Polymer pavement modifier and preparation method thereof

Abstract

The invention relates to the technical field of road engineering materials, in particular to a polymer pavement modifier and a preparation method thereof. The polymer pavement modifier comprises a component A and a component B, wherein the component A consists of epoxy resin, epoxy polyurethane, a titanate coupling agent and an epoxy active diluent; the component B consists of a silicon-containing flame-retardant curing agent, an amine curing agent, an anhydride curing agent and an accelerant; wherein the epoxy polyurethane is obtained by epoxidizing hydroxyl-terminated polybutadiene, then carrying out a prepolymerization reaction on the epoxidized hydroxyl-terminated polybutadiene and diisocyanate, and then carrying out a chain extension reaction, and the silicon-containing flame-retardant curing agent is obtained by reacting phenyl phosphonic dichloride, vanillin and 1, 3-bis (3-aminopropyl)-1, 1, 3, 3-tetramethyldisiloxane according to a molar ratio of 1: 2: 2. The polymer pavement modifier prepared by the invention can effectively improve the performance of asphalt, is suitable for paving and repairing pavements of steel bridge decks, tunnels, expressways and the like, and improves the traffic safety.

Description

Technical Field

[0001] The present invention relates to the technical field of road engineering materials, in particular to a polymer pavement modifier and a preparation method thereof. Background Art

[0002] Asphalt is an organic cementitious material commonly used in road construction. With the continuous development of the transportation industry, traditional asphalt concrete pavements are prone to rutting, cracking, and fatigue damage under heavy traffic conditions. Polymers are often used to modify asphalt to meet practical transportation needs.

[0003] Polymer modifiers used for asphalt modification are primarily categorized into three types: rubber, resin, and thermoplastic elastomer. Rubber modifiers include natural rubber, styrene-butadiene rubber, and polychloroprene rubber. Chinese Patent CN201410638673.X discloses a styrene-butadiene rubber-modified asphalt mixture and its preparation method. By mixing styrene-butadiene latex with emulsified asphalt, the mixture improves the asphalt's low-temperature crack resistance, but its high-temperature deformation resistance is poor. Resin modifiers, such as epoxy resin, can effectively improve the high-temperature stability of the base asphalt, but epoxy resins lack toughness and exhibit poor low-temperature crack resistance. Chinese Patent CN201410854109.1 discloses an asphalt modification and enhancement additive and its application. Mixing rubber powder with epoxy resin overcomes the low-temperature limitations of epoxy resin-modified asphalt alone, but poor compatibility between rubber and epoxy resins compromises the modification effect. Using both thermoplastic elastomers and epoxy resins as modifiers can effectively improve the base asphalt's high-temperature stability and low-temperature performance. Furthermore, most commonly used polymer modifiers are flammable. Fires on roads such as tunnels and highways often make evacuation and firefighting difficult, posing a serious threat to public safety. Therefore, there is a pressing need for a polymer pavement modifier for base asphalt modification to overcome these challenges. Summary of the Invention

[0004] The object of the present invention is to provide a polymer pavement modifier and a preparation method thereof to solve the problems raised in the above background technology.

[0005] In order to solve the above technical problems, the present invention provides the following technical solution: a polymer pavement modifier, comprising component A and component B, wherein component A and component B are mixed in a weight ratio of 1:(0.58-0.71); wherein: Component A comprises: by weight, 100 parts of epoxy resin, 6 to 9 parts of epoxy polyurethane, 2 to 4 parts of titanate coupling agent, and 6 to 8 parts of epoxy reactive diluent; Component B includes: 50-60 parts of silicon-containing flame retardant curing agent, 25-35 parts of amine curing agent, 0-5 parts of acid anhydride curing agent, and 1-2 parts of accelerator.

[0006] Furthermore, the preparation method of epoxy polyurethane is: S1: Dissolve hydroxybutane rubber in a cyclohexane / tetrahydrofuran solution, add m-chloroperbenzoic acid, react at 30-35°C, remove the cyclohexane / tetrahydrofuran solution solvent by distillation under reduced pressure, add anhydrous ethanol to purify and remove by-products, and dry the product at 40-50°C to constant weight to obtain epoxy hydroxybutane rubber; S2: Epoxy hydroxybutane rubber is dispersed in tetrahydrofuran, diisocyanate is added, and dibutyltin dilaurate is used as a catalyst. The reaction is carried out at 30-40°C for 60-90 minutes under nitrogen protection to obtain a prepolymer; 1,4-butanediol is added as a chain extender, and the reaction is continued for 60-90 minutes. The tetrahydrofuran is removed under reduced pressure to obtain an epoxy polyurethane.

