Stable rubber powder polymer composite modified asphalt and mixture

Abstract

This invention discloses a stabilized rubber powder polymer composite modified asphalt and its mixture, comprising the following preparation process: (1) reacting mercapto alcohol with triphenylmethanol, reacting with butene tricarboxylic acid and furanylacrylic acid to obtain product B; reacting with active magnesium, bromooctane, and o-dichlorobenzene; reacting with butenadic anhydride to obtain product D; reacting product B, product D, and sodium styrene sulfonate; reacting with trifluoroacetic acid and sodium hydroxide to obtain a reactive additive; (2) co-extruding with waste rubber powder to obtain a stabilized rubber powder polymer; (3) mixing with base asphalt to obtain modified asphalt. This invention prepares two unsaturated monomers from the above raw materials, copolymerizes them with sodium styrene sulfonate to obtain a reactive additive, co-extrudes it with waste rubber powder at high temperature to reconstruct the three-dimensional cross-linked structure, and improves the high-temperature performance of the prepared asphalt; and introduces carboxylates and thiols to strengthen the prepared stabilized rubber powder polymer, thereby improving the high-temperature performance, low-temperature performance, and fatigue resistance of the prepared modified asphalt.

Description

Technical Field

[0001] This invention relates to the field of asphalt technology, specifically to a stabilized polymer-modified asphalt and its mixture. Background Technology

[0002] Asphalt is commonly used in civil engineering as a waterproofing and anti-corrosion material. It also serves as a cementitious material for road structures, blending with different mineral materials to create asphalt pavements of varying structures. It is widely used in highways of all levels. To ensure the environmental adaptability of paved roads, SBS (Solid Polymer) is typically used to modify asphalt. SBS-modified asphalt possesses excellent comprehensive properties, maintaining good elasticity and toughness in various application environments, including high and low temperatures and ultraviolet radiation. However, its high cost limits the widespread adoption and application of SBS polymers. Currently, rubber powder-modified asphalt, which mixes recycled waste tire particles or rubber powder with asphalt, improves the high and low temperature performance of asphalt while also addressing the pollution problem caused by waste tires, significantly reducing costs. However, waste rubber powder-modified asphalt is prone to segregation and has high viscosity, often exhibiting severe aging problems during processing, storage, and use. This leads to a significant reduction in low-temperature crack resistance and fatigue resistance, resulting in pavement cracking and damage. Therefore, we propose a stabilized rubber powder polymer composite modified asphalt and its mixture. Summary of the Invention

[0003] The purpose of this invention is to provide a stable polymer-modified asphalt and mixture to solve the problems mentioned in the background art.

[0004] To solve the above-mentioned technical problems, the present invention provides the following technical solution: a stabilized polymer-modified asphalt, comprising the following preparation process:

[0005] (1) Preparation of reactive additives:

[0006] a. React 1,4-dimercapto-2,3-butanediol with triphenylmethanol to give product A; react product A with 1-butene-2,3,4-tricarboxylic acid and 3-(3-furanyl)acrylic acid to give product B;

[0007] b. Take active magnesium, bromooctane, and o-dichlorobenzene, and react them to obtain product C; react product C with maleic anhydride to obtain product D;

[0008] c. React products B and D with sodium styrene sulfonate to copolymerize and obtain product E; react it sequentially with trifluoroacetic acid and sodium hydroxide to obtain a reactive additive.

[0009] (2) Preparation of stable adhesive powder polymer:

[0010] Reactive additives were co-extruded with waste rubber powder to obtain a stable rubber powder polymer;

[0011] (3) Preparation of modified asphalt:

[0012] Modified asphalt is obtained by mixing stabilized rubber polymer powder with base asphalt.

[0013] Furthermore, step a. includes the following preparation process:

[0014] Dissolve 1,4-dimercapto-2,3-butanediol in diethyl ether, add sodium hydroxide, stir for 30–120 min, add triphenylmethanol, and react for 8–12 h; distill under reduced pressure, wash, and dry to obtain product A.

