CN114015245A - Stable rubber powder polymer composite modified asphalt and mixture - Google Patents
Stable rubber powder polymer composite modified asphalt and mixture Download PDFInfo
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- CN114015245A CN114015245A CN202111218353.5A CN202111218353A CN114015245A CN 114015245 A CN114015245 A CN 114015245A CN 202111218353 A CN202111218353 A CN 202111218353A CN 114015245 A CN114015245 A CN 114015245A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/26—Bituminous materials, e.g. tar, pitch
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
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- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/0075—Uses not provided for elsewhere in C04B2111/00 for road construction
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
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Abstract
The invention discloses a stable rubber powder polymer composite modified asphalt and a mixture, which comprises the following preparation processes: (1) mercapto alcohol reacts with triphenyl carbinol, and the mercapto alcohol reacts with butene tricarboxylic acid and furyl acrylic acid to obtain a product B; reacting active magnesium, bromooctane and o-dichlorobenzene; reacting with maleic anhydride to obtain a product D; reacting the product B, the 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 stable rubber powder polymer; (3) mixing with matrix asphalt to obtain modified asphalt. According to the invention, two unsaturated monomers are prepared from the raw materials, and are copolymerized with sodium styrene sulfonate to prepare the reactive additive, and the reactive additive is co-extruded with waste rubber powder at high temperature to reconstruct a three-dimensional cross-linking structure and improve the high-temperature performance of the prepared asphalt; and carboxylate and thiolate are introduced to strengthen the stable rubber powder polymer and improve the high temperature performance, the low temperature performance and the fatigue resistance of the modified asphalt.
Description
Technical Field
The invention relates to the technical field of asphalt, in particular to stable rubber powder polymer composite modified asphalt and a mixture.
Background
Asphalt is commonly used as a waterproof material and an anticorrosive material in civil engineering, can also be used as a pavement structure cementing material in road engineering, is matched with mineral materials with different compositions in proportion to form asphalt pavements with different structures, and is widely applied to all levels of highways. To ensure the environmental compatibility of the paved road, SBS is usually used to modify the asphalt. The SBS modified asphalt has excellent comprehensive performance, and can keep good elasticity and toughness in various application environments such as high and low temperature, ultraviolet radiation and the like. Although the SBS modified asphalt has excellent performance, the popularization and application of the SBS polymer are limited by the high cost of the SBS modified asphalt. In the current road surface paving material, the rubber powder modified asphalt mixes the recycled waste tire particles or rubber powder with asphalt, so that the high and low temperature performance of the asphalt is improved, the pollution problem of the waste tire is solved, and the cost is obviously reduced. However, the crumb rubber modified asphalt is easy to separate and has high viscosity, serious aging problems often exist in the processes of processing, storage, use and the like, and the cracking resistance and the fatigue resistance at low temperature are greatly reduced, so that the pavement is cracked and damaged. Therefore, we propose a stable rubber powder polymer composite modified asphalt and a mixture.
Disclosure of Invention
The invention aims to provide stable rubber powder polymer composite modified asphalt and a mixture, which are used for solving the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme: a stable rubber powder polymer composite modified asphalt comprises the following preparation processes:
(1) preparation of reactive additive:
a. taking 1, 4-dimercapto-2, 3-butanediol to react with triphenyl methanol to obtain a product A; reacting the product A with 1-butene-2, 3, 4-tricarboxylic acid and 3- (3-furyl) acrylic acid to obtain a product B;
b. taking active magnesium, bromooctane and o-dichlorobenzene, and reacting to obtain a product C; the product C reacts with maleic anhydride to obtain a product D;
c. taking the product B, the product D and sodium styrene sulfonate for reaction and copolymerization to obtain a product E; reacting with trifluoroacetic acid and sodium hydroxide in sequence to obtain a reactive additive;
(2) preparation of stable rubber powder polymer:
co-extruding the reactive additive and the waste rubber powder to obtain a stable rubber powder polymer;
(3) preparing modified asphalt:
and mixing the stable rubber powder polymer with the matrix asphalt to obtain the modified asphalt.
