Flexible high-hydrophobicity self-luminous life jacket and preparation method thereof

Abstract

The invention belongs to the technical field of 3D printing and flexible high-hydrophobicity self-luminous life jackets, and particularly relates to a flexible high-hydrophobicity self-luminous life jacket and a preparation method thereof. A self-luminous waterborne polyurethane emulsion of a hydrophobic modified energy-storage long-afterglow luminescent material is synthesized, the prepared self-luminous waterborne polyurethane emulsion is used for coating and post-processing a thermoplastic polyurethane elastomer (TPU) flexible life jacket part formed by SLS, and a luminous coating permeates into micro-gaps in the surface of the TPU part and is attached to the surface. And a firmly attached self-luminous coating is formed after curing, so that the hydrophobic property of the TPU life jacket product is obviously improved, and the self-luminous function in a dim and dark environment is also realized. The problems that a traditional fluorescent material is low in luminous intensity, incapable of continuously emitting light, poor in water resistance and the like are solved, and excellent high-hydrophobicity self-luminous performance is obtained on the premise that the original SLS forming process characteristics of the TPU life jacket are not changed and the mechanical property of the TPU life jacket is reserved.

Description

Technical Field

[0001] The present invention belongs to the technical field of 3D printing and flexible highly hydrophobic self-luminous life jackets, and specifically relates to a flexible highly hydrophobic self-luminous life jacket and a preparation method thereof, in particular to a post-processing functionalization technology of a life jacket component with a flexible highly hydrophobic self-luminous function that can be suitable for selective laser sintering. Background Art

[0002] Life jackets are emergency protection and rescue equipment that can provide safety precautions for people working on water and reduce casualties in emergencies such as drowning. Life jackets with high buoyancy, high strength and flexible wearing can provide good comfort for users while ensuring safety. Considering that life jackets may also be used at night or in waters with insufficient light, such as in environments where natural disasters cannot be fully illuminated, life jackets with self-luminous functions are particularly necessary, which can display warning information in dim or no light environments to improve search and rescue efficiency.

[0003] At present, the luminescent materials that can be used for coatings mainly include fluorescent materials, irradiation luminescent materials and photoluminescent energy storage materials. Fluorescent materials will only emit light when excited by ultraviolet rays of a specific wavelength. When the ultraviolet rays disappear, the fluorescent luminescence phenomenon ends, and there is no continuous luminescence condition; irradiation luminescent materials can absorb light energy under the irradiation of visible light, and convert the light energy into visible light again in the dark, with high luminescence intensity, but the addition of radioactive substances in irradiation luminescent materials is harmful to the human body and the environment, and their application is limited; photoluminescent energy storage materials can absorb and store the light energy of visible light or ultraviolet light and emit light in a dark environment, and the absorption of light energy-luminescence process can be repeated. Common photoluminescent energy storage materials are alkaline earth aluminates or silicate materials activated by rare earth ions, which have the advantages of high brightness, no radiation, and long luminescence time, but they have problems such as water resistance and poor compatibility with polymer coatings. The above-mentioned technologies have limitations such as high requirements for excitation conditions, short luminescence time, radioactive radiation, poor water resistance and compatibility, which are not conducive to the manufacture and popularization of self-luminous life jackets.

[0004] In addition, existing life jackets usually include inflatable, buoyancy material filled and composite life jackets. Among them, inflatable life jackets are easily damaged and ineffective in some complex use environments; buoyancy material filled and buoyancy material-inflatable composite life jackets include two parts: outer fabric and buoyancy filler, and the preparation process has many steps and is inconvenient to wear. Summary of the invention

[0005] In view of the problems in the existing luminous life jacket preparation technology that the fluorescent materials used in the luminous coating have low luminous intensity and cannot continuously emit self-luminescence, and the coatings using irradiation luminescent materials and rare earth activated aluminate long afterglow luminescent materials are prone to cause radiation hazards to the environment and human body during use, and have poor water resistance, the present invention proposes the following solutions.

[0006] The present invention uses SrNO3 and Al(NO)3·H2O as matrix elements, Eu 2+ 、Dy 3+ As an activator, a hydrophobically modified nano-scale strontium aluminate oxide powder was synthesized by a sol-gel method. The powder was compounded with an aqueous polyurethane emulsion to prepare a coating with excellent luminescent properties, which reduced the friction on the coating surface and improved the wear resistance of the coating. The synthesis process is simple and greatly reduces the cost; the aluminate luminescent emulsion modified by organic siloxane has good water resistance and cyclic luminescence stability, high afterglow brightness and long duration. A highly hydrophobic self-luminous coating was anchored on the surface of a flexible life jacket formed by selective laser sintering; the highly hydrophobic self-luminous coating was obtained by curing the highly hydrophobic energy storage long afterglow luminescent coating coated on the surface of the component.

[0007] In the present invention, the preparation of the highly hydrophobic energy storage long afterglow luminescent coating comprises the following steps:

[0008] Step (1.1): Dissolve europium oxide (Eu2O3) and dysprosium oxide (Dy2O3) in nitric acid solution to obtain an activator Eu 2 + 、Dy 3+ Nitrate solution; after dissolving strontium nitrate (SrNO3) and hydrated aluminum nitrate (Al(NO)3·H2O) in deionized water, add activator Eu 2+ 、Dy 3+ nitrate solution and citric acid, heating and stirring, continuing to add citric acid to adjust the solution pH value to 2-3, to obtain a uniform and transparent inorganic salt aqueous solution; heating and adding silane coupling agent ethanol solution and stirring to convert the solution into a sol, and drying to obtain hydrophobically modified strontium aluminate oxide powder;

[0009] Step (1.2): Mix the dried polyether polyol and polyisocyanate evenly under nitrogen protection, add dibutyltin dilaurate catalyst, continue stirring and react at 80-90°C, add 2,2-dihydroxymethylpropionic acid, film-forming aid and cross-linking agent, and continue to react at 80-90°C for a period of time; reduce the temperature of the reaction solution to 40-45°C, add acetone, and then add the hydrophobically modified strontium aluminate oxide powder obtained in step (1.1) to react; add triethylamine for neutralization; add deionized water and emulsify in an ice water bath; rotary evaporate the emulsion after emulsification to obtain a self-luminous water-based polyurethane emulsion containing a hydrophobically modified energy storage long afterglow luminescent material, that is, a highly hydrophobic energy storage long afterglow luminescent coating.

[0010] Furthermore, forming a highly hydrophobic self-luminous coating on the surface of a flexible life jacket formed by selective laser sintering comprises the following steps:

[0011] Step (2.1): preparing a clean and dry flexible life jacket component formed by selective laser sintering;

[0012] Step (2.2): placing the life jacket obtained in step (2.1) into a dipping container, injecting the highly hydrophobic energy storage long afterglow luminescent coating obtained in step (1.2) into the dipping container, and taking out the life jacket after the life jacket is fully dipped in the coating;

[0013] Step (2.3): Curing the life jacket with highly hydrophobic energy storage long afterglow luminous coating attached to the surface obtained in step (2.2) at 40-80°C, wherein the coating is cured and anchored on the surface of the life jacket to form a coating, thereby obtaining the flexible highly hydrophobic self-luminous life jacket.

[0014] As an optimized solution for the preparation of a flexible, highly hydrophobic, self-luminous life jacket, in step (1.1), the mass ratio of europium oxide (Eu2O3) to dysprosium oxide (Dy2O3) is 1:2 to 2:1; the inorganic salt aqueous solution is heated to 60 to 80°C, and then an ethanol solution of a silane coupling agent is added, and the mixture is reacted at a stirring speed of 300 to 500 r / min for 1 to 2 hours. When the solution is converted into a sol, the sol is dried at a constant temperature at 100 to 120°C for 5 to 10 hours to obtain a hydrophobically modified strontium aluminate oxide powder.

