CN116041975B - Graphene nano-sheet/block copolymer composite modified asphalt, and preparation method and application thereof - Google Patents

Graphene nano-sheet/block copolymer composite modified asphalt, and preparation method and application thereof Download PDF

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CN116041975B
CN116041975B CN202310288673.0A CN202310288673A CN116041975B CN 116041975 B CN116041975 B CN 116041975B CN 202310288673 A CN202310288673 A CN 202310288673A CN 116041975 B CN116041975 B CN 116041975B
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asphalt
styrene
block copolymer
graphene nano
acid
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CN116041975A (en
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丁永玲
孙华东
张爱勤
赵鲲鹏
屈磊
庞来学
周亮
熊大路
袁凯
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Shandong Jiaotong University
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Shandong Jiaotong University
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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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2265—Oxides; Hydroxides of metals of iron
    • C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2289—Oxides; Hydroxides of metals of cobalt
    • 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

Abstract

The invention discloses graphene nano-sheet/block copolymer composite modified asphalt, a preparation method and application thereof, and belongs to the technical field of nano-material modified asphalt. According to the invention, the graphene nano-sheet loaded with the metal oxide is prepared by a one-step in-situ method, and after the nano-sheet is subjected to functional modification, the graphene nano-sheet and the functional modified styrene block copolymer are used for modifying the matrix asphalt, so that the graphene nano-sheet/block copolymer composite modified asphalt is finally obtained. According to the invention, by adding the segmented copolymer and the graphene nano-sheet loaded with the oxide, the heating and self-repairing performances of the asphalt material under the induction of microwave heat are improved, and meanwhile, the prepared modified asphalt material has good comprehensive performance, excellent oxidation resistance and rutting resistance, difficult deformation, repairability and long service life.

Description

Graphene nano-sheet/block copolymer composite modified asphalt, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of nano material modified asphalt, and particularly relates to graphene nano sheet/block copolymer composite modified asphalt, a preparation method and application thereof.
Background
Asphalt materials can be gradually aged under the actions of ultraviolet rays, thermal oxygen, vehicle loads and the like during the service period of the pavement. Asphalt aging reduces the adhesion performance between asphalt and aggregate, so that asphalt pavement is subject to cracking, loosening, pits and other diseases. Studies show that asphalt concrete is a material with self-repairing property, after a certain intermittent time under a specific environment, partial microcracks in the asphalt concrete can be automatically closed, and the service performance of the asphalt concrete is gradually recovered, and the characteristic is mainly generated by thermodynamic actions such as infiltration, diffusion, mutual dissolution and the like of asphalt. At present, microcapsule self-repairing technology and thermal induction self-repairing technology are adopted to promote the self-repairing process of asphalt. The heat-induced self-repairing technology mainly depends on the characteristic that the self-repairing process of asphalt concrete has strong dependence on temperature, for example, when the temperature is low, the thermodynamic movement degree of asphalt molecules is low, and the self-repairing process of asphalt concrete cannot be realized through the actions of infiltration, diffusion, mutual dissolution and the like. In order to raise the self-repairing temperature of asphalt concrete, it is generally necessary to make the temperature of asphalt reach a certain temperature as soon as possible by means of auxiliary heat-induced heating. Therefore, there is a need to explore a modified asphalt capable of achieving self-healing properties by thermally induced warming.
Disclosure of Invention
The invention provides a preparation method of graphene nano-sheet/block copolymer composite modified asphalt, which comprises the following steps:
mixing graphene nano sheets with an organic solvent, and performing ultrasonic dispersion to obtain graphene nano sheet dispersion liquid; heating matrix asphalt to form uniform liquid, adding a block copolymer, and shearing at constant temperature to obtain block copolymer modified asphalt; and mixing the graphene nano sheet dispersion liquid with the block copolymer modified asphalt, shearing at constant temperature, adding a crosslinking stabilizer, and continuously shearing to obtain the graphene nano sheet/block copolymer composite modified asphalt.
In the preparation method of the graphene nano sheet/block copolymer composite modified asphalt, the raw materials are selected from the following components in parts by mass:
0.1 to 6 parts of graphene nano-sheets, 1 to 10 parts of organic solvent, 100 parts of matrix asphalt, 1 to 6 parts of block copolymer and 0.1 to 0.5 part of crosslinking stabilizer.
In the preparation method of the graphene nano sheet/block copolymer composite modified asphalt, the organic solvent is one or more selected from ethanol, N-butanol, N-dimethylformamide, azomethylpyrrolidone and propylene glycol; the matrix asphalt is selected from one or more of coal tar asphalt, petroleum asphalt and natural asphalt; the crosslinking stabilizer is selected from dipentaerythritol hexa (3-mercaptopropionate), ethylene glycol bis (3-mercaptopropionate), and tris [2- (3-mercaptopropionyloxy) ethyl ] ]One or more of isocyanurate, trimethylolpropane tri (3-mercaptopropionate) and pentaerythritol tetra (3-mercaptopropionate); the graphene nano sheet is selected from graphene nano sheets with metal oxide loaded on the surface by amination, and can be specifically selected from aminated Fe 3 O 4 -GNPs, aminated CoO-GNPs or aminated NiO-GNPs; the block copolymer is selected from the group consisting of carboxyl functional group modified styrene block copolymers, i.e., carboxylated styrene block copolymers.
In the preparation method of the graphene nano-sheet/block copolymer composite modified asphalt, the constant-temperature shearing condition is selected from the following conditions: shearing for 20-120 min at the temperature of 150-180 ℃ and at the speed of 3000-8000 r/min.
The invention provides a preparation method of the graphene nano sheet with the surface aminated and loaded with metal oxide, which comprises the following steps:
mixing graphite, metal salt and separating agent, grinding uniformly, placing in vacuum environment, reacting for 10-24 h at 150-250 ℃; washing a reaction product by adopting an organic solvent, then placing the reaction product in an air atmosphere, and annealing for 2-5 hours at 300-350 ℃ to obtain graphene nano sheets loaded with metal oxides; adding the graphene nano-sheets loaded with the metal oxides into a dispersing agent, carrying out ultrasonic treatment, adding an amino modifier, uniformly mixing, reacting for 6-24 hours at the temperature of 80-160 ℃, and cleaning by an organic solvent to obtain the graphene nano-sheets with the surface aminated and loaded with the metal oxides.
In the preparation method of the graphene nano-sheet with the surface aminated and loaded with the metal oxide, the mass ratio of the graphite to the metal salt to the separating agent to the dispersing agent to the amino modifier is selected from 1:0.2-2:2-6:10-30:3-10; the granularity of the graphite is selected from 50-5000 meshes; the metal salt is selected from at least one of the halides, acetates, nitrates, oxalates, carbonates and sulfates of Mn, co, fe, ni; the separating agent is at least one of maleic anhydride, maleimide, citraconic anhydride, polypropylene-maleic anhydride, dimethyl maleic anhydride, N-methyl maleimide, N-hydroxy maleimide, 4-maleimide butyric acid and 5-maleimide valeric acid; the dispersing agent is selected from one of dichloromethane, chloroform, anisole, toluene, N-dimethylformamide, N-dimethylacetamide and tetrahydrofuran; the amino modifier is selected from one of furfuryl amine, 2-furfuryl amide and 5-bromo-2-furfuryl amide; the organic solvent is selected from one of tetrahydrofuran, dichloromethane and chloroform.
