An antifouling and antiskid type road marking line composition and a preparation method thereof

Abstract

The application discloses a road marking material technical field, and relates to an anti-fouling and anti-skid road marking composition and a preparation method thereof. The composition is composed of a base resin, hyperbranched polyurethane-polydimethylsiloxane copolymer, quaternary ammonium salt functionalized nanocellulose-graphene composite particles, calcined haydite, glass microspheres, a plasticizer and a light stabilizer. The hyperbranched polyurethane-polydimethylsiloxane copolymer provides low surface energy characteristics, and the preparation process comprises the following steps: first, reacting diisocyanate with hyperbranched polyester polyol to generate a prepolymer, then introducing polydimethylsiloxane diol and a chain extender for polymerization, and finally adding a catalyst for reduced pressure distillation. The quaternary ammonium salt functionalized nanocellulose-graphene composite particles are prepared through a two-step modification process. The composition significantly improves the anti-fouling performance, anti-skid performance and weather resistance of the road marking, is suitable for the field of road marking, and has the advantages of long-term wear resistance, environmental protection and low cost.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of road marking materials, and particularly relates to an anti-fouling and anti-skid road marking composition and a preparation method thereof. BACKGROUND

[0002] As an important part of traffic safety facilities, the performance of road marking materials directly affects road safety and traffic management efficiency. Traditional marking materials have exposed many problems in the long-term use process, especially in the aspects of anti-fouling and anti-skid performance. The surface energy of ordinary marking paint is relatively high, which can easily lead to the penetration of oily pollutants and the adsorption of dust, seriously affecting the visibility and reflective effect of the marking. At the same time, the binding force between the anti-skid aggregate and the matrix material is weak, and the particles can easily fall off under repeated vehicle rolling, which can significantly reduce the friction coefficient of the road surface, especially in rainy and snowy weather conditions, which can easily cause traffic accidents. These problems seriously restrict the service life and functional performance of road markings.

[0003] The prior art mainly improves the surface performance of the marking by adding fluorine-containing polymers or organic silicon-based additives. Although this kind of modification method can reduce the surface energy of the material to a certain extent and improve the anti-fouling effect, it has obvious limitations. Fluorine-containing materials are high in cost and may cause environmental pollution, and the compatibility of organic silicon-based additives with the matrix resin is poor, which can easily cause migration and precipitation after long-term use. In addition, the existing anti-skid particle modification technology mainly uses physical coating or simple coupling treatment, which is difficult to realize the uniform dispersion and long-term stable fixation of the particles in the matrix. These problems make it difficult for the marking material to meet the needs of modern traffic management in terms of durability and functionality, especially in high-traffic and complex climate conditions.

[0004] With the continuous improvement of road construction standards, higher requirements are put forward for the comprehensive performance of road marking materials. Researchers have begun to explore the performance improvement of marking materials through molecular structure design and multi-functional component synergy. Hyperbranched polymers have unique three-dimensional structure and multiple end group characteristics, which exhibit unique advantages in improving the surface performance of materials. The application of nanocomposites provides a new possibility for improving the dispersibility and binding force of anti-skid particles. At the same time, the development of weather resistance modification technology creates conditions for prolonging the service life of marking materials. These technical innovations lay the foundation for the development of a new generation of high-performance road marking materials and promote the development of the industry towards higher efficiency, environmental protection and durability. SUMMARY

[0005] The present application relates to the technical field of road marking materials, and particularly relates to an anti-fouling and anti-skid road marking composition and a preparation method thereof.

[0006] The application achieves the above-mentioned purpose through the following technical solutions.

[0007] An anti-fouling and anti-skid type road marking line composition comprises the following raw materials in parts by weight:

[0008] Base resin: 500-650 parts by weight;

[0009] Hyperbranched polyurethane-polydimethylsiloxane copolymer: 60-100 parts by weight;

[0010] Quaternary ammonium salt functionalized nanocellulose-graphene composite particles: 120-200 parts by weight;

[0011] Calcined haydite: 180-280 parts by weight;

[0012] Glass microspheres: 60-100 parts by weight;

[0013] Dibutyl phthalate: 40-70 parts by weight;

[0014] Bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate: 6-10 parts by weight;

[0015] The preparation method of the hyperbranched polyurethane-polydimethylsiloxane copolymer comprises: A1, putting diisocyanate and hyperbranched polyester polyol into a reaction kettle, heating to 74-76 DEG C under nitrogen protection to generate an isocyanate-terminated prepolymer; A2, then adding polydimethylsiloxane diol and 1,4-butanediol, reacting at 80-82 DEG C, and finally adding stannous octoate to react and distill under reduced pressure.

