CN111286208B - Composite TB rubber powder modified asphalt and preparation method thereof - Google Patents
Composite TB rubber powder modified asphalt and preparation method thereof Download PDFInfo
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- 239000010426 asphalt Substances 0.000 title claims abstract description 203
- 239000000843 powder Substances 0.000 title claims abstract description 115
- 239000002131 composite material Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 108
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 105
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 102
- 239000004094 surface-active agent Substances 0.000 claims abstract description 30
- 238000003756 stirring Methods 0.000 claims abstract description 26
- 239000003381 stabilizer Substances 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 238000010008 shearing Methods 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 238000004321 preservation Methods 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 23
- 229920001577 copolymer Polymers 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 12
- LPJKDVHMUUZHRY-KVVVOXFISA-N (z)-octadec-9-en-1-amine;hydrochloride Chemical compound Cl.CCCCCCCC\C=C/CCCCCCCCN LPJKDVHMUUZHRY-KVVVOXFISA-N 0.000 claims description 11
- 238000011081 inoculation Methods 0.000 claims description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims description 9
- 239000002048 multi walled nanotube Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000002109 single walled nanotube Substances 0.000 claims description 5
- 230000008092 positive effect Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
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- 238000006477 desulfuration reaction Methods 0.000 description 2
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- 229920000642 polymer Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
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- 239000011230 binding agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
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- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
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- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
Classifications
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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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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- Chemical & Material Sciences (AREA)
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- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Road Paving Structures (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a composite TB rubber powder modified asphalt which comprises the following raw materials in parts by weight: 85-95 parts of TB rubber powder asphalt; 1-3 parts of carbon nanotubes; 2-3 parts of a stabilizer; 3-9 parts of a surfactant; the preparation method comprises the steps of heating TB rubber powder asphalt to be molten; melt blending: mixing carbon nano tubes, a surfactant and molten TB rubber powder asphalt, keeping the temperature to enable the TB rubber powder asphalt to be in a molten state, and shearing the material to enable the carbon nano tubes to be dispersed in the TB rubber powder asphalt to obtain composite asphalt; adding a stabilizer into the composite asphalt, stirring the materials under the heat preservation condition to uniformly disperse the stabilizer, stopping heating and keeping stirring until the asphalt is cooled to obtain the composite TB rubber powder modified asphalt. Compared with the prior art, the invention can maintain the good low-temperature crack resistance of the TB rubber powder modified asphalt, further optimize the high-temperature performance and the fatigue performance of the TB rubber powder modified asphalt, and obviously improve the adhesion performance of the TB rubber powder modified asphalt, thereby having positive effects on the further popularization and application of the TB rubber powder modified asphalt.
Description
Technical Field
The invention relates to modified asphalt, in particular to composite TB rubber powder modified asphalt and a preparation method thereof, which can be used for high-grade asphalt pavement construction and belong to the field of road engineering.
Background
TB (terminal blend) rubber powder modified asphalt is a novel asphalt and is gradually developed in recent years. The TB rubber powder modified asphalt is prepared by the steps of performing thorough desulfurization and degradation reaction on rubber powder in asphalt at high temperature, enabling the rubber powder subjected to desulfurization and degradation to be compatible with the asphalt, and adding SBS and sulfur into the asphalt to perform a crosslinking reaction, thereby forming stable rubber powder modified asphalt. Researches find that the TB rubber powder modified asphalt has good storage stability and outstanding low-temperature and fatigue performances, but a plurality of researches indicate that the TB rubber powder modified asphalt has insufficient adhesiveness and poor water damage resistance, which seriously limits the further popularization and application of the TB rubber powder modified asphalt.
