A luminescent intelligent detection supramolecular polyethylene fishing line wear-resistant coating and a preparation method thereof

Abstract

The application discloses a luminescent intelligent detection supramolecular polyethylene fishing line wear-resistant coating and a preparation method thereof, and relates to the technical field of fishing line functional coating and intelligent material. A urea-based pyrimidone grafted polycaprolactone supramolecular resin is used as a base body, a 'luminescence-sensing-wear resistance' integrated composite functional unit is constructed, and the coating is prepared through plasma interface modification and dip coating curing process. The application has the advantages that four-in-one function integration of long afterglow light visualization, corrosion intelligent monitoring, efficient self-repair and excellent wear resistance is realized simultaneously, the industry pain points of poor wear resistance, no self-repairing ability, single function and weak adhesion with the base body of the traditional luminescent fishing line coating are solved, through multi-mechanism synergistic wear-resistant design, the self-repairing efficiency of more than 90% is realized while the high hardness and low friction coefficient of the coating are ensured, and the service life of the fishing line is greatly prolonged.

Description

Technical Field

[0001] This invention relates to the field of functional coatings for fishing lines and smart materials, specifically to a wear-resistant coating for a luminescent smart detection supramolecular polyethylene fishing line and its preparation method. Background Technology

[0002] Polyethylene fishing lines are widely used in fishing and aquaculture due to their lightweight, high strength, and good corrosion resistance. When fishing at night or in deep water, a luminescent coating is needed to visualize the line's position. However, traditional luminescent fishing line coatings have several technical drawbacks: First, they have poor abrasion resistance, easily scratched and peeling from casting, pulling, and underwater friction, causing rapid decay of luminescence and polluting the aquatic environment. Second, they lack self-healing capabilities, requiring frequent line replacements after damage, increasing operating costs. Third, the luminescent material has poor compatibility with the substrate, easily agglomerating and affecting luminescence uniformity. Fourth, they only provide passive visualization, unable to reflect corrosion processes in complex environments such as oceans and saline-alkali lands, leading to corrosion diffusion and deterioration of the fishing line's performance. Fifth, their abrasion resistance mechanism is singular, unable to simultaneously resist abrasive wear, adhesive wear, and fatigue wear, limiting their service life. In existing technologies, supramolecular materials can achieve self-healing through dynamic reversible non-covalent interactions, but they are not effectively integrated with luminescence, corrosion sensing, and wear resistance. Rare earth terbium complexes have excellent fluorescence response characteristics and can achieve corrosion sensing, but they lack targeted wear resistance design and luminescence synergistic optimization. Traditional wear-resistant coatings mostly rely on single high-hardness fillers, which are prone to hardness and brittleness, and do not take into account intelligent functions. Therefore, developing a supramolecular polyethylene fishing line coating with p-hydroxybenzoic acid-uric acid terbium as the core sensing and luminescence unit, integrating efficient self-healing, long afterglow luminescence, intelligent corrosion early warning, and excellent wear resistance, has become an urgent direction to solve the functional needs in the fishing field. To this end, we propose a luminescent intelligent detection supramolecular polyethylene fishing line wear-resistant coating and its preparation method. Summary of the Invention

[0003] The purpose of this invention is to provide a light-emitting intelligent detection supramolecular polyethylene fishing line wear-resistant coating and its preparation method.

[0004] To achieve the above objectives, the present invention provides the following technical solution: a wear-resistant coating for a luminescent intelligent detection supramolecular polyethylene fishing line, wherein the core components of the wear-resistant coating include the following components: 10-15 parts of supramolecular matrix resin, 5-8 parts of luminescent-sensing-wear-resistant composite functional unit, 1-3 parts of interface modifier, 2-4 parts of wear-resistant reinforcing agent, 0.5-2 parts of auxiliary additives, and 60-80 parts of solvent; The supramolecular matrix resin is ureidopyrimidinone (UPy) grafted with polycaprolactone (PCL), which forms a dynamic cross-linked network through quadruple hydrogen bonds; The light-emitting-sensing-wear-resistant composite functional unit is p-hydroxybenzoic acid-uric acid terbium, SrAl2O4:Eu 2+ ,Dy 3+ A composite system of nano-Al2O3, in which p-hydroxybenzoic acid-uric acid terbium and SrAl2O4:Eu 2+ ,Dy 3+ The mass ratio is 1:2 to 1:4, and the mixture of p-hydroxybenzoic acid-uric acid terbium and SrAl2O4:Eu 2+ ,Dy 3+ The mass ratio of the composite luminescent system to nano-Al2O3 is 7:3 to 8:2, and nano-Al2O3 accounts for 20% to 30% of the total mass of the composite functional unit. The interface modifier is dopamine-modified polyethylene glycol (PEG). The wear-resistant reinforcing agent is composed of PTFE micro powder and PE wax in a mass ratio of 1:1 to 1:2. The auxiliary additives include antioxidant 1010, ultraviolet absorber UV-327, and polycarboxylate dispersant, with a mass ratio of 1:1:0.5 to 1. The solvent is a mixture of tetrahydrofuran (THF) and N,N-dimethylformamide (DMF), with a volume ratio of tetrahydrofuran to N,N-dimethylformamide of 3:1 to 5:1.

