processes. Among them, the braided structure formed by aramid fibers and polyester fibers provides excellent mechanical support. The epoxy resin modifier and silane coupling agent enhance the interfacial adhesion between the fiber and the matrix. Nano-silica and nano-zirconium phosphate are uniformly dispersed in the TPU matrix through surface modification treatment to form a rigid reinforcement phase, improving the seawater corrosion resistance. Through the synergistic effect of each component, the material not only has high-strength mechanical properties but also realizes the multi-functional combination of seawater corrosion resistance, anti-ultraviolet aging, flame retardancy, and antibacterial properties, meeting the long-term use requirements of inflatable boats in complex marine environments; 3. The present invention calculates the melting load retention rate of the actual active ingredients of the antibacterial intermediate, and flexibly selects the preparation scheme of the inflatable boat material in combination with the target value of the effective load retention rate in different inflatable boat production target requirements. When the melting load retention rate of the active ingredients meets the target value of the effective load retention rate, the antibacterial intermediate is incorporated into the preparation process of silanized nano-silica, avoiding the redundancy of the production process of separately preparing the antibacterial intermediate, reducing the production cost in the actual production process, making the entire preparation process of the inflatable boat material more flexible, shortening the production cycle, and balancing the antibacterial performance and production cost. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for use in the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative efforts.

[0018] Figure 1 FIG. is a flowchart of a method for preparing a high-strength and corrosion-resistant inflatable boat material according to an embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0019] To further illustrate each embodiment, the present invention provides accompanying drawings, which are part of the disclosure of the present invention. These drawings are mainly used to illustrate the embodiments and can be used in conjunction with the relevant descriptions in the specification to explain the operating principles of the embodiments. With reference to these contents, those of ordinary skill in the art should be able to understand other possible implementation manners and the advantages of the present invention. The components in the drawings are not drawn to scale, and similar component symbols are usually used to represent similar components.

[0020] According to an embodiment of the present invention, a high-strength corrosion-resistant inflatable boat material and a preparation method thereof are provided.

