CN117986889A - Conductive modified asphalt and preparation method and application thereof - Google Patents
Conductive modified asphalt and preparation method and application thereof Download PDFInfo
- Publication number
- CN117986889A CN117986889A CN202410151190.0A CN202410151190A CN117986889A CN 117986889 A CN117986889 A CN 117986889A CN 202410151190 A CN202410151190 A CN 202410151190A CN 117986889 A CN117986889 A CN 117986889A
- Authority
- CN
- China
- Prior art keywords
- conductive
- modified asphalt
- asphalt
- conductive filler
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000010426 asphalt Substances 0.000 title claims abstract description 107
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000011231 conductive filler Substances 0.000 claims abstract description 40
- 239000011159 matrix material Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 10
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 9
- 239000004970 Chain extender Substances 0.000 claims abstract description 7
- 125000000524 functional group Chemical group 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002131 composite material Substances 0.000 claims description 20
- 239000003607 modifier Substances 0.000 claims description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000001723 curing Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical group C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 4
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical group C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002048 multi walled nanotube Substances 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 2
- 239000002109 single walled nanotube Substances 0.000 claims description 2
- 238000012360 testing method Methods 0.000 claims description 2
- 238000013007 heat curing Methods 0.000 claims 2
- 229920002635 polyurethane Polymers 0.000 abstract description 13
- 239000004814 polyurethane Substances 0.000 abstract description 13
- 238000005325 percolation Methods 0.000 abstract description 11
- 238000011065 in-situ storage Methods 0.000 abstract description 4
- 238000010276 construction Methods 0.000 abstract description 3
- 238000001514 detection method Methods 0.000 abstract description 3
- 238000013329 compounding Methods 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 32
- 229910021393 carbon nanotube Inorganic materials 0.000 description 21
- 239000002041 carbon nanotube Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 16
- 239000000463 material Substances 0.000 description 11
- 239000011384 asphalt concrete Substances 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000000945 filler Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- -1 polytetrafluoroethylene Polymers 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003738 black carbon Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000005489 elastic deformation Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides conductive modified asphalt, a preparation method and application thereof, wherein the conductive modified asphalt comprises the following components in parts by weight: 100-200 parts of matrix asphalt, 10-30 parts of dihydric alcohol, 5-25 parts of diisocyanate, 1-3 parts of chain extender and 5-10 parts of conductive filler; the conductive filler contains polar functional groups. According to the invention, the conductive modified asphalt is prepared by a method of synchronously compounding polyurethane in-situ polymerization and polar conductive filler, so that the interfacial binding force between polyurethane and asphalt is enhanced, the mechanical properties such as modulus and the like of the modified asphalt are effectively improved, the rutting resistance is improved, the conductive filler is promoted to form a percolation network in the modified asphalt, the conductivity of the asphalt is improved, and the conductive percolation value is reduced. The conductive modified asphalt has good road performance and conductivity, can be used for construction of conductive pavement, and has good application prospect in the fields of pavement self-sensing, self-detection, heating deicing and the like.
Description
Technical Field
The invention belongs to the technical field of road engineering material preparation, and particularly relates to conductive modified asphalt, and a preparation method and application thereof.
Background
The development of smart travel has put new demands on road infrastructure since the 21 st century. The smart highway is an epoch-making product of the deep combination of a new generation of information technology and a traffic system, is changing the traveling mode of human beings, and is already a strategic place of struggle for all countries. The conductive asphalt concrete is used as the most typical self-sensing pavement material, so that traffic data and road performance can be monitored in real time, and the road utilization rate and the maintainability of the road are improved; the ice and snow can be melted by heating, so that the ice and snow resistance of the road is improved, and the road safety is improved; the intelligent road surface intelligent vehicle can be more involved in the high-tech fields of automatic driving, intelligent vehicle technology integration, energy collection and the like, so that the development of the conductive asphalt technology becomes a key core for pushing intelligent road surface construction. Therefore, the development of conductive asphalt with stable conductive performance has important significance.