[0005] As a further embodiment of the present invention: the supramolecular matrix resin is prepared by the following method: polycaprolactone diol and 2-isocyanoethyl methacrylate are reacted under the catalysis of dibutyltin dilaurate to generate isocyanate-terminated PCL prepolymer, and then ureidopyrimidinone (UPy) is added for grafting reaction. The reaction temperature is 70-80°C and the reaction time is 3-5 h.

[0006] As a further aspect of the present invention: the light-emitting-sensing-wear-resistant composite functional unit is prepared by the following method, including the following steps: S1. Preparation of p-hydroxybenzoic acid-uric acid terbium rare earth complex: p-hydroxybenzoic acid, uric acid, and TbCl3·6H2O were dissolved separately in anhydrous ethanol by ultrasonic dissolution. The pH was adjusted to 6-7 with dilute NaOH solution. After mixing, the mixture was placed in a polytetrafluoroethylene liner and reacted in a vacuum autoclave at 80-90℃ for 72-84h. The mixture was filtered and washed 3-5 times and dehydrated at 60-80℃ and vacuum degree ≤0.1MPa for 8-12h. S2, Preparation of p-hydroxybenzoic acid-uric acid terbium, SrAl2O4:Eu 2+ ,Dy 3+ Composite system: SrAl2O4:Eu 2+ ,Dy 3 +Dispersed in an ethanol solution containing ammonia, ultrasonically dispersed for 30-60 min to obtain a dispersion with a concentration of 5-10 mg / mL, p-hydroxybenzoic acid-terbium urate powder is added according to the mass ratio, stirred evenly, and then silane coupling agent KH550 is added. The amount of KH550 is 1%-3% of the total mass of the composite system, and stirring is continued for 1-2 h. S3. Preparation of luminescent-sensing-wear-resistant composite functional unit: The composite system obtained in step S2 is mixed with nano-Al2O3 at a mass ratio of 7:3 to 8:2. After ultrasonic dispersion for 40 to 60 min, tetraethyl orthosilicate is added. The mass-volume ratio of tetraethyl orthosilicate to the mixed system is 1.5 to 2 mL: 1 g. The mixture is stirred and reacted at 50 to 60 °C for 2 to 3 h. After centrifugation and washing, the mixture is dried at 80 to 100 °C for 2 to 4 h to obtain the luminescent-sensing-wear-resistant composite functional unit.

[0007] As a further aspect of the present invention: the wear-resistant coating of the polyethylene fishing line undergoes the following pretreatment: the polyethylene fishing line is placed in a plasma treatment device, with Ar / O2 mixed gas as the plasma source, power 100-150W, treatment time 2-5min, and then immersed in 1wt% dopamine-modified PEG solution at room temperature for 1-2h, and then dried at 60℃ for 30-60min.

[0008] In addition, this application also provides a method for preparing a wear-resistant coating of luminescent intelligent detection supramolecular polyethylene fishing line, the preparation method comprising the following steps: Step 1: Prepare supramolecular matrix resin for later use; Step 2: Prepare a light-emitting-sensing-wear-resistant composite functional unit for later use; Step 3: Pre-treat the polyethylene fishing line for later use; Step 4: Preparation of coating solution: Add supramolecular matrix resin to mixed solvent, stir to dissolve, and then add luminescence-sensing-wear-resistant composite functional unit, interface modifier, wear-resistant enhancement agent and auxiliary additives in sequence. Disperse ultrasonically for 40-60 minutes to obtain a uniform coating solution. Step 5, Coating and Curing: The pretreated polyethylene fishing line is immersed in the coating solution using the dip coating method at a speed of 5-10 mm / s. After being removed, it is dried at room temperature for 24 hours, and then placed in an oven at 80-100℃ for 12 hours to cure, forming a coating with a thickness of 5-20 μm. Step 6, Post-processing: Place the cured fishing line in a vacuum drying oven and vacuum dry at 60℃ for 12-24 hours to remove residual solvent and obtain the finished product.