[0015] Dissolve 1-butene-2,3,4-tricarboxylic acid and 3-(3-furanyl)acrylic acid in dichloromethane, control the temperature at 20-40℃, add dehydrating agent N,N'-dicyclohexylcarbodiimide, catalyst styrene-based cation exchange resin, and product A. Under nitrogen protection, stir the reaction for 12-24 hours, centrifuge, add anhydrous ethanol to the supernatant, centrifuge again, wash the precipitate, and dry to obtain product B.

[0016] Furthermore, step b. includes the following preparation process:

[0017] Take active magnesium and anhydrous diethyl ether, stir and mix them under nitrogen protection, add bromooctane and anhydrous diethyl ether, reflux at 35-42℃ for 60-90 min, cool, add a mixed solution of 1,3-bis(diphenylphosphine)propane nickel dichloride, o-dichlorobenzene and anhydrous diethyl ether, reflux for 58-60 h, cool to room temperature, slowly add hydrochloric acid, take the organic phase to wash, dry, and distill to obtain product C;

[0018] Take product C and maleic anhydride, add carbon disulfide and mix, stir, slowly add anhydrous aluminum chloride, reflux at 35-42℃ for 60-90 min, cool, slowly add ice water and concentrated hydrochloric acid, stir for 30-60 min, remove the aqueous phase, wash, extract, dry to obtain product D.

[0019] Furthermore, step c. includes the following preparation process:

[0020] Take product D, polymerization inhibitor, and deionized water, mix them under nitrogen protection, add a mixed aqueous solution of sodium styrene sulfonate and potassium persulfate initiator, react at 78-82℃ for 4-5 hours, add product B, and continue to react for 1-2 hours to obtain product E.

[0021] Add triethylsilane and trifluoroacetic acid, mix and stir for 30-60 min, add diethyl ether, precipitate, centrifuge, wash the precipitate and dry under vacuum; add sodium hydroxide to adjust the pH of the system to 7-8 to obtain a reactive additive.

[0022] Furthermore, step (2) includes the following processes:

[0023] Take reactive additives and waste rubber powder, dry them at 70-80℃ for 40-60 min, place them in an extruder, extrude them at 120-160℃ with a screw speed of 550-680 r / min, and obtain a stable rubber powder polymer.

[0024] Furthermore, step (3) includes the following processes:

[0025] The base asphalt is heated to 160–180°C, and a stabilized polymer powder is added. The mixture is stirred at 320–370 r / min for 1–3 h to obtain modified asphalt. Further, in step a., the molar ratio of 1,4-dimercapto-2,3-butanediol to triphenylmethanol is 1:(0.5–2.0); and the molar ratio of 1-butene-2,3,4-tricarboxylic acid, 3-(3-furanyl)acrylic acid, dehydrating agent, and product A in step a. is 1:(0.5–0.8):(0.8–10):(1.5–5.0).

[0026] Furthermore, in step b., the molar ratio of active magnesium, bromooctane, and o-dichlorobenzene is 1:(0.97-1.03):(0.38-0.42); and in step b., the molar ratio of product C and maleic anhydride is 1:(1.1-1.4).

[0027] Furthermore, in step c., the molar ratio of product B, product D, and sodium styrene sulfonate is 1:(1.0-2.0):(0.5-1.0); and the molar ratio of product E and trifluoroacetic acid in step c. is 1:(1.0-1.2).

[0028] The mass ratio of the reactive additive to the waste rubber powder is 1:(4-9); the mass ratio of the base asphalt to the stabilized rubber powder polymer is (78-83):(17-22).

[0029] In the above technical solution, the thiol group in 1,4-dimercapto-2,3-butanediol is grafted onto the hydroxyl group in triphenylmethanol under the action of sodium hydroxide to obtain product A; product A is then reacted with the carboxyl group in 1-butene-2,3,4-tricarboxylic acid and 3-(3-furanyl)acrylic acid under the action of a dehydrating agent and a catalyst to obtain a polycarboxylic acid containing a thiol protecting group and an unsaturated bond, namely product B;

[0030] Active magnesium first combines with bromooctane, then reacts with o-dichlorobenzene in the presence of 1,3-bis(diphenylphosphine)propane and nickel dichloride, replacing the chlorine group with octane to obtain product C. Subsequently, in the presence of aluminum chloride, maleic anhydride is grafted onto the benzene ring of product C to obtain a carboxylic acid containing a long alkyl chain with a double tail and unsaturated bonds, i.e., product D. The introduction of hydrophilic groups and the increase of hydrophobic long chains improve the adaptability of the prepared reactive additives, stable rubber polymers, and modified asphalt to high and low temperatures, enhancing their temperature resistance. In the preparation of asphalt mixtures, the bonding performance with aggregates is improved and stabilized, molecular linkages increase, and compressive and crack resistance is enhanced. It can effectively improve the high and low temperature resistance of the prepared asphalt mixtures while maintaining their crack resistance and fatigue resistance.

