A luminescent intelligent detection self-repairing supramolecular polyethylene fishing line coating and a preparation method thereof

Abstract

The application discloses a luminescent intelligent detection self-repairing supramolecular polyethylene fishing line coating and a preparation method thereof, and relates to the fields of fishing line functional coating and intelligent sensing technology.The coating core component comprises, by weight, 10-15 parts of a supramolecular matrix resin, 3-6 parts of a luminescent-sensing composite functional unit, 1-3 parts of an interface modifier, 0.5-2 parts of an auxiliary additive, and 60-80 parts of a solvent; the urea-based pyrimidone grafted polycaprolactone is used as the supramolecular matrix, and a rare earth complex and a long-afterglow material are used to construct the composite functional unit; and the coating adhesion is strengthened through plasma pretreatment and interface modification.The application synchronously realizes long-afterglow luminescence visualization, corrosion intelligent monitoring, efficient self-repairing and high wear resistance through multi-component cooperation and a step-by-step preparation process, solves the defects of single function, poor wear resistance and easy falling of traditional coatings, is suitable for night fishing, deep water fishing and other scenes, has simple and controllable process, and is suitable for large-scale production.

Description

Technical Field

[0001] This invention relates to the fields of functional coatings for fishing lines and intelligent sensing technology, specifically to a luminescent intelligent detection self-healing supramolecular polyethylene fishing line coating and its preparation method. Background Technology

[0002] Polyethylene (PE) 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, existing luminescent fishing line coatings have several technical drawbacks: First, they are functionally limited, only providing passive light emission and visualization, unable to reflect the corrosion process in complex aquatic environments, and lack self-healing capabilities. After being thrown or scratched, the luminescent performance rapidly and irreversibly decays, requiring frequent line replacements and resulting in high operating costs. Second, the coating has weak interfacial adhesion to the polyethylene matrix and poor wear resistance, making it prone to peeling and detachment during use. This not only causes performance failure but also pollutes the aquatic environment with the detached particles. Third, the luminescent material has poor compatibility with the resin matrix, easily leading to agglomeration, resulting in uneven light emission and poor stability, making it difficult to meet the long-term use requirements of complex corrosive environments such as deep water and the ocean. While existing technologies have included research on supramolecular self-healing materials and rare-earth luminescent materials, they have failed to effectively integrate self-healing, luminescence visualization, corrosion sensing, and high wear resistance. Furthermore, they have not conducted targeted interface optimization design for the non-polar characteristics of polyethylene fishing lines, thus failing to meet the fishing industry's demand for multifunctional, long-life, and highly stable fishing line coatings. Therefore, we propose a luminescent intelligent detection self-healing supramolecular polyethylene fishing line coating and its preparation method. Summary of the Invention

[0003] The purpose of this invention is to provide a luminescent intelligent detection self-healing supramolecular polyethylene fishing line coating and its preparation method.

[0004] To achieve the above objectives, the present invention provides the following technical solution: a luminescent intelligent detection self-healing supramolecular polyethylene fishing line coating, wherein the materials for preparing the fishing line coating, by weight, include the following components: 10-15 parts of supramolecular matrix resin, 3-6 parts of luminescent-sensing composite functional unit, 1-3 parts of interface modifier, 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 composite functional unit is Eu(DBM)3phen, SrAl2O4:Eu 2+ ,Dy 3+ The composite system, in which Eu(DBM)3phen and SrAl2O4:Eu2+ ,Dy 3+ The mass ratio is 1:2-1:4; The interface modifier is dopamine-modified polyethylene glycol (PEG). The auxiliary additives include antioxidant 1010, ultraviolet absorber UV-327 and polycarboxylate dispersant, with a mass ratio of 1:1:0.5-1. 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℃ and the reaction time is 3-5h.

[0006] As a further aspect of the present invention: the light-emitting-sensing composite functional unit is prepared by the following method, including the following steps: S1. Preparation of Eu(DBM)3phen rare earth complex: Dibenzoylmethane, o-phenanthroline, and EuCl3·6H2O were dissolved in anhydrous ethanol by ultrasonication. 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 Eu(DBM)3phen, SrAl2O4:Eu 2+ ,Dy 3+ Composite system: SrAl2O4:Eu 2+ ,Dy 3+ The dispersion was dispersed in an ethanol solution containing ammonia and ultrasonically dispersed for 30-60 min to obtain a dispersion with a concentration of 5-10 mg / mL. Eu(DBM)3phen powder was added according to the mass ratio, and after stirring evenly, silane coupling agent KH550 was added. The amount of KH550 was 1%-3% of the total mass of the composite system. Stirring was continued for 1-2 h. After centrifugation, the mixture was washed and dried at 80-100℃ for 2-4 h to obtain the luminescence-sensing composite functional unit.