[0009] As a further aspect of the present invention, the wear-resistant coating must meet the following performance indicators: repair efficiency ≥90% after 2 hours at 60℃, afterglow time ≥12 hours, fluorescence intensity change rate at 548nm in corrosive environment ≥28%, cross-cut test grade 0, wear rate ≤1.8% after 1000 cycles of 500g load test in Taber abrasion tester, luminescence intensity retention rate ≥89% after immersion in 3.5% NaCl solution for 30 days, no obvious corrosion after 100 hours of ASTM B117-23 standard salt spray test, pencil hardness ≥3H, coefficient of friction ≤0.25. Qualified coatings are retained, and unqualified coatings are discarded.

[0010] As a further aspect of the present invention: the luminescent intelligent detection supramolecular wear-resistant coating achieves functional integration through the synergistic effect of multiple components, the functions of each component being as follows: Matrix phase: UPy grafted PCL supramolecular resin constructs a dynamic cross-linking network through quadruple hydrogen bonds, providing the coating with efficient self-healing ability. At the same time, it acts as a carrier to ensure the uniform dispersion of various functional components. Its flexible segments can buffer frictional impact and inhibit fatigue wear. Luminescent-sensing-wear-resistant phase: p-hydroxybenzoic acid-uric acid terbium, SrAl2O4:Eu 2+ ,Dy 3+ The composite system of nano-Al2O3, p-hydroxybenzoic acid-terbium urate is sensitive to the pH value of the corrosive environment, and at 548 nm (Tb 3+ Characteristic fluorescence peaks) synchronously change fluorescence intensity to achieve visual monitoring, SrAl2O4:Eu 2+ ,Dy 3+ To ensure long afterglow luminescence, nano-Al2O3 (Mohs hardness 9) forms a wear-resistant skeleton to block abrasive cutting. After modification with a coupling agent, the compatibility of the three components is significantly improved. Interface-modified phase: Dopamine-modified PEG forms a coordination effect with the surface of polyethylene fishing line through catechol groups, which significantly improves the coating adhesion, solves the problem of interfacial bonding between non-polar matrix and coating, and avoids coating peeling off during friction. Wear-resistant reinforcing phase: PTFE micro powder and PE wax synergistically form a lubricating film, reducing the surface friction coefficient of the coating (from 0.5 to 0.8 to 0.1 to 0.25), inhibiting adhesive wear. At the same time, PE wax acts as a nucleating agent to promote matrix crystallization, further improving the coating hardness. Auxiliary phase: Antioxidant 1010 and UV-327 synergistically improve the aging resistance of the coating, while polycarboxylate dispersants prevent the aggregation of functional components, ensuring the uniformity and stability of the coating, and preventing fluorescence quenching caused by the aggregation of fluorescent dyes.

[0011] As a further aspect of the present invention: the preparation process consists of six core steps, with key parameters strictly controlled to ensure functional synergy. S11. Synthesis of supramolecular matrix resin: Through stepwise polymerization and grafting reaction, the reaction temperature and time are precisely controlled to ensure that the UPy groups are fully grafted to form a stable dynamic hydrogen bond network, taking into account both self-healing ability and mechanical toughness, and avoiding the increase of coating brittleness due to excessive crosslinking density. S21. Preparation of the luminescent-sensing-wear-resistant composite functional unit: First, a high-purity p-hydroxybenzoic acid-uric acid terbium rare earth complex is prepared, and then combined with SrAl2O4:Eu 2+ ,Dy 3+ By modifying the composite with coupling agents, and finally adding nano-Al2O3, an integrated unit of "luminescence-sensing-wear resistance" is constructed. Through chemical bonding and coating modification, agglomeration and shedding are avoided. S31. Fishing line pretreatment: Plasma treatment enhances the surface activity and polarity of PE, introduces active groups such as hydroxyl groups, and dopamine-modified PEG immersion further strengthens the interfacial bonding through catechol-metal coordination, laying the foundation for coating adhesion and reducing the risk of interfacial peeling during friction. S41. Coating solution preparation: Functional components are added in stages. First, the matrix resin is dissolved, and then the composite functional unit, interface modifier, wear-resistant reinforcing agent and auxiliary additives are added in sequence. Ultrasonic dispersion (40-60 min) is used to ensure uniform mixing of each component, especially to ensure the uniform dispersion of wear-resistant filler and luminescent-sensing components, and to avoid performance defects caused by excessively high local concentrations. S51. Coating and curing: Control the dipping speed (5-10mm / s) and curing parameters. After drying at room temperature for 24 hours, heat at 80-100℃ for 12 hours to ensure uniform coating thickness and good density (porosity <5%), while avoiding high temperature damage to the structure of functional components and promoting supramolecular network and interface bonding. S61. Post-treatment: Vacuum drying at 60℃ for 12-24h removes residual solvent, improves coating stability and density, further enhances wear resistance and corrosion resistance, and avoids internal defects in the coating caused by residual solvent.

