High-adhesion asphalt anti-stripping agent and preparation method thereof

Abstract

The invention relates to the technical field of asphalt, and discloses a high-adhesion asphalt anti-stripping agent and a preparation method thereof. Comprising the following operation steps: step 1, adding amino-branched titanium dioxide into N-methylaniline, and uniformly mixing to obtain a polyamine compound; and 2, uniformly mixing the terpene phenolic resin, the methyl phenyl silicone resin and the additive, adding the polyamine compound and calcium hydroxide, and uniformly mixing to obtain the high-adhesion asphalt anti-stripping agent.

Description

Technical Field

[0001] The present invention relates to the technical field of asphalt, in particular to a high-adhesion asphalt anti-stripping agent and a preparation method thereof. Background Art

[0002] During the use of asphalt pavement, the adhesion between asphalt and aggregate is a key factor affecting the quality and service life of the pavement. Under long-term exposure to sunlight or in a humid environment, the aging of asphalt and the intrusion of moisture will lead to a decrease in the adhesion between asphalt and aggregate, and then peeling will occur, seriously affecting the durability and safety of the pavement. To solve this problem, anti-stripping agents are widely used in asphalt mixtures.

[0003] At present, common asphalt anti-stripping agents include amines, organic acids, etc.; however, these traditional anti-stripping agents have some limitations; for example, although amine anti-stripping agents can improve the adhesion between asphalt and aggregate to a certain extent, they are easy to volatilize under high temperature environment and have poor thermal stability and aging resistance, resulting in the anti-stripping effect gradually decreasing over time; organic acid anti-stripping agents have limited resistance to water damage and are difficult to meet long-term use requirements; 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 aggregate, which limits their inhibitory effect on spalling.

[0004] In summary, it is of great significance to prepare a high-adhesion asphalt anti-stripping agent. Summary of the Invention

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

[0006] To achieve the above object, the present invention provides the following technical solutions:

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

[0008] Step 1: adding amino-branched titanium dioxide to N-methylaniline and uniformly mixing to obtain a polyamine complex;

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

[0010] More optimally, the raw materials of the high-adhesion asphalt anti-stripping agent include the following components: 50 to 60 parts of terpene phenolic resin, 20 to 30 parts of methylphenyl silicone resin, 10 to 20 parts of additives, 8 to 12 parts of polyamine complex, and 10 to 13 parts of calcium hydroxide, calculated by mass.

[0011] More optimally, the mass ratio of the amino-branched titanium dioxide to N-methylaniline is (2-3):1.

[0012] The more optimized preparation method of the additive is as follows: (1) adding 9,9-bis(4-aminophenyl)fluorene to DMF at 60-70° C. and mixing uniformly, adding trimethylolpropane triglycidyl ether and triethylamine, reacting for 4-6 hours, removing the solvent, and obtaining an intermediate product; (2) uniformly mixing the intermediate product with 1,4-butanediol, heating to 100-115° C. under a nitrogen atmosphere, adding tetrabutylammonium bromide, stirring for 20-24 hours, cooling to room temperature, adding tetrahydrofuran and mixing uniformly, adding it to deionized water for precipitation, centrifuging, washing, and drying to obtain the additive.

[0013] More optimally, the raw materials of the intermediate product include the following components: 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, calculated by mass.

[0014] More optimally, the raw materials of the additive include the following components: 6.5 to 6.53 parts of the intermediate product, 0.9 to 0.93 parts of 1,4-butanediol, and 0.16 to 0.25 parts of tetrabutylammonium bromide, calculated by mass.

[0015] The more optimized preparation method of the amino-branched titanium dioxide is as follows: (1) adding 3-aminopropyltriethoxysilane to an ethanol aqueous solution and uniformly mixing for 30 to 40 minutes, adding titanium dioxide-ethanol aqueous solution, stirring at 60 to 75° C. for 5 to 6 hours, filtering, washing, and drying to obtain amino-branched titanium dioxide; (2) under nitrogen protection, ultrasonically dispersing amino-branched titanium dioxide and diethylenetriamine in methanol, adding methyl acrylate, stirring at 30 to 40° C. for 8 to 12 hours, heating to 150 to 165° C., and stirring for 3 to 6 hours to obtain amino-branched titanium dioxide.

