A storage-energy luminescent phase change hot-melt marking material and its preparation method

Abstract

This invention provides an energy-storing, luminescent phase-change hot-melt road marking material and its preparation method, made from the following raw materials: C5 petroleum resin, glass microspheres, silane coupling agent, polyoxymethylene, polyoxyethylene, sodium sulfate, multi-walled carbon nanotubes, expanded graphite, oligomeric dopamine, isophorone diisocyanate, tetraethylenepentamine, perhydropolysilazane, N,N,N',N'-tetramethylbenzidine, 2,8-bis(diphenylphospho)dibenzo[b,d]thiophene, silica aerogel powder, nano-titanium dioxide powder, calcium carbonate powder, barite powder, lauric acid, palmitic acid, hexadecyltrimethylammonium bromide, polyethylene glycol octylphenyl ether, dioctyl phthalate, and acetic acid. While ensuring the visibility and durability of the road markings, this invention reduces high-temperature deformation and low-temperature cracking of the hot-melt road markings, minimizes the propagation of internal cracks, increases the service life of the hot-melt road markings, and reduces maintenance and repainting costs.

Description

Technical Field

[0001] This invention belongs to the field of road materials, and relates to hot-melt road marking materials, specifically to a high-performance road marking material and its preparation method. Background Art

[0002] Road traffic safety facilities are crucial for ensuring driving safety and reducing traffic accident rates. As basic traffic infrastructure, road markings are an important carrier of road traffic information, playing roles such as traffic channeling, alignment guidance, traffic diversion, and restriction indication, and are a vital means of ensuring driving safety. Hot-melt reflective road markings are widely used in engineering projects due to their lower cost, ease of construction, and all-weather visibility, which to some extent guarantees driving safety. The main advantages of hot-melt road markings include: ① Good wear resistance and stability, maintaining retroreflective effects for a relatively long time. ② Good production efficiency and economic benefits. Hot-melt paint has low cost, can be completed in a short time, and allows for traffic to resume shortly after construction, resulting in high socio-economic benefits. Currently, municipal roads and highways mainly use hot-melt markings as the primary road markings.

[0003] While hot-melt road marking materials have significant advantages, they also have drawbacks. Currently, the main problems with hot-melt road markings during use are poor crack resistance, high energy consumption, and severe pollution. In areas with large diurnal temperature variations, the markings are prone to cracking, leading to contamination and the shedding of numerous glass beads, causing a rapid decrease in retroreflective properties. Therefore, the medium- to long-term retroreflective coefficient of hot-melt road markings is generally low, and the markings suffer from poor integrity, exhibiting defects such as mesh cracking and detachment. Current research focuses on material improvement, enhancing its aging resistance and heat resistance; improving its processing technology to ensure good workability; and enhancing the retroreflective properties of hot-melt road markings to ensure good visibility under various lighting and weather conditions. However, existing hot-melt road markings still suffer from poor crack resistance. Under thermal cycling and vehicle wear, the cured markings crack. Furthermore, precipitation weakens the retroreflective properties of the glass beads and accelerates contamination and damage, making it impossible to provide consistently good visibility over the long term. Summary of the Invention

[0004] In view of the shortcomings of the existing technology, the purpose of this invention is to provide an energy-storing and light-emitting phase change hot-melt marking material and its preparation method, so as to solve the technical problem that the hot-melt marking materials in the existing technology cannot provide good visibility in a long-term stable manner.

[0005] To solve the above-mentioned technical problems, the present invention adopts the following technical solution:

[0006] A type of energy-storing luminescent phase-change hot-melt marking material is made from the following raw materials: C5 petroleum resin, glass microspheres, silane coupling agent, polyoxymethylene, polyoxyethylene, sodium sulfate, multi-walled carbon nanotubes, expanded graphite, oligomeric dopamine (PDA), isophorone diisocyanate (IPDI), tetraethylenepentamine (TEPA), perhydropolysilazane (PHPS), N,N,N',N'-tetramethylbenzidine (TMB), 2,8-bis(diphenylphospho)dibenzo[b,d]thiophene (PPT), silica aerogel powder, nano titanium dioxide powder, calcium carbonate powder, barite powder, lauric acid, palmitic acid, cetyltrimethylammonium bromide (CTAB), polyethylene glycol octylphenyl ether (Triton X-100), dioctyl phthalate (DOP), and acetic acid.

[0007] The present invention also has the following distinguishing technical features:

[0008] Specifically, by weight fraction, it is made from the following raw materials: 10%–20% C5 petroleum resin, 30%–33% glass microspheres, 0.1%–1% silane coupling agent, 3%–7% polyoxymethylene, 1%–5% polyoxyethylene, 3%–7% sodium sulfate, 0.1%–1% multi-walled carbon nanotubes, 0.2%–0.3% expanded graphite, 0.3%–1% isophorone diisocyanate, 0.3%–1% tetraethylenepentamine, 0.3%–1% perhydropolysilazane, and 1.5%–3% N,N,N',N'-tetramethylbenzyl chloride. Aniline, 1.5%–3% 2,8-bis(diphenylphospho)dibenzo[B,D]thiophene, 3%–6% silica aerogel powder, 0.1%–1.8% oligomeric dopamine, 1%–7% nano titanium dioxide powder, 6%–15% calcium carbonate powder, 8%–15% barite powder, 1%–8% lauric acid, 1%–5% palmitic acid, 0.4%–0.7% hexadecyltrimethylammonium bromide, 0.3%–0.5% polyethylene glycol octylphenyl ether, 1%–3% dioctyl phthalate, and 0.1%–0.5% acetic acid.

[0009] Preferably, by weight fraction, it comprises the following raw materials: 10%–20% C5 petroleum resin, 30%–33% glass microspheres, 0.1% silane coupling agent, 3%–5% polyoxymethylene, 1%–3% polyoxyethylene, 3%–4% sodium sulfate, 0.4%–0.8% multi-walled carbon nanotubes, 0.2% expanded graphite, 0.33%–0.67% isophorone diisocyanate, 0.33%–0.67% tetraethylenepentamine, 0.33%–0.67% perhydropolysilazane, and 1.5% N,N, N',N'-Tetramethylbenzidine, 1.5% 2,8-bis(diphenylphospho)dibenzo[B,D]thiophene, 4%–6% silica aerogel powder, 0.1%–0.5% oligomeric dopamine, 6%–7% nano titanium dioxide powder, 6%–15% calcium carbonate powder, 8%–10% barite powder, 1%–5% lauric acid, 1%–5% palmitic acid, 0.4% hexadecyltrimethylammonium bromide, 0.3% polyethylene glycol octylphenyl ether, 1%–2% dioctyl phthalate, and 0.1% acetic acid.

[0010] The most preferred composition, by weight fraction, is the following raw materials: 15% C5 petroleum resin, 30% glass microspheres, 0.1% silane coupling agent, 3% polyoxymethylene, 1% polyoxyethylene, 3% sodium sulfate, 0.8% multi-walled carbon nanotubes, 0.2% expanded graphite, 0.33% isophorone diisocyanate, 0.33% tetraethylenepentamine, 0.33% perhydropolysilazane, and 1.5% N,N,N',N'- Tetramethylbenzidine, 1.5% 2,8-bis(diphenylphospho)dibenzo[B,D]thiophene, 6% silica aerogel powder, 0.1% oligomeric dopamine, 6% nano titanium dioxide powder, 9% calcium carbonate powder, 10% barite powder, 5% lauric acid, 5% palmitic acid, 0.4% hexadecyltrimethylammonium bromide, 0.3% polyethylene glycol octylphenyl ether, 1% dioctyl phthalate, 0.1% acetic acid.

[0011] This invention also protects a method for preparing an energy-storing, light-emitting phase-change hot-melt marking material, the method comprising the following steps:

[0012] Step 1, Prepare the surface treatment agent:

[0013] A surface treatment agent for glass microspheres was prepared by preparing an aqueous solution of hexadecyltrimethylammonium bromide and polyethylene glycol octylphenyl ether with a mass concentration of 0.5%, adding a silane coupling agent, and adjusting the pH value to 3.5-5.5 with acetic acid.