[0031] Product D is first polymerized with sodium styrene sulfonate, and then product B is introduced to obtain a trimer. Trifluoroacetic acid removes the thiol protecting group from product B, and the process parameters are limited to obtain a polymer containing unsaturated bonds with multiple carboxyl and thiol groups. This polymer is then reacted with sodium hydroxide to obtain carboxylates and thiols. When co-extruded with waste rubber powder and mixed with asphalt, the ion pairs attract and aggregate with each other due to electrostatic attraction, which can improve the strength of the prepared stable rubber powder polymer and modified asphalt. Furthermore, the unsaturated bonds on the polymer are grafted onto waste rubber powder to further improve the strength of the prepared stable rubber powder polymer and modified asphalt.

[0032] The reactive additive is co-extruded with waste rubber powder at high temperature. The high temperature causes the disulfide bonds and carbon-sulfur bonds in the waste rubber powder to break, destroying the three-dimensional structure and achieving desulfurization of the waste rubber powder. Then it reacts with the additive to reconstruct the three-dimensional cross-linked structure. The whole system has a dense cross-linked network structure with strong intermolecular bonding. While ensuring its high-temperature performance, the modified asphalt can exhibit low-temperature performance and has a significant improvement in processing flow properties.

[0033] When the prepared stabilized rubber powder polymer is mixed with asphalt, the desulfurization and cracking reaction increases, the particle size of the stabilized rubber powder polymer decreases, and less light components of asphalt, rubber oil and carbon black are absorbed. The network structure of mutual adhesion is formed, the interaction between the rubber powder polymer and asphalt is improved, the rheological properties of the modified asphalt are improved, which is conducive to maintaining its high temperature performance, further improving the low temperature performance of the modified asphalt, and improving its fatigue resistance.

[0034] A stabilized polymer-modified asphalt mixture comprises 5.8 to 6.4 parts modified asphalt, 89 parts aggregate, and 11 parts mineral aggregate, wherein the aggregate comprises 30 parts of No. 1, 49 parts of No. 2, 2 parts of No. 3, 8 parts of No. 4, and 11 parts mineral aggregate.

[0035] In the above technical solution, the particle size of #1 is 10-15mm, the particle size of #2 is 5-10mm, the particle size of #3 is 3-5mm, and the particle size of #4 is 0-3mm.

[0036] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0037] The present invention relates to a stabilized rubber powder polymer composite modified asphalt and mixture, which uses 1,4-dimercapto-2,3-butanediol, triphenylmethanol, 1-butene-2,3,4-tricarboxylic acid, 3-(3-furanyl)acrylic acid, active magnesium, bromooctane, o-dichlorobenzene, and maleic anhydride as raw materials to prepare unsaturated monomers, and copolymerizes them with sodium styrene sulfonate to obtain a reactive additive containing polycarboxyl and polythiol groups with unsaturated bonds. This additive is then co-extruded with waste rubber powder at high temperature to reconstruct a three-dimensional cross-linked structure, improving the high-temperature performance of the prepared asphalt. Furthermore, carboxylates and thiols are introduced to reinforce the stabilized rubber powder polymer, improving the low-temperature performance and fatigue resistance of the prepared modified asphalt. Detailed Implementation

[0038] The technical solutions in the embodiments of the present invention will be clearly and completely described below. 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.