[0007] As a further aspect of the present invention: the polyethylene fishing line coated with the fishing line coating needs to undergo pretreatment. The pretreatment steps are as follows: place the polyethylene fishing line in a plasma treatment device, use Ar / O2 mixed gas as the plasma source, power 100-150W, treatment time 2-5min, then immerse it in 1wt% dopamine modified PEG solution, soak at room temperature for 1-2h, and then dry it at 60℃ for 30-60min.

[0008] In addition, this application also provides a method for preparing a luminescent intelligent detection self-healing supramolecular polyethylene fishing line coating, the preparation method comprising the following steps: Step 1: Prepare supramolecular matrix resin for later use; Step 2: Prepare the luminescence-sensing composite functional unit for later use; Step 3: Pre-treat the polyethylene fishing line. 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, then add luminescent-sensing composite functional unit, interface modifier and auxiliary additives in sequence, and ultrasonically disperse for 40-60 min to obtain 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 removal, it is dried at room temperature for 2-4 hours, and then placed in an oven at 80-100℃ for 1-2 hours to form 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 coating on the fishing line needs to meet the following performance indicators: repair efficiency ≥90% after 2 hours at 60℃, afterglow time ≥12 hours, fluorescence intensity change rate at 612nm in corrosive environment ≥25%; cross-cut test grade 0; wear rate ≤2.8% after 500g load and 1000 cycles of Taber abrasion test; luminescence intensity retention rate ≥88% after immersion in 3.5% NaCl solution for 30 days; no obvious corrosion after 100 hours of salt spray test according to ASTM B117-23 standard; qualified products are retained, unqualified products are discarded.

[0010] Compared with the prior art, the beneficial effects of the present invention by adopting the above technical solution are as follows: 1. This invention systematically integrates a supramolecular matrix resin with quadruple hydrogen bond dynamic crosslinking and a composite functional unit with both long afterglow luminescence and corrosion fluorescence response. Combined with multi-component functional synergistic formulation optimization, it solves the core defects of traditional fishing line coatings, such as single function and incompatibility between functional modules. It breaks through the technical bottleneck of the inability to integrate luminescence visualization, damage self-repair, and corrosion monitoring. Ultimately, it achieves the synergistic adaptation of multi-dimensional functions of fishing line coatings, enabling performance assurance and status warning throughout the entire use of fishing lines without additional equipment.

[0011] 2. This invention addresses the shortcomings of traditional luminescent coatings, such as easy agglomeration of functional powders, poor compatibility with matrix resins, rapid decay of luminescent performance after long-term use, and insufficient stability in water-resistant environments, by modifying rare earth complexes and aluminate long-afterglow materials with silane coupling agents and combining them with synergistic dispersion optimization using dispersants. It effectively avoids problems such as uneven luminescence and detachment caused by powder agglomeration, and ultimately achieves long-term stability of the coating's luminescent performance, significantly improving the environmental tolerance and durability of the luminescent function.

[0012] 3. This invention solves the industry pain points of traditional functional coatings, such as being "hard and brittle," having poor adhesion to non-polar substrates, and being unable to simultaneously achieve wear resistance, corrosion resistance, and self-healing performance, by designing flexible segments and dynamic hydrogen bond network structures in supramolecular matrix resins, combined with plasma activation of polyethylene fishing line substrates and interface anchoring optimization of interface modifiers. It effectively buffers frictional impacts during use, avoids coating failure problems such as scratches and peeling, and ultimately achieves a synergistic improvement in coating adhesion, wear resistance, corrosion resistance, and self-healing performance.

