Biomimetic self-healing compression-resistant cable sheath material for deep-sea floating wind power platforms and method of manufacturing the same

Abstract

The application relates to a bionic self-healing compression-resistant cable sheath material suitable for a deep-sea floating wind power platform and a manufacturing method thereof, and belongs to the field of special cable materials for deep-sea energy equipment. A technical scheme: a bionic base component is composed of hydrogenated nitrile rubber, polyether type thermoplastic polyurethane and ethylene-octene copolymer and is 100 parts; a dynamic reversible crosslinking system is composed of a compound containing a borate ester bond and a peroxide vulcanizing agent and is 10-20 parts; a deep-sea environment functional filler is 20-40 parts, and the deep-sea environment functional filler has a multi-level core-shell structure; an anti-fouling slow-release system is 5-12 parts; and a processing aid is 10-25 parts. Through the synergistic effect of the bionics principle, dynamic covalent chemistry and multi-scale functional fillers, the comprehensive performance of the material in the deep-sea extreme environment is broken through, the deep-sea environment adaptability and long-term service performance are excellent, and the technical problems of the existing deep-sea cable sheath material in the aspects of compression resistance, self-healing ability, anti-biofouling and low-temperature adaptability and the like are solved.

Description

Technical Field

[0001] This invention relates to a biomimetic self-healing pressure-resistant cable sheath material suitable for deep-sea floating wind power platforms and its manufacturing method, particularly a cable sheath material and its preparation method that can provide long-term stable service under the synergistic effects of multiple environmental factors such as high pressure, low temperature, dynamic fatigue, and biofouling in deep sea, belonging to the technical field of special cable materials for deep-sea energy equipment. Background Technology

[0002] As the global energy structure accelerates its transition towards clean and low-carbon energy, offshore wind power, as a crucial component of renewable energy, is gradually expanding from nearshore to deep-sea areas. Deep-sea floating wind power platforms are anchored hundreds of meters below the sea surface via mooring systems, and their associated dynamic cables are considered the "lifeline" of floating wind power, undertaking the critical task of power transmission. These cables are subjected to the combined effects of extreme marine environments such as high pressure, low temperature, high salt spray, strong biofouling, and cyclic bending fatigue, placing unprecedentedly stringent demands on the comprehensive performance of the sheath materials.

[0003] In the high-pressure environment of the deep sea, the hydrostatic pressure increases by approximately one atmosphere for every 10 meters of depth. At depths of hundreds or even thousands of meters, traditional rubber sheath materials undergo molecular chain rearrangement and a reduction in free volume under continuous high pressure—a phenomenon known as "hydrostatic densification." This process leads to increased material density, increased hardness, and a significant decrease in flexibility, ultimately causing microcracks and penetration failure, severely threatening the insulation performance and service life of cables. Regarding dynamic fatigue performance, floating wind power platforms experience complex six-degree-of-freedom motion under the combined influence of waves, currents, and wind. Dynamic cables undergo millions of cyclic bending and tensile deformations, and this repeated mechanical stress accumulates microscopic damage within the material. While traditional vulcanized rubber possesses good elasticity, once microcracks develop, they propagate and converge under continuous dynamic loads, eventually leading to sheath rupture, seawater infiltration, and catastrophic failures such as insulation breakdown. Regarding marine biofouling, deep-sea cables, constantly submerged in seawater, are highly susceptible to becoming attachment substrates for marine organisms such as barnacles, mussels, and algae. Biofouling not only increases the cable's weight and hydrodynamic load, altering its hydrodynamic characteristics, but these organisms also secrete acidic metabolic products that corrode the sheath material, seriously threatening the long-term safe operation of the cable. In terms of low-temperature resistance, the temperature of the deep sea bottom remains consistently low at 2-4°C, and in some polar regions even below 0°C. Under these temperature conditions, the molecular chain movement of traditional rubber materials is significantly restricted. When the temperature falls below its glass transition temperature, the material becomes hard and brittle, and its bending performance decreases sharply, failing to meet the dynamic service requirements of deep-sea wind power platforms.

[0004] To address the aforementioned technical challenges, several solutions have been proposed in existing technologies. For example, Chinese patent application CN117672604A discloses a puncture-resistant mobile cable for coal mines and its preparation method, which uses metal coordination bonds to impart repairability to the rubber composite material. This technology primarily targets mechanical damage scenarios in coal mines, achieving self-healing functionality through the reversibility of metal-ligand coordination bonds. However, this technology does not consider the synergistic effects of high pressure, low temperature, and biofouling in the deep sea, and the stability of the metal coordination bonds in the seawater environment needs further verification. Chinese patent application CN119978823A discloses a wear-resistant modified rubber cable material for new energy vehicles and its preparation method, using modified potassium titanate whiskers as reinforcing fillers to improve the wear resistance of the rubber material. This technology enhances the mechanical properties of the material through the one-dimensional rigid structure of the whiskers, but it does not involve the design of a dynamic cross-linking network, making it difficult to cope with fatigue problems under dynamic loads in the deep sea. Chinese patent application ZL201210069017.X discloses a self-crosslinking thermoplastic rubber cable material XL TPR. This material provides reversibility through physical crosslinking points such as ionic bonds, but its upper limit of working temperature is only 105℃, which cannot meet the long-term flexibility requirements in the low-temperature environment of the deep sea.