[0021] Now, the present invention will be further described in conjunction with the accompanying drawings and specific implementation manners: Embodiment 1: A high-strength corrosion-resistant inflatable boat material according to an embodiment of the present invention includes the following raw materials in parts by mass: 90-100 parts of TPU particles, 20-30 parts of aramid fiber, 15-20 parts of polyester fiber, 5-8 parts of nano-silica, 10-15 parts of epoxy resin modifier, 2-3 parts of ultraviolet absorber, 3-5 parts of nano-zirconium phosphate, 8-10 parts of flame retardant, 1-2 parts of silane coupling agent, 0.5-1 part of antioxidant, and 8-13 parts of antibacterial intermediate; Among them, the antibacterial intermediate is prepared by the following steps: Step 1: Add triclosan, nano-silica, and polyethylene wax to a mixer, heat up to 50°C, stir until the powder is uniform and free of agglomeration, the rotation speed of the mixer is 950 rpm, and the time is 18 minutes to obtain premix A; Step 2: Add premix A to a twin-screw extruder. The temperature of the first zone of the twin-screw extruder is 150°C, the second zone is 160°C, the third zone is 165°C, and the fourth zone is 170°C. Extrude and granulate by water cooling after melting at a screw rotation speed of 140 rpm, with the die hole diameter of the pelletizer being 2 mm and the pellet length being 2.5 mm, and dry at 60°C for 2 hours to obtain the antibacterial intermediate; A high-strength corrosion-resistant inflatable boat material and a preparation method thereof include the following preparation steps: S1: Weigh the following raw materials in parts by mass: 90-100 parts of TPU particles, 20-30 parts of aramid fiber, 15-20 parts of polyester fiber, 5-8 parts of nano-silica, 10-15 parts of epoxy resin modifier, 2-3 parts of ultraviolet absorber, 3-5 parts of nano-zirconium phosphate, 8-10 parts of flame retardant, 1-2 parts of silane coupling agent, 0.5-1 part of antioxidant, and 8-13 parts of antibacterial intermediate; S2. Dry the aramid fiber and polyester fiber in a vacuum drying oven at a temperature of 80°C, a vacuum degree of -0.1 MPa for 4 hours until the humidity ≤ 0.1%. Then, through a fiber knitting machine, knit with aramid fiber in the warp direction and polyester fiber in the weft direction at 18×18 strands / cm². After knitting, immerse it in the impregnating solution for 5 minutes, and cure at 80°C for 30 minutes. The impregnating solution is bisphenol A epoxy resin E-51 and curing agent T31 with a mass ratio of 1:0.3 to obtain the fiber cloth; S3. Mix silane coupling agent KH-550 and absolute ethanol at a ratio of 1:9, stir for 10 minutes to prepare the treatment solution. Add nano-silica into the treatment solution with a solid-liquid ratio of 1:5, and ultrasonically disperse at 60°C for 30 minutes. Then dry in an oven at 120°C for 2 hours and sieve through a 200-mesh sieve to obtain silanized nano-silica; S4. Mix TPU particles, epoxy resin modifier, ultraviolet absorber UV-531, flame retardant aluminum hydroxide, and antibacterial intermediate in a high-speed mixer at 500 rpm for 10 minutes. Add nano-zirconium phosphate and silanized nano-silica, heat up to 120°C, and vacuum degas for 15 minutes with a vacuum degree of -0.08 MPa. Then melt and blend through a twin-screw extruder, with zone 1 at 160°C, zone 2 at 175°C, zone 3 at 185°C, zone 4 at 190°C, a screw speed of 200 rpm, and a pellet length of 3 mm to obtain the modified TPU masterbatch; S5. Add the modified TPU masterbatch and nano-zirconium phosphate into a three-layer co-extrusion blown film machine, set the die temperature at 190°C and the melt temperature at 185°C, with a blow-up ratio of 2.5:1 and a traction speed of 10 m / min to blow-mold the outer corrosion-resistant film. Add the modified TPU masterbatch and silanized nano-silica with a die temperature of 185°C and a melt temperature of 180°C, a blow-up ratio of 2:1, and a traction speed of 8 m / min to blow-mold the inner airtight film; S6. Stack the outer corrosion-resistant film, inner airtight film, and fiber cloth in the order of outer corrosion-resistant film, fiber cloth, and inner airtight film, and hot-press them through a flat vulcanizing machine. Spray silane coupling agent between layers at a spraying amount of 0.1 g / m², preheat at 170°C for 5 minutes, pressurize at 175°C for 20 minutes, and cool down to room temperature at a gradient of 5°C / min to obtain the high-strength corrosion-resistant inflatable boat material.

[0022] The antibacterial intermediate joint preparation determination step is included in S3: Step 1: Mix the silane coupling agent and absolute ethanol at a ratio of 1:9, stir for 10 minutes at room temperature to obtain a treatment solution. Add triclosan to the treatment solution and stir until there are no visible suspended particles. The mass ratio of the treatment solution to triclosan is 100:1.2 to obtain an antibacterial treatment solution. Add nano-silica to the antibacterial treatment solution with a solid-liquid ratio of 1:5, ultrasonically disperse for 30 minutes at 60 °C, and dry in an oven at 120 °C for 2 hours and pass through a 200-mesh sieve to obtain silanized antibacterial nano-silica; Step 2: Calculate the effective load retention rate of the silanized antibacterial nano-silica. The specific steps are as follows: According to the specific surface area of nano-silica , Avogadro's constant , the cross-sectional area of a single triclosan molecule , and the molar mass of triclosan , calculate the theoretical maximum loading amount : ; It should be noted that in the calculation formula, calculate the theoretical maximum value of the mass of the antibacterial agent that can be loaded per unit mass of the carrier. Among them, through the specific surface area (the area provided per gram of the carrier) and the cross-sectional area of the antibacterial agent molecule molecules, calculate the number of molecules that can be "laid flat" on the surface of the carrier. Combining with Avogadro's constant , convert the number of molecules into the molar amount, and then through convert the molar amount into mass. The final result represents the mass of the antibacterial agent that can be loaded per gram of the carrier (g / g), that is, the theoretical maximum loading amount.

