CN111748210A

CN111748210A - Asphalt mixture with conductive function and preparation method thereof

Info

Publication number: CN111748210A
Application number: CN202010717042.2A
Authority: CN
Inventors: 赵俊
Original assignee: Individual
Current assignee: Individual
Priority date: 2020-07-23
Filing date: 2020-07-23
Publication date: 2020-10-09

Abstract

The invention discloses a preparation method of an asphalt mixture with a conductive function, which is characterized by comprising the following steps: (1) preparing a wear-resistant conductive material: mixing and stirring 10-15 wt% of phenol, 8-15 wt% of formaldehyde, 25-30 wt% of EDOT, 5-10 wt% of dicumyl peroxide, 5-10 wt% of reduced graphene oxide, 3-10 wt% of glass fiber, 2-8 wt% of silicon nitride and the rest of water, heating to 80-95 ℃, reacting for 4-10 hours, and preserving heat; (2) mixing asphalt and aromatic oil into the wear-resistant conductive material mixed solution; (3) and molding to obtain the asphalt mixture with the conductive function. The invention also provides the asphalt mixture with the conductive function, which has the performances of high conductivity, high strength and toughness, hydrophobicity, oxidation resistance, wear resistance and the like.

Description

Asphalt mixture with conductive function and preparation method thereof

Technical Field

The invention relates to the field of asphalt mixed materials, in particular to an asphalt mixture with a conductive function and a preparation method thereof.

Background

Asphalt is an organic gelled material which is composed of hydrocarbons with different molecular weights and nonmetal derivatives thereof and has the performances of water resistance, moisture resistance, corrosion resistance and the like, and is widely applied to pavement of road surfaces. However, when the existing asphalt material is used in a road for a long time, on one hand, the phenomena of oxidation, abrasion and the like can occur under the action of load and natural environment, so that the asphalt is aged, and the pavement performance is degraded; on the other hand, the snow removal of the insulated asphalt pavement in winter consumes manpower and material resources, and the temperature of the pavement can be raised to be higher than zero degrees centigrade by the conductive asphalt in a power-on mode, so that the snow removal purpose is achieved, and the problem of rear-end collision of automobiles caused by sliding of the snow pavement is prevented. In consideration of the two aspects, the asphalt mixture used for paving the road surface needs to have certain conductivity and also needs to have the performances of oxidation resistance, aging resistance and abrasion resistance, so that the driving safety of the road surface is ensured.

Disclosure of Invention

The invention aims to provide an asphalt mixture with a conductive function and a preparation method thereof, so as to solve the problems in the background technology.

In order to achieve the purpose, the invention provides the following technical scheme: the preparation method of the asphalt mixture with the conductive function is characterized by comprising the following steps of:

(1) preparing a wear-resistant conductive material: mixing and stirring 10-15 wt% of phenol, 8-15 wt% of formaldehyde, 25-30 wt% of EDOT, 5-10 wt% of dicumyl peroxide, 5-10 wt% of reduced graphene oxide, 3-10 wt% of glass fiber, 2-8 wt% of silicon nitride and the rest of water, heating to 80-95 ℃, reacting for 4-10 hours, and preserving heat;

wherein the dicumyl peroxide plays the role of a polymerization reaction catalyst and a curing agent, and can ensure that reactants are not excessively volatilized and oxidized within the range of 80-95 ℃, so that the polymerization reaction is stably carried out.

(2) Mixing: sequentially adding asphalt and aromatic oil into the mixed solution of the wear-resistant conductive material, raising the temperature to 165-175 ℃, and stirring for 30-60 min;

the further high-temperature fusion stirring is to uniformly mix the wear-resistant conductive material with the melted asphalt and the aromatic oil after the wear-resistant conductive material is fully compounded.

(3) Molding: and swelling the stirred mixture, keeping the temperature unchanged in the swelling process, and then performing shear test and development on the mixture to obtain the asphalt mixture with the conductive function.

Preferably, the mass ratio of the asphalt to the aromatic oil to the wear-resistant conductive material is 1:

(0.05-0.1)：(0.15-0.25)。

preferably, the swelling time in the molding step is 1 to 2 hours.

Preferably, the molding step is carried out for a development time of 2 to 4 hours.

The swelling and development process is to effectively absorb and disperse the filler at the stage of high-temperature melting of the organic matter so as to achieve the purpose of uniformity.

Preferably, the oxygen content of the reduced graphene oxide in the wear-resistant conductive material is 10 to 20 at%.

The oxygen content in the preferred range can ensure that the polycondensation reaction can be effectively carried out, and can also ensure the conductivity of the reduced graphene oxide after the reaction is finished.

Preferably, the particle size range of the reduced graphene oxide in the wear-resistant conductive material is 30-70nm, and the number of layers is 3-10.

Preferably, the diameter of the glass fiber in the wear-resistant conductive material is in the range of 0.5-3 μm.

Preferably, the grain size of the silicon carbide in the wear-resistant conductive material is 0.1-0.8 μm.

The size ranges of the reduced graphene oxide, the silicon carbide and the glass fiber are different by about one order of magnitude, so that the matching of particle sizes can be effectively realized, and the pores in the asphalt mixture are fully filled, thereby improving the mechanical property.

Preferably, the stirring speed is 800-.

The invention also provides the asphalt mixture with the conductive function prepared by the method.

Compared with the prior art, the invention has the beneficial effects that:

the phenolic resin has the characteristics of high mechanical strength, excellent heat resistance and the like, and PEDOT is a material with the conductivity as high as 10³The polymer long chain of S/cm and the reduced graphene oxide have the same functionHigh flexibility and 10⁴S/cm high-conductivity nano material. The monomer phenol, formaldehyde and EDOT can generate a structure in which high-conductivity long-chain PEDOT and high-strength long-chain phenolic resin are linked through a polymerization reaction at a high temperature, so that the tensile strength of the PEDOT is improved, and the PEDOT is separated from air water by utilizing the hydrophobicity of the PEDOT, and oxidation is prevented; meanwhile, as the surface of the reduced graphene oxide with the oxygen content of 10-20 at% is rich in-COOH, -OH and other groups, the reduced graphene oxide can be coated on the surfaces of PEDOT and phenolic resin through polycondensation reaction and hydrogen bonding between the EDOT, phenol and formaldehyde, so that the conductive path of the reduced graphene oxide is increased, the flexibility of the reduced graphene oxide is improved, the hydrophobicity of the reduced graphene oxide is improved due to the reduction of the oxygen content of the reduced graphene oxide after the reaction, and the oxidation resistance of the wear-resistant conductive material is further improved; the rigid material glass fiber, the silicon carbide and the flexible material reduced graphene oxide with the matched grain sizes can also fill large or small cracks or pores formed in the molding process, so that the stress of the asphalt pavement can be effectively buffered and dissipated when the asphalt pavement is deformed, and the mechanical property is improved. Therefore, the PEDOT, the phenolic resin, the reduced graphene oxide, the glass fiber and the silicon carbide are effectively compounded into a conductive path structure with high strength and toughness, hydrophobicity, oxidation resistance and wear resistance and long chain length by a monomer polymerization method and particle size matching, so that the defects that a common conductive nano material is small in size and a conductive path is easy to block are overcome, deformation of an asphalt pavement caused by extrusion or friction can be resisted, and the ageing resistance and heat resistance of an asphalt mixture are improved. The materials of the modified asphalt such as EDOT, glass fiber and the like used in the invention are all materials which are easily obtained in the market, and the preparation process is simple.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example one

The invention provides a preparation method of an asphalt mixture with a conductive function, which is characterized by comprising the following steps:

(1) preparing a wear-resistant conductive material: mixing and stirring phenol accounting for 10 wt%, formaldehyde accounting for 8 wt%, EDOT accounting for 25 wt%, dicumyl peroxide accounting for 10 wt%, reduced graphene oxide accounting for 10 wt%, glass fiber accounting for 10 wt%, silicon nitride accounting for 8 wt% and water accounting for the rest in parts by mass, heating to 80 ℃ to react for 4 hours, and then preserving heat;

(2) mixing: sequentially adding asphalt and aromatic oil into the mixed solution of the wear-resistant conductive material, raising the temperature to 165 ℃ and stirring for 30 min;

Wherein the mass ratio of the asphalt to the aromatic oil to the wear-resistant conductive material is 1: 0.05: 0.15; the swelling time in the molding step is 1 hour, and the development time is 2 hours; the oxygen content of the reduced graphene oxide in the wear-resistant conductive material is 10 at%; the particle size range of reduced graphene oxide in the wear-resistant conductive material is 30nm, the number of layers is 3, the particle size range of glass fiber in the wear-resistant conductive material is 0.5 mu m, and the particle size of silicon carbide is 0.1 mu m; the stirring speed is 800 r/min.

Example two

(1) preparing a wear-resistant conductive material: mixing and stirring 15 wt% of phenol, 15 wt% of formaldehyde, 30 wt% of EDOT, 5 wt% of dicumyl peroxide, 5 wt% of reduced graphene oxide, 3 wt% of glass fiber, 2 wt% of silicon nitride and the rest of water, heating to 95 ℃, reacting for 10 hours, and keeping the temperature;

(2) mixing: sequentially adding asphalt and aromatic oil into the mixed solution of the wear-resistant conductive material, raising the temperature to 175 ℃, and stirring for 60 min;

Wherein the mass ratio of the asphalt to the aromatic oil to the wear-resistant conductive material is 1: 0.1: 0.25; the swelling time in the molding step is 2 hours, and the development time is 4 hours; the oxygen content of the reduced graphene oxide in the wear-resistant conductive material is 20 at%; the particle size range of reduced graphene oxide in the wear-resistant conductive material is 70nm, the number of layers is 10, the particle size range of glass fiber is 3 microns, and the particle size of silicon carbide is 0.8 micron; the stirring speed is 2500 r/min.

EXAMPLE III

(1) preparing a wear-resistant conductive material: mixing and stirring phenol accounting for 12 wt%, formaldehyde accounting for 10 wt%, EDOT accounting for 28 wt%, dicumyl peroxide accounting for 7 wt%, reduced graphene oxide accounting for 6 wt%, glass fiber accounting for 5 wt%, silicon nitride accounting for 6 wt% and water accounting for the rest in parts by mass, heating to 90 ℃, reacting for 8 hours, and preserving heat;

(2) mixing: sequentially adding asphalt and aromatic oil into the mixed solution of the wear-resistant conductive material, raising the temperature to 170 ℃ and stirring for 45 min;

Wherein the mass ratio of the asphalt to the aromatic oil to the wear-resistant conductive material is 1: 0.08: 0.2; the swelling time and the development time in the molding step are 1.5 hours and 3 hours respectively; the oxygen content of the reduced graphene oxide in the wear-resistant conductive material is 18 at%; the particle size range of reduced graphene oxide in the wear-resistant conductive material is 40nm, the number of layers is 5, the particle size range of glass fiber is 1 mu m, and the particle size of silicon carbide in the wear-resistant conductive material is 0.3 mu m; the stirring speed is 1200 r/min.

In order to detect various properties of the prepared asphalt mixture, the following tests are respectively carried out:

(1) softening point: for detecting temperature stability performance. The detection method is that the asphalt sample is placed in a metal ring, a steel ball is placed on the metal ring, the metal ring is placed in water (5 ℃) or glycerol (32.5 ℃), the temperature is increased at the speed of 5 +/-0.5 ℃/min until the steel ball sinks to 25.4mm, and the temperature of the asphalt mixture is recorded as the softening point. The higher the softening point, the more temperature resistant the asphalt mix.

(2) Resistivity: and the method is used for detecting the conductivity. The detection mode is that the square resistance of the asphalt mixture is detected by a four-probe method, the thickness of the asphalt mixture is measured, and the resistivity is obtained by multiplying the numerical values of the square resistance and the thickness of the asphalt mixture. The lower the resistivity, the better the conductivity of the asphalt mixture.

(3) Ductility: for testing plasticity. The detection method is that the asphalt is made into an 8-shaped standard test piece, and the standard test piece is stretched to the length (cm) of the test piece at the temperature of 10 ℃ at the speed of 50mm per minute. The higher the ductility, the better the asphalt mixture plasticity.

Through comparative experiments on the three groups of examples, the fact that each group of examples can prepare the asphalt mixture with excellent performance can be obtained. Wherein the asphalt mixture with the conductive function prepared in the first embodiment has the softening point of 73.6 ℃, the resistivity of 13.9 omega-m and the ductility of 22.8 cm; the asphalt mixture with the conductive function prepared in the second embodiment has a softening point of 71.9 ℃, a resistivity of 15.6 omega-m and a ductility of 24.5 cm; the asphalt mixture having a conductive function obtained in example three had a softening point of 78.4 ℃, a resistivity of 11.2. omega. m, and a ductility of 29.8 cm. It can be seen that the softening point and ductility of the asphalt mixture prepared by the invention both meet the requirements specified in technical Specification for road asphalt pavement construction (JTG F40-2004), and simultaneously ensure lower resistivity.

Comparative example 1: the difference from the third example is that PEDOT in the wear-resistant conductive material is replaced by poly-p-phenylene, and the prepared asphalt mixture has the softening point of 68.2 ℃, the resistivity of 18.7 omega-m and the ductility of 22.9 cm.

Comparative example 2: the difference from the third example is that PEDOT in the wear-resistant conductive material is replaced by graphene, and the prepared asphalt mixture has the softening point of 67.4 ℃, the resistivity of 20.3 omega-m and the ductility of 27.2 cm.

Comparative example 3: the difference from the third embodiment is that the PEDOT in the wear-resistant conductive material is directly added at the later stage, rather than being compounded with phenolic resin through polymerization reaction, and the prepared asphalt mixture has the softening point of 68.3 ℃, the resistivity of 13.4 omega-m and the ductility of 23.5 cm.

It can be seen from comparative examples 1 and 2 that the addition of the polymer chain with poor conductivity or the conductive nano material with smaller size does not improve the conductivity of the asphalt mixture as good as that of the polymeric EDOT, and simultaneously, the softening point and the plasticity of the whole material are also reduced because the conductive filler is not effectively compounded with the phenolic resin. It can also be seen from comparative example 3 that, although PEDOT with high conductivity introduced at a later stage also improves the conductivity of the asphalt mixture, the conductive polymer which is easy to absorb moisture separates water in the air without the composite effect of the resin, and the ductility of the material is also reduced.

Comparative example 4: the difference from the third example is that the mixture is stirred and reacted by raising the temperature to 170 ℃ in one step, and the prepared asphalt mixture has the softening point of 62.7 ℃, the resistivity of 22.4 omega-m and the ductility of 21.6 cm. It can be seen that the excessive temperature causes the reaction materials phenol, formaldehyde and EDOT to be very volatile and oxidized, and the reaction materials are lost in time for polymerization reaction, so that the softening point and ductility of the asphalt mixture are greatly reduced, and the resistivity is improved. Therefore, the conductive materials are effectively compounded at low temperature and then fused at high temperature, so that the oxidation and the waste of the materials can be effectively avoided.

Comparative example 5: the difference from the third example is that only rigid materials of glass fiber and silicon carbide are used as the wear-resistant materials, and the prepared asphalt mixture has the softening point of 78.1 ℃, the resistivity of 12.0 omega-m and the ductility of 23.8 cm.

Comparative example 6: the difference from the third embodiment is that the wear-resistant material only adopts a flexible material to reduce the graphene oxide, and the prepared asphalt mixture has the softening point of 77.3 ℃, the resistivity of 12.4 omega-m and the ductility of 21.5 cm.

Comparative example 7: the difference from the third embodiment is that the grain diameters of the three component materials in the wear-resistant material are all 0.8 mu m, the softening point of the prepared asphalt mixture is 76.9 ℃, the resistivity is 12.2 omega.m, and the ductility is 22.2 cm.

It can be seen from the comparative examples 5 and 6 that the wear-resistant material lacking flexible material or lacking rigid material can reduce the mechanical properties of the asphalt mixture, while the wear-resistant material in the comparative example 7 has the same particle size, so that the asphalt mixture is not sufficiently filled, the mechanical properties are reduced, and the ductility is reduced.

Comparative example 8: the difference from the third example is that the oxygen content of the reduced graphene oxide is 50 at%, and the obtained asphalt mixture has a softening point of 77.3 ℃, a resistivity of 18.7 Ω · m, and a ductility of 23.1 cm.

Comparative example 9: the difference from the third example is that graphene is directly used instead of reduced graphene oxide, and the obtained asphalt mixture has a softening point of 78.5 ℃, a resistivity of 10.9 Ω · m, and a ductility of 18.8 cm.

Compared with the comparative examples 8 and 9, the reduced graphene oxide with high oxygen content has poor conductivity, and the conductivity of PEDOT is reduced due to moisture absorption, so that the resistivity of the asphalt mixture is increased; if the oxygen content is too low, the graphene does not participate in the reaction in the compounding process of the wear-resistant conductive material, which is equivalent to that the graphene is added in the asphalt mixture mechanically, although the conductivity is improved, the ductility is greatly reduced.

Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims

1. The preparation method of the asphalt mixture with the conductive function is characterized by comprising the following steps of:

2. The method for preparing asphalt mixture with conductive function according to claim 1, wherein the method comprises the following steps: the mass ratio of the asphalt to the aromatic oil to the wear-resistant conductive material is 1: (0.05-0.1): (0.15-0.25).

3. The method for preparing asphalt mixture with conductive function according to claim 1, wherein the method comprises the following steps: the swelling time in the molding step is 1 to 2 hours.

4. The method for preparing asphalt mixture with conductive function according to claim 1, wherein the method comprises the following steps: the development time in the molding step is 2-4 hours.

5. The method for preparing asphalt mixture with conductive function according to claim 1, wherein the method comprises the following steps: the oxygen content of the reduced graphene oxide in the wear-resistant conductive material is 10-20 at%.

6. The method for preparing asphalt mixture with conductive function according to claim 1, wherein the method comprises the following steps: the particle size range of the reduced graphene oxide in the wear-resistant conductive material is 30-70nm, and the number of layers is 3-10.

7. The method for preparing asphalt mixture with conductive function according to claim 1, wherein the method comprises the following steps: the diameter range of the glass fiber in the wear-resistant conductive material is 0.5-3 μm.

8. The method for preparing asphalt mixture with conductive function according to claim 1, wherein the method comprises the following steps: the grain diameter of the silicon carbide in the wear-resistant conductive material is 0.1-0.8 mu m.

9. The method for preparing asphalt mixture with conductive function according to claim 1, wherein the method comprises the following steps: the stirring speed is 800-.

10. An asphalt mixture having an electrically conductive function, which is obtained by the method according to any one of claims 1 to 9.