[0016] In the application, the preparation process of the hyperbranched polyurethane-polydimethylsiloxane copolymer is based on the step-by-step polymerization reaction mechanism. First, diisocyanate and hyperbranched polyester polyol undergo addition reaction under nitrogen protection to form an isocyanate-terminated prepolymer. In this step, nitrogen protection effectively isolates oxygen interference, ensures the selective reaction of isocyanate groups, promotes molecular chain segment movement by heating to a specific temperature range, and makes the reaction groups fully contact and form a stable prepolymer structure. The subsequently added polydimethylsiloxane diol and 1,4-butanediol act as chain extenders to participate in the reaction. The long chain structure of polydimethylsiloxane diol endows the material with low surface energy characteristics, and 1,4-butanediol provides rigid backbone support. Stannous octoate as a catalyst accelerates the chain growth reaction, and finally trace amounts of water and small molecule by-products are removed by reduced pressure distillation to form a copolymer with a regular molecular structure. The copolymer introduces hydrophobic polydimethylsiloxane segments into the polyurethane network through chemical bonding, forming a unique microphase separation structure and providing a basis for the material's long-lasting anti-fouling performance.

[0017] According to a preferred embodiment of the present application, the base resin is WANEX® 3411 (ethylene-vinyl acetate copolymer, EVA) from Wanhua Chemical Group Co., Ltd.

[0018] According to a preferred embodiment of the present application, the diisocyanate is WANNATE® HT-100 (isophorone diisocyanate, IPDI) from Wanhua Chemical Group Co., Ltd.

[0019] According to a preferred embodiment of the present application, the hyperbranched polyester polyol is HBPE-2000 (hyperbranched polyester polyol, molecular weight about 5000) from Zhejiang Royalstar Technology Co., Ltd.

[0020] According to a preferred embodiment of the present application, the reaction kettle is WHF-500 (500L stainless steel high-pressure reaction kettle) from Weihai Chemical Machinery Co., Ltd.

[0021] According to a preferred embodiment of the present application, the nitrogen gas is Air Liquide® Ultra High Purity Nitrogen (high purity nitrogen, purity ≥ 99.999%) from Liquefied Air (China) Investment Co., Ltd.

[0022] According to a preferred embodiment of the present application, the polydimethylsiloxane diol is BLUESIL® PDMS 1000 (polydimethylsiloxane diol, molecular weight 1000) from Bluestar Specialty Chemicals Co., Ltd.

[0023] According to a preferred embodiment of the present application, the 1,4-butanediol is PTMEG-1000 (1,4-butanediol, industrial grade) from China Petroleum Group Asset Management Co., Ltd.

[0024] According to a preferred embodiment of the present application, the stannous octoate is Stannous Octoate (stannous octoate, catalyst grade) from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0025] According to a preferred embodiment of the present application, the calcined chamotte is XFH-TL12 (calcined bauxite chamotte, particle size 1-2mm) from Henan Xinfuhua Refractory Co., Ltd.

[0026] According to a preferred embodiment of the present application, the glass microspheres are KSC-05 (solid glass microspheres, particle size 10-20μm, density 0.6g / cm³) from Shandong Kaisheng New Material Co., Ltd. or SSB-3 (hollow glass microspheres, particle size 20-30μm, density 0.3g / cm³) from Langfang Songshan Plastic Products Co., Ltd.

[0027] According to the preferred embodiment of the present application, the dibutyl phthalate is DBP-Industrial Grade (dibutyl phthalate, superior product) purchased from Nanjing Datang Chemical Co., Ltd.

[0028] According to the preferred embodiment of the present application, the bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate is Tinuvin® 770 (light stabilizer) purchased from Beijing Tianguang Additives Co., Ltd.

[0029] According to the preferred embodiment of the present application, in step A1, the molar ratio of diisocyanate to hyperbranched polyester polyol is (2-3):1; the temperature is raised to 74-76℃ and the reaction time is 2-3h.

[0030] According to the preferred embodiment of the present application, in step A2, the molar ratio of diisocyanate to polydimethylsiloxane diol, 1,4-butanediol is 1:0.6:0.4; the reaction time is 3-4h at 80-82℃.

[0031] According to the preferred embodiment of the present application, the preparation method of the quaternary ammonium salt functionalized nanocellulose-graphene composite particles comprises: B1, dispersing nanocellulose and graphene oxide in deionized water, adding 2,3-epoxypropyl trimethyl ammonium chloride after ultrasonic treatment, and reacting at 60-64℃; B2, after centrifugal washing, redispersed in ethanol, adding ammonia water to adjust the pH to 9-11, then adding 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, and reacting at 70-72℃, and filtering and drying.