[0015] As an optimized solution for the preparation method of a flexible highly hydrophobic self-luminous life jacket, in step (1.2), after lowering the temperature of the reaction liquid to 40-45°C, acetone is added, and then the hydrophobically modified strontium aluminate oxide powder obtained in step (1.1) is added, and the reaction is carried out for 30-60 minutes; triethylamine is added for neutralization for 30-60 minutes; deionized water is added and emulsified in an ice water bath, and the stirring speed during the emulsification process is 1000-2000r / min, and the stirring time is 30-60 minutes; finally, the emulsion after emulsification is rotary evaporated in a rotary evaporator to remove water and acetone, and the rotary evaporation temperature is 45-60°C to obtain a highly hydrophobic energy storage long afterglow luminescent coating.

[0016] As an optimized solution for the preparation method of a flexible, highly hydrophobic, self-luminous life jacket, in step (2.1), a three-dimensional mesh hollow life jacket component obtained by selective laser sintering of TPU powder is placed in clean water for cleaning, and then dried at 50 to 70°C for 3 to 5 hours to obtain a clean and dry life jacket component; in step (2.2), the life jacket component is rotated in a clockwise and counterclockwise direction for 3 to 5 cycles during the dipping process, and the life jacket component is lifted out of the coating after the rotation is completed, and this is repeated 1 to 3 times; in step (2.3), the life jacket is placed in a constant temperature box at 40 to 80°C and cured at the constant temperature for 4 to 8 hours.

[0017] As an optimized solution for the preparation method of a flexible, highly hydrophobic, self-luminous life jacket, the life jacket component is made of TPU powder by selective laser sintering.

[0018] As an optimized solution for the preparation method of a flexible, highly hydrophobic, self-luminous life jacket, the surface layer of the life jacket is closed; inside the surface layer is a three-dimensional mesh hollow structure, and the hollowness gradually increases from the near surface layer to the center.

[0019] As an optimized solution for the preparation method of a flexible, highly hydrophobic, self-luminous life jacket, in step (1.1), the silane coupling agent used for hydrophobic modification of strontium aluminate oxide is one or more of octadecyltrichlorosilane, γ-aminopropyltriethoxysilane or N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane; the amount of the silane coupling agent added is 0.5 to 3 parts by mass of strontium aluminate oxide.

[0020] As an optimized solution for the preparation method of a flexible, highly hydrophobic, self-luminous life jacket, in step (1.2), polyether polyol and polyisocyanate are used in a mass ratio of (2 to 5):1; the polyether polyol is one or more of polyethylene oxide glycol, polypropylene oxide glycol, and polymethylene glycol; the polyisocyanate is one or more of hydrogenated benzyl diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate; the film-forming aid is one or more of diethylene glycol butyl ether, propylene glycol methyl ether acetate, and propylene glycol butyl ether; the cross-linking agent is one or more of ethylenediamine, bisphenol A epoxy resin, and hexamethoxymethylene melamine.

[0021] The present invention further provides a flexible highly hydrophobic self-luminous life jacket, which is prepared by adopting the preparation method of the flexible highly hydrophobic self-luminous life jacket.

[0022] Beneficial Effects

[0023] (1) The present invention uses Sr and Al oxides as luminescent matrix, and rare earth ions Eu 2+ 、Dy 3+ As an activator, and hydrophobic modification was performed during the synthesis process, so that the prepared life jacket has excellent afterglow luminescence performance, and good water resistance and light resistance stability. The prepared life jacket can not only glow for a long time in a dark environment, but also maintain a stable luminescence effect in a humid environment.

[0024] (2) The present invention adopts a dip coating process to form a highly hydrophobic self-luminous coating on the surface of the life jacket, which is not limited by the outer structure of the life jacket and can be evenly coated on the surface of a life jacket of any shape, thereby improving the coating efficiency and the scope of application.

[0025] (3) The life jacket formed in one piece using SLS technology in the present invention not only has high buoyancy and strength, but also has the characteristics of being flexible to wear, thereby improving the comfort of the user. In particular, by adjusting the hollowing degree and distribution inside the life jacket, the buoyancy distribution can be optimized, the overall weight can be reduced, and the safety performance can be enhanced.

[0026] (4) The life jacket made by the present invention does not contain radioactive substances, has no radiation hazard to human body and environment, and meets modern environmental protection requirements.

[0027] (5) The present invention uses TPU powder to dip-coat a luminous, highly hydrophobic, energy-storing, long-afterglow luminous coating on a life jacket component formed by SLS. After the TPU powder is formed by SLS, there are usually a large number of micro-voids on the surface. The coating partially penetrates into the micro-voids and is anchored on the surface of the life jacket component after solidification, with high bonding strength, thereby improving the durability of the life jacket. DETAILED DESCRIPTION

[0028] The present invention is further illustrated by specific examples below. These examples are exemplary and are intended to illustrate the problem and explain the present invention, but are not intended to be limiting.

[0029] The solution of the subsequent embodiment of the present invention is to use a dip-coating process to coat the surface of the TPU life jacket product obtained by SLS printing with a layer of self-luminous aqueous polyurethane emulsion with nano-scale roughness and containing hydrophobically modified energy storage long afterglow luminescent material. After curing, a highly hydrophobic self-luminous life jacket product can be obtained.

[0030] The long afterglow luminescent material used in the subsequent embodiments of the present invention is composed of strontium nitrate and hydrated aluminum nitrate as matrix raw materials, Eu 2+ 、Dy 3+ As an activator, it is aggregated into nano-scale particles through the sol-gel method, and the surface of the particles is modified by an alcohol solution of organic siloxane to generate a highly hydrophobic self-luminous phosphor.

[0031] The preparation method of the hydrophobic energy storage long afterglow luminescent material is carried out according to the following steps:

[0032] Step 1: Dissolve europium oxide (Eu2O3) and dysprosium oxide (Dy2O3) in nitric acid solution, dissolve strontium nitrate (SrNO3) and hydrated aluminum nitrate (Al(NO)3·H2O) in deionized water, and then mix with the above-mentioned activator Eu 2+ and Dy 3+ The nitrate solution is mixed with citric acid, and the mixed solution is stirred and heated on a magnetic stirring device. During the stirring process, citric acid is continuously added to adjust the pH value of the solution to 3. The reaction temperature is set to 70°C, and an ethanol solution of a silane coupling agent is added and stirred. When the solution is converted into a sol, the sol is dried to obtain a hydrophobically modified strontium aluminate oxide powder as a luminescent matrix.

[0033] Step 2: After the dried polyether polyol and polyisocyanate are mixed evenly under nitrogen protection, a dibutyltin dilaurate catalyst is added, and the reaction is heated for a period of time, and then 2,2-dihydroxymethylpropionic acid, a film-forming aid and a cross-linking agent are added to continue the reaction; then the temperature is lowered, acetone is added, and the hydrophobically modified strontium aluminate oxide hydrophobic powder obtained in step (1) is added to react; triethylamine is added for neutralization; an appropriate amount of deionized water is added and emulsified in an ice water bath, and the emulsion after emulsification is completed is rotary evaporated to remove water and organic solvents such as acetone to obtain an aqueous polyurethane emulsion containing a modified hydrophobic energy storage long afterglow luminescent material.