[0023] According to the total mass of the modified silanized antibacterial nano-silica and the mass of the unmodified original nano-silica , calculate the actual loading amount : ; Based on the actual loading amount and the theoretical maximum loading amount , calculate the effective load retention rate in Step 1: ; Among them, are the highest temperature of the process temperature in Step 1 and the decomposition temperature of triclosan respectively, represent the ideal dispersion particle size and the measured particle size by dynamic light scattering DLS respectively; Step 3: According to the effective load retention rate , calculate the melt load retention rate after the melt process correction : ; Wherein, is the melt temperature in S4, the activation energy for triclosan decomposition, is the gas constant, are the time of the melting stage and the reference decomposition time, respectively; It should be noted that the activation energy for triclosan decomposition needs to be obtained by fitting through TGA testing, and the reference decomposition time is the time when the weight loss in TGA is 5%.

[0024] Step Four: According to the target value of the effective load retention rate in the current inflatable boat preparation requirements , judge the melt load retention rate : When ≥ , execute Step One to replace S3 and do not add antibacterial intermediates in S4; When < , execute S1 - S6 to prepare high-strength and corrosion-resistant inflatable boat materials.

[0025] Among them, the UV absorber used is UV-531, the flame retardant is aluminum hydroxide, the silane coupling agent is KH-550, the antioxidant is antioxidant-1010, and the epoxy resin modifier is bisphenol A epoxy resin E-51.

[0026] Example 2: This example is applicable to < for high-strength and corrosion-resistant inflatable boat materials. The specific process and preparation flow are as follows: First Step: Weigh the following raw materials by mass parts: 100 parts of TPU particles, 30 parts of aramid fiber, 20 parts of polyester fiber, 8 parts of nano-silica, 15 parts of epoxy resin modifier, 3 parts of UV absorber, 5 parts of nano-zirconium phosphate, 10 parts of flame retardant, 2 parts of silane coupling agent, 1 part of antioxidant, and 13 parts of antibacterial intermediate; Second Step: Dry the aramid fiber and polyester fiber in a vacuum drying oven at a temperature of 80°C, a vacuum degree of -0.1 MPa, and a time of 4 hours to make the humidity ≤ 0.1%. Then, through a fiber knitting machine, with the aramid fiber in the warp direction and the polyester fiber in the weft direction, knit at 18×18 roots / cm². After knitting, immerse it in the impregnating solution for 5 minutes, and cure at 80°C for 30 minutes. The impregnating solution is bisphenol A epoxy resin E-51 and curing agent T31, with a mass ratio of 1:0.3, to obtain fiber cloth; Step 3: Mix silane coupling agent KH-550 and absolute ethanol at a ratio of 1:9, stir for 10 min to prepare a treatment solution, add nano-silica into the treatment solution with a solid-liquid ratio of 1:5, ultrasonically disperse at 60 °C for 30 min, then dry in an oven at 120 °C for 2 hours, and sieve through a 200-mesh sieve to obtain silanized nano-silica; Step 4: Mix TPU particles, epoxy resin modifier, UV absorber UV-531, flame retardant aluminum hydroxide, and antibacterial intermediate in a high-speed mixer at 500 rpm for 10 min, add nano-zirconium phosphate and silanized nano-silica, heat up to 120 °C, degas under vacuum for 15 min with a vacuum degree of -0.08 MPa, and melt-blend through a twin-screw extruder, where the temperature of zone 1 is 160 °C, zone 2 is 175 °C, zone 3 is 185 °C, zone 4 is 190 °C, the screw speed is 200 rpm, and the pellet length is 3 mm to obtain modified TPU masterbatch; Step 5: Add the modified TPU masterbatch and nano-zirconium phosphate into a three-layer co-extrusion blown film machine, set the die temperature at 190 °C and the melt temperature at 185 °C, blow at a blow-up ratio of 2.5:1 and a traction speed of 10 m / min to obtain an outer corrosion-resistant film, and add the modified TPU masterbatch and silanized nano-silica with a die temperature of 185 °C and a melt temperature of 180 °C, blow at a blow-up ratio of 2:1 and a traction speed of 8 m / min to obtain an inner airtight film; Step 6: Thermally press the outer corrosion-resistant film, inner airtight film, and fiber cloth in the order of outer corrosion-resistant film, fiber cloth, and inner airtight film through a flat vulcanizing machine, spray silane coupling agent between layers with a spraying amount of 0.1 g / m², preheat at 170 °C for 5 min, pressurize at 175 °C for 20 min, and cool down to room temperature at a gradient of 5 °C / min to obtain a high-strength corrosion-resistant inflatable boat material; Among them, the UV absorber used is UV-531, the flame retardant is aluminum hydroxide, the silane coupling agent is KH-550, the antioxidant is antioxidant-1010, and the epoxy resin modifier is bisphenol A epoxy resin E-51.