[0014] Step 2, Surface treatment of glass microspheres:

[0015] The glass microspheres are surface treated by immersing them in the surface treatment agent prepared in step one for 1.5 min, then removing them and drying them at 110-120℃ to constant weight to obtain the treated glass microspheres.

[0016] Step 3: Preparation of organic energy-storing luminescent materials:

[0017] In a nitrogen atmosphere, N,N,N',N'-tetramethylbenzidine and 2,8-bis(diphenylphospho)dibenzo[B,D]thiophene were mixed and heated to 250°C, then rapidly cooled to room temperature to obtain an organic energy-storing luminescent material.

[0018] Step 4, Shell Covering:

[0019] Lauric acid, palmitic acid and polyoxyethylene are mixed and heated to 90°C. Then the organic energy storage luminescent material prepared in step three is added and dispersed by ultrasound. Isophorone diisocyanate and tetraethylenepentamine are added to obtain the shell-coated organic energy storage luminescent material.

[0020] Step 5: Preparation of organic energy storage and luminescent material phase change microcapsules:

[0021] In step four, all-hydrogen polysilazane and oligomeric dopamine are added to the shell-coated organic energy storage luminescent material. The mixture is then dispersed evenly using ultrasonic treatment to obtain a double-shell-encapsulated organic energy storage luminescent material phase change microcapsule.

[0022] Step 6, Prepare the mixture:

[0023] C5 petroleum resin was heated to 160℃ and molten. Then expanded graphite, silica aerogel powder, multi-walled carbon nanotubes and sodium sulfate were added. The mixture was stirred at a low speed of 400 for 5 minutes and then dispersed at a speed of 2000 r / min for 10 minutes to obtain a mixture.

[0024] Step 7, Dispersing the mixture:

[0025] Heat the mixture obtained in step six to 180°C, add polyoxymethylene and stir continuously until it melts and disperses evenly;

[0026] Step 8, Prepare solid coating:

[0027] Add nano titanium dioxide, calcium carbonate powder and barite powder to the uniformly dispersed mixture obtained in step seven, and stir continuously until it becomes uniform. Then add dioctyl phthalate, stir again until it becomes uniform, stop heating, remove it to a container, and let it cool naturally to room temperature to obtain a solid coating.

[0028] Step 9: Prepare energy-storing and light-emitting phase change thermal fusion marking material:

[0029] The solid coating obtained in step eight is crushed to 50-100 mesh, and the treated glass microspheres prepared in step two and the organic energy storage luminescent material phase change microcapsules obtained in step five are added. The mixture is then thoroughly mixed to obtain the energy storage luminescent phase change hot melt marking material.

[0030] Compared with the prior art, the present invention has the following technical effects:

[0031] (I) The hot-melt road marking material of this invention possesses energy storage and luminescence properties, along with lower construction temperature and excellent thermal cycling durability. While ensuring the visibility and durability of the markings, it reduces high-temperature deformation and low-temperature cracking of the hot-melt markings, minimizes the expansion of internal cracks, increases the service life of the markings, and reduces maintenance and repainting costs. Adding fluorescent powder to hot-melt road markings can achieve energy storage and luminescence, but traditional energy storage inorganic luminescent powders are expensive and easily hydrolyzed. Using organic energy storage luminescent materials, however, can significantly reduce the cost of adding luminescent powder.

[0032] (II) The energy storage and light-emitting phase change thermal fusion marking material provided by the present invention uses C5 petroleum resin, sodium sulfate, multi-walled carbon nanotubes and silica aerogel powder to construct intercalation layers. Expanded graphite interpenetrates with the intercalation layers to form a spatial interpenetrating structure. The added OPL phase change microcapsules can be encapsulated by the interpenetrating structure to avoid microcapsule damage. The addition of carbon nanotubes enhances the electrical conductivity of the material, which is conducive to the absorption of energy by the OPL material and achieves a long-term energy storage and light-emitting effect.

[0033] (III) The energy-storing luminescent phase change hot-melt marking material provided by this invention uses OPL phase change microcapsules. The OPL material, phase change material, and microcapsule shell can play a synergistic role. The luminescence efficiency of OPL material decreases at high temperatures and structural and performance degradation easily occurs in the hot-melt marking matrix. Directly adding phase change material to the coating matrix will change the performance of the coating. Using microcapsule encapsulation can stabilize the performance of OPL material and phase change material. The double-layer shell structure of microcapsules is beneficial to improving encapsulation and enhancing the material strength and adhesion to the coating substrate. At the same time, the carbon nanotubes intercalated in the hot-melt coating matrix can improve the energy absorption efficiency of OPL material. The above structures work together to improve the luminescence efficiency of OPL material in high-temperature environments, maintain the performance and structural stability of OPL material, prolong the luminescence time, enhance the temperature stability of hot-melt coating, and help alleviate the cracking of hot-melt markings. When the temperature is high, the phase change material absorbs heat, and the internal skeleton structure ensures the rigidity of the material, preventing the markings from deforming due to overheating, such as shifting or flowing. When the ambient temperature is low, the phase change material releases latent heat, relieving the internal temperature stress of the material and preventing the material from breaking due to excessive rigidity.

[0034] (IV) The energy storage and light-emitting phase change hot melt marking material provided by the present invention uses nano silicon carbide, nano titanium dioxide and calcium carbonate powder and barite powder to form a pigment and filler reinforcement system to improve the performance stability of the marking material; at the same time, nano titanium dioxide powder can reduce the adhesion of external environmental pollutants and enhance the color durability of the marking; nano silicon carbide can enhance the wear resistance of the marking and improve its service life.

[0035] (V) The preparation process of the energy storage and light-emitting phase change hot melt marking material provided by the present invention is simple and quick, and does not require the guidance of professional technicians. It can be carried out by referring to the description of the present invention. Attached Figure Description

[0036] Figure 1 The interface structure between the glass beads and the coating (Comparative Example 1).

[0037] Figure 2 This is the characteristic intercalation structure in Example 2.

[0038] Figure 3 The structure is a whisker-like structure that has not formed an intercalation structure (Comparative Example 2).

[0039] Figure 4 This is a schematic diagram of the double-shell structure of OPL phase change microcapsules.

[0040] The specific content of the present invention will be further explained in detail below with reference to the embodiments. Detailed Implementation

[0041] It should be noted that, unless otherwise specified, all raw materials used in this invention are those known in the prior art.

[0042] PDA stands for oligodopamine.

[0043] IPDI refers to isophorone diisocyanate.

[0044] TEPA refers to tetraethylenepentamine.

[0045] PHPS refers to perhydropolysilazane.

[0046] TMB refers to N,N,N',N'-tetramethylbenzidine.

[0047] PPT refers to 2,8-bis(diphenylphospho)dibenzo[b,d]thiophene.

[0048] CTAB refers to hexadecyltrimethylammonium bromide.

[0049] Triton X-100 refers to polyethylene glycol octylphenyl ether.

[0050] DOP refers to dioctyl phthalate.

[0051] Raw material specifications in this invention:

[0052] C5 petroleum resin has a softening point of 110-140℃ and is the main film-forming substance in hot-melt road marking paint.

[0053] The glass microspheres have a refractive index of 1.7 to 1.9 and a particle size of 0.1 to 0.85 mm.

[0054] The silane coupling agent is designated as KBM-602.

[0055] Silica aerogel is characterized by low density and high porosity, with a density of 1.1 g / cm³. 3 Specific surface area is 600m² 2 / g.

[0056] Polyoxymethylene has a crystallinity of 75% and a melting point of 180℃.

[0057] The melting point of polyethylene oxide is 87℃.

[0058] Multi-walled carbon nanotubes have a diameter of 10–50 nm and a length of 0.1–1 mm.

[0059] Expanded graphite has an expansion volume greater than 150 ml / g.

[0060] N,N,N',N'-Tetramethylbenzidine, 2,8-bis(diphenylphospho)dibenzo[B,D]thiophene, isophorone diisocyanate, tetraethylenepentamine, perhydropolysilazane, hexadecyltrimethylammonium bromide, and polyethylene glycol octylphenyl ether were all analytical grade reagents.

[0061] The calcium carbonate powder and barite powder have a mesh size of 600-1500 mesh and are of industrial grade.

[0062] Lauric acid, palmitic acid, and acetic acid are industrial grade.