The invention provides a preparation method of the styrene block copolymer modified by carboxyl functional groups, which comprises the following steps:
adding the styrene block copolymer and the compound containing the carboxyl functional group into an organic solvent, stirring uniformly, then adding an initiator, reacting for 4-24 hours at the temperature of 10-80 ℃, modifying the carboxyl functional group, removing the solvent after the reaction is finished, and drying to obtain the styrene block copolymer modified by the carboxyl functional group.
In the preparation method of the styrene block copolymer modified by the carboxyl functional group, the mass ratio of the styrene block copolymer to the compound containing the carboxyl functional group to the initiator to the organic solvent is selected from 1:0.001-0.4:0.001-0.05:10-60; the styrene block copolymer is selected from styrene-butadiene-styrene polymer (SBS), styrene-ethylene-butylene-styrene (SEBS), styrene-isoprene-styrene (SIS), styrene-isoprene-butadiene-styrene (SIBS), styrene-ethylene-propylene-styrene (SEPS), styrene-ethylene-propylene (SEP) block copolymer, styrene-ethylene-propylene-styrene (SEEPS), hydrogenated polybutadiene, hydrogenated polyisoprene, hydrogenated styrene-isoprene random copolymer, poly (styrene- [ (butadiene) 1-x- (ethylene-co-butylene) x ] -styrene), wherein x is the hydrogenation fraction of the molecule; the compound containing carboxyl functional groups is at least one of thiolactic acid, monothioisobutyric acid, thioglycollic acid, monothiobenzoic acid, monothion-propionic acid, monothioacetic acid, monothion-hexanoic acid, monothion-octanoic acid, thiosuccinic acid, methiopropionic acid, thiomalic acid, mercaptopropionic acid and thiosalicylic acid; the initiator is selected from photoinitiator or thermal initiator, and the photoinitiator is selected from benzophenone, benzoin dimethyl ether, benzoin derivative, benzil ketal derivative, alpha-hydroxyalkyl benzophenone, alpha-amine alkyl benzophenone, acyl phosphine oxide, esterified oxime ketone compound, aryl peroxyester compound, dialkoxyacetophenone, benzoyl formate and benzophenone; the thermal initiator is selected from azodiisobutyronitrile, azodiisoheptonitrile, azodicyanovaleric acid, dimethyl azodiisobutyrate, 2' -azobis (4-methoxy-2, 4-dimethylvaleronitrile), benzoyl peroxide, potassium persulfate, ammonium persulfate/potassium sulfite redox initiation system, ammonium persulfate/ferrous sulfate redox initiation system; the organic solvent is at least one selected from toluene, xylene, N-dimethylformamide, ethanol, isopropanol, dimethyl sulfoxide and chloroform.
The invention provides graphene nano-sheet/block copolymer composite modified asphalt prepared by the method.
The graphene nano-sheet/block copolymer composite modified asphalt can be selected from functionalized CoO-GNPs/SEPS modified asphalt and functionalized Fe 3 O 4 -GNPs/SEBS modified asphalt or functionalized NiO-GNPs/hydrogenated styrene-isoprene polymer composite modified asphalt.
The invention provides application of the graphene nano-sheet/block copolymer composite modified asphalt in aging self-repairing of road asphalt.
The beneficial effects of the invention are as follows:
(1) According to the invention, graphite is used as a raw material, a graphene nano sheet structure of a supported metal oxide is formed by a one-step in-situ growth method, and a netlike porous two-dimensional nano sheet structure is gradually formed in graphene.
(2) The two-dimensional graphene nano sheets are used as a framework material, so that molten asphalt can be uniformly coated on the surfaces of the graphene nano sheets, and the graphene nano sheets are uniformly dispersed in the asphalt, so that the interface combination between the graphene nano sheets and the asphalt is improved, the excellent performance and the enhancement effect of the oxide-loaded graphene nano sheets are fully exerted, and the modified asphalt has the characteristics of electric conduction, heat conduction and microwave heat induction.
(3) According to the invention, through amino-functionalized graphene nano-sheets loaded with metal oxides and blending with a styrene block copolymer modified by carboxyl functional groups, modified asphalt with dynamic crosslinking by ionic bonds and covalent bonds is prepared, two crosslinking reactions exist in the system, one is covalent crosslinking formed by a mercapto-alkene click reaction, namely, a polythiol crosslinking agent and double bonds on a molecular chain of the styrene block copolymer are subjected to click reaction, and the mixed system is subjected to covalent crosslinking; the other is dynamic ionic crosslinking between the functional groups amino and carboxyl. Therefore, covalent crosslinking in the nano modified system enables the molecular structure of the asphalt to be more compact, the ageing resistance, high temperature and bonding performance of the asphalt to be greatly improved, and meanwhile, dynamic reversible ionic bond crosslinking enables the repair and plastic reforming of modified asphalt-based materials to be possible.
(4) When the modified asphalt is prepared, the styrene block copolymer and the graphene nano sheet loaded with the oxide are added, so that the mechanical property of the asphalt material is improved, the repairing property of the asphalt material is improved, and the asphalt material is synergistic with other components, so that the prepared material has good comprehensive properties, excellent oxidation resistance and rutting resistance, difficult deformation, repairability and long service life.
(5) The styrene block copolymer modified by the amino-functionalized graphene nano-sheets loaded with the metal oxide and the carboxyl functional groups can form more stable pi-pi interaction with graphene, meanwhile, polymer molecules are adsorbed on the surface of the graphene through negative electron exchange, van der Waals force between graphene sheets is overcome, the problem of aggregation of the graphene is overcome through steric hindrance and electrostatic steric hindrance effect, and uniform and stable dispersion of the graphene nano-sheets in the asphalt is realized through electrostatic repulsion and steric hindrance effect, so that the problem of aggregation of the graphene in the asphalt is improved.
Drawings
FIG. 1 is Fe 3 O 4 -XRD patterns of GNPs;
FIG. 2 is Fe 3 O 4 -SEM photographs of GNPs;
FIG. 3 is an SEM photograph of CoO-GNPs; wherein, the magnification of the left image is 5000 times, and the magnification of the right image is 4 ten thousand times;
FIG. 4 is a plot of softening point, penetration and ductility for various modified asphalt;
FIG. 5 is a 48h segregation softening point difference for different modified asphalt;
FIG. 6 is a graph of the complex shear modulus of different modified asphalt;
FIG. 7 is a phase angle of different modified asphalt;
FIG. 8 is a graph of rutting factors for different modified asphalt;
FIG. 9 is Fe 3 O 4 GNPs (a graph) and Fe 3 O 4 Hysteresis loop of GNPs/SEBS modified asphalt (b graph);
FIG. 10 is a thermal infrared image of modified asphalt at various times of microwave thermal induction; wherein, the figures a-c are example 4, the figures d-f are comparative example 5, and the figures g-i are comparative example 4; a. the microwave treatment time of the d and g images is 10s, the microwave treatment time of the b, e and h images is 30s, and the microwave treatment time of the c, f and i images is 60s;
FIG. 11 is an SEM photograph of modified asphalt of comparative example 1 (panel a), comparative example 6 (panel b) and example 1 (panel c).