[0039] Example 1

[0040] (1) Preparation of reactive additives:

[0041] a. Dissolve 1,4-dimercapto-2,3-butanediol in diethyl ether, add sodium hydroxide, stir for 30 min, add triphenylmethanol, and react for 8 h; distill under reduced pressure, wash, and dry to obtain product A; the molar ratio of 1,4-dimercapto-2,3-butanediol to triphenylmethanol is 1:0.5;

[0042] Dissolve 1-butene-2,3,4-tricarboxylic acid and 3-(3-furanyl)acrylic acid in dichloromethane, control the temperature at 20℃, add dehydrating agent N,N'-dicyclohexylcarbodiimide, catalyst styrene-based cation exchange resin, and product A. Under nitrogen protection, stir the reaction for 12 h, centrifuge, add anhydrous ethanol to the supernatant, centrifuge again, wash the precipitate, and dry to obtain product B; the molar ratio of 1-butene-2,3,4-tricarboxylic acid, 3-(3-furanyl)acrylic acid, dehydrating agent, and product A is 1:0.5:0.8:1.5.

[0043] b. Take active magnesium and anhydrous diethyl ether, mix them under nitrogen protection, add bromooctane and anhydrous diethyl ether, reflux at 35°C for 60 min, cool, add a mixed solution of 1,3-bis(diphenylphosphine)propane nickel dichloride, o-dichlorobenzene and anhydrous diethyl ether, reflux for 58 h, cool to room temperature, slowly add hydrochloric acid, wash the organic phase, dry, and distill to obtain product C; the molar ratio of active magnesium, bromooctane and o-dichlorobenzene is 1:0.97:0.38;

[0044] Take product C and maleic anhydride, add carbon disulfide and mix, stir, slowly add anhydrous aluminum chloride, reflux at 35°C for 60 min, cool, slowly add ice water and concentrated hydrochloric acid, stir for 30 min, remove the aqueous phase, wash, extract, and dry to obtain product D; the molar ratio of product C to maleic anhydride is 1:1.1.

[0045] c. Take product D, polymerization inhibitor, and deionized water, mix them under nitrogen protection, add a mixed aqueous solution of sodium styrene sulfonate and potassium persulfate initiator, react at 78°C for 4 hours, add product B, and continue to react for 1 hour to obtain product E; the molar ratio of product B, product D, and sodium styrene sulfonate is 1:1.0:0.5.

[0046] Add triethylsilane and trifluoroacetic acid, mix and stir for 30 min, add diethyl ether, precipitate, centrifuge, wash the precipitate and vacuum dry; add sodium hydroxide to adjust the pH of the system to 7 to obtain a reactive additive; the molar ratio of product E to trifluoroacetic acid is 1:1.0;

[0047] (2) Preparation of stable adhesive powder polymer:

[0048] Take reactive additives and waste rubber powder, dry them at 70℃ for 40 min, place them in an extruder, and extrude them at 120-160℃ with a screw speed of 550 r / min to obtain a stable rubber powder polymer; the mass ratio of reactive additives to waste rubber powder is 1:4.

[0049] (3) Preparation of modified asphalt:

[0050] The base asphalt was heated to 160°C, and the stabilized polymer powder was added. The temperature was raised to 230°C within 15 minutes, and the mixture was stirred at 320 r / min for 1 hour to obtain the modified asphalt. The mass ratio of base asphalt to stabilized polymer powder was 83:17.

[0051] Example 2

[0052] (1) Preparation of reactive additives:

[0053] a. Dissolve 1,4-dimercapto-2,3-butanediol in diethyl ether, add sodium hydroxide, stir for 75 min, add triphenylmethanol, and react for 10 h; distill under reduced pressure, wash, and dry to obtain product A; the molar ratio of 1,4-dimercapto-2,3-butanediol to triphenylmethanol is 1:1.2.

[0054] Dissolve 1-butene-2,3,4-tricarboxylic acid and 3-(3-furanyl)acrylic acid in dichloromethane, control the temperature at 30℃, add dehydrating agent N,N'-dicyclohexylcarbodiimide, catalyst styrene-based cation exchange resin, and product A. Under nitrogen protection, stir and react for 18 h, centrifuge, take the supernatant, add anhydrous ethanol, centrifuge again, take the precipitate, wash, and dry to obtain product B; the molar ratio of 1-butene-2,3,4-tricarboxylic acid, 3-(3-furanyl)acrylic acid, dehydrating agent, and product A is 1:0.6:5:3.2;

