High adhesion asphalt anti-stripping agent and method of making same

Abstract

This invention relates to the field of asphalt technology and discloses a high-adhesion asphalt anti-stripping agent and its preparation method; including the following steps: Step 1: Add amino-branched titanium dioxide to N-methylaniline and mix evenly to obtain a polyamine complex; Step 2: Mix terpene phenolic resin, methyl phenyl silicone resin, and additives evenly, add the polyamine complex and calcium hydroxide, and mix evenly to obtain a high-adhesion asphalt anti-stripping agent.

Description

Technical Field

[0001] This invention relates to the field of asphalt technology, specifically to a high-adhesion asphalt anti-stripping agent and its preparation method. Background Technology

[0002] During the use of asphalt pavement, the adhesion between asphalt and aggregate is a key factor affecting pavement quality and service life. Long-term exposure to sunlight or in humid environments can lead to a decrease in the adhesion between asphalt and aggregate, resulting in spalling and seriously affecting the durability and safety of the pavement. To solve this problem, anti-stripping agents are widely used in asphalt mixtures.

[0003] Currently, common asphalt anti-stripping agents include amines and organic acids; however, these traditional anti-stripping agents have some limitations. For example, although amine anti-stripping agents can improve the adhesion between asphalt and aggregates to a certain extent, they are volatile at high temperatures and have poor thermal stability and aging resistance, resulting in a gradual decrease in anti-stripping effect over time. Organic acid anti-stripping agents have limited resistance to water damage and cannot meet the requirements for long-term use. At the same time, existing anti-stripping agents are not effective in improving adhesion and cannot effectively enhance the physical entanglement and cohesion between asphalt and aggregates, thus limiting their inhibitory effect on spalling.

[0004] In conclusion, the preparation of a highly adhesive asphalt anti-stripping agent is of great significance. Summary of the Invention

[0005] The purpose of this invention is to provide a high-adhesion asphalt anti-stripping agent and its preparation method to solve the problems raised in the prior art.

[0006] To achieve the above objectives, the present invention provides the following technical solution:

[0007] A method for preparing a high-adhesion asphalt anti-stripping agent includes the following steps:

[0008] Step 1: Add amino-branched titanium dioxide to N-methylaniline and mix evenly to obtain a polyamine complex;

[0009] Step 2: Mix terpene phenolic resin, methyl phenyl silicone resin and additives evenly, add polyamine complex and calcium hydroxide, mix evenly to obtain a high-adhesion asphalt anti-stripping agent.

[0010] In a more optimized form, the raw materials of the high-adhesion asphalt anti-stripping agent include the following components: by mass parts, 50-60 parts terpene phenolic resin, 20-30 parts methyl phenyl silicone resin, 10-20 parts additives, 8-12 parts polyamine complex, and 10-13 parts calcium hydroxide.

[0011] In a more optimized manner, the mass ratio of the amino-branched titanium dioxide to N-methylaniline is (2-3):1.

[0012] A more optimized method for preparing the additive is as follows: (1) 9,9-bis(4-aminophenyl)fluorene is added to DMF at 60-70°C and mixed evenly. Trimethylolpropane triglycidyl ether and triethylamine are added and reacted for 4-6 hours. The solvent is removed to obtain an intermediate product. (2) The intermediate product is mixed evenly with 1,4-butanediol and heated to 100-115°C under a nitrogen atmosphere. Tetrabutylammonium bromide is added and stirred for 20-24 hours. The mixture is cooled to room temperature and tetrahydrofuran is added and mixed evenly. The mixture is then added to deionized water to precipitate the precipitate. The precipitate is centrifuged, washed, and dried to obtain the additive.

[0013] In a more optimized form, the raw materials for the intermediate product include the following components: by mass parts, 3.4 to 3.5 parts of 9,9-bis(4-aminophenyl)fluorene, 3 to 3.03 parts of trimethylolpropane triglycidyl ether, and 0.1 to 0.3 parts of triethylamine.