Detailed Description
The magnetic material is used as a common microwave heat induction material, if the magnetic material can be applied to asphalt concrete, after the asphalt concrete is added with the microwave heat induction material, the material converts microwave electromagnetic energy into heat energy through various loss forms under the action of microwave irradiation released by a magnetron, so that the wave absorption effect of the concrete can be obviously enhanced, and the heating and self-repairing efficiency under heat induction can be improved. The graphene has the characteristics of ultra-thin, ultra-light, ultra-flexible, ultra-high strength, ultra-high conductivity, excellent heat conduction, light transmittance and the like, integrates various excellent performances such as high heat conduction coefficient, high electron mobility, low resistivity, high mechanical strength and the like, and has wide and huge application potential in various fields such as electronics, optics, magnetism, biomedicine, catalysis, energy storage, sensors and the like. According to the invention, graphene and a magnetic material are combined to be used as a modifier of the asphalt material, so as to try to improve the heating and self-repairing efficiency of the asphalt material under the induction of microwave heat. Meanwhile, the influence condition of the graphene material loaded with the magnetic oxide on the comprehensive performance of asphalt is verified, for example: tensile stress, electrical conductivity, thermal conductivity and the like, and can see whether the high-temperature-resistant and anti-fatigue performance, anti-aging performance, water damage resistance and the like can show better improvement advantages.
The matrix asphalt used in the following embodiments of the present invention is 70 # matrix asphalt manufactured by SK company, and the relevant technical indexes thereof are shown in table 1.
TABLE 1
Other terms used herein, unless otherwise indicated, generally have meanings commonly understood by those of ordinary skill in the art. The invention will be described in further detail below in connection with specific embodiments and with reference to the data. The following examples are intended to illustrate the invention and are not intended to limit the scope of the invention in any way.
Example 1
Preparation of graphene nano-sheet/block copolymer composite modified asphalt:
(1) Preparation of amino-functionalized supported Fe 3 O 4 Is a graphene nanoplatelet of (2)
Mixing 2 parts of graphite (500 meshes), 0.4 part of ferric nitrate and 4 parts of dimethyl maleic anhydride, grinding uniformly, placing in a glass bottle, vacuumizing, reacting for 12 hours at 180 ℃, washing the reaction product obtained by freeze drying with tetrahydrofuran, placing the reaction product in a muffle furnace at 300 ℃, and annealing for 2 hours in an air atmosphere to obtain the loaded Fe 3 O 4 Graphene nanoplatelets (Fe) 3 O 4 -GNPs). To loading Fe 3 O 4 Adding 20 parts of N, N-dimethylformamide into the graphene nano-sheet, carrying out ultrasonic treatment for 30min, adding 6 parts of 2-furfuryl amide, uniformly mixing, reacting for 6h at 80 ℃, and cleaning by tetrahydrofuran to obtain the surface amination load Fe 3 O 4 Graphene nanoplatelets of (i) aminated Fe 3 O 4 -GNPs。
(2) Preparation of carboxyl-functionalized styrene-ethylene-butene-styrene Block copolymers
6 parts of styrene-ethylene-butylene-styrene block copolymer (SEBS), 0.06 part of monothioisobutyric acid and 20 parts of dimethyl sulfoxide are mixed and stirred uniformly, then 0.006 part of alpha-aminoalkyl benzophenone is added, and the mixture is heated under ultraviolet light (365 nm, light intensity of 10 mW.cm) -2 ) And (3) carrying out reaction for 10 hours at 40 ℃ under irradiation, carrying out carboxyl functional group modification, removing a solvent by rotary evaporation, and drying to obtain the styrene-ethylene-butylene-styrene copolymer containing carboxyl functional group modification, namely carboxylated SEBS.
(3) Preparation of graphene nano-sheet/block copolymer composite modified asphalt
0.5 part of aminated Fe 3 O 4 Mixing GNPs with 5 parts of n-butanol, and performing ultrasonic dispersion to obtain aminated Fe 3 O 4 -GNPs dispersion. 100 parts of 70 # petroleum asphalt is heated to 150 ℃ to obtain uniform liquid, then 3 parts of carboxylated SEBS is added, and stirring and shearing are carried out at the constant temperature of 150 ℃ to obtain carboxylated SEBS modified asphalt. By amination of Fe 3 O 4 Mixing the GNPs dispersion liquid with carboxylated SEBS modified asphalt, shearing and stirring for 20min at 160 ℃ at 3000r/min, then adding 0.1 part of dipentaerythritol hexa (3-mercaptopropionate), shearing and stirring for 30min at 5000r/min to obtain functionalized Fe 3 O 4 GNPs/SEBS modified asphalt, i.e. graphene nanoplatelet/block copolymer composite modified asphalt.
Fe 3 O 4 The XRD patterns of the GNPs are shown in FIG. 1:
in the figure, the sharp diffraction peaks of 18.5 °, 30.2 °, 35.6 °, 43.3 °, 53.7 °, 57.1 ° and 62.8 ° correspond to Fe, respectively 3 O 4 (111) Diffraction peaks of the (220), (311), (400), (422), (511), (440) crystal planes, which indicate supported Fe 3 O 4 Has a spinel crystal structure with a pure cubic structure. Wherein the diffraction peak of about 20 degrees is the diffraction peak of the graphene nano-sheet, which indicates that Fe 3 O 4 The particles were successfully loaded onto graphene nanoplatelets.
Fe 3 O 4 SEM photographs of GNPs are shown in fig. 2:
due to the Fe on the surface of the graphene nano-sheet 3 O 4 Typical graphene lamellar micro-morphology can be observed in SEM images, so that the graphene nano-sheets have large specific surface area, and are favorable for the attachment and functional modification of magnetic nano-particles and asphalt. The graphene nano-sheets loaded with the magnetic particles are obtained by a one-step in-situ growth method, the magnetic particles are uniformly loaded on the surfaces of the graphene nano-sheets, aggregation phenomenon is avoided, and folds of graphene sheets are obvious, so that the graphene sheets are self-assembled into a three-dimensional structure when the graphene nano-sheet structure is formed, and the graphene sheets are freely combined and staggered in a high-temperature hydrothermal environment due to interaction of Van der Waals force and a separating agent between the sheets. At the same time, the separating agent is thermally decomposed to generate gas in the reaction process to form holes The porous structure on the surface of the graphene nano sheet can be completely maintained through freeze drying treatment, and the distribution of different pore diameters can be seen from fig. 2, so that the specific surface area of the graphene nano sheet is increased, sheet stacking is avoided, and meanwhile, the three-dimensional sheet porous structure can rapidly realize heat conduction in the microwave heat induction process. The graphene nano sheet structure loaded with the metal oxide not only effectively improves the conductivity and the energy density of the magnetic metal oxide, but also improves the stability and the uniformity of the metal oxide on the surface of the graphene nano sheet and the microwave heat induction yield.
Example 2
The preparation method of the graphene nano-sheet/block copolymer composite modified asphalt is shown in the above example 1; unlike example 1, in this example, fe is aminated 3 O 4 The amount of GNPs used was 1 part.
Example 3
The preparation method of the graphene nano-sheet/block copolymer composite modified asphalt is shown in the above example 1; unlike example 1, in this example, fe is aminated 3 O 4 The amount of GNPs used was 2 parts.
Example 4
Preparation of graphene nano-sheet/block copolymer composite modified asphalt:
(1) Preparation of amino-functionalized CoO-loaded graphene nanoplatelets
3 parts of graphite (1000 meshes), 1.5 parts of cobalt chloride and 9 parts of di-N-hydroxyl maleimide are mixed, ground uniformly, placed in a glass bottle, vacuumized, reacted for 10 hours at 220 ℃, then washed with methylene dichloride, and freeze-dried to obtain a reaction product, and then placed in a muffle furnace at 320 ℃ and annealed for 3 hours in an air atmosphere to obtain CoO-loaded graphene nano-sheets (CoO-GNPs). Adding 60 parts of anisole into the graphene nano-sheets loaded with the CoO, carrying out ultrasonic treatment for 30min, adding 15 parts of furfuryl amine, uniformly mixing, reacting for 10h at 100 ℃, and cleaning by dichloromethane to obtain the graphene nano-sheets with the surface aminated and loaded with the CoO, namely the aminated CoO-GNPs.
