A phosphorus-based material hybrid polymer coating, and a preparation method and application thereof

Abstract

The application belongs to the field of high polymers and provides a phosphorus-based material hybrid polymer coating. The phosphorus-based material hybrid polymer coating comprises the following components in parts by weight: 80-105 parts of resin, 2-10 parts of phosphorus-based material photoinitiator, 1-5 parts of photoinitiator, and 1-2 parts of leveling agent, wherein the resin comprises unsaturated double / triple bonds and acrylate units. In the application, a long-acting super-hydrophilic polymer heterogeneous network coating of phosphorus-based material hybrid is designed and prepared by constructing P-C bonds under UV curing. Unlike physical blending, the covalent P-C bonds between the phosphorus-based material and the polymer are generated through UV-induced radical reaction, resulting in the phosphorus-based material being firmly embedded in the polymer structure. The migration of the phosphorus-based material is regulated by UV, so that the phosphorus-based material is enriched on the surface of the coating. The phosphorus-based material can effectively prevent water from penetrating into the coating by its good water absorption capacity.

Description

Technical Field

[0001] The invention belongs to the field of polymer technology, and in particular relates to a phosphorus-based material hybrid polymer coating, a preparation method and an application thereof. Background Art

[0002] When saturated water vapor drops below its dew point, it begins to condense, forming a mist of tiny droplets that scatters visible light. For transparent materials, surface fogging significantly reduces light transmittance, leading to undesirable malfunctions in optical applications. For example, surface fog significantly affects the accuracy of optical and analytical instruments, such as infrared microscopes and clinical laparoscopes.

[0003] Scientists have currently developed many strategies involving super-hydrophobic surfaces and super-hydrophilic surfaces to achieve effective anti-fog. Super-hydrophobic surfaces eliminate the effects of fog droplets by causing water droplets to roll off the surface quickly, but are limited by the surface's own micro / nanostructure roughness (Advanced Materials, 2020, 32: 2002710). Unlike super-hydrophobic surfaces, anti-fog coatings based on super-hydrophilic polymers avoid atomization by rapidly diffusing fog droplets into a continuous water film, thereby effectively preventing light scattering. Therefore, in the field of anti-fog, super-hydrophilic surfaces are easier, more reliable, and more promising than super-hydrophobic surfaces (Advanced Functional Materials, 2021, 31: 2006687). However, as the water film on the super-hydrophilic surface grows to a certain thickness, the polymer-based coating loses its water-soluble components, and the coating will peel off and crack due to water absorption and swelling, resulting in its anti-fog failure (Langmuir, 2012, 28: 17193-17201). Therefore, the anti-fog effect of polymer-based coatings is usually limited to a short period of time due to their insufficient water resistance.

[0004] To improve the water resistance of polymer-based coatings, water-resistant organic compounds, such as hydrophobic organic components, are often added to the coating. Unfortunately, these organic compounds often weaken the hydrophilicity of the coating, resulting in a decrease in its anti-fog ability. Balancing the hydrophilicity and water resistance of polymer-based coatings remains a significant challenge (Journal of Coatings Technology and Research, 2018, 15:149-158).

[0005] Typically, hydrophilic inorganic nanomaterials can absorb and store water without swelling, thus providing a new strategy for regulating the balance between the hydrophilicity and water resistance of polymer-based coatings (Progress in Polymer Science, 2011, 36:945-979). In order to improve the overall performance of these organic-inorganic composite materials, more strategies are needed to regulate the compatibility, dispersibility and stability of inorganic nanomaterials in polymer coatings (Chemical Society Reviews, 2011, 40:696-753).

[0006] As a class of hydrophilic two-dimensional inorganic nanomaterials, phosphorus-based materials have excellent wear resistance and water adsorption capacity. On the other hand, phosphorus-based materials have excellent compatibility with hydrophilic polymers, resulting in phosphorus-based material-polymer nanocomposites generally having good stability. Unfortunately, the binding modes of black phosphorus and polymers reported so far are mostly weak physical blending rather than strong chemical bonding, which greatly affects the various properties of polymer coatings based on phosphorus-based materials. Therefore, although polymer coatings based on phosphorus-based materials are promising superhydrophilic materials, some huge challenges still need to be overcome, especially the chemical bonding and microstructural regulation between phosphorus-based materials and polymers. Summary of the Invention

[0007] The purpose of the present invention is to provide a phosphorus-based material hybrid polymer functional coating to achieve long-term lubrication, anti-fog, self-cleaning and flow-conducting properties.

[0008] The present invention provides a phosphorus-based material hybrid polymer coating, which comprises the following components in parts by weight:

[0009]

[0010] The resin comprises unsaturated double / triple bonds and acrylate units.

[0011] Further, the resin comprises:

[0012] Resin I

[0013] Resin II

[0014] Wherein, the resin I accounts for 38% to 62.5% of the total mass of the resin, and the resin II accounts for 37.5% to 62% of the total mass of the resin;

[0015] The phosphorus-based materials include nano-scale elemental phosphorus, nano-scale transition metal phosphides and nano-scale metal phosphates.

[0016] Furthermore, the nano-scale elemental phosphorus includes one or more of nano-scale black phosphorus, nano-scale red phosphorus and nano-scale fiber phosphorus.

[0017] The nanoscale black phosphorus morphology includes one or more of black phosphorus nanosheets, black phosphorus nanoparticles, and black phosphorus quantum dots. The black phosphorus nanosheets are black phosphorus nanosheets with a thickness of 2-50 nm, the black phosphorus quantum dots are black phosphorus nanoparticles with a hydrated particle size of less than 10 nm, and the black phosphorus nanoparticles are black phosphorus nanoparticles with a hydrated particle size of 20-300 nm.

[0018] The nano-scale red phosphorus has the shape of nano red phosphorus particles, and the particle size of the red phosphorus nanoparticles is between 80-500 nm.

[0019] The nano-scale fiber phosphorus has a morphology of nano-belts, a length of 100-250 nm, a width of 50-80 nm, and a thickness of 10-30 nm.

[0020] Furthermore, the nanoscale transition metal phosphide comprises one or more of copper phosphide, cobalt phosphide, iron phosphide, manganese phosphide, molybdenum phosphide, and nickel phosphide. The nanoscale transition metal phosphide has a morphology of one or more of quantum dots, nanosheets, nanobelts, and nanoparticles. The transition metal phosphide nanosheets are nanosheets with a thickness of 2-30 nm, the transition metal phosphide quantum dots are nanoparticles with a hydrated particle size of less than 10 nm, the transition metal phosphide nanobelts are 50-200 nm in length, 30-80 nm in width, and 5-20 nm in thickness, and the transition metal phosphide nanoparticles are nanoparticles with a hydrated particle size of 30-200 nm.