[0063] The C5 petroleum resin is an aliphatic C5 petroleum resin with a number average molecular weight of 1500.

[0064] The number average molecular weight of polyoxymethylene is 25,000.

[0065] The number average molecular weight of polyethylene oxide is 1×10⁻⁶. 6 .

[0066] The number-average molecular weight of oligodopamine is 400–1000.

[0067] The number average molecular weight of perhydropolysilazane is 1×10⁻⁶. 5 .

[0068] The CAS number for polyethylene glycol octylphenyl ether is 9002-93-1.

[0069] In this invention, a matrix framework and intercalation structure are constructed using resin, sodium sulfate, expanded graphite, multi-walled carbon nanotubes, and silica aerogel powder.

[0070] In this invention, a retroreflective component with better interfacial compatibility was prepared using glass microspheres, silane coupling agent, hexadecyltrimethylammonium bromide, and polyethylene glycol octylphenyl ether.

[0071] In this invention, N,N,N',N'-tetramethylbenzidine and 2,8-bis(diphenylphospho)dibenzo[B,D]thiophene are used as organic energy storage luminescent materials (OPL), and together with phase change regulating components (oligomeric dopamine, perhydropolysilazane, isophorone diisocyanate, tetraethylenepentamine, polyoxymethylene, polyoxyethylene, lauric acid, palmitic acid) to form a double-shell structure of organic energy storage luminescent phase change microcapsule containing OPL.

[0072] In this invention, OPL forms a stable free radical cation with the strong electron-donating molecule N,N,N',N'-tetramethylbenzidine, which in turn forms a rigid amorphous environment (matrix) with the strong electron-accepting molecule 2,8-bis(diphenylphospho)dibenzo[b,d]thiophene, which has high triplet energy, in order to achieve energy storage and luminescence of organic materials.

[0073] Following the above technical solutions, specific embodiments of the present invention are given below. It should be noted that the present invention is not limited to the following specific embodiments, and all equivalent modifications made based on the technical solutions of this application fall within the protection scope of the present invention.

[0074] Example 1:

[0075] This embodiment provides an energy-storing and light-emitting phase change thermal fusion marking material, which is made from the following raw materials in parts by weight: 10% C5 petroleum resin, 30% glass microspheres, 0.1% silane coupling agent, 3% polyoxymethylene, 0.33% IPDI, 0.33% TEPA, 0.33% PHPS, 1% polyoxyethylene, 3% sodium sulfate, 0.8% multi-walled carbon nanotubes, 0.2% expanded graphite, 1.5% TMB, 1.5% PPT, 5% silica aerogel powder, 0.1% PDA, 7% nano titanium dioxide powder, 15% calcium carbonate powder, 9% barite powder, 5% lauric acid, 5% palmitic acid, 0.4% hexadecyltrimethylammonium bromide (CTAB), 0.3% polyethylene glycol octylphenyl ether (Triton X-100), 1% dioctyl phthalate (DOP), and 0.1% acetic acid.

[0076] The preparation method of the energy-storing luminescent phase-change hot-melt marking material in this embodiment is carried out according to the following steps:

[0077] Step 1: Prepare a 0.5% aqueous solution of CTAB and Triton X-100, add a silane coupling agent, and adjust the pH to 3.5-5.5 using acetic acid to prepare a surface treatment agent for glass microspheres.

[0078] Step 2: The glass microspheres are surface treated with a surface treatment agent, that is, the glass microspheres are immersed in the surface treatment agent prepared in Step 1 for 1.5 min, and then dried at 110-120℃ to constant weight to obtain the treated glass microspheres.

[0079] Step 3: In a nitrogen atmosphere, TMB and PPT are mixed and heated to 250°C, then rapidly cooled to room temperature to obtain organic fluorescent material (OPL).

[0080] Step 4: Mix lauric acid, palmitic acid and polyethylene oxide and heat to 90°C. Disperse OPL in the mixture using ultrasound, add IPDI and TEPA and polymerize to obtain OPL material with shell coating.

[0081] Step 5: Add PHPS and PDA to the shell-coated organic energy storage luminescent material obtained in step 4, and use ultrasonic treatment to disperse the mixture evenly to obtain OPL phase change microcapsules wrapped in double-layer spherical shells.

[0082] Step 6: Heat C5 petroleum resin to 160°C in a molten state, then add expanded graphite, silica aerogel powder, multi-walled carbon nanotubes and sodium sulfate. Stir at a low speed of 400 for 5 minutes, then disperse at a speed of 2000 r / min for 10 minutes.

[0083] Step 7: Heat the mixture from Step 6 to 180°C, add polyoxymethylene and stir continuously until it melts and disperses evenly;

[0084] Step 8: Add nano titanium dioxide, calcium carbonate powder and barite powder to the uniformly dispersed mixture obtained in Step 7, and continue stirring until it becomes uniform. Then add DOP, stir again until it becomes uniform, stop heating, remove it to a container, and let it cool naturally to room temperature to obtain a solid coating.

[0085] Step 9: Crush the solid coating obtained in Step 8 to 50-100 mesh, add the treated glass microspheres prepared in Step 2 and the OPL phase change microcapsules obtained in Step 5, and mix them evenly to obtain the energy storage and light-emitting phase change hot melt marking material.

[0086] Example 2:

[0087] This example presents an energy-storing, light-emitting phase-change thermoplastic marking material, which, by weight, is made from the following raw materials: 15% C5 petroleum resin, 30% glass microspheres, 0.1% silane coupling agent, 3% polyoxymethylene, 0.33% IPDI, 0.33% TEPA, 0.33% PHPS, 1% polyoxyethylene, 3% sodium sulfate, 0.8% multi-walled carbon nanotubes, 0.2% expanded graphite, 1.5% TMB, 1.5% PPT, 6% silica aerogel powder, 0.1% PDA, 6% nano titanium dioxide powder, 9% calcium carbonate powder, 10% barite powder, 5% lauric acid, 5% palmitic acid, 0.4% cetyltrimethylammonium bromide (CTAB), 0.3% polyethylene glycol octylphenyl ether (Triton X-100), 1% dioctyl phthalate (DOP), and 0.1% acetic acid.

[0088] The preparation method of the above-mentioned energy-storing luminescent phase change hot-melt marking material is carried out according to the following steps:

[0089] Step 1: Prepare a 0.5% aqueous solution of CTAB and Triton X-100, add a silane coupling agent, and adjust the pH to 3.5-5.5 using acetic acid to prepare a surface treatment agent for glass microspheres.

[0090] Step 2: The glass microspheres are surface treated with a surface treatment agent, that is, the glass microspheres are immersed in the surface treatment agent prepared in Step 1 for 1.5 min, and then dried at 110-120℃ to constant weight to obtain the treated glass microspheres.

[0091] Step 3: In a nitrogen atmosphere, TMB and PPT are mixed and heated to 250°C, then rapidly cooled to room temperature to obtain organic fluorescent material (OPL).

[0092] Step 4: Mix lauric acid, palmitic acid and polyethylene oxide and heat to 90°C. Disperse OPL in the mixture using ultrasound, add IPDI and TEPA and polymerize to obtain OPL material with shell coating.

[0093] Step 5: Add PHPS and PDA to the shell-coated organic energy storage luminescent material obtained in step 4, and use ultrasonic treatment to disperse the mixture evenly to obtain OPL phase change microcapsules wrapped in double-layer spherical shells.

[0094] Step 6: Heat C5 petroleum resin to 160°C in a molten state, then add expanded graphite, silica aerogel powder, multi-walled carbon nanotubes and sodium sulfate. Stir at a low speed of 400 for 5 minutes, then disperse at a speed of 2000 r / min for 10 minutes.

[0095] Step 7: Heat the mixture from Step 6 to 180°C, add polyoxymethylene and stir continuously until it melts and disperses evenly;

[0096] Step 8: Add nano titanium dioxide, calcium carbonate powder and barite powder to the uniformly dispersed mixture obtained in Step 7, and continue stirring until it becomes uniform. Then add DOP, stir again until it becomes uniform, stop heating, remove it to a container, and let it cool naturally to room temperature to obtain a solid coating.

