High-weatherability hot-melt type road marking paint based on high molecular weight saturated polyester plasticizer and preparation method thereof

Abstract

This invention discloses a high-weather-resistant hot-melt road marking paint based on a high-molecular-weight saturated polyester plasticizer and its preparation method, belonging to the field of road traffic coating technology. By weight percentage, the marking paint consists of 12.00%~25.00% continuous phase matrix resin, 5.00%~10.00% inorganic coloring pigment, 42.00%~59.50% inorganic filler, 16.00%~23.00% reflective glass microspheres, 1.00%~5.00% terminal hydroxyl fully aliphatic saturated polyester plasticizer, and 0.50%~3.00% functional additives. The continuous phase matrix resin is composed of non-polar C5 petroleum resin and MAH-g-C5 resin in a ratio of 3:1 to 5:1. This invention utilizes the mechanochemical activation effect generated by high shear dispersion at 800~1200 r / min to achieve in-situ ring-opening semi-esterification reaction of acid anhydride and terminal hydroxyl groups at 150℃~165℃ without a catalyst, constructing a semi-crosslinked network structure. Simultaneously, neopentyl glycol and adipic acid condensate are selected, and the degradation is blocked by the steric hindrance of dimethyl. Combined with polyethylene wax and antioxidants, the problems of plasticizer migration and coating yellowing are completely solved, and it has extremely high retroreflective coefficient retention and weather resistance.

Description

Technical Field

[0001] This invention belongs to the field of road traffic safety materials technology, specifically relating to a high weather-resistant hot-melt road marking paint based on a high molecular weight saturated polyester plasticizer and its preparation method. Background Technology

[0002] Hot-melt reflective road marking paints dominate the application of road markings on modern high-grade highways. To reduce melt viscosity and improve film brittleness, the industry commonly relies on adding small-molecule liquids such as dioctyl phthalate (DOP) as plasticizers. However, traditional road marking paints have the following technical shortcomings in practical applications: First, the free migration of small-molecule plasticizers leads to coating embrittlement and retroreflection attenuation. Small-molecule plasticizers have low diffusion activation energy and are prone to thermodynamic migration and volatilization on hot summer roads, resulting in a sticky coating that attracts dust. In cold winter conditions, the loss of plasticizers reduces the free volume, making the coating prone to cracking, which in turn leads to the loss of embedded reflective microspheres.

[0003] Secondly, conventional macromolecular plasticizers have poor compatibility with non-polar matrices. Currently, the industry is attempting to use macromolecular polyesters as a substitute, but in actual harsh working conditions, it has been found that the coating is prone to peeling due to insufficient adhesion to the substrate, as well as severe accelerated yellowing. The causes are extremely complex and have not yet been effectively resolved by the industry.

[0004] Third, components containing aromatic or unsaturated structures are prone to photo-oxidative hydrolysis, leading to yellowing. Traditional resins and plasticizer skeletons are easily subjected to free radical chain degradation and chain breakage under ultraviolet light and acid vapors, causing white markings to yellow rapidly and reducing optical visibility.

[0005] Fourth, traditional modified formulations often neglect the problems of thermo-oxidative degradation and powder sedimentation under high-temperature processing, and lack the necessary rheology and antioxidant support, which makes the coatings very prone to discoloration and scorching during actual road construction at around 200℃. Summary of the Invention

[0006] The purpose of this invention is to overcome the shortcomings of existing technologies, such as easy migration of plasticizers, poor compatibility of macromolecular plasticizers, easy yellowing, and easy degradation during high-temperature construction. Through long-term research and development and numerous failed attempts, the inventors unexpectedly discovered and profoundly revealed the underlying causes of microscopic phase separation and degradation. Based on this, they provide a high-weather-resistant hot-melt road marking paint based on a high-molecular-weight saturated polyester plasticizer and its preparation method.

[0007] This invention is achieved through the following technical solution. The first aspect of this invention provides a high-weather-resistant hot-melt road marking paint based on a high-molecular-weight saturated polyester plasticizer. The marking paint is composed of the following components by weight percentage: and the sum of the weight percentages of the components listed below is 100.00%: Continuous phase matrix resin: 12.00%~25.00%; Inorganic coloring pigments: 5.00%~10.00%; Inorganic fillers: 42.00%~59.50%; Reflective glass microspheres: 16.00%~23.00%; Hydroxyl-terminated fully aliphatic saturated polyester plasticizer: 1.00%~5.00%; Functional additives: 0.50%~3.00%; The continuous phase matrix resin is composed of a non-polar C5 petroleum resin with a softening point of 95℃~105℃ and a maleic anhydride-grafted modified C5 petroleum resin (MAH-g-C5). The weight ratio of the non-polar C5 petroleum resin to the maleic anhydride-grafted modified C5 petroleum resin is 3:1 to 5:1, and the anhydride grafting rate of the maleic anhydride-grafted modified C5 petroleum resin is 1.5%~3.0%. The terminal hydroxyl fully aliphatic saturated polyester plasticizer is formed by the condensation polymerization of neopentyl glycol and adipic acid, and its number-average molecular weight Mn is 3000~5000. The functional additive is composed of polyethylene wax and hindered phenolic antioxidants.

[0008] Furthermore, the hydroxyl-terminated fully aliphatic saturated polyester plasticizer has a hydroxyl value of 25~45 mg KOH / g and an acid value of 0.5 mg KOH / g~2.0 mg KOH / g.

[0009] Furthermore, the non-polar C5 petroleum resin is an aliphatic hydrocarbon resin obtained by cationic polymerization of isoprene and isoprene, which together account for more than 50% of the total mass of the monomers.