[0055] b. Take active magnesium and anhydrous diethyl ether, mix them under nitrogen protection, add bromooctane and anhydrous diethyl ether, reflux at 38°C for 75 min, cool, add a mixed solution of 1,3-bis(diphenylphosphine)propane nickel dichloride, o-dichlorobenzene and anhydrous diethyl ether, reflux for 60 h, cool to room temperature, slowly add hydrochloric acid, take the organic phase to wash, dry, and distill to obtain product C; the molar ratio of active magnesium, bromooctane and o-dichlorobenzene is 1:1.0:0.40;

[0056] Take product C and maleic anhydride, add carbon disulfide and mix, stir, slowly add anhydrous aluminum chloride, reflux at 40°C for 75 min, cool, slowly add ice water and concentrated hydrochloric acid, stir for 45 min, remove the aqueous phase, wash, extract, and dry to obtain product D; the molar ratio of product C to maleic anhydride is 1:1.2.

[0057] c. Take product D, polymerization inhibitor, and deionized water, mix them under nitrogen protection, add a mixed aqueous solution of sodium styrene sulfonate and potassium persulfate initiator, react at 80°C for 4.5 h, add product B, and continue to react for 1.5 h to obtain product E; the molar ratio of product B, product D, and sodium styrene sulfonate is 1:1.5:0.8.

[0058] Add triethylsilane and trifluoroacetic acid, mix and stir for 45 min, add diethyl ether, precipitate, centrifuge, wash the precipitate and vacuum dry; add sodium hydroxide to adjust the pH of the system to 7.5 to obtain a reactive additive; the molar ratio of product E to trifluoroacetic acid is 1:1.1.

[0059] (2) Preparation of stable adhesive powder polymer:

[0060] Take reactive additives and waste rubber powder, dry them at 75℃ for 50 min, place them in an extruder, and extrude them at 120-160℃ with a screw speed of 600 r / min to obtain a stable rubber powder polymer; the mass ratio of reactive additives to waste rubber powder is 1:6.

[0061] (3) Preparation of modified asphalt:

[0062] The base asphalt was heated to 170°C, and the stabilized polymer powder was added. The temperature was raised to 240°C within 15 minutes, and the mixture was stirred at 350 r / min for 2 hours to obtain the modified asphalt. The mass ratio of base asphalt to stabilized polymer powder was 80:20.

[0063] Example 3

[0064] (1) Preparation of reactive additives:

[0065] a. Dissolve 1,4-dimercapto-2,3-butanediol in diethyl ether, add sodium hydroxide, stir for 120 min, add triphenylmethanol, and react for 12 h; distill under reduced pressure, wash, and dry to obtain product A; the molar ratio of 1,4-dimercapto-2,3-butanediol to triphenylmethanol is 1:2;

[0066] 1-Butene-2,3,4-tricarboxylic acid and 3-(3-furanyl)acrylic acid were dissolved in dichloromethane. The temperature was controlled at 40℃. N,N'-dicyclohexylcarbodiimide (a dehydrating agent), styrene-based cation exchange resin (a catalyst), and product A were added. The mixture was stirred and reacted for 24 hours under nitrogen protection. After centrifugation, the supernatant was added to anhydrous ethanol, centrifuged again, and the precipitate was washed and dried to obtain product B. The molar ratio of 1-butene-2,3,4-tricarboxylic acid, 3-(3-furanyl)acrylic acid, dehydrating agent, and product A was 1:0.8:10:5.

[0067] b. Take active magnesium and anhydrous diethyl ether, mix them under nitrogen protection, add bromooctane and anhydrous diethyl ether, reflux at 42℃ for 90 min, cool, add a mixed solution of 1,3-bis(diphenylphosphine)propane nickel dichloride, o-dichlorobenzene and anhydrous diethyl ether, reflux for 60 h, cool to room temperature, slowly add hydrochloric acid, take the organic phase to wash, dry, and distill to obtain product C; the molar ratio of active magnesium, bromooctane and o-dichlorobenzene is 1:1.03:0.42;

[0068] Take product C and maleic anhydride, add carbon disulfide and mix, stir, slowly add anhydrous aluminum chloride, reflux at 42℃ for 90 min, cool, slowly add ice water and concentrated hydrochloric acid, stir for 60 min, remove the aqueous phase, wash, extract, and dry to obtain product D; the molar ratio of product C to maleic anhydride is 1:1.4.

[0069] c. Take product D, polymerization inhibitor, and deionized water, mix them under nitrogen protection, add a mixed aqueous solution of sodium styrene sulfonate and potassium persulfate initiator, react at 82℃ for 5 hours, add product B, and continue to react for 2 hours to obtain product E; the molar ratio of product B, product D, and sodium styrene sulfonate is 1:2.0:1.0.

[0070] Add triethylsilane and trifluoroacetic acid, mix and stir for 60 min, add diethyl ether, precipitate, centrifuge, wash the precipitate and vacuum dry; add sodium hydroxide to adjust the pH of the system to 8 to obtain a reactive additive; the molar ratio of product E to trifluoroacetic acid is 1:1.2.

[0071] (2) Preparation of stable adhesive powder polymer:

[0072] Take reactive additives and waste rubber powder, dry them at 80℃ for 60 min, place them in an extruder, and extrude them at 120-160℃ with a screw speed of 680 r / min to obtain a stable rubber powder polymer; the mass ratio of reactive additives to waste rubber powder is 1:9.

[0073] (3) Preparation of modified asphalt:

[0074] The base asphalt was heated to 180°C, and the stabilized polymer powder was added. The temperature was raised to 250°C within 15 minutes, and the mixture was stirred at 370 r / min for 3 hours to obtain the modified asphalt. The mass ratio of base asphalt to stabilized polymer powder was 78:22.

[0075] Comparative Example 1

[0076] (1) Preparation of reactive additives:

[0077] Active magnesium and anhydrous diethyl ether were mixed under nitrogen protection by stirring. Bromooctane and anhydrous diethyl ether were added, and the mixture was refluxed at 35°C for 60 min. After cooling, a mixed solution of 1,3-bis(diphenylphosphine)propane, nickel dichloride, o-dichlorobenzene, and anhydrous diethyl ether was added, and the mixture was refluxed for 58 h. After cooling to room temperature, hydrochloric acid was slowly added, the organic phase was washed, dried, and distilled to obtain product A. The molar ratio of active magnesium, bromooctane, and o-dichlorobenzene was 1:0.97:0.38.

[0078] Take product A and maleic anhydride, add carbon disulfide and mix, stir, slowly add anhydrous aluminum chloride, reflux at 35°C for 60 min, cool, slowly add ice water and concentrated hydrochloric acid, stir for 30 min, remove the aqueous phase, wash, extract, and dry to obtain product B; the molar ratio of product A and maleic anhydride is 1:1.1.

[0079] c. Take product B, polymerization inhibitor, and deionized water, mix them under nitrogen protection, add a mixed aqueous solution of sodium styrene sulfonate and potassium persulfate initiator, react at 78°C for 4 hours to obtain product E; the molar ratio of product D to sodium styrene sulfonate is 1:0.5.

[0080] Add triethylsilane and trifluoroacetic acid, mix and stir for 30 min, add diethyl ether, precipitate, centrifuge, wash the precipitate and vacuum dry; add sodium hydroxide to adjust the pH of the system to 7 to obtain a reactive additive; the molar ratio of product E to trifluoroacetic acid is 1:1.0;

[0081] The other process steps are the same as in Example 1, and modified asphalt is obtained.

[0082] Comparative Example 2

[0083] c. Take product D, product B, polymerization inhibitor, and deionized water, mix them under nitrogen protection, add a mixed aqueous solution of sodium styrene sulfonate and potassium persulfate initiator, react at 78℃ for 5 hours to obtain product E; the molar ratio of product B, product D, and sodium styrene sulfonate is 1:1.0:0.5.

[0084] The other process steps are the same as in Example 1, and modified asphalt is obtained.

[0085] Comparative Example 3

[0086] (1) Preparation of reactive additives:

[0087] Acrylic acid, polymerization inhibitor, and deionized water were mixed under nitrogen protection. A mixed aqueous solution of sodium styrene sulfonate and potassium persulfate initiator was added, and the mixture was reacted at 78°C for 4 hours to obtain product E. The molar ratio of acrylic acid to sodium styrene sulfonate was 1:0.5.