[0034] Example 1

[0035] (1) Dissolve 0.1 g of europium oxide (Eu2O3) and 0.1 g of dysprosium oxide (Dy2O3) in nitric acid solution, dissolve 5 g of strontium nitrate (SrNO3) and 10 g of hydrated aluminum nitrate (Al(NO)3·H2O) in 100 ml of deionized water, and then mix with the activator Eu2O3. 2+ 、Dy 3 + nitrate solution, then add 1g of citric acid, and stir and heat the mixed solution on a magnetic stirring device for 3h at a stirring speed of 150r / min. During the stirring process, continue to add citric acid to adjust the solution pH to 3. Set the reaction temperature to 70°C, add 1.5g of octadecyltrichlorosilane in ethanol, stir at a speed of 300r / min, and react for 1h. When the solution is converted into a sol, dry the sol at a constant temperature for 5h at a drying temperature of 100°C to obtain a hydrophobically modified strontium aluminate oxide powder.

[0036] (2) After drying 100g of polyether polyol and 20g of polyisocyanate, 2ml of dibutyltin dilaurate catalyst was added and the mixture was reacted at 80°C for about 2h, with continuous stirring during the reaction. Then, 2ml of 2,2-dihydroxymethylpropionic acid, 6ml of ethylenediamine and 6ml of propylene glycol methyl ether acetate were added and the mixture was reacted at 80°C for 2h. The reaction liquid temperature was lowered to 40°C, 10ml of acetone was added, and then 5g of hydrophobically modified strontium aluminate oxide hydrophobic powder obtained in step (1) was added and the mixture was reacted for 1h. 2ml of triethylamine was added for neutralization for 30min. 375ml of deionized water was added and the mixture was emulsified in an ice water bath at a stirring speed of 1000r / min for 30min. Finally, the emulsion after emulsification was subjected to rotary evaporation for 1h at a rotary evaporation temperature of 50°C to obtain an aqueous polyurethane emulsion containing a modified hydrophobic energy storage long afterglow luminescent material.

[0037] (3) The three-dimensional hollow life jacket product obtained by selective laser sintering of TPU powder was placed in clean water for cleaning and dried at 50° C. for 3 h to obtain a clean and dry life jacket product;

[0038] (4) The life jacket obtained in step (3) is placed in a dipping box and fixed at the bottom of the box, and then the aqueous polyurethane emulsion containing the modified hydrophobic energy storage long afterglow luminescent material obtained in step (2) is slowly injected into the dipping box, the liquid level of the emulsion is 3 cm higher than the life jacket, the dipping time is 120 s, and the fixture for dipping and fixing the life jacket is rotated evenly in the clockwise direction and the counterclockwise direction for 3 circles respectively. After the rotation is completed, the life jacket is lifted from the emulsion and immersed in it for 3 times to obtain a life jacket with a highly hydrophobic energy storage long afterglow self-luminous coating attached to the surface;

[0039] (5) The highly hydrophobic self-luminous life jacket obtained in step (4) is placed in a constant temperature box, kept at 60° C., and cured for 6 hours.

[0040] Example 2

[0041] (1) Dissolve 0.25 g of europium oxide (Eu2O3) and 0.25 g of dysprosium oxide (Dy2O3) in nitric acid solution, dissolve 5 g of strontium nitrate (SrNO3) and 10 g of hydrated aluminum nitrate (Al(NO)3·H2O) in 100 ml of deionized water, and then mix with the activator Eu2O3. 2+ 、Dy 3 + nitrate solution, then add 1g of citric acid, and stir and heat the mixed solution on a magnetic stirring device for 3h at a stirring speed of 150r / min. During the stirring process, continue to add citric acid to adjust the solution pH to 3. Set the reaction temperature to 70°C, add 1.5g of octadecyltrichlorosilane in ethanol, stir at a speed of 300r / min, and react for 1h. When the solution is converted into a sol, dry the sol at a constant temperature for 5h at a drying temperature of 100°C to obtain a hydrophobically modified strontium aluminate oxide powder.

[0042] (2) After drying 100g of polyether polyol and 20g of polyisocyanate, 2ml of dibutyltin dilaurate catalyst was added and the mixture was reacted at 80°C for about 2h, with continuous stirring during the reaction. Then, 2ml of 2,2-dihydroxymethylpropionic acid, 6ml of ethylenediamine and 6ml of propylene glycol methyl ether acetate were added and the mixture was reacted at 80°C for 2h. The reaction liquid temperature was lowered to 40°C, 10ml of acetone was added, and then 5g of hydrophobically modified strontium aluminate oxide hydrophobic powder obtained in step (1) was added and the mixture was reacted for 1h. 2ml of triethylamine was added for neutralization for 30min. 375ml of deionized water was added and the mixture was emulsified in an ice water bath at a stirring speed of 1000r / min for 30min. Finally, the emulsion after emulsification was subjected to rotary evaporation for 1h at a rotary evaporation temperature of 50°C to obtain an aqueous polyurethane emulsion containing a modified hydrophobic energy storage long afterglow luminescent material.

[0043] (3) The three-dimensional hollow life jacket product obtained by selective laser sintering of TPU powder was placed in clean water for cleaning and dried at 50° C. for 3 h to obtain a clean and dry life jacket product;

[0044] (4) The life jacket obtained in step (3) is placed in a dipping box and fixed at the bottom of the box, and then the aqueous polyurethane emulsion containing the modified hydrophobic energy storage long afterglow luminescent material obtained in step (2) is slowly injected into the dipping box, the liquid level of the emulsion is 3 cm higher than the life jacket, the dipping time is 120 s, and the fixture for dipping and fixing the life jacket is rotated evenly in the clockwise direction and the counterclockwise direction for 3 circles respectively. After the rotation is completed, the life jacket is lifted from the emulsion and immersed in it for 3 times to obtain a life jacket with a highly hydrophobic energy storage long afterglow self-luminous coating attached to the surface;

[0045] (5) The highly hydrophobic self-luminous life jacket obtained in step (4) is placed in a constant temperature box, kept at 60° C., and cured for 6 hours.

[0046] Example 3

[0047] (1) Dissolve 0.5 g of europium oxide (Eu2O3) and 0.5 g of dysprosium oxide (Dy2O3) in nitric acid solution, dissolve 5 g of strontium nitrate (SrNO3) and 10 g of hydrated aluminum nitrate (Al(NO)3·H2O) in 100 ml of deionized water, and then add the activator Eu2O3 to the mixture. 2+ 、Dy 3 + nitrate solution, then add 1g of citric acid, and stir and heat the mixed solution on a magnetic stirring device for 3h at a stirring speed of 150r / min. During the stirring process, continue to add citric acid to adjust the solution pH to 3. Set the reaction temperature to 70°C, add 1.5g of octadecyltrichlorosilane in ethanol, stir at a speed of 300r / min, and react for 1h. When the solution is converted into a sol, dry the sol at a constant temperature for 5h at a drying temperature of 100°C to obtain a hydrophobically modified strontium aluminate oxide powder.

[0048] (2) After drying 100g of polyether polyol and 20g of polyisocyanate, 2ml of dibutyltin dilaurate catalyst was added and the mixture was reacted at 80°C for about 2h, with continuous stirring during the reaction. Then, 2ml of 2,2-dihydroxymethylpropionic acid, 6ml of ethylenediamine and 6ml of propylene glycol methyl ether acetate were added and the mixture was reacted at 80°C for 2h. The reaction liquid temperature was lowered to 40°C, 10ml of acetone was added, and then 5g of hydrophobically modified strontium aluminate oxide hydrophobic powder obtained in step (1) was added and the mixture was reacted for 1h. 2ml of triethylamine was added for neutralization for 30min. 375ml of deionized water was added and the mixture was emulsified in an ice water bath at a stirring speed of 1000r / min for 30min. Finally, the emulsion after emulsification was subjected to rotary evaporation for 1h at a rotary evaporation temperature of 50°C to obtain an aqueous polyurethane emulsion containing a modified hydrophobic energy storage long afterglow luminescent material.