[0010] Furthermore, the inorganic filler is a ternary mixed powder of heavy calcium carbonate, quartz sand and talc, and based on the total weight of the inorganic filler being 100 parts, the weight parts of heavy calcium carbonate, quartz sand and talc are 55~65 parts, 25~35 parts and 20~30 parts, respectively.

[0011] Furthermore, the reflective glass microspheres are optical glass microspheres whose surface is coated with an aminosilane coupling agent, and their particle size distribution is 40 mesh to 60 mesh.

[0012] Furthermore, the inorganic coloring pigment is rutile titanium dioxide that has undergone inorganic surface treatment with zirconium oxide and alumina.

[0013] A second aspect of the present invention provides a method for preparing the above-mentioned high weather-resistant hot-melt road marking paint based on a high molecular weight saturated polyester plasticizer, wherein the preparation method... The esterification is carried out without the addition of an esterification catalyst, It includes the following steps: S1. Homogeneous melting of the matrix: The non-polar C5 petroleum resin and the maleic anhydride-grafted modified C5 petroleum resin weighed according to the weight ratio are put into the reactor together. Under the stirring rate of 30~50 r / min, the temperature is stepped up to 150℃~165℃, so that the mixed resin crosses the glass transition zone and the critical point of viscous flow state to form a uniformly flowing hot melt matrix. S2. In-situ chemical anchoring: The reactor temperature is kept constant at 155~165℃. During this high-speed, high-shear stage, the circulating heat transfer oil forced cooling system of the reactor jacket is activated to remove excess mechanical heat generated by the intense internal friction of the high-viscosity melt in real time. The preheated, fluidized terminal hydroxyl fully aliphatic saturated polyester plasticizer and the functional additives are uniformly added dropwise to the hot-melt matrix. After the addition is completed, the stirring device is switched to a high-speed shear dispersion mode of 800~1200 r / min and dispersed for 15~20 minutes. This allows the anhydride groups on the maleic anhydride-grafted modified C5 petroleum resin chain to undergo a ring-opening semi-esterification reaction with the terminal hydroxyl groups of the plasticizer, constructing a semi-crosslinked network with one end of the polyester long chain covalently anchored in the matrix. In this step, a high-speed shear dispersion mode of 800~1200 r / min is used to disperse for 15~20 minutes. The internal frictional heat generated by the high shear field in the extremely high viscosity melt can be used to break through the esterification activation energy barrier under catalyst-free conditions. This allows the anhydride groups on the maleic anhydride-grafted modified C5 petroleum resin chain to undergo a ring-opening semi-esterification reaction with the terminal hydroxyl groups of the terminal hydroxyl fully aliphatic saturated polyester plasticizer without the release of small molecules. This results in the construction of a semi-crosslinked network with one end of the polyester long chain covalently anchored in the matrix. S3. Powder homogenization: Under the condition of maintaining the system temperature not lower than 160℃, the stirring device is adjusted to medium speed mode, and the inorganic coloring pigment and the inorganic filler after preheating and dehydration are added in batches. The mixture is continuously sheared at a specific medium shear rate of 500~600 r / min for 10~15 minutes until the coating melt presents a homogeneous fluid state with no obvious visible dry powder agglomeration on the macroscopic appearance. S4. Beading and Discharging: Reduce the stirring speed to a low speed mode of 20~40 r / min, add the surface-treated reflective glass microspheres, mix for 5~10 minutes, and then discharge and package.

[0014] Further, in step S1, the stepwise heating process includes: heating to 120°C at a heating rate of 2°C to 5°C / min and holding at that temperature for 5 to 10 minutes, and then heating to 150°C to 165°C at a heating rate of 1°C to 3°C / min; and the homogeneous melting process of the matrix is ​​carried out in an environment protected by nitrogen.

[0015] Furthermore, in step S2, the high-speed shear dispersion mode is provided by a shear dispersion device with a stator-rotor structure, and the rotor linear velocity is 15~25 m / s.

[0016] Compared with the prior art, the present invention has the following advantages: 1. Excellent anti-migration and temperature stability. This invention utilizes the extremely high viscosity resistance inherent in the coating matrix, applying a strong shear dispersion energy of 800 to 1200 r / min (rotor linear speed 15~25 m / s). This causes the instantaneously generated "microscopic hot spots" to overcome the esterification activation energy barrier under catalyst-free conditions, promoting a ring-opening semi-esterification reaction between the highly active anhydride groups on MAH-g-C5 and the terminal hydroxyl fully aliphatic saturated polyester plasticizer without the release of small molecules, thus achieving chemical anchoring. The use of nitrogen protection and step-by-step heating during the early melting stage effectively prevents premature thermo-oxidative aging of the matrix resin in air. Modulus adjustment of the high-density polyethylene wax (PE wax) in the chemical anchoring system significantly reduces the plasticizer loss rate, fundamentally improving the high-temperature anti-tackiness of the markings and their anti-cracking performance in harsh low-temperature environments (-10℃).

[0017] 2. Excellent interfacial adhesion and wear resistance limit response. This invention controls the weight ratio of non-polar C5 resin to MAH-g-C5 resin between 3:1 and 5:1, constructing a semi-crosslinked network structure with one end anchored and the other end free. This rheological property can effectively dissipate impact energy. The in-situ chemical anchoring effect endows the system with extremely strong "gripping force" for reflective microspheres. After 100,000 cycles of vehicle tire rolling, the retroreflection coefficient retention rate is excellent (significantly better than the control group, which only retains 25%~40% after deterioration). In addition, the PE wax in the functional additive system acts as an external lubricant, significantly reducing the risk of frictional thermal runaway during high-shear processing; the hindered phenolic antioxidant can preferentially capture carbon free radicals generated by thermal shear chain scission during the construction and boiling process at 150℃~200℃, blocking the thermo-oxidative degradation pathway and ensuring the whiteness of the coating after it leaves the autoclave.