[0005] In-depth analysis of existing technologies reveals several significant shortcomings in current deep-sea cable sheathing materials: In terms of compressive strength, existing technologies generally use a single homogeneous rubber matrix, such as ethylene propylene diene monomer (EPDM) and chloroprene rubber (CR). These materials are prone to densification under the high pressure environment of the deep sea. When the material is subjected to continuous hydrostatic pressure, the rubber molecular chains gradually rearrange and tend to pack tightly, resulting in a reduction in free volume and making the material harder and more brittle. More importantly, this densification process is often irreversible or only partially reversible. After long-term high-pressure service, the material has a large permanent compression deformation and a significant decrease in elastic recovery, which cannot meet the stringent requirements for long-term elasticity and flexibility of deep-sea dynamic cables.

[0006] Regarding self-healing properties, existing self-healing systems are mainly based on two types: microcapsule-based and intrinsic self-healing materials. Microcapsule-based self-healing materials release a repair agent upon damage, but this method suffers from limitations in the number of repair cycles, difficulty in capsule dispersion, and impact on the mechanical properties of the matrix. Intrinsic self-healing materials are typically based on dynamic covalent bonds or supramolecular interactions, such as Diels-Alder reactions, hydrogen bonds, and metal coordination bonds. However, these dynamic bonds often require specific triggering conditions (such as heating, light exposure, pH changes, etc.), making efficient self-healing difficult to achieve in the complex environments of deep-sea environments with low temperatures, high pressures, and high humidity. Especially for microcracks generated in dynamic cables during service, existing technologies struggle to achieve rapid, in-situ self-healing without external intervention.

[0007] In terms of biofouling resistance, traditional methods mainly rely on adding antifouling coatings. These coatings typically contain heavy metal ions such as copper and zinc, or toxic substances such as organotin compounds. While they offer some antifouling effect, the release of these toxic substances can cause serious pollution to the marine ecosystem, failing to meet the requirements of international marine environmental protection conventions. Recent developments in non-toxic antifouling technologies, such as low surface energy coatings and biomimetic microstructure surfaces, still require improvement in their antifouling durability under long-term immersion conditions. Especially for equipment like deep-sea cables that require long-term (over 20 years) service, existing antifouling technologies struggle to maintain effective antifouling performance throughout their entire lifespan.

[0008] Regarding low-temperature performance, traditional deep-sea cable sheath materials such as EPDM typically have a glass transition temperature between -40°C and -50°C. In low-temperature environments such as polar deep seas, these materials approach or remain in a glassy state, resulting in a significant decrease in flexibility and fatigue resistance. While plasticizers can lower the glass transition temperature, their migration and volatilization can affect the long-term performance stability of the material. Furthermore, the addition of plasticizers often reduces the material's strength and resistance to compressive settling, making it difficult to simultaneously meet the dual requirements of low-temperature flexibility and high-pressure resistance.

[0009] Regarding the synergistic effects of multiple environmental factors, deep-sea cable sheath materials must withstand the combined effects of high pressure, low temperature, dynamic fatigue, biofouling, and chemical corrosion during actual service. Existing technologies typically optimize designs for single environmental factors, lacking a comprehensive consideration of the synergistic effects of multiple environmental factors. For example, designs that improve the compressive strength of materials often reduce their flexibility; components that enhance self-healing properties may affect the mechanical strength and aging resistance of the material; and anti-biofouling additives may interfere with the formation of dynamic cross-linked networks.

[0010] Therefore, how to achieve synergistic optimization of multiple properties in a single material system is the core challenge currently facing deep-sea cable sheath material technology. Summary of the Invention

[0011] This invention proposes a biomimetic self-healing pressure-resistant cable sheath material and its manufacturing method suitable for deep-sea floating wind power platforms. Through the synergistic effect of biomimetic principles, dynamic covalent chemistry, and multi-scale functional fillers, the material achieves a breakthrough in comprehensive performance under extreme deep-sea environments, exhibiting excellent deep-sea environmental adaptability and long-term service performance. It solves the technical problems of existing deep-sea cable sheath materials in terms of pressure resistance, self-healing ability, resistance to biofouling, and low-temperature adaptability.

[0012] The technical solution of this invention is: A biomimetic self-healing pressure-resistant cable sheath material suitable for deep-sea floating wind power platforms, composed of the following components in parts by weight: The biomimetic matrix component, consisting of 100 parts, comprises hydrogenated nitrile butadiene rubber, polyether-type thermoplastic polyurethane, and ethylene-octene copolymer, wherein the mass ratio of the hydrogenated nitrile butadiene rubber, polyether-type thermoplastic polyurethane, and ethylene-octene copolymer is (4-6):(3-4):(1-2). 10-20 parts of a dynamic reversible crosslinking system, composed of a compound containing borate ester bonds and a peroxide vulcanizing agent, wherein the mass ratio of the compound containing borate ester bonds to the peroxide vulcanizing agent is (2-3):1; 20-40 parts of deep-sea environmental functional filler, wherein the deep-sea environmental functional filler has a multi-level core-shell structure, consisting of a modified potassium titanate whisker core, a mesoporous silica intermediate layer loaded with nano-cerium oxide, and a graphene oxide shell grafted with zwitterionic polymer from the inside out. 5-12 parts of the antifouling slow-release system are metal-organic framework materials loaded with natural antifouling agents; Processing aids: 10-25 parts.