[0012] Compared with the prior art, the beneficial effects of the present invention by adopting the above technical solution are as follows: 1. This invention constructs a composite functional unit integrating luminescence, sensing, and wear resistance by using supramolecular matrix resin as a continuous phase carrier. It synergistically integrates four core functions: long-afterglow luminescence visualization, intelligent corrosion monitoring, coating damage self-repair, and long-lasting wear protection. This solves the core defect of traditional luminescent fishing line coatings, which can only achieve basic position visualization and cannot simultaneously complete corrosion early warning, damage self-repair, and wear protection. It can achieve full-dimensional functional protection of fishing lines without additional supporting testing equipment, fully adapting to the diverse usage needs of complex fishing scenarios such as nighttime, deep water, and marine saline-alkali land, and greatly improving the comprehensive performance and scenario adaptability of fishing line coatings.

[0013] 2. This invention integrates a quadruple wear-resistant mechanism: a rigid skeleton supporting Al2O3, lubricating and friction-reducing PTFE / PE wax, a toughening supramolecular network, and interface-strengthening dopamine PEG. It uses a rigid wear-resistant filler to construct the coating's wear-resistant skeleton to block abrasive cutting, lubricating components to form a continuous lubricating film to reduce interfacial friction, a supramolecular dynamic network to buffer frictional impact, and an interface modifier to strengthen the adhesion between the coating and the fishing line substrate. This solves the problem of traditional fishing line coatings having a single wear-resistant mechanism, unable to simultaneously resist multiple forms of wear, and prone to scratches, peeling, and rapid performance degradation. It achieves comprehensive suppression of multiple types of wear, effectively avoiding interfacial peeling and structural damage during coating friction, and significantly extending the service life of the fishing line.

[0014] 3. This invention achieves uniform dispersion of functional components in the matrix resin by composite modification of rare earth luminescent complexes and long-afterglow luminescent materials, and integrated coating design with wear-resistant fillers, combined with dispersing agents. This solves the defects of traditional luminescent coatings, such as poor compatibility between luminescent materials and the matrix, easy agglomeration, passive luminescence visualization, and inability to intelligently respond to corrosive environments. It ensures the long-term stable long-afterglow luminescence performance of the coating, realizes intelligent fluorescence response in corrosive environments, and effectively avoids the fluorescence quenching problem caused by the agglomeration of luminescent components. It significantly improves the uniformity, stability, and intelligent sensing capability of coating luminescence.

[0015] 4. This invention utilizes the flexible segment design of a supramolecular dynamic cross-linked network, combined with the reinforcing effect of rigid wear-resistant fillers and the adhesion-enhancing effect of interface modifiers, to synergistically balance the hardness, toughness, self-healing performance, and intelligent responsiveness of the coating. This solves the common problem of traditional wear-resistant coatings being hard and brittle, and the inability to simultaneously achieve wear resistance, mechanical toughness, and damage self-healing performance. It ensures that the coating has excellent scratch and wear resistance, achieves efficient self-healing after damage, and maintains stable intelligent sensing performance in complex corrosive environments, thus achieving synergistic optimization and balance of multiple core properties of the coating.