[0049] (3) The three-dimensional hollow life jacket product obtained by selective laser sintering of TPU powder was placed in clean water for cleaning and dried at 50° C. for 3 h to obtain a clean and dry life jacket product;

[0050] (4) The life jacket obtained in step (3) is placed in a dipping box and fixed at the bottom of the box, and then the aqueous polyurethane emulsion containing the modified hydrophobic energy storage long afterglow luminescent material obtained in step (2) is slowly injected into the dipping box, the liquid level of the emulsion is 3 cm higher than the life jacket, the dipping time is 120 s, and the fixture for dipping and fixing the life jacket is rotated evenly in the clockwise direction and the counterclockwise direction for 3 circles respectively. After the rotation is completed, the life jacket is lifted from the emulsion and immersed in it for 3 times to obtain a life jacket with a highly hydrophobic energy storage long afterglow self-luminous coating attached to the surface;

[0051] (5) The highly hydrophobic self-luminous life jacket obtained in step (4) is placed in a constant temperature box, kept at 60° C., and cured for 6 hours.

[0052] Example 4

[0053] (1) Dissolve 0.25 g of europium oxide (Eu2O3) and 0.25 g of dysprosium oxide (Dy2O3) in nitric acid solution, dissolve 5 g of strontium nitrate (SrNO3) and 10 g of hydrated aluminum nitrate (Al(NO)3·H2O) in 100 ml of deionized water, and then mix with the activator Eu2O3. 2+ 、Dy 3 + nitrate solution, and then add 1g of citric acid. The mixed solution is stirred and heated on a magnetic stirring device for 3h at a stirring speed of 150r / min. During the stirring process, citric acid is continuously added to adjust the pH value of the solution to 3. The reaction temperature is set to 70°C, and an ethanol solution containing 0.5g of octadecyltrichlorosilane is added. The stirring speed is 300r / min. The reaction is carried out for 1h. When the solution is converted into a sol, the sol is dried at a constant temperature for 5h at a drying temperature of 100°C to obtain a hydrophobically modified strontium aluminate oxide powder.

[0054] (2) After drying 100g of polyether polyol and 20g of polyisocyanate, 2ml of dibutyltin dilaurate catalyst was added and the mixture was reacted at 80°C for about 2h, with continuous stirring during the reaction. Then, 2ml of 2,2-dihydroxymethylpropionic acid, 6ml of ethylenediamine and 6ml of propylene glycol methyl ether acetate were added and the mixture was reacted at 80°C for 2h. The reaction liquid temperature was lowered to 40°C, 10ml of acetone was added, and then 5g of hydrophobically modified strontium aluminate oxide hydrophobic powder obtained in step (1) was added and the mixture was reacted for 1h. 2ml of triethylamine was added for neutralization for 30min. 375ml of deionized water was added and the mixture was emulsified in an ice water bath at a stirring speed of 1000r / min for 30min. Finally, the emulsion after emulsification was subjected to rotary evaporation for 1h at a rotary evaporation temperature of 50°C to obtain an aqueous polyurethane emulsion containing a modified hydrophobic energy storage long afterglow luminescent material.

[0055] (3) The three-dimensional hollow life jacket product obtained by selective laser sintering of TPU powder was placed in clean water for cleaning and dried at 50° C. for 3 h to obtain a clean and dry life jacket product;

[0056] (4) The life jacket obtained in step (3) is placed in a dipping box and fixed at the bottom of the box, and then the aqueous polyurethane emulsion containing the modified hydrophobic energy storage long afterglow luminescent material obtained in step (2) is slowly injected into the dipping box, the liquid level of the emulsion is 3 cm higher than the life jacket, the dipping time is 120 s, and the fixture for dipping and fixing the life jacket is rotated evenly in the clockwise direction and the counterclockwise direction for 3 circles respectively. After the rotation is completed, the life jacket is lifted from the emulsion and immersed in it for 3 times to obtain a life jacket with a highly hydrophobic energy storage long afterglow self-luminous coating attached to the surface;

[0057] (5) The highly hydrophobic self-luminous life jacket obtained in step (4) is placed in a constant temperature box, kept at 60° C., and cured for 6 hours.

[0058] Example 5

[0059] (1) Dissolve 0.25 g of europium oxide (Eu2O3) and 0.25 g of dysprosium oxide (Dy2O3) in nitric acid solution, dissolve 5 g of strontium nitrate (SrNO3) and 10 g of hydrated aluminum nitrate (Al(NO)3·H2O) in 100 ml of deionized water, and then mix with the activator Eu2O3. 2+ 、Dy 3 +nitrate solution, and then add 1g of citric acid. The mixed solution is stirred and heated on a magnetic stirring device for 3h at a stirring speed of 150r / min. During the stirring process, citric acid is continuously added to adjust the pH value of the solution to 3. The reaction temperature is set to 70°C, and an ethanol solution containing 3g of octadecyltrichlorosilane is added. The stirring speed is 300r / min. The reaction is carried out for 1h. When the solution is converted into a sol, the sol is dried at a constant temperature for 5h at a drying temperature of 100°C to obtain a hydrophobically modified strontium aluminate oxide powder.

[0060] (2) After drying 100g of polyether polyol and 20g of polyisocyanate, 2ml of dibutyltin dilaurate catalyst was added and the mixture was reacted at 80°C for about 2h, with continuous stirring during the reaction. Then, 2ml of 2,2-dihydroxymethylpropionic acid, 6ml of ethylenediamine and 6ml of propylene glycol methyl ether acetate were added and the mixture was reacted at 80°C for 2h. The reaction liquid temperature was lowered to 40°C, 10ml of acetone was added, and then 5g of hydrophobically modified strontium aluminate oxide hydrophobic powder obtained in step (1) was added and the mixture was reacted for 1h. 2ml of triethylamine was added for neutralization for 30min. 375ml of deionized water was added and the mixture was emulsified in an ice water bath at a stirring speed of 1000r / min for 30min. Finally, the emulsion after emulsification was subjected to rotary evaporation for 1h at a rotary evaporation temperature of 50°C to obtain an aqueous polyurethane emulsion containing a modified hydrophobic energy storage long afterglow luminescent material.

[0061] (3) The three-dimensional hollow life jacket product obtained by selective laser sintering of TPU powder was placed in clean water for cleaning and dried at 50° C. for 3 h to obtain a clean and dry life jacket product;

[0062] (4) The life jacket obtained in step (3) is placed in a dipping box and fixed at the bottom of the box, and then the aqueous polyurethane emulsion containing the modified hydrophobic energy storage long afterglow luminescent material obtained in step (2) is slowly injected into the dipping box, the liquid level of the emulsion is 3 cm higher than the life jacket, the dipping time is 120 s, and the fixture for dipping and fixing the life jacket is rotated evenly in the clockwise direction and the counterclockwise direction for 3 circles respectively. After the rotation is completed, the life jacket is lifted from the emulsion and immersed in it for 3 times to obtain a life jacket with a highly hydrophobic energy storage long afterglow self-luminous coating attached to the surface;

[0063] (5) The highly hydrophobic self-luminous life jacket obtained in step (4) is placed in a constant temperature box, kept at 60° C., and cured for 6 hours.

[0064] Example 6

[0065] (1) Dissolve 0.25 g of europium oxide (Eu2O3) and 0.25 g of dysprosium oxide (Dy2O3) in nitric acid solution, dissolve 5 g of strontium nitrate (SrNO3) and 10 g of hydrated aluminum nitrate (Al(NO)3·H2O) in 100 ml of deionized water, and then mix with the activator Eu2O3. 2+ 、Dy 3 + nitrate solution, then add 1g of citric acid, and stir and heat the mixed solution on a magnetic stirring device for 3h at a stirring speed of 150r / min. During the stirring process, continue to add citric acid to adjust the solution pH to 3. Set the reaction temperature to 70°C, add 1.5g of octadecyltrichlorosilane in ethanol, stir at a speed of 300r / min, and react for 1h. When the solution is converted into a sol, dry the sol at a constant temperature for 5h at a drying temperature of 100°C to obtain a hydrophobically modified strontium aluminate oxide powder.