[0013] The hydrogenated nitrile butadiene rubber has an acrylonitrile content of 34%-38%, the polyether-type thermoplastic polyurethane has a hardness of 80A-90A, and the ethylene-octene copolymer has an octene content of 20%-30%.

[0014] The compound containing borate ester bonds includes at least one of pinacol phenylborate, ethylene glycol phenylborate, and glycerol phenylborate; the peroxide vulcanizing agent includes at least one of dicumyl peroxide, benzoyl peroxide, and 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane.

[0015] The modified potassium titanate whisker core has a diameter of 0.5-1 μm and an aspect ratio of 30-50; the shell thickness of the mesoporous silica intermediate layer loaded with nano-cerium oxide has 50-200 nm and the mesopore diameter has 2-10 nm; the sheet thickness of the graphene oxide shell grafted with zwitterionic polymer has 1-5 nm.

[0016] The zwitterionic polymer comprises at least one of sulfobetaine polymers and carboxybetaine polymers; the natural antifouling agent is a capsaicin derivative, which comprises at least one of N-vanillylnonanoamide and N-vanillyldecanoamide.

[0017] The metal-organic framework material is selected from at least one of MIL-101(Cr), MIL-101(Fe) and ZIF-8, and the loading of the natural antifouling agent is 30-40 wt%.

[0018] The processing aid is composed of the following components in parts by weight: 3-8 parts zinc oxide, 0.5-2 parts stearic acid, 1-5 parts antioxidant, and 5-15 parts plasticizer.

[0019] A method for preparing the above-mentioned biomimetic self-healing pressure-resistant cable sheath material suitable for deep-sea floating wind power platforms includes the following steps: Step S1: Prepare functional fillers for deep-sea environments; S1.1: The surface of potassium titanate whiskers is modified by amylation to obtain amino-modified whiskers; S1.2: A mesoporous silica intermediate layer loaded with nano-cerium oxide was coated on the surface of amino-modified whiskers using the sol-gel method; S1.3: Preparation of zwitterionic modified graphene oxide; S1.4: Amphoteric modified graphene oxide is coated onto the surface of mesoporous silica loaded with nano-cerium oxide by electrostatic self-assembly to obtain a functional filler for deep-sea environment. Step S2: Prepare an antifouling sustained-release system; Metal-organic framework materials were synthesized using a hydrothermal method, and natural antifouling agents were loaded into the pores of the metal-organic framework materials using a vacuum-assisted impregnation method. Step S3: Prepare the biomimetic matrix masterbatch; Hydrogenated nitrile butadiene rubber, polyether-type thermoplastic polyurethane, ethylene-octene copolymer, some deep-sea environmental functional fillers and processing aids are mixed to obtain a biomimetic matrix masterbatch. Step S4: Dynamic vulcanization; The biomimetic matrix masterbatch is fed into a twin-screw extruder for dynamic vulcanization. The vulcanization temperature is controlled at 150-170℃, the screw speed is 200-400rpm, and the residence time is 3-5 minutes to obtain dynamically vulcanized particles. Step S5: Final Refinement; The dynamic vulcanized particles, the remaining deep-sea environmental functional filler, the antifouling slow-release system, and the dynamic reversible crosslinking system are mixed together, and the mixing temperature is controlled to be ≤110℃ to obtain the final rubber. Step S6: Vulcanization molding; The final compound is vulcanized at a temperature of 160-180℃ for 15-25 minutes to obtain cable sheath material.

[0020] In step S1.1, the surface amination modification uses γ-aminopropyltriethoxysilane as a modifier, the modification temperature is 70-90℃, and the reaction time is 3-5 hours; in step S1.2, the sol-gel method uses tetraethyl orthosilicate as the silicon source, cerium nitrate as the cerium source, and hexadecyltrimethylammonium bromide as the template agent, the reaction pH is 9-10, the reaction temperature is 35-45℃, and the reaction time is 20-28 hours.

[0021] In step S2, the reaction temperature for the hydrothermal synthesis of metal-organic framework materials is 200-240℃, and the reaction time is 6-10 hours; the impregnation time for the vacuum-assisted impregnation method is 10-15 hours.

[0022] In step S5, the mixing temperature is 90-110℃ and the mixing time is 4-8 minutes; in step S6, the vulcanization molding is carried out using a flat vulcanizing machine and the vulcanization pressure is 10-20MPa.

[0023] The positive effects of this invention: First, in terms of compressive strength, the biomimetic microphase separation structure of this invention exhibits excellent compressive self-adaptive characteristics. By simulating the microstructure of sea cucumber dermal tissue, a dual continuous phase of "rigid microregions-flexible microregions" is constructed. Under the high pressure environment of the deep sea, the rigid microregions (TPU phase) bear the main load, and their high strength modulus effectively resists material densification; the flexible microregions (HNBR / POE phase) undergo moderate deformation to dissipate energy and maintain overall flexibility. After being treated with simulated deep-sea water pressure (10MPa) for 1000 hours, the compressive permanent deformation of the material of this invention is ≤12%, and the tensile strength retention rate is ≥90%, which is far superior to traditional EPDM materials (compressive permanent deformation ≥35%, strength retention rate ≤60%). This excellent compressive strength enables the material to serve for a long time in the high pressure environment of the deep sea without performance degradation.