[0027] Example 3: This example is applicable to < the high-strength corrosion-resistant inflatable boat material at and the specific process and preparation process are as follows: Weigh the following raw materials by mass parts: 90 parts of TPU particles, 20 parts of aramid fiber, 15 parts of polyester fiber, 5 parts of nano-silica, 10 parts of epoxy resin modifier, 2 parts of UV absorber, 3 parts of nano-zirconium phosphate, 8 parts of flame retardant, 1 part of silane coupling agent, 0.5 part of antioxidant, and 8 parts of antibacterial intermediate; Second step: Dry the aramid fiber and polyester fiber in a vacuum drying oven at a temperature of 80°C, a vacuum degree of -0.1 MPa, and a time of 4 hours to make the humidity ≤ 0.1%. Then, through a fiber braiding machine, braid with aramid fiber in the warp direction and polyester fiber in the weft direction at a density of 18×18 roots / cm². After braiding, immerse it in the impregnating solution for 5 minutes, and cure at a temperature of 80°C for 30 minutes. The impregnating solution is bisphenol A epoxy resin E-51 and curing agent T31 with a mass ratio of 1:0.3 to obtain a fiber cloth; Third step: Mix silane coupling agent KH-550 and absolute ethanol at a ratio of 1:9, stir for 10 minutes to prepare a treatment solution, add nano-silica to the treatment solution with a solid-liquid ratio of 1:5, and ultrasonically disperse at 60°C for 30 minutes. Then dry in an oven at 120°C for 2 hours and sieve through a 200-mesh sieve to obtain silanized nano-silica; Fourth step: Mix TPU particles, epoxy resin modifier, ultraviolet absorber UV-531, flame retardant aluminum hydroxide, and antibacterial intermediate in a high-speed mixer at 500 rpm for 10 minutes. Add nano-zirconium phosphate and silanized nano-silica, heat up to 120°C, and vacuum degas for 15 minutes with a vacuum degree of -0.08 MPa. Then melt and blend through a twin-screw extruder, with zone 1 at 160°C, zone 2 at 175°C, zone 3 at 185°C, zone 4 at 190°C, a screw speed of 200 rpm, and a pellet length of 3 mm to obtain modified TPU masterbatch; Fifth step: Add the modified TPU masterbatch and nano-zirconium phosphate to a three-layer co-extrusion blown film machine, set the die temperature at 190°C and the melt temperature at 185°C, blow with a blow-up ratio of 2.5:1 and a draw speed of 10 m / min to obtain an outer corrosion-resistant film. Add the modified TPU masterbatch and silanized nano-silica with a die temperature of 185°C and a melt temperature of 180°C, blow with a blow-up ratio of 2:1 and a draw speed of 8 m / min to obtain an inner airtight film; Sixth step: Stack the outer corrosion-resistant film, inner airtight film, and fiber cloth in the order of outer corrosion-resistant film, fiber cloth, and inner airtight film, and perform hot pressing through a flat vulcanizing machine. Spray silane coupling agent between layers with a spraying amount of 0.1 g / m², preheat at 170°C for 5 minutes, apply pressure at 175°C for 20 minutes, and cool down to room temperature at a gradient of 5°C / min to obtain a high-strength corrosion-resistant inflatable boat material; Among them, the ultraviolet absorber used is UV-531, the flame retardant is aluminum hydroxide, the silane coupling agent is KH-550, the antioxidant is antioxidant-1010, and the epoxy resin modifier is bisphenol A epoxy resin E-51.