[0066] (2) After drying 100g of polyether polyol and 20g of polyisocyanate, 2ml of dibutyltin dilaurate catalyst was added and the mixture was reacted at 80°C for about 2h, with continuous stirring during the reaction. Then, 2ml of 2,2-dihydroxymethylpropionic acid, 6ml of ethylenediamine and 6ml of propylene glycol methyl ether acetate were added and the mixture was reacted at 80°C for 2h. The reaction liquid temperature was lowered to 40°C, 10ml of acetone was added, and then 5g of hydrophobically modified strontium aluminate oxide hydrophobic powder obtained in step (1) was added and the mixture was reacted for 1h. 2ml of triethylamine was added for neutralization for 30min. 375ml of deionized water was added and the mixture was emulsified in an ice water bath at a stirring speed of 1000r / min for 30min. Finally, the emulsion after emulsification was subjected to rotary evaporation for 1h at a rotary evaporation temperature of 50°C to obtain an aqueous polyurethane emulsion containing a modified hydrophobic energy storage long afterglow luminescent material.

[0067] (3) The three-dimensional hollow life jacket product obtained by selective laser sintering of TPU powder was placed in clean water for cleaning and dried at 50° C. for 3 h to obtain a clean and dry life jacket product;

[0068] (4) The life jacket obtained in step (3) is placed in a dipping box and fixed at the bottom of the box, and then the aqueous polyurethane emulsion containing the modified hydrophobic energy storage long afterglow luminescent material obtained in step (2) is slowly injected into the dipping box, the liquid level of the emulsion is 3 cm higher than the life jacket, the dipping time is 120 s, and the fixture for dipping and fixing the life jacket is rotated evenly in the clockwise direction and the counterclockwise direction for 3 circles respectively. After the rotation is completed, the life jacket is lifted from the emulsion and immersed in it for 3 times to obtain a life jacket with a highly hydrophobic energy storage long afterglow self-luminous coating attached to the surface;

[0069] (5) The highly hydrophobic self-luminous life jacket obtained in step (4) is placed in a constant temperature box, kept at 60° C., and cured for 4 hours.

[0070] Example 7

[0071] (1) Dissolve 0.25 g of europium oxide (Eu2O3) and 0.25 g of dysprosium oxide (Dy2O3) in nitric acid solution, dissolve 5 g of strontium nitrate (SrNO3) and 10 g of hydrated aluminum nitrate (Al(NO)3·H2O) in 100 ml of deionized water, and then mix with the activator Eu2O3. 2+ 、Dy 3 + nitrate solution, then add 1g of citric acid, and stir and heat the mixed solution on a magnetic stirring device for 3h at a stirring speed of 150r / min. During the stirring process, continue to add citric acid to adjust the solution pH to 3. Set the reaction temperature to 70°C, add 1.5g of octadecyltrichlorosilane in ethanol, stir at a speed of 300r / min, and react for 1h. When the solution is converted into a sol, dry the sol at a constant temperature for 5h at a drying temperature of 100°C to obtain a hydrophobically modified strontium aluminate oxide powder.

[0072] (2) After drying 100g of polyether polyol and 20g of polyisocyanate, 2ml of dibutyltin dilaurate catalyst was added and the mixture was reacted at 80°C for about 2h, with continuous stirring during the reaction. Then, 2ml of 2,2-dihydroxymethylpropionic acid, 6ml of ethylenediamine and 6ml of propylene glycol methyl ether acetate were added and the mixture was reacted at 80°C for 2h. The reaction liquid temperature was lowered to 40°C, 10ml of acetone was added, and then 5g of hydrophobically modified strontium aluminate oxide hydrophobic powder obtained in step (1) was added and the mixture was reacted for 1h. 2ml of triethylamine was added for neutralization for 30min. 375ml of deionized water was added and the mixture was emulsified in an ice water bath at a stirring speed of 1000r / min for 30min. Finally, the emulsion after emulsification was subjected to rotary evaporation for 1h at a rotary evaporation temperature of 50°C to obtain an aqueous polyurethane emulsion containing a modified hydrophobic energy storage long afterglow luminescent material.

[0073] (3) The three-dimensional hollow life jacket product obtained by selective laser sintering of TPU powder was placed in clean water for cleaning and dried at 50° C. for 3 h to obtain a clean and dry life jacket product;

[0074] (4) The life jacket obtained in step (3) is placed in a dipping box and fixed at the bottom of the box, and then the aqueous polyurethane emulsion containing the modified hydrophobic energy storage long afterglow luminescent material obtained in step (2) is slowly injected into the dipping box, the liquid level of the emulsion is 3 cm higher than the life jacket, the dipping time is 120 s, and the fixture for dipping and fixing the life jacket is rotated evenly in the clockwise direction and the counterclockwise direction for 3 circles respectively. After the rotation is completed, the life jacket is lifted from the emulsion and immersed in it for 3 times to obtain a life jacket with a highly hydrophobic energy storage long afterglow self-luminous coating attached to the surface;

[0075] (5) The highly hydrophobic self-luminous life jacket obtained in step (4) is placed in a constant temperature box, kept at 60° C., and cured for 8 hours.

[0076] Example 8

[0077] (1) Dissolve 0.25 g of europium oxide (Eu2O3) and 0.25 g of dysprosium oxide (Dy2O3) in nitric acid solution, dissolve 5 g of strontium nitrate (SrNO3) and 10 g of hydrated aluminum nitrate (Al(NO)3·H2O) in 100 ml of deionized water, and then mix with the activator Eu2O3. 2+ 、Dy 3 + nitrate solution, then add 1g of citric acid, and stir and heat the mixed solution on a magnetic stirring device for 3h at a stirring speed of 150r / min. During the stirring process, continue to add citric acid to adjust the solution pH to 3. Set the reaction temperature to 70°C, add 1.5g of octadecyltrichlorosilane in ethanol, stir at a speed of 300r / min, and react for 1h. When the solution is converted into a sol, dry the sol at a constant temperature for 5h at a drying temperature of 100°C to obtain a hydrophobically modified strontium aluminate oxide powder.

[0078] (2) After drying 100g of polyether polyol and 20g of polyisocyanate, 2ml of dibutyltin dilaurate catalyst was added and the mixture was reacted at 80°C for about 2h, with continuous stirring during the reaction. Then, 2ml of 2,2-dihydroxymethylpropionic acid, 6ml of ethylenediamine and 6ml of propylene glycol methyl ether acetate were added and the mixture was reacted at 80°C for 2h. The reaction liquid temperature was lowered to 40°C, 10ml of acetone was added, and then 5g of hydrophobically modified strontium aluminate oxide hydrophobic powder obtained in step (1) was added and the mixture was reacted for 1h. 2ml of triethylamine was added for neutralization for 30min. 375ml of deionized water was added and the mixture was emulsified in an ice water bath at a stirring speed of 1000r / min for 30min. Finally, the emulsion after emulsification was subjected to rotary evaporation for 1h at a rotary evaporation temperature of 50°C to obtain an aqueous polyurethane emulsion containing a modified hydrophobic energy storage long afterglow luminescent material.