[0016] 5. This invention uses environmentally friendly coating components free of toxic and harmful substances to chemically bond and coat functional fillers. Simultaneously, it employs a simple, parameter-controllable dip-coating process to prepare the coating. This solves the problems of traditional coatings where functional fillers easily detach and pollute the water environment, the preparation process is complex and costly, the coating thickness is difficult to precisely control, and it is unsuitable for large-scale production. It effectively avoids water pollution caused by functional component detachment during coating use, while significantly simplifying the preparation process, allowing for precise control of coating thickness, and eliminating the need for complex supporting equipment during production, thus significantly reducing production costs and demonstrating excellent adaptability to large-scale production.

[0017] 6. This invention, through the synergistic functional design of multiple components in the coating, takes into account the coating's long afterglow luminescence performance, intelligent corrosion sensing capability, long-lasting wear resistance and protection, and damage self-repair capability. It solves the defects of traditional fishing line coatings, such as poor environmental adaptability, inability to meet the usage requirements of different fishing scenarios, and easy performance degradation in complex environments such as night, deep water, and high-salt corrosion in the ocean. It can meet the visualization requirements of night and deep water fishing, and can adapt to complex corrosive and high-friction environments such as the ocean and saline-alkali land. At the same time, it can be extended to cable protection scenarios such as aquaculture and marine monitoring, greatly expanding the coating's application scope and environmental adaptability. Attached Figure Description

[0018] Figure 1 This is a schematic diagram of the process flow for preparing the intelligent detection supramolecular wear-resistant coating in an embodiment of the present invention; Figure 2 This is a schematic diagram of the coating microstructure in an embodiment of the present invention; Figure 3 This is a schematic diagram illustrating the performance test comparison in an embodiment of the present invention. Detailed Implementation

[0019] The specific embodiments of the present invention will be further described below with reference to the accompanying drawings. It should be noted that the description of these embodiments is for the purpose of helping to understand the present invention, but does not constitute a limitation of the present invention.

[0020] Furthermore, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0021] Please see the appendix Figure 1 - Appendix Figure 3 The present invention discloses a light-emitting intelligent detection supramolecular polyethylene fishing line wear-resistant coating. The core components of the wear-resistant coating include the following components: 10-15 parts of supramolecular matrix resin, 5-8 parts of light-emitting-sensing-wear-resistant composite functional unit, 1-3 parts of interface modifier, 2-4 parts of wear-resistant reinforcing agent, 0.5-2 parts of auxiliary additives, and 60-80 parts of solvent. The supramolecular matrix resin is ureidopyrimidinone (UPy) grafted with polycaprolactone (PCL), which forms a dynamic cross-linked network through quadruple hydrogen bonds; The luminescent-sensing-wear-resistant composite functional unit is p-hydroxybenzoic acid-uric acid terbium and SrAl2O4:Eu 2+ ,Dy 3+ A composite system of nano-Al2O3, in which p-hydroxybenzoic acid-uric acid terbium and SrAl2O4:Eu 2+ ,Dy 3+ The mass ratio is 1:2 to 1:4, and the mixture of p-hydroxybenzoic acid-uric acid terbium and SrAl2O4:Eu 2+ ,Dy3+ The mass ratio of the composite luminescent system to nano-Al2O3 is 7:3 to 8:2, and nano-Al2O3 accounts for 20% to 30% of the total mass of the composite functional unit. The interface modifier is dopamine-modified polyethylene glycol (PEG); The wear-resistant reinforcing agent is composed of PTFE micro powder and PE wax in a mass ratio of 1:1 to 1:2; The auxiliary additives include antioxidant 1010, ultraviolet absorber UV-327 and polycarboxylate dispersant, with a mass ratio of 1:1:0.5 to 1; The solvent is a mixture of tetrahydrofuran (THF) and N,N-dimethylformamide (DMF), with a volume ratio of tetrahydrofuran to N,N-dimethylformamide of 3:1 to 5:1.

[0022] Example 1 By weight, the raw material composition is as follows: 12 parts supramolecular matrix resin, 6 parts luminescent-sensing-wear-resistant composite functional unit, 2 parts interface modifier, 3 parts wear-resistant reinforcing agent (PTFE micro powder to PE wax mass ratio 1:1.5), 1 part auxiliary additive (antioxidant 1010, UV-327 and polycarboxylate dispersant mass ratio 1:1:0.7), and 70 parts mixed solvent (THF to DMF volume ratio 4:1).