(2) Preparation of carboxyl-functionalized modified styrene-ethylene-propylene-styrene Block copolymer
3 parts of styrene-ethylene-propylene-styrene block copolymer (SEPS), 0.015 part of thiosuccinic acid and 45 parts of N, N-dimethylformamide are mixed and stirred uniformly, then 0.03 part of azodiisoheptanenitrile is added, the mixture is reacted for 6 hours at 60 ℃ to carry out carboxyl functional group modification, and then the solvent is removed by rotary evaporation and the mixture is dried to obtain the styrene-ethylene-propylene-styrene copolymer modified by carboxyl functional groups, namely carboxylated SEPS.
(3) Preparation of graphene nano-sheet/block copolymer composite modified asphalt
1 part of aminated CoO-GNPs was mixed with 6 parts of n-butanol, and subjected to ultrasonic dispersion to obtain a dispersion of aminated CoO-GNPs. 100 parts of coal tar pitch is heated to 160 ℃ to obtain uniform liquid, then 1 part of carboxylated SEPS is added, and stirring and shearing are carried out at the constant temperature of 160 ℃ to obtain carboxylated SEPS modified pitch. Mixing the amination CoO-GNPs dispersion liquid with carboxylated SEPS modified asphalt, shearing and stirring at 170 ℃ for 30min at 4000r/min, adding 0.2 part of ethylene glycol bis (3-mercaptopropionate), and shearing and stirring at 6000r/min for 30min to obtain the functionalized CoO-GNPs/SEPS modified asphalt, namely the graphene nano sheet/block copolymer composite modified asphalt.
SEM pictures of CoO-GNPs are shown in FIG. 3:
CoO crystal grains vertically and alternately grow on the surface of the wrinkled graphene nano-sheet. The thickness of the nano-sheet is about 30-50 nm. The surfaces of these corrugations facilitate the growth of CoO grains, thereby increasing the specific surface area of the composite material and expanding the interfacial contact between the material and asphalt.
Comparative example 1
The comparative example provides the unmodified No. 70 base asphalt produced by SK company, whose relevant index test data are shown in table 1.
Comparative example 2
This comparative example produced a carboxylated SEBS modified asphalt, the preparation method of which is shown in example 1 above; unlike example 1, in this comparative example, fe 3 O 4 Use of GNPsThe amount was 0 part.
The specific process is as follows:
6 parts of styrene-ethylene-butylene-styrene block copolymer (SEBS), 0.06 part of monothioisobutyric acid and 20 parts of dimethyl sulfoxide are mixed and stirred uniformly, then 0.006 part of alpha-aminoalkyl benzophenone is added, and the mixture is heated under ultraviolet light (365 nm, light intensity of 10 mW.cm) -2 ) And (3) carrying out reaction for 10 hours at 40 ℃ under irradiation, carrying out carboxyl functional group modification, removing a solvent by rotary evaporation, and drying to obtain the styrene-ethylene-butylene-styrene copolymer containing carboxyl functional group modification, namely carboxylated SEBS. 100 parts of 70 # petroleum asphalt is heated to 150 ℃ to obtain uniform liquid, then 3 parts of carboxylated SEBS is added, and stirring and shearing are carried out at the constant temperature of 150 ℃ to obtain carboxylated SEBS modified asphalt.
Comparative example 3
This comparative example produced a functionalized GNPs/SEBS modified asphalt, the preparation method of which was as described in example 1 above; unlike example 1, in this comparative example, the amount of ferric nitrate added was 0 part.
The specific process is as follows:
(1) Preparation of amino-functionalized graphene nanoplatelets
Mixing 2 parts of graphite (500 meshes) and 4 parts of dimethyl maleic anhydride, grinding uniformly, placing in a glass bottle, vacuumizing, reacting for 12 hours at 180 ℃, washing a reaction product obtained by freeze drying with tetrahydrofuran, placing the reaction product in a muffle furnace at 300 ℃, and annealing for 2 hours in an air atmosphere to obtain Graphene Nano Sheets (GNPs). Adding 20 parts of N, N-dimethylformamide into the graphene nano-sheets, carrying out ultrasonic treatment for 30min, adding 6 parts of 2-furfuryl amide, uniformly mixing, reacting for 6h at 80 ℃, and cleaning by tetrahydrofuran to obtain the surface aminated graphene nano-sheets, namely the aminated GNPs.
(2) Preparation of carboxyl-functionalized styrene-ethylene-butene-styrene Block copolymers
6 parts of styrene-ethylene-butylene-styrene block copolymer (SEBS), 0.06 part of monothioisobutyric acid and 20 parts of dimethyl sulfoxide are mixed and stirred uniformly, then 0.006 part of alpha-aminoalkyl benzophenone is added, and the mixture is heated in the presence of an ultraviolet light source (365 nm,the light intensity was 10mW cm -2 ) And (3) carrying out reaction for 10 hours at 40 ℃ under irradiation, carrying out carboxyl functional group modification, removing a solvent by rotary evaporation, and drying to obtain the styrene-ethylene-butylene-styrene copolymer containing carboxyl functional group modification, namely carboxylated SEBS.
(3) Preparation of graphene nano-sheet/styrene-ethylene-butylene-styrene polymer composite modified asphalt
Mixing 0.5 part of aminated GNPs with 5 parts of n-butanol, and performing ultrasonic dispersion to obtain an aminated GNPs dispersion liquid. 100 parts of 70 # petroleum asphalt is heated to 150 ℃ to obtain uniform liquid, then 3 parts of carboxylated SEBS is added, and stirring and shearing are carried out at the constant temperature of 150 ℃ to obtain carboxylated SEBS modified asphalt. Mixing the amination GNPs dispersion liquid with carboxylated SEBS modified asphalt, shearing and stirring for 20min at 160 ℃ at 3000r/min, then adding 0.1 part of dipentaerythritol hexa (3-mercaptopropionate), shearing and stirring for 30min at 5000r/min, and obtaining the graphene nano sheet/styrene-ethylene-butylene-styrene composite modified asphalt, namely the functionalized GNPs/SEBS modified asphalt.
Comparative example 4
This comparative example produced a carboxylated SEPS modified asphalt, the preparation method of which was as described in example 4 above; unlike example 4, in this example, coO-GNPs were used in an amount of 0 parts.
The specific process is as follows:
3 parts of styrene-ethylene-propylene-styrene block copolymer (SEPS), 0.015 part of thiosuccinic acid and 45 parts of N, N-dimethylformamide are mixed and stirred uniformly, then 0.03 part of azodiisoheptanenitrile is added, the mixture is reacted for 6 hours at 60 ℃ to carry out carboxyl functional group modification, and then the solvent is removed by rotary evaporation and the mixture is dried to obtain the styrene-ethylene-propylene-styrene copolymer modified by carboxyl functional groups, namely carboxylated SEPS. 100 parts of coal tar pitch is heated to 160 ℃ to obtain uniform liquid, then 1 part of carboxylated SEPS is added, and stirring and shearing are carried out at the constant temperature of 160 ℃ to obtain carboxylated SEPS modified pitch.