[0079] (3) The three-dimensional hollow life jacket product obtained by selective laser sintering of TPU powder was placed in clean water for cleaning and dried at 50° C. for 3 h to obtain a clean and dry life jacket product;

[0080] (4) The life jacket obtained in step (3) is placed in a dipping box and fixed at the bottom of the box, and then the aqueous polyurethane emulsion containing the modified hydrophobic energy storage long afterglow luminescent material obtained in step (2) is slowly injected into the dipping box, the liquid level of the emulsion is 3 cm higher than the life jacket, the dipping time is 120 s, and the fixture for dipping and fixing the life jacket is rotated evenly in the clockwise direction and the counterclockwise direction for 3 circles respectively. After the rotation is completed, the life jacket is lifted from the emulsion and immersed in it for 3 times to obtain a life jacket with a highly hydrophobic energy storage long afterglow self-luminous coating attached to the surface;

[0081] (5) The highly hydrophobic self-luminous life jacket obtained in step (4) is placed in a constant temperature box, kept at 40° C., and cured for 6 hours.

[0082] Example 9

[0083] (1) Dissolve 0.25 g of europium oxide (Eu2O3) and 0.25 g of dysprosium oxide (Dy2O3) in nitric acid solution, dissolve 5 g of strontium nitrate (SrNO3) and 10 g of hydrated aluminum nitrate (Al(NO)3·H2O) in 100 ml of deionized water, and then mix with the activator Eu2O3. 2+ 、Dy 3 + nitrate solution, then add 1g of citric acid, and stir and heat the mixed solution on a magnetic stirring device for 3h at a stirring speed of 150r / min. During the stirring process, continue to add citric acid to adjust the solution pH to 3. Set the reaction temperature to 70°C, add 1.5g of octadecyltrichlorosilane in ethanol, stir at a speed of 300r / min, and react for 1h. When the solution is converted into a sol, dry the sol at a constant temperature for 5h at a drying temperature of 100°C to obtain a hydrophobically modified strontium aluminate oxide powder.

[0084] (2) After drying 100g of polyether polyol and 20g of polyisocyanate, 2ml of dibutyltin dilaurate catalyst was added and the mixture was reacted at 80°C for about 2h, with continuous stirring during the reaction. Then, 2ml of 2,2-dihydroxymethylpropionic acid, 6ml of ethylenediamine and 6ml of propylene glycol methyl ether acetate were added and the mixture was reacted at 80°C for 2h. The reaction liquid temperature was lowered to 40°C, 10ml of acetone was added, and then 5g of hydrophobically modified strontium aluminate oxide hydrophobic powder obtained in step (1) was added and the mixture was reacted for 1h. 2ml of triethylamine was added for neutralization for 30min. 375ml of deionized water was added and the mixture was emulsified in an ice water bath at a stirring speed of 1000r / min for 30min. Finally, the emulsion after emulsification was subjected to rotary evaporation for 1h at a rotary evaporation temperature of 50°C to obtain an aqueous polyurethane emulsion containing a modified hydrophobic energy storage long afterglow luminescent material.

[0085] (3) The three-dimensional hollow life jacket product obtained by selective laser sintering of TPU powder was placed in clean water for cleaning and dried at 50° C. for 3 h to obtain a clean and dry life jacket product;

[0086] (4) The life jacket obtained in step (3) is placed in a dipping box and fixed at the bottom of the box, and then the aqueous polyurethane emulsion containing the modified hydrophobic energy storage long afterglow luminescent material obtained in step (2) is slowly injected into the dipping box, the liquid level of the emulsion is 3 cm higher than the life jacket, the dipping time is 120 s, and the fixture for dipping and fixing the life jacket is rotated evenly in the clockwise direction and the counterclockwise direction for 3 circles respectively. After the rotation is completed, the life jacket is lifted from the emulsion and immersed in it for 3 times to obtain a life jacket with a highly hydrophobic energy storage long afterglow self-luminous coating attached to the surface;

[0087] (5) The highly hydrophobic self-luminous life jacket obtained in step (4) is placed in a constant temperature box, kept at 80° C., and cured for 6 hours.

[0088] Comparative Example 1

[0089] (1) Dissolve 5 g of strontium nitrate (SrNO3) and 10 g of hydrated aluminum nitrate (Al(NO)3·H2O) in 100 ml of deionized water and mix with activator Eu 2+ 、Dy 3+ nitrate solution, then add 1g of citric acid, and stir and heat the mixed solution on a magnetic stirring device for 3h at a stirring speed of 150r / min. During the stirring process, continue to add citric acid to adjust the solution pH to 3. Set the reaction temperature to 70°C, add 1.5g of octadecyltrichlorosilane in ethanol, stir at a speed of 300r / min, and react for 1h. When the solution is converted into a sol, dry the sol at a constant temperature for 5h at a drying temperature of 100°C to obtain a hydrophobically modified strontium aluminate oxide powder.

[0090] (2) After drying 100g of polyether polyol and 20g of polyisocyanate, 2ml of dibutyltin dilaurate catalyst was added and the mixture was reacted at 80°C for about 2h, with continuous stirring during the reaction. Then, 2ml of 2,2-dihydroxymethylpropionic acid, 6ml of ethylenediamine and 6ml of propylene glycol methyl ether acetate were added and the mixture was reacted at 80°C for 2h. The reaction liquid temperature was lowered to 40°C, 10ml of acetone was added, and then 5g of hydrophobically modified strontium aluminate oxide hydrophobic powder obtained in step (1) was added and the mixture was reacted for 1h. 2ml of triethylamine was added for neutralization for 30min. 375ml of deionized water was added and the mixture was emulsified in an ice water bath at a stirring speed of 1000r / min for 30min. Finally, the emulsion after emulsification was subjected to rotary evaporation for 1h at a rotary evaporation temperature of 50°C to obtain an aqueous polyurethane emulsion containing a modified hydrophobic energy storage long afterglow luminescent material.

[0091] (3) The three-dimensional hollow life jacket product obtained by selective laser sintering of TPU powder was placed in clean water for cleaning and dried at 50° C. for 3 h to obtain a clean and dry life jacket product;

[0092] (4) The life jacket obtained in step (3) is placed in a dipping box and fixed at the bottom of the box, and then the aqueous polyurethane emulsion containing the modified hydrophobic energy storage long afterglow luminescent material obtained in step (2) is slowly injected into the dipping box, the liquid level of the emulsion is 3 cm higher than the life jacket, the dipping time is 120 s, and the fixture for dipping and fixing the life jacket is rotated evenly in the clockwise direction and the counterclockwise direction for 3 circles respectively. After the rotation is completed, the life jacket is lifted from the emulsion and immersed in it for 3 times to obtain a life jacket with a highly hydrophobic energy storage long afterglow self-luminous coating attached to the surface;

[0093] (5) The highly hydrophobic self-luminous life jacket obtained in step (4) is placed in a constant temperature box, kept at 60° C., and cured for 6 hours.

[0094] Comparative Example 2

[0095] (1) Dissolve 0.25 g of europium oxide (Eu2O3) and 0.25 g of dysprosium oxide (Dy2O3) in nitric acid solution, dissolve 5 g of strontium nitrate (SrNO3) and 10 g of hydrated aluminum nitrate (Al(NO)3·H2O) in 100 ml of deionized water, and then mix with the activator Eu2O3. 2+ 、Dy 3 +1g of nitrate solution was mixed, and 1g of citric acid was added. The mixed solution was stirred and heated on a magnetic stirring device for 3h at a stirring speed of 150r / min. During the stirring process, citric acid was continuously added to adjust the pH value of the solution to 3. The reaction temperature was set to 70°C and the stirring speed was 300r / min. The reaction was carried out for 1h. When the solution was converted into a sol, the sol was dried at a constant temperature for 5h at a drying temperature of 100°C to obtain strontium aluminate oxide powder.