[0021] The nano-scale metal phosphate includes one or more of calcium phosphate, manganese phosphate, zinc phosphate, and magnesium phosphate. The nano-scale metal phosphate is a nanoparticle with a size of 50-350 nm.

[0022] The present invention also provides a method for preparing a phosphorus-based material hybrid polymer coating, the method comprising the following steps:

[0023] 80-105 parts of resin, 2-10 parts of phosphorus-based material, 1-5 parts of photoinitiator and 1-2 parts of leveling agent are added to a solvent and mixed for 0.5 hours to obtain the phosphorus-based material hybrid polymer coating, wherein the resin includes unsaturated double / triple bonds and acrylate units.

[0024] Further, the resin comprises:

[0025] Resin I

[0026] Resin II

[0027] Wherein, the resin I accounts for 37.5% to 62% of the total mass of the resin, and the resin II accounts for 38% to 62.5% of the total mass of the resin;

[0028] The phosphorus-based materials include nano-scale elemental phosphorus, nano-scale transition metal phosphides and nano-scale metal phosphates.

[0029] Furthermore, the nanoscale transition metal phosphide is prepared by hydrothermal reaction using the nanoscale elemental phosphorus and a transition metal salt as raw materials.

[0030] The preparation method of the nano-scale metal phosphate is a hydrothermal method, which uses a soluble metal ion salt as a metal ion source and a soluble phosphate as a phosphorus source, and uses an aqueous solvent to directly synthesize metal phosphate nanoparticles.

[0031] Furthermore, the resin I is prepared by the following method:

[0032] 1) 4-Acryloylmorpholine reacts with polyetheramine via Michael addition reaction to generate intermediate 1.

[0033] 2) Tris(2-hydroxyethyl)isocyanurate triacrylate, intermediate 1, and polyethylene glycol diacrylate are reacted by Michael addition reaction to produce the resin I.

[0034] Furthermore, the resin II is prepared by the following method:

[0035] 1) Polyethylene glycol and isophorone diisocyanate undergo polymerization reaction to generate polyurethane with isocyanate terminal groups.

[0036] 2) Adding hydroxyethyl acrylate (HEA) for end-capping, with a molar ratio of polyurethane to HEA of 1:1-1.4, the reaction temperature being between 60-90° C., and the reaction being carried out for 6-12 hours to produce the resin II.

[0037] The present invention also provides an application of the phosphorus-based hybrid polymer coating as described in any of the above items in the optical field, characterized in that the phosphorus-based hybrid polymer coating is coated on an optical device, and a film is formed on the component after pre-baking and ultraviolet curing.

[0038] 1. The present invention designs a novel polymer heterogeneous network structure, which is composed of two novel polymers cross-linked after UV curing. Resin I and Resin II both have hydrophobic segments and hydrophilic segments, and have excellent adhesion to plastic substrates. Resin I and Resin II can be rapidly cross-linked and cured into a polymer heterogeneous network structure under UV light irradiation. On the one hand, the heterogeneous structure composed of the topological cross-linking of the two resins has strong mechanical properties, a large specific surface area, rich groups, and good adhesion to the substrate; on the other hand, compared with a single linear resin, the heterogeneous structure is mesh-shaped, and phosphorus-based materials are easier to fill and hybridize. While ensuring the long-term lubrication, anti-fog, self-cleaning, and flow-conducting properties of the coating, the mechanical properties of the coating can be improved.

[0039] 2. In the present invention, a long-lasting super-hydrophilic polymer heterogeneous network coating hybridized with phosphorus-based materials was designed and prepared by constructing PC bonds under UV curing. Unlike physical blending, the covalent PC bonds between the phosphorus-based material and the polymer are generated by UV-induced free radical reactions, resulting in the phosphorus-based material being firmly embedded in the polymer structure. The migration of the phosphorus-based material is regulated by UV to enrich the phosphorus-based material on the coating surface. The phosphorus-based material can effectively prevent water from penetrating into the interior of the coating through its own good water absorption capacity. While improving the mechanical properties of the coating, the water resistance and stability of the coating are also improved. The super-hydrophilic polymer coating hybridized with phosphorus-based materials exhibits excellent and long-lasting lubrication, anti-fog, self-cleaning and flow-conducting properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] Figure 1 The invention provides a method for preparing a phosphorus-based material hybrid polymer coating.

[0041] Figure 2 TEM image of black phosphorus nanosheets.

[0042] Figure 3 TEM image of copper phosphide quantum dots.

[0043] Figure 4 This is the SEM image of coating #1.

[0044] Figure 5 The following are photos of the coated and uncoated panels after fumigation for 1 minute and 60 minutes. DETAILED DESCRIPTION

[0045] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, the specific embodiments of the present invention are described in detail below with reference to the accompanying drawings, but they should not be understood as limiting the scope of implementation of the present invention.

[0046] The present invention provides a phosphorus-based hybrid polymer coating, which includes a resin and a phosphorus-based material. The resin includes an unsaturated double bond / triple bond structure and an acrylate structure, which results in the generation of carbon radicals during free radical polymerization. The carbon radicals react with phosphorus to form PC bonds, causing the phosphorus-based material to be firmly embedded in the polymer structure. The migration of the phosphorus-based material is regulated by UV so that the phosphorus-based material is enriched on the coating surface. The phosphorus-based material can effectively prevent water from penetrating into the interior of the coating through its own good water absorption capacity. While improving the mechanical properties of the coating, the water resistance and stability of the coating are also improved. The super-hydrophilic polymer coating hybridized with the phosphorus-based material exhibits excellent and long-lasting lubrication, anti-fog, self-cleaning and flow-guiding properties.

[0047] The present invention provides a phosphorus-based material hybrid polymer coating, which comprises the following components in parts by weight:

[0048]

[0049] The resin comprises unsaturated double / triple bonds and acrylate units.

[0050] The present invention utilizes two resins to form a heterogeneous network structure, achieving multiple benefits, including adhesion, mechanical properties, and hydrophilicity. The resins include Resin I and Resin II. Both Resin I and Resin II possess hydrophobic and hydrophilic segments, resulting in excellent adhesion to plastic substrates. Resins I and II rapidly crosslink and cure under UV light to form a polymer heterogeneous network structure, enhancing the coating's mechanical properties.