[0024] Secondly, regarding self-healing performance, this invention is the first to introduce dynamic covalent bonds of borate esters into deep-sea cable sheath materials, achieving water-mediated self-healing. In a seawater environment, microcracks generated in the material can self-heal within 24 hours, with a healing efficiency of ≥75% (based on elongation at break). This characteristic effectively prevents crack propagation caused by dynamic fatigue, increasing the dynamic bending life of the cable from 30 million cycles for traditional materials to over 100 million cycles. More importantly, this self-healing process requires no external intervention, relying entirely on seawater as the medium for triggering, making it highly compatible with the deep-sea environment and possessing extremely high practical value.

[0025] Third, regarding antifouling performance, the slow-release system of MOFs loaded with capsaicin derivatives in this invention achieves an ultra-long-lasting antifouling effect. The MOFs material has regular nanoscale pores, allowing for efficient loading of capsaicin derivatives. In seawater, the MOFs slowly degrade, releasing antifouling agents and forming a chemical gradient field on the material surface that resists biofouling. Capsaicin, as a natural alkaloid, effectively repels marine fouling organisms such as barnacles and mussels, and is environmentally friendly. After 18 months of sea-based testing in Qionghai, Hainan, the biofouling coverage rate of the material surface was ≤5%, while the biofouling coverage rate of ordinary rubber sheaths was ≥85%. This long-lasting antifouling performance can significantly reduce cable maintenance costs and extend service life.

[0026] Fourth, regarding low-temperature performance, this invention, through a ternary compound of HNBR / TPU / POE and a dynamic vulcanization process, lowers the glass transition temperature (Tg) of the material to -65℃, while maintaining an elongation at break of ≥300% at -60℃, meeting the requirements of polar deep-sea wind power development. This excellent low-temperature performance stems from the saturated molecular structure of HNBR, the low-temperature toughening effect of POE, and the synergistic effect of the microphase separation structure, enabling the material to maintain good flexibility and fatigue resistance even at extremely low temperatures.

[0027] Fifth, regarding aging resistance, the nano-cerium oxide in the multi-level core-shell functional filler of this invention, through... The cyclic capture of free radicals delays matrix aging; the zwitterionic modified graphene oxide shell extends the penetration path of water molecules and corrosive media. After 1008 hours of hot air aging (100℃), the material retains ≥88% of its tensile strength and ≥85% of its elongation at break, demonstrating excellent aging resistance.

[0028] Sixth, regarding environmental performance, all components of this invention are halogen-free and non-toxic materials, and the antifouling system uses natural capsaicin derivatives, fully complying with the Stockholm Convention on Persistent Organic Pollutants and international marine environmental protection requirements. Compared with traditional heavy metal antifouling agents, the antifouling system of this invention has no negative impact on the marine ecological environment, achieving a perfect balance between high performance and environmental friendliness. Attached Figure Description

[0029] Figure 1 This is a schematic diagram of the biomimetic microphase separation structure according to an embodiment of the present invention; the schematic diagram of the biomimetic microphase separation structure shows the three-phase structure of the HNBR continuous phase matrix, the TPU rigid micro-dispersed phase, and the POE interface phase; Figure 2 This is a schematic diagram of the multi-level core-shell structure of the deep-sea environmental functional filler according to an embodiment of the present invention; the multi-level core-shell structure of the deep-sea environmental functional filler includes a potassium titanate whisker core, a mesoporous silica-supported cerium oxide intermediate layer, and a zwitterionic modified graphene oxide shell. Figure 3 This is a schematic diagram of the self-healing mechanism of the dynamic reversible cross-linked network in an embodiment of the present invention; the self-healing mechanism of the dynamic reversible cross-linked network shows the initial state, the hydrolysis of borate ester bonds when cracks occur, and the network recombination after self-healing is completed; Figure 4 This is a schematic diagram of the material preparation process in an embodiment of the present invention; the material preparation process flow diagram shows the complete process from raw material preparation to final vulcanization molding. Detailed Implementation

[0030] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be described in detail below with reference to specific embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention.

[0031] A biomimetic self-healing pressure-resistant cable sheath material suitable for deep-sea floating wind power platforms, composed of the following components in parts by weight: The biomimetic matrix component, consisting of 100 parts, comprises hydrogenated nitrile butadiene rubber, polyether-type thermoplastic polyurethane, and ethylene-octene copolymer, wherein the mass ratio of the hydrogenated nitrile butadiene rubber, polyether-type thermoplastic polyurethane, and ethylene-octene copolymer is (4-6):(3-4):(1-2). 10-20 parts of a dynamic reversible crosslinking system, composed of a compound containing borate ester bonds and a peroxide vulcanizing agent, wherein the mass ratio of the compound containing borate ester bonds to the peroxide vulcanizing agent is (2-3):1; 20-40 parts of deep-sea environmental functional filler, wherein the deep-sea environmental functional filler has a multi-level core-shell structure, consisting of a modified potassium titanate whisker core, a mesoporous silica intermediate layer loaded with nano-cerium oxide, and a graphene oxide shell grafted with zwitterionic polymer from the inside out. 5-12 parts of the antifouling slow-release system are metal-organic framework materials loaded with natural antifouling agents; Processing aids: 10-25 parts.