Further, the step a comprises the following preparation process:
dissolving 1, 4-dimercapto-2, 3-butanediol in ether, adding sodium hydroxide, stirring for 30-120 min, adding trityl alcohol, and reacting for 8-12 h; carrying out reduced pressure distillation, washing and drying to obtain a product A;
dissolving 1-butene-2, 3, 4-tricarboxylic acid and 3- (3-furyl) acrylic acid in dichloromethane, controlling the temperature to be 20-40 ℃, adding a dehydrating agent N, N' -dicyclohexylcarbodiimide, a catalyst styrene cation exchange resin and a product A, stirring and reacting for 12-24 hours under the protection of nitrogen, centrifuging, taking supernate, adding absolute ethyl alcohol, centrifuging, taking precipitate, washing and drying to obtain a product B.
Further, the step b comprises the following preparation process:
taking active magnesium and anhydrous ether, stirring and mixing under the protection of nitrogen, adding octyl bromide and the anhydrous ether, carrying out reflux reaction at 35-42 ℃ for 60-90 min, cooling, adding a mixed solution of 1, 3-bis (diphenylphosphino) propane nickel dichloride, o-dichlorobenzene and the anhydrous ether, carrying out reflux reaction for 58-60 h, cooling to room temperature, slowly adding hydrochloric acid, taking an organic phase, washing, drying and distilling to obtain a product C;
and (3) taking the product C and maleic anhydride, adding carbon disulfide, mixing, stirring, slowly adding anhydrous aluminum chloride, carrying out reflux reaction at 35-42 ℃ for 60-90 min, cooling, slowly adding ice water and concentrated hydrochloric acid, stirring for 30-60 min, removing a water phase, washing, extracting and drying to obtain a product D.
Further, the step c comprises the following preparation process:
mixing the product D, a polymerization inhibitor and deionized water under the protection of nitrogen, adding a mixed aqueous solution of sodium styrene sulfonate and an initiator potassium persulfate, reacting for 4-5 h at 78-82 ℃, adding the product B, and continuing to react for 1-2 h to obtain a product E;
adding triethylsilane and trifluoroacetic acid, mixing, stirring for 30-60 min, adding diethyl ether, precipitating, centrifuging, washing the precipitate, and vacuum drying; and adding sodium hydroxide to adjust the pH of the system to 7-8 to obtain the reactive additive.
Further, the step (2) comprises the following processes:
taking the reactive additive and the waste rubber powder, drying at 70-80 ℃ for 40-60 min, placing in an extruder, extruding at 120-160 ℃, and obtaining the stable rubber powder polymer at the screw rotation speed of 550-680 r/min.
Further, the step (3) comprises the following processes:
heating the matrix asphalt to 160-180 ℃, adding the stable rubber powder polymer, and stirring at the rotating speed of 320-370 r/min for 1-3 h to obtain the modified asphalt. Further, in the step a, the molar ratio of 1, 4-dimercapto-2, 3-butanediol to triphenylmethanol is 1 (0.5-2.0); in the step a, the mol ratio of 1-butene-2, 3, 4-tricarboxylic acid, 3- (3-furyl) acrylic acid, the dehydrating agent and the product A is 1 (0.5-0.8) to (0.8-10) to (1.5-5.0).
Furthermore, the molar ratio of the active magnesium, the bromooctane and the o-dichlorobenzene in the step b is 1 (0.97-1.03) to 0.38-0.42; and b, the molar ratio of the product C to the maleic anhydride in the step b is 1 (1.1-1.4).
Furthermore, the molar ratio of the product B, the product D and the sodium styrene sulfonate in the step c is 1 (1.0-2.0) to 0.5-1.0; the molar ratio of the product E to the trifluoroacetic acid in the step c is 1 (1.0-1.2);
the mass ratio of the reactive additive to the waste rubber powder is 1 (4-9); the mass ratio of the matrix asphalt to the stable rubber powder polymer is (78-83) to (17-22).
