A polymer pavement modifier and a method for preparing the same

Abstract

The present application 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 component A composed of epoxy resin, epoxy-based polyurethane, titanate coupling agent and epoxy active diluent, and component B composed of silicon-containing flame-retardant curing agent, amine curing agent, acid anhydride curing agent and accelerator; wherein the epoxy-based polyurethane is obtained by pre-polymerization of diisocyanate after epoxydation of hydroxyl-terminated butadiene rubber, and then chain extension reaction; the silicon-containing flame-retardant curing agent is obtained by reaction of phenylphosphoryl dichloride, vanillin and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane in a molar ratio of 1:2:2. The polymer pavement modifier prepared by the present application can effectively improve the performance of asphalt, and is suitable for pavement and repair of steel bridge deck, tunnel, highway and the like, and improves traffic safety.

Description

Technical Field

[0001] This invention relates to the field of road engineering materials technology, specifically to a polymer pavement modifier and its preparation method. Background Technology

[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 problems such as rutting, cracking, and fatigue damage under heavy traffic conditions. Polymers are usually used to modify asphalt to meet the actual transportation needs.

[0003] Polymer modifiers used for asphalt modification are mainly classified into three types: rubber-based, resin-based, and thermoplastic elastomers. Rubber-based modifiers include natural rubber, styrene-butadiene rubber (SBR), and polychloroprene rubber (PCB). Chinese patent CN201410638673.X discloses a SBR-modified asphalt mixture and its preparation method, which improves the low-temperature crack resistance of asphalt by mixing SBR latex with emulsified asphalt, but its high-temperature deformation resistance is poor. Resin-based modifiers, such as epoxy resin, can effectively improve the high-temperature stability of base asphalt, but epoxy resin lacks toughness and has poor low-temperature crack resistance. Chinese patent CN201410854109.1 discloses an asphalt modification and reinforcing additive and its application, which uses a mixture of rubber powder and epoxy resin to overcome the low-temperature defects of asphalt modified with epoxy resin alone, but the poor compatibility of rubber and epoxy resin affects the modification effect. Using thermoplastic elastomers and epoxy resin together as modifiers can effectively improve the high-temperature stability and low-temperature performance of base asphalt. Furthermore, most commonly used polymer modifiers are flammable materials. Fires on tunnels, highways, and other road surfaces often pose significant challenges to evacuation and firefighting, severely endangering public safety. Therefore, it is essential to provide a polymer pavement modifier for modifying base asphalt to overcome the aforementioned problems in existing technologies. Summary of the Invention

[0004] The purpose of this invention is to provide a polymer road surface modifier and its preparation method to solve the problems mentioned in the background art.

[0005] To solve the above-mentioned technical problems, the present invention provides the following technical solution: a polymer pavement modifier, wherein the polymer pavement modifier comprises component A and component B, and component A and component B are mixed in a weight ratio of 1:(0.58~0.71); wherein:

[0006] Component A includes, by weight, 100 parts epoxy resin, 6-9 parts epoxy polyurethane, 2-4 parts titanate coupling agent, and 6-8 parts epoxy reactive diluent;

[0007] Component B includes: 50-60 parts of silicone 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.

[0008] Furthermore, the preparation method of epoxy-based polyurethane is as follows:

[0009] S1: Dissolve hydroxyl butadiene rubber in cyclohexane / tetrahydrofuran solution, add m-chloroperoxybenzoic acid, react at 30~35℃, remove the solvent cyclohexane / tetrahydrofuran solution by vacuum distillation, purify with anhydrous ethanol to remove byproducts, and dry the product at 40~50℃ to constant weight to obtain epoxy hydroxyl butadiene rubber.

[0010] S2: Epoxy hydroxyl rubber is dispersed in tetrahydrofuran, diisocyanate is added, and dibutyltin dilaurate is used as a catalyst. The reaction is carried out under nitrogen protection at 30-40℃ for 60-90 min to obtain a prepolymer. 1,4-Butanediol is added as a chain extender, and the reaction is continued for 60-90 min. Tetrahydrofuran is removed under reduced pressure to obtain epoxy polyurethane.

[0011] Furthermore, in S1, the volume ratio of cyclohexane to tetrahydrofuran in the cyclohexane / tetrahydrofuran solution is 4:1.

[0012] Furthermore, in S1, the weight ratio of m-chloroperoxybenzoic acid to butylated hydroxyl rubber is (18~22):100.

[0013] Furthermore, in S2, the diisocyanate is any one or more of isophorone diisocyanate, toluene diisocyanate, and diphenylmethane diisocyanate.

[0014] Furthermore, in S2, epoxy butyl hydroxyl rubber and diisocyanate react at a molar ratio of hydroxyl to isocyanate group of 1:(1.6~1.8).

[0015] Furthermore, in S2, during the chain extension reaction, the chain extension coefficient is 0.8~0.85.

[0016] Furthermore, the epoxy reactive diluent is any one or more of phenyl glycidyl ether, benzyl alcohol glycidyl ether, cashew phenol glycidyl ether, castor oil triglycidyl ether, and epoxidized soybean oil.

[0017] Furthermore, the preparation method of the silicon-containing flame retardant curing agent includes the following steps:

[0018] Vanillin was dispersed in ethyl acetate, and triethylamine was used as an acid-binding agent. Phenylphosphoryl dichloro was added under nitrogen protection at 0-5°C. The mixture was stirred and heated to 55-60°C for 24 hours. The precipitate was removed by filtration, and the filtrate was washed with saturated brine. The filtrate was concentrated and recrystallized to obtain a phosphorus-containing intermediate. The intermediate was dispersed in anhydrous ethanol, and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane was added under nitrogen. The mixture was heated to 50-60°C for 6-8 hours to obtain a silicon-containing flame-retardant curing agent.

[0019] Furthermore, the molar ratio of phenylphosphodichloro, vanillin, and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane is 1:2:2.

[0020] Furthermore, the amine curing agent is any one or more of octadecyl primary amine, oleylamine, decylamine, and cashew phenol amine.

[0021] Furthermore, the anhydride curing agent is any one or more of tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and methylhexahydrophthalic anhydride.

[0022] Furthermore, the accelerator is any one or more of tertiary amine accelerators, phenolic accelerators, and imidazole accelerators.

[0023] Compared with the prior art, the beneficial effects achieved by the present invention are 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 components B to obtain a polymer road surface modifier for asphalt modification.

[0024] In component A of this invention, the epoxy polyurethane is prepared by reacting hydroxyl butadiene rubber with m-chloroperoxybenzoic acid, then polymerizing it with diisocyanate, and finally undergoing a chain extension reaction. Its molecular chain segments contain epoxy groups, which can undergo cross-linking reactions with epoxy resin under the action of a curing agent, effectively improving the compatibility between the two. The mechanical properties of the cured polymer modifier are also better. In component B, phenylphosphodichloro, vanillin, and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane are reacted sequentially as raw materials. The phenolic hydroxyl groups in vanillin first react with phenylphosphodichloro, and the aldehyde groups then react with 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane to obtain a silicon-containing flame-retardant curing agent with amino groups at the end. Silicon, phosphorus, and nitrogen elements have a synergistic effect, jointly improving the flame-retardant efficiency. Compared to traditional curing agents, silicone-containing flame retardant curing agents also contain flexible Si-O-Si segments, which, together with epoxy-based polyurethane, improve the toughness of epoxy resins.

[0025] When the polymer pavement modifier of the present invention is mixed with asphalt, the polymer forms a three-dimensional network cross-linked structure after curing, which encapsulates the asphalt and thereby changes the thermoplasticity of the asphalt. The introduction of epoxy resin, polyurethane and organosilicon segments improves the temperature resistance, cold resistance and fatigue resistance of asphalt, making it suitable for paving and repairing steel bridge decks, tunnels, highways and other road surfaces. At the same time, it can also effectively reduce the risk of road fires and improve the safety of public transportation. Detailed Implementation

[0026] 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.

[0027] The materials used in this invention and their sources are as follows: 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 Additives and Oils Factory; the butylated hydroxyl rubber is from Liming Chemical Research Institute, with an average molecular weight of 4000; the epoxy reactive diluent is cashew phenol glycidyl ether from Hubei Jusheng Technology Co., Ltd., product number JS4129; and the accelerator is 2-methylimidazole from Shikoku Chemical Co., Ltd. of Japan, model 2MZ-A.

[0028] Example 1: A method for preparing a polymer road surface modifier, comprising the following steps:

[0029] Step 1: Mix 100kg epoxy resin, 6kg epoxy polyurethane, 2kg titanate coupling agent, and 6kg epoxy reactive diluent to obtain component A;

[0030] The preparation method of epoxy-based polyurethane is as follows:

[0031] S1: Dissolve hydroxyl butadiene rubber in cyclohexane / tetrahydrofuran solution (cyclohexane and tetrahydrofuran volume ratio of 4:1), add m-chloroperoxybenzoic acid, the weight ratio of m-chloroperoxybenzoic acid to hydroxyl butadiene rubber is 18:100; react at 30℃, remove the solvent cyclohexane / tetrahydrofuran solution by vacuum distillation, add anhydrous ethanol to purify and remove byproducts, and dry the product at 40℃ to constant weight to obtain epoxy hydroxyl butadiene rubber;

[0032] S2: Epoxy hydroxyl rubber was dispersed in tetrahydrofuran, and isophorone diisocyanate was added at a molar ratio of hydroxyl to isocyanate group of 1:1.6. Dibutyltin dilaurate was used as a catalyst, and the reaction was carried out at 30°C for 60 min under nitrogen protection to obtain a prepolymer. 1,4-Butanediol was added as a chain extender with a chain extension coefficient of 0.8, and the reaction was continued for 60 min. Tetrahydrofuran was removed under reduced pressure to obtain epoxy polyurethane.

[0033] 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;

[0034] The preparation method of the silicon-containing flame retardant curing agent includes the following steps:

[0035] Vanillin was dispersed in ethyl acetate, and triethylamine was used as an acid-binding agent. Phenylephrine dichloride was added under nitrogen protection at 0°C, and the mixture was stirred and heated to 55°C for 24 hours. The precipitate was removed by filtration, and the filtrate was washed with saturated brine. The filtrate was concentrated and recrystallized to obtain a phosphorus-containing intermediate. The intermediate was dispersed in anhydrous ethanol, and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane was added under nitrogen. The mixture was heated to 50°C for 6 hours to obtain a silicon-containing flame-retardant curing agent. The molar ratio of phenylphosphrine dichloride, vanillin, and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane was 1:2:2.

[0036] Step 3: Mix component A and component B at a weight ratio of 1:0.58 to obtain a polymer road surface modifier.

[0037] Example 2: A method for preparing a polymer road surface modifier, comprising the following steps:

[0038] Step 1: Mix 100kg epoxy resin, 7kg epoxy polyurethane, 3.4kg titanate coupling agent, and 7.1kg epoxy reactive diluent to obtain component A;

[0039] The preparation method of epoxy-based polyurethane is as follows:

[0040] S1: Dissolve hydroxyl butadiene rubber in cyclohexane / tetrahydrofuran solution (cyclohexane and tetrahydrofuran volume ratio of 4:1), add m-chloroperoxybenzoic acid, the weight ratio of m-chloroperoxybenzoic acid to hydroxyl butadiene rubber is 20:100; react at 33℃, remove the solvent cyclohexane / tetrahydrofuran solution by vacuum distillation, add anhydrous ethanol to purify and remove byproducts, and dry the product at 45℃ to constant weight to obtain epoxy hydroxyl butadiene rubber;

[0041] S2: Epoxy hydroxyl rubber was dispersed in tetrahydrofuran, and toluene diisocyanate was added at a molar ratio of hydroxyl to isocyanate group of 1:1.7. Dibutyltin dilaurate was used as a catalyst, and the reaction was carried out at 35°C for 70 min under nitrogen protection to obtain a prepolymer. 1,4-Butanediol was added as a chain extender with a chain extension coefficient of 0.82, and the reaction was continued for 80 min. Tetrahydrofuran was removed under reduced pressure to obtain epoxy polyurethane.

[0042] Step 2: Mix 55kg of silicone flame retardant curing agent, 31kg of oleylamine, 2kg of tetrahydrophthalic anhydride, and 1.2kg of accelerator to obtain component B;

[0043] The preparation method of the silicon-containing flame retardant curing agent includes the following steps:

[0044] Vanillin was dispersed in ethyl acetate, and triethylamine was used as an acid-binding agent. Phenylephosphosilicate dichloride was added under nitrogen protection at 3°C, and the mixture was stirred and heated to 58°C for 24 hours. The precipitate was removed by filtration, and the filtrate was washed with saturated brine. The filtrate was concentrated and recrystallized to obtain a phosphorus-containing intermediate. The intermediate was dispersed in anhydrous ethanol, and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane was added under nitrogen. The mixture was heated to 55°C for 7 hours to obtain a silicon-containing flame-retardant curing agent. The molar ratio of phenylphosphosilicate dichloride, vanillin, and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane was 1:2:2.

[0045] Step 3: Mix component A and component B at a weight ratio of 1:0.63 to obtain a polymer road surface modifier.

[0046] Example 3: A method for preparing a polymer road surface modifier, comprising the following steps:

[0047] Step 1: Mix 100kg epoxy resin, 9kg epoxy polyurethane, 4kg titanate coupling agent, and 8kg epoxy reactive diluent to obtain component A;

[0048] The preparation method of epoxy-based polyurethane is as follows:

[0049] S1: Dissolve hydroxyl butadiene rubber in cyclohexane / tetrahydrofuran solution (cyclohexane and tetrahydrofuran volume ratio of 4:1), add m-chloroperoxybenzoic acid, the weight ratio of m-chloroperoxybenzoic acid to hydroxyl butadiene rubber is 22:100; react at 35℃, remove the solvent cyclohexane / tetrahydrofuran solution by vacuum distillation, add anhydrous ethanol to purify and remove byproducts, and dry the product at 50℃ to constant weight to obtain epoxy hydroxyl butadiene rubber;

[0050] S2: Epoxy hydroxyl rubber was dispersed in tetrahydrofuran, and diphenylmethane diisocyanate was added at a molar ratio of hydroxyl to isocyanate group of 1:1.8. Dibutyltin dilaurate was used as a catalyst, and the reaction was carried out at 40°C for 90 min under nitrogen protection to obtain a prepolymer. 1,4-Butanediol was added as a chain extender with a chain extension coefficient of 0.85, and the reaction was continued for 90 min. Tetrahydrofuran was removed under reduced pressure to obtain epoxy polyurethane.

[0051] Step 2: Mix 60kg of silicone flame retardant curing agent, 35kg of decylamine, 5kg of methyltetrahydrophthalic anhydride, and 2kg of accelerator to obtain component B;

[0052] The preparation method of the silicon-containing flame retardant curing agent includes the following steps:

[0053] Vanillin was dispersed in ethyl acetate, and triethylamine was used as an acid-binding agent. Phenylephrine dichloride was added under nitrogen protection at 5°C, and the mixture was stirred and heated to 60°C for 24 hours. The precipitate was removed by filtration, and the filtrate was washed with saturated brine. The filtrate was concentrated and recrystallized to obtain a phosphorus-containing intermediate. The intermediate was dispersed in anhydrous ethanol, and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane was added under nitrogen. The mixture was heated to 60°C for 8 hours to obtain a silicon-containing flame-retardant curing agent. The molar ratio of phenylphosphrine dichloride, vanillin, and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane was 1:2:2.

[0054] Step 3: Mix component A and component B at a weight ratio of 1:0.71 to obtain a polymer road surface modifier.

[0055] Comparative Example 1: No epoxy groups were introduced into the polyurethane, and the remaining parameters were the same as in Example 1.

[0056] Step 1: Mix 100kg epoxy resin, 6kg polyurethane, 2kg titanate coupling agent, and 6kg epoxy reactive diluent to obtain component A;

[0057] The polyurethane is prepared as follows: hydroxyl butadiene rubber is dispersed in tetrahydrofuran, isophorone diisocyanate is added at a molar ratio of hydroxyl to isocyanate group of 1:1.6, and dibutyltin dilaurate is used as a catalyst. The reaction is carried out under nitrogen protection at 30°C for 60 min to obtain a prepolymer. 1,4-Butanediol is added as a chain extender with a chain extension coefficient of 0.8, and the reaction is continued for 60 min. Tetrahydrofuran is removed under reduced pressure to obtain polyurethane.

[0058] 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;

[0059] The preparation method of the silicon-containing flame retardant curing agent includes the following steps:

[0060] Vanillin was dispersed in ethyl acetate, and triethylamine was used as an acid-binding agent. Phenylephrine dichloride was added under nitrogen protection at 0°C, and the mixture was stirred and heated to 55°C for 24 hours. The precipitate was removed by filtration, and the filtrate was washed with saturated brine. The filtrate was concentrated and recrystallized to obtain a phosphorus-containing intermediate. The intermediate was dispersed in anhydrous ethanol, and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane was added under nitrogen. The mixture was heated to 50°C for 6 hours to obtain a silicon-containing flame-retardant curing agent. The molar ratio of phenylphosphrine dichloride, vanillin, and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane was 1:2:2.

[0061] Step 3: Mix component A and component B at a weight ratio of 1:0.58 to obtain a polymer road surface modifier.

[0062] Comparative Example 2: No silicon-containing flame retardant curing agent was added, and all other parameters were the same as in Example 2.

[0063] Step 1: Mix 100kg epoxy resin, 7kg epoxy polyurethane, 3.4kg titanate coupling agent, and 7.1kg epoxy reactive diluent to obtain component A;

[0064] The preparation method of epoxy-based polyurethane is as follows:

[0065] S1: Dissolve hydroxyl butadiene rubber in cyclohexane / tetrahydrofuran solution (cyclohexane and tetrahydrofuran volume ratio of 4:1), add m-chloroperoxybenzoic acid, the weight ratio of m-chloroperoxybenzoic acid to hydroxyl butadiene rubber is 20:100; react at 33℃, remove the solvent cyclohexane / tetrahydrofuran solution by vacuum distillation, add anhydrous ethanol to purify and remove byproducts, and dry the product at 45℃ to constant weight to obtain epoxy hydroxyl butadiene rubber;

[0066] S2: Epoxy hydroxyl rubber was dispersed in tetrahydrofuran, and toluene diisocyanate was added at a molar ratio of hydroxyl to isocyanate group of 1:1.7. Dibutyltin dilaurate was used as a catalyst, and the reaction was carried out at 35°C for 70 min under nitrogen protection to obtain a prepolymer. 1,4-Butanediol was added as a chain extender with a chain extension coefficient of 0.82, and the reaction was continued for 80 min. Tetrahydrofuran was removed under reduced pressure to obtain epoxy polyurethane.

[0067] Step 2: Mix 31 kg of oleylamine, 2 kg of tetrahydrophthalic anhydride, and 1.2 kg of accelerator to obtain component B;

[0068] Step 3: Mix component A and component B at a weight ratio of 1:0.63 to obtain a polymer road surface modifier.

[0069] Comparative Example 3: Magnesium hydroxide powder (activated magnesium hydroxide flame retardant of model YX105 from Dalian Yatai Technology New Materials Co., Ltd.) was used instead of silicon-containing flame retardant curing agent, and the other parameters were the same as in Example 3.

[0070] Step 1: Mix 100kg epoxy resin, 9kg epoxy polyurethane, 4kg titanate coupling agent, and 8kg epoxy reactive diluent to obtain component A;

[0071] The preparation method of epoxy-based polyurethane is as follows:

[0072] S1: Dissolve hydroxyl butadiene rubber in cyclohexane / tetrahydrofuran solution (cyclohexane and tetrahydrofuran volume ratio of 4:1), add m-chloroperoxybenzoic acid, the weight ratio of m-chloroperoxybenzoic acid to hydroxyl butadiene rubber is 22:100; react at 35℃, remove the solvent cyclohexane / tetrahydrofuran solution by vacuum distillation, add anhydrous ethanol to purify and remove byproducts, and dry the product at 50℃ to constant weight to obtain epoxy hydroxyl butadiene rubber;

[0073] S2: Epoxy hydroxyl rubber was dispersed in tetrahydrofuran, and diphenylmethane diisocyanate was added at a molar ratio of hydroxyl to isocyanate group of 1:1.8. Dibutyltin dilaurate was used as a catalyst, and the reaction was carried out at 40°C for 90 min under nitrogen protection to obtain a prepolymer. 1,4-Butanediol was added as a chain extender with a chain extension coefficient of 0.85, and the reaction was continued for 90 min. Tetrahydrofuran was removed under reduced pressure to obtain epoxy polyurethane.

[0074] Step 2: Mix 60 kg magnesium hydroxide, 35 kg decylamine, 5 kg methyltetrahydrophthalic anhydride, and 2 kg accelerator to obtain component B;

[0075] Step 3: Mix component A and component B at a weight ratio of 1:0.71 to obtain a polymer road surface modifier.

[0076] Experiment 1: The polymer pavement modifiers prepared in Examples 1-3 and Comparative Examples 1-3 were mixed with 70# base asphalt (from CNOOC Asphalt Co., Ltd.) at a weight ratio of 1:1 to obtain modified asphalt. The modified asphalt was then cured under the following conditions: 180℃ / 3h + 60℃ / 4d. The GB / T 528-2009 standard was adopted, and the specimens were prepared according to Type II specimens with a tensile rate of 500mm / min. The flame retardant performance was tested using the limiting oxygen index. The experimental results are shown in Table 1.

[0077] 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 gradation), and 0.7 kg of modified asphalt from Experiment 1 were added, mixed, heated to 165℃, stirred for 2 min, compacted using a roller mill, and cured at 60℃ for 4 days to obtain the modified asphalt mixture. The Marshall stability, Marshall flow value (60℃, 50 mm / min), and failure strain at -10℃ were tested according to the methods required by the "Test Procedure for Asphalt-Based Asphalt Mixtures for Highway Engineering" (JTG E20-2011). The experimental results are shown in Table 2.

[0078] Table 2. Test results of modified asphalt mixtures

[0079] Conclusions: In Experiment 1, the data from Example 1 and Comparative Example 1 show that introducing epoxy groups into polyurethane improves the compatibility between polyurethane and epoxy resin, resulting in better modification and effectively improving the mechanical properties of asphalt. The data from Example 2 and Comparative Example 2 show that the polymer pavement modifier exhibits better toughness and good flame-retardant properties after adding a silicon-containing flame-retardant curing agent. The data from Example 3 and Comparative Example 3 show that compared to magnesium hydroxide flame retardant, the addition of a silicon-containing flame-retardant curing agent provides a stronger flame-retardant effect and effectively avoids the problem of decreased mechanical properties caused by poor compatibility between inorganic flame-retardant materials and organic polymers. Furthermore, the data from Experiment 2 show that the modified asphalt mixtures prepared with the polymer pavement modifiers in Examples 1-3 have significantly better performance than those in Comparative Examples 1-3.

[0080] It should be noted that, in this document, relational terms such as "first" and "second" are used only to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, article, or apparatus.

[0081] 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 foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing a polymer road surface modifier, characterized in that: Includes the following steps: Step 1: Mix 100 parts epoxy resin, 6-9 parts epoxy polyurethane, 2-4 parts titanate coupling agent, and 6-8 parts epoxy reactive diluent by weight to obtain component A; The preparation method of epoxy-based polyurethane is as follows: S1: Dissolve hydroxyl butadiene rubber in cyclohexane / tetrahydrofuran solution, add m-chloroperoxybenzoic acid; react at 30~35℃, remove the solvent cyclohexane / tetrahydrofuran solution by vacuum distillation, purify with anhydrous ethanol to remove byproducts, and dry the product at 40~50℃ to constant weight to obtain epoxy hydroxyl butadiene rubber. S2: Epoxy hydroxyl rubber is dispersed in tetrahydrofuran, diisocyanate is added, and dibutyltin dilaurate is used as a catalyst. The reaction is carried out under nitrogen protection at 30-40℃ for 60-90 min to obtain a prepolymer. 1,4-Butanediol is added as a chain extender, and the reaction is continued for 60-90 min. Tetrahydrofuran is removed under reduced pressure to obtain epoxy polyurethane. Step 2: By weight, mix 50-60 parts of silicone 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 to obtain component B; The preparation method of the silicon-containing flame retardant curing agent is as follows: Vanillin was dispersed in ethyl acetate, and triethylamine was used as an acid-binding agent. Phenylphosphoryl dichloro was added under nitrogen protection at 0-5°C. The mixture was stirred and heated to 55-60°C for 24 hours. The precipitate was removed by filtration, and the filtrate was washed with saturated brine. The filtrate was concentrated and recrystallized to obtain a phosphorus-containing intermediate. The intermediate was dispersed in anhydrous ethanol, and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane was added under nitrogen. The mixture was heated to 50-60°C for 6-8 hours to obtain a silicon-containing flame-retardant curing agent. Step 3: Mix component A and component B at a weight ratio of 1:(0.58~0.71) to obtain a polymer road surface modifier.

2. The method for preparing the polymer road surface modifier according to claim 1, characterized in that: In S1, the weight ratio of m-chloroperoxybenzoic acid to hydroxyl rubber is (18~22):

100.

3. The method for preparing the polymer road surface modifier according to claim 1, characterized in that: In S2, epoxy hydroxyl-butadiene rubber and diisocyanate react at a molar ratio of hydroxyl to isocyanate group of 1:(1.6~1.8); during the chain extension reaction, the chain extension coefficient is 0.8~0.

85.

4. The method for preparing the polymer road surface modifier according to claim 1, characterized in that: In S2, the diisocyanate is any one or more of isophorone diisocyanate, toluene diisocyanate, and diphenylmethane diisocyanate.

5. The method for preparing the polymer road surface modifier according to claim 1, characterized in that: In step 1, the epoxy reactive diluent is any one or more of phenyl glycidyl ether, benzyl alcohol glycidyl ether, cashew phenol glycidyl ether, castor oil triglycidyl ether, and epoxidized soybean oil.

6. The method for preparing the polymer road surface modifier according to claim 1, characterized in that: The molar ratio of phenylphosphodichloro, vanillin, and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane is 1:2:

2.

7. The method for preparing the polymer road surface modifier according to claim 1, characterized in that: In step 2, the amine curing agent is any one or more of octadecyl primary amine, oleylamine, decylamine, and cashew phenol 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 tertiary amine accelerators, phenolic accelerators, and imidazole accelerators.

8. The polymer road surface modifier prepared by the preparation method according to any one of claims 1 to 7.

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