A nanomaterial is a material having at least one dimension in the range of 1-100 nanometers. When the size of the particle is small to the nanometer level, the property is transformed from quantitative change to qualitative change, and the mechanical, thermal, electrical, magnetic and optical properties of the particle are fundamentally changed. The nano particles have small size and large specific surface area, and the atoms on the surface account for a large proportion. Because surface atoms have unsaturated dangling bonds, the property is unstable, so that the activity of the nanoparticles is greatly increased, and a system consisting of nanoparticles shows many special properties different from a common bulk macroscopic material system, such as surface and interface effects, small-size effects, quantum size effects, macroscopic quantum tunneling effects and the like. Based on these special properties, the addition of nanopowder to traditional materials can greatly improve the performance or bring unexpected properties, which has become an important way to improve the performance of materials.
Carbon Nanotubes (CNTs) are a type of nanomaterial that is a single atom thick sheet of graphite rolled into a seamless hollow cylinder of approximately one nanometer in diameter. The number of graphene sheets can be divided into: single-walled carbon nanotubes (SWCNTs) and multi-walled carbon nanotubes (MWCNTs). CNTs were found by Iijima (1991). The CNTs have the characteristics of high strength, high Young modulus, high ductility, large length/diameter ratio, high specific surface energy, good electrical conductivity and thermal conductivity, good adhesion with a matrix, low addition amount and the like, so that the CNTs are widely applied to various industries at present. However, at present, the research on the modified asphalt adopting the CNTs is relatively limited, and the preparation process of the CNTs modified asphalt is not yet determined.
Disclosure of Invention
The invention aims to overcome the defect of insufficient adhesive property of the common TB rubber powder modified asphalt in the prior art and provide the composite TB rubber powder modified asphalt and the preparation method thereof.
The purpose of the invention can be realized by the following technical scheme:
the composite TB rubber powder modified asphalt comprises the following raw materials in parts by weight:
the carbon nano-tube is selected from single-wall carbon nano-tube or multi-wall carbon nano-tube or the mixture of the two.
The carbon nano tube has an outer diameter of 15-40 nm, a diameter length of 10-30 μm and a bulk density of 1.2-1.8 g/cm 3. The surfactant is a mixture of oleylamine hydrochloride and a high molecular weight alkyl ammonium salt copolymer; the mass ratio of the oleylamine hydrochloride to the high molecular weight alkyl ammonium salt copolymer is 1.4-2.6.
The number average molecular weight of the high molecular weight alkyl ammonium salt copolymer is 318.6-426.4 (g/mol).
The mass ratio of the surfactant to the carbon nano tubes is 3: 1-5: 1, preferably 3: 1.
The stabilizer is polyethylene terephthalate.
According to the invention, a certain amount of carbon nanotubes, a surfactant and a stabilizer are doped, the carbon nanotube/TB rubber powder composite modified asphalt is prepared by a melt blending preparation method, the special properties of the carbon nanotubes and the unique reaction of the activated carbon nanotubes and the asphalt remarkably improve the adhesion performance of the TB rubber powder composite modified asphalt, and the defect of insufficient adhesion performance of the common TB rubber powder modified asphalt is overcome.
In the process of modifying TB rubber powder asphalt by adopting the carbon nano tubes, how to keep the carbon nano tubes dispersed in the asphalt is very critical, and because the carbon nano tubes have very large specific surface area, very strong van der Waals force action exists between the tubes, and each nano carbon nano tube reaches about 0.5ev, and the carbon nano tubes exist in an agglomerated state and are difficult to disperse in a common state and are insoluble in water and an organic solvent. Therefore, the carbon nanotubes need to be modified to be easily dispersed in a solvent, and the modification method can be classified into covalent modification and non-covalent modification according to the existence of covalent bond. The non-covalent modification method combines the surface electrons of the carbon nano tube with the electrons in other organic molecules through-conjugation and coordination effects, does not damage the structure of the carbon nano tube, and thus obtains the functional carbon nano tube with the unchanged structure. Surfactants are one of the common means of non-covalent modification. The surface active agent is wrapped outside the carbon nano tube to change the surface property of the carbon nano tube. The surface active agent is added to improve the surface characteristics of the carbon nano tubes, and the carbon nano tube aggregate is helped to overcome strong van der Waals force to be unwound and dispersed into the asphalt to form a stable interface with the asphalt polymer. The experiment shows that the ratio of the surfactant: carbon nanotubes ═ 3:1 (weight portion), the surface active agent just can wrap the outer surface of all the carbon nano tubes, and the dispersion stability of the carbon nano tubes in the asphalt is best. The surfactant has strong wettability, can promote the rubber powder surface to generate an organic molecular layer, and changes hydrophilicity into hydrophilicity, so that the adhesion performance and the water damage resistance of the asphalt are obviously improved.