[0013] 4. This invention solves the problems of traditional fishing line coatings by using an environmentally friendly formula system free of toxic and harmful substances, combined with a precisely controllable dip-coating process. These problems include the easy shedding of functional powders that pollute the water environment, complex and cumbersome preparation processes, inability to precisely control coating thickness, and difficulty in adapting to large-scale mass production. This avoids water pollution caused by coating shedding, simplifies the production process, and ultimately achieves green and environmentally friendly coating preparation. The coating thickness can be flexibly controlled to meet the production needs of industrial-scale mass production. 5. This invention solves the problem of traditional fishing line coatings being unable to adapt to both low-light environments with long afterglow luminescence, corrosive environments with intelligent fluorescence response, and complex working conditions with self-healing and wear and corrosion resistance. It achieves a wide range of adaptability for fishing line coatings by taking into account long afterglow luminescence in low-light environments, intelligent fluorescence response in corrosive environments, and self-healing and wear and corrosion resistance under complex working conditions. It also breaks through the limitation of a single coating being only suitable for specific fishing scenarios, and finally achieves wide adaptability of fishing line coatings for multiple scenarios, which can meet the usage needs of various recreational fishing, aquaculture and other different working conditions. Attached Figure Description

[0014] Figure 1This is a schematic diagram of the process flow for preparing the luminescent intelligent detection self-healing supramolecular 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; Figure 4 This is a schematic diagram comparing performance indicators in an embodiment of the present invention. Detailed Implementation

[0015] 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.

[0016] 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.

[0017] Please see the appendix Figure 1 -Appendix Figure 4 This invention discloses a luminescent intelligent detection self-healing supramolecular polyethylene fishing line coating. The materials used to prepare the fishing line coating, by weight, include the following components: 10-15 parts of supramolecular matrix resin, 3-6 parts of luminescent-sensing composite functional unit, 1-3 parts of interface modifier, 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 composite functional unit is Eu(DBM)3phen, SrAl2O4:Eu 2+ ,Dy 3+ The composite system, in which Eu(DBM)3phen and SrAl2O4:Eu 2+ ,Dy 3+ The mass ratio is 1:2-1:4; The interface modifier is dopamine-modified polyethylene glycol (PEG); The auxiliary additives include antioxidant 1010, ultraviolet absorber UV-327 and polycarboxylate dispersant, with a mass ratio of 1:1:0.5-1; 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.

[0018] Example 1 By weight, the raw material composition is as follows: 12 parts supramolecular matrix resin, 4 parts luminescent-sensing composite functional unit, 2 parts interface modifier, 1 part auxiliary additive (antioxidant 1010, UV-327 and polycarboxylate dispersant in a mass ratio of 1:1:0.7), and 70 parts mixed solvent (THF and DMF in a volume ratio of 4:1).

[0019] 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 the light-emitting-sensing composite functional unit: Preparation of S10 and Eu(DBM)3phen: Dibenzoylmethane, o-phenanthroline, and EuCl3·6H2O 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. The mixture was filtered and washed 5 times, and then dehydrated at 70℃ and vacuum degree ≤0.1MPa for 10h. S20, Eu(DBM)3phen, SrAl2O4:Eu 2+ ,Dy 3+ Preparation of composite system: SrAl2O4:Eu 2+ ,Dy 3+ The dispersion was dispersed in an ethanol solution containing ammonia and ultrasonically dispersed for 45 min to obtain a dispersion with a concentration of 8 mg / mL. Eu(DBM)3phen powder (mass ratio 1:3) was added and stirred evenly. Then, silane coupling agent KH550 (2% of the total mass of the composite system) was added and stirred for another 1.5 h. After centrifugation and washing, the mixture was dried at 90 °C for 3 h to obtain the luminescence-sensing composite functional unit. 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, stirred and dissolved, and then 4 parts of luminescent-sensing composite functional unit, 2 parts of interface modifier 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.

[0020] 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 612nm was 32% (in a corrosive environment). The cross-cut test grade is 0, and the wear rate after 1000 cycles in the Taber abrasion tester is 2.0%. After being soaked in 3.5% NaCl solution for 30 days, the luminescence intensity retention rate was 91%, and no obvious corrosion was observed after 100 hours of salt spray testing (ASTM B117-23 standard).

[0021] Example 2 By weight, the raw material composition is as follows: 10 parts supramolecular matrix resin, 3 parts luminescent-sensing composite functional unit, 1 part interface modifier, 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).

[0022] 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 612 nm was 25% (in a corrosive environment). The cross-cut test grade was 0, and the wear rate after 1000 cycles in the Taber abrasion tester was 2.8%. After being soaked in 3.5% NaCl solution for 30 days, the luminescence intensity retention rate was 88%, and no obvious corrosion was observed after 100 hours of salt spray testing (ASTM B117-23 standard).