[0032] In the present application, the preparation of the quaternary ammonium salt functionalized nanocellulose-graphene composite particles adopts a step-by-step surface modification strategy, and the reaction mechanism involves grafting polymerization and charge regulation. In the initial stage, nanocellulose and graphene oxide are uniformly dispersed in deionized water by ultrasonic treatment, forming a stable suspension system. The ultrasonic cavitation breaks the van der Waals force between the particles, allowing nanocellulose to uniformly adhere to the surface of graphene. Subsequently, the epoxy reagent is added to the system and reacts with the hydroxyl groups on the surface of cellulose at a mild temperature, forming stable ether bonds and imparting preliminary cationic activity to the particles. The pH adjustment step neutralizes the system charge with ammonia water, creating a favorable environment for subsequent reactions. Finally, the introduction of quaternary ammonium salt precursors undergoes nucleophilic substitution under alkaline conditions, forming positively charged quaternary ammonium salt groups on the surface of the particles. This functionalization process not only imparts excellent antibacterial properties to the particles, but also significantly improves the dispersion stability through electrostatic repulsion. The two-dimensional sheet structure of graphene and the fiber network of nanocellulose form a synergistic reinforcement effect, providing excellent mechanical support and wear resistance to the composite material.

[0033] According to the preferred embodiment of the present application, the nanocellulose is purchased from Henglian-Nano-Cel (nanocellulose, diameter 10-20 nm, length 1-5 μm) of Shandong Henglian New Material Co., Ltd.

[0034] According to the preferred embodiment of the present application, the graphene oxide is purchased from SixthElement-GO (graphene oxide, thickness 2-5 nm) of Changzhou Sixth Element Material Technology Co., Ltd.

[0035] According to the preferred embodiment of the present application, the deionized water is purchased from WaHaHa-DI-Water (deionized water, resistivity ≥ 18.2 MΩ·cm) of Wahaha Group Co., Ltd.

[0036] According to the preferred embodiment of the present application, the 2,3-epoxypropyl trimethyl ammonium chloride is purchased from McLean-EPGTA (2,3-epoxypropyl trimethyl ammonium chloride, purity ≥ 98%) of Shanghai McLean Biochemical Technology Co., Ltd.

[0037] According to the preferred embodiment of the present application, the ethanol is purchased from Lianhong-EtOH (ethanol, analytical pure, ≥ 99.7%) of Jiangsu Lianhong Technology Co., Ltd.

[0038] According to the preferred embodiment of the present application, the ammonia water is purchased from Xilong-Ammonia (ammonia water, analytical pure, 25%-28%) of Xilong Scientific Co., Ltd.

[0039] According to the preferred embodiment of the present application, the 3-chloro-2-hydroxypropyl trimethyl ammonium chloride is purchased from Aladdin-CHPTAC (3-chloro-2-hydroxypropyl trimethyl ammonium chloride, purity ≥ 99%) of Aladdin Reagent (Shanghai) Co., Ltd.

[0040] According to the preferred embodiment of the present application, in step B1, the mass ratio of nanocellulose and graphene oxide is (3-5):1; the ultrasonic treatment time is 35-40 min; and the reaction time at 60-64℃ is 12-14 h.

[0041] According to the preferred embodiment of the present application, in step B2, the reaction time at 70-72℃ is 6-8 h.

[0042] The present application also provides a preparation method of the anti-fouling and anti-skid road marking composition, and the steps include:

[0043] S1, the hyperbranched polyurethane-polydimethylsiloxane copolymer and the base resin are put into a high-speed mixer and stirred at 130-132℃;

[0044] S2, adding quaternary ammonium salt functionalized nanocellulose-graphene composite particles, calcined haydite, glass microspheres, dibutyl phthalate and bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate are mixed;

[0045] S3, melt extrusion by a twin-screw extruder, and cooling and granulation.

[0046] In the present application, the preparation process of the composition is based on the blending and forming mechanism of the multiphase system, and the effective synergy between the components is realized by staged mixing. In the initial mixing stage, the hyperbranched polyurethane-polydimethylsiloxane copolymer with pre-polymerization completed and the base resin are mechanically blended under high temperature conditions. The high-speed shearing action promotes the full stretching of the polymer molecular chain, forming a uniform phase interface. Temperature control is crucial in this stage, which not only ensures the fluidity of the resin, but also avoids the degradation of functional components caused by high temperature. The functional particles added subsequently are uniformly dispersed by extending the mixing time, while the plasticizer molecules are embedded between the polymer segments to reduce the glass transition temperature. The high temperature and high pressure environment in the twin-screw extrusion process promotes the further homogenization of the components. The melt material forms a directional arrangement structure under the action of screw shearing, and after cooling and solidification, a composite material with stable microstructure is obtained. This multi-scale composite system realizes the synergistic optimization of the mechanical properties and functional characteristics of the material, ultimately endowing the road marking line with excellent anti-fouling and anti-skid performance and long-term weather resistance.