Comparative example 5
This comparative example produced a functionalized GNPs/SEPS modified asphalt, the preparation method of which was as described in example 4 above; unlike example 4, in this comparative example, the addition amount of cobalt chloride was 0 part.
The specific process is as follows:
(1) Preparation of amino-functionalized graphene nanoplatelets
3 parts of graphite (1000 meshes) and 9 parts of di-N-hydroxyl maleimide are mixed, ground uniformly, placed in a glass bottle, vacuumized, reacted for 10 hours at 220 ℃, then the reaction product obtained through freeze drying is washed by methylene dichloride, and then the reaction product is placed in a muffle furnace at 320 ℃ and annealed for 3 hours in an air atmosphere, so that Graphene Nano Sheets (GNPs) are obtained. Adding 60 parts of anisole into the graphene nano-sheets, carrying out ultrasonic treatment for 30min, adding 15 parts of furfuryl amine, uniformly mixing, reacting for 10h at 100 ℃, and cleaning by methylene dichloride to obtain the surface amino graphene nano-sheets, namely amino GNPs.
(2) Preparation of carboxyl-functionalized modified styrene-ethylene-propylene-styrene Block copolymer
3 parts of styrene-ethylene-propylene-styrene block copolymer (SEPS), 0.015 part of thiosuccinic acid and 45 parts of N, N-dimethylformamide are mixed and stirred uniformly, then 0.03 part of azodiisoheptanenitrile is added, the mixture is reacted for 6 hours at 60 ℃ to carry out carboxyl functional group modification, and then the solvent is removed by rotary evaporation and the mixture is dried to obtain the styrene-ethylene-propylene-styrene copolymer modified by carboxyl functional groups, namely carboxylated SEPS.
(3) Preparation of functionalized GNPs/SEPS modified asphalt
1 part of aminated GNPs and 6 parts of n-butanol were mixed and subjected to ultrasonic dispersion to obtain an aminated GNPs dispersion. 100 parts of coal tar pitch is heated to 160 ℃ to obtain uniform liquid, then 1 part of carboxylated SEPS is added, and stirring and shearing are carried out at the constant temperature of 160 ℃ to obtain carboxylated SEPS modified pitch. Mixing the amination GNPs dispersion liquid with carboxylated SEPS modified asphalt, shearing and stirring at 170 ℃ for 30min at 4000r/min, adding 0.2 part of ethylene glycol bis (3-mercaptopropionate), and shearing and stirring at 6000r/min for 30min to obtain graphene nano-sheet/styrene-ethylene-propylene-styrene composite modified asphalt, namely the functionalized GNPs/SEPS modified asphalt.
Comparative example 6
Comparative example A Fe was prepared 3 O 4 -GNPs/SEBS modified bitumen, the preparation method of which is shown in example 1 above; unlike example 1, in this comparative example, fe 3 O 4 Neither GNPs nor SEBS were functionally modified.
The specific process is as follows:
(1) Preparation of Supported Fe 3 O 4 Is a graphene nanoplatelet of (2)
Mixing 2 parts of graphite (500 meshes), 0.4 part of ferric nitrate and 4 parts of dimethyl maleic anhydride, grinding uniformly, placing in a glass bottle, vacuumizing, reacting for 12 hours at 180 ℃, washing the reaction product obtained by freeze drying with tetrahydrofuran, placing the reaction product in a muffle furnace at 300 ℃, and annealing for 2 hours in an air atmosphere to obtain the loaded Fe 3 O 4 The graphene nano-sheets of (2) are used for obtaining the loaded Fe 3 O 4 Graphene nanoplatelets of (i.e. Fe) 3 O 4 -GNPs。
(2) Preparation of Supported Fe 3 O 4 Graphene nano-sheet modified asphalt
0.5 part of Fe 3 O 4 Mixing GNPs with 5 parts of n-butanol, and performing ultrasonic dispersion to obtain Fe 3 O 4 -GNPs dispersion. 100 parts of No. 70 petroleum asphalt is heated to 150 ℃ to obtain uniform liquid, then 3 parts of SEBS is added, and stirring and shearing are carried out at the constant temperature of 150 ℃ to obtain the SEBS modified asphalt. Fe is added to 3 O 4 Mixing the GNPs dispersion with SEBS modified asphalt, shearing and stirring for 20min at 160 ℃ at 3000r/min, adding 0.1 part of dipentaerythritol hexa (3-mercaptopropionate), shearing and stirring for 30min at 5000r/min to obtain unfunctionalized load Fe 3 O 4 Graphene nano-sheet/styrene-ethylene-butylene-styrene composite modified asphalt, namely Fe 3 O 4 -GNPs/SEBS modified bitumen.
Modified asphalt performance test
We believe that as nanomaterial graphene derivatives, fe is supported 3 O 4 After the graphene nano-sheet is modified by amino functional groups, the surface of the graphene nano-sheet contains a large amount ofPolar or oxygen-containing groups such as amino, hydroxyl, carboxyl, epoxy and lipid groups enable the polymer to have higher active sites, and be easily bonded and compounded with a carboxyl functionalized styrene block copolymer matrix, and can be used as a reinforcing material of a polymer, so that the high-temperature mechanical property, ageing resistance and other properties of the material can be remarkably improved. The indexes such as penetration, ductility, softening point, viscosity and the like are basic performance indexes of asphalt, and the influence on the basic performance indexes of asphalt after the graphene nano-sheets and the block polymers are compositely added is examined according to the requirements in the test procedure of asphalt and asphalt mixture for highway engineering (JTG E20-2011).
The test results are shown below:
1. softening point, penetration and ductility
Fig. 4 shows the softening point, penetration and ductility of various modified asphalt.
The softening point of the asphalt can reflect the capability of keeping the original viscosity and plasticity of the asphalt when the asphalt is heated, namely heat resistance, and the addition of the modifier can reduce the influence of temperature on the deformation of the asphalt, so that the consistency of the asphalt is high, the asphalt has excellent high-temperature stability and is not easy to deform at high temperature. Penetration can be used to evaluate the viscosity of solid asphalt. The penetration is reduced, which means that the modifier thickens asphalt after being added into matrix asphalt, and plays a certain role in hardening asphalt, thereby reducing the influence of temperature rise on asphalt fluidity. The ductility can reflect the plasticity of asphalt, i.e. asphalt is deformed under the action of external force without damage, and the deformed shape can be maintained after the external force is removed.
As can be seen from fig. 4:
from comparative examples 2 and 3, it is understood that when the metal oxide or the graphene nanoplatelets supporting the metal oxide are absent, the prepared modified asphalt is deteriorated in both softening point and penetration. As is clear from examples 1 to 3, fe was aminated 3 O 4 An increase in the amount of GNPs incorporated, both the softening point and the penetration tend to be excellent, i.e. the softening point tends to increase gradually and the penetration tends to decrease gradually; the ductility tends to deteriorate, i.e. the ductility tends to decrease gradually, but still meets the specifications The requirement on the ductility of the modified asphalt is satisfied. When aminating Fe 3 O 4 When the addition amount of GNPs reaches 2 parts by weight, the softening point is at most 72.3 ℃ and the penetration is at least 42; therefore, on the basis of meeting the requirements of technical specifications on the ductility of the modified asphalt, the amino Fe can be added 3 O 4 The use amount of the GNPs greatly improves the performance of the modified asphalt, including indexes such as softening point, penetration and the like.