[0023] Preparation steps: Preparation of supramolecular matrix resin: Polycaprolactone diol and 2-isocyanoethyl methacrylate were reacted under the catalysis of dibutyltin dilaurate to generate isocyanate-terminated PCL prepolymer, and then ureidopyrimidinone (UPy) was added. The reaction was carried out at 75°C for 4 hours to obtain UPy-grafted PCL supramolecular matrix resin. Fabrication of a light-emitting-sensing-wear-resistant composite functional unit: Preparation of p-hydroxybenzoic acid-uric acid terbium: p-hydroxybenzoic acid, uric acid, and TbCl3·6H2O were dissolved in anhydrous ethanol, and the pH was adjusted to 6.5 with dilute NaOH solution. After mixing, the mixture was placed in a polytetrafluoroethylene liner and reacted in a vacuum autoclave at 85℃ for 78h. After filtration and washing 5 times, water was removed for 10h at 70℃ and vacuum degree ≤0.1MPa. p-Hydroxybenzoic acid-uric acid terbium, SrAl2O4:Eu 2+ ,Dy 3+ Preparation of composite system with nano-Al2O3: SrAl2O4:Eu 2+ ,Dy 3+Dispersed in an ethanol solution containing ammonia, ultrasonically dispersed for 45 min to obtain a dispersion with a concentration of 8 mg / mL, p-hydroxybenzoic acid-terbium urate powder (mass ratio 1:3) was added, stirred evenly, and then silane coupling agent KH550 (2% of the total mass of the composite system) was added, and stirring was continued for 1.5 h. Preparation of luminescent-sensing-wear-resistant composite functional unit: The above composite system was mixed with nano Al2O3 at a mass ratio of 7.5:2.5, ultrasonically dispersed for 50 min, and then tetraethyl orthosilicate (mass-volume ratio of 1.8 mL:1 g to the mixed system) was added. The mixture was stirred at 55 °C for 2.5 h, centrifuged and washed, and then dried at 90 °C for 3 h. Fishing line pretreatment: The polyethylene fishing line was placed in a plasma treatment device with Ar / O2 mixed gas as the plasma source, power 120W, treatment time 3min, and then soaked in 1wt% dopamine modified PEG solution at room temperature for 1.5h and dried at 60℃ for 45min. Coating solution preparation: 12 parts of supramolecular matrix resin were added to 70 parts of mixed solvent and stirred to dissolve. Then, 6 parts of luminescence-sensing-wear-resistant composite functional unit, 2 parts of interface modifier, 3 parts of wear-resistant reinforcing agent and 1 part of auxiliary additive were added in sequence and ultrasonically dispersed for 50 min. Coating and curing: The dip coating method was adopted, with a dip coating speed of 8 mm / s. After removal, the coating was dried at room temperature for 3 hours, and then placed in a 90℃ oven for heating and curing for 1.5 hours to form a coating with a thickness of 12 μm. Post-processing: Vacuum drying at 60℃ for 18 hours to remove residual solvent, yielding the finished product.

[0024] The performance of the finished product was tested, and the results are as follows: the repair efficiency was 94% (repaired at 60℃ for 2 hours), the afterglow time was 16 hours, and the fluorescence intensity change rate at 548nm was 35% (in a corrosive environment). The cross-cut test grade is 0, the wear rate after Taber abrasion test (500g load, 1000 cycles) is 1.3%, the pencil hardness is 3H, and the coefficient of friction is 0.22; After immersion in 3.5% NaCl solution for 30 days, the luminescence intensity retention rate was 92%, and no obvious corrosion was observed after 100 hours of salt spray testing (ASTM B117-23 standard).

[0025] Example 2 By weight, the raw material composition is as follows: 10 parts supramolecular matrix resin, 5 parts luminescent-sensing-wear-resistant composite functional unit, 1 part interface modifier, 2 parts wear-resistant reinforcing agent (PTFE micro powder and PE wax in a mass ratio of 1:1), 0.5 parts auxiliary additives (antioxidant 1010, UV-327 and polycarboxylate dispersant in a mass ratio of 1:1:0.5), and 60 parts mixed solvent (THF and DMF in a volume ratio of 3:1).