[0088] Sodium hydroxide was added to adjust the pH of the system to 7 to obtain a reactive additive; the molar ratio of product E to trifluoroacetic acid was 1:1.0.

[0089] The other process steps are the same as in Example 1, and modified asphalt is obtained.

[0090] Comparative Example 4

[0091] Take waste rubber powder, dry it at 70℃ for 40 min, add an activator, place it in an extruder, extrude it at 120~160℃, and the screw speed is 550 r / min to obtain the rubber powder polymer.

[0092] The base asphalt was heated to 160°C, and the stabilized polymer powder was added. The temperature was raised to 230°C within 15 minutes, and the mixture was stirred at 320 r / min for 1 hour to obtain the modified asphalt. The mass ratio of base asphalt to polymer powder was 83:17.

[0093] The modified asphalt obtained in Examples 1-3 and Comparative Examples 1-4 above was configured with the following weight components: 6.4 parts modified asphalt, 89 parts aggregate, and 11 parts mineral aggregate, wherein the aggregate includes 30 parts of No. 1, 49 parts of No. 2, 2 parts of No. 3, 8 parts of No. 4, and 11 parts of mineral aggregate, to prepare asphalt mixture.

[0094] experiment

[0095] The modified asphalt obtained in Examples 1-3 and Comparative Examples 1-4 was used to prepare samples, and their properties were tested and the test results were recorded:

[0096] Modified asphalt was used as a sample. According to JTGE20-2011, the penetration (25℃), softening point, ductility (5℃), elastic recovery, rotational viscosity (160℃) and fatigue life of the sample were tested. The experimental temperature in the fatigue life test was 5℃, the strain level was 5%, and the fatigue life was the number of shears corresponding to the sample modulus decreasing to 50% of the initial modulus.

[0097] Asphalt mixtures were used as samples. The high-temperature stability of the samples was evaluated by the dynamic stability of the rutting test, the water stability of the samples was evaluated by the residual strength ratio of the freeze-thaw splitting test, and the low-temperature crack resistance of the samples was evaluated by the small beam bending test.

[0098]

[0099]

[0100]

[0101] Based on the data in the table above, the following conclusions can be clearly drawn:

[0102] The modified asphalt and mixtures obtained in Examples 1-3 are compared with those obtained in Comparative Examples 1-4. The test results show that the modified asphalt and mixtures obtained in Examples 1-3 have better comprehensive performance, and the high-temperature rheological properties of the asphalt are positively correlated with the high-temperature rutting resistance of its mixture. This fully demonstrates that the present invention has improved the high and low temperature resistance and fatigue resistance of the modified asphalt and mixture. Furthermore, Comparative Examples 1-4 fully demonstrate that the components used in the present invention and the settings of the preparation process have a promoting effect on improving the comprehensive performance of the modified asphalt and mixture.

[0103] 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 a process method article or apparatus.

[0104] 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, or improvements 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 stabilized polymer-modified asphalt, characterized in that: The following preparation processes are included: (1) Preparation of reactive additives: a. React 1,4-dimercapto-2,3-butanediol with triphenylmethanol to give product A; react product A with 1-butene-2,3,4-tricarboxylic acid and 3-(3-furanyl)acrylic acid to give product B; b. Take active magnesium, bromooctane, and o-dichlorobenzene, and react them to obtain product C; react product C with maleic anhydride to obtain product D; c. React products B and D with sodium styrene sulfonate to copolymerize and obtain product E; react it sequentially with trifluoroacetic acid and sodium hydroxide to obtain a reactive additive. (2) Preparation of stable adhesive polymer powder: Reactive additives were co-extruded with waste rubber powder to obtain a stable rubber powder polymer; (3) Preparation of modified asphalt: The modified asphalt is obtained by mixing the stabilized polymer powder with the base asphalt. Step (1) includes the following preparation process: a. Dissolve 1,4-dimercapto-2,3-butanediol in diethyl ether, add sodium hydroxide, stir for 30-120 min, add triphenylmethanol, and react for 8-12 h; distill under reduced pressure, wash, and dry to obtain product A; 1-Butene-2,3,4-tricarboxylic acid and 3-(3-furanyl)acrylic acid were dissolved in dichloromethane. The temperature was controlled at 20-40℃. N,N'-dicyclohexylcarbodiimide, styrene-based cation exchange resin, and product A were added. The mixture was stirred and reacted under nitrogen protection for 12-24 hours. After centrifugation, the supernatant was added to anhydrous ethanol and centrifuged again. The precipitate was washed and dried to obtain product B. b. Take active magnesium and anhydrous diethyl ether, stir and mix them under nitrogen protection, add bromooctane and anhydrous diethyl ether, reflux at 35-42℃ for 60-90 min, cool, add a mixed solution of 1,3-bis(diphenylphosphine)propane nickel dichloride, o-dichlorobenzene and anhydrous diethyl ether, reflux for 58-60 h, cool to room temperature, slowly add hydrochloric acid, take the organic phase to wash, dry, and distill to obtain product C; Take product C and maleic anhydride, add carbon disulfide and mix, stir, slowly add anhydrous aluminum chloride, reflux at 35-42℃ for 60-90 min, cool, slowly add ice water and concentrated hydrochloric acid, stir for 30-60 min, remove the aqueous phase, wash, extract, dry to obtain product D; c. Take product D, polymerization inhibitor, and deionized water, mix them under nitrogen protection, add a mixed aqueous solution of sodium styrene sulfonate and potassium persulfate initiator, react at 78-82℃ for 4-5 hours, add product B, and continue to react for 1-2 hours to obtain product E. Add triethylsilane and trifluoroacetic acid, mix and stir for 30-60 min, add diethyl ether, precipitate, centrifuge, wash the precipitate and dry under vacuum; add sodium hydroxide to adjust the pH of the system to 7-8 to obtain the reactive additive. In step a., the molar ratio of 1,4-dimercapto-2,3-butanediol to triphenylmethanol is 1:(0.5-2.0); the molar ratio of 1-butene-2,3,4-tricarboxylic acid, 3-(3-furanyl)acrylic acid, dehydrating agent, and product A is 1:(0.5-0.8):(0.8-10):(1.5-5.0). In step b., the molar ratio of active magnesium, bromooctane, and o-dichlorobenzene is 1:(0.97-1.03):(0.38-0.42); the molar ratio of product C and maleic anhydride is 1:(1.1-1.4). In step c., the molar ratio of product B, product D, and sodium styrene sulfonate is 1:(1.0-2.0):(0.5-1.0); in step c., the molar ratio of product E and trifluoroacetic acid is 1:(1.0-1.2).

2. The method for preparing a stabilized polymer-modified asphalt according to claim 1, characterized in that: Step (2) includes the following processes: Take reactive additives and waste rubber powder, dry them at 70-80℃ for 40-60 min, place them in an extruder, extrude them at 120-160℃ with a screw speed of 550-680 r / min, and obtain a stable rubber powder polymer.

3. The method for preparing a stabilized polymer-modified asphalt according to claim 1, characterized in that: Step (3) includes the following processes: Heat the base asphalt to 160-180℃, add the stabilized rubber powder polymer, stir at 320-370 r / min for 1-3 h, add 0.15%-0.25% calcium chloride and stir evenly to obtain stabilized rubber powder modified asphalt.

4. The method for preparing a stabilized polymer-modified asphalt according to claim 2, characterized in that: The mass ratio of the reactive additive to the waste rubber powder is 1:(4-9).

5. The method for preparing a stabilized polymer-modified asphalt according to claim 3, characterized in that: The mass ratio of the base asphalt to the stabilized rubber polymer is (78-83):(17-22).

6. A stable polymer-modified asphalt prepared by any one of claims 1-5.

7. A stable polymer-modified asphalt mixture prepared from a stabilized polymer-modified asphalt according to claim 6, characterized in that: It includes 5.8 to 6.4 parts modified asphalt, 89 parts aggregate, and 11 parts mineral aggregate, wherein the aggregate includes 30 parts of No. 1, 49 parts of No. 2, 2 parts of No. 3, 8 parts of No. 4, and 11 parts mineral aggregate.

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