[0047] According to the preferred embodiment of the present application, in step S1, the mass ratio of the hyperbranched polyurethane-polydimethylsiloxane copolymer to the base resin is 1:3; the stirring time at 130-132℃ is 25-30min.

[0048] According to the preferred embodiment of the present application, in step S2, the mixing time is 1-2h.

[0049] According to the preferred embodiment of the present application, in step S3, the temperature of the melt extrusion by the twin-screw extruder is 170-175℃.

[0050] The present application has the following advantages:

[0051] The anti-fouling and anti-skid road marking line composition prepared by the present application has achieved significant improvement in comprehensive performance. By introducing the hyperbranched polyurethane-polydimethylsiloxane copolymer, the surface energy of the material is effectively reduced, forming a stable low surface energy structure, which significantly enhances the anti-fouling performance of the marking line. The unique molecular structure of this copolymer not only provides excellent hydrophobic and oleophobic properties, but also forms a firm interfacial bond through chemical bonding with the base resin, enabling the marking line to effectively resist the accumulation of oily pollutants and dust during long-term use, maintaining clear identification effect. Experimental results show that the composition exhibits excellent anti-pollution ability, significantly prolonging the cleaning cycle and maintenance interval of the marking line.

[0052] In terms of anti-skid performance, the application realizes efficient combination of anti-skid particles and base materials through innovative application of quaternary ammonium salt functionalized nanocellulose-graphene composite particles. Such composite particles not only have excellent dispersion stability, but also can form a firm chemical bonding network with the base, effectively solving the technical problem of easy falling of traditional anti-skid particles. At the same time, the synergistic effect of nanocellulose and graphene significantly improves the mechanical strength and wear resistance of the marking line, so that the anti-skid performance remains stable in long-term use. Even in severe weather conditions, the marking line can still maintain a high friction coefficient, providing reliable safety protection for vehicles and greatly reducing the risk of traffic accidents.

[0053] In addition, the composition of the application also exhibits excellent weather resistance and service life. Through the synergistic effect of various functional components, the material can still maintain stable physical and chemical properties under complex environmental conditions such as ultraviolet radiation, temperature changes and humidity fluctuations. The addition of light stabilizers effectively inhibits the aging process of the material, preventing yellowing and embrittlement. The overall structural design of the composite material enables the marking line to have excellent impact resistance and flexibility, which can adapt to different road conditions and use environments. These performance advantages not only reduce road maintenance costs, but also improve traffic safety levels, having significant social and economic benefits, and providing an innovative solution for the development of a new generation of high-performance road marking materials. DETAILED DESCRIPTION

[0054] The following detailed description is only used to further illustrate the application, and cannot be understood as limiting the scope of protection of the application. Those skilled in the art can make some non-essential improvements and adjustments to the application based on the above application content. Example 1

[0055] Base resin 550g, hyperbranched polyurethane-polydimethylsiloxane copolymer 80g, quaternary ammonium salt functionalized nanocellulose-graphene composite particles 150g, calcined ceramsite 220g, glass microspheres 80g, dibutyl phthalate 50g, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate 8g. Among them, the preparation process of the hyperbranched polyurethane-polydimethylsiloxane copolymer is as follows: first, diisocyanate 37.5g and hyperbranched polyester polyol 15g are put into a reaction kettle, and the temperature is raised to 75℃ under nitrogen protection conditions. The isocyanate pre-polymer is generated after constant temperature reaction for 2.5 hours; then polydimethylsiloxane diol 22.5g and 1,4-butanediol 7.5g are added to the reaction kettle, and the reaction is carried out under constant temperature conditions of 81℃ for 3.5 hours; finally, stannous octoate catalyst 0.03g is added to the reaction system for reaction, and trace amount of water and small molecule by-products are removed by reduced pressure distillation to obtain the hyperbranched polyurethane-polydimethylsiloxane copolymer.

[0056] The preparation process of the quaternary ammonium salt functionalized nanocellulose-graphene composite particles is as follows: first, nanocellulose 120 g and graphene oxide 30 g are dispersed in 400 mL of deionized water, and ultrasonic treatment is performed for 38 minutes to uniformly disperse the system, then 2,3-epoxypropyl trimethyl ammonium chloride 7.2 g is added, and the reaction is carried out at a constant temperature of 62°C for 13 hours; after the reaction is completed, centrifugal washing is performed 3 times to remove unreacted reagents, then the washed product is redispersed in 300 mL of ethanol, ammonia water is added to adjust the pH value of the system to 10, then 3-chloro-2-hydroxypropyl trimethyl ammonium chloride 4.8 g is added, and the reaction is carried out at a constant temperature of 71°C for 7 hours; after the reaction is completed, filtration is performed and 100 mL of ethanol is used to wash 2 times, then drying is performed in a vacuum drying oven at 60°C for 8 hours, and the quaternary ammonium salt functionalized nanocellulose-graphene composite particles are obtained.