[0051] The present invention provides a resin I, the structural formula of which is shown below:

[0052]

[0053] The preparation of resin I is achieved by the following route:

[0054]

[0055] The specific reaction steps are as follows: 1) 4-Acryloylmorpholine reacts with polyetheramine via a Michael addition reaction to produce Intermediate 1. The reaction conditions are: the solvent is one or more solvents such as ethyl acetate, propylene glycol methyl ether, and butyl acetate. The molar ratio of 4-Acryloylmorpholine to polyetheramine to solvent is between 1:1-1.4:18-28, the reaction temperature is between 40-80°C, and the reaction time is between 6-12 hours. After completion of the reaction, the solvent is removed to produce Intermediate 1. 2) Tris(2-hydroxyethyl)isocyanurate triacrylate, Intermediate 1, and polyethylene glycol diacrylate are reacted via a Michael addition reaction to produce Resin I. The reaction conditions are: the solvent is one or more solvents such as ethyl acetate, propylene glycol methyl ether, and butyl acetate. The molar ratio of tris(2-hydroxyethyl)isocyanurate triacrylate, intermediate 1, polyethylene glycol diacrylate, and solvent is between 1:1-1.4:1-1.4:25-35. The reaction temperature is between 60-100°C and the reaction time is between 12-20 hours. After the reaction is completed, the solvent is removed to obtain resin I.

[0056] Acrylate structures usually have poor hydrophilicity or poor adhesion, and the two are difficult to be compatible. While designing the acrylate group, the resin I structure introduces monomers such as 4-acryloylmorpholine and isocyanuric acid to increase adhesion while providing hydrophilicity.

[0057] The present invention provides a resin II, the structural formula of which is shown below:

[0058]

[0059] The preparation of resin II is achieved by the following route:

[0060]

[0061] The specific reaction steps are as follows: 1) Polyethylene glycol and isophorone diisocyanate undergo a polymerization reaction to produce a polyurethane with isocyanate end groups. The specific reaction conditions are as follows: the solvent is one or more solvents such as ethyl acetate and butyl acetate. The molar ratio of polyethylene glycol, isophorone diisocyanate, and solvent is between 1:1-1.4:20-35. The reaction temperature is between 80-110°C and the reaction time is between 8-12 hours. After the reaction is completed, 2) hydroxyethyl acrylate (HEA) is added for end-capping. The molar ratio of polyurethane to HEA is between 1:1-1.4. The reaction temperature is between 60-90°C and the reaction time is between 6-12 hours.

[0062] Resin II is a polyurethane acrylate structure, which generally has better adhesion. Polyurethane acrylate generally has a hydrophobic structure. Resin II introduces polyether into the acrylate structure to improve hydrophilicity.

[0063] In one embodiment, the resin comprises:

[0064] Resin I

[0065] Resin II

[0066] Wherein, the resin I accounts for 38% to 62.5% of the total mass of the resin, and the resin II accounts for 37.5% to 62% of the total mass of the resin;

[0067] The phosphorus-based materials include nano-scale elemental phosphorus, nano-scale transition metal phosphides and nano-scale metal phosphates.

[0068] In one embodiment, the phosphorus-based hybrid polymer coating includes resin I (40-50 parts), resin II (40-55 parts), phosphorus-based material (2-10 parts), photoinitiator TPO (1-5 parts), and leveling agent (1-2 parts).

[0069] If the proportion of phosphorus-based materials is too low, it will not be effective, and if it is too high, it will affect the transparency of the coating. Therefore, it is more appropriate to be between 2-10 parts.

[0070] If the photoinitiator content is higher than 5 parts, a large number of free radicals will be generated under ultraviolet light, resulting in a low molecular weight of the final three-dimensional network polymer formed after the coating is cured, making the coating film brittle and the adhesion poor, while also increasing the cost of the coating; if the photoinitiator content is lower than 1 part, insufficient free radicals will be generated under ultraviolet light, resulting in a large amount of residual resin and monomer that has not been photopolymerized, causing the final coating film to have poor surface drying, be sticky, and be unusable.

[0071] Leveling agents are substances that can effectively reduce the surface tension of coatings, improve their leveling and uniformity, and promote the formation of a flat, smooth, and uniform coating film during the drying process. The leveling agent described in the present invention is an acrylic leveling agent with a molecular weight between 8,000 and 15,000.

[0072] Furthermore, the nano-scale elemental phosphorus includes one or more of nano-scale black phosphorus, nano-scale red phosphorus and nano-scale fiber phosphorus.

[0073] The morphology of the nanoscale black phosphorus includes one or more of black phosphorus nanosheets, black phosphorus nanoparticles, and black phosphorus quantum dots.

[0074] The black phosphorus nanosheets are black phosphorus nanosheets with a thickness of 2-50 nm.

[0075] The black phosphorus quantum dots are black phosphorus nanoparticles with a hydrated particle size of less than 10 nm.

[0076] The black phosphorus nanoparticles are black phosphorus nanoparticles with a hydrated particle size of 20-300 nm.

[0077] The preparation method of the black phosphorus nanosheets and black phosphorus quantum dots refers to patent CN201711310056.7, and the preparation method of black phosphorus nanoparticles refers to patent CN201610539443.7.

[0078] The nano-scale red phosphorus has the shape of nano red phosphorus particles, and the particle size of the red phosphorus nanoparticles is between 80-500 nm.

[0079] The red phosphorus nanoparticles are prepared by ball milling. High-purity red phosphorus and steel balls are placed in a 50 cm 3 The steel ball to red phosphorus ratio was 30-40:1 in a steel can. The ball milling process was carried out for 4-8 hours under an inert atmosphere (argon) at a speed of 300-500 rpm. The ball-milled sample was removed, dispersed in NMP, centrifuged, washed twice, and dried.

[0080] The nano-scale fiber phosphorus has a morphology of nano-belts, a length of 100-250 nm, a width of 50-80 nm, and a thickness of 10-30 nm.

[0081] The nanofiber phosphorus preparation method comprises dispersing crystalline red phosphorus in N-methylpyrrolidone (NMP), adding a surfactant, and ultrasonically preparing the nanofiber phosphorus. The mass-to-volume ratio of the crystalline red phosphorus to NMP is 1-2:1 mg / ml; the mass ratio of the crystalline red phosphorus to the surfactant is 3-5:1; the surfactant is one or more of fatty alcohol polyoxyethylene ether (AEO) and sodium lauryl sulfate (SDS). The ultrasonic treatment lasts for 5-10 hours at a power of 2-4W.

[0082] Furthermore, the nanoscale transition metal phosphide includes one or more of copper phosphide, cobalt phosphide, iron phosphide, manganese phosphide, molybdenum phosphide, and nickel phosphide.

[0083] The morphology of the nanoscale transition metal phosphide is one or more of quantum dots, nanosheets, nanobelts, and nanoparticles.

[0084] The nano-scale transition metal phosphide nanosheets are nanosheets with a thickness of 2-30 nm.

[0085] Nanoscale transition metal phosphide quantum dots are nanoparticles with a hydrated particle size of less than 10 nm.