In the technical scheme, under the action of sodium hydroxide, sulfydryl in 1, 4-dimercapto-2, 3-butanediol reacts with hydroxyl in trityl alcohol for grafting to obtain a product A; the product A reacts with carboxyl in 1-butene-2, 3, 4-tricarboxylic acid and 3- (3-furyl) acrylic acid under the action of a dehydrating agent and a catalyst to obtain polycarboxylic acid containing a mercapto protecting group and an unsaturated bond, namely a product B;
firstly, combining active magnesium with bromooctane, then reacting with o-dichlorobenzene under the action of 1, 3-bis (diphenylphosphino) propane nickel dichloride, and substituting chlorine groups on the o-dichlorobenzene by utilizing octane to obtain a product C; then under the action of aluminum chloride, maleic anhydride is grafted on a benzene ring of the product C to obtain carboxylic acid containing alkyl long-chain double tails and unsaturated bonds, namely a product D; the introduction of hydrophilic groups and the addition of hydrophobic long chains can improve the adaptability of the prepared reactive additive, stable rubber powder polymer and modified asphalt to high and low temperatures, and improve the temperature resistance; when the asphalt mixture is prepared, the bonding performance between the asphalt mixture and the sand is improved and stable, the molecular coupling is increased, and the compression resistance and crack resistance are enhanced; the high-temperature and low-temperature resistance of the prepared asphalt mixture can be effectively improved, and the crack resistance and the fatigue resistance of the asphalt mixture are kept;
polymerizing the product D with sodium styrene sulfonate, and introducing the product B to prepare a trimer; removing the sulfhydryl protecting group in the product B by trifluoroacetic acid, and limiting the process parameters to obtain a polycarboxyl and polymercapto polymer containing unsaturated bonds; reacting the obtained product with sodium hydroxide to obtain carboxylate and thiolate; when the modified asphalt is co-extruded with waste rubber powder and mixed with asphalt, ion pairs in the waste rubber powder are mutually attracted and aggregated due to electrostatic interaction, so that the strength of the prepared stable rubber powder polymer and the prepared modified asphalt can be improved; the unsaturated bond on the modified asphalt is grafted with the waste rubber powder, so that the strength of the prepared stable rubber powder polymer and the modified asphalt is further improved;
the prepared reactive additive is co-extruded with waste rubber powder at high temperature, so that disulfide bonds and carbon-sulfur bonds in the waste rubber powder are broken and the three-dimensional structure is destroyed at high temperature, the waste rubber powder is desulfurized, then the reactive additive reacts with the additive to reconstruct the three-dimensional cross-linked structure, the whole system is in a compact cross-linked network structure, the intermolecular combination is firm, the high-temperature performance of the modified asphalt is ensured, the low-temperature performance of the modified asphalt can be shown, and the processing flow performance is greatly improved;
when the prepared stable rubber powder polymer is mixed with asphalt, the desulfurization and cracking reaction is increased, the particle size of the stable rubber powder polymer is reduced, fewer asphalt light components, rubber oil, carbon black and the like are absorbed, a mutually-adhered network structure is formed, the interaction between the rubber powder polymer and the asphalt is improved, the rheological property of the modified asphalt is improved, the high-temperature performance of the modified asphalt is favorably maintained, the low-temperature performance of the modified asphalt is further improved, and the fatigue resistance of the modified asphalt is improved;
a stable rubber powder polymer composite modified asphalt mixture comprises 5.8-6.4 parts of modified asphalt, 89 parts of aggregate and 11 parts of mineral aggregate, wherein the aggregate comprises 30 parts of No. 1, 49 parts of No. 2, No. 8 and No. 4 and 11 parts of mineral aggregate.
In the technical scheme, the grain diameter of No. 1 is 10-15 mm, the grain diameter of No. 2 is 5-10 mm, the grain diameter of No. 3 is 3-5 mm, and the grain diameter of No. 4 is 0-3 mm;
compared with the prior art, the invention has the following beneficial effects:
the stable rubber powder polymer composite modified asphalt and the mixture thereof are prepared by preparing unsaturated monomers by using 1, 4-dimercapto-2, 3-butanediol, trityl alcohol, 1-butene-2, 3, 4-tricarboxylic acid, 3- (3-furyl) acrylic acid, active magnesium, bromooctane, o-dichlorobenzene and maleic anhydride as raw materials, copolymerizing the unsaturated monomers with sodium styrene sulfonate to prepare a reaction type additive containing polycarboxyl and multi-mercapto of unsaturated bonds, co-extruding the reaction type additive with waste rubber powder at high temperature to reconstruct a three-dimensional cross-linking structure, and improving the high-temperature performance of the prepared asphalt; and carboxylate and thiolate are introduced to strengthen the stable rubber powder polymer and improve the low temperature performance and the fatigue resistance of the modified asphalt.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Preparation of reactive additive:
a. dissolving 1, 4-dimercapto-2, 3-butanediol in diethyl ether, adding sodium hydroxide, stirring for 30min, adding trityl alcohol, and reacting for 8 h; carrying out reduced pressure distillation, washing and drying to obtain a product A; the mol ratio of the 1, 4-dimercapto-2, 3-butanediol to the triphenylmethanol is 1: 0.5;
dissolving 1-butene-2, 3, 4-tricarboxylic acid and 3- (3-furyl) acrylic acid in dichloromethane, controlling the temperature at 20 ℃, adding a dehydrating agent N, N' -dicyclohexylcarbodiimide, a catalyst styrene cation exchange resin and a product A, stirring and reacting for 12 hours under the protection of nitrogen, centrifuging, taking supernate, adding absolute ethyl alcohol, centrifuging, taking precipitate, washing and drying to obtain a product B; the mol ratio of the 1-butene-2, 3, 4-tricarboxylic acid, the 3- (3-furyl) acrylic acid, the dehydrating agent and the product A is 1:0.5:0.8: 1.5;
b. taking active magnesium and anhydrous ether, stirring and mixing under the protection of nitrogen, adding octyl bromide and the anhydrous ether, carrying out reflux reaction for 60min at 35 ℃, cooling, adding a mixed solution of 1, 3-bis (diphenylphosphino) propane nickel dichloride, o-dichlorobenzene and the anhydrous ether, carrying out reflux reaction for 58h, cooling to room temperature, slowly adding hydrochloric acid, taking an organic phase, washing, drying and distilling to obtain a product C; the molar ratio of the active magnesium to the bromooctane to the o-dichlorobenzene is 1:0.97: 0.38;
taking the product C and maleic anhydride, adding carbon disulfide, mixing, stirring, slowly adding anhydrous aluminum chloride, refluxing at 35 ℃ for 60min, cooling, slowly adding ice water and concentrated hydrochloric acid, stirring for 30min, removing a water phase, washing, extracting and drying to obtain a product D; the molar ratio of the product C to the maleic anhydride is 1: 1.1;
c. mixing the product D, a polymerization inhibitor and deionized water under the protection of nitrogen, adding a mixed aqueous solution of sodium styrene sulfonate and an initiator potassium persulfate, reacting for 4 hours at 78 ℃, adding the product B, and continuing to react for 1 hour to obtain a product E; the molar ratio of the product B to the product D to the sodium styrene sulfonate is 1:1.0: 0.5;
adding triethylsilane and trifluoroacetic acid, mixing, stirring for 30min, adding diethyl ether, precipitating, centrifuging, washing the precipitate, and vacuum drying; adding sodium hydroxide to adjust the pH value of the system to 7 to obtain a reactive additive; the molar ratio of the product E to the trifluoroacetic acid is 1: 1.0;
(2) preparation of stable rubber powder polymer:
drying the reactive additive and the waste rubber powder for 40min at 70 ℃, putting the dried mixture into an extruder, extruding the mixture at 120-160 ℃, and obtaining a stable rubber powder polymer at the screw rotation speed of 550 r/min; the mass ratio of the reactive additive to the waste rubber powder is 1: 4;
(3) preparing modified asphalt:
heating the matrix asphalt to 160 ℃, adding the stable rubber powder polymer, heating to 230 ℃ within 15min, and stirring at the rotating speed of 320r/min for 1h to obtain modified asphalt; the mass ratio of the matrix asphalt to the stable rubber powder polymer is 83: 17.
Example 2
(1) Preparation of reactive additive:
a. dissolving 1, 4-dimercapto-2, 3-butanediol in diethyl ether, adding sodium hydroxide, stirring for 75min, adding trityl alcohol, and reacting for 10 h; carrying out reduced pressure distillation, washing and drying to obtain a product A; the mol ratio of the 1, 4-dimercapto-2, 3-butanediol to the triphenylmethanol is 1: 1.2;
dissolving 1-butene-2, 3, 4-tricarboxylic acid and 3- (3-furyl) acrylic acid in dichloromethane, controlling the temperature at 30 ℃, adding a dehydrating agent N, N' -dicyclohexylcarbodiimide, a catalyst styrene cation exchange resin and a product A, stirring and reacting for 18 hours under the protection of nitrogen, centrifuging, taking supernate, adding absolute ethyl alcohol, centrifuging, taking precipitate, washing and drying to obtain a product B; the mol ratio of the 1-butene-2, 3, 4-tricarboxylic acid, the 3- (3-furyl) acrylic acid, the dehydrating agent and the product A is 1:0.6:5: 3.2;
b. taking active magnesium and anhydrous ether, stirring and mixing under the protection of nitrogen, adding octyl bromide and the anhydrous ether, carrying out reflux reaction at 38 ℃ for 75min, cooling, adding a mixed solution of 1, 3-bis (diphenylphosphino) propane nickel dichloride, o-dichlorobenzene and the anhydrous ether, carrying out reflux reaction for 60h, cooling to room temperature, slowly adding hydrochloric acid, taking an organic phase, washing, drying and distilling to obtain a product C; the molar ratio of the active magnesium to the bromooctane to the o-dichlorobenzene is 1:1.0: 0.40;