[0028] Example 4: This example is applicable to ≥ high-strength corrosion-resistant inflatable boat materials at, and the specific process and preparation process are as follows: Step 1: Weigh the following raw materials by mass parts: 90 parts of TPU particles, 20 parts of aramid fiber, 15 parts of polyester fiber, 5 parts of nano-silica, 10 parts of epoxy resin modifier, 2 parts of ultraviolet absorber, 3 parts of nano-zirconium phosphate, 8 parts of flame retardant, 1 part of silane coupling agent, and 0.5 part of antioxidant; Step 2: Dry the aramid fiber and polyester fiber in a vacuum drying oven at a temperature of 80 °C, a vacuum degree of -0.1 MPa, and a time of 4 hours to make the humidity ≤ 0.1%. Weave them with an aramid fiber warp and a polyester fiber weft at 18×18 threads / cm² through a fiber braiding machine. After weaving, immerse them in an impregnating solution for 5 minutes, and cure at a temperature of 80 °C for 30 minutes. The impregnating solution is bisphenol A type epoxy resin E-51 and curing agent T31 with a mass ratio of 1:0.3 to obtain a fiber cloth; Step 3: Mix the silane coupling agent and absolute ethanol at a ratio of 1:9, stir at room temperature for 10 minutes to obtain a treatment solution. Add triclosan to the treatment solution and stir until there are no visible suspended particles. The mass ratio of the treatment solution to triclosan is 100:1.2 to obtain an antibacterial treatment solution. Add nano-silica to the antibacterial treatment solution with a solid-liquid ratio of 1:5, ultrasonically disperse at 60 °C for 30 minutes, and dry in a drying oven at 120 °C for 2 hours and pass through a 200-mesh sieve to obtain silanized antibacterial nano-silica; Step 4: Mix the TPU particles, epoxy resin modifier, ultraviolet absorber UV-531, and flame retardant aluminum hydroxide in a high-speed mixer at 500 rpm for 10 minutes. Add nano-zirconium phosphate and silanized antibacterial nano-silica, heat up to 120 °C, and vacuum degas for 15 minutes with a vacuum degree of -0.08 MPa. Melt and blend through a twin-screw extruder, where the temperature of zone 1 is 160 °C, zone 2 is 175 °C, zone 3 is 185 °C, zone 4 is 190 °C, the screw speed is 200 rpm, and the pellet length is 3 mm to obtain modified TPU masterbatch; Step 5: Add the modified TPU masterbatch and nano-zirconium phosphate to a three-layer co-extrusion blown film machine, set the die temperature at 190 °C and the melt temperature at 185 °C, blow at a blow-up ratio of 2.5:1 and a draw speed of 10 m / min to blow-mold the outer corrosion-resistant film. Add the modified TPU masterbatch and silanized antibacterial nano-silica with a die temperature of 185 °C and a melt temperature of 180 °C, blow at a blow-up ratio of 2:1 and a draw speed of 8 m / min to blow-mold the inner airtight film; Step 6: Thermally press the outer corrosion-resistant film, inner airtight film, and fiber cloth in the order of outer corrosion-resistant film, fiber cloth, and inner airtight film through a flat vulcanizing machine, spray silane coupling agent between layers with a spraying amount of 0.1 g / m², preheat at 170 °C for 5 minutes, pressurize at 175 °C for 20 minutes, and cool down to room temperature at a gradient of 5 °C / min to obtain a high-strength corrosion-resistant inflatable boat material; Among them, the ultraviolet absorber used is UV-531, the flame retardant is aluminum hydroxide, the silane coupling agent is KH-550, the antioxidant is antioxidant-1010, and the epoxy resin modifier is bisphenol A epoxy resin E-51.