[0096] (2) After drying 100g of polyether polyol and 20g of polyisocyanate, 2ml of dibutyltin dilaurate catalyst was added and the mixture was reacted at 80°C for about 2h, with continuous stirring during the reaction. Then, 2ml of 2,2-dihydroxymethylpropionic acid, 6ml of ethylenediamine and 6ml of propylene glycol methyl ether acetate were added and the mixture was reacted at 80°C for 2h. The reaction liquid temperature was lowered to 40°C, 10ml of acetone was added, and then 5g of strontium aluminate oxide powder obtained in step (1) was added and the mixture was reacted for 1h. 2ml of triethylamine was added for neutralization for 30min. 375ml of deionized water was added and the mixture was emulsified in an ice water bath at a stirring speed of 1000r / min for 30min. Finally, the emulsion after emulsification was subjected to rotary evaporation for 1h at a rotary evaporation temperature of 50°C to obtain an aqueous polyurethane emulsion containing an energy storage long afterglow luminescent material.

[0097] (3) The three-dimensional hollow life jacket product obtained by selective laser sintering of TPU powder was placed in clean water for cleaning and dried at 50° C. for 3 h to obtain a clean and dry life jacket product;

[0098] (4) The life jacket obtained in step (3) is placed in a dipping box and fixed at the bottom of the box, and then the aqueous polyurethane emulsion containing the energy storage long afterglow luminescent material obtained in step (2) is slowly injected into the dipping box, the liquid level of the emulsion is 3 cm higher than the life jacket, the dipping time is 120 s, and the fixture for dipping and fixing the life jacket is rotated evenly in the clockwise direction and the counterclockwise direction for 3 circles respectively. After the rotation is completed, the life jacket is lifted from the emulsion and immersed in it for 3 times to obtain a life jacket with an energy storage long afterglow self-luminous coating attached to the surface;

[0099] (5) The highly hydrophobic self-luminous life jacket obtained in step (4) is placed in a constant temperature box, kept at 60° C., and cured for 6 hours.

[0100] Effect verification

[0101] The following performance tests were performed on the life jackets coated with highly hydrophobic self-luminous coatings obtained in Examples 1 to 9 and Comparative Examples 1 and 2: at room temperature, using an afterglow characteristic tester, D65 standard light source excitation, excitation illumination of 1000 lx, excitation time of 5 min, and referring to GB / T 43716-2024 to record the afterglow brightness of the luminous coating greater than 10 mcd·m -2 The contact angle meter was used to measure the static contact angle (WCA) of deionized water on the surface of the tested luminescent coating. Each sample was tested three times at different points and the average value was taken. The test results are shown in Table 1.

[0102] Table 1 Performance test results

[0103]

[0104] The data in Table 1 show that the fluorescence properties of the life jackets molded by SLS are excellent. The fluorescence brightness and duration of the self-luminous coating are significantly affected by the dosage of rare earth activating ions, and its hydrophobicity is mainly related to the curing conditions of the coating.

[0105] As shown in the test results of Examples 1 to 3, as the amount of rare earth elements increases, the brightness of the luminescent coating will increase. The increase in the concentration of rare earth particle activators will fill the crystal coordination field environment provided by the strontium aluminate oxide matrix as much as possible, so that the number of luminescent centers increases and the luminescent performance of the material improves; however, when the concentration of the activator reaches a certain concentration and continues to increase, the probability of luminescent centers colliding with each other increases, causing part of the energy transmitted by the matrix to be dissipated in a non-radiative form, and the luminescent performance of the material will be reduced.

[0106] As shown in the test results of Examples 2, 4 and 5, with the increase in the amount of coupling agent octadecyltrichlorosilane, the brightness of the luminescent coating shows a trend of first increasing and then decreasing. This is because with the addition of organic siloxane, the surface of the strontium aluminate oxide luminescent powder is modified, which improves the affinity of the powder to the aqueous polyurethane, which is beneficial for grafting it to the aqueous polyurethane segment to prevent it from contacting water and causing a quenching effect; however, adding too much siloxane will increase the hydrophilic groups on the surface of the coating, resulting in a decrease in its hydrophobic properties. The weak durability of the coating may cause water to penetrate into the life jacket during use, which will adversely affect the luminescent performance and durability of the luminescent coating.

[0107] As shown in the test results of Examples 2, 6 to 9, the conditions such as the temperature and curing time during the curing of the highly hydrophobic self-luminous coating will also affect its hydrophobic properties. Since the hydrophobicity of the waterborne polyurethane coating is mainly due to the low free energy and a certain roughness of the coating surface, as the curing temperature increases, the curing rate of the self-luminous coating will accelerate, which is conducive to the formation of a dense and wear-resistant coating. However, too high a curing temperature may cause bubbles to form when the coating is cured, resulting in tiny pores and reducing the hydrophobic properties; the surface morphology of the luminous coating gradually stabilizes with the extension of the curing time, and it is difficult to form sufficient roughness if the curing time is insufficient. When the curing temperature is 60°C and the curing time is 6h, the water contact angle of the self-luminous coating can reach 151°, which has super hydrophobic properties.

[0108] Compared with Examples 1 to 9, Comparative Examples 1 and 2 are examples in which no rare earth ion activator is added and no organosiloxane modifier is used, respectively. Strontium aluminate oxide itself does not have luminescent properties. 2+ and Dy 3+ As an activator, it fills the lattice space to form a luminescent center, absorbs external light energy and is activated to transition to an excited state. When the light is stopped, the high-energy state of Eu 2+ 、Dy 3+ The ions release energy in the form of fluorescence and return to the ground state; adding organosiloxane to the strontium aluminate oxide powder during its synthesis to modify it can increase its affinity with water-based polyurethane, graft it onto the polyurethane chain segment, improve its water resistance and prolong the luminescence time.

[0109] The above-mentioned multiple embodiments have shown excellent performance test results. In order to make the highly hydrophobic self-luminous coating life jacket have excellent luminous effect and good hydrophobic performance during implementation, the raw materials and coating curing conditions of Example 2 may be preferred.

[0110] The above experiments and results show that in view of the existing luminous life jacket preparation technology, such as high requirements for excitation conditions, short luminescence time, radioactive radiation, poor water resistance and compatibility, a layer of highly hydrophobic self-luminous coating can be coated on the surface of the TPU flexible life jacket parts printed by SLS, giving the life jacket excellent high hydrophobic and self-luminous effects, and improving the wearer's visibility under dim and lightless conditions. Compared with the schemes of fluorescent materials and irradiated luminescent materials, the first advantage of this scheme is that the long afterglow energy storage luminescent material that can be activated by visible light and can continuously emit light for several hours is prepared by a simple sol-gel method, the rare earth activation ions and the matrix have good mixing uniformity, low reaction temperature, energy saving, stable cyclic luminescence performance and safe and radiation-free; the second advantage is that the strontium aluminate oxide is modified by using organic siloxane and grafted onto the waterborne polyurethane chain segment, so as to obtain better luminescence durability; the third advantage is that the surface of the life jacket parts made by SLS is densely covered with micro-voids, which is conducive to the full bonding of the coating, further improving the bonding strength and durability. At the same time, the above experiments also found that the scheme needs to be implemented with attention to the rare earth ion concentration and the amount of organosiloxane used in the synthesis process of long afterglow energy storage luminescent materials will directly affect the luminescence brightness of the long afterglow oxide powder, and then affect the luminescence performance and durability of the coating, while the hydrophobicity and service life of the coating will also be affected by the curing conditions of the luminescent coating. Therefore, it is necessary to select suitable raw materials and use a specific range of rare earth ion concentrations and the amount of organosiloxane and curing conditions to obtain excellent high hydrophobic self-luminescence effect and excellent durability.