[0018] 3. Excellent optical durability and resistance to photo-oxidative yellowing. This invention limits the number-average molecular weight (Mn) of the polyester to 3000-5000, controls the hydroxyl value to 25-45 mg KOH / g, and the acid value to 0.5 mg KOH / g-2.0 mg KOH / g, and uses neopentyl glycol (NPG) and adipic acid monomers for synthesis. The unique quaternary carbon atom structure of NPG constructs a "steric hindrance" defense line on both sides, effectively blocking the attack of nucleophiles on the main chain ester bonds. This molecular-level defense system, combined with the intrinsic UV resistance of the all-aliphatic carbon chain, the free radical scavenging effect of hindered phenolic antioxidants, and the synergistic effect of rutile titanium dioxide with inorganic surface treatment of alumina and zirconium oxide, enables the coating to strongly resist photo-oxidative degradation. After 1000 hours of accelerated fluorescent UV exposure aging test, its yellowing index increase ( YI) not exceeding 2.0. Attached Figure Description

[0019] Figure 1 For Example 1 and Comparative Example 6, the organic phase extracts within the cured system were obtained in the wavenumber range of 4000~400 cm⁻¹. -1 Comparison of Fourier transform infrared (FT-IR) spectra between the two. Detailed Implementation

[0020] The present invention will be further illustrated by way of embodiments below, but the present invention is not limited to the scope of the embodiments described herein.

[0021] The technical solution of the present invention is as follows: A high-weather-resistant hot-melt road marking paint based on a high molecular weight saturated polyester plasticizer, wherein the marking paint is composed of the following components by weight percentage: and the sum of the weight percentages of the following components is 100.00%: Continuous phase matrix resin: 12.00%~25.00%; Inorganic coloring pigments: 5.00%~10.00%; Inorganic fillers: 42.00%~59.50%; Reflective glass microspheres: 16.00%~23.00%; Hydroxyl-terminated fully aliphatic saturated polyester plasticizer: 1.00%~5.00%; Functional additives: 0.50%~3.00%; The continuous phase matrix resin is composed of a non-polar C5 petroleum resin with a softening point of 95℃~105℃ and a maleic anhydride-grafted modified C5 petroleum resin (MAH-g-C5). The weight ratio of the non-polar C5 petroleum resin to the maleic anhydride-grafted modified C5 petroleum resin is 3:1 to 5:1, and the anhydride grafting rate of the maleic anhydride-grafted modified C5 petroleum resin is 1.5%~3.0%. The terminal hydroxyl fully aliphatic saturated polyester plasticizer is formed by the condensation polymerization of neopentyl glycol and adipic acid, and its number-average molecular weight Mn is 3000~5000. The functional additive is composed of polyethylene wax and hindered phenolic antioxidants.

[0022] Raw material specifications (key commercial material models): 1. Non-polar C5 petroleum resin: A special aliphatic resin for road marking paint, polymerized from isoprene and isoprene, using model YH1288S from Ningbo Jinhai Chenguang Chemical Co., Ltd., with a softening point of 100℃.

[0023] 2. Preferred commercially available models: ADK CIZER PN-400 (number average molecular weight Mn of 4000, hydroxyl value of 35 mg KOH / g, acid value of 0.8 mg KOH / g) and ADK CIZER PN-1030 (number average molecular weight Mn of 3000, hydroxyl value of 35 mg KOH / g, acid value of 0.8 mg KOH / g) from ADEKA Corporation of Japan.

[0024] A general preparation method for custom polyester (applicable to polyester plasticizers with non-commercially available specific parameters, such as Mn=1500, 3500, 4500, 5000, 7000, and test samples with specific hydroxyl / acid values): Using a conventional melt polycondensation method, neopentyl glycol and adipic acid are added to a reactor at a set molar ratio, with 0.05%~0.1% tetrabutyl titanate added as a catalyst. Under the protection of high-purity nitrogen, the temperature is slowly raised to 200℃~220℃ for esterification. During the later stages of the reaction, a vacuum system is connected for dehydration under reduced pressure. During this period, the acid value and molecular weight of the system are monitored in real time (GPC method). When the reaction system reaches the set target molecular weight and target hydroxyl value, and the acid value drops to a predetermined range (e.g., below 2.0 mg KOH / g), heating is stopped, and the material is discharged after cooling, thus obtaining the corresponding custom polyester plasticizer.

[0025] Inorganic coloring pigment: R-996 rutile titanium dioxide from Longbai Group is selected, and it is treated with zirconium oxide and alumina inorganic surface treatment.

[0026] Functional additives include high-density polyethylene wax (PE wax) produced by SCGC Company of Thailand with a melting point of 110°C, and Irganox 1010 hindered phenolic antioxidant from BASF.

[0027] MAH-g-C5 resin: Commercially available industrial-grade products (with a nominal anhydride grafting rate ranging from 1.5% to 3.0%) were used. Unless otherwise specified (Examples 2 and 3), the specific batches of resin actually purchased and used in each example of this invention had an anhydride grafting rate of 2.2%.

[0028] Reflective glass microspheres: Optical microspheres with surface treatment of γ-aminopropyltriethoxysilane (KH-550).