As can be seen from the requirements of JTGF40-2004 on the relevant indexes of the modified asphalt in technical Specification for Highway asphalt pavement construction (Table 2), the modified asphalt prepared by the embodiment of the invention meets the requirements of the specification I-D.
TABLE 2
2. Isolation softening Point difference
FIG. 5 shows the 48h segregation softening point differences for various modified asphalts.
Segregation is the difference between the upper softening point and the lower softening point of asphalt in a segregation pipe under the condition of 48 hours of specified temperature after the asphalt is prepared, and can characterize the storage stability of the asphalt. The smaller the segregation softening point difference, the better the storage stability of the asphalt.
As can be seen from FIG. 5, the aminated Fe 3 O 4 The difference between the upper and lower softening points of the modified asphalt is affected to a certain extent by GNPs, and as can be seen from Table 2, the difference between the 48h segregation softening points of each modified asphalt meets the requirements of JTGF40-2004 technical Specification for highway asphalt pavement construction. Examples 1 to 3 have smaller difference in softening point than comparative examples 2 and 3, and follow Fe 3 O 4 An increase in the amount of GNPs added, a reduction in the segregation softening point difference to some extent, mainly due to the amination of Fe 3 O 4 The GNPs nano-sheets are lamellar structures, are inserted into asphalt in lamellar form, and form a stable system with the asphalt; at the same time, aminate Fe 3 O 4 The GNPs nano-sheets and the carboxylated styrene block copolymer enable the asphalt to generate corresponding chemical co-polymerization with the polymer and the graphene nano-sheet composite modifierThe valence crosslinking reaction and the dynamic ionic crosslinking reaction, thereby improving the storage stability of asphalt.
As can be seen from the above-mentioned test results of the difference in softening point, penetration, ductility and segregation softening point, the aminated Fe 3 O 4 GNPs are capable of greatly improving the high temperature properties, adhesion properties and storage stability of the modified asphalt.
3. Complex shear modulus and phase angle
And (3) performing a temperature scanning test on the composite modified asphalt by adopting DSR. The complex modulus (G) and phase angle (δ) of the modified asphalt were measured by DSR, where complex shear modulus G is an indicator of the total resistance of the asphalt to deformation, and phase angle δ is an indicator reflecting the viscous and elastic deformation components of the asphalt to evaluate the viscoelastic properties of each modified asphalt under repeated shear loads. The larger G means that the modified asphalt material has higher stiffness, and has good flow deformation resistance in a high-temperature environment, so that the modified asphalt has more excellent deformation resistance and rutting resistance. A smaller δ means better elastic properties of the asphalt, and a larger δ means better viscous properties of the asphalt. Under the high-temperature environment, the modified asphalt with larger delta has poorer deformation resistance and is easier to permanently deform, so that the modified asphalt with larger G and smaller delta has better high-temperature rheological property.
FIG. 6 shows the complex shear modulus of various modified asphalt. Fig. 7 shows the phase angles of various modified asphalts.
From this, the trend of change of G and δ is consistent for the six different asphalt samples, i.e., G decreases with increasing temperature, and δ increases with increasing temperature. This means that the higher the temperature, the better the asphalt flow properties, and on the other hand, the poorer the resistance to deformation.
The G profile decreases in a parabolic fashion, while the delta profile increases in a linear fashion. At 40 ℃, the initial G values of comparative example 1 (matrix asphalt) were 55346Pa, the delta values were 65.19 °, the G and delta initial test values of comparative example 2, comparative example 3 and the modified asphalt of examples 1-3 were 67356Pa,812279Pa,116167pa, 129254 Pa,152225Pa, respectively; 61.9 °,61.2 °,57.52 °,54.27 °,52.34 °. At the position ofAfter modification with GNPs and/or SEBS, i.e. comparative examples 2 and 3, the G of the modified bitumen increases slightly. In the amination of Fe 3 O 4 After modification of GNPs and carboxylated SEBS (examples 1-3), modified bitumen G follows the amination of Fe 3 O 4 The amount of GNPs added increases significantly, and δ decreases significantly with increasing amount of GNPs added. The difference in G values between the comparative examples and the examples becomes smaller with increasing temperature, but the aminated Fe 3 O 4 The greater the amount of GNPs incorporated, the greater the G value of the modified asphalt, the unchanged the trend; the delta change trend is consistent with the initial delta, and the delta difference of different modified asphalt at higher temperature is smaller. The modified asphalt of example 3 had a maximum G value at 40 ℃ which was increased by about 71.85% compared to the modified asphalt of comparative example 2 and about 1.11 times compared to the base asphalt (comparative example 1). This is because asphalt is a viscoelastic material, and the elastic properties of asphalt gradually change into viscous properties as the temperature increases. Wherein G of comparative example 1 is the minimum at each temperature, indicating that its elastic properties are the worst. Comparative examples 2 and 3 were sub-functional Fe 3 O 4 The relatively good elastic properties of the GNPs/SEBS modified asphalts (examples 1 to 3), i.e.several modified asphalts, the good high-temperature deformation resistance of example 3, the poor high-temperature deformation resistance of comparative example 1, also indicate that the aminated Fe 3 O 4 GNPs and carboxylated SEBS both have the capability of improving the shearing resistance of asphalt, the composite of the two materials can improve the high-temperature deformation resistance of asphalt to a certain extent, and aminated Fe 3 O 4 The improvement effect of GNPs is more pronounced.
DSR results indicate that the addition of aminated Fe 3 O 4 After GNPs and carboxylated SEBS, fe is aminated based on the combined action of ionic bonds and covalent cross-links 3 O 4 The increase in friction and other interactions between graphene nanoplatelets and polymers further results in an increase in the resistance of the asphalt cement molecules by GNPs and carboxylated SEBS being fully absorbed and crosslinked in the asphalt cement, which strengthens the overall consistency of the asphalt binder, giving it a higher high temperature stability.
4. Rut factor
The rutting factor is the ratio of G to the sine value (sin delta) of the phase angle, and can be used for evaluating the rutting resistance of asphalt.
Fig. 8 shows rutting factors for various modified asphalt.
As can be seen from fig. 8, the change trend was consistent with the change trend of the composite modulus, and the test value decreased in a parabolic manner with increasing temperature. The initial rutting factors of comparative examples 1 to 3 and examples 1 to 3 were 94891Pa,104113Pa,119165Pa,137625Pa,158893Pa,193172Pa, respectively, at 40 ℃; when the test temperature reaches 80 ℃, the rutting factors are finally 5001Pa,5362Pa,6076Pa,6916Pa,7845Pa and 9514Pa respectively.
The test results show that the rutting factors of examples 1-3 are significantly higher than those of comparative examples at the same temperature as compared with comparative examples 1-3. This illustrates aminated Fe 3 O 4 The addition of GNPs obviously improves the high-temperature rheological property of asphalt, and along with the increase of the blending amount, the modified asphalt has more excellent high-temperature deformation resistance, thereby being beneficial to reducing the generation of diseases such as rutting, high-temperature structural damage and the like. This further confirms that the aminated Fe 3 O 4 The two-dimensional platy nano material can effectively improve the elastic performance of the modified asphalt under the condition that the GNPs and the carboxylated SEBS are mixed with an asphalt binder. The linear structure and high-density functional group bond of carboxylated SEBS optimize the amination Fe 3 O 4 The interfacial and mechanical properties of GNPs, while promoting the formation of better network structures for the modified asphalt, further enhance the ability of the asphalt binder to store elastic energy.
5. Hysteresis loop
Magnetostatic properties are closely related to electromagnetic properties and microwave absorption capacity of the material.