[0057] The preparation process of the anti-fouling and anti-skid type road marking line composition is as follows: first, the hyperbranched polyurethane-polydimethylsiloxane copolymer 80 g prepared above and the base resin 550 g are put into a high-speed mixer, and stirring is performed at a constant temperature of 131°C for 28 minutes to uniformly mix the two components; then the quaternary ammonium salt functionalized nanocellulose-graphene composite particles 150 g, calcined ceramsite 220 g, glass microspheres 80 g, dibutyl phthalate 50 g, and bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate 8 g are added to the mixed system, and mixing is continued for 1.5 hours to uniformly disperse all components; finally, the uniformly mixed material is melt-extruded through a twin-screw extruder at a constant temperature of 172°C, the screw rotation speed is controlled to be 200 revolutions / minute, the residence time of the material in the extruder is 3 minutes, and after cooling in a cooling water tank, the material is cut into particles to obtain the anti-fouling and anti-skid type road marking line composition. Example 2

[0058] The specific implementation is the same as Example 1, except that the base resin 500 g, the hyperbranched polyurethane-polydimethylsiloxane copolymer 60 g, the quaternary ammonium salt functionalized nanocellulose-graphene composite particles 120 g, the calcined haydite 180 g, the glass microspheres 60 g, the dibutyl phthalate 40 g, and the bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate 6 g. The hyperbranched polyurethane-polydimethylsiloxane copolymer preparation step is to put the diisocyanate and the hyperbranched polyester polyol into a reaction kettle, heat to 74°C under nitrogen protection, and react to generate an isocyanate-terminated prepolymer. The molar ratio of diisocyanate to hyperbranched polyester polyol is 2:1, the reaction time is 2 h, then polydimethylsiloxane diol and 1,4-butanediol are added, and the reaction is carried out at 80°C. The molar ratio of diisocyanate to polydimethylsiloxane diol and 1,4-butanediol is 1:0.6:0.4, and the reaction time is 3 h. Finally, stannous octoate is added, and the reaction is reduced pressure distilled. The quaternary ammonium salt functionalized nanocellulose-graphene composite particle preparation step is to disperse nanocellulose and graphene oxide in deionized water, and then add 2,3-epoxypropyltrimethylammonium chloride after ultrasonic treatment. The mass ratio of nanocellulose to graphene oxide is 3:1, the ultrasonic treatment time is 35 min, the reaction temperature is 60°C, and the reaction time is 12 h. After centrifugation and washing, it is redispersed in ethanol, ammonia water is added to adjust the pH to 9, and then 3-chloro-2-hydroxypropyltrimethylammonium chloride is added. The reaction temperature is 70°C, and the reaction time is 6 h. Filter and dry. The anti-staining and anti-skid road marking composition preparation step is to put the hyperbranched polyurethane-polydimethylsiloxane copolymer and the base resin into a high-speed mixer, stir at 130°C, and stir for 25 min. Add quaternary ammonium salt functionalized nanocellulose-graphene composite particles, calcined haydite, glass microspheres, dibutyl phthalate, and bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate. The mixing time is 1 h, melt extruded through a twin-screw extruder, and the melt extrusion temperature is 170°C. Cool and granulate. Example 3

[0059] The specific implementation of Example 1 is different in that the base resin is 650 g, the hyperbranched polyurethane-polydimethylsiloxane copolymer is 100 g, the quaternary ammonium salt functionalized nanocellulose-graphene composite particles are 200 g, the calcined ceramsite is 280 g, the glass microspheres are 100 g, the dibutyl phthalate is 70 g, and the bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate is 10 g. The hyperbranched polyurethane-polydimethylsiloxane copolymer preparation step is to put diisocyanate and hyperbranched polyester polyol into a reaction kettle, heat to 76°C under nitrogen protection, and react to generate an isocyanate-terminated prepolymer. The molar ratio of diisocyanate to hyperbranched polyester polyol is 3:1, the reaction time is 3h, then polydimethylsiloxane diol and 1,4-butanediol are added, the molar ratio of diisocyanate to polydimethylsiloxane diol and 1,4-butanediol is 1:0.6:0.4, the reaction time is 4h, and finally stannous octoate is added and reduced pressure distillation is performed. The quaternary ammonium salt functionalized nanocellulose-graphene composite particle preparation step is to disperse nanocellulose and graphene oxide in deionized water, ultrasonic treatment, then add 2,3-epoxypropyltrimethylammonium chloride, the mass ratio of nanocellulose to graphene oxide is 5:1, the ultrasonic treatment time is 40 min, the reaction temperature is 64°C, the reaction time is 14h, centrifugal washing is performed, then redispersion in ethanol is performed, ammonia water is added to adjust the pH to 11, then 3-chloro-2-hydroxypropyltrimethylammonium chloride is added, the reaction temperature is 72°C, and the reaction time is 8h. Filtration and drying are performed. The anti-staining and anti-skid road marking composition preparation step is to put the hyperbranched polyurethane-polydimethylsiloxane copolymer and the base resin into a high-speed mixer, stir at 132°C, the stirring time is 30 min, then add the quaternary ammonium salt functionalized nanocellulose-graphene composite particles, the calcined ceramsite, the glass microspheres, the dibutyl phthalate, and the bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, the mixing time is 2h, melt extrusion is performed through a twin-screw extruder, and the melt extrusion temperature is 175°C. Cooling and granulation are performed.