[0029] Example Section Example 1: Formula: 14.80% non-polar C5 resin, 3.70% MAH-g-C5 resin (resin ratio 4:1); 7.50% rutile titanium dioxide; 50.00% inorganic filler (including 26.09% heavy calcium carbonate, 13.04% quartz sand, and 10.87% talc, with an internal center-to-weight ratio of 60:30:25); 19.50% reflective glass microspheres; 2.50% polyester plasticizer (PN-400, Mn=4000); 2.00% functional additives (1.80% PE wax, 0.20% antioxidant 1010). The total amount of all components is 100.00%.

[0030] Preparation: S1. Add mixed resin to a nitrogen-filled reactor. While stirring at 40 r / min, first heat to 120℃ at 3℃ / min and hold for 8 minutes, then heat to 158℃ in steps at 2℃ / min to complete melting; S2. Add preheated plasticizer and additives. Start the stator and rotor equipment (linear speed 20 m / s, rotation speed 1000 r / min) within the range of 160℃~165℃ for high shear dispersion for 18 minutes to carry out the semi-esterification reaction, and simultaneously start the reactor jacket circulating heat transfer oil forced cooling system to control the temperature; S3. At 160℃, add preheated powder in batches and continue shearing at a medium shear rate of 600 r / min for 10 minutes; S4. Reduce the rotation speed to 30 r / min, add microspheres, and mix for 8 minutes before discharging.

[0031] Example 2: Formulation: 9.60% non-polar C5 resin, 2.40% MAH-g-C5 resin (anhydride grafting rate determined to be 1.5%) (resin ratio 4:1); 5.00% rutile titanium dioxide; 56.50% inorganic filler (including 29.48% heavy calcium carbonate, 14.74% quartz sand, and 12.28% talc, internal weight ratio 60:30:25); 23.00% reflective glass microspheres; 1.00% polyester plasticizer (PN-1030, Mn=3000); 2.50% functional additives (2.30% PE wax, 0.20% antioxidant 1010). The total amount of all components is 100.00%.

[0032] Preparation: S1 Nitrogen gas is introduced, and the mixture is stirred at 30 r / min, heated to 120℃ at 2℃ / min and held for 5 minutes, then heated to 150℃ at 1℃ / min to melt; S2 Plasticizer and additives are added in the range of 155℃~160℃, and the rotor linear speed is set to 15 m / s, and the high shear speed is set to 800 r / min for 15 minutes to carry out the semi-esterification reaction, while the forced cooling system of circulating heat transfer oil in the jacket of the reactor is turned on simultaneously to control the temperature; S3 Preheated powder is added in batches at 160℃, and shearing is carried out continuously at a medium shear rate of 500 r / min for 15 minutes; S4 Microbeads are added and stirred at 20 r / min for 5 minutes before discharging.

[0033] Example 3: Formula: 20.00% non-polar C5 resin, 5.00% MAH-g-C5 resin (anhydride grafting rate of 3.0%) (resin ratio 4:1); 10.00% rutile titanium dioxide; 43.00% inorganic filler (including 22.43% heavy calcium carbonate, 11.22% quartz sand, and 9.35% talc, internal weight ratio 60:30:25); 16.00% reflective glass microspheres; 4.00% polyester plasticizer (customized according to the aforementioned method, Mn=5000); 2.00% functional additives (1.80% PE wax, 0.20% antioxidant 1010). The total amount of all components is 100.00%.

[0034] Preparation: S1 Nitrogen gas is introduced, and the temperature is raised to 120℃ at 5℃ / min and held for 10 minutes under stirring at 50 r / min, then raised to 165℃ at 3℃ / min to melt; S2 Plasticizer and additives are added in the range of 160℃~165℃, and the rotor linear speed is set to 25 m / s, and the rotation speed is 1200 r / min for high shear for 20 minutes to carry out the semi-esterification reaction; S3 At 165℃, preheated powder is added in batches and sheared continuously at a medium shear rate of 550 r / min for 12 minutes; S4 The speed is reduced to 40 r / min, microspheres are added and stirred for 10 minutes before discharging.

[0035] Example 4: Formulation: 13.88% non-polar C5 resin, 4.62% MAH-g-C5 resin (the ratio of the two types of resin is 3:1); the remaining components and preparation process are the same as in Example 1.

[0036] Example 5: Formulation: 15.42% non-polar C5 resin, 3.08% MAH-g-C5 resin (the ratio of the two types of resin is 5:1); the remaining components and preparation process are the same as in Example 1.

[0037] Example 6: Formulation: 14.80% non-polar C5 resin, 3.70% MAH-g-C5 resin; 7.50% titanium dioxide; 47.50% inorganic filler (including 24.78% heavy calcium carbonate, 12.39% quartz sand, and 10.33% talc, with an internal weight ratio of 60:30:25); 19.50% reflective glass microspheres; 5.00% polyester plasticizer (PN-400); 2.00% functional additives (1.80% PE wax and 0.20% antioxidant 1010); the preparation process is the same as in Example 1.

[0038] Example 7: Formulation: Replace the polyester plasticizer in Example 1 with 2.50% of the same type of polyester with Mn=3500 customized according to the aforementioned method; the remaining components and preparation process are the same as in Example 1.

[0039] Example 8: Formulation: Replace the polyester plasticizer in Example 1 with 2.50% of the same type of polyester with Mn=4500 customized according to the aforementioned method; the remaining components and preparation process are the same as in Example 1.

[0040] Example 9: This embodiment aims to verify the performance response when the internal weight ratio of the inorganic filler is at the lower limit of the claim, so as to form a clear comparison with the center gradation of Example 1.