[0029] Comparative Example 1: Remove the raw material "antibacterial intermediate" used in Example 2, and keep the other raw materials unchanged to prepare the inflatable boat material; Comparative Example 2: Remove the raw material "antibacterial intermediate" used in Example 3, and keep the other raw materials unchanged to prepare the inflatable boat material; Example 5: Perform performance tests on the inflatable boat materials obtained in Examples 2, 3 and Comparative Examples 1, 2, including water contact angle test, seawater resistance test, and antibacterial effect test. The test results are shown in Table 1: Table 1: Performance Test Table of Inflatable Boat Materials Product group Water contact angle (°) Seawater resistance (weight loss rate, %) Antibacterial effect (bacteriostasis rate, %) Example 2 117 0.18 98 Example 3 108 0.31 97 Comparative example 1 115 1.23 32 Comparative example 2 109 1.38 26 Among them, the hydrophobic property test is to use a water contact angle tester produced by Defei Company in Germany to test the water contact angle. If the water contact angle is greater than 90°, it shows hydrophobicity; Among them, the seawater resistance test is carried out with reference to the standard ISO 4433-1:1997 "Thermoplastic plastic pipes - Resistance to liquid chemicals - Classification - Part 1: Method of immersion test". Cut the inflatable boat materials produced in Examples 2, 3 and Comparative Examples 1, 2 into 5 cm × 5 cm sheet samples. After soaking in seawater for 120 days, test the mass loss percentage to characterize the seawater resistance. The smaller the mass loss percentage, the better the seawater resistance.

[0030] Among them, the antibacterial effect test is to detect the antibacterial rate of Examples 2, 3 and Comparative Examples 1, 2 against the target bacteria after 24 hours by the shake flask method.

[0031] In summary, the present invention realizes the dual optimization of the surface properties and internal structure of the material by adding an antibacterial intermediate to the raw materials and performing silanization treatment on nano-silica. The introduction of the antibacterial intermediate endows the material with excellent antibacterial properties, which can effectively inhibit the attachment and reproduction of marine microorganisms. The nano-silica after silanization treatment can enhance the interfacial bonding force with the TPU matrix and improve the filler dispersion. The combination of the two not only improves the antibacterial effect of the material, but also improves the hydrophobicity and seawater erosion resistance of the material by forming a dense surface structure, which is beneficial to solving the problem of performance degradation of inflatable boat materials caused by microbial erosion and seawater corrosion in the marine environment; By calculating the melting load retention rate of the actual active ingredient of the antibacterial intermediate and combining it with the target value of the active load retention rate in the production requirements of different inflatable boats, the preparation scheme of the inflatable boat material is flexibly selected. When the melting load retention rate of the active ingredient meets the target value of the active load retention rate, the antibacterial intermediate is incorporated into the preparation process of silanized nano-silica, avoiding the redundancy of the production process of separately preparing the antibacterial intermediate, reducing the production cost in the actual production process, making the entire preparation process of the inflatable boat material more flexible, shortening the production cycle, and balancing the antibacterial performance and production cost.

[0032] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A high-strength, corrosion-resistant inflatable boat material, characterized in that: The invention comprises the following raw materials in parts by weight: 90-100 parts of TPU particles, 20-30 parts of aramid fibers, 15-20 parts of polyester fibers, 5-8 parts of nano-silicon dioxide, 10-15 parts of epoxy resin modifiers, 2-3 parts of anti-ultraviolet agents, 3-5 parts of nano-zirconium phosphates, 8-10 parts of flame retardants, 1-2 parts of silane coupling agents, 0.5-1 parts of antioxidants, and 8-13 parts of antibacterial intermediates; Wherein, the antibacterial intermediate is prepared by the following steps: Step 1, add triclosan, nano-silicon dioxide and polyethylene wax into a mixer, heat to 50°C, and stir until the powder is uniform and free of agglomerates to obtain premix A; Step 2: Add premix A into a twin-screw extruder, melt-extrude, water-cool, and pelletize, and dry at 60° C. for 2 hours to obtain an antibacterial intermediate.