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

[0017] Compared with the prior art, the present invention has the following beneficial effects:

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

[0019] Among them, terpene phenolic resin and methylphenyl silicone resin have good compatibility; terpene phenolic resin contains phenolic hydroxyl (-OH) and aromatic ring structure, in which the phenolic hydroxyl can hydrogen bond or chemically adsorb with aggregate, forming a strong interfacial bonding force; the terpene olefin chain segment in the resin has good compatibility with the oil in asphalt, allowing the phenolic hydroxyl to be directionally adsorbed on the aggregate surface, preventing moisture from invading the interface;

[0020] However, terpene phenolic resin has poor UV protection, and long-term exposure to sunlight will affect the adhesion of the anti-stripping agent. In order to solve this problem, in the scheme, methylphenyl silicone resin has certain UV protection, so it is beneficial to improve the aging resistance of the anti-stripping agent. The phenyl group on it is a hydrophobic group, which has good compatibility with the aromatic hydrocarbon structure of asphalt, and can improve the dispersion of the anti-stripping agent in the asphalt phase, forming a more uniform interface adsorption layer. The silicone resin molecular chain segments relieve interfacial stress concentration through the energy dissipation mechanism, reducing peeling caused by fatigue cracking.

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

[0022] Among them, the polyamine complex includes amino-branched titanium dioxide and N-methylaniline; in the scheme, the amino-branched titanium dioxide is first modified with 3-aminopropyltriethoxysilane to prepare amino-branched titanium dioxide; then the amino group on the amino-branched titanium dioxide and the double bond on the methyl acrylate undergo nucleophilic addition (Michael addition) to obtain an intermediate containing an amino group and an ester group; then the temperature is raised to 150-165°C, and then the ester group and the amino group undergo a self-condensation reaction to generate an amide bond (-CONH-) and release methanol. It is necessary to increase the content of the amino group to prevent the ester group from remaining, and obtain amino-branched titanium dioxide with a three-dimensional network structure; titanium dioxide itself has good UV resistance, and the formation of a three-dimensional network structure can effectively improve the aging resistance of the asphalt anti-stripping agent; however, excessive addition will cause the asphalt anti-stripping agent to become more brittle, so the addition of N-methylaniline in the scheme alleviates the brittleness while synergistically enhancing the UV resistance of the asphalt anti-stripping agent, which is beneficial to enhance the adhesion of the asphalt anti-stripping agent.

[0023] In addition, the amino groups of amino-branched titanium dioxide and N-methylaniline can react with the silanol (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; its combination with N-methylaniline can improve the wettability of terpene phenolic resin and methylphenyl silicone resin to asphalt and aggregate, making the anti-stripping agent easier to disperse on the aggregate surface and enhancing adhesion.

[0024] However, terpene phenolic resin and methylphenyl silicone resin increase the viscosity of the anti-stripping agent, thereby reducing the fluidity of the two in asphalt and aggregate, thus affecting the adhesion. To solve this problem, the solution uses additives and polyamine complexes to dilute the viscosity and increase the fluidity, which is beneficial to improving the adhesion of the anti-stripping agent.

[0025] In the scheme, the amino group on 9,9-bis(4-aminophenyl)fluorene reacts with the epoxy group on trimethylolpropane triglycidyl ether in a molar ratio of 1:1 to obtain an intermediate product containing a fluorene group and an epoxy group; then the epoxy group on the intermediate product reacts with 1,4-butanediol in a molar ratio of 1:1 to obtain an additive containing polyhydroxyl and epoxy groups; the additive has a fluorene ring structure as a rigid skeleton and has strong hydrophobicity and aging resistance; and 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 group 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 the methylphenyl silicone resin, thereby improving the adhesion and aging resistance of the anti-stripping agent. DETAILED DESCRIPTION

[0027] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0028] In the following specific embodiments, parts are by mass. In this embodiment, it should be noted that the purchase manufacturers of all raw materials involved in the present invention are not subject to any special restrictions, and illustratively include: 9,9-bis(4-aminophenyl)fluorene has a CAS number of 15499-84-0; trimethylolpropane triglycidyl ether has a CAS number of 30499-70-8; triethylamine has a CAS number of 121-44-8; 1,4-butanediol has a CAS number of 110-63-4; 3-aminopropyltriethoxysilane has a CAS number of 919-30-2; methyl acrylate has a CAS number of 96-33-3; N-methylaniline has a CAS number of 100-61-8; terpene phenolic resin has a CAS number of 002; methylphenyl silicone resin has a CAS number of 9345; and calcium hydroxide has a CAS number of 1305-62-0.

