Long afterglow luminescent pavement material and preparation method thereof

Abstract

The application belongs to the field of plastic modification and particularly relates to a long-afterglow luminous pavement material and a preparation method thereof. 15-30 parts of modified luminous master batch A, 45-150 parts of rigid resin particles B, 3-6 parts of unsaturated monomer, 0.2-0.5 parts of initiator and 0.2-0.4 parts of antioxidant are blended and extruded through a double-screw extruder, wherein the modified luminous master batch A is prepared by stirring and infiltrating 20-40 parts of luminous powder and 0.01-0.03 parts of surface modifier, and adding 4-12 parts of compatilizer and 0.5-2 parts of dispersant. The luminous particles have good afterglow effect, are easy to be coated, have good adhesion, high strength and wear resistance, and have controllable shape and size.

Description

Technical Field

[0001] This invention belongs to the field of plastic modification, specifically relating to a long afterglow luminescent pavement material and its preparation method. Background Technology

[0002] With the increasing burden of urban and rural traffic, addressing lighting factors that affect road safety, such as how to deal with traffic safety hazards caused by sudden power outages in tunnels, and improving nighttime driving safety on rural roads are urgent issues that need to be resolved. Self-luminous pavement can continuously emit light for several hours at night, thus meeting the needs of highway lighting and increasing the harmony between the road and its surrounding environment. The practice of luminous pavement can not only provide illumination for main roads but also make roads safer and more efficient; luminous pavement can reduce carbon emissions; compared to the previous complete darkness of roads at night, luminous pavement can improve the visibility of nighttime travelers; luminous pavement is not only practical but also highly aesthetically pleasing, adding to the urban nightscape. In recent years, with the increase in traffic in various regions, traffic safety problems caused by lighting issues have become frequent. Road lighting needs new methods to improve its effectiveness. Existing self-luminous pavement materials have problems such as low luminous intensity, short luminous time, poor water resistance, short lifespan, low pavement strength, uneven luminous brightness, and difficulty in practical application. Summary of the Invention

[0003] To address the above problems, the present invention aims to provide a long afterglow luminescent pavement material and its preparation method.

[0004] To achieve the above objectives, the technical solution of the present invention is as follows:

[0005] A long-afterglow luminescent pavement material, by weight, is obtained by co-extrusion of 15-30 parts modified luminescent masterbatch A, 45-150 parts rigid resin particles B, 3-6 parts unsaturated monomer, 0.2-0.5 parts initiator and 0.2-0.4 parts antioxidant through a twin-screw extruder; wherein, by weight, modified luminescent masterbatch A contains 20-40 parts luminescent powder, 0.01-0.03 parts surface modifier for stirring and wetting, 4-12 parts compatibilizer and 0.5-2 parts dispersant.

[0006] The modified luminescent masterbatch A is prepared by mixing the components in a screw-driven kneader according to the above proportions, and then extruding, crushing and granulating them by screw extrusion.

[0007] The luminescent powder is a lanthanide rare earth ion-doped aluminate or silicate with a fineness of 100-500 mesh.

[0008] The surface modifier is silane coupling agent KH550 and / or titanate 101; wherein, the surface modifier improves the water resistance of the luminescent powder, avoids hydrolysis under long-term outdoor conditions, and improves the compatibility and bonding strength with the resin.

[0009] The compatibilizer is at least one of maleic anhydride-grafted polypropylene (PP-g-MAH), acrylic acid-grafted polypropylene (PP-g-AA), and glycidyl methacrylate melt-grafted polypropylene (PP-g-GMA); the above compatibilizer improves the compatibility of the resin with asphalt and powder, and enhances the uniformity and adhesion of the modified resin.

[0010] The dispersant is a hyperbranched polyester and / or erucamide.

[0011] The luminescent powder has the composition SrAl2O4∶Eu 2+ Dy 3+ BaMgAl 10 O 17 Eu 2+ La 3+ or CaTiO3∶Pr 3+ Er 3 + .

[0012] The rigid resin particles B are prepared by co-extrusion using a twin-screw extruder after uniformly mixing 100-200 parts of transparent resin, 4-10 parts of tackifying resin, and 3-8 parts of rigid particles by weight.

[0013] The transparent resin is at least one of polystyrene PS, in-situ toughened polystyrene HIPS, polycarbonate PC, polyethylene terephthalate PET, polyacrylonitrile AS, and transparent nylon TR55; the selected transparent resin is required to have high transparency, good light energy transmission, and be suitable for light transmission inside; and also have high strength and hardness.

[0014] The tackifying resin is (C5, C9) hydrogenated petroleum resin and / or indene resin; the selected tackifying resin improves the homogeneity between the components and increases the adhesion between the luminescent resin particles and the asphalt overlay layer.