[0060] Comparative Example 1

[0061] The specific implementation of Example 1 is different in that the base resin is 650 g, the hyperbranched polyurethane-polydimethylsiloxane copolymer is 100 g, the quaternary ammonium salt functionalized nanocellulose-graphene composite particles are 200 g, the calcined ceramsite is 280 g, the glass microspheres are 100 g, the dibutyl phthalate is 70 g, and the bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate is 10 g. The hyperbranched polyurethane-polydimethylsiloxane copolymer preparation step is to put diisocyanate and hyperbranched polyester polyol into a reaction kettle, heat to 76°C under nitrogen protection, and react to generate an isocyanate-terminated prepolymer. The molar ratio of diisocyanate to hyperbranched polyester polyol is 3:1, the reaction time is 3h, then polydimethylsiloxane diol and 1,4-butanediol are added, the molar ratio of diisocyanate to polydimethylsiloxane diol and 1,4-butanediol is 1:0.6:0.4, the reaction time is 4h, and finally stannous octoate is added and reduced pressure distillation is performed. The quaternary ammonium salt functionalized nanocellulose-graphene composite particle preparation step is to disperse nanocellulose and graphene oxide in deionized water, ultrasonic treatment, then add 2,3-epoxypropyltrimethylammonium chloride, the mass ratio of nanocellulose to graphene oxide is 5:1, the ultrasonic treatment time is 40 min, the reaction temperature is 64°C, the reaction time is 14h, centrifugal washing is performed, then redispersion in ethanol is performed, ammonia water is added to adjust the pH to 11, then 3-chloro-2-hydroxypropyltrimethylammonium chloride is added, the reaction temperature is 72°C, and the reaction time is 8h. Filtration and drying are performed. The anti-staining and anti-skid road marking composition preparation step is to put the hyperbranched polyurethane-polydimethylsiloxane copolymer and the base resin into a high-speed mixer, stir at 132°C, the stirring time is 30 min, then add the quaternary ammonium salt functionalized nanocellulose-graphene composite particles, the calcined ceramsite, the glass microspheres, the dibutyl phthalate, and the bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, the mixing time is 2h, melt extrusion is performed through a twin-screw extruder, and the melt extrusion temperature is 175°C. Cooling and granulation are performed.

[0062] Comparative Example 2

[0063] The specific implementation is the same as that of Example 1, except that the base resin is 550 g, the quaternary ammonium salt functionalized nanocellulose-graphene composite particles are 150 g, the calcined haydite is 220 g, the glass microspheres are 80 g, the dibutyl phthalate is 50 g, and the bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate is 8 g. The preparation method is to stir the quaternary ammonium salt functionalized nanocellulose-graphene composite particles and the base resin in a high-speed mixer at 131 ℃, the stirring time is 28 min, the calcined haydite, the glass microspheres, the dibutyl phthalate, and the bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate are added, the mixing time is 1.5 h, and then the mixture is melt-extruded through a twin-screw extruder, the temperature for melt-extrusion is 172 ℃, and the melt-extruded product is cooled and granulated.

[0064] Comparative Example 3

[0065] The specific implementation is the same as that of Example 1, except that the base resin is 550 g, the calcined haydite is 220 g, the glass microspheres are 80 g, the dibutyl phthalate is 50 g, and the bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate is 8 g. The preparation method is to stir the base resin in a high-speed mixer at 131 ℃, the stirring time is 28 min, the calcined haydite, the glass microspheres, the dibutyl phthalate, and the bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate are added, the mixing time is 1.5 h, and then the mixture is melt-extruded through a twin-screw extruder, the temperature for melt-extrusion is 172 ℃, and the melt-extruded product is cooled and granulated.