In the process of the invention, the polyethylene glycol terephthalate is added at the last stage of the development of the modified asphalt, so that the compatibility of the asphalt can be greatly improved, the agglomeration of carbon nano tubes can be well prevented, the dispersion phase is more uniform in a dispersion medium, the consumption of a vulcanization stabilizer can be reduced, the viscosity of the asphalt is reduced, and the construction workability is improved.
In the process of the invention, the scanning electron microscope is used for observing the section morphology of the modified asphalt containing 1% and 3% of the CNTs additive, and the fact that the section of the CNTs modified asphalt has a plurality of fibers pointing to the stretching direction is found, and the fibers are mutually connected to form a good network structure; with the increase of the addition amount of CNTs, the fiber network becomes more compact and stronger in connectivity. The observation appearance is locally amplified to find that the CNTs have a pull-out behavior at the root, and the conclusion that the CNTs network can enhance the stress performance of the asphalt and inhibit the crack expansion in a bridging mode to prolong the fatigue life is finally obtained by combining the macroscopic experiment result. The CNTs and the asphalt form a fiber network, so that chemical crosslinking and physical winding can be performed between the rubber powder and the asphalt to play a coupling role, and the deformation capability of the asphalt and the adhesion of the asphalt and aggregate are improved; the internal components of the carbon nano tube/TB rubber powder composite modified asphalt are closely crosslinked, and moisture is difficult to enter three-phase interfaces of rubber powder particles, asphalt and aggregate, so that the water damage resistance of the carbon nano tube/TB rubber powder composite modified asphalt is improved.
The invention also provides a preparation method of the composite TB rubber powder modified asphalt, which comprises the following steps:
preheating: heating TB rubber powder asphalt to be molten;
melt blending: mixing carbon nano tubes, a surfactant and molten TB rubber powder asphalt, keeping the temperature to enable the TB rubber powder asphalt to be in a molten state, and shearing the material to enable the carbon nano tubes to be dispersed in the TB rubber powder asphalt to obtain composite asphalt;
inoculation: adding a stabilizer into the composite asphalt, stirring the materials under the heat preservation condition to uniformly disperse the stabilizer, stopping heating and keeping stirring until the asphalt is cooled to obtain the composite TB rubber powder modified asphalt.
In the process of melt blending, the temperature of the TB rubber powder asphalt in a molten state is 200 +/-10 ℃; the shearing treatment is to shear for 1.5 to 2 hours at the speed of 2500 +/-50 r/min by using a shearing machine.
In the inoculation process, after the stabilizer is added, the temperature of the material is kept at 200 +/-10 ℃, and the time for stirring the material under the heat preservation condition is 0.3-0.7 hour.
Compared with the prior art, the invention can maintain the good low-temperature crack resistance of the TB rubber powder modified asphalt, further optimize the high-temperature performance and the fatigue performance of the TB rubber powder modified asphalt, and obviously improve the adhesion performance of the TB rubber powder modified asphalt, thereby having positive effect on the large-scale application of the TB rubber powder modified asphalt.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the invention.