[0032] The hydrogenated nitrile butadiene rubber has an acrylonitrile content of 34%-38%, the polyether-type thermoplastic polyurethane has a hardness of 80A-90A, and the ethylene-octene copolymer has an octene content of 20%-30%.

[0033] The compound containing borate ester bonds includes at least one of pinacol phenylborate, ethylene glycol phenylborate, and glycerol phenylborate; the peroxide vulcanizing agent includes at least one of dicumyl peroxide, benzoyl peroxide, and 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane.

[0034] The modified potassium titanate whisker core has a diameter of 0.5-1 μm and an aspect ratio of 30-50; the shell thickness of the mesoporous silica intermediate layer loaded with nano-cerium oxide has 50-200 nm and the mesopore diameter has 2-10 nm; the sheet thickness of the graphene oxide shell grafted with zwitterionic polymer has 1-5 nm.

[0035] The zwitterionic polymer comprises at least one of sulfobetaine-type polymers and carboxybetaine-type polymers; the natural antifouling agent is a capsaicin derivative, which comprises at least one of N-vanillylnonanoamide and N-vanillyldecanoamide.

[0036] The metal-organic framework material is selected from at least one of MIL-101(Cr), MIL-101(Fe), and ZIF-8, and the loading of the natural antifouling agent is 30-40 wt%.

[0037] The processing aid is composed of the following components in parts by weight: 3-8 parts zinc oxide, 0.5-2 parts stearic acid, 1-5 parts antioxidant, and 5-15 parts plasticizer.

[0038] A method for preparing the above-mentioned biomimetic self-healing pressure-resistant cable sheath material suitable for deep-sea floating wind power platforms, characterized by comprising the following steps: Step S1: Prepare functional fillers for deep-sea environments; S1.1: The surface of potassium titanate whiskers is modified by amylation to obtain amino-modified whiskers; S1.2: A mesoporous silica intermediate layer loaded with nano-cerium oxide was coated on the surface of amino-modified whiskers using the sol-gel method; S1.3: Preparation of zwitterionic modified graphene oxide; S1.4: Amphoteric modified graphene oxide is coated onto the surface of mesoporous silica loaded with nano-cerium oxide by electrostatic self-assembly to obtain a functional filler for deep-sea environment. Step S2: Prepare an antifouling sustained-release system; Metal-organic framework materials were synthesized using a hydrothermal method, and natural antifouling agents were loaded into the pores of the metal-organic framework materials using a vacuum-assisted impregnation method. Step S3: Prepare the biomimetic matrix masterbatch; Hydrogenated nitrile butadiene rubber, polyether-type thermoplastic polyurethane, ethylene-octene copolymer, some deep-sea environmental functional fillers and processing aids are mixed to obtain a biomimetic matrix masterbatch. Step S4: Dynamic vulcanization; The biomimetic matrix masterbatch is fed into a twin-screw extruder for dynamic vulcanization. The vulcanization temperature is controlled at 150-170℃, the screw speed is 200-400rpm, and the residence time is 3-5 minutes to obtain dynamically vulcanized particles. Step S5: Final Refinement; The dynamic vulcanized particles, the remaining deep-sea environmental functional filler, the antifouling slow-release system, and the dynamic reversible crosslinking system are mixed together, and the mixing temperature is controlled to be ≤110℃ to obtain the final rubber. Step S6: Vulcanization molding; The final compound is vulcanized at a temperature of 160-180℃ for 15-25 minutes to obtain cable sheath material.

[0039] In step S1.1, the surface amination modification uses γ-aminopropyltriethoxysilane as a modifier, the modification temperature is 70-90℃, and the reaction time is 3-5 hours; in step S1.2, the sol-gel method uses tetraethyl orthosilicate as the silicon source, cerium nitrate as the cerium source, and hexadecyltrimethylammonium bromide as the template agent, the reaction pH is 9-10, the reaction temperature is 35-45℃, and the reaction time is 20-28 hours.

[0040] In step S2, the reaction temperature for the hydrothermal synthesis of metal-organic framework materials is 200-240℃, and the reaction time is 6-10 hours; the impregnation time for the vacuum-assisted impregnation method is 10-15 hours.

[0041] In step S5, the mixing temperature is 90-110℃ and the mixing time is 4-8 minutes.