The common asphalt concrete pavement has high resistivity, belongs to a poor electric conductor, and needs to be added with conductive media such as graphite, carbon black and the like to improve the conductivity. When the content of the conductive medium exceeds a certain critical value (percolation threshold), chains can be connected in the matrix, electrons make the material conductive through chain movement, and percolation transition from the insulator to the conductor occurs. At present, the research on conductive asphalt concrete generally takes a mixture of asphalt and aggregate as a research object, conductive filler is directly mixed into an insulating mixture, and rigid filler is mainly dispersed in a matrix asphalt phase and is used as a conductive medium and also as a road modifier of the matrix asphalt, so that the following main problems may exist in the material design which looks like 'double effect': (1) the percolation threshold is high. The surface chemical activity of the non-modified conductive filler is low, and the conductive network is built only through the surface adsorption of the filler, so that the percolation threshold is relatively high, and the defects of unstable conductive performance, high cost and the like are caused; (2) cause asphalt to be brittle. The carbon-based filler in asphalt concrete forms a network structure, the addition amount is large, the strength of asphalt can be improved by using the carbon-based filler as an inorganic rigid material, but when the addition amount is large, the asphalt can be embrittled, the formation of microcracks is accelerated, the asphalt pavement performance is accelerated, and a large number of cracks can be generated to cut off a conductive path.
To solve the above problems, researchers have attempted to compound conductive fillers of different shapes to promote the formation of a conductive network. For example, graphite powder and steel fiber modified asphalt concrete, wherein graphite forms a clustered aggregate through short-range contact, and steel fibers with large length-diameter ratio construct a conductive path through long-range bridging and short-range loop effects, but the lubricating effect of the graphite can weaken the cohesiveness of asphalt, reduce the strength and durability of the asphalt concrete, and seriously deteriorate the road performance. When the particle size of the graphite powder is smaller than 0.075mm, the graphite powder can play a role of partial mineral powder filler, and the mineral aggregate grading composition and the volume index of the asphalt concrete are affected. The problem that the steel fiber is difficult to disperse in the preparation process of asphalt concrete limits the mixing amount of the steel fiber, and the use requirement of the conductivity cannot be met. As another example, patent CN117024978a discloses a mesoporous carbon modified conductive asphalt and a preparation method thereof, although the method takes an asphalt phase as a research object, a large amount of water is needed to be added in the preparation process for diluting a coupling agent so as to enhance the interfacial force between a conductive filler and the asphalt, but a large amount of water is introduced in the preparation process, and high temperature mixing at 145-165 ℃ is adopted to evaporate the water, so that the preparation temperature is higher; in addition, if all the water cannot be effectively removed, the mechanical properties of the asphalt can be degraded; and its examples have conductivity reduced by only one order of magnitude as compared with the comparative examples, and the effect of improving conductivity is not ideal.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a conductive modified asphalt cement and a preparation method thereof, which solve the problems that the conductive performance of the conventional conductive asphalt is unstable, the addition amount of carbon-based filler is large, the asphalt is brittle, and the formation of microcracks is accelerated.
In order to achieve the above purpose, the present invention adopts the following scheme: the conductive asphalt comprises the following components in parts by weight: 100-200 parts of matrix asphalt, 10-30 parts of dihydric alcohol, 5-25 parts of diisocyanate, 1-3 parts of chain extender and 5-10 parts of conductive filler; the conductive filler contains polar functional groups, and is divided into a conductive filler 1 and a conductive filler 2.
Preferably, the dihydric alcohol is polyethylene glycol, polytetrahydrofuran ether glycol or polypropylene glycol; the diisocyanate is diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate or dicyclohexylmethane diisocyanate; the chain extender is 4,4' -methylenebis (2-chloroaniline), 1, 4-butanediol or ethylene glycol; the conductive filler 1 and the conductive filler 2 may be independently selected from single-walled carbon nanotubes or multi-walled carbon nanotubes.
The invention also provides a preparation method of the conductive modified asphalt, which comprises the following steps:
1) And (3) under inert atmosphere, uniformly stirring the dihydric alcohol and the diisocyanate, and performing polymerization reaction to obtain the prepolymer.
2) And (2) adding conductive filler 1 into the prepolymer obtained in the step (1) to react for 10-20 min, and then adding a chain extender to react for 30-60 s in a mixing way to obtain the composite modifier.
3) And (3) heating matrix asphalt to 100-130 ℃ for softening, adding conductive filler 2, uniformly stirring, adding the composite modifier obtained in the step (2), fully reacting, and heating and curing to obtain the conductive modified asphalt.
Thus, a large number of functional groups (including hydroxyl, carboxyl, amino and the like) contained in the polar conductive filler can chemically react with isocyanate groups in the prepolymer (polyurethane) to obtain the composite modifier with higher stability. And then blending the composite modifier with the matrix asphalt by an in-situ polymerization method, and further carrying out chemical reaction on unreacted diisocyanate and polar functional groups in the matrix asphalt to enable the composite modified material to be uniformly dispersed in the asphalt, wherein the composite modifier has extremely high stability, so that the polar conductive filler can be uniformly adsorbed on polyurethane in the modified asphalt, a conductive network structure passage is formed in the asphalt, and the conductivity of the modified asphalt is enhanced.