taking the product C and maleic anhydride, adding carbon disulfide, mixing, stirring, slowly adding anhydrous aluminum chloride, performing reflux reaction at 40 ℃ for 75min, cooling, slowly adding ice water and concentrated hydrochloric acid, stirring for 45min, removing a water phase, washing, extracting and drying to obtain a product D; the molar ratio of the product C to the maleic anhydride is 1: 1.2;
c. mixing the product D, a polymerization inhibitor and deionized water under the protection of nitrogen, adding a mixed aqueous solution of sodium styrene sulfonate and an initiator potassium persulfate, reacting for 4.5h at 80 ℃, adding the product B, and continuing to react for 1.5h to obtain a product E; the molar ratio of the product B to the product D to the sodium styrene sulfonate is 1:1.5: 0.8;
adding triethylsilane and trifluoroacetic acid, mixing, stirring for 45min, adding diethyl ether, precipitating, centrifuging, washing the precipitate, and vacuum drying; adding sodium hydroxide to adjust the pH value of the system to 7.5 to obtain a reactive additive; the molar ratio of the product E to trifluoroacetic acid is 1: 1.1;
(2) preparation of stable rubber powder polymer:
taking the reactive additive and the waste rubber powder, drying for 50min at 75 ℃, putting the mixture into an extruder, extruding at 120-160 ℃, and obtaining a stable rubber powder polymer at the screw rotation speed of 600 r/min; the mass ratio of the reactive additive to the waste rubber powder is 1: 6;
(3) preparing modified asphalt:
heating matrix asphalt to 170 ℃, adding a stable rubber powder polymer, heating to 240 ℃ within 15min, and stirring at the rotating speed of 350r/min for 2h to obtain modified asphalt; the mass ratio of the matrix asphalt to the stable rubber powder polymer is 80: 20.
Example 3
(1) Preparation of reactive additive:
a. dissolving 1, 4-dimercapto-2, 3-butanediol in diethyl ether, adding sodium hydroxide, stirring for 120min, adding trityl alcohol, and reacting for 12 h; carrying out reduced pressure distillation, washing and drying to obtain a product A; the mol ratio of the 1, 4-dimercapto-2, 3-butanediol to the triphenylmethanol is 1: 2;
dissolving 1-butene-2, 3, 4-tricarboxylic acid and 3- (3-furyl) acrylic acid in dichloromethane, controlling the temperature at 40 ℃, adding a dehydrating agent N, N' -dicyclohexylcarbodiimide, a catalyst styrene cation exchange resin and a product A, stirring for reacting for 24 hours under the protection of nitrogen, centrifuging, taking supernate, adding absolute ethyl alcohol, centrifuging, taking precipitate, washing and drying to obtain a product B; the mol ratio of the 1-butene-2, 3, 4-tricarboxylic acid, the 3- (3-furyl) acrylic acid, the dehydrating agent and the product A is 1:0.8:10: 5;
b. taking active magnesium and anhydrous ether, stirring and mixing under the protection of nitrogen, adding octyl bromide and the anhydrous ether, carrying out reflux reaction for 90min at 42 ℃, cooling, adding a mixed solution of 1, 3-bis (diphenylphosphino) propane nickel dichloride, o-dichlorobenzene and the anhydrous ether, carrying out reflux reaction for 60h, cooling to room temperature, slowly adding hydrochloric acid, taking an organic phase, washing, drying and distilling to obtain a product C; the molar ratio of the active magnesium to the bromooctane to the o-dichlorobenzene is 1:1.03: 0.42;
taking the product C and maleic anhydride, adding carbon disulfide, mixing, stirring, slowly adding anhydrous aluminum chloride, refluxing at 42 ℃ for 90min, cooling, slowly adding ice water and concentrated hydrochloric acid, stirring for 60min, removing a water phase, washing, extracting and drying to obtain a product D; the molar ratio of the product C to the maleic anhydride is 1: 1.4;
c. mixing the product D, a polymerization inhibitor and deionized water under the protection of nitrogen, adding a mixed aqueous solution of sodium styrene sulfonate and an initiator potassium persulfate, reacting for 5 hours at 82 ℃, adding the product B, and continuing to react for 2 hours to obtain a product E; the molar ratio of the product B to the product D to the sodium styrene sulfonate is 1:2.0: 1.0;
adding triethylsilane and trifluoroacetic acid, mixing, stirring for 60min, adding diethyl ether, precipitating, centrifuging, washing the precipitate, and vacuum drying; adding sodium hydroxide to adjust the pH value of the system to 8 to obtain a reactive additive; the molar ratio of the product E to trifluoroacetic acid is 1: 1.2;
(2) preparation of stable rubber powder polymer:
drying the reactive additive and the waste rubber powder for 60min at 80 ℃, putting the dried waste rubber powder and the waste rubber powder into an extruder, extruding the mixture at 120-160 ℃, and obtaining a stable rubber powder polymer at the screw rotation speed of 680 r/min; the mass ratio of the reactive additive to the waste rubber powder is 1: 9;
(3) preparing modified asphalt:
heating matrix asphalt to 180 ℃, adding a stable rubber powder polymer, heating to 250 ℃ within 15min, and stirring at the rotating speed of 370r/min for 3h to obtain modified asphalt; the mass ratio of the matrix asphalt to the stable rubber powder polymer is 78: 22.
Comparative example 1
(1) Preparation of reactive additive:
taking active magnesium and anhydrous ether, stirring and mixing under the protection of nitrogen, adding octyl bromide and the anhydrous ether, carrying out reflux reaction for 60min at 35 ℃, cooling, adding a mixed solution of 1, 3-bis (diphenylphosphino) propane nickel dichloride, o-dichlorobenzene and the anhydrous ether, carrying out reflux reaction for 58h, cooling to room temperature, slowly adding hydrochloric acid, taking an organic phase, washing, drying and distilling to obtain a product A; the molar ratio of the active magnesium to the bromooctane to the o-dichlorobenzene is 1:0.97: 0.38;
taking the product A and maleic anhydride, adding carbon disulfide, mixing, stirring, slowly adding anhydrous aluminum chloride, refluxing at 35 ℃ for 60min, cooling, slowly adding ice water and concentrated hydrochloric acid, stirring for 30min, removing a water phase, washing, extracting and drying to obtain a product B; the molar ratio of the product A to the maleic anhydride is 1: 1.1;
c. mixing the product B, a polymerization inhibitor and deionized water under the protection of nitrogen, adding a mixed aqueous solution of sodium styrene sulfonate and an initiator potassium persulfate, and reacting at 78 ℃ for 4 hours to obtain a product E; the molar ratio of the product D to the sodium styrene sulfonate is 1: 0.5;
adding triethylsilane and trifluoroacetic acid, mixing, stirring for 30min, adding diethyl ether, precipitating, centrifuging, washing the precipitate, and vacuum drying; adding sodium hydroxide to adjust the pH value of the system to 7 to obtain a reactive additive; the molar ratio of the product E to the trifluoroacetic acid is 1: 1.0;
the other process steps are the same as those in example 1, and modified asphalt is obtained.
Comparative example 2
c. Mixing the product D, the product B, a polymerization inhibitor and deionized water under the protection of nitrogen, adding a mixed aqueous solution of sodium styrene sulfonate and an initiator potassium persulfate, and reacting at 78 ℃ for 5 hours to obtain a product E; the molar ratio of the product B to the product D to the sodium styrene sulfonate is 1:1.0: 0.5;
the other process steps are the same as those in example 1, and modified asphalt is obtained.
Comparative example 3
(1) Preparation of reactive additive:
mixing acrylic acid, a polymerization inhibitor and deionized water under the protection of nitrogen, adding a mixed aqueous solution of sodium styrene sulfonate and an initiator potassium persulfate, and reacting at 78 ℃ for 4 hours to obtain a product E; the mol ratio of the acrylic acid to the styrene sodium sulfonate is 1: 0.5;
adding sodium hydroxide to adjust the pH value of the system to 7 to obtain a reactive additive; the molar ratio of the product E to the trifluoroacetic acid is 1: 1.0;
the other process steps are the same as those in example 1, and modified asphalt is obtained.
Comparative example 4
Taking waste rubber powder, drying at 70 ℃ for 40min, adding an activating agent, placing in an extruder, extruding at 120-160 ℃, and obtaining a rubber powder polymer at the screw rotation speed of 550 r/min;
heating the matrix asphalt to 160 ℃, adding the stable rubber powder polymer, heating to 230 ℃ within 15min, and stirring at the rotating speed of 320r/min for 1h to obtain modified asphalt; the mass ratio of the matrix asphalt to the rubber powder polymer is 83: 17.
The modified asphalt obtained in the above examples 1-3 and comparative examples 1-4 was prepared by the following components by weight: 6.4 parts of modified asphalt, 89 parts of aggregate and 11 parts of mineral aggregate, wherein the aggregate comprises 30 parts of No. 1, No. 49, No. 2, No. 3, No. 8 and No. 4 and 11 parts of mineral aggregate, and the asphalt mixture is prepared.
Experiment of
Samples were prepared from the modified asphalts obtained in examples 1 to 3 and comparative examples 1 to 4, and the properties thereof were measured and the results were recorded:
taking modified asphalt as a sample, and testing the penetration (25 ℃), softening point, ductility (5 ℃), elastic recovery, rotational viscosity (160 ℃) and fatigue life of the sample according to JTGE 20-2011; wherein the experimental temperature in the fatigue life test is 5 ℃, the strain level is 5%, and the fatigue life is the shearing frequency corresponding to the sample modulus reduced to 50% of the initial modulus;
taking the asphalt mixture as a sample, evaluating the high-temperature stability of the sample by using the dynamic stability of a rutting test, evaluating the water stability of the sample by using the residual strength ratio of a freeze-thaw splitting test, and evaluating the low-temperature crack resistance of the sample by using a trabecular bending test;
from the data in the table above, it is clear that the following conclusions can be drawn:
the modified asphalt and the mixture obtained in the examples 1 to 3 are compared with the modified asphalt and the mixture obtained in the comparative examples 1 to 4, and the detection results show that the modified asphalt and the mixture obtained in the examples 1 to 3 have better comprehensive performance, and the high-temperature rheological property of the asphalt is positively correlated with the high-temperature anti-rutting capability of the mixture, which fully shows that the invention realizes the improvement of the high-temperature resistance, the low-temperature resistance and the fatigue resistance of the modified asphalt and the mixture; and the comparative examples 1 to 4 can fully illustrate that the components used in the invention and the arrangement of the preparation process thereof have a promoting effect on the improvement of the comprehensive performance of the prepared modified asphalt and the mixture.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Furthermore, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process method article or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process method article or apparatus.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement and improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of stable rubber powder polymer composite modified asphalt is characterized by comprising the following steps: the preparation method comprises the following preparation processes:
(1) preparation of reactive additive:
a. taking 1, 4-dimercapto-2, 3-butanediol to react with triphenyl methanol to obtain a product A; reacting the product A with 1-butene-2, 3, 4-tricarboxylic acid and 3- (3-furyl) acrylic acid to obtain a product B;
b. taking active magnesium, bromooctane and o-dichlorobenzene, and reacting to obtain a product C; the product C reacts with maleic anhydride to obtain a product D;
c. taking the product B, the product D and sodium styrene sulfonate for reaction and copolymerization to obtain a product E; reacting with trifluoroacetic acid and sodium hydroxide in sequence to obtain a reactive additive;
(2) preparation of stable rubber powder polymer:
co-extruding the reactive additive and the waste rubber powder to obtain a stable rubber powder polymer;
(3) preparing modified asphalt:
and mixing the stable rubber powder polymer with the matrix asphalt to obtain the modified asphalt.