[0026] The preparation steps were the same as in Example 1, only the corresponding parameters were adjusted to the scope defined in the claims. Performance test results are as follows: repair efficiency was 91% (repaired at 60℃ for 2 hours), luminescence afterglow time was 12 hours, and the fluorescence intensity change rate at 548 nm was 28% (in a corrosive environment). The cross-cut test grade is 0, the wear rate after Taber abrasion test (500g load, 1000 cycles) is 1.8%, the pencil hardness is 3H, and the coefficient of friction is 0.25; After being soaked in 3.5% NaCl solution for 30 days, the luminescence intensity retention rate was 89%, and no obvious corrosion was observed after 100 hours of salt spray testing (ASTM B117-23 standard).

[0027] Example 3 By weight, the raw material composition is as follows: 15 parts supramolecular matrix resin, 8 parts luminescent-sensing-wear-resistant composite functional unit, 3 parts interface modifier, 4 parts wear-resistant reinforcing agent (PTFE micro powder to PE wax mass ratio 1:2), 2 parts auxiliary additives (antioxidant 1010, UV-327 and polycarboxylate dispersant mass ratio 1:1:1), and 80 parts mixed solvent (THF to DMF volume ratio 5:1).

[0028] The preparation steps were the same as in Example 1, only the corresponding parameters were adjusted to the scope defined in the claims. Performance test results are as follows: repair efficiency was 95% (repaired at 60℃ for 2 hours), luminescence afterglow time was 18 hours, and the fluorescence intensity change rate at 548 nm was 38% (in a corrosive environment). The cross-cut test grade is 0, the wear rate after Taber abrasion test (500g load, 1000 cycles) is 1.1%, the pencil hardness is 4H, and the coefficient of friction is 0.20; After being soaked in 3.5% NaCl solution for 30 days, the luminescence intensity retention rate was 94%, and no obvious corrosion was observed after 100 hours of salt spray testing (ASTM B117-23 standard).

[0029] While the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the invention. Any variations and modifications can be made by those skilled in the art without departing from the spirit and scope of the invention. Therefore, any modifications, equivalent changes, and alterations made to the above embodiments based on the technical essence of the present invention, without departing from the scope of the invention, fall within the protection scope defined by the claims of the present invention.

Claims

1. A light-emitting intelligent detection supramolecular polyethylene wear-resistant coating for fishing lines, characterized in that, The core components of the wear-resistant coating include the following: 10-15 parts of supramolecular matrix resin, 5-8 parts of luminescent-sensing-wear-resistant composite functional unit, 1-3 parts of interface modifier, 2-4 parts of wear-resistant reinforcing agent, 0.5-2 parts of auxiliary additives, and 60-80 parts of solvent. The supramolecular matrix resin is ureidopyrimidinone grafted with polycaprolactone, which forms a dynamic cross-linking network through quadruple hydrogen bonds; The light-emitting-sensing-wear-resistant composite functional unit is p-hydroxybenzoic acid-uric acid terbium, SrAl2O4:Eu 2+ ,Dy 3+ A composite system of nano-Al2O3, in which terbium p-hydroxybenzoic acid-uric acid and SrAl2O4:Eu 2+ ,Dy 3+ The mass ratio is 1:2 to 1:4, and the mixture of p-hydroxybenzoic acid-uric acid terbium and SrAl2O4:Eu 2+ ,Dy 3+ The mass ratio of the composite luminescent system to nano-Al2O3 is 7:3 to 8:2, and nano-Al2O3 accounts for 20% to 30% of the total mass of the composite functional unit. The interface modifier is dopamine-modified polyethylene glycol; The wear-resistant reinforcing agent is composed of PTFE micro powder and PE wax in a mass ratio of 1:1 to 1:

2. The auxiliary additives include antioxidant 1010, ultraviolet absorber UV-327, and polycarboxylate dispersant, with a mass ratio of 1:1:0.5 to 1. The solvent is a mixture of tetrahydrofuran and N,N-dimethylformamide, with a volume ratio of tetrahydrofuran to N,N-dimethylformamide of 3:1 to 5:

1.

2. The wear-resistant coating for a luminescent intelligent detection supramolecular polyethylene fishing line according to claim 1, characterized in that: The supramolecular matrix resin is prepared by the following method: polycaprolactone diol and 2-isocyanoethyl methacrylate are reacted under the catalysis of dibutyltin dilaurate to generate isocyanate-terminated PCL prepolymer, and then ureidopyrimidinone is added for grafting reaction. The reaction temperature is 70-80℃ and the reaction time is 3-5h.