[0097] Step 9: Crush the solid coating obtained in Step 8 to 50-100 mesh, add the treated glass microspheres prepared in Step 2 and the OPL phase change microcapsules obtained in Step 5, and mix them evenly to obtain the energy storage and light-emitting phase change hot melt marking material.

[0098] Example 3:

[0099] This example presents an energy-storing, light-emitting phase-change thermoplastic marking material, which, by weight, is made from the following raw materials: 20% C5 petroleum resin, 30% glass microspheres, 0.1% silane coupling agent, 3% polyoxymethylene, 0.33% IPDI, 0.33% TEPA, 0.33% PHPS, 1% polyoxyethylene, 3% sodium sulfate, 0.8% multi-walled carbon nanotubes, 0.2% expanded graphite, 1.5% TMB, 1.5% PPT, 6% silica aerogel powder, 0.1% PDA, 6% nano titanium dioxide powder, 6% calcium carbonate powder, 8% barite powder, 5% lauric acid, 5% palmitic acid, 0.4% cetyltrimethylammonium bromide (CTAB), 0.3% polyethylene glycol octylphenyl ether (Triton X-100), 1% dioctyl phthalate (DOP), and 0.1% acetic acid.

[0100] The preparation method of the above-mentioned energy-storing luminescent phase change hot-melt marking material is carried out according to the following steps:

[0101] Step 1: Prepare a 0.5% aqueous solution of CTAB and Triton X-100, add a silane coupling agent, and adjust the pH to 3.5-5.5 using acetic acid to prepare a surface treatment agent for glass microspheres.

[0102] Step 2: The glass microspheres are surface treated with a surface treatment agent, that is, the glass microspheres are immersed in the surface treatment agent prepared in Step 1 for 1.5 min, and then dried at 110-120℃ to constant weight to obtain the treated glass microspheres.

[0103] Step 3: In a nitrogen atmosphere, TMB and PPT are mixed and heated to 250°C, then rapidly cooled to room temperature to obtain organic fluorescent material (OPL).

[0104] Step 4: Mix lauric acid, palmitic acid and polyethylene oxide and heat to 90°C. Disperse OPL in the mixture using ultrasound, add IPDI and TEPA and polymerize to obtain OPL material with shell coating.

[0105] Step 5: Add PHPS and PDA to the shell-coated organic energy storage luminescent material obtained in step 4, and use ultrasonic treatment to disperse the mixture evenly to obtain OPL phase change microcapsules wrapped in double-layer spherical shells.

[0106] Step 6: Heat C5 petroleum resin to 160°C in a molten state, then add expanded graphite, silica aerogel powder, multi-walled carbon nanotubes and sodium sulfate. Stir at a low speed of 400 for 5 minutes, then disperse at a speed of 2000 r / min for 10 minutes.

[0107] Step 7: Heat the mixture from Step 6 to 180°C, add polyoxymethylene and stir continuously until it melts and disperses evenly;

[0108] Step 8: Add nano titanium dioxide, calcium carbonate powder and barite powder to the uniformly dispersed mixture obtained in Step 7, and continue stirring until it becomes uniform. Then add DOP, stir again until it becomes uniform, stop heating, remove it to a container, and let it cool naturally to room temperature to obtain a solid coating.

[0109] Step 9: Crush the solid coating obtained in Step 8 to 50-100 mesh, add the treated glass microspheres prepared in Step 2 and the OPL phase change microcapsules obtained in Step 5, and mix them evenly to obtain the energy storage and light-emitting phase change hot melt marking material.

[0110] Example 4:

[0111] This example presents an energy-storing, light-emitting phase-change thermoplastic marking material, which, by weight, is made from the following raw materials: 15% C5 petroleum resin, 33% glass microspheres, 0.1% silane coupling agent, 3% polyoxymethylene, 0.33% IPDI, 0.33% TEPA, 0.33% PHPS, 1% polyoxyethylene, 3% sodium sulfate, 0.8% multi-walled carbon nanotubes, 0.2% expanded graphite, 1.5% TMB, 1.5% PPT, 6% silica aerogel powder, 0.1% PDA, 6% nano titanium dioxide powder, 8% calcium carbonate powder, 8% barite powder, 5% lauric acid, 5% palmitic acid, 0.4% cetyltrimethylammonium bromide (CTAB), 0.3% polyethylene glycol octylphenyl ether (Triton X-100), 1% dioctyl phthalate (DOP), and 0.1% acetic acid.

[0112] The preparation method of the above-mentioned energy-storing luminescent phase change hot-melt marking material is carried out according to the following steps:

[0113] Step 1: Prepare a 0.5% aqueous solution of CTAB and Triton X-100, add a silane coupling agent, and adjust the pH to 3.5-5.5 using acetic acid to prepare a surface treatment agent for glass microspheres.

[0114] Step 2: The glass microspheres are surface treated with a surface treatment agent, that is, the glass microspheres are immersed in the surface treatment agent prepared in Step 1 for 1.5 min, and then dried at 110-120℃ to constant weight to obtain the treated glass microspheres.

[0115] Step 3: In a nitrogen atmosphere, TMB and PPT are mixed and heated to 250°C, then rapidly cooled to room temperature to obtain organic fluorescent material (OPL).

[0116] Step 4: Mix lauric acid, palmitic acid and polyethylene oxide and heat to 90°C. Disperse OPL in the mixture using ultrasound, add IPDI and TEPA and polymerize to obtain OPL material with shell coating.

[0117] Step 5: Add PHPS and PDA to the shell-coated organic energy storage luminescent material obtained in step 4, and use ultrasonic treatment to disperse the mixture evenly to obtain OPL phase change microcapsules wrapped in double-layer spherical shells.

[0118] Step 6: Heat C5 petroleum resin to 160°C in a molten state, then add expanded graphite, silica aerogel powder, multi-walled carbon nanotubes and sodium sulfate. Stir at a low speed of 400 for 5 minutes, then disperse at a speed of 2000 r / min for 10 minutes.

[0119] Step 7: Heat the mixture from Step 6 to 180°C, add polyoxymethylene and stir continuously until it melts and disperses evenly;

[0120] Step 8: Add nano titanium dioxide, calcium carbonate powder and barite powder to the uniformly dispersed mixture obtained in Step 7, and continue stirring until it becomes uniform. Then add DOP, stir again until it becomes uniform, stop heating, remove it to a container, and let it cool naturally to room temperature to obtain a solid coating.

[0121] Step 9: Crush the solid coating obtained in Step 8 to 50-100 mesh, add the treated glass microspheres prepared in Step 2 and the OPL phase change microcapsules obtained in Step 5, and mix them evenly to obtain the energy storage and light-emitting phase change hot melt marking material.

[0122] Example 5:

[0123] This example presents an energy-storing luminescent phase-change thermoplastic marking material, which, by weight, is made from the following raw materials: 15% C5 petroleum resin, 30% glass microspheres, 0.1% silane coupling agent, 5% polyoxymethylene, 0.33% IPDI, 0.33% TEPA, 0.33% PHPS, 1% polyoxyethylene, 3% sodium sulfate, 0.4% multi-walled carbon nanotubes, 0.2% expanded graphite, 1.5% TMB, 1.5% PPT, 4% silica aerogel powder, 0.5% PDA, 6% nano titanium dioxide powder, 9% calcium carbonate powder, 10% barite powder, 5% lauric acid, 5% palmitic acid, 0.4% cetyltrimethylammonium bromide (CTAB), 0.3% polyethylene glycol octylphenyl ether (Triton X-100), 1% dioctyl phthalate (DOP), and 0.1% acetic acid.

[0124] The preparation method of the above-mentioned energy-storing luminescent phase change hot-melt marking material is carried out according to the following steps:

[0125] Step 1: Prepare a 0.5% aqueous solution of CTAB and Triton X-100, add a silane coupling agent, and adjust the pH to 3.5-5.5 using acetic acid to prepare a surface treatment agent for glass microspheres.

[0126] Step 2: The glass microspheres are surface treated with a surface treatment agent, that is, the glass microspheres are immersed in the surface treatment agent prepared in Step 1 for 1.5 min, and then dried at 110-120℃ to constant weight to obtain the treated glass microspheres.

[0127] Step 3: In a nitrogen atmosphere, TMB and PPT are mixed and heated to 250°C, then rapidly cooled to room temperature to obtain organic fluorescent material (OPL).