2. The preparation method of the stable rubber powder polymer composite modified asphalt as claimed in claim 1, wherein the preparation method comprises the following steps: the step (1) comprises the following preparation process:
a. dissolving 1, 4-dimercapto-2, 3-butanediol in ether, adding sodium hydroxide, stirring for 30-120 min, adding trityl alcohol, and reacting for 8-12 h; carrying out reduced pressure distillation, washing and drying to obtain a product A;
dissolving 1-butene-2, 3, 4-tricarboxylic acid and 3- (3-furyl) acrylic acid in dichloromethane, controlling the temperature to be 20-40 ℃, adding a dehydrating agent N, N' -dicyclohexylcarbodiimide, a catalyst styrene cation exchange resin and a product A, stirring and reacting for 12-24 hours under the protection of nitrogen, centrifuging, taking supernate, adding absolute ethyl alcohol, centrifuging, taking precipitate, washing and drying to obtain a product B;
b. taking active magnesium and anhydrous ether, stirring and mixing under the protection of nitrogen, adding octyl bromide and the anhydrous ether, carrying out reflux reaction at 35-42 ℃ for 60-90 min, cooling, adding a mixed solution of 1, 3-bis (diphenylphosphino) propane nickel dichloride, o-dichlorobenzene and the anhydrous ether, carrying out reflux reaction for 58-60 h, cooling to room temperature, slowly adding hydrochloric acid, taking an organic phase, washing, drying and distilling to obtain a product C;
taking the product C and maleic anhydride, adding carbon disulfide, mixing, stirring, slowly adding anhydrous aluminum chloride, carrying out reflux reaction at 35-42 ℃ for 60-90 min, cooling, slowly adding ice water and concentrated hydrochloric acid, stirring for 30-60 min, removing a water phase, washing, extracting and drying to obtain a product D;
c. mixing the product D, a polymerization inhibitor and deionized water under the protection of nitrogen, adding a mixed aqueous solution of sodium styrene sulfonate and an initiator potassium persulfate, reacting for 4-5 h at 78-82 ℃, adding the product B, and continuing to react for 1-2 h to obtain a product E;
adding triethylsilane and trifluoroacetic acid, mixing, stirring for 30-60 min, adding diethyl ether, precipitating, centrifuging, washing the precipitate, and vacuum drying; and adding sodium hydroxide to adjust the pH of the system to 7-8 to obtain the reactive additive.
3. The preparation method of the stable rubber powder polymer composite modified asphalt as claimed in claim 1, wherein the preparation method comprises the following steps: the step (2) comprises the following processes:
taking the reactive additive and the waste rubber powder, drying at 70-80 ℃ for 40-60 min, placing in an extruder, extruding at 120-160 ℃, and obtaining the stable rubber powder polymer at the screw rotation speed of 550-680 r/min.
4. The preparation method of the stable rubber powder polymer composite modified asphalt as claimed in claim 1, wherein the preparation method comprises the following steps: the step (3) comprises the following processes:
heating the matrix asphalt to 160-180 ℃, adding the stable rubber powder polymer, stirring at the rotating speed of 320-370 r/min for 1-3 h, adding 0.15-0.25% of calcium chloride, and uniformly stirring to obtain the stable rubber powder modified asphalt.
5. The preparation method of the stable rubber powder polymer composite modified asphalt as claimed in claim 2, wherein the preparation method comprises the following steps: in the step a, the molar ratio of 1, 4-dimercapto-2, 3-butanediol to triphenylmethanol is 1 (0.5-2.0); the mol ratio of the 1-butene-2, 3, 4-tricarboxylic acid, the 3- (3-furyl) acrylic acid, the dehydrating agent and the product A is 1 (0.5-0.8) to (0.8-10) to (1.5-5.0);
in the step b, the molar ratio of the active magnesium to the bromooctane to the o-dichlorobenzene is 1 (0.97-1.03) to 0.38-0.42; the molar ratio of the product C to the maleic anhydride is 1 (1.1-1.4).
6. The preparation method of the stable rubber powder polymer composite modified asphalt as claimed in claim 2, wherein the preparation method comprises the following steps: in the step c, the molar ratio of the product B to the product D to the sodium styrene sulfonate is 1 (1.0-2.0) to 0.5-1.0; the molar ratio of the product E to the trifluoroacetic acid in the step c is 1 (1.0-1.2).
7. The preparation method of the stable rubber powder polymer composite modified asphalt as claimed in claim 3, wherein the preparation method comprises the following steps: the mass ratio of the reactive additive to the waste rubber powder is 1 (4-9).
8. The preparation method of the stable rubber powder polymer composite modified asphalt as claimed in claim 4, wherein the preparation method comprises the following steps: the mass ratio of the matrix asphalt to the stable rubber powder polymer is (78-83) to (17-22).
9. A stabilized rubber powder polymer composite modified asphalt prepared by the preparation method according to any one of claims 1 to 8.
10. The stable rubber powder polymer composite modified asphalt mixture prepared from the stable rubber powder polymer composite modified asphalt according to claim 9, is characterized in that: the asphalt comprises 5.8-6.4 parts of modified asphalt, 89 parts of aggregate and 11 parts of mineral aggregate, wherein the aggregate comprises 30 parts of No. 1, No. 49, No. 2, No. 3, No. 8 and No. 4, and 11 parts of mineral aggregate.
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