[0111] In addition, SLS molding has a high degree of flexibility, so the above scheme can be used to manufacture life jackets with conventional structures, and can also be used to conveniently manufacture life jackets with hollow and gradient hollow structures inside. By adjusting the degree and distribution of hollowing, the buoyancy distribution can be optimized and the wearing comfort can be improved, while reducing the overall weight, thereby enhancing safety performance. SLS can be used to manufacture life jackets that fit the human body curve better, improve wearing comfort and reduce activity restrictions. SLS can also be used to manufacture life jackets with a dense wear-resistant layer on the surface and a gradient hollow structure with gradually increasing hollowing from the near surface to the center, so as to prevent moisture penetration, reduce weight and float, and be flexible and elastic, enhance the strength and durability of the product, and provide a good comfortable experience for the wearer. Thermoplastic polyurethane elastomer (TPU) used in the manufacture of life jackets is a kind of polyurethane material. On the one hand, it has the characteristics of low melting point and adjustable ratio of soft and hard segments. On the other hand, it has excellent flexibility, water resistance and high wear resistance, which is just suitable for SLS technology and matches the use requirements of life jackets.

[0112] The above embodiments are exemplary, and their purpose is to illustrate the technical concept and features of the present invention so that people familiar with the technology in this field can understand the content of the present invention and implement it accordingly, and they cannot be used to limit the protection scope of the present invention. Any equivalent changes or modifications made according to the spirit of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for preparing a flexible, highly hydrophobic, self-luminous life jacket, characterized in that: Anchoring a highly hydrophobic self-luminous coating on the surface of a flexible life jacket formed by selective laser sintering; The highly hydrophobic self-luminous coating is obtained by curing a highly hydrophobic energy storage long afterglow luminous coating coated on the surface of the workpiece; The preparation of the highly hydrophobic energy storage long afterglow luminescent coating comprises the following steps: Step (1.1): Dissolve europium oxide (Eu2O3) and dysprosium oxide (Dy2O3) in nitric acid solution to obtain an activator Eu 2+ 、Dy 3+ Nitrate solution; after dissolving strontium nitrate (SrNO3) and hydrated aluminum nitrate (Al(NO)3·H2O) in deionized water, add activator Eu 2+ 、Dy 3+ nitrate solution and citric acid, heating and stirring, continuing to add citric acid to adjust the pH value of the solution to 2-3, to obtain a uniform and transparent inorganic salt aqueous solution; heating and adding an ethanol solution of a silane coupling agent and stirring to convert the solution into a sol, and drying to obtain a hydrophobically modified strontium aluminate oxide powder; Step (1.2): Mix the dried polyether polyol and polyisocyanate evenly under nitrogen protection, add dibutyltin dilaurate catalyst, continue stirring and react at 80-90°C, add 2,2-dihydroxymethylpropionic acid, film-forming aid and cross-linking agent, and continue to react at 80-90°C for a period of time; reduce the temperature of the reaction solution to 40-45°C, add acetone, and then add the hydrophobically modified strontium aluminate oxide powder obtained in step (1.1) to react; add triethylamine for neutralization; add deionized water and emulsify in an ice water bath; rotary evaporate the emulsion after emulsification to obtain a self-luminous water-based polyurethane emulsion containing a hydrophobically modified energy storage long afterglow luminescent material, i.e., a highly hydrophobic energy storage long afterglow luminescent coating.

2. The method for preparing the flexible highly hydrophobic self-luminous life jacket according to claim 1, characterized in that: Forming a highly hydrophobic self-luminous coating on the surface of a flexible life jacket formed by selective laser sintering includes the following steps: Step (2.1): prepare a clean and dry flexible life jacket component to be formed by selective laser sintering; Step (2.2): placing the life jacket obtained in step (2.1) into a dipping container, injecting the highly hydrophobic energy storage long afterglow luminescent coating obtained in step (1.2) into the dipping container, and taking out the life jacket after the life jacket is fully dipped in the coating; Step (2.3): curing the life jacket with the highly hydrophobic energy storage long afterglow luminescent coating attached to the surface obtained in step (2.2) at 40-80° C., wherein the coating is cured and anchored on the surface of the life jacket to form a coating, thereby obtaining the flexible highly hydrophobic self-luminous life jacket.

3. The method for preparing the flexible highly hydrophobic self-luminous life jacket according to claim 2, characterized in that: In step (1.1), the mass ratio of europium oxide (Eu2O3) to dysprosium oxide (Dy2O3) is 1:2~2:1; the inorganic salt aqueous solution is heated to 60~80°C, and then an ethanol solution of a silane coupling agent is added, and the mixture is reacted at a stirring speed of 300~500r / min for 1~2h. When the solution is converted into a sol, the sol is dried at a constant temperature at 100~120°C for 5~10h to obtain a hydrophobically modified strontium aluminate oxide powder.

4. The method for preparing the flexible highly hydrophobic self-luminous life jacket according to claim 2, characterized in that: In step (1.2), after lowering the temperature of the reaction liquid to 40-45°C, acetone is added, and then the hydrophobically modified strontium aluminate oxide powder obtained in step (1.1) is added, and the reaction is carried out for 30-60 minutes; triethylamine is added for neutralization for 30-60 minutes; deionized water is added and emulsified in an ice water bath, and the stirring speed during the emulsification process is 1000-2000 r / min, and the stirring time is 30-60 minutes; finally, the emulsion after emulsification is rotary evaporated in a rotary evaporator to remove water and acetone, and the rotary evaporation temperature is 45-60°C to obtain a highly hydrophobic energy storage long afterglow luminescent coating.

5. The method for preparing the flexible highly hydrophobic self-luminous life jacket according to claim 2, characterized in that: In step (2.1), the three-dimensional mesh hollow life jacket product obtained by selective laser sintering of TPU powder is placed in clean water for cleaning, and then dried at 50-70°C for 3-5 hours to obtain a clean and dry life jacket product; in step (2.2), during the dipping process, the life jacket product is rotated in the clockwise direction and the counterclockwise direction for 3-5 cycles respectively, and after the rotation is completed, the life jacket product is lifted out of the coating, and this is repeated 1-3 times; in step (2.3), the life jacket is placed in a constant temperature box at 40-80°C and cured at the constant temperature for 4-8 hours.

6. The method for preparing the flexible highly hydrophobic self-luminous life jacket according to any one of claims 1 to 5, characterized in that: The life jacket component is made of TPU powder through selective laser sintering.

7. The method for preparing the flexible highly hydrophobic self-luminous life jacket according to claim 6, characterized in that: The surface of the life jacket is closed; The surface layer is a three-dimensional mesh hollow structure, and the hollowness gradually increases from the near surface to the center.

8. The method for preparing the flexible highly hydrophobic self-luminous life jacket according to claim 6, characterized in that: In step (1.1), the silane coupling agent used for hydrophobic modification of strontium aluminate oxide is one or more of octadecyltrichlorosilane, γ-aminopropyltriethoxysilane or N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane; the amount of the silane coupling agent added is 0.5-3 parts by mass of the strontium aluminate oxide.

9. The method for preparing the flexible highly hydrophobic self-luminous life jacket according to claim 6, characterized in that: In step (1.2), the polyether polyol and the polyisocyanate are used in a mass ratio of (2-5):1; the polyether polyol is one or more of polyethylene oxide glycol, polypropylene oxide glycol, and polymethylene glycol; the polyisocyanate is one or more of hydrogenated benzyl diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate; the film-forming aid is one or more of diethylene glycol butyl ether, propylene glycol methyl ether acetate, and propylene glycol butyl ether; and the cross-linking agent is one or more of ethylenediamine, bisphenol A epoxy resin, and hexamethoxymethylene melamine.

10. A flexible, highly hydrophobic, self-luminous life jacket, characterized in that: The flexible, highly hydrophobic, self-luminous life jacket is prepared by the preparation method of any one of claims 1 to 9.

Images