[0014] In a more optimized form, the raw materials for the additive include the following components: by mass parts, 6.5 to 6.53 parts of intermediate product, 0.9 to 0.93 parts of 1,4-butanediol, and 0.16 to 0.25 parts of tetrabutylammonium bromide.

[0015] A more optimized method for preparing the amino-branched titanium dioxide is as follows: (1) 3-aminopropyltriethoxysilane is added to an ethanol aqueous solution and mixed evenly for 30-40 minutes, then titanium dioxide-ethanol aqueous solution is added, and the mixture is stirred at 60-75°C for 5-6 hours. The mixture is then filtered, washed, and dried to obtain amino-branched titanium dioxide; (2) Under nitrogen protection, amino-branched titanium dioxide and diethylenetriamine are ultrasonically dispersed in methanol, methyl acrylate is added, and the mixture is stirred at 30-40°C for 8-12 hours. The temperature is then raised to 150-165°C and stirred for 3-6 hours to obtain amino-branched titanium dioxide.

[0016] More optimized, the mass ratio of 3-aminopropyltriethoxysilane to titanium dioxide is (0.05-0.1):1; the raw material of the amino-branched titanium dioxide includes the following components: by mass parts, 1.5-2.5 parts amino-branched titanium dioxide, 0.3-0.4 parts diethylenetriamine, and 0.82-0.85 parts methyl acrylate.

[0017] Compared with the prior art, the beneficial effects of the present invention are:

[0018] In this scheme, terpene phenolic resin, methyl phenyl silicone resin, and additives are uniformly mixed, and then polyamine complex and calcium hydroxide are added and mixed uniformly to obtain a high-adhesion asphalt anti-stripping agent.

[0019] Among them, terpene phenolic resin and methyl phenyl silicone resin have good compatibility; terpene phenolic resin contains phenolic hydroxyl (-OH) and aromatic ring structure, in which the phenolic hydroxyl can undergo hydrogen bonding or chemical adsorption with aggregate to form a strong interfacial bonding force; the terpene olefin segments in the resin have good compatibility with the oil in the asphalt, so that the phenolic hydroxyl can be directionally adsorbed on the surface of the aggregate and prevent moisture from penetrating the interface.

[0020] However, terpene phenolic resins have poor UV protection properties, and prolonged exposure to sunlight can affect the adhesion of anti-stripping agents. To address this issue, the proposed solution incorporates methylphenyl silicone resin, which possesses certain UV protection properties, thus improving the aging resistance of the anti-stripping agent. Furthermore, the phenyl groups on the resin are hydrophobic and have good compatibility with the aromatic hydrocarbon structure of asphalt, improving the dispersion of the anti-stripping agent in the asphalt phase and forming a more uniform interfacial adsorption layer. The silicone resin molecular chain segments alleviate interfacial stress concentration through an energy dissipation mechanism, reducing spalling caused by fatigue cracking.

[0021] To further improve the UV protection of the anti-stripping agent, a polyamine complex containing amino-branched titanium dioxide and N-methylaniline is added to the formulation.

[0022] The polyamine complex comprises amino-branched titanium dioxide and N-methylaniline. In this scheme, the amino-branched titanium dioxide is first modified with 3-aminopropyltriethoxysilane to form amino-branched titanium dioxide. Then, the amino groups on the amino-branched titanium dioxide undergo nucleophilic addition (Michael addition) with the double bonds on methyl acrylate, yielding an intermediate containing amino and ester groups. The temperature is then raised to 150–165°C, where the ester groups and amino groups undergo a self-condensation reaction, generating amide bonds (-CONH-) and releasing methanol. To prevent ester group residue, the amino content needs to be increased, resulting in amino-branched titanium dioxide with a three-dimensional network structure. Titanium dioxide itself has good UV protection, and the formation of a three-dimensional network structure can effectively improve the aging resistance of the asphalt anti-stripping agent. However, excessive addition can lead to increased brittleness of the asphalt anti-stripping agent. Therefore, the addition of N-methylaniline in this scheme alleviates brittleness while synergistically enhancing the UV protection of the asphalt anti-stripping agent, thereby improving its adhesion.