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

[0030] The raw materials were prepared in advance; the preparation method of the additive was as follows: (1) 3.48 parts of 9,9-bis(4-aminophenyl)fluorene were added to 20 parts of DMF at 70°C and mixed uniformly, 3.02 parts of trimethylolpropane triglycidyl ether and 0.15 parts of triethylamine were added, the reaction was continued for 5 hours, and the solvent was removed to obtain an intermediate product; (2) 6.51 parts of the intermediate product were mixed uniformly with 0.9 parts of 1,4-butanediol, heated to 110°C under a nitrogen atmosphere, 0.18 parts of tetrabutylammonium bromide were added, stirred for 24 hours, cooled to room temperature, tetrahydrofuran was added and mixed uniformly, and then the mixture was added to deionized water for precipitation, and the mixture was repeated three times; centrifugation, washing, and drying were performed to obtain the additive;

[0031] The preparation method of amino-branched titanium dioxide is as follows: (1) adding 3-aminopropyltriethoxysilane to an ethanol aqueous solution (concentration of 80wt%) and uniformly mixing for 40 minutes, adding titanium dioxide-ethanol aqueous solution, stirring at 70°C for 5 hours, filtering, washing, and drying to obtain amino-branched titanium dioxide; wherein the mass ratio of 3-aminopropyltriethoxysilane to titanium dioxide is 0.08:1; (2) under nitrogen protection, ultrasonically dispersing 2 parts of amino-branched titanium dioxide and 0.3 parts of diethylenetriamine in methanol, adding 0.82 parts of methyl acrylate, stirring at 40°C for 12 hours, heating to 150°C, and stirring for 5 hours to obtain amino-branched titanium dioxide;

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

[0033] Step 2: Evenly mix 55 parts of terpene phenolic resin, 20 parts of methylphenyl silicone resin, and 10 parts of additives, add 8 parts of polyamine complex and 10 parts of calcium hydroxide, and evenly mix 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] The raw materials were prepared in advance; the preparation method of the additive was as follows: (1) 3.48 parts of 9,9-bis(4-aminophenyl)fluorene were added to 20 parts of DMF at 70°C and mixed uniformly, 3.02 parts of trimethylolpropane triglycidyl ether and 0.15 parts of triethylamine were added, the reaction was continued for 5 hours, and the solvent was removed to obtain an intermediate product; (2) 6.51 parts of the intermediate product were mixed uniformly with 0.9 parts of 1,4-butanediol, heated to 115°C under a nitrogen atmosphere, 0.18 parts of tetrabutylammonium bromide were added, stirred for 24 hours, cooled to room temperature, tetrahydrofuran was added and mixed uniformly, and then the mixture was added to deionized water for precipitation, and the mixture was repeated three times; centrifugation, washing, and drying were performed to obtain the additive;

[0036] The preparation method of amino-branched titanium dioxide is as follows: (1) adding 3-aminopropyltriethoxysilane to an ethanol aqueous solution (concentration of 80wt%) and uniformly mixing for 40 minutes, adding titanium dioxide-ethanol aqueous solution, stirring at 70°C for 5 hours, filtering, washing, and drying to obtain amino-branched titanium dioxide; wherein the mass ratio of 3-aminopropyltriethoxysilane to titanium dioxide is 0.08:1; (2) under nitrogen protection, ultrasonically dispersing 2 parts of amino-branched titanium dioxide and 0.3 parts of diethylenetriamine in methanol, adding 0.82 parts of methyl acrylate, stirring at 40°C for 12 hours, heating to 150°C, and stirring for 5 hours to obtain amino-branched titanium dioxide;

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

[0038] Step 2: Evenly mix 60 parts of terpene phenolic resin, 25 parts of methylphenyl silicone resin, and 20 parts of additives, add 12 parts of polyamine complex and 10 parts of calcium hydroxide, and evenly mix 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] The raw materials are prepared in advance; the additive is prepared by the following method: (1) 3.48 parts of 9,9-bis(4-aminophenyl)fluorene are added to 20 parts of DMF at 70°C and uniformly mixed, 3.02 parts of trimethylolpropane triglycidyl ether and 0.15 parts of triethylamine are added, and the reaction is carried out for 5 hours, and then the solvent is removed to obtain an intermediate product; (2) 6.51 parts of the intermediate product 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 is added, stirred for 24 hours, cooled to room temperature, and then uniformly mixed with tetrahydrofuran, and then added to deionized water to precipitate, and the operation is repeated three times; centrifuged, washed, and dried to obtain the additive;

[0041] The amino branched titanium dioxide is prepared by the following method: (1) 3-aminopropyl triethoxysilane is added to an ethanol aqueous solution (concentration of 80 wt%) and uniformly mixed for 40 minutes, and then titanium dioxide-ethanol aqueous solution is added, and stirred at 70°C for 5 hours, and then filtered, washed, and dried to obtain amino titanium dioxide; wherein the mass ratio of 3-aminopropyl triethoxysilane to titanium dioxide is 0.08:1; (2) under the protection of nitrogen, 2 parts of amino titanium dioxide and 0.3 parts of diethylenetriamine are ultrasonically dispersed in methanol, 0.82 parts of methyl acrylate is added, and stirred at 40°C for 12 hours, and then heated to 150°C and stirred for 5 hours to obtain amino branched titanium dioxide;

[0042] Step 1: the amino branched titanium dioxide is added to N-methylaniline to obtain a polyamine composite; wherein the mass ratio of the amino branched titanium dioxide to N-methylaniline is 2:1;

[0043] Step 2: 60 parts of terpene phenolic resin, 20 parts of methylphenyl silicone resin, and 15 parts of the additive are uniformly mixed, and then 12 parts of the polyamine composite and 12 parts of calcium hydroxide are added and uniformly mixed to obtain the high-adhesion asphalt anti-stripping agent.

[0044] Comparative Example 1 is based on Example 2, and only N-methylaniline is introduced;

[0045] The raw materials are prepared in advance; the additive is prepared by the following method: (1) 3.48 parts of 9,9-bis(4-aminophenyl)fluorene are added to 20 parts of DMF at 70°C and uniformly mixed, 3.02 parts of trimethylolpropane triglycidyl ether and 0.15 parts of triethylamine are added, and the reaction is carried out for 5 hours, and then the solvent is removed to obtain an intermediate product; (2) 6.51 parts of the intermediate product 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 is added, stirred for 24 hours, cooled to room temperature, and then uniformly mixed with tetrahydrofuran, and then added to deionized water to precipitate, and the operation is repeated three times; centrifuged, washed, and dried to obtain the additive;

[0046] The 60 parts of terpene phenolic resin, 25 parts of methyl phenyl silicone resin, 20 parts of additive are uniformly mixed, 10 parts of N-methyl aniline and 10 parts of calcium hydroxide are added and uniformly mixed to obtain the high adhesion asphalt anti-stripping agent.

[0047] Comparative Example 2 is based on Example 2, the amino branched titanium dioxide is replaced by aminated titanium dioxide;

[0048] The raw materials are pre-prepared; the preparation method of the additive is: (1) 3.48 parts of 9, 9-bis (4-aminophenyl) fluorene is added to 70℃ 20 parts of DMF and uniformly mixed, 3.02 parts of trimethylolpropane triglycidyl ether and 0.15 parts of triethylamine are added, and the reaction is carried out for 5 hours; the solvent is removed to obtain an intermediate product; (2) 6.51 parts of the intermediate product and 0.9 parts of 1, 4-butanediol are uniformly mixed, heated to 100℃ under nitrogen atmosphere, 0.18 parts of tetrabutylammonium bromide is added, stirred for 48 hours, cooled to room temperature, and then added to deionized water after uniformly mixed with tetrahydrofuran, and precipitated, repeated three times; centrifuged, washed and dried to obtain the additive;

[0049] The preparation method of the amino branched titanium dioxide is: (1) 3-aminopropyl triethoxysilane is added to an ethanol aqueous solution (concentration of 80wt%) and uniformly mixed for 40 minutes, and then titanium dioxide-ethanol aqueous solution is added, stirred at 70℃ for 5 hours, filtered, washed and dried to obtain the aminated titanium dioxide;

[0050] Step 1: the aminated titanium dioxide is added to N-methyl aniline and uniformly mixed to obtain a polyamine complex; wherein the mass ratio of the amino branched titanium dioxide and N-methyl aniline is 2:1;

[0051] Step 2: 60 parts of terpene phenolic resin, 25 parts of methyl phenyl silicone resin, 20 parts of additive are uniformly mixed, 12 parts of the polyamine complex and 10 parts of calcium hydroxide are added and uniformly mixed to obtain the high adhesion asphalt anti-stripping agent.

[0052] Comparative Example 3 is based on Example 2, and 9, 9-bis (4-aminophenyl) fluorene is not introduced;

[0053] The raw materials are pre-prepared; the preparation method of the additive is: 3.02 parts of trimethylolpropane triglycidyl ether and 0.9 parts of 1, 4-butanediol are uniformly mixed, heated to 115℃ under nitrogen atmosphere, 0.18 parts of tetrabutylammonium bromide is added, stirred for 24 hours, cooled to room temperature, and then added to deionized water after uniformly mixed with tetrahydrofuran, and precipitated, repeated three times; centrifuged, washed and dried to obtain the additive;

[0054] The preparation method of the amino branched titanium dioxide is: (1) 3-aminopropyl triethoxysilane is added into an ethanol aqueous solution (the concentration is 80 wt%) and uniformly mixed for 40 minutes, titanium dioxide-ethanol aqueous solution is added, stirring is carried out at 70°C for 5 hours, filtration, washing and drying are carried out, and amino titanium dioxide is obtained; wherein the mass ratio of 3-aminopropyl triethoxysilane to titanium dioxide is 0.08:1; (2) under the protection of nitrogen, 2 parts of amino titanium dioxide and 0.3 parts of diethylenetriamine are ultrasonically dispersed in methanol, 0.82 parts of methyl acrylate is added, stirring is carried out at 40°C for 12 hours, the temperature is increased to 150°C, and stirring is carried out for 5 hours, and amino branched titanium dioxide is obtained;

[0055] Step 1: the amino branched titanium dioxide is added into N-methylaniline and uniformly mixed, and a polyamine composite is obtained; wherein the mass ratio of the amino branched titanium dioxide to N-methylaniline is (2-3):1;

[0056] Step 2: 60 parts of terpene phenolic resin, 25 parts of methylphenyl silicone resin and 20 parts of an additive are uniformly mixed, 12 parts of the polyamine composite and 10 parts of calcium hydroxide are added, and uniform mixing is carried out, and high-adhesion asphalt anti-stripping agent is obtained.

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

[0058] The raw material is prepared in advance; the preparation method of the additive is: (1) 3.48 parts of 9,9-bis(4-aminophenyl)fluorene is added into 20 parts of DMF at 70°C and uniformly mixed, 3.02 parts of trimethylolpropane triglycidyl ether and 0.15 parts of triethylamine are added, reaction is carried out for 5 hours, and the solvent is removed, and an intermediate product is obtained; (2) 6.51 parts of the intermediate product is uniformly mixed with 0.9 parts of 1,4-butanediol, heated to 115°C under a nitrogen atmosphere, 0.18 parts of tetrabutylammonium bromide is added, stirring is carried out for 24 hours, the temperature is cooled to room temperature, and the solvent is removed, and the additive is obtained;

[0059] The preparation method of the amino branched titanium dioxide is: (1) 3-aminopropyl triethoxysilane is added into an ethanol aqueous solution (the concentration is 80 wt%) and uniformly mixed for 40 minutes, titanium dioxide-ethanol aqueous solution is added, stirring is carried out at 70°C for 5 hours, filtration, washing and drying are carried out, and amino titanium dioxide is obtained; wherein the mass ratio of 3-aminopropyl triethoxysilane to titanium dioxide is 0.08:1; (2) under the protection of nitrogen, 2 parts of amino titanium dioxide and 0.3 parts of diethylenetriamine are ultrasonically dispersed in methanol, 0.82 parts of methyl acrylate is added, stirring is carried out at 40°C for 12 hours, the temperature is increased to 150°C, and stirring is carried out for 5 hours, and amino branched titanium dioxide is obtained;

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

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

[0062] Detection test; (1) 100 g of No. 70 base asphalt was heated to 150° C., and 0.3 g of the high-adhesion asphalt anti-stripping agent prepared in Examples 1 to 3 and Comparative Examples 1 to 4 was added under high-speed stirring, and mixed uniformly at 1000 r / min for 5 minutes to obtain anti-stripping asphalt;

[0063] (2) Take 6 pieces of the above-prepared anti-stripping asphalt and place them in a UV aging box with an ultraviolet intensity of 1200 μw / cm 2 The aging temperature was 60°C and the aging time was 5 days. 42 basalt particles with a size of 15 to 20 mm were washed and dried, and the mass of 6 aggregates of each particle was weighed. The aggregates were placed in preheated anti-stripping asphalt (anti-stripping asphalt before and after aging) and mixed for 50 seconds. The excess anti-stripping asphalt was removed by hanging and cooled at 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 Procedure for Asphalt and Asphalt Mixtures for Highway Engineering" (JTGE20-2011).