[0023] Example 3 By weight, the raw material composition is as follows: 15 parts supramolecular matrix resin, 6 parts luminescent-sensing composite functional unit, 3 parts interface modifier, 2 parts auxiliary additives (antioxidant 1010, UV-327 and polycarboxylate dispersant in a mass ratio of 1:1:1), and 80 parts mixed solvent (THF and DMF in a volume ratio of 5:1).

[0024] 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 612 nm was 35% (in a corrosive environment). The cross-cut test grade is 0, and the wear rate after 1000 cycles in the Taber abrasion tester is 1.7%. After being soaked in 3.5% NaCl solution for 30 days, the luminescence intensity retention rate was 93%, and no obvious corrosion was observed after 100 hours of salt spray testing (ASTM B117-23 standard).

[0025] 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 luminescent intelligent detection self-healing supramolecular polyethylene fishing line coating, characterized in that: The materials used to prepare the fishing line coating, by weight, include the following components: 10-15 parts of supramolecular matrix resin, 3-6 parts of luminescent-sensing composite functional unit, 1-3 parts of interface modifier, 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 composite functional unit is Eu(DBM)3phen, SrAl2O4:Eu 2+ ,Dy 3+ The composite system, in which Eu(DBM)3phen and SrAl2O4:Eu 2+ ,Dy 3+ The mass ratio is 1:2-1:4; The interface modifier is dopamine-modified polyethylene glycol; The auxiliary additives include antioxidant 1010, ultraviolet absorber UV-327 and polycarboxylate dispersant, with a mass ratio of 1:1:0.5-1. 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 luminescent intelligent detection self-healing supramolecular polyethylene fishing line coating 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 luminescent intelligent detection self-healing supramolecular polyethylene fishing line coating according to claim 2, characterized in that: The light-emitting-sensing composite functional unit is prepared by the following method, including the following steps: S1. Preparation of Eu(DBM)3phen rare earth complex: Dibenzoylmethane, o-phenanthroline, and EuCl3·6H2O were dissolved in anhydrous ethanol by ultrasonication. 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 Eu(DBM)3phen, SrAl2O4:Eu 2+ ,Dy 3+ Composite system: SrAl2O4:Eu 2+ ,Dy 3+ The dispersion was dispersed in an ethanol solution containing ammonia and ultrasonically dispersed for 30-60 min to obtain a dispersion with a concentration of 5-10 mg / mL. Eu(DBM)3phen powder was added according to the mass ratio, and after stirring evenly, silane coupling agent KH550 was added. The amount of KH550 was 1%-3% of the total mass of the composite system. Stirring was continued for 1-2 h. After centrifugation, the mixture was washed and dried at 80-100℃ for 2-4 h to obtain the luminescence-sensing composite functional unit.

4. The luminescent intelligent detection self-healing supramolecular polyethylene fishing line coating according to claim 3, characterized in that: The polyethylene fishing line coated with the fishing line coating needs to undergo pretreatment. The pretreatment steps are as follows: place the polyethylene fishing line in a plasma treatment device, use Ar / O2 mixed gas as the plasma source, power 100-150W, treatment time 2-5min, then soak it in 1wt% dopamine modified PEG solution, soak it at room temperature for 1-2h, and then dry it at 60℃ for 30-60min.

5. The method for preparing the luminescent intelligent detection self-healing supramolecular polyethylene fishing line coating 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 the luminescence-sensing composite functional unit for later use; Step 3: Pre-treat the polyethylene fishing line. 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, then add luminescent-sensing composite functional unit, interface modifier and auxiliary additives in sequence, and ultrasonically disperse for 40-60 min to obtain 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 removal, it is dried at room temperature for 2-4 hours, and then placed in an oven at 80-100℃ for 1-2 hours to form 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 self-healing supramolecular polyethylene fishing line coating according to claim 1, characterized in that: The coating on the fishing line must meet the following performance indicators: repair efficiency ≥90% after 2 hours at 60℃, afterglow time ≥12 hours, fluorescence intensity change rate at 612nm in corrosive environment ≥25%; cross-cut test grade 0; wear rate ≤2.8% after 500g load and 1000 cycles of Taber abrasion test; luminescence intensity retention rate ≥88% after immersion in 3.5% NaCl solution for 30 days; no obvious corrosion after 100 hours of ASTM B117-23 standard salt spray test. Qualified products are retained, and unqualified products are discarded.

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