[0066] Performance Test

[0067] The anti-fouling road marking compositions prepared in Examples 1-3 and Comparative Examples 1-3 above are subjected to performance tests according to the following methods:

[0068] 1. Anti-fouling test: The static contact angle of the material surface with oleic acid (analytical pure, purity ≥ 99.5%) is measured by a contact angle measuring instrument (Krüss DSA25). Before the test, the marking material is cut into a 50 mm x 50 mm sample and adjusted in a temperature of 23 ± 2 ℃ and a humidity of 50 ± 5% for 24 hours. When measuring, 5 μL of an oleic acid droplet is added to the surface of the sample, the droplet profile is recorded by a video optical contact angle measuring system, and the contact angle value is automatically calculated within 0.1 seconds. Five test points are selected from the center and four corners of each sample, and the average value is taken.

[0069] 2. Stain wiping residual rate test: According to ASTM D3218 method, the cover glass coated with marking line material (size 75 mm x 25 mm) was immersed in oleic acid contaminated liquid (mass concentration 10 g / L) for 24 hours, then taken out, wiped back and forth 10 times with standard cotton cloth (warp and weft density 133 x 72 per inch, gram weight 140 g / m2) under 5N pressure, and immediately after wiping, the weight gain of the cotton cloth was weighed with an electronic balance with an accuracy of 0.1 mg, and the percentage of residual contaminant mass to the initial contaminant liquid mass was calculated.

[0070] 3. Anti-slip test: The pendulum friction coefficient (BPN) under dry and wet conditions was determined by a pendulum friction coefficient tester (TRRL type, pendulum mass 1500 g, pendulum arm length 0.5 m) according to GB / T 26544-2011 standard. Before testing, the marking line sample (length x width x thickness = 300 mm x 150 mm x 5 mm) was fixed on a horizontal test bench. Dry state test was directly performed, and wet state test required uniform spraying of deionized water (water amount 5 mL / cm2) on the surface of the sample and completing the test within 30 seconds. Each sample was tested 6 times and the average value was taken.

[0071] 4. Abrasion test: After 5000 cycles of circular friction with a Taber abrasion tester (CS-17 grinding wheel, load 1 kg, rotation speed 60 r / min), the BPN value was determined again, and the decrease rate formula was (initial BPN - BPN after abrasion) / initial BPN x 100%; The weather resistance test was carried out according to GB / T 16422.3 standard for QUV accelerated aging test (UVB-313 lamp, irradiation intensity 0.71 W / m2@340 nm, 8h light / 4h condensation cycle). After aging for 1000 hours, the sample was taken out, adjusted in a temperature of 23±2℃ and humidity of 50±5% for 2 hours, and the color difference ΔE (CIE Lab color space, Lab* value taking 5-point average value) was measured with a colorimeter (X-Rite Ci64, measurement aperture 8 mm). At the same time, the tensile strength before and after aging was tested according to GB / T 528-2009 standard (dumbbell type sample size 50 mm x 4 mm x 2 mm, tensile speed 500 mm / min), and the tensile strength retention rate formula was calculated as (tensile strength after aging) / (initial tensile strength) x 100%.

[0072] 5. Dispersion stability test: The distribution state of the composite particles in the matrix was observed by scanning electron microscopy (SEM, SU8010, acceleration voltage 15 kV). The sample was prepared by spraying gold on the surface of the marking material (thickness 5 nm). Five different fields were selected for photographing and the particle aggregation index was analyzed by ImageJ software. The uniformity of particle dispersion was measured by a laser particle size analyzer (Malvern Mastersizer 3000, refractive index 1.520, absorption rate 0.1). The coefficient of variation CV was calculated according to the formula: standard deviation / average value x 100%.

[0073] 6. Performance test results:

[0074] Table 1: Performance test results of each example and comparative example

[0075]

[0076] As can be seen from Table 1, the comparison results of Examples 1-3 and Comparative Examples 1-3 show that the present application successfully solves the three technical problems existing in the prior art: in terms of stain resistance, the contact angle of Examples 1-3 is significantly higher than that of Comparative Examples 1-3 (Example 1 contact angle 116±2° vs. Comparative Example 1 102±4°), and the stain wiping residual rate is greatly reduced (Example 1 residual rate 2.8% vs. Comparative Example 1 18.6%), proving that the hyperbranched polyurethane-polydimethylsiloxane copolymer effectively prevents oily pollutants from penetrating through its low surface energy characteristics and microphase separation structure, solving the technical problem of traditional marking materials being easily attached by oil stains and difficult to clean; in terms of slip resistance, the dry-state BPN value of Examples 1-3 reaches 79-82, and the wet-state BPN value remains at 64-68, which is significantly better than that of Comparative Examples 1-3 (dry-state BPN highest 77, wet-state BPN lowest 52), and the BPN drop rate after 5000 times of abrasion is only 7.3-8.9% (the highest of the comparative example is 18.1%), which shows that the quaternary ammonium salt functionalized nanocellulose-graphene composite particles achieve efficient fixation of anti-slip particles through electrostatic repulsion and mechanical bite effect, overcoming the problem of traditional anti-slip particles falling off leading to the decay of anti-slip performance; in terms of weather resistance, the color difference ΔE of Examples 1-3 after QUV aging for 1000 hours is only 1.8-2.1 (the highest of the comparative example is 4.8), and the tensile strength retention rate is as high as 90-92% (the lowest of the comparative example is 82%), verifying that the dynamic hydrogen bond network of the hyperbranched polyurethane-polydimethylsiloxane copolymer and the synergistic reinforcing effect of the composite particles can effectively resist ultraviolet aging, solving the technical bottleneck of traditional marking materials being prone to yellowing and brittle, which shortens the service life, and the dispersion CV value of 8.5-9.2% is much lower than that of the comparative example of 14.1-18.6%, indicating that the functional particles achieve uniform and stable distribution in the matrix, further improving the durability of the comprehensive performance.