2. The high-strength, corrosion-resistant inflatable boat material according to claim 1, characterized in that: The mass ratio of triclosan, nano-silicon dioxide and polyethylene wax used in step 1 is 1:90:0.1, the mixer speed is 950 rpm, and the time is 18 minutes.

3. The high-strength, corrosion-resistant inflatable boat material according to claim 1, characterized in that: The screw speed of the twin-screw extruder used in step 2 is 140 rpm, the die hole diameter of the pelletizer is 2 mm, the pelletizing length is 2.5 mm, the twin-screw extruder zone 1 is 150°C, zone 2 is 160°C, zone 3 is 165°C, and zone 4 is 170°C.

4. A high-strength, corrosion-resistant inflatable boat material and a preparation method thereof as claimed in any one of claims 1 to 3, characterized in that: The method comprises the following preparation steps: S1. Weigh the following raw materials by mass: 90-100 parts of TPU particles, 20-30 parts of aramid fibers, 15-20 parts of polyester fibers, 5-8 parts of nano-silicon dioxide, 10-15 parts of epoxy resin modifiers, 2-3 parts of anti-ultraviolet agents, 3-5 parts of nano-zirconium phosphates, 8-10 parts of flame retardants, 1-2 parts of silane coupling agents, 0.5-1 parts of antioxidants, and 8-13 parts of antibacterial intermediates; S2, drying the aramid fiber and the polyester fiber in a vacuum drying oven for 4 hours to make the humidity ≤0.1%, weaving the aramid fiber in the warp direction and the polyester fiber in the weft direction through a fiber weaving machine, and immersing the fiber in an impregnation liquid for 5 minutes after weaving, and curing at 80°C for 30 minutes to obtain a fiber cloth; S3, mixing a silane coupling agent with anhydrous ethanol at a ratio of 1:9, stirring for 10 minutes to prepare a treatment solution, adding nano-silicon dioxide to the treatment solution, ultrasonically dispersing for 30 minutes, drying in an oven for 2 hours, and sieving to obtain silanized nano-silicon dioxide; S4, mixing TPU particles, epoxy resin modifier, anti-ultraviolet agent, flame retardant, and antibacterial intermediate in a high-speed mixer for 10 minutes, adding nano zirconium phosphate and silanized nano silicon dioxide, heating to 120° C., vacuum degassing for 15 minutes, and melt blending through a twin-screw extruder to obtain a modified TPU masterbatch; S5, adding the modified TPU masterbatch and nano zirconium phosphate into a three-layer co-extrusion film blowing machine, blow molding to obtain an outer corrosion-resistant film, adding the modified TPU masterbatch and silanized nano silicon dioxide into a three-layer co-extrusion film blowing machine, blow molding to obtain an inner airtight film; S6. Hot pressing is carried out in the order of outer corrosion-resistant film, fiber cloth and inner airtight film through a flat vulcanizer, silane coupling agent is sprayed between the layers, preheating is carried out at 170°C for 5 minutes, pressurizing is carried out at 175°C for 20 minutes, and gradient cooling is carried out to obtain a high-strength corrosion-resistant inflatable boat material.