[0042] In step S6, the vulcanization molding is performed using a flat vulcanizing machine with a vulcanization pressure of 10-20 MPa. Example 1

[0043] This embodiment provides a biomimetic self-healing pressure-resistant cable sheath material suitable for deep-sea floating wind power platforms, comprising the following components by weight: Bionic matrix composition: 100 parts, consisting of 50 parts hydrogenated nitrile butadiene rubber (HNBR, acrylonitrile content 36%), 35 parts polyether thermoplastic polyurethane (TPU, hardness 85A), and 15 parts ethylene-octene copolymer (POE, octene content 25%). Dynamic reversible crosslinking system: 14 parts, composed of 10 parts of pinacol phenylborate and 4 parts of dicumyl peroxide (DCP); Deep-sea environment functional packing material: 30 parts, which is a composite packing material with a "multi-level core-shell-gradient channel" structure; Antifouling sustained-release system: 8 parts, which are MIL-101(Cr) type MOF materials loaded with capsaicin derivatives; Processing aids: 18 parts, consisting of 5 parts zinc oxide, 1 part stearic acid, 2 parts antioxidant 445 (4,4'-bis(α,α-dimethylbenzyl)diphenylamine), and 10 parts dioctyl adipate.

[0044] The preparation method of the material in this embodiment includes the following steps: Step S1: Preparation of functional fillers for deep-sea environments

[0045] S1.1: Take 100g of potassium titanate whiskers (diameter 0.5-1μm, aspect ratio 30-50), disperse them in anhydrous ethanol, add 6g of γ-aminopropyltriethoxysilane (KH-550), reflux at 80℃ for 4 hours, filter after the reaction, wash with ethanol 3 times, and vacuum dry at 80℃ for 12 hours to obtain amino-modified whiskers.

[0046] S1.2: Disperse the above-mentioned amino-modified whiskers in an ethanol / water (volume ratio 1:1) mixed solution, add 2g of hexadecyltrimethylammonium bromide (CTAB) as a template agent, stir to dissolve, and then slowly add 100g of tetraethyl orthosilicate (TEOS) and cerium nitrate. The mixed solution was adjusted to pH 9-10 with ammonia and reacted at 40°C for 24 hours. After the reaction, the mixture was filtered, washed with ethanol, dried at 80°C for 12 hours, and then calcined at 550°C for 5 hours to remove the template agent, yielding a mesoporous silica-coated potassium titanate whisker intermediate loaded with nano-cerium oxide, denoted as F1-1.

[0047] S1.3: Take 10g of graphene oxide and disperse it in deionized water. Sonicate the dispersion for 1 hour, add 20g of sulfobetaine monomer and 0.5g of ammonium persulfate, and react at 70℃ for 6 hours. After the reaction is completed, centrifuge, wash and freeze dry to obtain zwitterionic modified graphene oxide, denoted as F1-2.

[0048] S1.4: Disperse 50g of F1-1 in deionized water, adjust the pH to 4.0 with hydrochloric acid, slowly add F1-2 dispersion (containing about 5g of F1-2), stir for 2 hours to complete electrostatic self-assembly, centrifuge and dry to obtain deep-sea environmental functional filler, denoted as F1.

[0049] Step S2: Preparation of antifouling slow-release system

[0050] S2.1: MIL-101(Cr) type MOFs material was synthesized by hydrothermal method. 5g of chromium nitrate nonahydrate, 3.3g of terephthalic acid and 0.4mL of hydrofluoric acid were dissolved in 60mL of deionized water, transferred to a high-pressure reactor, and reacted at 220℃ for 8 hours. After cooling, the mixture was filtered, washed with ethanol, and activated at 150℃ for 12 hours to obtain MIL-101(Cr) material.

[0051] S2.2: 10g of the above MIL-101(Cr) material was immersed in 200mL of an ethanol solution (concentration 50mg / mL) of capsaicin derivative (N-vanillylnonamide), and the material was loaded under vacuum for 12 hours. After loading, the material was centrifuged, the surface residual antifouling agent was washed with ethanol, and the material was vacuum dried at 60°C for 12 hours to obtain MOFs loaded with capsaicin derivative, denoted as R1, with a loading amount of about 35wt%.

[0052] Step S3: Preparation of biomimetic matrix masterbatch

[0053] S3.1: Weigh the following by weight: 50 parts hydrogenated nitrile butadiene rubber (HNBR, acrylonitrile content 36%), 35 parts polyether thermoplastic polyurethane (TPU, hardness 85A), 15 parts ethylene-octene copolymer (POE, octene content 25%); processing aids: 5 parts zinc oxide, 1 part stearic acid, 2 parts antioxidant 445 (4,4'-bis(α,α-dimethylbenzyl)diphenylamine), 10 parts dioctyl adipate.

[0054] S3.2: Put HNBR, TPU and POE into a mixer and plasticize at 110°C for 3 minutes. Add half of F1 (15 parts), zinc oxide, stearic acid, antioxidant and dioctyl adipate, mix for 8 minutes, discharge the glue, and obtain biomimetic matrix masterbatch M1.

[0055] Step S4: Dynamic vulcanization

[0056] S4.1: Feed M1 into a parallel co-rotating twin-screw extruder. Set the barrel temperature to: 130℃ for the feed section, 160℃ for the mixing section, and 150℃ for the die head. Set the screw speed to 300 rpm and the residence time to 4 minutes. Extrude and granulate to obtain dynamic vulcanized granules D1.

[0057] Step S5: Final Refinement

[0058] S5.1: Put D1 into an internal mixer, add the remaining F1 (15 parts) and R1 (8 parts), mix at 100°C for 6 minutes, add the dynamic reversible crosslinking system: 10 parts of pinacol phenylborate and 4 parts of dicumyl peroxide (DCP), mix for 2 minutes, discharge the glue, and obtain the final compound G1.