[0086] The nanoscale transition metal phosphide nanobelts have a length of 50-200 nm, a width of 30-80 nm, and a thickness of 5-20 nm.

[0087] The nano-scale transition metal phosphide nanoparticles are nanoparticles with a hydrated particle size of 30-200 nm.

[0088] The nanoscale transition metal phosphide is prepared by directly using nanoscale elemental phosphorus and transition metal salt as raw materials through a hydrothermal reaction, which is a topochemical transformation of elemental phosphorus.

[0089] Specifically, transition metal phosphide quantum dots can be prepared by reacting black phosphorus quantum dots with transition metal salts. Transition metal phosphide nanosheets can be prepared by reacting black phosphorus nanosheets with transition metal salts. Transition metal phosphide nanobelts can be prepared by reacting fibrous phosphorus with transition metal salts. Transition metal phosphide nanoparticles can be prepared by reacting black phosphorus or red phosphorus nanoparticles with transition metal salts.

[0090] The transition metal salt includes one or more of copper chloride, copper nitrate, cobalt chloride, cobalt nitrate, ferric chloride, ferric nitrate, manganese chloride, manganese nitrate, molybdenum chloride, molybdenum nitrate, nickel chloride, and nickel nitrate.

[0091] When elemental phosphorus is dispersed in a solvent, its lone pair electrons and surface defects lead to a negative surface potential, which favors the attraction between elemental phosphorus and transition metal ions. The embedded transition metal ions react with phosphorus and ultimately transform into transition metal phosphides.

[0092] Compared with fiber phosphorus and red phosphorus, black phosphorus is more stable, so the reaction needs to occur in a strongly alkaline environment.

[0093] One specific preparation method of nano-scale transition metal phosphides is: disperse fiber phosphorus or red phosphorus nanoparticles in an organic solvent, add transition metal salt, and heat to react to obtain transition metal phosphide nanobelts or nanoparticles.

[0094] Furthermore, the molar ratio of the fiber phosphorus or red phosphorus nanoparticles to the transition metal salt is 1:1.2-1.5; preferably, the organic solvent is selected from one of NMP, N,N-dimethylformamide (DMF), and ethylene glycol; the reaction temperature of the heating reaction is 100-180°C; and the reaction time is 6h-12h.

[0095] The second specific preparation method of nanoscale transition metal phosphides is: dispersing black phosphorus quantum dots, black phosphorus nanosheets, or black phosphorus nanoparticles in an organic solvent, adding a transition metal salt and a strong base, and heating the mixture for reaction to obtain transition metal phosphide quantum dots, nanosheets, or nanoparticles.

[0096] Furthermore, the molar ratio of the black phosphorus quantum dots or black phosphorus nanosheets or black phosphorus nanoparticles to the transition metal salt is 1:1.3-1.6; preferably, the organic solvent is selected from one of NMP, N,N-dimethylformamide (DMF), and ethylene glycol; the strong base is one or more of potassium methoxide and sodium ethoxide; the reaction temperature of the heating reaction is 140-180°C; and the reaction time is 4h-8h.

[0097] The nano-scale metal phosphate includes one or more of calcium phosphate, manganese phosphate, zinc phosphate and magnesium phosphate.

[0098] The nano-scale metal phosphate is nanoparticles with a size between 50 and 350 nm.

[0099] The preparation method of the nano-scale metal phosphate is a hydrothermal method, which uses a soluble metal ion salt as a metal ion source and a soluble phosphate as a phosphorus source, and uses an aqueous solvent to directly synthesize metal phosphate nanoparticles.

[0100] See Figure 1 In one embodiment, the method for preparing the phosphorus-based material hybrid polymer coating comprises the following steps:

[0101] 80-105 parts of resin, 2-10 parts of phosphorus-based material, 1-5 parts of photoinitiator and 1-2 parts of leveling agent are added to a solvent and mixed for 0.5 hours to obtain the phosphorus-based material hybrid polymer coating, wherein the resin includes unsaturated double / triple bonds and acrylate units.

[0102] Further, the resin comprises:

[0103] Resin I

[0104] Resin II

[0105] Wherein, the resin I accounts for 37.5% to 62% of the total mass of the resin, and the resin II accounts for 38% to 62.5% of the total mass of the resin;

[0106] The phosphorus-based materials include nano-scale elemental phosphorus, nano-scale transition metal phosphides and nano-scale metal phosphates.

[0107] Furthermore, the nanoscale transition metal phosphide is prepared by hydrothermal reaction using the nanoscale elemental phosphorus and a transition metal salt as raw materials.

[0108] The preparation method of the nano-scale metal phosphate is a hydrothermal method, which uses a soluble metal ion salt as a metal ion source and a soluble phosphate as a phosphorus source, and uses an aqueous solvent to directly synthesize metal phosphate nanoparticles.

[0109] Furthermore, the resin I is prepared by the following method:

[0110] 1) 4-Acryloylmorpholine reacts with polyetheramine via Michael addition reaction to generate intermediate 1.

[0111] 2) Tris(2-hydroxyethyl)isocyanurate triacrylate, intermediate 1, and polyethylene glycol diacrylate are reacted by Michael addition reaction to produce the resin I.

[0112] Furthermore, the resin II is prepared by the following method:

[0113] 1) Polyethylene glycol and isophorone diisocyanate undergo polymerization reaction to generate polyurethane with isocyanate terminal groups.

[0114] 2) Adding hydroxyethyl acrylate (HEA) for end-capping, with a molar ratio of polyurethane to HEA of 1:1-1.4, the reaction temperature being between 60-90° C., and the reaction being carried out for 6-12 hours to produce the resin II.

[0115] The present invention also provides an application of the phosphorus-based hybrid polymer coating as described in any of the above items in the optical field, characterized in that the phosphorus-based hybrid polymer coating is coated on an optical device, and a film is formed on the component after pre-baking and ultraviolet curing.

[0116] The film forming method is as follows: apply the coating liquid on the plate, pre-bake at 60-80℃ for 2-3 minutes, and cure under UV LED light for 30-60 seconds with an energy of 500-1000mJ / cm 2 The coating method is one of spraying, curtain coating, drip coating, scraping or rolling.

[0117] The optical device plate selected for the coating is one of glass, PC (polycarbonate) plate, PMMA (polymethyl methacrylate) plate and PET (polyethylene terephthalate).

[0118] In the embodiments provided by the present invention, Examples 1-5 are methods for preparing resin I, Examples 6-8 are methods for preparing resin II, and Examples 9-36 are methods for preparing phosphorus-based materials.