3. The wear-resistant coating for a luminescent intelligent detection supramolecular polyethylene fishing line according to claim 1, characterized in that: The light-emitting-sensing-wear-resistant composite functional unit is prepared by the following method, including the following steps: S1. Preparation of p-hydroxybenzoic acid-uric acid terbium rare earth complex: p-hydroxybenzoic acid, uric acid, and TbCl3·6H2O were dissolved separately in anhydrous ethanol by ultrasonic dissolution. The pH was adjusted to 6-7 with dilute NaOH solution. After mixing, the mixture was placed in a polytetrafluoroethylene liner and reacted in a vacuum autoclave at 80-90℃ for 72-84h. The mixture was filtered and washed 3-5 times and dehydrated at 60-80℃ and vacuum degree ≤0.1MPa for 8-12h. S2, Preparation of p-hydroxybenzoic acid-uric acid terbium, SrAl2O4:Eu 2+ ,Dy 3+ Composite system: SrAl2O4:Eu 2+ ,Dy 3+ Dispersed in an ethanol solution containing ammonia, ultrasonically dispersed for 30-60 min to obtain a dispersion with a concentration of 5-10 mg / mL, p-hydroxybenzoic acid-terbium urate powder is added according to the mass ratio, stirred evenly, and then silane coupling agent KH550 is added. The amount of KH550 is 1%-3% of the total mass of the composite system, and stirring is continued for 1-2 h. S3. Preparation of luminescent-sensing-wear-resistant composite functional unit: The composite system obtained in step S2 is mixed with nano-Al2O3 at a mass ratio of 7:3 to 8:

2. After ultrasonic dispersion for 40 to 60 min, tetraethyl orthosilicate is added. The mass-volume ratio of tetraethyl orthosilicate to the mixed system is 1.5 to 2 mL: 1 g. The mixture is stirred and reacted at 50 to 60 °C for 2 to 3 h. After centrifugation and washing, the mixture is dried at 80 to 100 °C for 2 to 4 h to obtain the luminescent-sensing-wear-resistant composite functional unit.

4. The wear-resistant coating for a luminescent intelligent detection supramolecular polyethylene fishing line according to claim 1, characterized in that: The wear-resistant coating of the polyethylene fishing line undergoes the following pretreatment: the polyethylene fishing line is placed in a plasma treatment device with Ar / O2 mixed gas as the plasma source, power 100-150W, treatment time 2-5min, and then immersed in 1wt% dopamine-modified PEG solution at room temperature for 1-2h. After removal, it is dried at 60℃ for 30-60min.

5. The method for preparing the wear-resistant coating of luminescent intelligent detection supramolecular polyethylene fishing line according to any one of claims 1-4, characterized in that, The preparation method includes the following steps: Step 1: Prepare supramolecular matrix resin for later use; Step 2: Prepare a light-emitting-sensing-wear-resistant composite functional unit for later use; Step 3: Pre-treat the polyethylene fishing line for later use; Step 4: Preparation of coating solution: Add supramolecular matrix resin to mixed solvent, stir to dissolve, and then add luminescence-sensing-wear-resistant composite functional unit, interface modifier, wear-resistant enhancement agent and auxiliary additives in sequence. Disperse ultrasonically for 40-60 minutes to obtain a uniform coating solution. Step 5, Coating and Curing: The pretreated polyethylene fishing line is immersed in the coating solution using the dip coating method at a speed of 5-10 mm / s. After being removed, it is dried at room temperature for 24 hours, and then placed in an oven at 80-100℃ for 12 hours to cure, forming a coating with a thickness of 5-20 μm. Step 6, Post-processing: Place the cured fishing line in a vacuum drying oven and vacuum dry at 60℃ for 12-24 hours to remove residual solvent and obtain the finished product.

6. The luminescent intelligent detection supramolecular polyethylene fishing line wear-resistant coating according to claim 1, characterized in that, The wear-resistant coating must meet the following performance indicators: repair efficiency ≥90% after 2 hours at 60℃, afterglow time ≥12 hours, fluorescence intensity change rate at 548nm in corrosive environment ≥28%, cross-cut test grade 0, wear rate ≤1.8% after 1000 cycles of 500g load on a Taber abrasion tester, luminescence intensity retention rate ≥89% after immersion in 3.5% NaCl solution for 30 days, no obvious corrosion after 100 hours of ASTM B117-23 standard salt spray test, pencil hardness ≥3H, and coefficient of friction ≤0.

25. Qualified coatings will be retained, while unqualified coatings will be discarded.

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