Preferably, the inert atmosphere is nitrogen or argon.
Preferably, the temperature of the polymerization reaction in step 1) is 50 to 60 ℃; the time is 10-30 min.
Preferably, the temperature of the reaction in step 2) is 50 to 60 ℃.
Preferably, in the step 3), the mass ratio of the matrix asphalt to the composite modifier is 10:1-5; the mass ratio of the conductive filler 1 to the conductive filler 2 is 1:2 to 10.
Preferably, the heating curing temperature in the step 3) is 50-100 ℃ and the curing time is 2-12 h.
Compared with the prior art, the invention has the following beneficial effects:
1. According to the invention, the conductive modified asphalt is prepared by a method of synchronously compounding polyurethane in-situ polymerization and polar conductive filler, the polar conductive filler is firstly involved in-situ polymerization of polyurethane monomers to obtain conductive composite prepolymer, and then the conductive composite prepolymer is synchronously compounded with matrix asphalt, so that unreacted and complete diisocyanate further chemically reacts with polar functional groups in the matrix asphalt. Therefore, the invention forms a stable cross-linked network structure through the interaction among asphalt, polyurethane and polar conductive filler, on one hand, the interfacial binding force between the polyurethane and the asphalt is enhanced, the mechanical properties such as modulus and the like of the modified asphalt are effectively improved, and the rutting resistance and the high temperature performance are improved; in another aspect, the conductive filler is promoted to form a percolation network in the modified asphalt, the conductivity of the asphalt is improved, and the conductive percolation value is reduced. The conductive asphalt has good road performance and conductivity, can be used for construction of conductive pavement, and has good application prospect in the fields of pavement self-sensing, self-detection, heating deicing and the like.
2. According to the invention, through the synergistic compatibility of the components, the compatibility of the components is improved, so that the conductive filler is crosslinked into a stable percolation network structure among the components, the percolation threshold of the conductive filler is effectively reduced, and solvents such as water or dispersing agents are not added, so that the addition amount of the conductive filler is small, and the problems of unstable conductive performance, asphalt brittleness caused by large addition amount of carbon-based materials and the like in the conventional conductive asphalt are solved. The invention has the advantages of wide sources of raw materials, simple preparation process, low energy consumption in the production process, reduced carbon emission, easy industrialized mass production, and provides theoretical basis and technical support for promoting intelligent highways.
Drawings
FIG. 1 is a graph showing complex modulus |G| -frequency relationship at 60℃for different conductive modified asphalt prepared according to the present invention.
FIG. 2 is a graph showing the delta-frequency relationship of phase angles of different conductive modified asphalt prepared by the invention at 60 ℃.
FIG. 3 is an infrared spectrum of different conductive modified asphalt prepared by the invention.
FIG. 4 is a microstructure view of different conductive modified asphalt prepared by the invention under an optical microscope.
FIG. 5 is a microstructure of the different conductive modified asphalt prepared according to the present invention at 80℃and 180℃respectively.
Detailed Description
The following specific embodiments of the present application are provided, and it should be noted that the present application is not limited to the following specific embodiments, and all equivalent changes made on the basis of the technical scheme of the present application fall within the protection scope of the present application.
1. A preparation method of conductive modified asphalt.
Example 1
The conductive modified asphalt is prepared by the following method:
(1) Under nitrogen atmosphere, 30g of polyethylene glycol is poured into a four-neck flask and stirred at a speed of 200rpm for 15min, then 24g of diphenylmethane diisocyanate is added and stirred uniformly, and polymerization reaction is carried out for 10min at a constant temperature of 50 ℃ to obtain a prepolymer.
(2) Adding 0.38g of carbon nano tube into the prepolymer obtained in the step (1), reacting for 5min, adding 2.7g of 4,4' -methylenebis (2-chloroaniline), uniformly mixing, and reacting for 30s to obtain 57.08g of composite modifier.
(3) And (2) heating 50g of 70# matrix asphalt to 120 ℃ in an oil bath for softening, continuously stirring at a speed of 500rpm to enable the matrix asphalt to enter a flowing state, adding 2.5g of carbon nano tubes, stirring for 5min, adding 12.5g of the composite modifier obtained in the step (2), stopping the reaction after stirring for 5min, pouring the mixture into a polytetrafluoroethylene disc, and placing the polytetrafluoroethylene disc into a vacuum oven at 80 ℃ for curing for 2h to obtain the conductive modified asphalt.