The composite TB rubber powder modified asphalt comprises the following raw materials in parts by weight:
the following are the specific components and functions of each raw material:
the carbon nanotubes are selected from single-wall carbon nanotubes or multi-wall carbon nanotubes or a mixture of the two; the carbon nanotube has an outer diameter of 15 to 40nm, a diameter of 10 to 30 μm, and a bulk density of 1.2 to 1.8g/cm 3 。
Surfactant (b): the surfactant is a mixture of oleylamine hydrochloride and a high molecular weight alkylammonium salt copolymer; the mass ratio of the oleylamine hydrochloride to the high molecular weight alkylammonium salt copolymer is 1.4-2.6, preferably 2: 1, and the number average molecular weight of the high molecular weight alkylammonium salt copolymer is 318.6-426.4 (g/mol).
The carbon nano tubes have extremely large specific surface area, so that extremely strong van der Waals force action exists among the tubes, and each nano carbon nano tube reaches about 0.5ev, and the carbon nano tubes exist in an agglomerated state and are difficult to disperse in a normal state, and are insoluble in water and an organic solvent. Therefore, the carbon nanotubes need to be modified to be easily dispersed in a solvent, and the modification method can be classified into covalent modification and non-covalent modification according to the existence of covalent bond. The non-covalent modification method utilizes the passage of electrons on the surface of the carbon nano tube and electrons in other organic molecules
And (4) combining conjugation and coordination effects, and not damaging the structure of the carbon nanotube, thereby obtaining the functional carbon nanotube with the unchanged structure. Surfactants are one of the common means of non-covalent modification. The surface active agent is wrapped outside the carbon nano-tube to change the surface property of the carbon nano-tube. The surface active agent is added to improve the surface characteristics of the carbon nano tubes, and is helpful for the carbon nano tube agglomerates to overcome strong van der Waals force to be disentangled and dispersed in the asphalt to form a stable interface with the asphalt polymer. The experiment shows that the ratio of the surfactant: carbon nanotubes ═ 3: 1-5: 1, preferably 3:1 (weight portion), the surface active agent can just wrap the outer surface of all the carbon nano tubes, and the dispersion stability of the carbon nano tubes in the asphalt is the best. The surfactant has strong wettability, can promote the rubber powder surface to generate an organic molecular layer, and changes hydrophilicity into hydrophilicity, so that the adhesion performance and the water damage resistance of the asphalt are obviously improved.
A stabilizer: the stabilizer is polyethylene glycol terephthalate, and the polyethylene glycol terephthalate is added at the last stage of development of the modified asphalt, so that the compatibility of the asphalt can be greatly improved, the agglomeration of carbon nano tubes can be well prevented, the dispersion phase is more uniform in a dispersion medium, the consumption of the vulcanization stabilizer can be reduced, the viscosity of the asphalt is reduced, and the workability of construction is improved.
In the process of the invention, the morphology of the modified asphalt section of 1% and 3% of the CNTs additive is observed by using a scanning electron microscope, and the CNTs modified asphalt section is found to have a plurality of fibers pointing to the stretching direction, and the fibers are mutually connected to form a good network structure; with the increase of the addition amount of CNTs, the fiber network becomes more compact and stronger in connectivity. The observation morphology is locally amplified to discover that the CNTs have pull-out behavior at the root, and the conclusion that the CNTs network can enhance the stress performance of the asphalt and inhibit the crack propagation in a bridging mode to prolong the fatigue life is finally obtained by combining the macroscopic experiment result. The CNTs and the asphalt form a fiber network, so that chemical crosslinking and physical winding can be performed between the rubber powder and the asphalt to play a coupling role, and the deformation capability of the asphalt and the adhesion of the asphalt and aggregate are improved; the internal components of the carbon nano tube/TB rubber powder composite modified asphalt are closely crosslinked, and moisture is difficult to enter three-phase interfaces of rubber powder particles, asphalt and aggregate, so that the water damage resistance of the carbon nano tube/TB rubber powder composite modified asphalt is improved.