[0128] Step 4: Mix lauric acid, palmitic acid and polyethylene oxide and heat to 90°C. Disperse OPL in the mixture using ultrasound, add IPDI and TEPA and polymerize to obtain OPL material with shell coating.

[0129] Step 5: Add PHPS and PDA to the shell-coated organic energy storage luminescent material obtained in step 4, and use ultrasonic treatment to disperse the mixture evenly to obtain OPL phase change microcapsules wrapped in double-layer spherical shells.

[0130] Step 6: Heat C5 petroleum resin to 160°C in a molten state, then add expanded graphite, silica aerogel powder, multi-walled carbon nanotubes and sodium sulfate. Stir at a low speed of 400 for 5 minutes, then disperse at a speed of 2000 r / min for 10 minutes.

[0131] Step 7: Heat the mixture from Step 6 to 180°C, add polyoxymethylene and stir continuously until it melts and disperses evenly;

[0132] Step 8: Add nano titanium dioxide, calcium carbonate powder and barite powder to the uniformly dispersed mixture obtained in Step 7, and continue stirring until it becomes uniform. Then add DOP, stir again until it becomes uniform, stop heating, remove it to a container, and let it cool naturally to room temperature to obtain a solid coating.

[0133] Step 9: Crush the solid coating obtained in Step 8 to 50-100 mesh, add the treated glass microspheres prepared in Step 2 and the OPL phase change microcapsules obtained in Step 5, and mix them evenly to obtain the energy storage and light-emitting phase change hot melt marking material.

[0134] Example 6:

[0135] This example presents an energy-storing luminescent phase-change thermoplastic marking material, which, by weight, is made from the following raw materials: 12% C5 petroleum resin, 33% glass microspheres, 0.1% silane coupling agent, 5% polyoxymethylene, 0.67% IPDI, 0.67% TEPA, 0.67% PHPS, 3% polyoxyethylene, 3% sodium sulfate, 0.8% multi-walled carbon nanotubes, 0.2% expanded graphite, 1.5% TMB, 1.5% PPT, 6% silica aerogel powder, 0.1% PDA, 6% nano titanium dioxide powder, 6% calcium carbonate powder, 8% barite powder, 5% lauric acid, 5% palmitic acid, 0.4% cetyltrimethylammonium bromide (CTAB), 0.3% polyethylene glycol octylphenyl ether (Triton X-100), 1% dioctyl phthalate (DOP), and 0.1% acetic acid.

[0136] The preparation method of the above-mentioned energy-storing luminescent phase change hot-melt marking material is carried out according to the following steps:

[0137] Step 1: Prepare a 0.5% aqueous solution of CTAB and Triton X-100, add a silane coupling agent, and adjust the pH to 3.5-5.5 using acetic acid to prepare a surface treatment agent for glass microspheres.

[0138] Step 2: The glass microspheres are surface treated with a surface treatment agent, that is, the glass microspheres are immersed in the surface treatment agent prepared in Step 1 for 1.5 min, and then dried at 110-120℃ to constant weight to obtain the treated glass microspheres.

[0139] Step 3: In a nitrogen atmosphere, TMB and PPT are mixed and heated to 250°C, then rapidly cooled to room temperature to obtain organic fluorescent material (OPL).

[0140] Step 4: Mix lauric acid, palmitic acid and polyethylene oxide and heat to 90°C. Disperse OPL in the mixture using ultrasound, add IPDI and TEPA and polymerize to obtain OPL material with shell coating.

[0141] Step 5: Add PHPS and PDA to the shell-coated organic energy storage luminescent material obtained in step 4, and use ultrasonic treatment to disperse the mixture evenly to obtain OPL phase change microcapsules wrapped in double-layer spherical shells.

[0142] Step 6: Heat C5 petroleum resin to 160°C in a molten state, then add expanded graphite, silica aerogel powder, multi-walled carbon nanotubes and sodium sulfate. Stir at a low speed of 400 for 5 minutes, then disperse at a speed of 2000 r / min for 10 minutes.

[0143] Step 7: Heat the mixture from Step 6 to 180°C, add polyoxymethylene and stir continuously until it melts and disperses evenly;

[0144] Step 8: Add nano titanium dioxide, calcium carbonate powder and barite powder to the uniformly dispersed mixture obtained in Step 7, and continue stirring until it becomes uniform. Then add DOP, stir again until it becomes uniform, stop heating, remove it to a container, and let it cool naturally to room temperature to obtain a solid coating.

[0145] Step 9: Crush the solid coating obtained in Step 8 to 50-100 mesh, add the treated glass microspheres prepared in Step 2 and the OPL phase change microcapsules obtained in Step 5, and mix them evenly to obtain the energy storage and light-emitting phase change hot melt marking material.

[0146] Example 7:

[0147] This example presents an energy-storing, light-emitting phase-change thermoplastic marking material, which, by weight, is made from the following raw materials: 17% C5 petroleum resin, 31% glass microspheres, 0.1% silane coupling agent, 5% polyoxymethylene, 0.67% IPDI, 0.67% TEPA, 0.67% PHPS, 3% polyoxyethylene, 4% sodium sulfate, 0.8% multi-walled carbon nanotubes, 0.2% expanded graphite, 1.5% TMB, 1.5% PPT, 6% silica aerogel powder, 0.1% PDA, 6% nano titanium dioxide powder, 8% calcium carbonate powder, 10% barite powder, 1% lauric acid, 1% palmitic acid, 0.4% cetyltrimethylammonium bromide (CTAB), 0.3% polyethylene glycol octylphenyl ether (Triton X-100), 1% dioctyl phthalate (DOP), and 0.1% acetic acid.

[0148] The preparation method of the above-mentioned energy-storing luminescent phase change hot-melt marking material is carried out according to the following steps:

[0149] Step 1: Prepare a 0.5% aqueous solution of CTAB and Triton X-100, add a silane coupling agent, and adjust the pH to 3.5-5.5 using acetic acid to prepare a surface treatment agent for glass microspheres.

[0150] Step 2: The glass microspheres are surface treated with a surface treatment agent, that is, the glass microspheres are immersed in the surface treatment agent prepared in Step 1 for 1.5 min, and then dried at 110-120℃ to constant weight to obtain the treated glass microspheres.

[0151] Step 3: In a nitrogen atmosphere, TMB and PPT are mixed and heated to 250°C, then rapidly cooled to room temperature to obtain organic fluorescent material (OPL).

[0152] Step 4: Mix lauric acid, palmitic acid and polyethylene oxide and heat to 90°C. Disperse OPL in the mixture using ultrasound, add IPDI and TEPA and polymerize to obtain OPL material with shell coating.

[0153] Step 5: Add PHPS and PDA to the shell-coated organic energy storage luminescent material obtained in step 4, and use ultrasonic treatment to disperse the mixture evenly to obtain OPL phase change microcapsules wrapped in double-layer spherical shells.

[0154] Step 6: Heat C5 petroleum resin to 160°C in a molten state, then add expanded graphite, silica aerogel powder, multi-walled carbon nanotubes and sodium sulfate. Stir at a low speed of 400 for 5 minutes, then disperse at a speed of 2000 r / min for 10 minutes.

[0155] Step 7: Heat the mixture from Step 6 to 180°C, add polyoxymethylene and stir continuously until it melts and disperses evenly;

[0156] Step 8: Add nano titanium dioxide, calcium carbonate powder and barite powder to the uniformly dispersed mixture obtained in Step 7, and continue stirring until it becomes uniform. Then add DOP, stir again until it becomes uniform, stop heating, remove it to a container, and let it cool naturally to room temperature to obtain a solid coating.

[0157] Step 9: Crush the solid coating obtained in Step 8 to 50-100 mesh, add the treated glass microspheres prepared in Step 2 and the OPL phase change microcapsules obtained in Step 5, and mix them evenly to obtain the energy storage and light-emitting phase change hot melt marking material.

[0158] Example 8:

[0159] This example presents an energy-storing, light-emitting phase-change thermoplastic marking material, which, by weight, is made from the following raw materials: 15% C5 petroleum resin, 30% glass microspheres, 0.1% silane coupling agent, 3% polyoxymethylene, 0.33% IPDI, 0.33% TEPA, 0.33% PHPS, 1% polyoxyethylene, 3% sodium sulfate, 0.8% multi-walled carbon nanotubes, 0.2% expanded graphite, 1.5% TMB, 1.5% PPT, 6% silica aerogel powder, 0.1% PDA, 6% nano titanium dioxide powder, 8% calcium carbonate powder, 10% barite powder, 5% lauric acid, 5% palmitic acid, 0.4% cetyltrimethylammonium bromide (CTAB), 0.3% polyethylene glycol octylphenyl ether (Triton X-100), 2% dioctyl phthalate (DOP), and 0.1% acetic acid.

[0160] The preparation method of the above-mentioned energy-storing luminescent phase change hot-melt marking material is carried out according to the following steps:

[0161] Step 1: Prepare a 0.5% aqueous solution of CTAB and Triton X-100, add a silane coupling agent, and adjust the pH to 3.5-5.5 using acetic acid to prepare a surface treatment agent for glass microspheres.

[0162] Step 2: The glass microspheres are surface treated with a surface treatment agent, that is, the glass microspheres are immersed in the surface treatment agent prepared in Step 1 for 1.5 min, and then dried at 110-120℃ to constant weight to obtain the treated glass microspheres.

[0163] Step 3: In a nitrogen atmosphere, TMB and PPT are mixed and heated to 250°C, then rapidly cooled to room temperature to obtain organic fluorescent material (OPL).

[0164] Step 4: Mix lauric acid, palmitic acid and polyethylene oxide and heat to 90°C. Disperse OPL in the mixture using ultrasound, add IPDI and TEPA and polymerize to obtain OPL material with shell coating.

[0165] Step 5: Add PHPS and PDA to the shell-coated organic energy storage luminescent material obtained in step 4, and use ultrasonic treatment to disperse the mixture evenly to obtain OPL phase change microcapsules wrapped in double-layer spherical shells.

[0166] Step 6: Heat C5 petroleum resin to 160°C in a molten state, then add expanded graphite, silica aerogel powder, multi-walled carbon nanotubes and sodium sulfate. Stir at a low speed of 400 for 5 minutes, then disperse at a speed of 2000 r / min for 10 minutes.

[0167] Step 7: Heat the mixture from Step 6 to 180°C, add polyoxymethylene and stir continuously until it melts and disperses evenly;

[0168] Step 8: Add nano titanium dioxide, calcium carbonate powder and barite powder to the uniformly dispersed mixture obtained in Step 7, and continue stirring until it becomes uniform. Then add DOP, stir again until it becomes uniform, stop heating, remove it to a container, and let it cool naturally to room temperature to obtain a solid coating.

[0169] Step 9: Crush the solid coating obtained in Step 8 to 50-100 mesh, add the treated glass microspheres prepared in Step 2 and the OPL phase change microcapsules obtained in Step 5, and mix them evenly to obtain the energy storage and light-emitting phase change hot melt marking material.

[0170] Comparative Example 1:

[0171] This example presents an energy-storing, light-emitting phase-change hot-melt marking material, which, by weight, is made from the following raw materials: 15% C5 petroleum resin, 30% glass microspheres, 3% polyoxymethylene, 0.33% IPDI, 0.33% TEPA, 0.33% PHPS, 1% polyoxyethylene, 3% sodium sulfate, 0.2% expanded graphite, 1.5% TMB, 1.5% PPT, 6% silica aerogel powder, 0.8% PDA, 6% nano titanium dioxide powder, 10% calcium carbonate powder, 10% barite powder, 5% lauric acid, 5% palmitic acid, and 1% dioctyl phthalate (DOP).

[0172] The preparation method of the above-mentioned energy-storing luminescent phase change hot-melt marking material is carried out according to the following steps:

[0173] Step 1: In a nitrogen atmosphere, TMB and PPT are mixed and heated to 250°C, then rapidly cooled to room temperature to obtain organic fluorescent material (OPL).

[0174] Step 2: Mix lauric acid, palmitic acid and polyethylene oxide and heat to 90°C. Disperse OPL in the mixture using ultrasound, and add IPDI and TEPA to polymerize and obtain OPL material with shell coating.

[0175] Step 3: Add PHPS and PDA to the material obtained in Step 2, and use ultrasonic treatment to disperse the mixture evenly to obtain OPL phase change microcapsules encapsulated in a double-layered spherical shell.

[0176] Step 4: Heat C5 petroleum resin to 160℃ to a molten state, then add expanded graphite, silica aerogel powder and sodium sulfate, stir at a low speed of 400 for 5 minutes, and then disperse at a speed of 2000 r / min for 10 minutes.

[0177] Step 5: Heat the mixture from Step 4 to 180°C, add polyoxymethylene and stir continuously until it melts and disperses evenly;

[0178] Step 7: Add nano titanium dioxide, calcium carbonate powder and barite powder to the material in Step 5, stir continuously until it is uniform, then add DOP, stir again until it is uniform, then stop heating, remove it to a container, and let it cool naturally to room temperature to obtain a solid coating.

[0179] Step 8: Crush the solid coating obtained in Step 6 to 50-100 mesh, add the treated glass microspheres prepared in Step 2 and the OPL phase change microcapsules obtained in Step 3, and mix them evenly to obtain the energy storage and light-emitting phase change hot melt marking material.

[0180] Comparative Example 2:

[0181] This example presents an energy-storing, light-emitting phase-change thermoplastic marking material, which, by weight, is made from the following raw materials: 15% C5 petroleum resin, 30% glass microspheres, 0.1% silane coupling agent, 1% IPDI, 1% TEPA, 1% PHPS, 3% polyoxyethylene, 0.8% multi-walled carbon nanotubes, 0.2% expanded graphite, 3.5% TMB, 3.5% PPT, 0.1% PDA, 6% nano titanium dioxide powder, 13% calcium carbonate powder, 10% barite powder, 5% lauric acid, 5% palmitic acid, 0.4% hexadecyltrimethylammonium bromide (CTAB), 0.3% polyethylene glycol octylphenyl ether (Triton X-100), 1% dioctyl phthalate (DOP), and 0.1% acetic acid.

[0182] The preparation method of the above-mentioned energy-storing luminescent phase change hot-melt marking material is carried out according to the following steps:

[0183] Step 1: Prepare a 0.5% aqueous solution of CTAB and Triton X-100, add a silane coupling agent, and adjust the pH to 3.5-5.5 using acetic acid to prepare a surface treatment agent for glass microspheres.

[0184] Step 2: The glass microspheres are surface treated with a surface treatment agent, that is, the glass microspheres are immersed in the surface treatment agent prepared in Step 1 for 1.5 min, and then dried at 110-120℃ to constant weight to obtain the treated glass microspheres.

[0185] Step 3: In a nitrogen atmosphere, TMB and PPT are mixed and heated to 250°C, then rapidly cooled to room temperature to obtain organic fluorescent material (OPL).

[0186] Step 4: Mix lauric acid, palmitic acid and polyethylene oxide and heat to 90°C. Disperse OPL in the mixture using ultrasound, add IPDI and TEPA and polymerize to obtain OPL material with shell coating.

[0187] Step 5: Add PHPS and PDA to the shell-coated organic energy storage luminescent material obtained in step 4, and use ultrasonic treatment to disperse the mixture evenly to obtain OPL phase change microcapsules wrapped in double-layer spherical shells.

[0188] Step 6: Heat C5 petroleum resin to 160°C in a molten state, then add expanded graphite, multi-walled carbon nanotubes and sodium sulfate, stir at a low speed of 400 for 5 minutes, and then disperse at a speed of 2000 r / min for 10 minutes.

[0189] Step 7: Heat the mixture from Step 6 to 180°C;

[0190] Step 8: Add nano titanium dioxide, calcium carbonate powder and barite powder to the uniformly dispersed mixture obtained in Step 7, and continue stirring until it becomes uniform. Then add DOP, stir again until it becomes uniform, stop heating, remove it to a container, and let it cool naturally to room temperature to obtain a solid coating.

[0191] Step 9: Crush the solid coating obtained in Step 8 to 50-100 mesh, add the treated glass microspheres prepared in Step 2 and the OPL phase change microcapsules obtained in Step 5, and mix them evenly to obtain the energy storage and light-emitting phase change hot melt marking material.

[0192] Comparative Example 3:

[0193] This example presents an energy-storing, light-emitting phase-change thermoplastic marking material, which, by weight, is made from the following raw materials: 20% C5 petroleum resin, 30% glass microspheres, 0.1% silane coupling agent, 3% polyoxymethylene, 0.33% IPDI, 0.33% TEPA, 0.33% PHPS, 1% polyoxyethylene, 3% sodium sulfate, 0.8% multi-walled carbon nanotubes, 0.3% expanded graphite, 1.5% TMB, 1.5% PPT, 6% silica aerogel powder, 6% nano titanium dioxide powder, 6% calcium carbonate powder, 9% barite powder, 5% lauric acid, 5% palmitic acid, 0.4% hexadecyltrimethylammonium bromide (CTAB), 0.3% polyethylene glycol octylphenyl ether (Triton X-100), and 0.1% acetic acid.

[0194] The preparation method of the above-mentioned energy-storing luminescent phase change hot-melt marking material is carried out according to the following steps:

[0195] Step 1: Prepare a 0.5% aqueous solution of CTAB and Triton X-100, add a silane coupling agent, and adjust the pH to 3.5-5.5 using acetic acid to prepare a surface treatment agent for glass microspheres.

[0196] Step 2: The glass microspheres are surface treated with a surface treatment agent, that is, the glass microspheres are immersed in the surface treatment agent prepared in Step 1 for 1.5 min, and then dried at 110-120℃ to constant weight to obtain the treated glass microspheres.

[0197] Step 3: In a nitrogen atmosphere, TMB and PPT are mixed and heated to 250°C, then rapidly cooled to room temperature to obtain organic fluorescent material (OPL).

[0198] Step 4: Mix lauric acid, palmitic acid and polyethylene oxide and heat to 90°C. Disperse OPL in the mixture using ultrasound, add IPDI and TEPA and polymerize to obtain OPL material with shell coating.

[0199] Step 5: Add PHPS to the shell-coated organic energy storage and luminescent material obtained in Step 4, and use ultrasonic treatment to disperse the mixture evenly to obtain OPL phase change microcapsules wrapped in double-layer spherical shells.

[0200] Step 6: Heat C5 petroleum resin to 160°C in a molten state, then add expanded graphite, silica aerogel powder, multi-walled carbon nanotubes and sodium sulfate. Stir at a low speed of 400 for 5 minutes, then disperse at a speed of 2000 r / min for 10 minutes.

[0201] Step 7: Heat the mixture from Step 6 to 180°C, add polyoxymethylene and stir continuously until it melts and disperses evenly;

[0202] Step 8: Add nano titanium dioxide, calcium carbonate powder and barite powder to the uniformly dispersed mixture obtained in Step 7, and continue stirring. After stirring until it reaches a uniform state, stop heating, remove it to a container, and let it cool naturally to room temperature to obtain a solid coating.

[0203] Step 9: Crush the solid coating obtained in Step 8 to 50-100 mesh, add the treated glass microspheres prepared in Step 2 and the OPL phase change microcapsules obtained in Step 5, and mix them evenly to obtain the energy storage and light-emitting phase change hot melt marking material.

[0204] Comparative Example 4:

[0205] This example presents an energy-storing and light-emitting phase change thermal fusion marking material, which is made from the following raw materials by weight: 15% C5 petroleum resin, 30% glass microspheres, 0.1% silane coupling agent, 7% polyoxymethylene, 0.67% IPDI, 0.67% TEPA, 0.67% PHPS, 2% polyoxyethylene, 3% sodium sulfate, 0.8% multi-walled carbon nanotubes, 1.5% TMB, 1.5% PPT, 6% silica aerogel powder, 0.1% PDA, 6% nano titanium dioxide powder, 9% calcium carbonate powder, 10% barite powder, 1% dioctyl phthalate (DOP), and 0.1% acetic acid.

[0206] The preparation method of the above-mentioned energy-storing luminescent phase change hot-melt marking material is carried out according to the following steps:

[0207] Step 1: Prepare a 0.5% aqueous solution of CTAB and Triton X-100, add a silane coupling agent, and adjust the pH to 3.5-5.5 using acetic acid to prepare a surface treatment agent for glass microspheres.

[0208] Step 2: The glass microspheres are surface treated with a surface treatment agent, that is, the glass microspheres are immersed in the surface treatment agent prepared in Step 1 for 1.5 min, and then dried at 110-120℃ to constant weight to obtain the treated glass microspheres.

[0209] Step 3: In a nitrogen atmosphere, TMB and PPT are mixed and heated to 250°C, then rapidly cooled to room temperature to obtain organic fluorescent material (OPL).

[0210] Step 4: Heat the polyethylene oxide to 90°C, disperse the OPL in it using ultrasonication, add IPDI and TEPA to polymerize and obtain the shell-coated OPL material.

[0211] Step 5: Add PHPS and PDA to the shell-coated organic energy storage luminescent material obtained in step 4, and use ultrasonic treatment to disperse the mixture evenly to obtain OPL phase change microcapsules wrapped in double-layer spherical shells.

[0212] Step 6: Heat C5 petroleum resin to 160℃ in a molten state, then add silica aerogel powder, multi-walled carbon nanotubes and sodium sulfate, stir at a low speed of 400 for 5 minutes, and then disperse at a speed of 2000 r / min for 10 minutes.

[0213] Step 7: Heat the mixture from Step 6 to 180°C, add polyoxymethylene and stir continuously until it melts and disperses evenly;

[0214] Step 8: Add nano titanium dioxide, calcium carbonate powder and barite powder to the uniformly dispersed mixture obtained in Step 7, and continue stirring until it becomes uniform. Then add DOP, stir again until it becomes uniform, stop heating, remove it to a container, and let it cool naturally to room temperature to obtain a solid coating.

[0215] Step 9: Crush the solid coating obtained in Step 8 to 50-100 mesh, add the treated glass microspheres prepared in Step 2 and the OPL phase change microcapsules obtained in Step 5, and mix them evenly to obtain the energy storage and light-emitting phase change hot melt marking material.

[0216] Performance testing

[0217] In use, the energy-storing luminescent phase-change hot-melt road marking material is directly added to the hot-melt marking equipment for melting and application. Abrasion resistance, low-temperature crack resistance, and heating stability tests are conducted according to the requirements of JT / T 280-2022 "Road Marking Paint". The afterglow time of the marking is tested using a spectrophotometer. Specific performance indicators are as follows:

[0218]

[0219] Samples of the melted road marking paint were taken and subjected to microstructural analysis using a scanning electron microscope (SEM). Characteristic structures such as... Figures 1 to 3 As shown, where, Figure 1 The glass bead and coating interface structure is shown in Comparative Example 1. Figure 2 This is a characteristic intercalation structure of Example 2. Figure 3 The structure is a whisker-like structure that has not formed an intercalation structure (Comparative Example 2).

[0220] contrast Figure 1 and Figure 2 Comparative Example 1, which did not contain multi-walled carbon nanotubes, coupling agents, CTAB, etc., had a relatively loose structure. At the interface between the glass microspheres and the coating, the bonding tightness between the pigments / fillers and the resin matrix was low, and no intercalated structure was formed. In terms of macroscopic performance, Comparative Example 1 showed cracks in the low-temperature crack resistance test, while the examples showed no cracks. Figure 1 and Figure 3 Adding multi-walled carbon nanotubes but without adding expanded graphite or other materials can form a characteristic whisker-like structure, but the structure has poor adhesion to phosphors, resulting in a reduced afterglow time and a slight improvement in wear resistance. Figure 4 This is a schematic diagram of the double-shell structure of OPL phase change microcapsules.

[0221] contrast Figure 2 and Figure 1 and Figure 3 The embodiment forming the intercalation structure exhibits superior overall performance compared to the comparative example, demonstrating that:

[0222] First, expanded graphite, multi-walled carbon nanotubes, sodium sulfate and C5 resin have a synergistic enhancement effect in the formation of energy storage and luminescence phase change materials, which improves the coating effect and strength of the coating matrix.

[0223] Secondly, the double-layer capsule structure can provide good protection for the formation of OPL material. The phase change material improves the high-temperature luminescence efficiency of OPL material and reduces the temperature stress of the coating matrix, thus reducing cracking.

[0224] Third, the intercalation structure and OPL phase change microcapsules have a synergistic enhancement effect, which not only improves the encapsulation and protection of the phase change microcapsules, but also improves the luminescence efficiency of the OPL material. Adding a certain component alone cannot produce the expected effect of the embodiment.

[0225] As can be seen from the above embodiments, adding phase change materials to form an interpenetrating structure can improve the thermal stability of the material. The interpenetrating structure and phase change materials also encapsulate and protect the OPL phase change microcapsules, extending the fluorescence afterglow time of the hot-melt road markings to a certain extent. It also improves the wear resistance and low-temperature crack resistance of the markings, thus extending their service life. Therefore, this hot-melt road marking material not only has a long afterglow time but also significantly extends the service life of road markings. Therefore, the energy-storing luminescent hot-melt road marking material of the present invention has good applicability and can effectively solve the problems of poor crack resistance and short service life of current hot-melt road markings, showing broad application prospects.

Claims

1. A type of energy-storing, light-emitting phase-change hot-melt marking material, characterized in that, Made from the following raw materials: C5 petroleum resin, glass microspheres, silane coupling agent, polyoxymethylene, polyoxyethylene, sodium sulfate, multi-walled carbon nanotubes, expanded graphite, oligomeric dopamine, isophorone diisocyanate, tetraethylenepentamine, perhydropolysilazane, N,N,N',N'-tetramethylbenzidine, 2,8-bis(diphenylphospho)dibenzo[b,d]thiophene, silica aerogel powder, nano titanium dioxide powder, calcium carbonate powder, barite powder, lauric acid, palmitic acid, hexadecyltrimethylammonium bromide, polyethylene glycol octylphenyl ether, dioctyl phthalate, and acetic acid; The preparation method of the energy-storing luminescent phase change hot-melt marking material is carried out according to the following steps: Step 1, Prepare the surface treatment agent: A surface treatment agent for glass microspheres was prepared by preparing an aqueous solution of cetyltrimethylammonium bromide and polyethylene glycol octylphenyl ether with a mass concentration of 0.5%, adding a silane coupling agent, and adjusting the pH value to 3.5-5.5 with acetic acid. Step 2, Surface treatment of glass microspheres: The glass microspheres are surface treated by immersing them in the surface treatment agent prepared in step one for 1.5 min, then removing them and drying them at 110-120℃ to constant weight to obtain the treated glass microspheres. Step 3: Preparation of organic energy-storing luminescent materials: In a nitrogen atmosphere, N,N,N',N'-tetramethylbenzidine and 2,8-bis(diphenylphospho)dibenzo[B,D]thiophene were mixed and heated to 250°C, then rapidly cooled to room temperature to obtain an organic energy-storing luminescent material. Step 4, Shell Covering: Lauric acid, palmitic acid and polyoxyethylene are mixed and heated to 90°C. Then the organic energy storage luminescent material prepared in step three is added and dispersed by ultrasound. Isophorone diisocyanate and tetraethylenepentamine are added to obtain the shell-coated organic energy storage luminescent material. Step 5: Preparation of organic energy storage and luminescent material phase change microcapsules: In step four, all-hydrogen polysilazane and oligomeric dopamine are added to the shell-coated organic energy storage luminescent material. The mixture is then dispersed evenly using ultrasonic treatment to obtain a double-shell-encapsulated organic energy storage luminescent material phase change microcapsule. Step 6, Prepare the mixture: C5 petroleum resin was heated to 160℃ and molten. Then expanded graphite, silica aerogel powder, multi-walled carbon nanotubes and sodium sulfate were added. The mixture was stirred at a low speed of 400 for 5 minutes and then dispersed at a speed of 2000 r / min for 10 minutes to obtain a mixture. Step 7, Dispersing the mixture: Heat the mixture obtained in step six to 180°C, add polyoxymethylene and stir continuously until it melts and disperses evenly; Step 8, Prepare solid coating: Add nano titanium dioxide, calcium carbonate powder and barite powder to the uniformly dispersed mixture obtained in step seven, and stir continuously until it becomes uniform. Then add dioctyl phthalate, stir again until it becomes uniform, stop heating, remove it to a container, and let it cool naturally to room temperature to obtain a solid coating. Step 9: Prepare energy-storing and light-emitting phase change thermal fusion marking material: The solid coating obtained in step eight is crushed to 50-100 mesh, and the treated glass microspheres prepared in step two and the organic energy storage luminescent material phase change microcapsules obtained in step five are added. The mixture is then thoroughly mixed to obtain the energy storage luminescent phase change hot melt marking material.

2. The energy-storing luminescent phase change hot-melt marking material as described in claim 1, characterized in that, By weight fraction, it is made from the following raw materials: 10%–20% C5 petroleum resin, 30%–33% glass microspheres, 0.1%–1% silane coupling agent, 3%–7% polyoxymethylene, 1%–5% polyoxyethylene, 3%–7% sodium sulfate, 0.1%–1% multi-walled carbon nanotubes, 0.2%–0.3% expanded graphite, 0.3%–1% isophorone diisocyanate, 0.3%–1% tetraethylenepentamine, 0.3%–1% perhydropolysilazane, and 1.5%–3% N,N,N',N'-tetramethylbenzidine. 1.5%–3% of 2,8-bis(diphenylphospho)dibenzo[B,D]thiophene, 3%–6% of silica aerogel powder, 0.1%–1.8% of oligodopamine, 1%–7% of nano titanium dioxide powder, 6%–15% of calcium carbonate powder, 8%–15% of barite powder, 1%–8% of lauric acid, 1%–5% of palmitic acid, 0.4%–0.7% of hexadecyltrimethylammonium bromide, 0.3%–0.5% of polyethylene glycol octylphenyl ether, 1%–3% of dioctyl phthalate, and 0.1%–0.5% of acetic acid.

3. The energy-storing luminescent phase change hot-melt marking material as described in claim 2, characterized in that, By weight fraction, it consists of the following raw materials: 10%–20% C5 petroleum resin, 30%–33% glass microspheres, 0.1% silane coupling agent, 3%–5% polyoxymethylene, 1%–3% polyoxyethylene, 3%–4% sodium sulfate, 0.4%–0.8% multi-walled carbon nanotubes, 0.2% expanded graphite, 0.33%–0.67% isophorone diisocyanate, 0.33%–0.67% tetraethylenepentamine, 0.33%–0.67% perhydropolysilazane, and 1.5% N,N,N'- N'-Tetramethylbenzidine, 1.5% 2,8-bis(diphenylphospho)dibenzo[B,D]thiophene, 4%–6% silica aerogel powder, 0.1%–0.5% oligomeric dopamine, 6%–7% nano titanium dioxide powder, 6%–15% calcium carbonate powder, 8%–10% barite powder, 1%–5% lauric acid, 1%–5% palmitic acid, 0.4% hexadecyltrimethylammonium bromide, 0.3% polyethylene glycol octylphenyl ether, 1%–2% dioctyl phthalate, and 0.1% acetic acid.

4. The energy-storing luminescent phase change hot-melt marking material as described in claim 3, characterized in that, By weight fraction, it consists of the following raw materials: 15% C5 petroleum resin, 30% glass microspheres, 0.1% silane coupling agent, 3% polyoxymethylene, 1% polyoxyethylene, 3% sodium sulfate, 0.8% multi-walled carbon nanotubes, 0.2% expanded graphite, 0.33% isophorone diisocyanate, 0.33% tetraethylenepentamine, 0.33% perhydropolysilazane, and 1.5% N,N,N',N'-tetramethyl... Benzidine, 1.5% 2,8-bis(diphenylphospho)dibenzo[B,D]thiophene, 6% silica aerogel powder, 0.1% oligodopamine, 6% nano titanium dioxide powder, 9% calcium carbonate powder, 10% barite powder, 5% lauric acid, 5% palmitic acid, 0.4% hexadecyltrimethylammonium bromide, 0.3% polyethylene glycol octylphenyl ether, 1% dioctyl phthalate, 0.1% acetic acid.

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