5. The high-strength, corrosion-resistant inflatable boat material and preparation method thereof according to claim 4, characterized in that: The S3 includes the antibacterial intermediate joint preparation determination step: Step 1: Mix a silane coupling agent and anhydrous ethanol at a ratio of 1:9, stir at room temperature for 10 minutes to obtain a treatment liquid, add triclosan to the treatment liquid and stir until no suspended particles are visually observed, the mass ratio of the treatment liquid to triclosan is 100:1.2 to obtain an antibacterial treatment liquid, add nano-silicon dioxide to the antibacterial treatment liquid, the solid-liquid ratio is 1:5, ultrasonically disperse at 60°C for 30 minutes, and dry in a drying oven at 120°C for 2 hours and pass through a 200-mesh sieve to obtain silanized antibacterial nano-silicon dioxide; Step 2: Calculate the effective load retention rate of silanized antibacterial nano-silica, and the specific steps are as follows: According to the specific surface area of ​​nano-silicon dioxide , Avogadro's constant , the cross-sectional area of ​​a single triclosan molecule 、The molar mass of triclosan , calculate the theoretical maximum load : ； According to the total mass of modified silanized antibacterial nano-silica Compared with the original unmodified nanosilica mass , calculate the actual load : ； Based on actual load Theoretical maximum load , calculate the effective load retention rate in step 1 : ； in, are the highest process temperature in step 1 and the decomposition temperature of triclosan, They represent the ideal dispersed particle size and the particle size measured by dynamic light scattering (DLS), respectively; Step 3: Based on the effective load retention rate , calculate the melt load retention rate after the melting process correction : ； in, is the melting temperature in S4, Triclosan decomposition activation energy, is the gas constant, are the melting stage time and the reference decomposition time, respectively; Step 4: According to the current inflatable boat preparation requirements, the effective load retention rate target value , retention rate of melt load Make a judgment: when ≥ When S3 is replaced by S4, step 1 is performed, and no antimicrobial intermediate is added to S4; when < When performing S1-S6, a high-strength, corrosion-resistant inflatable boat material is obtained.

6. The high-strength, corrosion-resistant inflatable boat material and preparation method thereof according to claim 4, characterized in that: The temperature of the vacuum drying oven in S2 is set to 80°C, the vacuum degree is -0.1MPa, the weaving parameters are 18×18 strands / cm², the impregnation liquid is bisphenol A epoxy resin E-51 and curing agent T31, and the mass ratio of bisphenol A epoxy resin E-51 to curing agent T31 is 1:0.

3.

7. The high-strength, corrosion-resistant inflatable boat material and preparation method thereof according to claim 4, characterized in that: The solid-liquid ratio of nano-silicon dioxide to the treatment liquid in S3 is 1:5, the ultrasonic dispersion temperature is set at 60° C., the oven temperature is set at 120° C., and the sieving parameter is set at 200 meshes.

8. The high-strength, corrosion-resistant inflatable boat material and preparation method thereof according to claim 4, characterized in that: The TPU particles, epoxy resin modifier, anti-ultraviolet agent, flame retardant and antibacterial intermediate in the S4 are mixed in a high-speed mixer at a mixing parameter of 500 rpm, a vacuum degree of vacuum degassing of -0.08 MPa, a twin-screw extruder at 160°C in zone 1, 175°C in zone 2, 185°C in zone 3 and 190°C in zone 4, a screw speed of 200 rpm and a pelletizing length of 3 mm.

9. The high-strength, corrosion-resistant inflatable boat material and preparation method thereof according to claim 4, characterized in that: When the outer corrosion-resistant film in S5 is blown, the die temperature is set at 190°C, the melt temperature is set at 185°C, the blowing ratio is 2.5:1, and the pulling speed is 10m / min. When the inner airtight film is blown, the die temperature is 185°C, the melt temperature is set at 180°C, the blowing ratio is 2:1, and the pulling speed is 8m / min. The amount of silane coupling agent sprayed between layers in S6 is 0.1g / m², the pressurization is segmented pressurization, the parameters are set from 0 to 10MPa / 2min to 25MPa / 5min, and the gradient cooling parameters are set from 5°C / min to room temperature.

10. The high-strength, corrosion-resistant inflatable boat material and preparation method thereof according to claim 4, characterized in that: The anti-ultraviolet agent is UV-531, the flame retardant is aluminum hydroxide, the silane coupling agent is KH-550, the antioxidant is antioxidant-1010, and the epoxy resin modifier is bisphenol A epoxy resin E-51.

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