The preparation method of the composite TB rubber powder modified asphalt comprises the following steps:
(1) preheating: heating the TB rubber powder asphalt to 200 +/-10 ℃ to melt the TB rubber powder asphalt;
(2) melt blending: mixing carbon nanotubes, a surfactant and molten TB rubber powder asphalt, keeping the temperature at 200 +/-10 ℃, and shearing the mixture for 1.5-2 hours at the speed of 2500 +/-50 r/min by using a high-speed shearing rheometer to disperse the aggregated carbon nanotubes so that the carbon nanotubes are uniformly dispersed in the asphalt;
(3) inoculation: and adding a stabilizer into the composite asphalt, stirring for 0.3-0.7 h at 200 +/-10 ℃ by using a mechanical stirrer, stopping heating, and continuously stirring until the asphalt is cooled to finally obtain the uniformly dispersed carbon nano tube/TB rubber powder composite modified asphalt.
The following is a specific implementation process of the invention:
example 1
The carbon nano tube/TB rubber powder composite modified asphalt is prepared by the following method:
(1) preheating: firstly, 92 parts of TB rubber powder modified asphalt is heated to 200 ℃;
(2) melt blending: weighing 1.5 parts of carbon nanotubes and 4.5 parts of surfactant (a mixture of oleylamine hydrochloride and a high molecular weight alkyl ammonium salt copolymer according to a mass ratio of 2, wherein the number average molecular weight of the high molecular weight alkyl ammonium salt copolymer is 372(g/mol)) to be mixed with molten asphalt, maintaining the mixture at 200 ℃, and shearing the mixture at a speed of 2500r/min for 1.5 hours by using a high-speed shearing rheometer to disperse the aggregated carbon nanotubes so that the carbon nanotubes are uniformly dispersed in the asphalt;
(3) inoculation: adding 2 parts of stabilizer (polyethylene glycol terephthalate) into the composite asphalt, stirring for 0.5h at 200 ℃ by using a mechanical stirrer, stopping heating and continuously stirring until the asphalt is cooled, and finally obtaining the uniformly dispersed carbon nano tube/TB rubber powder composite modified asphalt.
Example 2
The carbon nano tube/TB rubber powder composite modified asphalt is prepared by the following method:
(1) preheating: firstly, 89 parts of TB rubber powder modified asphalt is heated to 200 ℃;
(2) melt blending: weighing 2 parts of carbon nanotubes and 6 parts of surfactant (a mixture of oleylamine hydrochloride and a high molecular weight alkyl ammonium salt copolymer according to a mass ratio of 1.5, wherein the number average molecular weight of the high molecular weight alkyl ammonium salt copolymer is 372(g/mol)) and mixing with molten asphalt, maintaining the temperature at 200 ℃, and shearing for 1.5 hours at a speed of 2500r/min by using a high-speed shearing rheometer to disperse the aggregated carbon nanotubes so that the carbon nanotubes are uniformly dispersed in the asphalt;
(3) inoculation: adding 3 parts of stabilizer (polyethylene glycol terephthalate) into the composite asphalt, stirring for 0.5h at 200 ℃ by using a mechanical stirrer, stopping heating and continuously stirring until the asphalt is cooled, and finally obtaining the uniformly dispersed carbon nano tube/TB rubber powder composite modified asphalt.
Example 3
The carbon nano tube/TB rubber powder composite modified asphalt is prepared by the following method:
(1) preheating: firstly, 85 parts of TB rubber powder modified asphalt is heated to 200 ℃;
(2) melt blending: weighing 3 parts of carbon nanotubes and 9 parts of surfactant (a mixture of oleylamine hydrochloride and a high molecular weight alkyl ammonium salt copolymer according to a mass ratio of 1.5, wherein the number average molecular weight of the high molecular weight alkyl ammonium salt copolymer is 372(g/mol)) and mixing with molten asphalt, maintaining the temperature at 200 ℃, and shearing for 1.5 hours at a speed of 2500r/min by using a high-speed shearing rheometer to disperse the aggregated carbon nanotubes so that the carbon nanotubes are uniformly dispersed in the asphalt;
(3) inoculation: adding 3 parts of stabilizer (polyethylene glycol terephthalate) into the composite asphalt, stirring for 0.5h at 200 ℃ by using a mechanical stirrer, stopping heating and continuously stirring until the asphalt is cooled, and finally obtaining the uniformly dispersed carbon nano tube/TB rubber powder composite modified asphalt.
Example 4
The carbon nano tube/TB rubber powder composite modified asphalt is prepared by the following method:
(1) preheating: firstly, 85 parts of TB rubber powder modified asphalt is heated to 200 ℃;
(2) melt blending: weighing 3 parts of carbon nanotubes, 9 parts of a surfactant (a mixture of oleylamine hydrochloride and a high molecular weight alkylammonium salt copolymer according to a mass ratio of 1.4, wherein the number average molecular weight of the high molecular weight alkylammonium salt copolymer is 318.6(g/mol)) and mixing with molten asphalt, maintaining the temperature at 200 ℃, and shearing for 2 hours at a speed of 2450r/min by using a high-speed shearing rheometer to disperse the aggregated carbon nanotubes so that the carbon nanotubes are uniformly dispersed in the asphalt;
(3) inoculation: adding 3 parts of stabilizer (polyethylene glycol terephthalate) into the composite asphalt, stirring for 0.3h at 200 ℃ by using a mechanical stirrer, stopping heating and continuously stirring until the asphalt is cooled, and finally obtaining the uniformly dispersed carbon nano tube/TB rubber powder composite modified asphalt.
Example 5
The carbon nano tube/TB rubber powder composite modified asphalt is prepared by the following method:
(1) preheating: firstly, 85 parts of TB rubber powder modified asphalt is heated to 200 ℃;
(2) melt blending: weighing 3 parts of carbon nanotubes and 9 parts of surfactant (a mixture of oleylamine hydrochloride and a high molecular weight alkyl ammonium salt copolymer according to a mass ratio of 2.6, wherein the number average molecular weight of the high molecular weight alkyl ammonium salt copolymer is 426.4(g/mol)) and mixing with molten asphalt, maintaining the temperature at 200 ℃, and shearing for 1.5 hours at a speed of 2550r/min by using a high-speed shearing rheometer to disperse the aggregated carbon nanotubes so that the carbon nanotubes are uniformly dispersed in the asphalt;
(3) inoculation: adding 3 parts of stabilizer (polyethylene glycol terephthalate) into the composite asphalt, stirring for 0.7h at 200 ℃ by using a mechanical stirrer, stopping heating and continuously stirring until the asphalt is cooled, and finally obtaining the uniformly dispersed carbon nano tube/TB rubber powder composite modified asphalt.
Comparative example 1
The comparative example is common TB rubber powder modified asphalt.
Comparative example 2
The PE modifier/TB rubber powder composite modified asphalt is prepared by the following method:
(1) the asphalt is put into an oven, and the TB rubber powder modified asphalt is heated at 140 ℃ (within one hour as much as possible and not more than one and a half hours).
(2) And stirring 5 parts of PE modifier and 95 parts of TB rubber powder modified asphalt for 2 hours at 180 ℃, wherein the temperature rise is completed within 15min in the stirring process, and the highest temperature cannot exceed 185 ℃.
(3) The stirred composite modified asphalt needs to be manually stirred before each use, and is used after being completely and uniformly stirred.
Comparative example 3
The rock asphalt/TB rubber powder composite modified asphalt is prepared by the following method:
(1) the asphalt is put into an oven, and the TB rubber powder modified asphalt is heated at 140 ℃ (within one hour as much as possible and not more than one and a half hours).
(2) Stirring 10 parts of weighed rock asphalt and 90 parts of TB rubber powder modified asphalt at 180 ℃ for 2 hours, wherein in the stirring process, the temperature rise is completed within 15min, and the highest temperature cannot exceed 185 ℃.
(3) The stirred composite modified asphalt needs to be manually stirred before each use, and is used after being completely and uniformly stirred.
Comparative example 4
The SBS \ TB rubber powder composite modified asphalt is prepared by the following method:
(1) the asphalt is put into an oven, and the TB rubber powder modified asphalt is heated at 140 ℃ (within one hour as much as possible and not more than one and a half hours).
(2) Stirring the weighed 4.5 parts of SBS block copolymer and 94.5 parts of TB rubber powder modified asphalt at 180 ℃ for 2 hours, wherein in the stirring process, the temperature rise is completed within 15min, and the highest temperature cannot exceed 185 ℃.
(3) The stirred composite modified asphalt needs to be manually stirred before each use, and is used after being completely and uniformly stirred.
Performance testing
The PG grade of the asphalt is determined according to the performance-based asphalt binder grading specification of SHRP in America, the performance tests of the composite TB rubber powder modified asphalt prepared in the examples 1-3 and the comparative examples 1-4 are respectively carried out according to the JTG E20-2011 of the Industrial Standard road engineering asphalt and mixture test Specification of the department of transportation, the asphalt mixture adopts AR-AC-13 type, and the oilstone ratio is 4.7%. The test results are shown in table 1:
TABLE 1 comparison of Performance test results of examples 1-3 and comparative examples 1-4
The PG grading represents the performance grading of the asphalt, such as PG58-22, which means that the physical performance of the asphalt meets the road requirement within the temperature range of-22 to 58 ℃, wherein 58 represents a high-temperature grade and-22 represents a low-temperature grade, the higher the high-temperature grade is, the stronger the high-temperature rutting resistance of the asphalt is, and the smaller the low-temperature grade is, the better the low-temperature cracking resistance of the asphalt is; the adhesion grade is that a boiling method is adopted, the stripping condition of the aggregate coated asphalt film is observed after certain test conditions are passed, the percentage adhesion grade of the stripping area is evaluated according to visual inspection, and the higher the grade is, the better the adhesion performance of the asphalt is; TSR means to carry out freeze-thaw cycle on the asphalt mixture under specified conditions, and the measured splitting damage strength ratio of the mixture before and after water damage is used for evaluating the water stability of the asphalt mixture; the fatigue times of 1250 epsilon mu Nf50 refer to the stress action times when the stiffness modulus of the asphalt mixture trabecula is reduced to 50 percent of the initial stiffness modulus under the strain of 1250 epsilon mu in a strain-controlled four-point bending fatigue test, and the higher the stress action times, the stronger the fatigue resistance of the asphalt mixture is, and the longer the fatigue life is.
The experimental data show that: compared with the comparative example, the PG high-temperature grade of the composite TB rubber powder modified asphalt prepared by the invention in the examples 1-3 is slightly improved and the low-temperature grade is unchanged compared with the common TB rubber powder modified asphalt, which shows that the high-temperature rutting resistance of the composite TB rubber powder modified asphalt is improved to a certain extent and the excellent low-temperature cracking resistance is still maintained; the adhesion grade and TSR of the examples 1-3 are obviously improved, which shows that the adhesion performance of the composite TB rubber powder modified asphalt is obviously improved; the fatigue times of 1250 epsilon mu Nf50 of the examples 1 to 3 are larger than those of the comparative examples 1 to 4, which shows that the fatigue performance of the composite TB rubber powder modified asphalt is also improved.
The comparative example 1 is common TB rubber powder modified asphalt, the comparative example 2 is chemical modification of the TB rubber powder modified asphalt by the PE modifier, and test results show that the modification effect is not obvious. The comparative example 3 is that rock asphalt chemically modifies the TB rubber powder modified asphalt, and the high-temperature performance, the adhesion performance and the fatigue performance of the obtained rock asphalt/TB rubber powder composite modified asphalt are improved to a certain extent, but the low-temperature performance is reduced. The comparative example 3 is that the SBS block copolymer is used for chemically modifying the TB rubber powder modified asphalt, the high-temperature performance, the adhesion performance and the fatigue performance of the obtained SBS/TB rubber powder composite modified asphalt are improved to a small extent, and the low-temperature performance is kept unchanged.
As can be seen from the comparison of the data of the examples 1-3 and the comparative examples 1-4, the carbon nano tube \ TB rubber powder composite modified asphalt still maintains the excellent low-temperature performance of the TB rubber powder, the high-temperature performance and the fatigue performance are improved, and the asphalt adhesion and the water damage resistance of the mixture are obviously improved. The conventional modifiers such as SBS, PE and rock asphalt can improve the performance of the TB rubber powder modified asphalt without the carbon nano tube.
In conclusion, the carbon nanotube/TB rubber powder composite modified asphalt prepared by the technology can maintain the good low-temperature crack resistance of the TB rubber powder modified asphalt, further optimize the high-temperature performance and the fatigue performance of the TB rubber powder modified asphalt, and obviously improve the adhesion performance of the TB rubber powder modified asphalt. The invention has positive effect on large-scale application of TB rubber powder modified asphalt.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (4)
1. The preparation method of the composite TB rubber powder modified asphalt is characterized in that the raw materials comprise the following components in parts by weight:
85-95 parts of TB rubber powder asphalt;
1-3 parts of carbon nanotubes;
2-3 parts of a stabilizer;
3-9 parts of a surfactant;
the carbon nano tube has the outer diameter of 15-40 nm, the diameter length of 10-30 mu m and the bulk density of 1.2-1.8 g/cm 3 ;
The surfactant is a mixture of oleylamine hydrochloride and a high molecular weight alkyl ammonium salt copolymer; the mass ratio of the oleylamine hydrochloride to the high molecular weight alkyl ammonium salt copolymer is 1.4-2.6;
the mass ratio of the surfactant to the carbon nano tube is 3: 1-5: 1, the internal components of the composite TB rubber powder modified asphalt are tightly crosslinked, and moisture is difficult to enter a three-phase interface of rubber powder particles, the TB rubber powder modified asphalt and aggregate;
the number average molecular weight of the high molecular weight alkyl ammonium salt copolymer is 318.6-426.4 g/mol;
the stabilizer is polyethylene glycol terephthalate;
the preparation method comprises the following steps:
preheating: heating TB rubber powder asphalt to be molten;
melt blending: mixing carbon nano tubes, a surfactant and molten TB rubber powder asphalt, keeping the temperature to enable the TB rubber powder asphalt to be in a molten state, and shearing the material to enable the carbon nano tubes to be dispersed in the TB rubber powder asphalt to obtain composite asphalt;
inoculation: adding a stabilizer into the composite asphalt, stirring the materials under the heat preservation condition to uniformly disperse the stabilizer, stopping heating and keeping stirring until the asphalt is cooled to obtain the composite TB rubber powder modified asphalt.
2. The method for preparing composite TB rubber powder modified asphalt as claimed in claim 1, wherein the carbon nanotubes are selected from single-walled carbon nanotubes or multi-walled carbon nanotubes or a mixture of the two.
3. The method for preparing the composite TB rubber powder modified asphalt as claimed in claim 1, wherein in the process of melt blending, the temperature of the TB rubber powder asphalt in a molten state is 200 +/-10 ℃; the shearing treatment is to shear for 1.5 to 2 hours at the speed of 2500 +/-50 r/min by using a shearing machine.
4. The preparation method of the composite TB rubber powder modified asphalt as claimed in claim 1, wherein in the inoculation process, after the stabilizer is added, the temperature of the material is kept at 200 +/-10 ℃, and the time for stirring the material under the heat preservation condition is 0.3-0.7 hour.
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