FIG. 9 shows aminated Fe 3 O 4 GNPs (a) and functionalized Fe 3 O 4 -GNPs/SEBS modified bitumen (b) hysteresis loop.
As can be seen from FIG. 9, aminated Fe 3 O 4 -GNPs and functionalized Fe 3 O 4 GNPs/SEBS modified asphalt (example 1)The hysteresis loops all exhibit a typical narrow S-shape, which suggests that the Fe is functionalized 3 O 4 GNPs/SEBS modified asphalt and aminated Fe 3 O 4 GNPs are all low coercivity soft magnetic materials. When the applied magnetic field reached 5000Oe, both samples exhibited saturation magnetization, indicating the presence of ferromagnetic behavior. Moreover, both the coercivity and the remanence of the two samples were close to 0, and no hysteresis was observed, showing superparamagnetism. With aminated Fe 3 O 4 Functionalized Fe compared to GNPs 3 O 4 The saturation magnetization of the GNPs/SEBS modified bitumen was slightly reduced (from 66.8emu/g to 55.8 emu/g) mainly due to the addition of nonmagnetic bitumen material. Proper saturation magnetization and coercivity contribute to excellent microwave absorption properties of the modified asphalt.
6. Thermal infrared image
The temperature rising characteristic of the modified asphalt under the induction of microwave heat is studied by using a T420 infrared thermal imager of FLIR company. Under the action of microwave radiation, the surface temperature distribution of the magnetic graphene-based filler tends to be uneven due to the difference of heat transfer capacity between the magnetic graphene-based fillers. The change of the color reflects the temperature distribution of the sample to be measured, and the lighter the color is, the higher the temperature is; the darker the color, the lower the temperature.
FIG. 10 shows thermal infrared images of modified asphalt at various times of microwave thermal induction; wherein a to c are examples 4, d to f are comparative examples 5, and g to i are comparative examples 4; a. d and g are 10s, b, e and h are 30s, c, f and i are 60s;
as can be seen from fig. 10, the modified asphalt of comparative example 4 had little color change during the whole microwave heating process, and the average temperatures of the microwave heating for 10s, 30s and 60s were 25 ℃,43 ℃ and 45 ℃ respectively, and the tendency of the thermal image to lighten during the microwave heating process was not obvious. The average temperatures after microwave heating in comparative example 5 were 30 ℃,57 ℃ and 65 ℃, respectively, mainly because graphene nanoplatelets have good heat conduction characteristics. Whereas the functionalized CoO-GNPs/SEPS modified asphalt of example 4 had average temperatures of 40℃for 10s, 90℃for 30s and 95℃for 60s, respectively, for microwave heating. Transferring heat through the asphalt mortar filled between the aminated CoO-GNPs and carboxylated SEPS, the lighter color only appearing in the separated areas early in the microwave heating process; then, the area becomes larger until it covers the entire specimen. This demonstrates that aminated CoO-GNPs combine the advantageous properties of both CoO and GNPs, and have the ability to efficiently absorb and conduct heat energy as modifiers, thereby improving the self-healing properties of the modified asphalt by microwave heating techniques. Also after 10s of heating the surface temperature increases significantly and after 30s of heating the concentrated high temperature zone reaches about 90 c, which is considered to be the ideal temperature for good healing properties without overheating. Therefore, by controlling the content of the aminated CoO-GNPs nanoplatelets and the microwave irradiation time, the desired heating efficiency and uniformity can be achieved. The graphene nano sheet structure loaded with the metal oxide fully plays the excellent performance and the enhancement effect of the graphene nano sheet loaded with the oxide, so that the modified asphalt has the characteristics of electric conduction, heat conduction and microwave heat induction. Therefore, based on the microwave thermal induction and dynamic reversible ionic bond crosslinking effect, the obtained modified asphalt material can realize self-repairing and plastic-reforming.
7. SEM image
Fig. 11 shows SEM photographs of the modified asphalt described in comparative example 1 (a), comparative example 6 (b) and example 1 (c).
As can be seen from fig. 11, the surface of the matrix asphalt is in a relatively flat state (fig. a). When the graphene nano-sheet loaded with the metal oxide and the styrene block copolymer are not modified by the functional group and added into asphalt, the asphalt surface presents a plurality of aggregated large particle states (figure b). When the amino functionalized graphene nano-sheet loaded with metal oxide and the styrene block copolymer modified by carboxyl functional groups are added into asphalt, the amino functionalized graphene nano-sheet loaded with metal oxide and the styrene block copolymer can be stably and uniformly dispersed in the asphalt, and fine granular solids appear on the surface of the asphalt, so that an aggregation phenomenon is not generated (figure c).
The styrene segmented copolymer surface modified by the amino functionalized graphene nano-sheets loaded with the metal oxide and the carboxyl functional groups contains a large number of functional groups, and in the mixing process of the styrene segmented copolymer surface modified by the amino functionalized graphene nano-sheets loaded with the metal oxide and the carboxyl functional groups and the asphalt molecules, the functional groups can form more stable pi-pi interaction, meanwhile, polymer molecules are adsorbed on the surface of graphene through negative electron exchange, so that Van der Waals force between graphene sheets is overcome, the problem of aggregation of graphene is overcome, the steric hindrance and the electrostatic steric hindrance effect are formed, and uniform and stable dispersion of graphene nano-sheets in the asphalt is realized through the electrostatic repulsion and the steric hindrance effect, so that the problem of aggregation of graphene in the asphalt is improved.
The invention also provides other possible embodiments, as follows:
example 5
Preparation of graphene nano-sheet/block copolymer composite modified asphalt:
(1) Preparation of amino-functionalized NiO-loaded graphene nanosheets
5 parts of graphite (2000 meshes), 5 parts of nickel oxalate and 15 parts of 5-maleimide valeric acid are mixed, ground uniformly, placed in a glass bottle, vacuumized, reacted for 24 hours at 150 ℃, then the reaction product obtained by freeze drying is washed with N, N-dimethylacetamide, and then the reaction product is placed in a muffle furnace at 330 ℃ and annealed for 4 hours in an air atmosphere, so that NiO-loaded graphene nano-sheets (NiO-GNPs) are obtained. Adding 75 parts of chloroform into the NiO-loaded graphene nano-sheets, carrying out ultrasonic treatment for 30min, adding 30 parts of 5-bromo-2-furamide, uniformly mixing, reacting for 14h at 120 ℃, and cleaning by using N, N-dimethylacetamide to obtain the graphene nano-sheets with the NiO-loaded surface, namely the aminated NiO-GNPs.
(2) Preparation of carboxyl-functionalized modified hydrogenated styrene-isoprene copolymer
4 parts of hydrogenated styrene-isoprene copolymer, 0.4 part of thiosalicylic acid and 80 parts of N, N-dimethylformamide are mixed and stirred uniformly, then 0.04 part of ammonium persulfate is added, the mixture is reacted for 4 hours at 80 ℃ to carry out carboxyl functional group modification, then the solvent is removed through rotary evaporation, and the mixture is dried to obtain the hydrogenated styrene-isoprene copolymer containing carboxyl functional group modification, namely carboxylated hydrogenated styrene-isoprene copolymer.
(3) Preparation of functional composite modified asphalt
5 parts of aminated NiO-GNPs and 25 parts of N, N-dimethylformamide were mixed and subjected to ultrasonic dispersion to obtain an aminated NiO-GNPs dispersion. 100 parts of coal tar pitch is heated to 180 ℃ to obtain uniform liquid, then 4 parts of carboxylated hydrogenated styrene-isoprene copolymer is added, and stirring and shearing are carried out at the constant temperature of 180 ℃ to obtain carboxylated hydrogenated styrene-isoprene copolymer modified pitch. Mixing the amination NiO-GNPs dispersion liquid with carboxylated hydrogenated styrene-isoprene copolymer modified asphalt, shearing and stirring for 20min at 180 ℃ at 5000r/min, adding 0.3 part of tris [2- (3-mercaptopropionyloxy) ethyl ] isocyanurate, and shearing and stirring for 40min at 7000r/min to obtain the functionalized NiO-GNPs/hydrogenated styrene-isoprene polymer composite modified asphalt, namely the graphene nano sheet/block copolymer composite modified asphalt.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the invention in any way, and any person skilled in the art may make modifications or alterations to the disclosed technical content to the equivalent embodiments. However, any simple modification, equivalent variation and variation of the above embodiments according to the technical substance of the present invention still fall within the protection scope of the technical solution of the present invention.

Claims (5)

1. The preparation method of the graphene nano sheet/block copolymer composite modified asphalt is characterized by comprising the following steps:
mixing graphene nano sheets with an organic solvent, and performing ultrasonic dispersion to obtain graphene nano sheet dispersion liquid; heating matrix asphalt to form uniform liquid, adding a block copolymer, and shearing at constant temperature to obtain block copolymer modified asphalt; mixing the graphene nano sheet dispersion liquid with block copolymer modified asphalt, shearing at constant temperature, then adding a crosslinking stabilizer, and continuing shearing to obtain graphene nano sheet/block copolymer composite modified asphalt;
the organic solvent is one or more selected from ethanol, N-butanol, N dimethylformamide, azomethyl pyrrolidone and propylene glycol; the matrix asphalt is selected from one or more of coal tar asphalt, petroleum asphalt and natural asphalt; the crosslinking stabilizer is one or more selected from dipentaerythritol hexa (3-mercaptopropionate), ethylene glycol bis (3-mercaptopropionate), tris [2- (3-mercaptopropionyloxy) ethyl ] isocyanurate, trimethylolpropane tris (3-mercaptopropionate) and pentaerythritol tetra (3-mercaptopropionate); the graphene nano-sheets are selected from graphene nano-sheets with surface aminated loaded with metal oxides; the block copolymer is selected from styrene block copolymers modified by carboxyl functional groups;
The preparation method of the graphene nano sheet with the surface aminated and loaded with the metal oxide comprises the following steps:
mixing graphite, metal salt and separating agent, grinding uniformly, placing in vacuum environment, reacting for 10-24 h at 150-250 ℃; washing a reaction product by adopting an organic solvent, then placing the reaction product in an air atmosphere, and annealing for 2-5 hours at 300-350 ℃ to obtain graphene nano sheets loaded with metal oxides; adding graphene nano sheets loaded with metal oxides into a dispersing agent, carrying out ultrasonic treatment, adding an amino modifier, uniformly mixing, reacting for 6-24 hours at 80-160 ℃, and cleaning by an organic solvent to obtain the graphene nano sheets with the surface aminated and loaded with the metal oxides;
the mass ratio of the graphite to the metal salt to the separating agent to the dispersing agent to the amino modifier is selected from 1:0.2-2:2-6:10-30:3-10; the granularity of the graphite is selected from 50-5000 meshes; the metal salt is selected from ferric nitrate, cobalt chloride or nickel oxalate; the separating agent is at least one of maleic anhydride, maleimide, citraconic anhydride, polypropylene-maleic anhydride, dimethyl maleic anhydride, N-methyl maleimide, N-hydroxy maleimide, 4-maleimide butyric acid and 5-maleimide valeric acid; the dispersing agent is selected from one of dichloromethane, chloroform, anisole, toluene, N-dimethylformamide, N-dimethylacetamide and tetrahydrofuran; the amino modifier is selected from one of furfuryl amine, 2-furfuryl amide and 5-bromo-2-furfuryl amide; the organic solvent is selected from one of tetrahydrofuran, dichloromethane and chloroform;
The preparation method of the styrene block copolymer modified by the carboxyl functional group comprises the following steps:
adding a styrene block copolymer and a compound containing carboxyl functional groups into an organic solvent, stirring uniformly, then adding an initiator, reacting for 4-24 hours at the temperature of 10-80 ℃, modifying the carboxyl functional groups, removing the solvent after the reaction is finished, and drying to obtain the styrene block copolymer modified by the carboxyl functional groups;
the mass ratio of the styrene block copolymer to the compound containing carboxyl functional groups to the initiator to the organic solvent is selected from 1:0.001-0.4:0.001-0.05:10-60; the styrene block copolymer is selected from styrene-butadiene-styrene polymer (SBS), styrene-ethylene-butylene-styrene (SEBS), styrene-isoprene-styrene (SIS), styrene-isoprene-butadiene-styrene (SIBS), styrene-ethylene-propylene-styrene (SEPS), styrene-ethylene-propylene (SEP) block copolymer, styrene-ethylene-propylene-styrene (SEEPS), hydrogenated polybutadiene, hydrogenated polyisoprene, hydrogenated styrene-isoprene random copolymer, poly (styrene- [ (butadiene) 1-x- (ethylene-co-butylene) x ] -styrene), wherein x is the hydrogenation fraction of the molecule; the compound containing carboxyl functional groups is at least one of thiolactic acid, monothioisobutyric acid, thioglycollic acid, monothiobenzoic acid, monothion-propionic acid, monothioacetic acid, monothion-hexanoic acid, monothion-octanoic acid, thiosuccinic acid, methiopropionic acid, thiomalic acid, mercaptopropionic acid and thiosalicylic acid; the initiator is selected from photoinitiator or thermal initiator, and the photoinitiator is selected from benzophenone, benzoin dimethyl ether, benzoin derivative, benzil ketal derivative, alpha-hydroxyalkyl benzophenone, alpha-amine alkyl benzophenone, acyl phosphine oxide, esterified oxime ketone compound, aryl peroxyester compound, dialkoxyacetophenone, benzoyl formate and benzophenone; the thermal initiator is selected from azodiisobutyronitrile, azodiisoheptonitrile, azodicyanovaleric acid, dimethyl azodiisobutyrate, 2' -azobis (4-methoxy-2, 4-dimethylvaleronitrile), benzoyl peroxide, potassium persulfate, ammonium persulfate/potassium sulfite redox initiation system, ammonium persulfate/ferrous sulfate redox initiation system; the organic solvent is at least one selected from toluene, xylene, N-dimethylformamide, ethanol, isopropanol, dimethyl sulfoxide and chloroform.
2. The preparation method according to claim 1, wherein the raw materials are selected from the following raw materials in parts by mass: 0.1 to 6 parts of graphene nano-sheets, 1 to 10 parts of organic solvent, 100 parts of matrix asphalt, 1 to 6 parts of block copolymer and 0.1 to 0.5 part of crosslinking stabilizer.
3. The method of claim 1, wherein the constant temperature shearing conditions are selected from the group consisting of: shearing for 20-120 min at the temperature of 150-180 ℃ and at the speed of 3000-8000 r/min.
4. A graphene nanoplatelet/block copolymer composite modified asphalt prepared by the method of any one of claims 1 to 3.
5. The application of the graphene nano-sheet/block copolymer composite modified asphalt in road asphalt aging self-repairing according to claim 4.
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