[0059] Step S6: Vulcanization molding

[0060] S6.1: G1 is vulcanized at 170°C for 20 minutes on a flat vulcanizing machine at a pressure of 15 MPa to obtain sample S1.

[0061] Performance testing

[0062] The performance of sample S1 prepared in this embodiment was tested, and the test results are as follows: (1) Compressive strength: After being treated for 1000 hours under simulated deep-sea water pressure (10MPa) at a depth of 1000 meters, the permanent compression deformation was 11.2% and the tensile strength retention rate was 92.3%.

[0063] (2) Self-healing performance: After being soaked in seawater for 24 hours, the scratch healing efficiency reached 78% (based on the recovery rate of elongation at break).

[0064] (3) Dynamic bending fatigue performance: Under simulated deep-sea dynamic load conditions, the dynamic bending life reaches 102 million cycles.

[0065] (4) Antifouling performance: After 18 months of actual sea application in the Qionghai waters of Hainan, the surface biofouling coverage rate was 4.2%.

[0066] (5) Low temperature performance: The glass transition temperature is -63℃ and the elongation at break is 325% at -60℃.

[0067] (6) Aging resistance: After 1008 hours of hot air aging (100℃), the tensile strength retention rate is 89.5% and the elongation at break retention rate is 87.2%. Example 2

[0068] This embodiment provides a cable sheath material with higher self-healing efficiency. The difference from Embodiment 1 is that the amount of pinacol phenylborate in the dynamic reversible crosslinking system is adjusted to 15 parts, the amount of DCP is adjusted to 5 parts, and the other components and preparation process are the same as in Embodiment 1, resulting in sample S2.

[0069] Performance test results: After immersion in seawater for 24 hours, the scratch healing efficiency reached 82%, and the dynamic bending life reached 138 million cycles. This indicates that appropriately increasing the density of the dynamic cross-linked network can significantly improve the material's self-healing ability and fatigue resistance while maintaining mechanical properties. Example 3

[0070] This embodiment provides a cable sheath material optimized for ultra-high pressure environments (water depths of over 1500 meters). The difference from Embodiment 1 is that the biomimetic matrix composition ratio is adjusted to 60 parts HNBR, 30 parts TPU, and 10 parts POE. Other components and preparation processes are the same as in Embodiment 1, resulting in sample S3.

[0071] Performance test results: After 1000 hours of treatment under simulated water depth of 1500 meters (15 MPa), the compression set was 9.6%, and the tensile strength retention rate was 94.2%. This indicates that by increasing the proportion of HNBR, improving the saturation and pressure resistance of the matrix, the ultra-high pressure adaptability of the material can be significantly improved.

[0072] Comparative Example 1

[0073] Sample D1 was prepared using traditional ethylene propylene diene monomer (EPDM) rubber as the sheath material and following a conventional vulcanization process.

[0074] Performance test results: After 1000 hours of treatment under simulated deep-sea water pressure (10MPa) at 1000 meters, the compression set was 38.5%, the tensile strength retention rate was 52.3%, the dynamic bending life was 32 million cycles, and the surface biofilm coverage rate was 87.6% after 18 months in the real sea.

[0075] Comparative Example 2

[0076] Sample D2 was obtained by using the self-healing rubber material with metal coordination bonds disclosed in Chinese patent application CN117672604A.

[0077] Performance test results: After 1000 hours of treatment under simulated deep-sea water pressure (10MPa) at 1000 meters, the compression set was 25.8% and the tensile strength retention rate was 68.7%; self-healing requires heating to 60℃ to achieve and cannot self-heal in the low-temperature environment of the deep sea.

[0078] The test results of the above embodiments and comparative examples show that the biomimetic self-healing pressure-resistant cable sheath material of the present invention has excellent comprehensive performance in the extreme environment of the deep sea, which is significantly better than the prior art.

[0079] The above description is merely a preferred embodiment of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A biomimetic self-healing pressure-resistant cable sheath material suitable for deep-sea floating wind power platforms, characterized in that... It consists of the following components in parts by weight: The biomimetic matrix component, consisting of 100 parts, comprises hydrogenated nitrile butadiene rubber, polyether-type thermoplastic polyurethane, and ethylene-octene copolymer, wherein the mass ratio of the hydrogenated nitrile butadiene rubber, polyether-type thermoplastic polyurethane, and ethylene-octene copolymer is (4-6):(3-4):(1-2). 10-20 parts of a dynamic reversible crosslinking system, composed of a compound containing borate ester bonds and a peroxide vulcanizing agent, wherein the mass ratio of the compound containing borate ester bonds to the peroxide vulcanizing agent is (2-3):1; 20-40 parts of deep-sea environmental functional filler, wherein the deep-sea environmental functional filler has a multi-level core-shell structure, consisting of a modified potassium titanate whisker core, a mesoporous silica intermediate layer loaded with nano-cerium oxide, and a graphene oxide shell grafted with zwitterionic polymer from the inside out. 5-12 parts of the antifouling slow-release system are metal-organic framework materials loaded with natural antifouling agents; Processing aids: 10-25 parts.

