Carbon-reducing pollution-reducing type super-crosslinking porous purification modifier and preparation method thereof

Abstract

The invention provides a carbon and pollution reducing type super-crosslinking porous purification modifier and a preparation method, the modifier structurally comprises a shell and a core located in the shell, the shell is hydrogenated black T-T, and pores with the pore diameter of 100-200 nm are formed in the shell; and the core is an HCP. The hydrogenated black T-T is a hydrogenated black titanium dioxide-tourmaline composite visible light catalytic material. And the HCP is a carbazolyl five-membered heterocyclic single-heteroatom compound functionalized super-crosslinked porous material. The five-membered heterocyclic single heteroatom compound is pyrrole, thiophene or furan. The catalyst is prepared from the following raw materials in parts by weight: 2 parts of carbazole, 1 part of a five-membered heterocyclic single heteroatom compound, 4 parts of dimethoxymethane and 5 parts of anhydrous FeCl3. 10 parts of tourmaline micro powder, 20 parts of butyl titanate, 14 parts of acetic acid and 2 parts of dopamine hydrochloride. The modifier disclosed by the invention is a core-shell type modifier with high specific surface area, rich surface active sites and a catalytic degradation function, is used for efficient adsorption and catalytic degradation of polycyclic aromatic hydrocarbon, sulfide and volatile organic compounds in asphalt flue gas, and can realize emission reduction and purification of modified asphalt in the whole life cycle.

Description

Technical Field

[0001] This invention belongs to the field of road materials technology, and relates to modifiers, specifically to a carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier and its preparation method. Background Technology

[0002] Currently, road construction in my country mainly focuses on asphalt pavement. However, a series of environmental protection challenges remain in the construction and operation of asphalt pavement, such as: the large amount of smoke generated by hot-mix asphalt mixtures during construction polluting the environment; and the emission of volatile harmful substances from asphalt pavement and vehicle exhaust from roadside vehicles polluting the atmosphere during operation. To reduce pollutant emissions from hot-mix asphalt mixtures, research has been conducted both domestically and internationally on some hot-mix emission-reducing modified asphalt and mixture technologies. The emission reduction principle involves adding inhibitors, warm-mix agents, or flame retardants to asphalt to modify it and reduce the release of harmful asphalt smoke. However, the emission reduction and purification effects are mainly concentrated in the construction stage of asphalt mixture mixing and paving, and have not achieved emission reduction and purification throughout the construction, operation, and entire life cycle of asphalt pavement. Furthermore, vehicle exhaust emissions within the roadside area should also be reduced and purified. Summary of the Invention

[0003] To address the shortcomings of existing technologies, the present invention aims to provide a carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier and its preparation method, thereby solving the technical problem that modified asphalt in the prior art is difficult to achieve emission reduction and purification throughout its entire life cycle.

[0004] To solve the above-mentioned technical problems, the present invention adopts the following technical solution: A carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier, wherein the structure of the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier includes a shell and a core located in the shell, wherein the shell is hydrogenated black TT; and the core is HCP.

[0005] The hydrogenated black TT is a hydrogenated black titanium dioxide-tourmaline composite visible light catalytic material.

[0006] The HCP is a carbazole-based five-membered heterocyclic single-heteroatom compound functionalized hypercrosslinked porous material.

[0007] The five-membered heterocyclic single-heteroatom compound is pyrrole, thiophene, or furan.

[0008] The present invention also has the following technical features: Preferably, the average particle size of the hydrogenated black TT is 500 nm; and the average particle size of the HCP is 2 μm.

[0009] Specifically, by weight, it is made from the following raw materials: 2 parts carbazole, 1 part five-membered heterocyclic monoheteroatom compound, 4 parts dimethoxymethane, 5 parts anhydrous FeCl3; 10 parts tourmaline powder, 20 parts tetrabutyl titanate, 14 parts acetic acid, and 2 parts dopamine hydrochloride.

[0010] Furthermore, the carbon-reducing and pollution-reducing super-crosslinked porous purification modifier is used to prepare modified asphalt with a full life cycle self-purification function; the modified asphalt with a full life cycle self-purification function is made from the following raw materials by weight: 80-86 parts of road asphalt, 10-15 parts of carbon-reducing and pollution-reducing super-crosslinked porous purification modifier, 4-5 parts of silane coupling agent, and the sum of the weight parts of the raw materials is 100 parts.

[0011] Preferably, the material is made from the following raw materials in parts by weight: 82 parts road asphalt, 14 parts carbon-reducing and pollution-reducing super-crosslinked porous purification modifier, and 4 parts silane coupling agent.

[0012] Specifically, the preparation method of the modified asphalt with full life cycle self-cleaning function is as follows: road asphalt is heated to 165℃~175℃, carbon-reducing and pollution-reducing super-crosslinked porous purification modifier, silane coupling agent and road asphalt are added to a mixing tank and stirred to obtain a swollen mixture; the swollen mixture is pumped into a high-speed shear machine for multi-stage cyclic shearing, and the sheared modified asphalt is transferred to a development tank and continuously stirred at low speed for 1~3 hours to obtain modified asphalt with full life cycle self-cleaning function.

[0013] This invention also protects a method for preparing the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier as described above, the method comprising the following steps: Step 1: Using carbazole as the main monomer and a five-membered heterocyclic monoheteroatom compound as the comonomer, HCP is synthesized through a one-step Friedel-Crafts alkylation reaction.

[0014] Step 2: Using tourmaline micro powder and tetrabutyl titanate as raw materials, nano-titanium dioxide-tourmaline composite photocatalytic materials are prepared by sol-gel technology. Then, hydrogenated black TT is obtained by high-temperature hydrogenation reduction blackening method at 500℃~600℃.

[0015] Step 3: Pretreatment of the HCP obtained in Step 1. In an ice-water bath, the pretreated HCP is added to a three-necked flask containing Tris-hydrochloric acid buffer and sonicated. Dopamine hydrochloride is then added, followed by sonication. The mixture is then magnetically stirred in an ice-water bath. After the reaction is complete, the intermediate product PDA@HCP is obtained. Step 4: Disperse the hydrogenated black TT obtained in Step 2 in water, then add the intermediate product PDA@HCP obtained in Step 3 to the dispersion, mix evenly under ultrasonic conditions, and transfer to a hydrothermal reactor to react at 120-140℃. After the reaction is completed, filter, wash and vacuum dry to obtain the intermediate product hydrogenated black TT@PDA@HCP.

[0016] Step 5: The intermediate product hydrogenated black TT@PDA@HCP is placed in an ultraviolet aging test chamber and continuously degraded under high temperature and ultraviolet light conditions; after the total degradation time is reached, the residual sample is taken out, washed, and vacuum dried to obtain the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier.

[0017] Step one specifically includes the following steps: Step 101: Carbazole and the five-membered heterocyclic monoheteroatom compound are dissolved in 1,2-dichloroethane respectively and placed in a double-necked flask. Dimethoxymethane and anhydrous FeCl3 are added under a nitrogen atmosphere to obtain a mixture.

[0018] Step 102: Heat the mixture obtained in step 101 to 80°C in an oil bath, and then continue to stir under visible light irradiation for 24 hours.

[0019] Step 103: Collect the product after the reaction is complete, filter it repeatedly with anhydrous methanol until the filtrate is clear, and obtain the filtered crude sample.

[0020] Step 104: Place the crude sample filtered in step 103 into a Soxhlet extraction tube and extract with anhydrous methanol for 24 hours to obtain the extracted sample.

[0021] Step 105: Take out the sample extracted in step 104 and dry it under vacuum at 80°C for 12 hours to obtain carbazole-functionalized hypercrosslinked porous material.

[0022] Step two specifically includes the following steps: Step 201: Mix tetrabutyl titanate, acetic acid and anhydrous ethanol and stir for 1 hour to obtain a mixed solution.

[0023] Step 202: Add tourmaline powder to the mixed solution from step 201 and disperse it ultrasonically for 0.5 hours to obtain a tourmaline powder suspension.

[0024] Step 203: Mix anhydrous ethanol and deionized water, then add the mixture dropwise to the tourmaline micro powder suspension obtained in step 202 while stirring, to gradually obtain a semi-gel-like tourmaline micro powder suspension.

[0025] Step 204: Add 20wt% dilute hydrochloric acid to the semi-gel tourmaline micro powder suspension obtained in step 203, and stir continuously for 3 hours to obtain titanium dioxide-tourmaline composite sol.

[0026] Step 205: Centrifuge the titanium dioxide-tourmaline composite sol obtained in step 204 to obtain tourmaline micro powder coated with titanium dioxide. Then, calcine the tourmaline micro powder coated with titanium dioxide in air at 550°C for 3 hours to obtain nano-titanium dioxide-tourmaline composite photocatalytic material.

[0027] Step 206: The nano-titanium dioxide-tourmaline composite photocatalyst material obtained in step 205 is placed in a tube furnace and calcined at 500℃~600℃ for 4 hours under normal pressure in a hydrogen atmosphere to obtain hydrogenated black TT.

[0028] Step three specifically includes the following steps: Step 301: First, HCP is pretreated by alternating washing with 20wt% HCl solution and 20wt% NaOH solution for 5 cycles. Then, the pretreated HCP is weighed, soaked in anhydrous ethanol for 12 hours, and then washed with deionized water until neutral to obtain pretreated HCP.

[0029] Step 302: In an ice-water bath, add the HCP pretreated in step 301 to a three-necked flask containing 500 mL of 0.1 M Tris-hydrochloric acid buffer, sonicate for 30 min, add dopamine hydrochloride, sonicate for another 30 min, and then magnetically stir the reaction in an ice-water bath for 12 h. After the reaction is complete, the reaction product is obtained.

[0030] Step 303: Centrifuge the reaction product obtained in step 302, wash it 5 times with deionized water, and then dry it under vacuum at 80°C for 24 hours to obtain the intermediate product PDA@HCP.

[0031] Step five specifically includes the following steps: Step 501: Place the intermediate product hydrogenated black TT@PDA@HCP into an ultraviolet aging test chamber with a wavelength of 200-400nm and a light intensity of 15mW / cm² and heat it to 300℃ for 4 hours to degrade PDA (polydopamine).

[0032] Step 502: After the total degradation time reaches 4 hours, the ultraviolet light source is turned off, and the temperature is gradually lowered to room temperature. The residual sample is then removed, rinsed with deionized water, and vacuum dried to finally obtain the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier.

[0033] Compared with the prior art, the present invention has the following technical effects: (I) The modifier of the present invention is a core-shell type modifier with high specific surface area, abundant surface active sites and catalytic degradation function. It is used for the efficient adsorption and catalytic degradation of polycyclic aromatic hydrocarbons (PAHs), sulfides and volatile organic compounds (VOCs) in asphalt flue gas, and can realize emission reduction and purification of modified asphalt throughout its entire life cycle.

[0034] (II) The carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier prepared in this invention is a purifier with a yolk-shell structure similar to an eggshell. It possesses a core with a strong adsorption capacity and a porous structure, providing a rapid diffusion channel (10-50 nm), reducing the transport resistance of pollutants in flue gas, conforming to a pseudo-second-order kinetic model, and exhibiting a faster adsorption rate. Isotherm studies revealed that the adsorption process of HCP conforms to the Langmuir model, indicating monolayer adsorption. Enhanced adsorption site density and a micron-sized cavity reactor result in HCP having a large specific surface area, which is beneficial for improving its adsorption capacity for organic matter.

[0035] (III) The modifier of the present invention can effectively adsorb asphalt fumes and vehicle exhaust. At the same time, the permanent polarization effect of tourmaline negative ion powder, the visible photocatalytic degradation ability of hydrogenated black titanium dioxide, and the microporous structure of porous organic material HCP can effectively solve the clogging and saturation problems of traditional adsorption materials, and realize the adsorption and degradation purification of pollutants throughout the entire life cycle of roads.

[0036] (IV) The modified agent of this invention, with its core carbazole-based heteroatom-functionalized hypercrosslinked porous polymer material and polydopamine, exhibits a strong adsorption capacity for asphalt fumes and exhaust gases through a synergistic effect. HCP has a large specific surface area, and the introduction of azo or phthalazinone groups provides more adsorption sites, enhancing adsorption performance. Simultaneously, the conjugated system of carbazole and thiophene strengthens the material's rigidity, reducing pore collapse, and enhances the affinity for aromatic molecules through π-π interactions, resulting in an adsorption capacity for sulfides far exceeding that of traditional adsorbents.

[0037] (V) The modified agent of this invention, with its hydrogenated black TT shell, possesses highly efficient catalytic degradation capabilities for pollutants. The black hydrogenated black titanium dioxide-tourmaline microparticles are relatively uniform, and the surface has numerous loading sites. Electron microscopy reveals that its surface is microscopically uneven, exhibiting a stepped structure and containing uneven nanopores. This structure increases the specific surface area and facilitates the adhesion of substances to be photocatalytically degraded. The hydrogenation treatment creates Ti³⁺ / oxygen vacancy defect energy levels in the band gap of H-TiO2, reducing the energy required for electron transitions and extending the light absorption range from ultraviolet to visible light and even the near-infrared region. The introduction of tourmaline further modulates the band structure. XPS valence state spectroscopy analysis reveals that the valence band top position of the H-TiO2-tourmaline composite material shifts downward, enhancing its redox ability.

[0038] (VI) The yolk-shell structure cavity of the modifier of the present invention can be used as a highly efficient micron reactor. The internal space can be used for the storage of pollutants, effectively exposing the active sites of the core, increasing the contact time between the reactants and the active sites, thereby improving catalytic activity and mass transfer efficiency, and realizing the adsorption and efficient degradation and purification of pollutants.

[0039] (VII) The carbon-reducing and pollution-reducing super-crosslinked porous purification modifier of the present invention has good thermal and chemical stability. Thermogravimetric analysis results show that HCP can still be maintained above 70% at 800℃. HCP is insoluble in dilute solutions of sodium hydroxide and hydrochloric acid, as well as in common organic solvents such as dichloromethane and methanol. Hydrogenated black TT has excellent photothermal conversion performance, and local temperature increase can accelerate reaction kinetics.

[0040] (VIII) The cavity of the egg yolk-shell structure of the modifier of the present invention helps to realize multiple reflections of light in the cavity, effectively prolonging the light action time, thereby improving the photocatalytic efficiency.

[0041] (IX) The natural spontaneous polarization electric field of tourmaline in the eggshell of the modifier of the present invention can promote the separation of photogenerated electron-hole pairs, while its dielectric properties enhance the material's adsorption capacity for organic pollutants. Attached Figure Description

[0042] Figure 1(a) is a diagram of the penetration and softening point in Examples 1 to 9.

[0043] Figure 1(b) is a ductility diagram for Examples 1 to 9.

[0044] Figure 2(a) is a comparison of the penetration before and after aging of Example 1 and Comparative Examples 8 to 10.

[0045] Figure 2(b) is a comparison of the softening points of Example 1 and Comparative Examples 8 to 10 before and after aging.

[0046] Figure 2(c) is a comparison of the ductility before and after aging of Example 1 and Comparative Examples 8 to 10.

[0047] Figure 3 This is a graph showing the emission reduction rate of the emission reduction and purification modified asphalt in Examples 1 to 9.

[0048] Figure 4 This is a comparison chart of the emission reduction effects of modified asphalt in Example 5 and Comparative Examples 1 to 7.

[0049] Figure 5 These are exhaust gas purification rate diagrams for Examples 1 to 9.

[0050] Figure 6 This is a comparison chart of the exhaust gas purification rates of Example 5 and Comparative Examples 1 to 7.

[0051] The specific content of the present invention will be further explained in detail below with reference to the embodiments. Detailed Implementation

[0052] It should be noted that, unless otherwise specified, all raw materials and equipment used in this invention are those known in the prior art.

[0053] This embodiment provides a carbon-reducing and pollution-reducing super-crosslinked porous purification modifier. The structure of the carbon-reducing and pollution-reducing super-crosslinked porous purification modifier is a spherical egg yolk-eggshell porous structure, including a shell and a core located in the shell. The shell is hydrogenated black TT and has pores with a pore size between 100 and 200 nm. The core is HCP.

[0054] Hydrogenated black TT is a hydrogenated black titanium dioxide-tourmaline composite visible light catalytic material.

[0055] HCP is a supercrosslinked porous material functionalized from a carbazole-based five-membered heterocyclic single-heteroatom compound.

[0056] Five-membered heterocyclic monoheteroatom compounds are pyrrole (tetrahydropyrrole), thiophene (tetrahydrothiophene), or furan (tetrahydrofuran). Specifically, carbazole-pyrrole-functionalized hypercrosslinked porous materials are denoted as HCP-CP; carbazole-thiophene-functionalized hypercrosslinked porous materials are denoted as HCP-CT; and carbazole-furan-functionalized hypercrosslinked porous materials are denoted as HCP-CF.

[0057] In this invention, the average particle size of hydrogenated black TT is 500 nm; the average particle size of HCP is 2 μm.

[0058] In this invention, the amount of reagents not specified is always in excess, and those skilled in the art may use excess according to the actual situation.

[0059] In this invention, the tourmaline micro powder has a particle size of 0.5 μm. The main chemical components of the tourmaline micro powder are: Al2O3 34.98%, B2O3 10.94%, K2O 0.036%, Na2O 0.91%, MgO 0.2%, SiO2 34.6%, Fe2O3 15.8%, and CaO trace amounts.

[0060] The following are specific embodiments of the present invention. It should be noted that the present invention is not limited to the following specific embodiments. All equivalent modifications made based on the technical solutions of this application fall within the protection scope of the present invention.

[0061] Example 1: This embodiment provides a carbon-reducing and pollution-reducing super-crosslinked porous purification modifier, which is made from the following raw materials in parts by weight: 2 parts carbazole, 1 part pyrrole, 4 parts dimethoxymethane, 5 parts anhydrous FeCl3; 10 parts tourmaline micro powder, 20 parts tetrabutyl titanate, 14 parts acetic acid, and 2 parts dopamine hydrochloride.

[0062] The preparation method of the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier in this embodiment includes the following steps: Step 1: Using carbazole as the main monomer and pyrrole as the comonomer, HCP is synthesized through a one-step Friedel-Crafts alkylation reaction.

[0063] Step one specifically includes the following steps: Step 101: Dissolve carbazole and pyrrole in 1,2-dichloroethane respectively and place them in a two-necked flask. Add dimethoxymethane and anhydrous FeCl3 under a nitrogen atmosphere to obtain a mixture.

[0064] Step 102: Heat the mixture obtained in step 101 to 80°C in an oil bath, and then continue to stir under mild visible light irradiation for 24 hours.

[0065] Step 103: Collect the product after the reaction is complete, filter it repeatedly with anhydrous methanol until the filtrate is clear, and obtain the filtered crude sample.

[0066] Step 104: Place the crude sample filtered in step 103 into a Soxhlet extraction tube and extract with anhydrous methanol for 24 hours to obtain the extracted sample.

[0067] Step 105: Take out the sample extracted in step 104 and dry it under vacuum at 80°C for 12 hours to obtain carbazole-functionalized hypercrosslinked porous material.

[0068] Step 2: Using tourmaline micro powder and tetrabutyl titanate as raw materials, nano-titanium dioxide-tourmaline composite photocatalytic materials are prepared by sol-gel technology, and then hydrogenated black TT is obtained by high-temperature hydrogenation reduction blackening method.

[0069] Step two specifically includes the following steps: Step 201: Mix tetrabutyl titanate, acetic acid and anhydrous ethanol and stir for 1 hour to obtain a mixed solution.

[0070] Step 202: Add tourmaline powder to the mixed solution from step 201 and disperse it ultrasonically for 0.5 hours to obtain a tourmaline powder suspension.

[0071] Step 203: Mix anhydrous ethanol and deionized water, then add the mixture dropwise to the tourmaline micro powder suspension obtained in step 202 while stirring, to gradually obtain a semi-gel-like tourmaline micro powder suspension.

[0072] Step 204: Add 20wt% dilute hydrochloric acid to the semi-gel tourmaline micro powder suspension obtained in step 203, and stir continuously for 3 hours to obtain titanium dioxide-tourmaline composite sol.

[0073] Step 205: Centrifuge the titanium dioxide-tourmaline composite sol obtained in step 204 to obtain tourmaline micro powder coated with titanium dioxide. Then, calcine the tourmaline micro powder coated with titanium dioxide in air at 550°C for 3 hours to obtain nano-titanium dioxide-tourmaline composite photocatalytic material.

[0074] Step 206: Place the nano-titanium dioxide-tourmaline composite photocatalyst material obtained in step 205 into a tube furnace and calcine it at 500°C for 4 hours under normal pressure in a hydrogen atmosphere to obtain hydrogenated black TT (named hydrogenated black TT-500).

[0075] Step 3: Pretreatment of the HCP obtained in Step 1. In an ice-water bath, the pretreated HCP is added to a three-necked flask containing Tris-hydrochloric acid buffer and sonicated. Dopamine hydrochloride is then added, followed by sonication. The mixture is then magnetically stirred in an ice-water bath. After the reaction is complete, the intermediate product PDA@HCP is obtained. Step three specifically includes the following steps: Step 301: First, HCP is pretreated by alternating washing with 20wt% HCl solution and 20wt% NaOH solution for 5 cycles. Then, the pretreated HCP is weighed, soaked in anhydrous ethanol for 12 hours, and then washed with deionized water until neutral to obtain pretreated HCP.

[0076] Step 302: In an ice-water bath, add the HCP pretreated in step 301 to a three-necked flask containing 500 mL of 0.1 M Tris-hydrochloric acid buffer, sonicate for 30 min, add dopamine hydrochloride, sonicate for another 30 min, and then magnetically stir the reaction in an ice-water bath for 12 h. After the reaction is complete, the reaction product is obtained.

[0077] Step 303: Centrifuge the reaction product obtained in step 302, wash it 5 times with deionized water, and then dry it under vacuum at 80°C for 24 hours to obtain the intermediate product PDA@HCP.

[0078] Step 4: Disperse the hydrogenated black TT obtained in Step 2 in water, then add the intermediate product PDA@HCP obtained in Step 3 to the dispersion, mix evenly under ultrasonic conditions, and transfer to a hydrothermal reactor to react at 120-140℃. After the reaction is completed, filter, wash and vacuum dry to obtain the intermediate product hydrogenated black TT@PDA@HCP.

[0079] Step 5: The intermediate product hydrogenated black TT@PDA@HCP is placed in an ultraviolet aging test chamber and continuously degraded PDA (polydopamine) under high temperature and ultraviolet light conditions; after the total degradation time is reached, the residual sample is taken out, washed, and vacuum dried to obtain a carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier.

[0080] Step five specifically includes the following steps: Step 501: Place the intermediate product hydrogenated black TT@PDA@HCP into an ultraviolet aging test chamber with a wavelength of 200-400nm and a light intensity of 15mW / cm² and heat it to 300℃ for 4 hours to degrade PDA (polydopamine).

[0081] Step 502: After the total degradation time reaches 4 hours, turn off the ultraviolet light source, gradually cool down to room temperature, remove the residual sample, rinse with deionized water, and vacuum dry to finally obtain a carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier.

[0082] The carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier of this embodiment is used to prepare modified asphalt with a self-cleaning function throughout its entire life cycle. The modified asphalt with a self-cleaning function throughout its entire life cycle is made from the following raw materials in parts by weight: 82 parts road asphalt, 14 parts carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier, and 4 parts silane coupling agent.

[0083] The road asphalt is 70# base asphalt. In this embodiment, the road asphalt can also be replaced with 90# base asphalt, SBS modified asphalt, or rubber powder modified asphalt as needed. Both the SBS modified asphalt and rubber powder modified asphalt are commonly known and widely used types.

[0084] The silane coupling agent is γ-aminopropyltriethoxysilane coupling agent (KH-550).

[0085] The preparation method of the modified asphalt with full life cycle self-cleaning function in this embodiment is as follows: road asphalt is heated to 165℃~175℃, carbon-reducing and pollution-reducing super-crosslinked porous purification modifier, silane coupling agent and road asphalt are added to a mixing tank and stirred to allow the polymer particles to fully absorb the light components of asphalt and swell, thus obtaining a swollen mixture; the swollen mixture is pumped into a high-speed shearing machine for multi-stage cyclic shearing, and the sheared modified asphalt is transferred to a development tank and continuously stirred at low speed for 1~3 hours to promote the extension of polymer molecular chains to form a three-dimensional network structure, thus obtaining modified asphalt with full life cycle self-cleaning function.

[0086] Example 2: This embodiment provides a carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier, which is basically the same as the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier given in Example 1.

[0087] The preparation method of the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier in this embodiment is basically the same as the preparation method of the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier given in Example 1, with the only difference being: Step 206: The nano-titanium dioxide-tourmaline composite photocatalyst material obtained in step 205 is placed in a tubular furnace and calcined at 550°C for 4 hours under normal pressure in a hydrogen atmosphere to obtain hydrogenated black TT (named hydrogenated black TT-550).

[0088] The carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier of this embodiment is used to prepare modified asphalt with a self-cleaning function throughout its entire life cycle. The formulation of the modified asphalt with a self-cleaning function throughout its entire life cycle is the same as the formulation of the modified asphalt with a self-cleaning function throughout its entire life cycle given in Example 1.

[0089] The preparation method of the modified asphalt with full life cycle self-cleaning function in this embodiment is the same as the preparation method of the modified asphalt with full life cycle self-cleaning function given in Example 1.

[0090] Example 3: This embodiment provides a carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier, which is basically the same as the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier given in Example 1.

[0091] The preparation method of the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier in this embodiment is basically the same as the preparation method of the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier given in Example 1, with the only difference being: Step 206: The nano-titanium dioxide-tourmaline composite photocatalyst material obtained in step 205 is placed in a tubular furnace and calcined at 600°C for 4 hours under normal pressure in a hydrogen atmosphere to obtain hydrogenated black TT (named hydrogenated black TT-600).

[0092] The carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier of this embodiment is used to prepare modified asphalt with a self-cleaning function throughout its entire life cycle. The formulation of the modified asphalt with a self-cleaning function throughout its entire life cycle is the same as the formulation of the modified asphalt with a self-cleaning function throughout its entire life cycle given in Example 1.

[0093] The preparation method of the modified asphalt with full life cycle self-cleaning function in this embodiment is the same as the preparation method of the modified asphalt with full life cycle self-cleaning function given in Example 1.

[0094] Example 4: This embodiment provides a carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier, which is basically the same as the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier given in Example 1. The difference is that thiophene of equal mass is used to replace pyrrole in Example 1.

[0095] The preparation method of the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier in this embodiment is basically the same as that given in Example 1, except that the formulation of the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier is different. In this embodiment, the formulation of the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier given in this embodiment is used.

[0096] The carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier of this embodiment is used to prepare modified asphalt with a self-cleaning function throughout its entire life cycle. The formulation of the modified asphalt with a self-cleaning function throughout its entire life cycle is basically the same as the formulation of the modified asphalt with a self-cleaning function throughout its entire life cycle given in Example 1, the only difference being the formulation of the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier. In this embodiment, the formulation of the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier given in this embodiment is used.

[0097] The preparation method of the modified asphalt with full life cycle self-cleaning function in this embodiment is the same as the preparation method of the modified asphalt with full life cycle self-cleaning function given in Example 1.

[0098] Example 5: This embodiment provides a carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier, which is basically the same as the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier given in Example 1. The difference is that thiophene of equal mass is used to replace pyrrole in Example 1.

[0099] The preparation method of the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier in this embodiment is basically the same as that given in Example 1, except that the formulation of the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier is different. In this embodiment, the formulation of the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier given in this embodiment is used.

[0100] The difference lies in step 206, where the nano-titanium dioxide-tourmaline composite photocatalyst material obtained in step 205 is placed in a tubular furnace and calcined at 550°C for 4 hours under normal pressure in a hydrogen atmosphere to obtain hydrogenated black TT (named hydrogenated black TT-550).

[0101] The carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier of this embodiment is used to prepare modified asphalt with a self-cleaning function throughout its entire life cycle. The formulation of the modified asphalt with a self-cleaning function throughout its entire life cycle is basically the same as the formulation of the modified asphalt with a self-cleaning function throughout its entire life cycle given in Example 1. The only difference is that the formulation of the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier is different. In this embodiment, the formulation of the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier given in this embodiment is used.

[0102] The preparation method of the modified asphalt with full life cycle self-cleaning function in this embodiment is the same as the preparation method of the modified asphalt with full life cycle self-cleaning function given in Example 1.

[0103] Example 6: This embodiment provides a carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier, which is basically the same as the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier given in Example 1. The difference is that thiophene of equal mass is used to replace pyrrole in Example 1.

[0104] The preparation method of the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier in this embodiment is basically the same as that given in Example 1, except that the formulation of the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier is different. In this embodiment, the formulation of the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier given in this embodiment is used.

[0105] The difference lies in step 206, where the nano-titanium dioxide-tourmaline composite photocatalyst material obtained in step 205 is placed in a tubular furnace and calcined at 600°C for 4 hours under normal pressure in a hydrogen atmosphere to obtain hydrogenated black TT (named hydrogenated black TT-600).

[0106] The carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier of this embodiment is used to prepare modified asphalt with a self-cleaning function throughout its entire life cycle. The formulation of the modified asphalt with a self-cleaning function throughout its entire life cycle is basically the same as the formulation of the modified asphalt with a self-cleaning function throughout its entire life cycle given in Example 1. The only difference is that the formulation of the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier is different. In this embodiment, the formulation of the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier given in this embodiment is used.

[0107] The preparation method of the modified asphalt with full life cycle self-cleaning function in this embodiment is the same as the preparation method of the modified asphalt with full life cycle self-cleaning function given in Example 1.

[0108] Example 7: This embodiment provides a carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier, which is basically the same as the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier given in Example 1. The difference is that furan of equal mass is used to replace pyrrole in Example 1.

[0109] The preparation method of the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier in this embodiment is basically the same as that given in Example 1, except that the formulation of the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier is different. In this embodiment, the formulation of the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier given in this embodiment is used.

[0110] The carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier of this embodiment is used to prepare modified asphalt with a self-cleaning function throughout its entire life cycle. The formulation of the modified asphalt with a self-cleaning function throughout its entire life cycle is basically the same as the formulation of the modified asphalt with a self-cleaning function throughout its entire life cycle given in Example 1, the only difference being the formulation of the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier. In this embodiment, the formulation of the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier given in this embodiment is used.

[0111] The preparation method of the modified asphalt with full life cycle self-cleaning function in this embodiment is the same as the preparation method of the modified asphalt with full life cycle self-cleaning function given in Example 1.

[0112] Example 8: This embodiment provides a carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier, which is basically the same as the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier given in Example 1. The difference is that furan of equal mass is used to replace pyrrole in Example 1.

[0113] The preparation method of the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier in this embodiment is basically the same as that given in Example 1, except that the formulation of the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier is different. In this embodiment, the formulation of the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier given in this embodiment is used.

[0114] The difference lies in step 206, where the nano-titanium dioxide-tourmaline composite photocatalyst material obtained in step 205 is placed in a tubular furnace and calcined at 550°C for 4 hours under normal pressure in a hydrogen atmosphere to obtain hydrogenated black TT (named hydrogenated black TT-550).

[0115] The carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier of this embodiment is used to prepare modified asphalt with a self-cleaning function throughout its entire life cycle. The formulation of the modified asphalt with a self-cleaning function throughout its entire life cycle is basically the same as the formulation of the modified asphalt with a self-cleaning function throughout its entire life cycle given in Example 1. The only difference is that the formulation of the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier is different. In this embodiment, the formulation of the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier given in this embodiment is used.

[0116] The preparation method of the modified asphalt with full life cycle self-cleaning function in this embodiment is the same as the preparation method of the modified asphalt with full life cycle self-cleaning function given in Example 1.

[0117] Example 9: This embodiment provides a carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier, which is basically the same as the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier given in Example 1. The difference is that furan of equal mass is used to replace pyrrole in Example 1.

[0118] The preparation method of the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier in this embodiment is basically the same as that given in Example 1, except that the formulation of the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier is different. In this embodiment, the formulation of the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier given in this embodiment is used.

[0119] The difference lies in step 206, where the nano-titanium dioxide-tourmaline composite photocatalyst material obtained in step 205 is placed in a tubular furnace and calcined at 600°C for 4 hours under normal pressure in a hydrogen atmosphere to obtain hydrogenated black TT (named hydrogenated black TT-600).

[0120] The carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier of this embodiment is used to prepare modified asphalt with a self-cleaning function throughout its entire life cycle. The formulation of the modified asphalt with a self-cleaning function throughout its entire life cycle is basically the same as the formulation of the modified asphalt with a self-cleaning function throughout its entire life cycle given in Example 1. The only difference is that the formulation of the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier is different. In this embodiment, the formulation of the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier given in this embodiment is used.

[0121] The preparation method of the modified asphalt with full life cycle self-cleaning function in this embodiment is the same as the preparation method of the modified asphalt with full life cycle self-cleaning function given in Example 1.

[0122] Comparative Example 1: This comparative example provides a modified asphalt, which differs from the modified asphalt in Example 1 in that the modifier in this comparative example is a carbazole-pyrrole-functionalized hypercrosslinked porous material HCP-CP, and an equal amount of carbazole-pyrrole-functionalized hypercrosslinked porous material HCP-CP is used to replace the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier in Example 1.

[0123] The preparation method of the modified asphalt in this comparative example is basically the same as the preparation method of the modified asphalt with full life cycle self-cleaning function given in Example 1. The only difference is that the formula of the modifier is different. In this comparative example, the modifier formula given in this comparative example is used.

[0124] Comparative Example 2: This comparative example provides a modified asphalt, which differs from the modified asphalt in Example 1 in that the modifier in this comparative example is carbazothiophene-functionalized hypercrosslinked porous material HCP-CT, and an equal amount of carbazothiophene-functionalized hypercrosslinked porous material HCP-CT is used to replace the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier in Example 1.

[0125] The preparation method of the modified asphalt in this comparative example is basically the same as the preparation method of the modified asphalt with full life cycle self-cleaning function given in Example 1. The only difference is that the formula of the modifier is different. In this comparative example, the modifier formula given in this comparative example is used.

[0126] Comparative Example 3: This comparative example provides a modified asphalt, which differs from the modified asphalt in Example 1 in that the modifier in this comparative example is a carbazole-furan-functionalized hypercrosslinked porous material HCP-CF, and an equal amount of carbazole-furan-functionalized hypercrosslinked porous material HCP-CF is used to replace the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier in Example 1.

[0127] The preparation method of the modified asphalt in this comparative example is basically the same as the preparation method of the modified asphalt with full life cycle self-cleaning function given in Example 1. The only difference is that the formula of the modifier is different. In this comparative example, the modifier formula given in this comparative example is used.

[0128] Comparative Example 4: This comparative example provides a modified asphalt, which differs from the modified asphalt in Example 1 in that the modifier in this comparative example is hydrogenated black TT-500, and an equal amount of hydrogenated black TT-500 is used to replace the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier in Example 1.

[0129] The preparation method of the modified asphalt in this comparative example is basically the same as the preparation method of the modified asphalt with full life cycle self-cleaning function given in Example 1. The only difference is that the formula of the modifier is different. In this comparative example, the modifier formula given in this comparative example is used.

[0130] Comparative Example 5: This comparative example provides a modified asphalt, which differs from the modified asphalt in Example 1 in that the modifier in this comparative example is hydrogenated black TT-550, and an equal amount of hydrogenated black TT-550 is used to replace the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier in Example 1.

[0131] The preparation method of the modified asphalt in this comparative example is basically the same as the preparation method of the modified asphalt with full life cycle self-cleaning function given in Example 1. The only difference is that the formula of the modifier is different. In this comparative example, the modifier formula given in this comparative example is used.

[0132] Comparative Example 6: This comparative example provides a modified asphalt, which differs from the modified asphalt in Example 1 in that the modifier in this comparative example is hydrogenated black TT-600, and an equal amount of hydrogenated black TT-600 is used to replace the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier in Example 1.

[0133] The preparation method of the modified asphalt in this comparative example is basically the same as the preparation method of the modified asphalt with full life cycle self-cleaning function given in Example 1. The only difference is that the formula of the modifier is different. In this comparative example, the modifier formula given in this comparative example is used.

[0134] Comparative Example 7: This comparative example provides a modified asphalt, which differs from the modified asphalt in Example 1 in that the modifier in this comparative example is polydopamine (PDA), and an equal amount of polydopamine (PDA) is used to replace the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier in Example 1. Any polydopamine (PDA) commonly known in the art can be used.

[0135] The preparation method of the modified asphalt in this comparative example is basically the same as the preparation method of the modified asphalt with full life cycle self-cleaning function given in Example 1. The only difference is that the formula of the modifier is different. In this comparative example, the modifier formula given in this comparative example is used.

[0136] Comparative Example 8: This comparative example provides one type of asphalt, namely 70# asphalt, and commercially available products can be used.

[0137] Comparative Example 9: This comparative example provides one type of asphalt, namely SBS asphalt, and commercially available products can be used.

[0138] Comparative Example 10: This comparative example provides one type of asphalt, namely SBR modified asphalt, and commercially available products can be used.

[0139] Performance testing: The performance test of self-cleaning modified asphalt includes three parts: basic performance test, emission reduction effect test, and purification effect test. According to the test procedure of "Asphalt and Asphalt Mixture for Highway Engineering" (JTGE20-2011), the three major indicators of self-cleaning modified asphalt are determined to clarify the change law of road performance of self-cleaning modified asphalt; the emission of harmful substances of asphalt pavement throughout the whole life cycle is tested, and the emission reduction rate of asphalt smoke and the purification rate of vehicle exhaust gas of asphalt pavement during the construction, operation and maintenance periods are calculated to explore the environmental effects of self-cleaning modified asphalt in emission reduction and purification.

[0140] First, basic performance: As shown in Figures 1(a) to 2(c), the basic road performance properties of the self-cleaning modified asphalt, such as penetration, ductility and softening point, meet the relevant technical requirements of the "Technical Specification for Construction of Highway Asphalt Pavement" (JTGF40-2004) and can be used in the road field.

[0141] Compared with base asphalt, self-cleaning modified asphalt has a higher softening point and ductility, indicating that the high-temperature and low-temperature performance of self-cleaning modified asphalt is superior to that of base asphalt.

[0142] By comparing Examples 1-9, it can be found that the softening point of the self-cleaning modified asphalt is related to the type of five-membered heterocyclic single-heteroatom compound comonomer of the carbazole-functionalized hypercrosslinked porous material and the calcination temperature of the nano-TiO2-tourmaline composite photocatalyst material in a hydrogen atmosphere. This is because the thiophene ring conjugated structure enhances molecular polarity, has a strong ability to adsorb asphaltene, and has a more stable network structure at high temperatures; the pyrrole group has moderate polarity, but its molecular chain rigidity is weaker than that of thiophene; the furan ring has lower polarity, slightly poorer compatibility with asphalt, and weak high-temperature stability. The hydrogenated black titanium dioxide-tourmaline composite forms highly active oxygen vacancies at 550℃, which enhances the photocatalytic decomposition ability and inhibits the oxidative crosslinking of asphalt; the spontaneous polarization effect of tourmaline is optimized, improving the carrier separation efficiency and delaying molecular chain breakage. The change in ductility is mainly regulated by the polarity of the modifier: the conjugated structure of the thiophene ring enhances the flexibility of the molecular chain, has a strong ability to adsorb light components of asphalt, and has better phase deformation ability at low temperatures; the furan ring has lower polarity, limited swelling degree, and moderate low-temperature ductility; the pyrrole group has strong rigidity, low degree of freedom of molecular chain movement, and the smallest ductility. Example 5 has the highest softening point (62℃) and the best ductility (38.6cm), and the ductility and softening point are synergistically improved in the thiophene-based system, breaking through the traditional negative correlation limitation.

[0143] After thin-film oven + UV aging, Example 5 showed a higher penetration residual ratio, a smaller increase in softening point, and the smallest decrease in ductility compared to the comparative examples. The three major indicators showed little fluctuation, indicating that the self-cleaning modified asphalt has better high and low temperature stability than base asphalt, SBS modified asphalt, and SBR modified asphalt, and is better able to meet the long-term stable use of asphalt pavement.

[0144] Second, emission reduction effect: To comprehensively evaluate the emission reduction efficacy of self-cleaning modified asphalt throughout its entire life cycle, it is necessary to test its emission reduction efficacy during the construction and operation phases of asphalt pavement, as well as its emission reduction efficacy during the curing period. The calculation method for the emission reduction rate of asphalt mixtures at different stages is as follows: ; In the formula: The asphalt fume emission reduction rate of self-cleaning modified asphalt mixture at different stages; The concentration of asphalt fumes emitted by ordinary hot-mix asphalt mixtures at different stages; The concentration of asphalt fumes emitted by self-cleaning modified asphalt mixtures at different stages.

[0145] The test results are shown in Table 1. Figure 3 and Figure 4 As shown.

[0146] Table 1. Life-cycle emission reduction efficacy of Examples 1 to 9 and Comparative Examples 1 to 7

[0147] From Table 1, Figure 3 and Figure 4 As can be seen from Examples 1 to 9, the emission reduction rate during the asphalt pavement construction period is 42.7%–58.0%, the emission reduction rate during the asphalt pavement operation period is 39.4%–57.5%, and the emission reduction rate during the asphalt pavement maintenance period is 37.5%–52.0%. Among them, the emission reduction rate of each pollutant emission stage in Example 5 is greater than 50%, indicating that the self-cleaning asphalt prepared by the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier has excellent emission reduction capabilities. With the extension of the life cycle, the self-cleaning modified asphalt exhibits good anti-attenuation ability, with the maximum emission reduction attenuation rate being 8.5% in Example 9, indicating that the self-cleaning modified asphalt prepared by this invention has excellent asphalt smoke emission reduction effect throughout the entire life cycle.

[0148] Third, purification effect: Purification efficiency refers to the ability of asphalt pavement to reduce CO2 emissions from vehicle exhaust during its operation. X HC and NO X To determine the purification efficacy of the self-purifying modified asphalt developed in this invention, the concentration of exhaust gas before and after absorption and degradation by the self-purifying modified asphalt mixture was measured, and the purification rate was calculated as follows: [Further details on the absorption and degradation of major gaseous pollutants are needed for accurate translation.] ; In the formula: The vehicle exhaust purification rate; This refers to the initial emission concentration of vehicle exhaust. This refers to the concentration of vehicle exhaust gas after it has been absorbed and degraded by the self-purifying modified asphalt mixture.

[0149] The test results are shown in Table 2. Figure 5 and Figure 6 As shown.

[0150] Table 2. Vehicle exhaust emission reduction efficiency of each embodiment and comparative examples 1-7

[0151] From Table 2, Figure 5 and Figure 6 It can be seen that the exhaust gas purification rate of each embodiment is 51.0% to 64.0%, which shows excellent exhaust gas purification efficiency. Among them, the exhaust gas purification rate of Embodiment 5 is the highest, at 64.0%, which is the best exhaust gas purification efficiency. Moreover, the self-purifying asphalt exhaust gas purification rate of the embodiments shows the same trend as the asphalt fume emission reduction efficiency. This is because the components of automobile exhaust gas and asphalt fume are partially the same. The modified asphalt of this invention, which has a self-purification function throughout its entire life cycle, adsorbs hydrocarbons HC through π-π stacking of thiophene-based HCP. The black TiO2-tourmaline catalyst material is hydrogenated at 550℃ to excite electron-hole pairs under visible light, decomposing NOx and CO to achieve exhaust gas purification. Its exhaust gas purification mechanism is similar to that of asphalt fume emission reduction mechanism.

[0152] Summarize: As shown in Figures 1(a) to 2(c), compared with base asphalt, the purified modified asphalt has a higher softening point and ductility, indicating that the purified modified asphalt has better high-temperature and low-temperature performance than base asphalt. After thin-film oven + UV aging, Example 5, compared with the comparative examples, has a higher penetration residual ratio, a smaller increase in softening point, and the smallest decrease in ductility. The three major indicators show small fluctuations, indicating that the purified modified asphalt has better high-temperature and low-temperature stability than base asphalt, SBS modified asphalt, and SBR modified asphalt, and is better able to meet the long-term stable use of asphalt pavement.

[0153] like Figure 3As shown, by comparing Examples 1-9, it can be found that the emission reduction effect of asphalt fumes is regulated by the five-membered heterocyclic single-heteroatom compound and the catalytic temperature of the composite visible light photocatalyst in the modifier. The emission reduction rate of the HCP group is slightly higher than that of the HCP-CF group, and the emission reduction rate of the HCP-CT group is higher than that of the HCP-doped group and the HCP-CF group. The emission reduction effect of the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier using HCP-CT is the best because the sulfur atom conjugated structure of thiophene enhances adsorption stability and anti-aging properties. The emission reduction performance of the HCP group is slightly worse because nitrogen atoms only provide polar adsorption sites and do not form a conjugated structure. The emission reduction performance of the HCP-CF group is the worst because oxygen atoms have high electronegativity and weak heat resistance. The emission reduction rates of Examples 2, 5, and 8 are higher than those of other examples in the same group. This is because the hydrogenated black TiO2-tourmaline composite visible light photocatalyst was obtained by calcination under normal pressure in a hydrogen atmosphere, and 550℃ is the optimal temperature. The heat treatment temperature of the catalytic material directly determines the modifier's efficiency. At 550℃, the oxygen vacancy density is highest, the catalytic activity is strongest, and the emission reduction performance reaches its peak. Examples 3, 6, and 9 show the worst performance throughout the entire life cycle. This is because high temperatures cause the pores of the catalytic material to collapse, reducing the specific surface area. Therefore, Example 5 has the best asphalt fume emission reduction effect throughout the entire life cycle, achieving 58.0% during the asphalt pavement construction period, 57.5% during the asphalt pavement operation period, and 52.0% during the asphalt pavement maintenance period. Therefore, Example 5 is the preferred example for optimal emission reduction performance.

[0154] Depend on Figure 4It can be seen that the emission reduction efficiency of Comparative Example 1 decreased significantly compared to Example 5 at each stage. As shown in Comparative Examples 1-3, Comparative Example 2, which replaced 14 parts of the carbon-reducing and pollution-reducing super-crosslinked porous purification modifier with 14 parts of individual HCP-CT cores, exhibited higher emission reduction performance than the other two groups. The principle behind this has been explained above and will not be repeated here. Similarly, as shown in Comparative Examples 4-6, Comparative Example 5, which replaced 14 parts of the carbon-reducing and pollution-reducing super-crosslinked porous purification modifier with 14 parts of individual hydrogenated black nano-TiO2-tourmaline composite photocatalyst material (TT-550), also exhibited higher emission reduction performance than the other two groups. Comparative Example 7, which replaced 14 parts of the carbon-reducing and pollution-reducing super-crosslinked porous purification modifier with 14 parts of individual polydopamine (PDA), lacked a conjugated structure and catalytic function, resulting in the weakest emission reduction performance. The emission reduction rates of Comparative Examples 1-7 in each stage are far lower than those of Example 5 in each stage. This is because Comparative Examples 1-7 all use single-component purification modifiers, which lack synergistic effects and result in a sharp decline in performance. Comparative Examples 1-3 use a single HCP, relying solely on physical adsorption; Comparative Examples 4-6 use a single catalytic material without adsorption network support, leading to rapid activity decay at high temperatures. Example 5 employs a spherical yolk-shell porous structure, with a shell of hydrogenated black TT and a core of HCP-CT, a carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier. Through the synergistic effect of physical adsorption and chemical catalysis, it significantly improves smoke suppression efficiency, effectively degrading asphalt smoke adsorbed into the cavity. This solves the clogging and saturation problems of traditional adsorption materials, thereby achieving efficient adsorption and degradation purification of pollutants throughout the entire life cycle of roads.

[0155] pass Figure 3 , Figure 4It can be seen that the emission reduction rates of all groups show a downward trend over time from the construction period to the operation period and then to the maintenance period, but the rate of reduction varies significantly: the peak emission reduction rate of Example 5 is 58.0%, which decreases by 6.0% from the construction period to the maintenance period, while the peak emission reduction rate of Comparative Example 7 is only 22.6%, which decreases by 8.6% from the construction period to the maintenance period. Examples 1 to 9 use composite modifiers as purification modifiers, and the average rate of reduction is 7.8%; Comparative Examples 1 to 7 use single components as purification modifiers and the average rate of reduction is 12.5%, which is significantly higher than that of Examples 1 to 9. In Examples 1-3, the average attenuation rate of HCP composite modifier as the purification modifier was 8.1%, which is due to the pyrrole nitrogen atom providing polar adsorption sites and partial stability, but it is easily oxidized at high temperatures. In Examples 4-6, the average attenuation rate of HCP-CT composite modifier as the purification modifier was 5.3%, which is due to the thiophene sulfur atom forming a rigid conjugated structure, which has strong resistance to ultraviolet aging. In Examples 7-9, the average attenuation rate of HCP-CF composite modifier as the purification modifier was 7.6%, which is due to the high electronegativity of furanyl oxygen atom, the large flexibility of the molecular chain, and heat resistance. The adsorption efficiency was weak. In Comparative Examples 1-3, the average attenuation rate using a single HCP as a purification modifier was 10.2%. This was because the single HCP lacked catalytic decomposition, and the micropores were gradually filled, resulting in a decrease in adsorption efficiency. In Comparative Examples 4-6, the average attenuation rate using a single hydrogenated black TT as a purification modifier was 13.1%. The attenuation rate of Comparative Example 5, which selected 550℃ as the optimal temperature, was lower than the other two groups. This was because at 550℃, the oxygen vacancy density of the hydrogenated black titanium dioxide-tourmaline composite catalyst was maximized, promoting the decomposition of polycyclic aromatic hydrocarbons. At 600℃, the pores collapsed, the specific surface area decreased, and the activity sharply decreased.

[0156] Depend on Figure 6It can be seen that the single HCP group (Comparative Examples 1-3) relies solely on physical adsorption, with a purification rate ≤44.0%; the single catalyst material group (Comparative Examples 4-6) has a purification rate ≤32.0% due to its small specific surface area and high photogenerated electron recombination rate; Comparative Example 7, polydopamine, lacks conjugated structure and catalytic active sites, relies solely on weak physical adsorption, and is easily decomposed under ultraviolet light, with a purification rate of only 15.0%. A comparison between the single HCP group and the single catalyst material group reveals that the former has a higher exhaust gas purification rate than the latter, indicating that HCP contributes more to the exhaust gas purification rate than hydrogenated black TT. The examples use carbazole-based heterocyclic hypercrosslinked porous materials (HCP) to provide a high specific surface area for adsorbing exhaust gas pollutants (such as NOx and CO), while the hydrogenated black titanium dioxide-tourmaline composite catalyst material oxidizes and degrades pollutants through photogenerated electron-hole pairs, forming an "adsorption-catalysis" synergy. Example 5 is the optimal solution, as the sulfur atoms of thiophene enhance electron transfer efficiency, maximizing the oxygen vacancy density of the catalyst material, resulting in a purification rate of 64.0%, far exceeding that of a single component. Therefore, Example 5 solves the problem that hot-mix emission reduction asphalt has not yet achieved the purification of automobile exhaust, and has excellent purification effect on automobile exhaust.

Claims

1. A carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier, characterized in that, The structure of the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier includes a shell and a core located in the shell. The shell is hydrogenated black TT, and the core is HCP. The hydrogenated black TT is a hydrogenated black titanium dioxide-tourmaline composite visible light catalytic material; The HCP is a carbazole-based five-membered heterocyclic single-heteroatom compound functionalized hypercrosslinked porous material; The five-membered heterocyclic monoheteroatom compound is pyrrole, thiophene, or furan.

2. The carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier as described in claim 1, characterized in that, The average particle size of the hydrogenated black TT is 500 nm; the average particle size of the HCP is 2 μm.

3. The carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier as described in claim 1, characterized in that, It is made from the following raw materials in parts by weight: 2 parts carbazole, 1 part five-membered heterocyclic monoheteroatom compound, 4 parts dimethoxymethane, 5 parts anhydrous FeCl3; 10 parts tourmaline powder, 20 parts tetrabutyl titanate, 14 parts acetic acid, and 2 parts dopamine hydrochloride.

4. The carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier according to any one of claims 1 to 3, characterized in that, The aforementioned carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier is used to prepare modified asphalt with a self-cleaning function throughout its entire life cycle. The modified asphalt with a self-cleaning function throughout its entire life cycle is made from the following raw materials by weight: 80-86 parts of road asphalt, 10-15 parts of carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier, and 4-5 parts of silane coupling agent, with the sum of the weight parts of the raw materials being 100 parts.

5. The carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier as described in claim 4, characterized in that, The method for preparing modified asphalt with full life cycle self-cleaning function is as follows: road asphalt is heated to 165℃~175℃, carbon-reducing and pollution-reducing super-crosslinked porous purification modifier, silane coupling agent and road asphalt are added to a mixing tank and stirred to obtain a swollen mixture; the swollen mixture is pumped into a high-speed shearing machine for multi-stage cyclic shearing, and the sheared modified asphalt is transferred to a development tank and stirred at low speed for 1~3 hours to obtain modified asphalt with full life cycle self-cleaning function.

6. A method for preparing the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier as described in claim 3, characterized in that, The method includes the following steps: Step 1: Using carbazole as the main monomer and a five-membered heterocyclic single-heteroatom compound as the comonomer, HCP is synthesized through a one-step Friedel-Crafts alkylation reaction. Step 2: Using tourmaline micro powder and tetrabutyl titanate as raw materials, nano-titanium dioxide-tourmaline composite photocatalytic materials are prepared by sol-gel technology. Then, hydrogenated black TT is obtained by high-temperature hydrogenation reduction blackening method at 500℃~600℃. Step 3: Pretreatment of the HCP obtained in Step 1. In an ice-water bath, the pretreated HCP is added to a three-necked flask containing Tris-hydrochloric acid buffer and sonicated. Dopamine hydrochloride is then added, followed by sonication. The mixture is then magnetically stirred in an ice-water bath. After the reaction is complete, the intermediate product PDA@HCP is obtained. Step 4: Disperse the hydrogenated black TT obtained in Step 2 in water, then add the intermediate product PDA@HCP obtained in Step 3 to the dispersion, mix evenly under ultrasonic conditions, and transfer to a hydrothermal reactor to react at 120-140℃. After the reaction is completed, filter, wash and vacuum dry to obtain the intermediate product hydrogenated black TT@PDA@HCP. Step 5: The intermediate product hydrogenated black TT@PDA@HCP is placed in an ultraviolet aging test chamber and continuously degraded under high temperature and ultraviolet light conditions; after the total degradation time is reached, the residual sample is taken out, washed, and vacuum dried to obtain the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier.

7. The preparation method of the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier as described in claim 6, characterized in that, Step one specifically includes the following steps: Step 101: Carbazole and a five-membered heterocyclic monoheteroatom compound are dissolved in 1,2-dichloroethane respectively and placed in a two-necked flask. Dimethoxymethane and anhydrous FeCl3 are added under a nitrogen atmosphere to obtain a mixture. Step 102: Heat the mixture obtained in step 101 to 80°C in an oil bath, and then continue to stir under visible light irradiation for 24 hours. Step 103: Collect the product after the reaction is complete, filter it repeatedly with anhydrous methanol until the filtrate is clear, and obtain the filtered crude sample. Step 104: Place the crude sample filtered in step 103 into a Soxhlet extraction tube and extract with anhydrous methanol for 24 hours to obtain the extracted sample. Step 105: Take out the sample extracted in step 104 and dry it under vacuum at 80°C for 12 hours to obtain carbazole-functionalized hypercrosslinked porous material.

8. The preparation method of the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier as described in claim 6, characterized in that, Step two specifically includes the following steps: Step 201: Mix tetrabutyl titanate, acetic acid and anhydrous ethanol and stir for 1 hour to obtain a mixed solution; Step 202: Add tourmaline powder to the mixed solution from step 201 and disperse it ultrasonically for 0.5 hours to obtain a tourmaline powder suspension. Step 203: Mix anhydrous ethanol and deionized water and add it dropwise to the tourmaline micro powder suspension obtained in step 202 while stirring, gradually obtaining a semi-gel tourmaline micro powder suspension. Step 204: Add 20wt% dilute hydrochloric acid to the semi-gel tourmaline micro powder suspension obtained in step 203, and stir continuously for 3 hours to obtain titanium dioxide-tourmaline composite sol. Step 205: Centrifuge the titanium dioxide-tourmaline composite sol obtained in step 204 to obtain tourmaline micro powder coated with titanium dioxide. Then, calcine the tourmaline micro powder coated with titanium dioxide in air at 550°C for 3 hours to obtain nano-titanium dioxide-tourmaline composite photocatalytic material. Step 206: Place the nano-titanium dioxide-tourmaline composite photocatalyst material obtained in step 205 into a tube furnace and calcine it at 500℃~600℃ for 4 hours under normal pressure in a hydrogen atmosphere to obtain hydrogenated black TT.

9. The preparation method of the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier as described in claim 6, characterized in that, Step three specifically includes the following steps: Step 301: First, HCP is pretreated by washing it alternately with 20wt% HCl solution and 20wt% NaOH solution for 5 cycles. Then, the pretreated HCP is weighed, soaked in anhydrous ethanol for 12 hours, and then washed with deionized water until neutral to obtain the pretreated HCP. Step 302: In an ice-water bath, add the HCP pretreated in step 301 to a three-necked flask containing 500 mL of 0.1 M Tris-hydrochloric acid buffer, sonicate for 30 min, add dopamine hydrochloride, sonicate for 30 min, and then magnetically stir the reaction in an ice-water bath for 12 h. After the reaction is completed, the reaction product is obtained. Step 303: Centrifuge the reaction product obtained in step 302, wash it 5 times with deionized water, and then dry it under vacuum at 80°C for 24 hours to obtain the intermediate product PDA@HCP.

10. The preparation method of the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier as described in claim 6, characterized in that, Step five specifically includes the following steps: Step 501: Place the intermediate product hydrogenated black TT@PDA@HCP into an ultraviolet aging test chamber with a wavelength of 200-400nm and a light intensity of 15mW / cm² and heat it to 300℃ for 4 hours to degrade PDA (polydopamine). Step 502: After the total degradation time reaches 4 hours, the ultraviolet light source is turned off, and the temperature is gradually lowered to room temperature. The residual sample is then removed, rinsed with deionized water, and vacuum dried to finally obtain the carbon-reducing and pollution-reducing hypercrosslinked porous purification modifier.

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