[0007] Furthermore, in S1, in the cyclohexane / tetrahydrofuran solution, the volume ratio of cyclohexane to tetrahydrofuran is 4:1.

[0008] Furthermore, in S1, the weight ratio of m-chloroperbenzoic acid to hydroxybutyl rubber is (18-22):100.

[0009] Furthermore, in S2, the diisocyanate is any one or more of isophorone diisocyanate, toluene diisocyanate, and diphenylmethane diisocyanate.

[0010] Furthermore, in S2, epoxy hydroxybutane rubber reacts with diisocyanate at a molar ratio of hydroxyl group to isocyanate group of 1:(1.6~1.8).

[0011] Furthermore, in S2, during the chain extension reaction, the chain extension coefficient is 0.8 to 0.85.

[0012] Furthermore, the epoxy reactive diluent is any one or more of phenyl glycidyl ether, benzyl alcohol glycidyl ether, cardanol glycidyl ether, castor oil triglycidyl ether, and epoxidized soybean oil.

[0013] Furthermore, the preparation method of the silicon-containing flame retardant curing agent comprises the following steps: Vanillin is dispersed in ethyl acetate, and triethylamine is used as an acid-binding agent. Phenylphosphoryl dichloride is added under nitrogen protection at 0-5°C, and the temperature is raised to 55-60°C with stirring for 24 hours. The precipitate is removed by filtration, and the filtrate is washed with saturated brine. The filtrate is concentrated and recrystallized to obtain a phosphorus-containing intermediate; the intermediate is dispersed in anhydrous ethanol, and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane is added under nitrogen environment. The temperature is raised to 50-60°C and the reaction is carried out for 6-8 hours to obtain a silicon-containing flame retardant curing agent.

[0014] Furthermore, the molar ratio of phenylphosphoryl dichloride, vanillin, and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane is 1:2:2.

[0015] Furthermore, the amine curing agent is any one or more of octadecyl primary amine, oleylamine, decylamine, and cardanol aldehyde amine.

[0016] Furthermore, the acid anhydride curing agent is any one or more of tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and methylhexahydrophthalic anhydride.

[0017] Furthermore, the accelerator is any one or more of a tertiary amine accelerator, a phenol accelerator, and an imidazole accelerator.

[0018] Compared with the prior art, the beneficial effect achieved by the present invention is as follows: the present invention uses epoxy polyurethane, epoxy resin, etc. as component A, and silicon-containing flame retardant curing agent, amine curing agent, acid anhydride curing agent, etc. as component B, and mixes components A and B to obtain a polymer pavement modifier for asphalt modification.

[0019] In component A of the present invention, epoxy polyurethane is prepared by first reacting butyl hydroxyl rubber with meta-chloroperbenzoic acid, then polymerizing with diisocyanate, and finally undergoing a chain extension reaction. Its molecular chain segments contain epoxy groups, which can undergo a cross-linking reaction with epoxy resin under the action of a curing agent, effectively improving the compatibility of the two, and the mechanical properties of the polymer modifier after curing are better. In component B, phenylphosphoryl dichloride, vanillin, and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane are reacted in sequence. The phenolic hydroxyl group in vanillin first reacts with phenylphosphoryl dichloride, and the aldehyde group then reacts with 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane to obtain a silicon-containing flame retardant curing agent with an amino end group, wherein the silicon, phosphorus, and nitrogen elements produce a synergistic effect to jointly improve the flame retardant efficiency. Compared with traditional curing agents, silicon-containing flame retardant curing agents also contain flexible Si-O-Si segments, which work together with epoxy polyurethane to improve the toughness of epoxy resin.

[0020] The polymer pavement modifier of the present invention is mixed with asphalt. After curing, the polymer forms a three-dimensional network cross-linked structure, which wraps the asphalt, thereby changing the thermoplasticity of the asphalt. The introduction of epoxy resin, polyurethane and silicone chain segments improves the heat resistance, cold resistance and fatigue resistance of the asphalt, making it suitable for paving and repairing steel bridge decks, tunnels, highways and other roads. At the same time, it can also effectively reduce the risk of road fires and improve public transportation safety. DETAILED DESCRIPTION

[0021] The technical solutions in the embodiments of the present application will be clearly and completely described below with the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments of the present application, all other embodiments obtained by a person of ordinary skill in the art without creative work fall within the protection scope of the present application.

[0022] The materials used in the present application and their sources: the epoxy resin is bisphenol A type epoxy resin E51 from Hebei Linyuan Fine Chemical Co., Ltd.; the titanate coupling agent is TC-311 from Tianchang Tianchen Chemical Auxiliary Oil Factory; the hydroxyl-terminated polybutadiene is from Liming Chemical Research Institute, and the average molecular weight is 4000; the epoxy active diluent is cashew phenol glycidyl ether from Hubei Jusheng Technology Co., Ltd., and the item number is JS4129; the accelerator is 2-methylimidazole from Japan Shikoku Chemicals, and the model number is 2MZ-A.

[0023] Embodiment 1: A preparation method of a polymer pavement modifier, comprising the following steps: Step 1: 100 kg of epoxy resin, 6 kg of epoxy-based polyurethane, 2 kg of titanate coupling agent, and 6 kg of epoxy active diluent are mixed to obtain component A; The preparation method of the epoxy-based polyurethane is as follows: S1: The hydroxyl-terminated polybutadiene is dissolved in a cyclohexane / tetrahydrofuran solution (the volume ratio of cyclohexane to tetrahydrofuran is 4:1), and meta-chloroperoxybenzoic acid is added, and the weight ratio of meta-chloroperoxybenzoic acid to hydroxyl-terminated polybutadiene is 18:100; the reaction is carried out at 30℃, and the solvent cyclohexane / tetrahydrofuran solution is removed by reduced pressure distillation; after the by-product is removed by adding anhydrous ethanol for purification, the product is dried at 40℃ until the weight is constant, to obtain epoxy-based hydroxyl-terminated polybutadiene; S2: The epoxy-based hydroxyl-terminated polybutadiene is dispersed in tetrahydrofuran, isophorone diisocyanate is added in a molar ratio of hydroxyl to isocyanate group of 1:1.6, and dibutyltin dilaurate is used as a catalyst, and the reaction is carried out at 30℃ for 60 min under nitrogen protection, to obtain a prepolymer; 1,4-butanediol is added as a chain extender, the chain extension coefficient is 0.8, and the reaction is continued for 60 min, and the tetrahydrofuran is removed by reduced pressure, to obtain the epoxy-based polyurethane.

[0024] Step 2: 50 kg of a silicon-containing flame-retardant curing agent, 25 kg of octadecyl primary amine, and 1 kg of an accelerator are mixed to obtain component B; The preparation method of the silicon-containing flame-retardant curing agent comprises the following steps: Vanillin is dispersed in ethyl acetate, triethylamine is used as an acid-binding agent, phenylphosphoryl dichloride is added at 0°C under nitrogen protection, the temperature is raised to 55°C with stirring, and the reaction is carried out for 24 hours. The precipitate is filtered to remove, and the filtrate is washed with saturated brine. The filtrate is concentrated and recrystallized to obtain a phosphorus-containing intermediate; the intermediate is dispersed in anhydrous ethanol, 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane is added under nitrogen environment, the temperature is raised to 50°C, and the reaction is carried out for 6 hours to obtain a silicon-containing flame retardant curing agent, wherein the molar ratio of phenylphosphoryl dichloride, vanillin, and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane is 1:2:2; Step 3: Component A and component B are mixed in a weight ratio of 1:0.58 to obtain a polymer pavement modifier.

[0025] Example 2: A method for preparing a polymer pavement modifier, comprising the following steps: Step 1: 100 kg of epoxy resin, 7 kg of epoxy polyurethane, 3.4 kg of titanate coupling agent, and 7.1 kg of epoxy reactive diluent were mixed to obtain component A; Wherein, the preparation method of epoxy polyurethane is: S1: Dissolve HTBR in a cyclohexane / tetrahydrofuran solution (cyclohexane:tetrahydrofuran volume ratio of 4:1), add m-chloroperbenzoic acid, and the weight ratio of m-chloroperbenzoic acid to HTBR is 20:100; react at 33°C, remove the cyclohexane / tetrahydrofuran solution solvent by vacuum distillation, add anhydrous ethanol to purify and remove by-products, and dry the product at 45°C to constant weight to obtain epoxy HTBR; S2: Disperse epoxy hydroxybutane rubber in tetrahydrofuran, add toluene diisocyanate at a molar ratio of hydroxyl group to isocyanate group of 1:1.7, use dibutyltin dilaurate as a catalyst, and react at 35°C under nitrogen protection for 70 minutes to obtain a prepolymer; add 1,4-butanediol as a chain extender with a chain extension coefficient of 0.82, continue the reaction for 80 minutes, and remove tetrahydrofuran under reduced pressure to obtain epoxy polyurethane.

[0026] Step 2: 55 kg of a silicon-containing flame retardant curing agent, 31 kg of oleylamine, 2 kg of tetrahydrophthalic anhydride, and 1.2 kg of an accelerator were mixed to obtain component B; The preparation method of the silicon-containing flame retardant curing agent comprises the following steps: Vanillin is dispersed in ethyl acetate, triethylamine is used as an acid-binding agent, phenylphosphoryl dichloride is added at 3°C ​​under nitrogen protection, the temperature is raised to 58°C with stirring, and the reaction is carried out for 24 hours. The precipitate is filtered to remove, and the filtrate is washed with saturated brine. The filtrate is concentrated and recrystallized to obtain a phosphorus-containing intermediate; the intermediate is dispersed in anhydrous ethanol, 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane is added under nitrogen environment, and the temperature is raised to 55°C and the reaction is carried out for 7 hours to obtain a silicon-containing flame retardant curing agent, wherein the molar ratio of phenylphosphoryl dichloride, vanillin, and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane is 1:2:2; Step 3: Component A and component B are mixed in a weight ratio of 1:0.63 to obtain a polymer pavement modifier.

[0027] Example 3: A method for preparing a polymer pavement modifier, comprising the following steps: Step 1: 100 kg of epoxy resin, 9 kg of epoxy polyurethane, 4 kg of titanate coupling agent, and 8 kg of epoxy reactive diluent are mixed to obtain component A; Wherein, the preparation method of epoxy polyurethane is: S1: Dissolve HTBR in a cyclohexane / tetrahydrofuran solution (cyclohexane:tetrahydrofuran volume ratio of 4:1), add m-chloroperbenzoic acid, and the weight ratio of m-chloroperbenzoic acid to HTBR is 22:100; react at 35°C, remove the cyclohexane / tetrahydrofuran solution solvent by vacuum distillation, add anhydrous ethanol to purify and remove by-products, and dry the product at 50°C to constant weight to obtain epoxy HTBR; S2: Disperse epoxy hydroxybutane rubber in tetrahydrofuran, add diphenylmethane diisocyanate at a molar ratio of hydroxyl group to isocyanate group of 1:1.8, use dibutyltin dilaurate as a catalyst, and react at 40°C under nitrogen protection for 90 minutes to obtain a prepolymer; add 1,4-butanediol as a chain extender with a chain extension coefficient of 0.85, continue the reaction for 90 minutes, and remove tetrahydrofuran under reduced pressure to obtain epoxy polyurethane.

[0028] Step 2: 60 kg of a silicon-containing flame retardant curing agent, 35 kg of decylamine, 5 kg of methyltetrahydrophthalic anhydride, and 2 kg of an accelerator were mixed to obtain component B; The preparation method of the silicon-containing flame retardant curing agent comprises the following steps: Vanillin is dispersed in ethyl acetate, triethylamine is used as an acid-binding agent, phenylphosphoryl dichloride is added at 5°C under nitrogen protection, the temperature is raised to 60°C with stirring, and the reaction is carried out for 24 hours. The precipitate is removed by filtration, and the filtrate is washed with saturated brine. The filtrate is concentrated and recrystallized to obtain a phosphorus-containing intermediate; the intermediate is dispersed in anhydrous ethanol, 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane is added under nitrogen environment, the temperature is raised to 60°C, and the reaction is carried out for 8 hours to obtain a silicon-containing flame retardant curing agent, wherein the molar ratio of phenylphosphoryl dichloride, vanillin, and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane is 1:2:2; Step 3: Component A and component B are mixed in a weight ratio of 1:0.71 to obtain a polymer pavement modifier.

[0029] Comparative Example 1: No epoxy group was introduced into the polyurethane, and the other parameters were the same as those in Example 1.

[0030] Step 1: 100 kg epoxy resin, 6 kg polyurethane, 2 kg titanate coupling agent, and 6 kg epoxy reactive diluent are mixed to obtain component A; Among them, the preparation method of polyurethane is as follows: dispersing butyl hydroxyl rubber in tetrahydrofuran, adding isophorone diisocyanate at a molar ratio of hydroxyl group to isocyanate group of 1:1.6, using dibutyltin dilaurate as a catalyst, reacting at 30°C for 60 minutes under nitrogen protection to obtain a prepolymer; adding 1,4-butanediol as a chain extender with a chain extension coefficient of 0.8, continuing the reaction for 60 minutes, removing tetrahydrofuran under reduced pressure, and obtaining polyurethane.

[0031] Step 2: Mix 50 kg of silicon-containing flame retardant curing agent, 25 kg of octadecyl primary amine, and 1 kg of accelerator to obtain component B; The preparation method of the silicon-containing flame retardant curing agent comprises the following steps: Vanillin is dispersed in ethyl acetate, triethylamine is used as an acid-binding agent, phenylphosphoryl dichloride is added at 0°C under nitrogen protection, the temperature is raised to 55°C with stirring, and the reaction is carried out for 24 hours. The precipitate is filtered to remove, and the filtrate is washed with saturated brine. The filtrate is concentrated and recrystallized to obtain a phosphorus-containing intermediate; the intermediate is dispersed in anhydrous ethanol, 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane is added under nitrogen environment, the temperature is raised to 50°C, and the reaction is carried out for 6 hours to obtain a silicon-containing flame retardant curing agent, wherein the molar ratio of phenylphosphoryl dichloride, vanillin, and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane is 1:2:2; Step 3: Component A and component B are mixed in a weight ratio of 1:0.58 to obtain a polymer pavement modifier.

[0032] Comparative Example 2: No silicon-containing flame retardant curing agent was added, and the remaining parameters were the same as those in Example 2.

[0033] Step 1: 100 kg of epoxy resin, 7 kg of epoxy polyurethane, 3.4 kg of titanate coupling agent, and 7.1 kg of epoxy reactive diluent were mixed to obtain component A; Wherein, the preparation method of epoxy polyurethane is: S1: Dissolve HTBR in a cyclohexane / tetrahydrofuran solution (cyclohexane:tetrahydrofuran volume ratio of 4:1), add m-chloroperbenzoic acid, and the weight ratio of m-chloroperbenzoic acid to HTBR is 20:100; react at 33°C, remove the cyclohexane / tetrahydrofuran solution solvent by vacuum distillation, add anhydrous ethanol to purify and remove by-products, and dry the product at 45°C to constant weight to obtain epoxy HTBR; S2: Disperse epoxy hydroxybutane rubber in tetrahydrofuran, add toluene diisocyanate at a molar ratio of hydroxyl group to isocyanate group of 1:1.7, use dibutyltin dilaurate as a catalyst, and react at 35°C under nitrogen protection for 70 minutes to obtain a prepolymer; add 1,4-butanediol as a chain extender with a chain extension coefficient of 0.82, continue the reaction for 80 minutes, and remove tetrahydrofuran under reduced pressure to obtain epoxy polyurethane.

[0034] Step 2: 31 kg of oleylamine, 2 kg of anhydride tetrahydrophthalic anhydride, and 1.2 kg of accelerator were mixed to obtain component B; Step 3: Component A and component B are mixed in a weight ratio of 1:0.63 to obtain a polymer pavement modifier.

[0035] Comparative Example 3: The silicon-containing flame retardant curing agent was replaced with magnesium hydroxide powder (from Dalian Yatai Technology New Materials Co., Ltd., activated magnesium hydroxide flame retardant model number YX105). The other parameters were the same as those in Example 3.

[0036] Step 1: 100 kg of epoxy resin, 9 kg of epoxy polyurethane, 4 kg of titanate coupling agent, and 8 kg of epoxy reactive diluent are mixed to obtain component A; Wherein, the preparation method of epoxy polyurethane is: S1: Dissolve HTBR in a cyclohexane / tetrahydrofuran solution (cyclohexane:tetrahydrofuran volume ratio of 4:1), add m-chloroperbenzoic acid, and the weight ratio of m-chloroperbenzoic acid to HTBR is 22:100; react at 35°C, remove the cyclohexane / tetrahydrofuran solution solvent by vacuum distillation, add anhydrous ethanol to purify and remove by-products, and dry the product at 50°C to constant weight to obtain epoxy HTBR; S2: Disperse epoxy hydroxybutane rubber in tetrahydrofuran, add diphenylmethane diisocyanate at a molar ratio of hydroxyl group to isocyanate group of 1:1.8, use dibutyltin dilaurate as a catalyst, and react at 40°C under nitrogen protection for 90 minutes to obtain a prepolymer; add 1,4-butanediol as a chain extender with a chain extension coefficient of 0.85, continue the reaction for 90 minutes, and remove tetrahydrofuran under reduced pressure to obtain epoxy polyurethane.

[0037] Step 2: 60 kg of magnesium hydroxide, 35 kg of decylamine, 5 kg of methyltetrahydrophthalic anhydride, and 2 kg of accelerator were mixed to obtain component B; Step 3: Component A and component B are mixed in a weight ratio of 1:0.71 to obtain a polymer pavement modifier.

[0038] Experiment 1: The polymer pavement modifiers prepared in Examples 1 to 3 and Comparative Examples 1 to 3 were mixed with 70# base asphalt (from China National Offshore Oil Corporation) in a weight ratio of 1:1 to obtain modified asphalt. The modified asphalt was cured under the following curing conditions: 180°C / 3h+60°C / 4d. The GB / T 528-2009 standard was adopted, and the specimens were prepared according to Type II test strips at a tensile rate of 500 mm / min. The limiting oxygen index was used to test the flame retardancy. The experimental results are shown in Table 1. Table 1. Test results of various properties of modified asphalt Experiment 2: 9 kg of aggregate, 1 kg of mineral powder (aggregate from Jiangsu Jurong Maodi Group Co., Ltd., mineral powder from Shandong Kefa Building Materials Co., Ltd., both EA-10 grade), and 0.7 kg of the modified asphalt from Experiment 1 were added to the mixture. The mixture was heated to 165°C, mixed for 2 minutes, compacted using a roller roller method, and cured at 60°C for 4 days to produce a modified asphalt mixture. Samples were prepared and tested for Marshall stability, Marshall flow value (60°C, 50 mm / min), and failure strain at -10°C using the methods specified in the "Test Procedure for Asphalt-Based Asphalt Mixtures for Highway Engineering" (JTG E20-2011). The results are shown in Table 2.

[0039] Table 2. Test results of modified asphalt mixture

[0040] Conclusion: In Experiment 1, the data from Example 1 and Comparative Example 1 show that the introduction of epoxy groups into polyurethane improves the compatibility of polyurethane with epoxy resin, resulting in a better modification effect and effectively improving the mechanical properties of asphalt. The data from Example 2 and Comparative Example 2 show that after adding a silicon-containing flame retardant curing agent, the polymer pavement modifier has better toughness and good flame retardant properties. The data from Example 3 and Comparative Example 3 show that compared with the magnesium hydroxide flame retardant, the addition of a silicon-containing flame retardant curing agent has a stronger flame retardant effect and effectively avoids the problem of poor compatibility between inorganic flame retardant materials and organic polymers causing a decrease in mechanical properties. In addition, the data from Experiment 2 show that the performance of the modified asphalt mixture prepared with the polymer pavement modifiers in Examples 1-3 is significantly better than that of Comparative Examples 1-3.

[0041] It should be noted that, in this document, relational terms such as first and second, etc., are used only to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual relationship or order between these entities or operations. Moreover, the terms "comprises," "comprising," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that includes a list of elements includes not only those elements but also other elements not explicitly listed, or elements inherent to such process, method, article, or apparatus.

[0042] Finally, it should be noted that the above descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art will be able to modify the technical solutions described in the aforementioned embodiments or substitute equivalents for some of the technical features. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention shall be included within the scope of protection of the present invention.

Claims

1. A method for preparing a polymer pavement modifier, characterized in that: The following steps are involved: Step 1: Mix 100 parts of epoxy resin, 6 to 9 parts of epoxy polyurethane, 2 to 4 parts of titanate coupling agent, and 6 to 8 parts of epoxy reactive diluent by weight to obtain component A; Step 2: Mix 50-60 parts of a silicon-containing flame retardant curing agent, 25-35 parts of an amine curing agent, 0-5 parts of an acid anhydride curing agent, and 1-2 parts of an accelerator, by weight, to obtain component B; Step 3: Mix component A and component B in a weight ratio of 1: (0.58~0.71) to obtain a polymer pavement modifier.

2. The method for preparing a polymer pavement modifier according to claim 1, wherein: In step 1, the preparation method of epoxy polyurethane is: S1: Dissolve hydroxybutane rubber in a cyclohexane / tetrahydrofuran solution, add m-chloroperbenzoic acid; react at 30-35°C, remove the cyclohexane / tetrahydrofuran solution solvent by vacuum distillation, add anhydrous ethanol to purify and remove by-products, and dry the product at 40-50°C to constant weight to obtain epoxy hydroxybutane rubber; S2: Disperse epoxy hydroxybutane rubber in tetrahydrofuran, add diisocyanate, use dibutyltin dilaurate as catalyst, react at 30-40°C for 60-90 minutes under nitrogen protection to obtain a prepolymer; add 1,4-butanediol as a chain extender, continue the reaction for 60-90 minutes, remove tetrahydrofuran under reduced pressure to obtain epoxy polyurethane.

3. The method for preparing the polymer pavement modifier according to claim 2, wherein: In S1, the weight ratio of m-chloroperbenzoic acid to hydroxybutyl rubber is (18~22):

100.

4. The method for preparing a polymer pavement modifier according to claim 2, wherein: In S2, epoxy hydroxybutane rubber and diisocyanate react at a molar ratio of hydroxyl group to isocyanate group of 1:(1.6~1.8); during the chain extension reaction, the chain extension coefficient is 0.8~0.

85.

5. The method for preparing the polymer pavement modifier according to claim 2, wherein: In S2, the diisocyanate is any one or more of isophorone diisocyanate, toluene diisocyanate, and diphenylmethane diisocyanate.

6. The method for preparing a polymer pavement modifier according to claim 1, wherein: In step 1, the epoxy reactive diluent is any one or more of phenyl glycidyl ether, benzyl alcohol glycidyl ether, cardanol glycidyl ether, castor oil triglycidyl ether, and epoxidized soybean oil.

7. The method for preparing a polymer pavement modifier according to claim 1, wherein: In step 2, the preparation method of the silicon-containing flame retardant curing agent is: Vanillin is dispersed in ethyl acetate, and triethylamine is used as an acid-binding agent. Phenylphosphoryl dichloride is added under nitrogen protection at 0-5°C, and the temperature is raised to 55-60°C with stirring for 24 hours. The precipitate is removed by filtration, and the filtrate is washed with saturated brine. The filtrate is concentrated and recrystallized to obtain a phosphorus-containing intermediate; the intermediate is dispersed in anhydrous ethanol, and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane is added under nitrogen environment. The temperature is raised to 50-60°C and the reaction is carried out for 6-8 hours to obtain a silicon-containing flame retardant curing agent.

8. The method for preparing a polymer pavement modifier according to claim 7, wherein: The molar ratio of phenylphosphoryl dichloride, vanillin and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane is 1:2:

2.

9. The method for preparing a polymer pavement modifier according to claim 1, wherein: In step 2, the amine curing agent is any one or more of octadecyl primary amine, oleylamine, decylamine, and cardanol aldehyde amine; the acid anhydride curing agent is any one or more of tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and methylhexahydrophthalic anhydride; and the accelerator is any one or more of a tertiary amine accelerator, a phenol accelerator, and an imidazole accelerator.

10. The polymer pavement modifier prepared by the preparation method according to any one of claims 1 to 9.

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