[0077] The above embodiments only express several implementation manners of the present application, and the description is more specific and detailed, but it should not be understood as a limitation on the patent scope of the present application. It should be noted that for ordinary skilled persons in the art, without departing from the concept of the present application, several modifications and improvements can be made, which are within the protection scope of the present application.

Claims

1. A dirt-resistant and anti-slip road marking composition, characterized in that, Including the following parts by weight of raw materials: Ethylene-vinyl acetate copolymer: 500-650 parts by weight; Hyperbranched polyurethane-polydimethylsiloxane copolymer: 60-100 parts by weight; Quaternary ammonium salt functionalized nanocellulose-graphene oxide composite particles: 120-200 parts by weight; Calcined ceramsite: 180-280 parts by weight; Glass microspheres: 60-100 parts by weight; Dibutyl phthalate: 40-70 parts by weight; bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate: 6-10 parts by weight; The hyperbranched polyurethane-polydimethylsiloxane copolymer is prepared by the following method: A1, diisocyanate and hyperbranched polyester polyol are added to a reactor and heated to 74-76°C under nitrogen protection to generate terminal isocyanate prepolymer; A2, polydimethylsiloxane diol and 1,4-butanediol are then added and reacted at 80-82°C, and finally stannous octoate is added and reacted under reduced pressure.

2. The anti-fouling and anti-slip road marking composition according to claim 1, characterized in that, In step A1, the molar ratio of diisocyanate to hyperbranched polyester polyol is 2-3:1; the reaction time is 2-3 hours after heating to 74-76℃.

3. The anti-fouling and anti-slip road marking composition according to claim 1, characterized in that, In step A2, the molar ratio of diisocyanate to polydimethylsiloxane diol and 1,4-butanediol is 1:0.6:0.4; the reaction time is 3-4 h at 80-82 °C.

4. The anti-fouling and anti-slip road marking composition according to claim 1, characterized in that, The quaternary ammonium salt functionalized nanocellulose-graphene oxide composite particles are prepared by the following method: B1, nanocellulose and graphene oxide are dispersed in deionized water, ultrasonically treated, and then 2,3-epoxypropyltrimethylammonium chloride is added and reacted at 60-64℃; B2, after centrifugation and washing, they are redispersed in ethanol, ammonia is added to adjust the pH to 9-11, and then 3-chloro-2-hydroxypropyltrimethylammonium chloride is added and reacted at 70-72℃, filtered and dried.

5. The anti-fouling and anti-slip road marking composition according to claim 4, characterized in that, In step B1, the mass ratio of nanocellulose to graphene oxide is 3-5:1; the ultrasonic treatment time is 35-40 min; and the reaction time at 60-64℃ is 12-14 h.

6. The anti-fouling and anti-slip road marking composition according to claim 4, characterized in that, In step B2, the reaction time is 6-8 hours at 70-72℃.

7. A method for preparing a dirt-resistant and anti-slip road marking composition according to any one of claims 1-6, characterized in that step... include: S1. Add the hyperbranched polyurethane-polydimethylsiloxane copolymer and the ethylene-vinyl acetate copolymer to a high-speed mixer and stir at 130-132°C. S2, mixed with quaternary ammonium salt functionalized nanocellulose-graphene oxide composite particles, calcined ceramsite, glass microspheres, dibutyl phthalate and bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate; S3. The material is melt-extruded through a twin-screw extruder and then cooled and granulated.

8. The preparation method according to claim 7, characterized in that, In step S1, the mass ratio of hyperbranched polyurethane-polydimethylsiloxane copolymer to ethylene-vinyl acetate copolymer is 1:3; the stirring time at 130-132℃ is 25-30 min.

9. The preparation method according to claim 7, characterized in that, In step S2, the mixing time is 1-2 hours.

10. The preparation method according to claim 7, characterized in that, In step S3, the temperature of the twin-screw extruder melt extrusion is 170-175℃.

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