2. The biomimetic self-healing pressure-resistant cable sheath material suitable for deep-sea floating wind power platforms according to claim 1, characterized in that: The hydrogenated nitrile butadiene rubber has an acrylonitrile content of 34%-38%, the polyether-type thermoplastic polyurethane has a hardness of 80A-90A, and the ethylene-octene copolymer has an octene content of 20%-30%.

3. The biomimetic self-healing pressure-resistant cable sheath material suitable for deep-sea floating wind power platforms according to claim 1, characterized in that: The compound containing borate ester bonds includes at least one of pinacol phenylborate, ethylene glycol phenylborate, and glycerol phenylborate; the peroxide vulcanizing agent includes at least one of dicumyl peroxide, benzoyl peroxide, and 2,5-dimethyl-2,5-dihexane.

4. The biomimetic self-healing pressure-resistant cable sheath material suitable for deep-sea floating wind power platforms according to claim 1, characterized in that: The modified potassium titanate whisker core has a diameter of 0.5-1 μm and an aspect ratio of 30-50; the shell thickness of the mesoporous silica intermediate layer loaded with nano-cerium oxide has 50-200 nm and the mesopore diameter has 2-10 nm; the sheet thickness of the graphene oxide shell grafted with zwitterionic polymer has 1-5 nm.

5. The biomimetic self-healing pressure-resistant cable sheath material suitable for deep-sea floating wind power platforms according to claim 1, characterized in that: The zwitterionic polymer comprises at least one of sulfobetaine polymers and carboxybetaine polymers; the natural antifouling agent is a capsaicin derivative, which comprises at least one of N-vanillylnonanoamide and N-vanillyldecanoamide.

6. The biomimetic self-healing pressure-resistant cable sheath material suitable for deep-sea floating wind power platforms according to claim 1, characterized in that: The processing aid is composed of the following components in parts by weight: 3-8 parts zinc oxide, 0.5-2 parts stearic acid, 1-5 parts antioxidant, and 5-15 parts plasticizer.

7. A method for manufacturing a biomimetic self-healing pressure-resistant cable sheath material suitable for deep-sea floating wind power platforms as described in any one of claims 1-6, characterized in that... Includes the following steps: Step S1: Prepare functional fillers for deep-sea environments; S1.1: The surface of potassium titanate whiskers is modified by amylation to obtain amino-modified whiskers; S1.2: A mesoporous silica intermediate layer loaded with nano-cerium oxide was coated on the surface of amino-modified whiskers using the sol-gel method; S1.3: Preparation of zwitterionic modified graphene oxide; S1.4: Amphoteric modified graphene oxide is coated onto the surface of mesoporous silica loaded with nano-cerium oxide by electrostatic self-assembly to obtain a functional filler for deep-sea environment. Step S2: Prepare an antifouling sustained-release system; Metal-organic framework materials were synthesized using a hydrothermal method, and natural antifouling agents were loaded into the pores of the metal-organic framework materials using a vacuum-assisted impregnation method. Step S3: Prepare the biomimetic matrix masterbatch; Hydrogenated nitrile butadiene rubber, polyether-type thermoplastic polyurethane, ethylene-octene copolymer, some deep-sea environmental functional fillers and processing aids are mixed to obtain a biomimetic matrix masterbatch. Step S4: Dynamic vulcanization; The biomimetic matrix masterbatch is fed into a twin-screw extruder for dynamic vulcanization. The vulcanization temperature is controlled at 150-170℃, the screw speed is 200-400rpm, and the residence time is 3-5 minutes to obtain dynamically vulcanized particles. Step S5: Final Refinement; The dynamic vulcanized particles, the remaining deep-sea environmental functional filler, the antifouling slow-release system, and the dynamic reversible crosslinking system are mixed together, and the mixing temperature is controlled to be ≤110℃ to obtain the final rubber. Step S6: Vulcanization molding; The final compound is vulcanized at a temperature of 160-180℃ for 15-25 minutes to obtain cable sheath material.

8. A method for manufacturing a biomimetic self-healing pressure-resistant cable sheath material suitable for deep-sea floating wind power platforms according to claim 7, characterized in that: In step S1.1, the surface amination modification uses γ-aminopropyltriethoxysilane as a modifier, the modification temperature is 70-90℃, and the reaction time is 3-5 hours; in step S1.2, the sol-gel method uses tetraethyl orthosilicate as the silicon source, cerium nitrate as the cerium source, and hexadecyltrimethylammonium bromide as the template agent, the reaction pH is 9-10, the reaction temperature is 35-45℃, and the reaction time is 20-28 hours.

9. A method for manufacturing a biomimetic self-healing pressure-resistant cable sheath material suitable for deep-sea floating wind power platforms according to claim 7, characterized in that: In step S2, the reaction temperature for the hydrothermal synthesis of metal-organic framework materials is 200-240℃, and the reaction time is 6-10 hours; the impregnation time for the vacuum-assisted impregnation method is 10-15 hours.

10. A method for manufacturing a biomimetic self-healing pressure-resistant cable sheath material suitable for deep-sea floating wind power platforms according to claim 7, characterized in that: In step S5, the mixing temperature is 90-110℃ and the mixing time is 4-8 minutes; in step S6, the vulcanization molding is carried out using a flat vulcanizing machine and the vulcanization pressure is 10-20MPa.

Images