[0119] Preparation of Resin I:

[0120] Example 1

[0121] In a three-necked flask, 1 mol of 4-acryloylmorpholine and 1 mol of polyetheramine were dissolved in 18 mol of ethyl acetate. The mixture was reacted at 40°C for 6 h, and then the solvent was removed. 1 mol of tris(2-hydroxyethyl)isocyanurate triacrylate, 1 mol of polyethylene glycol diacrylate, and 25 mol of ethyl acetate were added, and the mixture was reacted at 60°C for 12 h. After the reaction was completed, the solvent was removed, and the mixture was washed with water and filtered to obtain resin I.

[0122] Example 2

[0123] In a three-necked flask, 1 mol of 4-acryloylmorpholine and 1.2 mol of polyetheramine were dissolved in 22 mol of ethyl acetate. The mixture was reacted at 60°C for 9 h, and then the solvent was removed. 1.2 mol of tris(2-hydroxyethyl)isocyanurate triacrylate, 1.2 mol of polyethylene glycol diacrylate, and 30 mol of ethyl acetate were added, and the mixture was reacted at 80°C for 16 h. After the reaction was completed, the solvent was removed, and the mixture was washed with water and filtered to obtain resin I.

[0124] Example 3

[0125] In a three-necked flask, 1 mol of 4-acryloylmorpholine and 1.1 mol of polyetheramine were dissolved in 26 mol of propylene glycol methyl ether. The mixture was reacted at 50°C for 10 h, and then the solvent was removed. 1.1 mol of tris(2-hydroxyethyl)isocyanurate triacrylate, 1.1 mol of polyethylene glycol diacrylate, and 28 mol of propylene glycol methyl ether were added, and the mixture was reacted at 70°C for 14 h. After the reaction was completed, the solvent was removed, and the mixture was washed with water and filtered to obtain Resin I.

[0126] Example 4

[0127] In a three-necked flask, 1 mol of 4-acryloylmorpholine and 1.3 mol of polyetheramine were dissolved in 24 mol of butyl acetate. The mixture was reacted at 70°C for 12 h, and then the solvent was removed. 1.3 mol of tris(2-hydroxyethyl)isocyanurate triacrylate, 1.3 mol of polyethylene glycol diacrylate, and 32 mol of butyl acetate were added, and the mixture was reacted at 90°C for 18 h. After the reaction was completed, the solvent was removed, and the mixture was washed with water and filtered to obtain Resin I.

[0128] Example 5

[0129] In a three-necked flask, 1 mol of 4-acryloylmorpholine and 1.4 mol of polyetheramine were dissolved in 28 mol of ethyl acetate. The mixture was reacted at 80°C for 12 h, and then the solvent was removed. 1.4 mol of tris(2-hydroxyethyl)isocyanurate triacrylate, 1.4 mol of polyethylene glycol diacrylate, and 35 mol of ethyl acetate were added, and the mixture was reacted at 100°C for 20 h. After the reaction was completed, the solvent was removed, and the mixture was washed with water and filtered to obtain resin I.

[0130] Preparation of Resin II:

[0131] Example 6

[0132] Dissolve 1 mol of polyethylene glycol in 20 mol of ethyl acetate to obtain a dropwise solution. Place 1 mol of isophorone diisocyanate in a three-necked flask and add the solution dropwise at room temperature with stirring at 200 rpm. The reaction is continued at 80°C for 8 hours, followed by the addition of 1 mol of HEA. The reaction is continued at 60°C for 6 hours. After evaporation of the solvent, the mixture is filtered and dried in vacuo to obtain Resin II.

[0133] Example 7

[0134] Dissolve 1 mol of polyethylene glycol in 35 mol of butyl acetate to obtain a dropwise solution. Place 1.2 mol of isophorone diisocyanate in a three-necked flask and add the solution dropwise at room temperature with stirring at 200 rpm. The reaction proceeds at 90°C for 10 hours, followed by the addition of 1.2 mol of HEA. The reaction continues at 80°C for 8 hours. After evaporation of the solvent, the mixture is filtered and dried in vacuo to yield Resin II.

[0135] Example 8

[0136] Dissolve 1 mol of polyethylene glycol in 25 mol of ethyl acetate to obtain a dropwise solution. Place 1.4 mol of isophorone diisocyanate in a three-necked flask and add the solution dropwise at room temperature with stirring at 200 rpm. The reaction is continued at 110°C for 12 hours, followed by the addition of 1.4 mol of HEA. The reaction is continued at 90°C for 12 hours. After evaporation of the solvent, the mixture is filtered and dried in vacuo to obtain Resin II.

[0137] The molecular weight of resin I increases from Examples 1 to 5, and the molecular weight of resin II increases from Examples 6 to 8, the viscosity increases, the mechanical properties and hydrophilic properties increase, and the fluidity and solubility deteriorate. The performance change trends in the coating are the same.

[0138] Preparation of phosphorus-based materials:

[0139] Example 9

[0140] Preparation of black phosphorus nanosheets and black phosphorus quantum dots

[0141] The preparation method refers to patent CN201711310056.7. Figure 2 TEM image of black phosphorus nanosheets.

[0142] Example 10

[0143] Preparation of black phosphorus nanoparticles

[0144] The preparation method refers to patent CN201610539443.7.

[0145] Example 11

[0146] Preparation of red phosphorus nanoparticles

[0147] Put high-purity red phosphorus and steel balls into a 50 cm 3 steel tank, the ratio of steel ball to red phosphorus is 30:1. The ball milling process is carried out in an inert atmosphere (argon) for 4 hours at a speed of 300 r / min. Take out the ball milled sample, disperse in NMP, centrifuge, wash twice, dry.

[0148] Example 12

[0149] Preparation of red phosphorus nanoparticles

[0150] Put high-purity red phosphorus and steel balls into a 50 cm 3 steel tank, the ratio of steel ball to red phosphorus is 40:1. The ball milling process is carried out in an inert atmosphere (argon) for 6 hours at a speed of 500 r / min. Take out the ball milled sample, disperse in NMP, centrifuge, wash twice, dry.

[0151] Example 13

[0152] Preparation of crystalline red phosphorus

[0153] Refer to patent CN202010541350.4 to prepare crystalline red phosphorus.

[0154] Example 14

[0155] Preparation of fibrous phosphorus

[0156] Take 150 mg of crystalline red phosphorus, disperse in 150 ml of N-methyl pyrrolidone (NMP), add 30 mg of fatty alcohol polyoxyethylene ether (AEO), and use a probe ultrasonic for 5 hours at a power of 2W to prepare.

[0157] Example 15

[0158] Preparation of fibrous phosphorus

[0159] Take 150 mg of crystalline red phosphorus, disperse in 75 ml of N-methyl pyrrolidone (NMP), add 50 mg of sodium lauryl sulfate (SDS), and use a probe ultrasonic for 10 hours at a power of 4W to prepare.

[0160] Example 16

[0161] Preparation of metal copper phosphide nanobelt

[0162] Disperse 1 mol of fibrous phosphorus obtained in Example 14 in 50 ml of N-methyl pyrrolidone (NMP), add 1.2 mol of copper chloride, stir uniformly, and then add to a reaction kettle, react at 100°C for 6h, centrifuge, wash with ethanol twice, and dry to obtain.

[0163] Example 17

[0164] Preparation of Copper Phosphide Nanobelts

[0165] 1 mol of the fiber phosphorus obtained in Example 15 was dispersed in 50 ml of N-methylpyrrolidone (NMP), and 1.5 mol of copper nitrate was added. After stirring evenly, the mixture was added to a reactor. The mixture was reacted at 120° C. for 6 h, centrifuged, washed twice with ethanol, and dried to obtain the product.

[0166] Example 18

[0167] Preparation of Metal Cobalt Phosphide Nanobelts

[0168] 1 mol of the fiber phosphorus obtained in Example 14 was dispersed in 50 ml of N-methylpyrrolidone (NMP), and 1.3 mol of cobalt chloride was added. After stirring evenly, the mixture was added to a reactor. The mixture was reacted at 100° C. for 6 h, centrifuged, washed twice with ethanol, and dried to obtain the product.

[0169] Example 19

[0170] Preparation of Metal Cobalt Phosphide Nanobelts

[0171] 1 mol of the fiber phosphorus obtained in Example 15 was dispersed in 50 ml of N-methylpyrrolidone (NMP), and 1.4 mol of copper nitrate was added. After stirring evenly, the mixture was added to a reactor. The mixture was reacted at 140° C. for 8 h, centrifuged, washed twice with ethanol, and dried to obtain the product.

[0172] Example 20

[0173] Preparation of Metal Iron Phosphide Nanobelts

[0174] 1 mol of the fiber phosphorus obtained in Example 14 was dispersed in 50 ml of N,N-dimethylformamide (DMF), and 1.3 mol of ferric chloride was added. After stirring evenly, the mixture was added to a reactor. The mixture was reacted at 130° C. for 6 h, centrifuged, washed twice with ethanol, and dried to obtain the product.

[0175] Example 21

[0176] Preparation of Metal Iron Phosphide Nanobelts

[0177] 1 mol of the fiber phosphorus obtained in Example 15 was dispersed in 50 ml of N,N-dimethylformamide (DMF), and 1.2 mol of ferric nitrate was added. After stirring evenly, the mixture was added to a reactor. The mixture was reacted at 140° C. for 8 h, centrifuged, washed twice with ethanol, and dried to obtain the product.

[0178] Example 22

[0179] Preparation of Metal Manganese Phosphide Nanobelts

[0180] 1 mol of the fiber phosphorus obtained in Example 14 was dispersed in 50 ml of ethylene glycol, and 1.3 mol of manganese chloride was added. After stirring evenly, the mixture was added to the reactor. The mixture was reacted at 150° C. for 10 h, centrifuged, washed twice with ethanol, and dried to obtain the product.

[0181] Example 23

[0182] Preparation of Metal Manganese Phosphide Nanobelts

[0183] 1 mol of the fiber phosphorus obtained in Example 15 was dispersed in 50 ml of ethylene glycol, and 1.2 mol of manganese nitrate was added. After stirring evenly, the mixture was added to the reactor. The mixture was reacted at 160° C. for 12 h, centrifuged, washed twice with ethanol, and dried to obtain the product.

[0184] Example 24

[0185] Preparation of Metal Molybdenum Phosphide Nanobelts

[0186] 1 mol of the fiber phosphorus obtained in Example 14 was dispersed in 50 ml of N,N-dimethylformamide (DMF), 1.3 mol of molybdenum chloride was added, stirred evenly, and then added to the reactor. After reacting at 150° C. for 10 h, the mixture was centrifuged, washed twice with ethanol, and dried to obtain the product.

[0187] Example 25

[0188] Preparation of Metal Molybdenum Phosphide Nanobelts

[0189] 1 mol of the fiber phosphorus obtained in Example 15 was dispersed in 50 ml of N,N-dimethylformamide (DMF), 1.2 mol of molybdenum nitrate was added, stirred evenly and added to the reactor, reacted at 170°C for 11 hours, centrifuged, washed twice with ethanol, and dried to obtain.

[0190] Example 26

[0191] Preparation of nickel phosphide nanoribbons

[0192] 1 mol of the fiber phosphorus obtained in Example 14 was dispersed in 50 ml of ethylene glycol, and 1.3 mol of nickel chloride was added. After stirring evenly, the mixture was added to a reactor. The mixture was reacted at 180° C. for 9 h, centrifuged, washed twice with ethanol, and dried to obtain the product.

[0193] Example 27

[0194] Preparation of nickel phosphide nanoribbons

[0195] 1 mol of the fiber phosphorus obtained in Example 15 was dispersed in 50 ml of ethylene glycol, and 1.4 mol of nickel nitrate was added. After stirring evenly, the mixture was added to a reactor. The mixture was reacted at 160° C. for 8 h, centrifuged, washed twice with ethanol, and dried to obtain the product.

[0196] Example 28

[0197] Preparation of metal phosphide nanoparticles

[0198] Copper phosphide, cobalt phosphide, iron phosphide, molybdenum phosphide, nickel phosphide nanoparticles can be prepared by replacing the fibrous phosphorus raw material in the preparation method of metal phosphide nanoribbons in examples 16-27 with red phosphorus nanoparticles in examples 11-12.

[0199] Example 29

[0200] Preparation of metal copper phosphide nanosheet / quantum dot

[0201] 1 mol of black phosphorus nanosheet or black phosphorus quantum dot obtained in example 9 was dispersed in 50 ml of NMP, 1.3 mol of copper chloride and 0.05 mol of potassium methoxide were added, and after stirring uniformly, they were added into a reaction kettle, reacted at 140°C for 4 h, centrifuged, washed with ethanol for 2 times, and dried to obtain. Figure 2 TEM image of copper phosphide quantum dot.

[0202] Example 30

[0203] Preparation of metal copper phosphide nanosheet / quantum dot

[0204] 1 mol of black phosphorus nanosheet or black phosphorus quantum dot obtained in example 9 was dispersed in 50 ml of DMF, 1.6 mol of copper nitrate and 0.05 mol of sodium ethoxide were added, and after stirring uniformly, they were added into a reaction kettle, reacted at 180°C for 8 h, centrifuged, washed with ethanol for 2 times, and dried to obtain.

[0205] Example 31

[0206] Preparation of metal copper phosphide nanosheet / quantum dot

[0207] 1 mol of black phosphorus nanosheet or black phosphorus quantum dot obtained in example 9 was dispersed in 50 ml of ethylene glycol, 1.5 mol of copper chloride and 0.05 mol of sodium ethoxide were added, and after stirring uniformly, they were added into a reaction kettle, reacted at 160°C for 6 h, centrifuged, washed with ethanol for 2 times, and dried to obtain.

[0208] Example 32

[0209] Preparation of metal phosphide nanosheet / quantum dot

[0210] Similar to the preparation methods in examples 29-31, the transition metal salt is replaced with cobalt salt, iron salt, manganese salt, molybdenum salt, nickel salt respectively to obtain corresponding cobalt phosphide, iron phosphide, manganese phosphide, molybdenum phosphide, nickel phosphide nanosheet / quantum dot.

[0211] Example 33

[0212] Preparation of metal phosphide nanoparticles

[0213] Similar to the preparation method of Examples 29-32, the corresponding metal phosphide nanoparticles can be prepared by replacing the black phosphorus nanosheets or black phosphorus quantum dots raw materials with black phosphorus nanoparticles.

[0214] Example 34

[0215] Preparation of calcium phosphate nanoparticles

[0216] 100 ml of sodium phosphate aqueous solution with a concentration of 1 mol / L was added to a three-necked flask, and 1 mol of calcium chloride was added. After stirring evenly, the solution was transferred to a reactor. After reacting at 120° C. for 10 h, calcium phosphate nanoparticles were obtained by washing with water and centrifuging.

[0217] Example 35

[0218] Preparation of magnesium phosphate nanoparticles

[0219] 100 ml of sodium phosphate aqueous solution with a concentration of 10 mol / L was added to a three-necked flask, and 1 mol of magnesium chloride was added. After stirring evenly, the solution was transferred to a reactor. After reacting at 120° C. for 10 h, magnesium phosphate nanoparticles were obtained by washing with water and centrifuging.

[0220] Example 36

[0221] Preparation of zinc phosphate nanoparticles

[0222] 100 ml of sodium phosphate aqueous solution with a concentration of 10 mol / L was added to a three-necked flask, and 1 mol of zinc chloride was added. After stirring evenly, the mixture was transferred to a reactor. After reacting at 120° C. for 10 h, zinc phosphate nanoparticles were obtained by washing with water and centrifuging.

[0223] Example 36

[0224] Preparation of manganese phosphate nanoparticles

[0225] 100 ml of sodium phosphate aqueous solution with a concentration of 10 mol / L was added to a three-necked flask, and 1 mol of manganese chloride was added. After stirring evenly, the solution was transferred to a reactor. After reacting at 120° C. for 10 h, the solution was washed with water and centrifuged to obtain manganese phosphate nanoparticles.

[0226] All phosphorus-based materials in Examples 9 to 36 were observed for their morphology by electron microscopy and tested for their structure by XRD, and the results showed that the phosphorus-based materials were successfully prepared.

[0227] Example 37

[0228] Preparation of phosphorus-based hybrid polymer coatings

[0229] The phosphorus-based material hybrid polymer coating involved in the present invention is as follows: accurately weigh each component, add 40-50 parts by weight of resin I, 40-55 parts by weight of resin II, 2-10 parts by weight of phosphorus-based material, 1-5 parts by weight of photoinitiator TPO and 1-2 parts by weight of leveling agent to a solvent, and mix for 0.5 hours to obtain the coating.

[0230] When Resin I is less than 40 parts or greater than 50 parts, and Resin II is less than 40 parts or greater than 55 parts, the heterogeneous network coating is uneven. When the phosphorus-based material ratio is less than 2 parts, the hydrophilicity and water resistance of the coating are minimally affected. When it is greater than 10 parts, the coating becomes opaque. When the photoinitiator ratio is greater than 5 parts, the coating becomes brittle and has poor adhesion. When the photoinitiator ratio is less than 1 part, the coating does not dry well and becomes sticky and unusable.

[0231] The components and component contents of the phosphorus-based hybrid polymer coating are shown in Table 1. In the present invention, the solvent can be one or more of ethyl acetate, butyl acetate, isopropyl alcohol, and ethanol. In this embodiment, butyl acetate: isopropyl alcohol: ethanol = 4:3:3 (volume ratio) is used as the solvent, and the total weight of the solvent is 0.3-3 times the total weight of the other components.

[0232] Table 1 Phosphorus-based material hybrid super-hydrophilic polymer heterogeneous network coating composition

[0233]

[0234] Application Example 1

[0235] Preparation of super-hydrophilic polymer heterogeneous network coatings hybridized with phosphorus-based materials

[0236] The coating #1-15 prepared in Example 36 was applied to the plate, pre-baked at 60-80°C for 2-3 minutes, and cured under UV LED light for 30-60 seconds with an energy of 500-1000 mJ / cm 2 The coating method is one of spray coating, flow coating, drip coating, blade coating or roller coating. The plate is one of PC, PET, PMMA and glass.

[0237] Characterization of superhydrophilic polymer heterogeneous network coatings hybridized with phosphorus-based materials

[0238] All coatings in Application Example 1 were characterized by SEM, XRD, and infrared spectroscopy, and the results demonstrated the successful preparation of super-hydrophilic polymer heterogeneous network coatings hybridized with phosphorus-based materials. Figure 4 This is the SEM image of coating #1.

[0239] Performance testing:

[0240] Coating water contact angle test

[0241] The coatings #1-15 prepared in Example 1 were tested using a water contact angle tester, and the water contact angles were found to be 4-15°, indicating that the coatings had excellent hydrophilicity. The test method was carried out in accordance with GB / T 30693.

[0242] Coating anti-fog performance test

[0243] The plates containing coatings numbered #1-15 prepared in Application Example 1 were placed 10 cm above a water bath and fumigated for 60 minutes. The water in the water bath was heated to 65-70° C., and no fogging occurred on any of the samples. Figure 5 The photos show the panels with and without coating after fumigation for 1 minute and 60 minutes. The test method is based on EN 166.

[0244] Coating lubrication test

[0245] The plates with coatings #1-15 prepared in Example 1 were tested on a ball-on-disc tribometer. Their coefficients of friction ranged from 0.02 to 0.08, while the uncoated plates had a coefficient of friction of 0.26, demonstrating their excellent lubricity. The testing method was conducted in accordance with HB 7056-2004.

[0246] Coating flow test

[0247] The plates prepared in Application Example 1 and containing coatings numbered #1-15 were tested by a flow conductivity tester. The water flow was completely spread out without any retention, indicating the excellent flow conductivity of the coatings.

[0248] Self-cleaning ability test

[0249] After the panels with coatings #1-15 prepared in Example 1 were exposed to air for one month, no noticeable dust was found on their surfaces. However, the uncoated panels showed significant dust adhesion, demonstrating the coating's excellent self-cleaning capabilities. The testing method was conducted in accordance with GB / T 31815-2015.

[0250] Water resistance test

[0251] The anti-fog performance of the panels containing coatings #1-15 prepared in Example 1 was tested after being immersed in water for 72-120 hours. The test results were in accordance with GB / 1733-1993.

[0252] High temperature accelerated aging test

[0253] Plates prepared in Example 1 and containing coatings #1-15 were subjected to high-temperature accelerated aging testing. The test samples were placed in a 200°C oven for 1000-1500 hours. The coatings showed no noticeable peeling, delamination, or wrinkling before and after aging. The testing method was conducted in accordance with GB / T 2423.2-2008.

[0254] Durability testing

[0255] Environmental testing was performed on panels containing coatings #1-15, prepared in Example 1. The samples were placed in an open-air environment for 1-2 years. The coatings showed no noticeable peeling, flaking, or wrinkling before and after aging. The testing method was conducted in accordance with ASTM G154.

[0256] Adhesion test

[0257] The adhesion of the panels containing coatings numbered #1-15 prepared in Application Example 1 was tested using the 100-grid test method. The adhesion was all level 0 (highest). The test method was carried out in accordance with GB / T 9286-1998.

[0258] Mechanical properties testing

[0259] The mechanical properties of the plates containing coatings #1-15 prepared in Example 1 were tested. Flexibility was tested using a bend tester according to GB / T 6742-86. The results showed that even the smallest diameter shaft did not damage the coating. Impact strength was tested using a drop hammer tester according to ISO 6272-1993, indicating an impact resistance greater than 18 N·m. Hardness was tested using a pencil hardness tester according to ASTM D3363, indicating a hardness between 3H and 5H. These results demonstrate the excellent mechanical properties of the coating.

Claims

1. A phosphorus-based hybrid polymer coating, characterized in that: The composition comprises the following components in parts by weight: wherein the resin comprises unsaturated double / triple bonds and acrylate units; The resin comprises: Wherein, the resin I accounts for 38% to 62.5% of the total mass of the resin, and the resin II accounts for 37.5% to 62% of the total mass of the resin; The phosphorus-based material is selected from any one of nano-scale elemental phosphorus, nano-scale transition metal phosphide or nano-scale metal phosphate.

2. The phosphorus-based hybrid polymer coating according to claim 1, characterized in that: The nano-scale elemental phosphorus includes one or more of nano-scale black phosphorus, nano-scale red phosphorus and nano-scale fiber phosphorus; The morphology of the nanoscale black phosphorus includes one or more of black phosphorus nanosheets, black phosphorus nanoparticles, and black phosphorus quantum dots. The black phosphorus nanosheets are black phosphorus nanosheets with a thickness of 2-50 nm. The black phosphorus quantum dots are black phosphorus nanoparticles with a hydrated particle size of less than 10 nm. The black phosphorus nanoparticles are black phosphorus nanoparticles with a hydrated particle size of 20-300 nm. The nanoscale red phosphorus has the form of nano red phosphorus particles, and the particle size of the nano red phosphorus particles is between 80-500 nm; The nano-scale fiber phosphorus has a morphology of nano-belts, a length of 100-250 nm, a width of 50-80 nm, and a thickness of 10-30 nm.

3. The phosphorus-based hybrid polymer coating according to claim 1, characterized in that: The nanoscale transition metal phosphide comprises one or more of copper phosphide, cobalt phosphide, iron phosphide, manganese phosphide, molybdenum phosphide, and nickel phosphide. The morphology of the nanoscale transition metal phosphide is one or more of quantum dots, nanosheets, nanobelts, and nanoparticles. The transition metal phosphide nanosheets are nanosheets with a thickness of 2-30 nm, the transition metal phosphide quantum dots are nanoparticles with a hydrated particle size of less than 10 nm, the transition metal phosphide nanobelts are 50-200 nm in length, 30-80 nm in width, and 5-20 nm in thickness, and the transition metal phosphide nanoparticles are nanoparticles with a hydrated particle size of 30-200 nm. The nano-scale metal phosphate includes one or more of calcium phosphate, manganese phosphate, zinc phosphate, and magnesium phosphate. The nano-scale metal phosphate is nanoparticles with a size between 50 and 350 nm.

4. A method for preparing a phosphorus-based hybrid polymer coating, characterized in that: The following steps are involved: 80-105 parts of resin, 2-10 parts of phosphorus-based material, 1-5 parts of photoinitiator and 1-2 parts of leveling agent are added to a solvent and mixed for 0.5 hours to obtain the phosphorus-based material hybrid polymer coating, wherein the resin includes unsaturated double / triple bonds and acrylate units; The resin comprises: Wherein, the resin I accounts for 37.5% to 62% of the total mass of the resin, and the resin II accounts for 38% to 62.5% of the total mass of the resin; The phosphorus-based material is selected from any one of nano-scale elemental phosphorus, nano-scale transition metal phosphide or nano-scale metal phosphate.

5. The method for preparing the phosphorus-based material hybrid polymer coating according to claim 4, characterized in that: The nanoscale transition metal phosphide is prepared by hydrothermal reaction using the nanoscale elemental phosphorus and a transition metal salt as raw materials; The preparation method of the nano-scale metal phosphate is a hydrothermal method, which uses a soluble metal ion salt as a metal ion source and a soluble phosphate as a phosphorus source, and uses an aqueous solvent to directly synthesize metal phosphate nanoparticles.

6. The method for preparing the phosphorus-based material hybrid polymer coating according to claim 4, wherein: The resin I was prepared by the following method: 1) 4-Acryloylmorpholine reacts with polyetheramine via Michael addition reaction to generate intermediate 1; 2) Tris(2-hydroxyethyl)isocyanurate triacrylate, intermediate 1, and polyethylene glycol diacrylate are reacted by Michael addition reaction to produce the resin I.

7. The method for preparing the phosphorus-based hybrid polymer coating according to claim 4, wherein: The resin II is prepared by the following method: 1) Polyethylene glycol and isophorone diisocyanate undergo polymerization reaction to generate polyurethane with isocyanate terminal groups; 2) Adding hydroxyethyl acrylate (HEA) for end-capping, with a molar ratio of polyurethane to HEA of 1:1-1.4, the reaction temperature being between 60-90° C., and the reaction being carried out for 6-12 hours to produce the resin II.

8. Use of the phosphorus-based hybrid polymer coating according to any one of claims 1 to 3 in the field of optics, characterized in that: The phosphorus-based material hybrid polymer coating is coated on an optical device, and is pre-baked and ultraviolet-cured to form a film on the optical device.

Images