[0064] Table 1

[0065] Area peeling rate 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] Conclusion: Comparative Example 1 is based on Example 2, and only N-methylaniline is introduced; this results in a decrease in the aging resistance of the anti-stripping agent, thereby reducing the adhesion performance of the anti-stripping asphalt; Comparative Example 2 is based on Example 2, and amino-branched titanium dioxide is replaced with amino-ditioic acid titanium dioxide; because amino-ditioic acid titanium dioxide is not a three-dimensional network structure, the water resistance and aging resistance of the anti-stripping agent are reduced, thereby reducing the adhesion performance of the anti-stripping asphalt; Comparative Example 3 is based on Example 2, and 9,9-bis(4-aminophenyl)fluorene is not introduced; this reduces the strong hydrophobicity and aging resistance of the additive, thereby affecting the performance of the asphalt anti-stripping agent; Comparative Example 4 is based on Example 2, and the mass ratio of amino-branched titanium dioxide and N-methylaniline is increased to 5:1; this results in an increase in the brittleness of the anti-stripping agent, thereby reducing the performance of the asphalt anti-stripping agent.

[0067] It will be apparent to those skilled in the art that the application is not limited to the details of the above-exemplified embodiments and that the present application can be implemented in other particular forms without departing from the spirit or essential characteristics of the present application. The embodiments should therefore be considered in all respects as illustrative and not restrictive, the scope of the application being indicated by the appended claims rather than by the above description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

Claims

1. A method for preparing a high-adhesion asphalt anti-stripping agent, characterized in that: The following steps are included: Step 1: adding amino-branched titanium dioxide to N-methylaniline and uniformly mixing to obtain a polyamine complex; Step 2: Evenly mix the terpene phenolic resin, methylphenyl silicone resin and additives, add the polyamine complex and calcium hydroxide, and evenly mix to obtain a high-adhesion asphalt anti-stripping agent.

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: 50 to 60 parts of terpene phenolic resin, 20 to 30 parts of methylphenyl silicone resin, 10 to 20 parts of additives, 8 to 12 parts of polyamine complex, and 10 to 13 parts of calcium hydroxide, calculated by mass.

3. The method for preparing a high-adhesion asphalt anti-stripping agent according to claim 1, characterized in that: The mass ratio of the amino-branched titanium dioxide to N-methylaniline is (2-3):

1.

4. The method for preparing a high-adhesion asphalt anti-stripping agent according to claim 1, characterized in that: The preparation method of the additive is as follows: (1) adding 9,9-bis(4-aminophenyl)fluorene to DMF at 60-70° C. and uniformly mixing, adding trimethylolpropane triglycidyl ether and triethylamine, reacting for 4-6 hours, removing the solvent, and obtaining an intermediate product; (2) uniformly mixing the intermediate product with 1,4-butanediol, heating to 100-115° C. under a nitrogen atmosphere, adding tetrabutylammonium bromide, stirring for 20-24 hours, cooling to room temperature, adding tetrahydrofuran and uniformly mixing, adding the mixture to deionized water for precipitation, centrifuging, washing, and drying to obtain the additive.

5. The method for preparing a high-adhesion asphalt anti-stripping agent according to claim 4, characterized in that: The raw materials of the intermediate product include the following components: 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, calculated by mass.

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

7. The method for preparing a high-adhesion asphalt anti-stripping agent according to claim 1, characterized in that: The preparation method of the amino-branched titanium dioxide is as follows: (1) adding 3-aminopropyltriethoxysilane to an ethanol aqueous solution and uniformly mixing for 30 to 40 minutes, adding titanium dioxide-ethanol aqueous solution, stirring at 60 to 75° C. for 5 to 6 hours, filtering, washing, and drying to obtain amino-branched titanium dioxide; (2) under nitrogen protection, ultrasonically dispersing amino-branched titanium dioxide and diethylenetriamine in methanol, adding methyl acrylate, stirring at 30 to 40° C. for 8 to 12 hours, heating to 150 to 165° C., and stirring for 3 to 6 hours to obtain amino-branched titanium dioxide.

8. The method for preparing a high-adhesion asphalt anti-stripping agent according to claim 7, characterized in that: The mass ratio of the 3-aminopropyltriethoxysilane to titanium dioxide is (0.05-0.1):1; the raw materials of the amino-branched titanium dioxide include the following components: 1.5-2.5 parts of amino-branched titanium dioxide, 0.3-0.4 parts of diethylenetriamine, and 0.82-0.85 parts of methyl acrylate, calculated by mass.

9. A high-adhesion asphalt anti-stripping agent prepared according to the method for preparing a high-adhesion asphalt anti-stripping agent according to any one of claims 1 to 8.