[0041] Formula: 14.80% non-polar C5 resin, 3.70% MAH-g-C5 resin (resin ratio 4:1); 7.50% rutile titanium dioxide; 50.00% inorganic filler (including 27.50% heavy calcium carbonate, 12.50% quartz sand, and 10.00% talc, strictly meeting the internal lower limit weight ratio of 55:25:20); 19.50% reflective glass microspheres; 2.50% polyester plasticizer (PN-400, Mn=4000); 2.00% functional additives (1.80% PE wax, 0.20% antioxidant 1010). The total amount of all components is 100.00%.

[0042] Preparation: The operation steps, temperature and time parameters of S1 to S4 are completely consistent with those of Example 1.

[0043] Example 10: This embodiment aims to verify the performance response when the internal weight ratio of the inorganic filler is at the upper limit of the claim, so as to form a clear comparison with the center gradation of Example 1.

[0044] Formula: 14.80% non-polar C5 resin, 3.70% MAH-g-C5 resin (resin ratio 4:1); 7.50% rutile titanium dioxide; 50.00% inorganic filler (including 25.00% heavy calcium carbonate, 13.46% quartz sand, and 11.54% talc, strictly meeting the internal upper limit weight ratio of 65:35:30); 19.50% reflective glass microspheres; 2.50% polyester plasticizer (PN-400, Mn=4000); 2.00% functional additives (1.80% PE wax, 0.20% antioxidant 1010). The total amount of all components is 100.00%.

[0045] Preparation: The operation steps, temperature and time parameters of S1 to S4 are completely consistent with those of Example 1.

[0046] Example 11: Formulation: Replace the polyester plasticizer in Example 1 with a custom product (Mn=4000, hydroxyl value 25 mg KOH / g, acid value 0.5 mg KOH / g) 2.50%; the remaining components and preparation process are the same as in Example 1.

[0047] Example 12: Formulation: Replace the polyester plasticizer in Example 1 with a custom product (Mn=4000, hydroxyl value 45 mg KOH / g, acid value 1.9 mg KOH / g) 2.50%; the remaining components and preparation process are the same as in Example 1.

[0048] Comparative examples (Comparative Examples 1-13) Comparative Example 1: Formula: 16.50% conventional non-polar C5 resin (excluding MAH modification), 2.00% EVA resin; 7.50% rutile titanium dioxide; 50.00% inorganic filler (including 26.09% heavy calcium carbonate, 13.04% quartz sand, and 10.87% talc); 19.50% reflective glass microspheres; 2.50% DOP small molecule plasticizer; 2.00% functional additives (1.80% PE wax, 0.20% antioxidant 10100). Total: 100.00%.

[0049] Preparation: The resin and additives are mixed and melted at a low speed at 150°C, and then powder and microspheres are added for physical blending and discharge.

[0050] Comparative Example 2: formula: Non-polar C5 resin 14.80%, MAH-g-C5 resin 3.70% (resin ratio 4:1); rutile titanium dioxide 7.50%; inorganic filler 50.00% (including heavy calcium carbonate 26.09%, quartz sand 13.04%, and talc 10.87%); reflective glass microspheres 19.50%; DOP small molecule plasticizer 2.50% (equal replacement for PN-400 hydroxyl-terminated polyester plasticizer in Example 1); functional additives 2.00% (PE wax 1.80%, antioxidant 1010 0.20%). The total amount of all components is 100.00%.

[0051] preparation: The preparation process is completely consistent with that in Example 1.

[0052] S1 Add the mixed resin to the nitrogen-filled reactor, and under stirring at 40 r / min, first heat to 120℃ at 3℃ / min and hold for 8 minutes, then heat to 158℃ in a stepwise manner at 2℃ / min to complete the melting. Add preheated DOP and additives to S2, and start the stator and rotor equipment (linear speed 20 m / s, rotation speed 1000 r / min) for high shear dispersion for 18 minutes within the range of 160℃~165℃. S3 is added in batches of preheated powder at 160℃; S4 Reduce the speed to 30r / min, add microbeads, and gently mix for 8 minutes before discharging.

[0053] Comparative Example 3: Formulation: 2.50% of linear 1,4-butanediol-adipic acid polyester plasticizer (customized by replacing neopentyl glycol with 1,4-butanediol according to the aforementioned method, without dimethyl steric hindrance shielding, Mn=4000) replaces the PN-400 plasticizer in Example 1; the remaining components are the same as in Example 1.

[0054] Preparation: To prevent extreme scorching caused by the high activity of linear chains, the high shear dispersion time in stage S2 was shortened to 12 minutes, and the rest of the process was the same as in Example 1.

[0055] Comparative Example 4: Formulation: Replace the polyester plasticizer in Example 1 with 2.50% of the same type of polyester with Mn=1500 customized according to the aforementioned method; the remaining components and preparation process are the same as in Example 1.

[0056] Comparative Example 5: Formulation: Replace the polyester plasticizer in Example 1 with 2.50% of the same type of polyester with Mn=7000 customized according to the aforementioned method; the remaining components and preparation process are the same as in Example 1.

[0057] Comparative Example 6: Formula: The components are configured exactly the same as in Example 1.

[0058] Preparation: S1 was melted by stepwise heating to 158℃ under nitrogen gas and stirring at 40 r / min; S2 was prepared by adding preheated plasticizer and additives, without high shear dispersion, and only by maintaining low-speed conventional stirring at 40 r / min for 18 minutes in the range of 160℃~165℃, which lacked mechanical and chemical activation and could not break through the energy barrier; S3 was prepared by adding powder in batches at 160℃; S4 was prepared by adding microbeads at 30 r / min and mixing for 8 minutes before discharging.

[0059] Comparative Example 7: Formulation: 9.25% non-polar C5 resin, 9.25% MAH-g-C5 resin (the ratio of the two types of resin is 1:1); the remaining components and preparation process are the same as in Example 1.

[0060] Comparative Example 8: Formulation: 16.82% non-polar C5 resin, 1.68% MAH-g-C5 resin (ratio of the two types of resin 10:1); the remaining components and preparation process are the same as in Example 1.

[0061] Comparative Example 9: Formulation: 10.40% non-polar C5 resin, 2.60% MAH-g-C5 resin; 7.50% titanium dioxide; 50.00% inorganic filler; 19.50% reflective glass microspheres; 8.00% polyester plasticizer (PN-400); 2.00% functional additives; the preparation process is the same as in Example 1.

[0062] Comparative Example 10: Formulation: 16.40% non-polar C5 resin, 4.10% MAH-g-C5 resin; 7.50% titanium dioxide; 50.00% inorganic filler; 19.50% reflective glass microspheres; 0.50% polyester plasticizer (PN-400); 2.00% functional additives; the preparation process is the same as in Example 1.

[0063] Comparative Example 11: Formulation: Replace the polyester plasticizer in Example 1 with a custom product (Mn=4000, hydroxyl value 35 mg KOH / g, acid value 4.0 mg KOH / g) 2.50%; the remaining components and preparation process are the same as in Example 1.

[0064] Comparative Example 12: Formulation: Replace the polyester plasticizer in Example 1 with a custom product (Mn=4000, hydroxyl value 10 mg KOH / g, acid value 0.8 mg KOH / g) 2.50%; the remaining components and preparation process are the same as in Example 1.

[0065] Comparative Example 13: Formulation: The non-polar C5 resin in Example 1 was replaced with an equal amount of alicyclic C5 petroleum resin polymerized with dicyclopentadiene (DCPD) as the main monomer (14.80%); the remaining components and preparation process were the same as in Example 1.

[0066] Comparative Example 14: Formulation: The matrix resin, titanium dioxide, microspheres, plasticizer and functional additives are in the same proportion as in Example 1. 0.10% of tetrabutyl titanate is added as a conventional esterification catalyst, and the inorganic filler is finely adjusted to 49.90% so that the sum of all components is strictly 100.00%.

[0067] Preparation: S1 is the same as in Example 1; S2 After adding the preheated plasticizer, additives and catalyst, do not turn on high shear dispersion, but only maintain low speed conventional stirring at 40 r / min for 18 minutes in the range of 160℃~165℃; S3 Add powder in batches at 160℃; S4 Add microbeads at 30 r / min and continue to mix for 8 minutes before discharging.

[0068] Experimental testing and data analysis Test methods and standards: Apparent viscosity at 180℃ hot melt: The apparent viscosity was measured using a Brookfield DV-II+ Pro rotational viscometer with an SC4-27 rotor at a constant temperature of 20 r / min and 180℃. The unit is Pa·s.

[0069] High temperature accelerates migration and loss rate: Place the coating sample in an 80℃ drying oven for 10 days and calculate the loss rate.

[0070] Crack resistance under harsh low temperatures: Refer to Appendix B of JT / T 280-2022, and perform 30 freeze-thaw cycles alternating between a -10℃ low-temperature chamber and room temperature.

[0071] Ultraviolet aging yellowing increase: Referring to GB / T 23987-2009 "Artificial climate aging and artificial radiation exposure of paints and varnishes", a UVA-340 fluorescent ultraviolet lamp was used, with an irradiance of 0.76 W / (m²·nm) @340nm. An alternating cycle of 8 hours of light exposure (60℃) and 4 hours of condensation (50℃) was used. After 1000 hours of continuous exposure, the yellowing index difference ΔYI was measured using a colorimeter.

[0072] Taibo wear measurement: Referencing GB / T 1768-2006, using a CS-17 type rubber grinding wheel, run 1000 cycles under a 1000g load, and record the mass loss (mg).

[0073] Retroreflection coefficient retention rate: The MMLS3 (third-generation one-third scale accelerated load test system) standard accelerated wear tester was used. The single wheel axle load was set to 2.7 kN, the tire pressure to 0.7 MPa, and the rolling speed to 5000 times / hour. After a cumulative rolling of 100,000 times, the remaining retroreflection brightness coefficient was tested in accordance with the provisions of GB / T 16311-2009.

[0074] Interfacial peel strength retention rate: In accordance with the provisions of Appendix B of JT / T 280-2022, the coating was applied to the surface of a standard cement concrete test block, and after curing, it was placed in an alternating cycle of 80℃ high temperature (90% relative humidity) and -10℃ low temperature environment for 30 cycles. The interfacial pull-out strength before and after the cycle was tested using a digital pull-out tester, and the retention rate was calculated.

[0075] Fourier Transform Infrared Spectroscopy (FT-IR) Testing: FT-IR Sample Preparation: The cured coating sample was pulverized to below 200 mesh and added to tetrahydrofuran (THF) solvent at a mass ratio of 1:50. The mixture was ultrasonically extracted at room temperature for 30 minutes. The supernatant was then coated onto a KBr salt plate and dried in an infrared oven to evaporate the solvent. The sample was then subjected to FT-IR spectroscopy at 4000–4000 cm⁻¹. - ¹ Scan within the range.

[0076] Performance test data statistics table:

[0077] Experimental data analysis: 1. Infrared Spectroscopy (FT-IR) Microscopic Mechanism Analysis: The coatings of Example 1 and Comparative Example 6 were tested using the above-described Fourier Transform Infrared Spectroscopy (FT-IR) testing method. Figure 1 As shown, Comparative Example 6, which did not undergo high shear stress, was at 1780 cm⁻¹ -1 and 1850 cm -1 The vicinity of the free anhydride bimodal peaks was clearly preserved; however, the free anhydride bimodal peaks of Example 1 disappeared, except at 1730–1740 cm⁻¹. - In addition to the carbonyl stretching vibration peak of aliphatic esters appearing at ¹, there is also a peak at 1700–1715 cm⁻¹. - ¹ Overlapping shoulder peaks of the free carboxylic acid carbonyl groups inevitably released during the semi-esterification reaction were observed in the range of 2500–3300 cm⁻¹. - The region ¹ shows a distinct broadened carboxyl OH stretching vibration band. These characteristics fully demonstrate that under high shear activation, the system overcame the activation energy barrier and underwent a ring-opening half-esterification reaction, achieving in-situ chemical bonding between the polar polyester and the C5 resin network.

[0078] 2. Influence of Terminal Hydroxyl Structure on Anti-migration and Physical-Mechanical Properties: Comparing the test data of Example 1 and Comparative Example 2, it can be seen that under the same conditions of resin matrix ratio and high-shear activation process (1000 r / min), when a conventional inactive small molecule plasticizer (DOP) without active terminal hydroxyl groups is used to replace the terminal hydroxyl fully aliphatic saturated polyester plasticizer of the present invention in equal amounts, the high-temperature migration loss rate of the system increases significantly from 0.02% to 5.12%. During the -10℃ freeze-thaw cycle, the coating changes from intact to large-area cracking, and the retroreflection coefficient retention rate after 100,000 rolling cycles decreases from 52.40% to 28.40%. The performance difference caused by the substitution of a single variable indicates that the excellent anti-migration performance and structural stability of the coating of the present invention essentially rely on the chemical anchoring bond induced by the terminal hydroxyl groups of the macromolecular polyester and the grafted anhydride of MAH-g-C5 under high shear. This micro-network effectively improves the compatibility between the non-polar matrix and the polar plasticizer, inhibits the thermodynamic migration path of the plasticizer, and thus enhances the durability of the marking coating under extreme temperature alternation and high-frequency rolling.

[0079] 3. Critical ratio response of hindered rheological network: Data from Examples 1, 4, and 5 and Comparative Examples 7 and 8 show that controlling the ratio of nonpolar C5 resin to MAH-g-C5 resin within the range of 3:1 to 5:1 can establish a suitable hindered rheological network. This is a reasonable ratio range to avoid gelation of the coating system during high-temperature processing while maintaining good suspension and sedimentation capabilities of glass microspheres.

[0080] 4. Effect of polyester molecular weight on melt properties: Data from Examples 1, 7, and 8 and Comparative Examples 4 and 5 show that when the number-average molecular weight Mn of the hydroxyl-terminated polyester is between 3000 and 5000, the coating can achieve a better balance between molecular chain entanglement damping and hot melt apparent viscosity, which satisfies both the leveling properties during construction and ensures the cohesive strength after curing.

[0081] 5. Verification of the underlying logic of steric conformation to combat aging: Example 1 (using neopentyl glycol framework) after UV aging, the increase in the yellowing index ( YI) was only 1.2, while Comparative Example 3 (using a straight-chain butanediol backbone) YI increased significantly to 5.8. This indicates that the steric hindrance introduced by the quaternary carbon atom in neopentyl glycol can effectively hinder the attack of nucleophiles on the ester bond, and plays a decisive role in improving the coating's resistance to photo-oxidative hydrolysis.

[0082] 6. Influence of Plasticizer Characteristic Parameters on Resin Monomers: Comparing Examples 1, 11, and 12 with Comparative Examples 11 and 12, it can be seen that a low polyester hydroxyl value (Comparative Example 12) results in insufficient effective crosslinking density, leading to an increase in high-temperature loss rate to 0.06%; while a high acid value (Comparative Example 11) easily accelerates ester bond degradation during UV aging, leading to... The YI value increased to 3.5, potentially causing micro-corrosion interference with interfacial adhesion. The hydroxyl value and low acid value range defined in the examples achieved a good balance between grafting efficiency and overall weather resistance. Furthermore, Comparative Example 13, using an alicyclic C5 resin polymerized from dicyclopentadiene (DCPD), exhibited increased yellowing due to the residual cyclic double bond structure and compatibility differences. The fact that YI is 2.8 and that it easily induces phase separation, causing the interface retention rate to drop to 81.4%, confirms that the use of aliphatic monomers polymerized from "isoprene and isoprene" as a nonpolar matrix is ​​necessary to achieve the comprehensive performance of this invention.

[0083] 7. Verification of the necessity of catalyst-free mechanochemical synergistic effect: Comparing Example 1, Comparative Example 6 (without high shear) and Comparative Example 14 (with catalyst + without high shear), it can be seen that although the addition of conventional tetrabutyl titanate catalyst can promote the cross-linking of esterification network under low shear environment to a certain extent (the mechanical properties of Comparative Example 14 are slightly better than those of Comparative Example 6), the small molecule heavy metal catalyst remaining in the coating constitutes an irreversible photo-oxidative degradation hotspot, causing the yellowing index of Comparative Example 14 to soar to 5.5 after UV aging. The "catalyst-free + high shear temperature control" combination of the present invention uniquely achieves a perfect closed loop of system interface anchoring and extreme weather resistance.

[0084] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely illustrative of the principles of the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the present invention as claimed. The scope of protection of this invention is defined by the appended claims and their equivalents.

Claims

1. A high-weather-resistant hot-melt road marking paint based on a high molecular weight saturated polyester plasticizer, characterized in that, The road marking paint is composed of the following components by weight percentage: and the sum of the weight percentages of the following components is 100.00%: Continuous phase matrix resin: 12.00%~25.00%; Inorganic coloring pigments: 5.00%~10.00%; Inorganic fillers: 42.00%~59.50%; Reflective glass microspheres: 16.00%~23.00%; Hydroxyl-terminated fully aliphatic saturated polyester plasticizer: 1.00%~5.00%; Functional additives: 0.50%~3.00%; The continuous phase matrix resin is composed of non-polar C5 petroleum resin with a softening point of 95℃~105℃ and maleic anhydride-grafted modified C5 petroleum resin. The weight ratio of the non-polar C5 petroleum resin to the maleic anhydride-grafted modified C5 petroleum resin is 3:1 to 5:1, and the anhydride grafting rate of the maleic anhydride-grafted modified C5 petroleum resin is 1.5%~3.0%. The terminal hydroxyl fully aliphatic saturated polyester plasticizer is formed by the condensation polymerization of neopentyl glycol and adipic acid, and its number-average molecular weight Mn is 3000~5000. The functional additive is composed of polyethylene wax and hindered phenolic antioxidants.

2. The high weather-resistant hot-melt road marking paint based on high molecular weight saturated polyester plasticizer according to claim 1, characterized in that, The hydroxyl-terminated fully aliphatic saturated polyester plasticizer has a hydroxyl value of 25~45 mg KOH / g and an acid value of 0.5 mg KOH / g~2.0 mg KOH / g.

3. The high weather-resistant hot-melt road marking paint based on high molecular weight saturated polyester plasticizer according to claim 1, characterized in that, The non-polar C5 petroleum resin is an aliphatic hydrocarbon resin obtained by cationic polymerization of isoprene and isoprene, which together account for more than 50% of the total mass of the monomers.

4. The high weather-resistant hot-melt road marking paint based on high molecular weight saturated polyester plasticizer according to claim 1, characterized in that, The inorganic filler is a ternary mixed powder of heavy calcium carbonate, quartz sand and talc, and based on the total weight of the inorganic filler as 100 parts, the weight parts of heavy calcium carbonate, quartz sand and talc are 55~65 parts, 25~35 parts and 20~30 parts respectively.

5. The high weather-resistant hot-melt road marking paint based on high molecular weight saturated polyester plasticizer according to claim 1, characterized in that, The reflective glass microspheres are optical glass microspheres whose surface has been coated with an aminosilane coupling agent, and their particle size distribution is 40 mesh to 60 mesh.

6. The high weather-resistant hot-melt road marking paint based on high molecular weight saturated polyester plasticizer according to claim 1, characterized in that, The inorganic coloring pigment is rutile titanium dioxide that has undergone inorganic surface treatment with zirconium oxide and alumina.

7. A method for preparing a high-weather-resistant hot-melt road marking paint based on a high molecular weight saturated polyester plasticizer as described in any one of claims 1 to 6, characterized in that, The preparation method is carried out without the addition of an external esterification catalyst and includes the following steps: S1. Homogeneous melting of the matrix: The non-polar C5 petroleum resin and the maleic anhydride-grafted modified C5 petroleum resin weighed according to the weight ratio are put into the reactor together. Under the stirring rate of 30~50 r / min, the temperature is stepped up to 150℃~165℃, so that the mixed resin crosses the glass transition zone and the critical point of viscous flow state to form a uniformly flowing hot melt matrix. S2. In-situ chemical anchoring: The temperature of the reactor is kept constant at 155~165℃. During this high-speed and strong shear stage, the circulating heat transfer oil forced cooling system of the reactor jacket is turned on to remove the excess mechanical heat generated by the intense internal friction of the high-viscosity melt in real time. The preheated terminal hydroxyl fully aliphatic saturated polyester plasticizer and the functional additives are uniformly dripped into the hot melt matrix. After the addition is complete, switch the stirring device to the high-speed shear dispersion mode of 800~1200 r / min and disperse for 15~20 minutes to allow the anhydride groups on the maleic anhydride graft-modified C5 petroleum resin chain to undergo a ring-opening semi-esterification reaction with the terminal hydroxyl groups of the plasticizer, thereby constructing a semi-crosslinked network with one end of the polyester long chain covalently anchored in the matrix. S3. Powder homogenization: Under the condition of maintaining the system temperature not lower than 160℃, the stirring device is adjusted to medium speed mode, and the inorganic coloring pigment and the inorganic filler after preheating and dehydration are added in batches. The mixture is continuously sheared at a specific medium shear rate of 500~600 r / min for 10~15 minutes until the coating melt presents a homogeneous fluid state with no obvious visible dry powder agglomeration on the macroscopic appearance. S4. Beading and Discharging: Reduce the stirring speed to a low speed mode of 20~40 r / min, add the surface-treated reflective glass microspheres, mix for 5~10 minutes, and then discharge and package.

8. The preparation method of high weather-resistant hot-melt road marking paint based on high molecular weight saturated polyester plasticizer according to claim 7, characterized in that, In step S1, the stepped heating process includes: heating to 120°C at a heating rate of 2°C to 5°C / min and holding for 5 to 10 minutes, and then heating to 150°C to 165°C at a heating rate of 1°C to 3°C / min; and the homogeneous melting process of the matrix is ​​carried out in an environment protected by nitrogen.

9. The preparation method of the high weather-resistant hot-melt road marking paint based on a high molecular weight saturated polyester plasticizer according to claim 7, characterized in that, In step S2, the high-speed shear dispersion mode is provided by a shear dispersion device with a stator-rotor structure, and the rotor linear velocity is 15~25 m / s.

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