Example 2
The conductive modified asphalt is prepared by the following method:
(1) Under nitrogen atmosphere, 30g of polyethylene glycol is poured into a four-neck flask and stirred at a speed of 200rpm for 15min, then 24g of diphenylmethane diisocyanate is added and stirred uniformly, and polymerization reaction is carried out for 10min at a constant temperature of 50 ℃ to obtain a prepolymer.
(2) Adding 0.76g of carbon nano tube into the prepolymer obtained in the step (1) for reaction for 5min, then adding 2.7g of 4,4' -methylenebis (2-chloroaniline), uniformly mixing, and reacting for 30s to obtain 57.46g of composite modifier;
(3) And (2) heating 50g of 70# matrix asphalt to 120 ℃ in an oil bath for softening, continuously stirring at a speed of 500rpm to enable the matrix asphalt to enter a flowing state, adding 2.5g of carbon nano tubes, stirring for 5min, adding 12.5g of the composite modifier obtained in the step (2), stopping the reaction after stirring for 5min, pouring the mixture into a polytetrafluoroethylene disc, and placing the polytetrafluoroethylene disc into a vacuum oven at 80 ℃ for curing for 2h to obtain the conductive modified asphalt.
Comparative example 1
Carbon nanotubes were not added to both the matrix pitch and the composite modifier, and the procedure was the same as in example 1.
Comparative example 2
The procedure of example 1 was followed except that no carbon nanotubes were added to the composite modifier.
2. Performance detection
1. The electrically conductive modified asphalt prepared in examples 1 to 2 and comparative examples 1 to 2 was subjected to rheological property test, the apparatus was kept at 60℃by using a Dynamic Shear Rheometer (DSR), the temperature was generally regarded as the highest temperature of the asphalt pavement, the strain was fixed at 1%, and the high-temperature rheological property of the modified asphalt was measured by scanning from high frequency to low frequency in a frequency scanning range of 100 to 0.01Hz by using dynamic frequency scanning. The storage modulus G' may reflect the ability of the asphalt material to resist elastic deformation, and the composite modulus |g| may reflect the ability of the asphalt material to resist rutting, the larger the |g| value, the better the resistance to rutting. The phase angle δ reflects the viscoelasticity of the material, with values between 0 and 90 °, when δ=0°, the material exhibits pure elasticity, and when δ=90°, the material exhibits pure tackiness. For asphalt in a high temperature state, an excessively high delta value leads to tackiness of the road surface, the rut resistance is reduced, and the lower the delta value is, the better the elasticity is, namely, the larger the deformation recovery capability is, and the rut resistance is improved.
The complex modulus |g| of different conductive modified asphalt as a function of frequency is shown in fig. 1. As can be seen from the graph, the complex modulus |g| of the modified asphalt after adding the carbon nanotubes is improved as compared with comparative examples 1 and 2, and the rutting resistance of the modified asphalt is improved as the complex modulus |g| is also improved as the content of the carbon nanotubes is increased. The invention adopts a two-step method, and carbon nano tubes are respectively added into matrix asphalt and polyurethane prepolymer, so that polar conductive filler respectively forms a certain cross-linked network structure in the matrix asphalt and polyurethane prepolymer, and then the polar conductive filler is melt-blended to further form a more stable percolation network, so that the modified asphalt shows more excellent resistance capability.
The phase angle delta of the different modified asphalt as a function of frequency is shown in figure 2. As can be seen from the graph, compared with comparative examples 1 and 2, the rutting resistance of the modified asphalt is obviously improved after the carbon nanotubes are added, and the rutting resistance of the modified asphalt is gradually improved along with the increase of the carbon nanotube content.
2. The conductive modified asphalt prepared in examples 1-2 and comparative examples 1-2 was characterized by characteristic functional groups, by fourier transform infrared spectroscopy (FTIR), with a wave number range of 400-4000 cm -1 and a resolution of 4cm -1, and the results are shown in fig. 3.
As can be seen from the figure, the absorption peak at 1723cm -1 is mainly a carbonyl vibration peak in the urethane group, indicating successful synthesis of the polyurethane modified asphalt in the comparative examples and examples. The absorption peak at 3328cm -1 was a hydroxyl vibration peak, no significant hydroxyl vibration peak appeared in comparative example 1, but a weaker hydroxyl vibration peak appeared in comparative example 2, and it was further found that a significant hydroxyl vibration peak appeared in example 1, indicating that the composite modifier contained a large amount of hydroxyl groups, and this absorption peak was more significant in example 2, which was related to a further increase in the carbon nanotube content in the polyurethane. The infrared results verify that the presence of hydroxyl groups in the carbon nanotubes results in a strong interfacial force between the conductive filler and polyurethane in the examples.