[0023] Furthermore, the amino groups of amino-branched titanium dioxide and N-methylaniline can react with the silanol groups (Si-OH) on the surface of acidic aggregates (such as granite and basalt) to form stable chemical bonds, reducing the damage of water molecules to the interface. When used in combination with N-methylaniline, it can improve the wettability of terpene phenolic resin and methyl phenyl silicone resin to asphalt and aggregates, making it easier for anti-stripping agents to disperse on the aggregate surface and enhancing adhesion.

[0024] However, terpene phenolic resins and methyl phenyl silicone resins can increase the viscosity of anti-stripping agents, thereby reducing their fluidity in asphalt and aggregates and affecting their adhesion. To solve this problem, the solution uses additives and polyamine complexes to dilute the viscosity and improve fluidity, which in turn helps to improve the adhesion of the anti-stripping agent.

[0025] In this scheme, the amino group on 9,9-bis(4-aminophenyl)fluorene reacts with the epoxy group on trimethylolpropane triglycidyl ether in a 1:1 molar ratio to obtain an intermediate product containing fluorene groups and epoxy groups. Then, the epoxy groups on the intermediate product are reacted with 1,4-butanediol in a 1:1 molar ratio to obtain an additive containing polyhydroxyl and epoxy groups. The additive has a rigid skeleton with a fluorene ring structure, which has strong hydrophobicity and aging resistance. Furthermore, the terpene phenolic resin and the additive containing polyhydroxyl and epoxy groups form a continuous phase through hydrogen bonds and chemical bonds, forming an interpenetrating network, thereby improving the overall adhesion and aging resistance of the anti-stripping agent.

[0026] Calcium hydroxide can promote the reaction of the hydroxyl groups of the additive with the aggregate surface to form a calcium silicate-hydroxyl complex; neutralize the acidity of asphalt and improve the stability of the anti-stripping agent; the additive and polyamine complex can reduce the viscosity of the terpene phenolic resin and improve the fluidity of the anti-stripping agent in asphalt and aggregate. After curing, a three-dimensional network structure is formed between the active sites on the additive, polyamine complex and terpene phenolic resin, which synergistically improves the hydrophobicity with methylphenyl silicone resin, thereby improving the adhesion and aging resistance of the anti-stripping agent. Detailed Implementation

[0027] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0028] In the following specific embodiments, the parts are by weight. In this embodiment, it should be noted that there are no special restrictions on the purchase manufacturers of all the raw materials involved in this invention. Exemplary examples include: 9,9-bis(4-aminophenyl)fluorene, CAS number 15499-84-0; trimethylolpropane triglycidyl ether, CAS number 30499-70-8; triethylamine, CAS number 121-44-8; 1,4-butanediol, CAS number 110-63-4; 3-aminopropyltriethoxysilane, CAS number 919-30-2; methyl acrylate, CAS number 96-33-3; N-methylaniline, CAS number 100-61-8; terpene phenolic resin, item number 002; methylphenyl silicone resin, item number 9345; and calcium hydroxide, CAS number 1305-62-0.

[0029] Example 1: A method for preparing a high-adhesion asphalt anti-stripping agent, comprising the following steps:

[0030] Raw material pre-preparation; The preparation method of the additive is as follows: (1) 3.48 parts of 9,9-bis(4-aminophenyl)fluorene are added to 20 parts of DMF at 70℃ and mixed evenly. 3.02 parts of trimethylolpropane triglycidyl ether and 0.15 parts of triethylamine are added. The reaction is carried out for 5 hours, the solvent is removed, and the intermediate product is obtained. (2) 6.51 parts of the intermediate product are mixed evenly with 0.9 parts of 1,4-butanediol. The mixture is heated to 110℃ under a nitrogen atmosphere. 0.18 parts of tetrabutylammonium bromide are added and stirred for 24 hours. The mixture is cooled to room temperature. Tetrahydrofuran is added and mixed evenly. The mixture is then added to deionized water to precipitate. This process is repeated three times. The mixture is centrifuged, washed, and dried to obtain the additive.

[0031] The preparation method of amino-branched titanium dioxide is as follows: (1) 3-aminopropyltriethoxysilane is added to an ethanol aqueous solution (concentration of 80wt%) and mixed evenly for 40 minutes. Then, titanium dioxide-ethanol aqueous solution is added and stirred at 70°C for 5 hours. After filtration, washing and drying, amino-branched titanium dioxide is obtained. The mass ratio of 3-aminopropyltriethoxysilane to titanium dioxide is 0.08:1. (2) Under nitrogen protection, 2 parts of amino-branched titanium dioxide and 0.3 parts of diethylenetriamine are ultrasonically dispersed in methanol. 0.82 parts of methyl acrylate are added and stirred at 40°C for 12 hours. The temperature is raised to 150°C and stirred for 5 hours to obtain amino-branched titanium dioxide.

[0032] Step 1: Add amino-branched titanium dioxide to N-methylaniline and mix evenly to obtain a polyamine complex; wherein the mass ratio of amino-branched titanium dioxide to N-methylaniline is 2:1;

[0033] Step 2: Mix 55 parts of terpene phenolic resin, 20 parts of methyl phenyl silicone resin, and 10 parts of additives evenly, add 8 parts of polyamine complex and 10 parts of calcium hydroxide, mix evenly to obtain a high-adhesion asphalt anti-stripping agent.

[0034] Example 2: A method for preparing a high-adhesion asphalt anti-stripping agent, comprising the following steps:

[0035] Raw material pre-preparation; The preparation method of the additive is as follows: (1) 3.48 parts of 9,9-bis(4-aminophenyl)fluorene are added to 20 parts of DMF at 70℃ and mixed evenly. 3.02 parts of trimethylolpropane triglycidyl ether and 0.15 parts of triethylamine are added. The reaction is carried out for 5 hours, the solvent is removed, and the intermediate product is obtained. (2) 6.51 parts of the intermediate product are mixed evenly with 0.9 parts of 1,4-butanediol. The mixture is heated to 115℃ under a nitrogen atmosphere. 0.18 parts of tetrabutylammonium bromide are added and stirred for 24 hours. The mixture is cooled to room temperature. Tetrahydrofuran is added and mixed evenly. The mixture is then added to deionized water to precipitate. This process is repeated three times. The mixture is centrifuged, washed, and dried to obtain the additive.

[0036] The preparation method of amino-branched titanium dioxide is as follows: (1) 3-aminopropyltriethoxysilane is added to an ethanol aqueous solution (concentration of 80wt%) and mixed evenly for 40 minutes. Then, titanium dioxide-ethanol aqueous solution is added and stirred at 70°C for 5 hours. After filtration, washing and drying, amino-branched titanium dioxide is obtained. The mass ratio of 3-aminopropyltriethoxysilane to titanium dioxide is 0.08:1. (2) Under nitrogen protection, 2 parts of amino-branched titanium dioxide and 0.3 parts of diethylenetriamine are ultrasonically dispersed in methanol. 0.82 parts of methyl acrylate are added and stirred at 40°C for 12 hours. The temperature is raised to 150°C and stirred for 5 hours to obtain amino-branched titanium dioxide.

[0037] Step 1: Add amino-branched titanium dioxide to N-methylaniline and mix evenly to obtain a polyamine complex; wherein the mass ratio of amino-branched titanium dioxide to N-methylaniline is (2-3):1;

[0038] Step 2: Mix 60 parts of terpene phenolic resin, 25 parts of methyl phenyl silicone resin, and 20 parts of additives evenly, add 12 parts of polyamine complex and 10 parts of calcium hydroxide, mix evenly to obtain a high-adhesion asphalt anti-stripping agent.

[0039] Example 3: A method for preparing a high-adhesion asphalt anti-stripping agent, comprising the following steps:

[0040] Raw material pre-preparation; The preparation method of the additive is as follows: (1) 3.48 parts of 9,9-bis(4-aminophenyl)fluorene are added to 20 parts of DMF at 70℃ and mixed evenly. 3.02 parts of trimethylolpropane triglycidyl ether and 0.15 parts of triethylamine are added. The reaction is carried out for 5 hours, the solvent is removed, and the intermediate product is obtained. (2) 6.51 parts of the intermediate product are mixed evenly with 0.9 parts of 1,4-butanediol. The mixture is heated to 115℃ under a nitrogen atmosphere. 0.18 parts of tetrabutylammonium bromide are added and stirred for 24 hours. The mixture is cooled to room temperature. Tetrahydrofuran is added and mixed evenly. The mixture is then added to deionized water to precipitate. This process is repeated three times. The mixture is centrifuged, washed, and dried to obtain the additive.

[0041] The preparation method of amino-branched titanium dioxide is as follows: (1) 3-aminopropyltriethoxysilane is added to an ethanol aqueous solution (concentration of 80wt%) and mixed evenly for 40 minutes. Then, titanium dioxide-ethanol aqueous solution is added and stirred at 70°C for 5 hours. After filtration, washing and drying, amino-branched titanium dioxide is obtained. The mass ratio of 3-aminopropyltriethoxysilane to titanium dioxide is 0.08:1. (2) Under nitrogen protection, 2 parts of amino-branched titanium dioxide and 0.3 parts of diethylenetriamine are ultrasonically dispersed in methanol. 0.82 parts of methyl acrylate are added and stirred at 40°C for 12 hours. The temperature is raised to 150°C and stirred for 5 hours to obtain amino-branched titanium dioxide.

[0042] Step 1: Add amino-branched titanium dioxide to N-methylaniline and mix evenly to obtain a polyamine complex; wherein the mass ratio of amino-branched titanium dioxide to N-methylaniline is 2:1;

[0043] Step 2: Mix 60 parts of terpene phenolic resin, 20 parts of methyl phenyl silicone resin, and 15 parts of additives evenly, add 12 parts of polyamine complex and 12 parts of calcium hydroxide, mix evenly to obtain a high-adhesion asphalt anti-stripping agent.

[0044] Comparative Example 1 is based on Example 2, but introduces N-methylaniline alone;

[0045] Raw material pre-preparation; The preparation method of the additive is as follows: (1) 3.48 parts of 9,9-bis(4-aminophenyl)fluorene are added to 20 parts of DMF at 70℃ and mixed evenly. 3.02 parts of trimethylolpropane triglycidyl ether and 0.15 parts of triethylamine are added. The reaction is carried out for 5 hours, the solvent is removed, and the intermediate product is obtained; (2) 6.51 parts of the intermediate product are mixed evenly with 0.9 parts of 1,4-butanediol. The mixture is heated to 115℃ under a nitrogen atmosphere. 0.18 parts of tetrabutylammonium bromide are added and stirred for 24 hours. The mixture is cooled to room temperature. Tetrahydrofuran is added and mixed evenly. The mixture is then added to deionized water to precipitate. This process is repeated three times. The mixture is centrifuged, washed, and dried to obtain the additive.

[0046] 60 parts of terpene phenolic resin, 25 parts of methyl phenyl silicone resin, and 20 parts of additives were mixed evenly, and then 10 parts of N-methylaniline and 10 parts of calcium hydroxide were added and mixed evenly to obtain a high-adhesion asphalt anti-stripping agent.

[0047] Comparative Example 2 is based on Example 2, except that the amino-branched titanium dioxide is replaced with amino-branched titanium dioxide;

[0048] Raw material pre-preparation; The preparation method of the additive is as follows: (1) 3.48 parts of 9,9-bis(4-aminophenyl)fluorene are added to 20 parts of DMF at 70℃ and mixed evenly. 3.02 parts of trimethylolpropane triglycidyl ether and 0.15 parts of triethylamine are added. The reaction is carried out for 5 hours, the solvent is removed, and the intermediate product is obtained. (2) 6.51 parts of the intermediate product are mixed evenly with 0.9 parts of 1,4-butanediol. The mixture is heated to 100℃ under a nitrogen atmosphere. 0.18 parts of tetrabutylammonium bromide are added and stirred for 48 hours. The mixture is cooled to room temperature. Tetrahydrofuran is added and mixed evenly. The mixture is then added to deionized water to precipitate. This process is repeated three times. The mixture is centrifuged, washed, and dried to obtain the additive.

[0049] The preparation method of amino-branched titanium dioxide is as follows: (1) 3-aminopropyltriethoxysilane is added to an ethanol aqueous solution (concentration of 80wt%) and mixed evenly for 40 minutes. Then, titanium dioxide-ethanol aqueous solution is added and stirred at 70°C for 5 hours. After filtration, washing and drying, amino-branched titanium dioxide is obtained.

[0050] Step 1: Add aminated titanium dioxide to N-methylaniline and mix evenly to obtain a polyamine complex; wherein the mass ratio of aminated titanium dioxide to N-methylaniline is 2:1;

[0051] Step 2: Mix 60 parts of terpene phenolic resin, 25 parts of methyl phenyl silicone resin, and 20 parts of additives evenly, add 12 parts of polyamine complex and 10 parts of calcium hydroxide, mix evenly to obtain a high-adhesion asphalt anti-stripping agent.

[0052] Comparative Example 3 is based on Example 2, but without the introduction of 9,9-bis(4-aminophenyl)fluorene;

[0053] Raw material pre-preparation; The additive preparation method is as follows: 3.02 parts of trimethylolpropane triglycidyl ether and 0.9 parts of 1,4-butanediol are uniformly mixed, heated to 115°C under a nitrogen atmosphere, 0.18 parts of tetrabutylammonium bromide are added, stirred for 24 hours, cooled to room temperature, tetrahydrofuran is added and mixed uniformly, and then added to deionized water to precipitate. This process is repeated three times; centrifugation, washing, and drying are performed to obtain the additive;

[0054] The preparation method of amino-branched titanium dioxide is as follows: (1) 3-aminopropyltriethoxysilane is added to an ethanol aqueous solution (concentration of 80wt%) and mixed evenly for 40 minutes. Then, titanium dioxide-ethanol aqueous solution is added and stirred at 70°C for 5 hours. After filtration, washing and drying, amino-branched titanium dioxide is obtained. The mass ratio of 3-aminopropyltriethoxysilane to titanium dioxide is 0.08:1. (2) Under nitrogen protection, 2 parts of amino-branched titanium dioxide and 0.3 parts of diethylenetriamine are ultrasonically dispersed in methanol. 0.82 parts of methyl acrylate are added and stirred at 40°C for 12 hours. The temperature is raised to 150°C and stirred for 5 hours to obtain amino-branched titanium dioxide.

[0055] Step 1: Add amino-branched titanium dioxide to N-methylaniline and mix evenly to obtain a polyamine complex; wherein the mass ratio of amino-branched titanium dioxide to N-methylaniline is (2-3):1;

[0056] Step 2: Mix 60 parts of terpene phenolic resin, 25 parts of methyl phenyl silicone resin, and 20 parts of additives evenly, add 12 parts of polyamine complex and 10 parts of calcium hydroxide, mix evenly to obtain a high-adhesion asphalt anti-stripping agent.

[0057] Comparative Example 4 is based on Example 2, but the mass ratio of amino-branched titanium dioxide to N-methylaniline is increased to 5:1;

[0058] Raw material pre-preparation; The preparation method of the additive is as follows: (1) 3.48 parts of 9,9-bis(4-aminophenyl)fluorene are added to 20 parts of DMF at 70℃ and mixed evenly. 3.02 parts of trimethylolpropane triglycidyl ether and 0.15 parts of triethylamine are added and reacted for 5 hours. The solvent is removed to obtain the intermediate product; (2) 6.51 parts of the intermediate product are added to 0.9 parts of 1,4-butanediol and mixed evenly. The mixture is heated to 115℃ under a nitrogen atmosphere. 0.18 parts of tetrabutylammonium bromide are added and stirred for 24 hours. The mixture is cooled to room temperature and the solvent is removed to obtain the additive;

[0059] The preparation method of amino-branched titanium dioxide is as follows: (1) 3-aminopropyltriethoxysilane is added to an ethanol aqueous solution (concentration of 80wt%) and mixed evenly for 40 minutes. Then, titanium dioxide-ethanol aqueous solution is added and stirred at 70°C for 5 hours. After filtration, washing and drying, amino-branched titanium dioxide is obtained. The mass ratio of 3-aminopropyltriethoxysilane to titanium dioxide is 0.08:1. (2) Under nitrogen protection, 2 parts of amino-branched titanium dioxide and 0.3 parts of diethylenetriamine are ultrasonically dispersed in methanol. 0.82 parts of methyl acrylate are added and stirred at 40°C for 12 hours. The temperature is raised to 150°C and stirred for 5 hours to obtain amino-branched titanium dioxide.

[0060] Step 1: Add amino-branched titanium dioxide to N-methylaniline and mix evenly to obtain a polyamine complex; wherein the mass ratio of amino-branched titanium dioxide to N-methylaniline is 5:1;

[0061] Step 2: Mix 60 parts of terpene phenolic resin, 25 parts of methyl phenyl silicone resin, and 20 parts of additives evenly, add 12 parts of polyamine complex and 10 parts of calcium hydroxide, mix evenly to obtain a high-adhesion asphalt anti-stripping agent.

[0062] Test; (1) Take 100g of No. 70 base asphalt and heat it to 150°C. Add 0.3g of high-adhesion asphalt anti-stripping agent prepared by Examples 1-3 and Comparative Examples 1-4 under high-speed stirring. Mix evenly for 5 minutes at 1000r / min to obtain anti-stripping asphalt;

[0063] (2) Take 6 samples of each of the above-prepared anti-stripping asphalts and place them in an ultraviolet aging chamber with an ultraviolet intensity of 1200 μw / cm. 2 The aging temperature was 60℃ and the aging time was 5 days. 42 basalt stones of 15-20mm size were taken, cleaned, dried, and 6 stones of each type were weighed. The aggregates were then placed separately in preheated anti-stripping asphalt (anti-stripping asphalt before and after aging) and mixed for 50 seconds. Excess anti-stripping asphalt was removed by hanging, and the mixture was cooled to room temperature. The aggregates coated with anti-stripping asphalt were then placed in boiling water for 10 minutes. The area stripping rate (%) was calculated according to the "Test Procedures for Asphalt and Asphalt Mixtures in Highway Engineering" (JTGE20-2011).

[0064] Table 1

[0065] Peeling rate per unit area before aging (%) Area peeling rate after aging (%) Example 1 4.21 4.72 Example 2 3.84 4.14 Example 3 3.93 4.35 Comparative Example 1 14.72 23.67 Comparative Example 2 12.24 20.43 Comparative Example 3 10.65 16.78 Comparative Example 4 11.84 18.94

[0066] Conclusions: Comparative Example 1, based on Example 2, introduced N-methylaniline alone, which reduced the aging resistance of the anti-stripping agent, thus decreasing the adhesion performance of the anti-stripping asphalt. Comparative Example 2, based on Example 2, replaced the amino-branched titanium dioxide with amino-modified titanium dioxide. Because amino-modified titanium dioxide is not a three-dimensional network structure, it reduced the water resistance and aging resistance of the anti-stripping agent, thus decreasing the adhesion performance of the anti-stripping asphalt. Comparative Example 3, based on Example 2, did not introduce 9,9-bis(4-aminophenyl)fluorene, which reduced the strong hydrophobicity and aging resistance of the additive, thus affecting the performance of the asphalt anti-stripping agent. Comparative Example 4, based on Example 2, increased the mass ratio of amino-branched titanium dioxide to N-methylaniline to 5:1, which increased the brittleness of the anti-stripping agent, thus reducing the performance of the asphalt anti-stripping agent.

[0067] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, it is intended that all variations falling within the meaning and scope of equivalents of the claims be included within the present invention.

Claims

1. A method for preparing a high-adhesion asphalt anti-stripping agent, characterized in that: The following steps are included: Step 1: Add amino-branched titanium dioxide to N-methylaniline and mix evenly to obtain a polyamine complex; Step 2: Mix terpene phenolic resin, methyl phenyl silicone resin and additives evenly, add polyamine complex and calcium hydroxide, mix evenly to obtain a high-adhesion asphalt anti-stripping agent; The mass ratio of the amino-branched titanium dioxide to N-methylaniline is (2~3):1; The preparation method of the amino-branched titanium dioxide is as follows: (1) 3-aminopropyltriethoxysilane is added to an ethanol aqueous solution and mixed evenly for 30-40 minutes. Then, titanium dioxide-ethanol aqueous solution is added and stirred at 60-75°C for 5-6 hours. The mixture is then filtered, washed, and dried to obtain amino-branched titanium dioxide; (2) Under nitrogen protection, amino-branched titanium dioxide and diethylenetriamine are ultrasonically dispersed in methanol. Methyl acrylate is added and stirred at 30-40°C for 8-12 hours. The temperature is then raised to 150-165°C and stirred for 3-6 hours to obtain amino-branched titanium dioxide. The preparation method of the additive is as follows: (1) 9,9-bis(4-aminophenyl)fluorene is added to DMF at 60~70℃ and mixed evenly. Trimethylolpropane triglycidyl ether and triethylamine are added and reacted for 4~6 hours. The solvent is removed to obtain the intermediate product; (2) The intermediate product is mixed evenly with 1,4-butanediol and heated to 100~115℃ under a nitrogen atmosphere. Tetrabutylammonium bromide is added and stirred for 20~24 hours. After cooling to room temperature, tetrahydrofuran is added and mixed evenly. The mixture is then added to deionized water to precipitate. After centrifugation, washing, and drying, the additive is obtained.

2. The method for preparing a high-adhesion asphalt anti-stripping agent according to claim 1, characterized in that: The raw materials of the high-adhesion asphalt anti-stripping agent include the following components: by mass, 50-60 parts terpene phenolic resin, 20-30 parts methyl phenyl silicone resin, 10-20 parts additives, 8-12 parts polyamine complex, and 10-13 parts calcium hydroxide.

3. The method for preparing a high-adhesion asphalt anti-stripping agent according to claim 1, characterized in that: The raw materials for the intermediate product include the following components: by mass, 3.4 to 3.5 parts of 9,9-bis(4-aminophenyl)fluorene, 3 to 3.03 parts of trimethylolpropane triglycidyl ether, and 0.1 to 0.3 parts of triethylamine.

4. The method for preparing a high-adhesion asphalt anti-stripping agent according to claim 1, characterized in that: The raw materials for the additive include the following components: by mass, 6.5 to 6.53 parts of intermediate product, 0.9 to 0.93 parts of 1,4-butanediol, and 0.16 to 0.25 parts of tetrabutylammonium bromide.

5. The method for preparing a high-adhesion asphalt anti-stripping agent according to claim 1, characterized in that: The mass ratio of 3-aminopropyltriethoxysilane to titanium dioxide is (0.05~0.1):1; the raw material of the amino-branched titanium dioxide includes the following components: by mass parts, 1.5~2.5 parts amino-branched titanium dioxide, 0.3~0.4 parts diethylenetriamine, and 0.82~0.85 parts methyl acrylate.

6. The high-adhesion asphalt anti-stripping agent prepared by the preparation method according to any one of claims 1 to 5.