[0015] The rigid particles are at least one of 80-200 mesh glass microspheres, silicon carbide, silicon nitride, quartz powder, and corundum powder.

[0016] The unsaturated monomer is at least one of bisphenol A glycerol dimethacrylate, trimethylolpropane triacrylate (TMPTA), hexanediol diacrylate (HDDA), glyceryl triacrylate (OTA), and triallyl isocyanurate (TAIC). Since the density of the luminescent powder is around 3.6 and its specific gravity is high, the grafting and crosslinking of the unsaturated monomer improves the melt strength of the material, reduces uneven sedimentation of inorganic powder during processing, and significantly improves the strength, hardness, wear resistance, and anti-slip properties of the resin, avoiding powdering and peeling of the cover layer.

[0017] The initiator is at least one of bis(tert-butylperoxyisopropylbenzene) (BIPB) and di(diisopropylbenzene) peroxide (DCP).

[0018] The preparation method of long afterglow luminescent pavement material involves mixing luminescent masterbatch A, rigid composite particles B, unsaturated monomers, initiators, and antioxidants evenly according to the above proportions, and then extruding them through a twin-screw extruder at an extrusion temperature of 190-210℃ and a screw speed of 120-200 r / min. After extrusion, the material is granulated to obtain long afterglow luminescent pavement particles.

[0019] By designing the die size of a twin-screw extruder, long afterglow luminescent road surface particles of different shapes and sizes (4-9mm) are granulated. The particle size of the luminescent resin should be less than 9mm to ensure the anti-skid performance of the road surface.

[0020] The obtained long-afterglow luminescent particles are evenly spread on the surface during the construction of the overlay layer, and the long-afterglow luminescent pavement is obtained by compaction with a road roller using the residual heat of the overlay layer.

[0021] The synergistic effect of the components in this invention avoids problems such as low load-bearing capacity of luminescent pavement materials, easy delamination, collapse and other defects, and short pavement life.

[0022] Advantages of this invention:

[0023] Lanthanide rare-earth ion-doped aluminate or silicate rare-earth element luminescent materials are known for their stable performance, high brightness, ultra-long afterglow time, and absence of any radioactive elements, earning them the title of green and energy-saving materials. However, these materials have poor moisture resistance and are easily hydrolyzed in the presence of water, significantly reducing their brightness and afterglow time. This invention improves the water resistance of the luminescent powder by surface modification, thus maintaining its high brightness and ultra-long afterglow characteristics.

[0024] It is made by combining high-strength, high-rigidity transparent resin with transparent elastic tackifying resin, and adding rigid particles such as silicon nitride and corundum to achieve functions such as high transparency, wear resistance, anti-slip, and a combination of rigidity and toughness.

[0025] The synergistic effect of the components of the material in this invention enables the luminescent pavement material to have long afterglow, high strength, wear resistance, anti-slip properties, and easy construction. Furthermore, it avoids problems such as low load-bearing capacity, easy delamination, collapse, and short pavement life of luminescent pavement materials. Detailed Implementation

[0026] The following examples further illustrate specific embodiments of the present invention. It should be noted that the specific embodiments described herein are merely for illustration and explanation and are not intended to limit the scope of the present invention.

[0027] The luminescent powder used in the following embodiments has the composition SrAl2O4∶Eu 2+Dy 3+ BaMgAl 10 O 17 Eu 2+ La 3+ or CaTiO3∶Pr 3+ Er 3+ All of these materials are commercially available. The materials used in the examples are all available from Foshan Julang Optical Materials Co., Ltd., and can also be prepared on-site according to existing records.

[0028] All components in the following examples are by weight; all additives are commercially available.

[0029] Example 1

[0030] Preparation of long-afterglow luminescent pavement materials:

[0031] (1) Take 25 parts of 100 mesh BaMgAl 10 O 17 Eu 2+ La 3+ 0.01 parts of silane coupling agent KH550 were stirred and impregnated, then mixed with 5 parts of acrylic acid-grafted polypropylene (PP-g-AA) and 0.5 parts of carboxyl-terminated hyperbranched polyester in a screw kneader. The mixture was then extruded through a screw at a temperature of 170℃ and a screw speed of 120 r / min. The resulting product was pulverized and granulated to obtain 30.51 parts of modified luminescent masterbatch A.

[0032] (2) Mix 120 parts of polycarbonate (PC), 5 parts of indene resin (coumarone indene resin), and 3 parts of 200-mesh corundum powder evenly, and then add them to a twin-screw extruder for co-extrusion. The extrusion temperature is 210℃ and the screw speed is 120r / min. Prepare 128 parts of rigid resin particles B.

[0033] (3) Mix 30.51 parts of luminescent masterbatch A, 128 parts of rigid resin particles B, 2 parts of bisphenol A glycerol dimethacrylate, 1 part of triallyl isocyanurate TAIC, 0.2 parts of bis-tert-butyl peroxide isopropylbenzene BIPB, 0.1 parts of antioxidant 168, and 0.2 parts of 1010 evenly, and then extrude them through a twin-screw extruder. The extrusion temperature is 190℃ and the screw speed is 140r / min. By designing the die size, hexagonal luminescent particles with a length of 8mm and a cross-sectional side length of 4mm are granulated.

[0034] Example 2

[0035] Preparation of long-afterglow luminescent pavement materials:

[0036] (1) Mix 30 portions of 300 mesh SrAl2O4∶Eu 2+ Dy 3+0.02 parts of titanate 101 were stirred and impregnated, then mixed thoroughly with 7 parts of glycidyl methacrylate melt-grafted polypropylene (PP-g-GMA) and 0.5 parts of erucamide in a screw kneader, followed by screw extrusion at 180℃ and 120 r / min. 37.52 parts of modified luminescent masterbatch A were obtained by pulverization and granulation.

[0037] (2) 150 parts of polyethylene terephthalate (PET), 6 parts of C9 hydrogenated petroleum resin, and 3 parts of 100-mesh silicon carbide were mixed evenly and then added to a twin-screw extruder for co-extrusion. The extrusion temperature was 250℃ and the screw speed was 140 r / min. 159 parts of rigid resin particles B were obtained.

[0038] (3) 37.52 parts of luminescent masterbatch A, 159 parts of rigid resin particles B, 4 parts of glyceryl triacrylate OTA, 1 part of triallyl isocyanurate TAIC, 0.3 parts of bis-tert-butyl peroxide isopropylbenzene BIPB, 0.2 parts of antioxidant 1078, and 0.1 parts of 618 were mixed evenly and then co-extruded through a twin-screw extruder at an extrusion temperature of 230℃ and a screw speed of 160r / min. By designing the die size, triangular luminescent particles with a length of 7mm and a cross-sectional side length of 5mm were granulated.

[0039] Example 3

[0040] Preparation of long-afterglow luminescent pavement materials:

[0041] (1) 210g of 500-mesh CaTiO3∶Pr 3+ Er 3+ 0.09g of silane coupling agent KH550 was stirred and impregnated, then mixed thoroughly with 35g of maleic anhydride-grafted polypropylene (PP-g-MAH) and 5g of hydroxyl-terminated hyperbranched polyester in a screw kneader. The mixture was then extruded through a screw at 200℃ and a screw speed of 120r / min. 250.09g of modified luminescent masterbatch A was obtained by pulverization and granulation.

[0042] (2) 900g of transparent nylon TR55, 35g of C5 hydrogenated petroleum resin, and 32g of 200-mesh glass microspheres were mixed evenly and then added to a twin-screw extruder for co-extrusion. The extrusion temperature was 220℃ and the screw speed was 150r / min. 967g of rigid resin particles B were prepared.

[0043] (3) 250.09g of luminescent masterbatch A, 967g of rigid resin particles B, 30g of bisphenol A glycerol dimethacrylate, 10g of hexanediol diacrylate HDDA, 2.5g of dicumyl peroxide DCP, 0.7g of antioxidant 1010 and 0.9g of 618 were mixed evenly and then co-extruded through a twin-screw extruder at an extrusion temperature of 210℃ and a screw speed of 180r / min. By designing the die size, quadrilateral luminescent particles with a length of 8mm and a cross-sectional side length of 5mm were granulated.

[0044] Example 4

[0045] Preparation of long-afterglow luminescent pavement materials:

[0046] (1) 4 kg of 100 mesh SrAl2O4∶Eu 2+ Dy 3+ 0.002 kg of titanate 101 was stirred and impregnated, then mixed thoroughly with 0.8 kg of glycidyl methacrylate melt-grafted polypropylene (PP-g-GMA) and 0.09 kg of hydroxyl-terminated hyperbranched polyester in a screw kneader. The mixture was then extruded through a screw extruder at 190℃ and 120 r / min. The resulting product was pulverized and granulated to obtain 4.892 kg of modified luminescent masterbatch A.

[0047] (2) 20 kg of polystyrene (PS), 0.9 kg of indene resin, and 0.5 kg of 80-mesh corundum powder were mixed evenly and then added to a twin-screw extruder for co-extrusion. The extrusion temperature was 210℃ and the screw speed was 180 r / min. 21.4 kg of rigid resin particles B were obtained.

[0048] (3) Mix 4.892 kg of luminescent masterbatch A, 21.4 kg of rigid resin particles B, 0.4 kg of bisphenol A glycerol dimethacrylate, 0.1 kg of trimethylolpropane triacrylate (TMPTA), 0.02 kg of di-tert-butylperoxyisopropylbenzene (BIPB), 0.02 kg of antioxidant 1076, and 0.01 kg of 618 evenly, and then extrude them through a twin-screw extruder at an extrusion temperature of 210°C and a screw speed of 200 r / min. By designing the die size, granulate cylindrical luminescent particles with a length of 9 mm and a cross-sectional diameter of 9 mm.

[0049] test

[0050] The luminescence performance and peel strength of the above embodiments were tested. The luminescence performance was tested according to the afterglow test method with an excitation illuminance of 1010 lx for 10 min. The luminescence brightness was tested and the time required to reach the lower limit of visual visibility (0.3 mcd / m2) was estimated based on the decay curve. The peel strength was tested according to the adhesion test between asphalt and coarse aggregate in T0616-1993. The particle size of the luminescent particles was less than 13.2 mm, and the test was conducted using the water immersion method at 80℃±1℃.

[0051]

[0052] In this embodiment of the invention, the long-afterglow luminescent particles have a high afterglow brightness and an afterglow time far exceeding 12 hours; the requirements for the peeling performance of coarse aggregates are: greater than or equal to level 4 for urban expressways and main roads; and greater than or equal to level 3 for secondary roads and below. In this embodiment, the adhesion of the luminescent particles meets the requirements.

Claims

1. A long-afterglow luminescent pavement material, characterized in that: The mixture is obtained by blending and extruding 15-30 parts of modified luminescent masterbatch A, 45-150 parts of rigid resin particles B, 3-6 parts of unsaturated monomer, 0.2-0.5 parts of initiator and 0.2-0.4 parts of antioxidant by weight through a twin-screw extruder. The modified luminescent masterbatch A, by weight, comprises 20-40 parts luminescent powder, 0.01-0.03 parts surface modifier (for stirring and wetting), 4-12 parts compatibilizer, and 0.5-2 parts dispersant; the luminescent powder is a lanthanide rare earth ion-doped aluminate with a fineness of 100-500 mesh; the surface modifier is silane coupling agent KH550 and / or titanate 101; the compatibilizer is at least one of maleic anhydride-grafted polypropylene (PP-g-MAH), acrylic acid-grafted polypropylene (PP-g-AA), and glycidyl methacrylate melt-grafted polypropylene (PP-g-GMA); and the dispersant is hyperbranched polyester and / or erucamide. The rigid resin particles B are prepared by co-extrusion using a twin-screw extruder after uniformly mixing 100-200 parts of transparent resin, 4-10 parts of tackifying resin, and 3-8 parts of rigid particles by weight. The unsaturated monomer is at least one of bisphenol A glycerol dimethacrylate, trimethylolpropane triacrylate (TMPTA), hexanediol diacrylate (HDDA), glyceryl triacrylate (OTA), and triallyl isocyanurate (TAIC). The initiator is at least one of bis-tert-butylperoxyisopropylbenzene (BIPB) and diisopropylbenzene peroxy (DCP). The transparent resin is at least one of polystyrene PS, in-situ toughened polystyrene HIPS, polycarbonate PC, polyethylene terephthalate PET, polyacrylonitrile AS, and transparent nylon TR55; The tackifying resin is C5 or C9 hydrogenated petroleum resin and / or indene resin; The rigid particles are at least one of 80-200 mesh glass microspheres, silicon carbide, silicon nitride, quartz powder, and corundum powder.

2. The long afterglow luminescent pavement material according to claim 1, characterized in that: The modified luminescent masterbatch A is prepared by mixing the components in a screw-driven kneader according to the above proportions, and then extruding, crushing and granulating them by screw extrusion.

3. The long afterglow luminescent pavement material according to claim 1, characterized in that: The luminescent powder has the composition SrAl2O4∶Eu 2+ Dy 3+ or BaMgAl 10 O 17 Eu 2+ La 3+ .

4. A method for preparing the long afterglow luminescent pavement material according to claim 1, characterized in that: According to the above proportions, the luminescent masterbatch A, rigid composite particles B, unsaturated monomers, initiators, and antioxidants are mixed evenly and then co-extruded through a twin-screw extruder at an extrusion temperature of 190-210℃ and a screw speed of 120-200 r / min. After extrusion, the particles are granulated to obtain long-afterglow road luminescent particles.

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