3. The microstructure of the film samples of the conductive modified asphalt prepared in comparative examples 1 to 2 and examples 1 to 2 was observed using the light transmission mode of an optical microscope, and the results are shown in fig. 4.
As can be seen from the figure, comparative example 1 is a homogeneous matrix without any network structure; when the carbon nanotubes are directly added into the matrix asphalt (comparative example 2), the black carbon nanotubes exhibit independently dispersed islands-in-the-sea phases, failing to form conductive network paths; in example 1, a large amount of carbon nanotubes were observed and connected to each other to form a continuous network structure by adding a small amount of carbon nanotubes (0.4% of the mass of the matrix pitch) during the polyurethane synthesis. Further, the amount of carbon nanotubes added during polyurethane synthesis (example 2) was increased, and the conductive network path formed by the carbon nanotubes became denser and more uniform.
4. To verify the high temperature resistance of the prepared conductive modified asphalt of examples 1 to 2 was heated to 80 ℃ and 180 ℃ respectively, while observing the microstructure thereof under an optical microscope, and the result is shown in fig. 5.
As can be seen from the graph, the conductive modified asphalt prepared by the invention has no obvious change of the internal microstructure at 80 ℃ and 180 ℃. Therefore, the network structure of the conductive modified asphalt is hardly changed along with the temperature rise, which proves that the conductive modified asphalt has high-temperature stability.
5. To verify the conductivity of the conductive modified asphalt prepared in the present invention, the conductive modified asphalt prepared in examples 1 to 2 and comparative examples 1 to 2 were tested using a high resistance meter to prepare a wafer, and the results are shown in table 1.
TABLE 1
It can be seen from table 1 that when CNT conductive material was not added to the pitch (comparative example 1), the resistivity was on the order of 10 12, whereas the magnitude of the decrease in resistance and resistivity was not significant, and the order of magnitude was unchanged, by adding only a large amount of carbon nanotubes to the polyurethane prepolymer (comparative example 2). Further, when the carbon nanotubes form a network structure of conductive paths within the pitch (example 1), the resistivity of the conductive modified pitch is reduced from the original 10 12 to 10 8; the content of carbon nanotubes in the pitch was increased again (example 2), which had little effect on the resistance and resistivity.
In conclusion, the conductive modified asphalt prepared by the invention improves rutting resistance and high-temperature stability while improving conductivity, and can meet the use requirement of the existing conductive asphalt.
Finally, it is noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the applicant has described the present invention in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention, and it is intended to be covered by the scope of the claims of the present invention.
Claims (10)
1. The conductive modified asphalt is characterized by comprising the following components in parts by weight: 100-200 parts of matrix asphalt, 10-30 parts of dihydric alcohol, 5-25 parts of diisocyanate, 1-3 parts of chain extender and 5-10 parts of conductive filler; the conductive filler contains polar functional groups, and is divided into a conductive filler 1 and a conductive filler 2.
2. The electrically conductive modified asphalt of claim 1, wherein the glycol is polyethylene glycol, polytetrahydrofuran ether glycol, or polypropylene glycol; the diisocyanate is diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate or dicyclohexylmethane diisocyanate; the chain extender is 4,4' -methylenebis (2-chloroaniline), 1, 4-butanediol or ethylene glycol.
3. The electrically conductive modified asphalt according to claim 1, wherein the electrically conductive filler 1 and the electrically conductive filler 2 are independently selected from single-walled carbon nanotubes or multi-walled carbon nanotubes.
4. A method for preparing the electrically conductive modified asphalt as claimed in any one of claims 1 to 3, comprising the steps of:
1) Stirring dihydric alcohol and diisocyanate uniformly in an inert atmosphere, and then carrying out polymerization reaction to obtain a prepolymer;
2) Adding conductive filler 1 into the prepolymer obtained in the step 1) to react for 10-20 min, and then adding a chain extender to react for 30-60 s in a mixing way to obtain a composite modifier;
3) And (3) heating matrix asphalt to 100-130 ℃ for softening, adding conductive filler 2, uniformly stirring, adding the composite modifier obtained in the step (2), fully reacting, and heating and curing to obtain the conductive asphalt.
5. The method for producing a conductive modified asphalt according to claim 4, wherein the inert atmosphere is nitrogen or argon.
6. The method for producing a conductive modified asphalt according to claim 4, wherein the polymerization reaction temperature in step 1) is 50 to 60 ℃; the time is 10-30 min.
7. The process for producing a conductive modified asphalt according to claim 4, wherein the reaction temperature in step 2) is 50 to 60 ℃.
8. The method for producing a conductive modified asphalt according to claim 4, wherein the mass ratio of the matrix asphalt to the composite modifier in step 3) is 10 (1-5); the mass ratio of the conductive filler 1 to the conductive filler 2 is 1 (2-10).
9. The method for producing a conductive modified asphalt according to claim 4, wherein the temperature of the heat curing in step 3) is 50 to 100℃and the time of the heat curing is 2 to 12 hours.
10. Use of a conductive modified asphalt as defined in any one of claims 1 to 3 or prepared by a method as defined in any one of claims 5 to 9 for self-sensing, self-testing or deicing of road surfaces by heating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410151190.0A CN117986889A (en) | 2024-02-01 | 2024-02-01 | Conductive modified asphalt and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410151190.0A CN117986889A (en) | 2024-02-01 | 2024-02-01 | Conductive modified asphalt and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117986889A true CN117986889A (en) | 2024-05-07 |
Family
ID=90889198
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410151190.0A Pending CN117986889A (en) | 2024-02-01 | 2024-02-01 | Conductive modified asphalt and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117986889A (en) |
-
2024
- 2024-02-01 CN CN202410151190.0A patent/CN117986889A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhao et al. | Effect of aminated nanocrystal cellulose on proton conductivity and dimensional stability of proton exchange membranes | |
| Chen et al. | Self-healing polymer composites based on hydrogen bond reinforced with graphene oxide | |
| CN110453562B (en) | Method for improving self-healing of cold-mix asphalt mixture based on nano carbon fiber | |
| KR100895696B1 (en) | A Method for Preparation of Silicone Rubber/Carbon Nanotube Composites with Electrical Insulating Properties | |
| CN111218113B (en) | g-C3N4CNT (carbon nano tube) nano hybrid material modified PPESK (Polytetrafluoroethylene-styrene-ethylene-styrene) lubricating film and preparation method thereof | |
| CN116640457B (en) | Modified asphalt for waterproof coiled material and preparation method thereof | |
| CN111154279A (en) | Graphene/carbon nanotube modified epoxy resin asphalt material and preparation method thereof | |
| Duan et al. | Nano-attapulgite functionalization by silane modification for preparation of covalently-integrated epoxy/TMPTMA nanocomposites | |
| CN114874591B (en) | Conductive super-crosslinked conjugated polymer electromagnetic wave absorbing material and preparation method thereof | |
| CN117986889A (en) | Conductive modified asphalt and preparation method and application thereof | |
| Hu et al. | Nanoparticle dispersion and glass transition behavior of polyimide-grafted silica nanocomposites | |
| CN111072311A (en) | Modifier for improving anti-rutting performance of asphalt concrete and preparation method thereof | |
| Gao et al. | Synthesis of a novel mesoporous inorganic–organic hybrid and its application in epoxy resins | |
| CN113861706B (en) | Modified asphalt containing nano material and application thereof | |
| CN113861641B (en) | Sulfonic acid ionic liquid element-containing polyurethane modified carbon nanotube/PLA/PBAT composite material | |
| CN113845751A (en) | Epoxy resin-based electromagnetic shielding composite material and preparation method and application thereof | |
| CN114716835A (en) | High-performance asphalt warm-mixing agent and preparation method and application thereof | |
| CN113429693A (en) | Preparation method and application of quaternized carbon nanotube modified polystyrene insulation board | |
| Jiang et al. | Surface modified halloysite nanotube enhanced imine-based epoxy composites with high self-healing efficiency and excellent mechanical properties | |
| CN114369220A (en) | Thermoplastic polyurethane elastomer nano composite material and preparation method thereof | |
| CN116102894B (en) | Organogel modified asphalt and preparation method thereof | |
| CN118063784A (en) | Nano material grafted block copolymer composite modified asphalt and waterproof application | |
| CN116515171B (en) | Polymer composite nano zinc oxide microsphere, preparation method and application thereof | |
| CN117164282B (en) | Modified asphalt mixture and preparation method thereof | |
| CN113213461A (en) | Crystalline graphene and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination |