Anti-stripping and anti-aging agent, its preparation and application

Abstract

This invention discloses an anti-stripping and anti-aging agent, its preparation method, and its application. The anti-stripping and anti-aging agent of this invention comprises the following raw materials: styrene-butadiene-styrene copolymer, styrene-butadiene rubber, polyethylene oxide, styrene-modified phenol, p-phenylenediamine compounds, coupling agents, and antioxidants. The preparation method of the anti-stripping and anti-aging agent includes: mixing the above materials evenly, followed by kneading and extrusion to obtain the anti-stripping and anti-aging agent. The anti-stripping and anti-aging agent of this invention is in granular form and, when used in airport runway asphalt, can significantly improve the adhesion strength of airport runway asphalt, improve its anti-stripping performance, enhance its heat aging resistance, and exhibit strong adaptability to the high-temperature wake environment of aircraft.

Description

Technical Field

[0001] This invention belongs to the field of petroleum industry and basic materials chemistry, specifically relating to an anti-stripping and anti-aging agent and its preparation method, which is particularly suitable for airport runway asphalt. Background Technology

[0002] Asphalt concrete is a commonly used pavement material for airport runways, connecting taxiways, and taxiways. It features rapid construction, convenient maintenance, and the ability to be repaired without interrupting operations overnight, making it widely adopted by most airports both domestically and internationally. Asphalt concrete pavement structures offer excellent performance, effectively reducing turbulence during aircraft landing and improving airport operational safety.

[0003] The asphalt mixture on airport runways is easily scorched and detached by the high-temperature exhaust blast from jet aircraft. The exhaust blast reaches temperatures of 850℃-900℃ and speeds of 180m / s, spreading elliptically onto the runway surface, where the temperature drops to 150℃-200℃. Actual measurements show that when similar tests were conducted using J-6 fighter jets, the runway surface temperature at a distance of 10-11.5m from the aircraft's exhaust nozzle was 105℃-110℃. This rapid temperature rise and subsequent drop after an aircraft passes creates frequent temperature fluctuations, especially in winter when northern airport runways are typically below freezing. The rapid temperature rise after an aircraft taxis subjectes the runway material to frequent freeze-thaw cycles. This process easily leads to asphalt aging, fatigue, and even damage, as well as aggregate detachment. If ingested by an aircraft engine, this can cause a serious flight accident. Therefore, improving the high-temperature stability and resistance to coarse aggregate detachment of asphalt concrete materials is an important research direction for enhancing civil aviation safety. Currently, high-performance polymer-modified asphalt is commonly used for airport asphalt runways worldwide to address pavement deformation and aggregate detachment issues caused by aircraft wake heating and high shear stress. However, the actual results are not ideal. After a period of use, pavement bulges, cracks, and aggregate detachment occur frequently, leading to flight safety hazards and increased maintenance costs. Tan Yue et al. from Tongji University analyzed the phenomenon of FOD (Formaldehyde Depletion) caused by coarse aggregate detachment from asphalt concrete pavements and proposed engineering treatment measures. Weng Xingzhong et al. from the Air Force Engineering University analyzed the temperature variation law of tensile strength and high-temperature stress fatigue characteristics of asphalt concrete pavement materials through extensive statistical data, concluding that changes in strength under high-temperature stress can seriously affect runway safety. Currently, there are no anti-stripping and anti-aging agents specifically developed for the problem of asphalt concrete aggregate detachment caused by the high-temperature wake of jet aircraft on airport runways. Summary of the Invention

[0004] To address the shortcomings of existing technologies, this invention provides an anti-stripping and anti-aging agent, its preparation method, and its application. When used in airport runway asphalt, this anti-stripping and anti-aging agent can significantly improve the asphalt's anti-stripping and anti-aging properties.

[0005] This invention provides an anti-stripping and anti-aging agent, comprising the following raw materials in parts by weight:

[0006] 1-9 parts styrene-butadiene-styrene copolymer, 1-9 parts styrene-butadiene rubber, 1-7 parts polyethylene oxide, 2-8 parts styrene-modified phenol, 1-8 parts p-phenylenediamine compounds, 0.1-0.7 parts coupling agent, and 0.3-0.7 parts antioxidant.

[0007] Preferably, the anti-stripping and anti-aging agent comprises, by weight parts, the following raw materials:

[0008] 2-8 parts styrene-butadiene-styrene copolymer, 2-8 parts styrene-butadiene rubber, 2-6 parts polyethylene oxide, 3-7 parts styrene-modified phenol, 2-7 parts p-phenylenediamine compounds, 0.2-0.6 parts coupling agent, 0.4-0.6 parts antioxidant.

[0009] The styrene-butadiene-styrene copolymer is linear or star-shaped, with an average relative molecular mass of 110,000 to 250,000.

[0010] The styrene-butadiene rubber contains 25wt% to 45wt% styrene by mass; preferably, the particle size of the styrene-butadiene rubber is not greater than 20mm.

[0011] The molecular weight of the polyoxyethylene is 150,000 to 4,000,000, preferably 160,000 to 3,900,000.

[0012] The styrene is one or more of monostyrene, bistyrene, and tristyrene.

[0013] The p-phenylenediamine compounds are selected from one or more of N,N'-diphenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, and N-phenyl-N'-isopropyl-p-phenylenediamine.

[0014] The coupling agent is selected from one or more of silane coupling agents, aluminate coupling agents, and titanate coupling agents.

[0015] The antioxidant is selected from one or more of 2,6-di-tert-butyl-p-cresol, hydroquinone dibenzyl ether, dilaurate thiodipropionate, trinonylphenyl phosphite, octadecyl thiodipropionate, and poly(2,2,4-trimethyl-1,2-dihydroquinone).

[0016] The asphalt anti-stripping and anti-aging agent is granular with a particle size of 2-5 mm.

[0017] A second aspect of the present invention provides a method for preparing the above-mentioned anti-stripping and anti-aging agent, comprising:

[0018] Styrene-butadiene-styrene copolymer, styrene-butadiene rubber, polyethylene oxide, styrene-modified phenol, p-phenylenediamine compounds, coupling agents, and antioxidants are mixed evenly, then kneaded and granulated to obtain an anti-peeling and anti-aging agent.

[0019] The mixing process is achieved using conventional mixing equipment, such as a kneader.

[0020] Furthermore, the mixing conditions are as follows: mixing temperature is 155℃~175℃, and mixing time is 45~75min.

[0021] The granulation is achieved using conventional extrusion granulation equipment, such as a screw extruder. The extrusion granulation conditions are as follows: extrusion granulation temperature 155℃~175℃.

[0022] Furthermore, the anti-stripping and anti-aging agent prepared by the method provided in the second aspect is in granular form with a particle size of 2 to 5 mm.

[0023] A third aspect of the present invention provides an anti-stripping and anti-aging asphalt, comprising: petroleum asphalt and the above-mentioned anti-stripping and anti-aging agent.

[0024] In the anti-stripping and anti-aging asphalt, the amount of anti-stripping and anti-aging agent accounts for 2% to 3% of the mass of the anti-stripping and anti-aging asphalt.

[0025] Furthermore, in the anti-stripping and aging-resistant asphalt, the petroleum asphalt can be conventional petroleum asphalt used for airport runways, and can be at least one of straight-run asphalt, oxidized asphalt, blended asphalt, solvent-de-oiled asphalt, and polymer-modified asphalt.

[0026] The fourth aspect of the present invention provides a method for preparing the anti-stripping and aging-resistant asphalt, comprising: first heating and melting petroleum asphalt, adding the anti-stripping and aging-resistant agent, mixing evenly, and then developing to obtain the anti-stripping and aging-resistant asphalt.

[0027] Furthermore, in the preparation method of the anti-stripping and aging-resistant asphalt of the present invention, the asphalt is heated to a melting temperature of 155℃~175℃, the mixing temperature (e.g., stirring) is 155℃~175℃, and the mixing time can be 45~75min. The development temperature is 155℃~175℃, and the development time is 4~8 hours.

[0028] The anti-stripping and anti-aging agent of this invention is particularly suitable for use in airport runway asphalt.

[0029] The anti-stripping and aging-resistant asphalt provided by this invention is suitable for airport runway asphalt.

[0030] The present invention has the following beneficial effects:

[0031] 1. The anti-stripping and anti-aging agent of this invention can not only significantly improve the anti-stripping performance of asphalt, but also improve the heat aging resistance of asphalt. It has strong adaptability to the high-temperature wake environment of aircraft, can improve the anti-stripping performance of airport asphalt runways, reduce stone detachment, extend the service life of runways, and reduce the incidence of flight accidents.

[0032] 2. The anti-stripping and anti-aging agent of this invention is in granular form, which is easy to transport and store.

[0033] 3. In the preparation method of the anti-stripping and anti-aging agent of the present invention, a coupling agent is used as an initiator. Styrene-butadiene-styrene copolymer, styrene-butadiene rubber, polyethylene oxide, styrene-modified phenol, p-phenylenediamine compounds, and antioxidants are fused in a kneader and screw extrusion process. The components work together to form a product with high viscosity and flexibility, as well as good polarity and anti-aging properties. This allows the anti-stripping and anti-aging agent to enable asphalt to have good high-temperature peeling resistance and aging resistance under high-temperature conditions, and to adapt to the blowing of high-temperature exhaust gas from aircraft onto the runway surface, reducing stone spalling. Detailed Implementation

[0034] The technical solution of the present invention will be described in detail below with reference to the embodiments, but the present invention is not limited to the following embodiments. In the present invention, wt% is a mass fraction.

[0035] This invention presents a method for simulating high-temperature aircraft exhaust fumes: An aircraft engine (e.g., a replaced engine) is connected to a cylindrical, heated, high-temperature resistant material at its tail. During the experiment, the asphalt to be tested is melted and placed in a metal tray, spread out as a thin film with a thickness of 3mm ± 0.3mm. The tray containing the asphalt film is placed at the bottom of the cylindrical body and secured firmly. The bottom of the cylindrical body has a heating function to maintain the asphalt temperature in the tray at 60℃ ± 20℃ (simulating road surface temperature during hot summer). The engine is turned on, allowing high-temperature exhaust gas to enter from one end of the cylindrical body and exit from the other, blowing over the asphalt film continuously for 30 minutes, followed by a 10-minute pause, repeating this process multiple times. One experimental cycle is 240 hours, starting from the initial blowing. The asphalt is then removed, and its properties are analyzed and compared with those before the simulation experiment. This simulates the condition of asphalt on airport runways (especially the takeoff section) under long-term exposure to high-temperature aircraft exhaust fumes, examining changes in asphalt properties, particularly its resistance to spalling.

[0036] In this invention, the asphalt adhesion strength is obtained by testing with a pull-out tester. The instrument and testing method are as follows:

[0037] Instruments and equipment: PosiTest AT-A pull-out tester; tester parameters: pull-out rate 150 psi / s; test range 0-2000 psi; test method as follows:

[0038] Weigh 0.03g of asphalt onto the test surface of the spindle. Place the asphalt-coated spindle on a hot plate. After the asphalt melts, spread it evenly within 10 seconds. Simultaneously, quickly transfer a preheated stainless steel plate to a horizontal workbench. Place the asphalt-coated spindle onto the stainless steel plate and allow it to cool to room temperature (approximately 1 hour). The liquid asphalt spreads evenly under the weight of the spindle and, after cooling, bonds to the spindle and stainless steel plate, forming an asphalt film thickness of approximately 0.1mm. Place the cooled stainless steel plate and spindle in an environmental chamber (temperature: 20℃; relative humidity: 50%RH) for 1 hour, then remove them and test the adhesion using a PosiTest AT-A tester. Record the pull-out strength value when the spindle separates from the metal plate. This value characterizes the asphalt's resistance to peeling; a higher value indicates better resistance.

[0039] Example 1

[0040] Pre-crush styrene-butadiene rubber with a styrene content of 25 wt% to a particle size of 6–14 mm, and set aside. Heat the kneader for later use.

[0041] Weigh out 20.0 kg of linear styrene-butadiene-styrene copolymer with an average relative molecular mass of 110,000, 20.0 kg of pulverized styrene-butadiene rubber, 20.0 kg of polyethylene oxide with a molecular weight of 160,000, 30.0 kg of monostyrene-modified phenol, 20.0 kg of N-phenyl-N'-isopropyl-p-phenylenediamine, 2.0 kg of aluminate coupling agent, and 4.0 kg of dilauryl thiodipropionate. Place these ingredients in a kneader and mix at 156℃ for 46 min. Then extrude and granulate at 156℃. Cut the granules to a size of 2 mm to obtain the anti-peeling and anti-aging agent. The raw material amounts used in preparing the anti-peeling and anti-aging agent are shown in Table 1.

[0042] Example 2

[0043] Pre-crush styrene-butadiene rubber with a styrene content of 45 wt% to a particle size of 7–17 mm, and set aside. Heat the kneader for later use.

[0044] Weigh out 80.0 kg of star-shaped styrene-butadiene-styrene copolymer with an average relative molecular mass of 250,000, 80.0 kg of pulverized styrene-butadiene rubber, 60.0 kg of polyethylene oxide with a molecular weight of 3.9 million, 70.0 kg of bis-styrene phenol, 70.0 kg of N,N'-diphenyl-p-phenylenediamine, 6.0 kg of titanate coupling agent, and 6.0 kg of poly(2,2,4-trimethyl-1,2-dihydroquinone). Place these ingredients in a kneader and mix at 174℃ for 74 min. Then extrude and granulate at 174℃. Cut the granules to a size of 2 mm to obtain the anti-peeling and anti-aging agent. The raw material amounts used in preparing the anti-peeling and anti-aging agent are shown in Table 1.

[0045] Example 3

[0046] Pre-crush styrene-butadiene rubber with a styrene content of 35 wt% to a particle size of 6–19 mm, and set aside. Heat the kneader for later use.

[0047] Weigh out 50.0 kg of linear styrene-butadiene-styrene copolymer with an average relative molecular mass of 180,000, 50.0 kg of pulverized styrene-butadiene rubber, 40.0 kg of polyethylene oxide with a molecular weight of 2 million, 50.0 kg of tristylated phenol, 45.0 kg of N-cyclohexyl-N'-phenyl-p-phenylenediamine, 4.0 kg of silane coupling agent (KH560), and 5.0 kg of trinonylphenyl phosphite. Place these ingredients in a kneader and mix at 165℃ for 60 min. Then extrude and granulate at 165℃. Cut the granules to a size of 2 mm to obtain the anti-peeling and anti-aging agent. The raw material amounts used in preparing the anti-peeling and anti-aging agent are shown in Table 1.

[0048] Example 4

[0049] The anti-stripping and anti-aging agent obtained in Example 1 was added to petroleum asphalt (Zhenhai 70A) produced by Zhenhai Petrochemical Company, which had a penetration of 65 dmm at 25°C and had been melted at 156°C. The weight ratio of petroleum asphalt to anti-stripping and anti-aging agent was 97:3. The mixture was stirred at a constant temperature of 156°C for 46 minutes, followed by development at a constant temperature of 156°C for 4 hours to obtain anti-stripping and anti-aging asphalt.

[0050] The adhesion strength of the anti-stripping and aging-resistant asphalt was tested using a pull-out tester, and the results are shown in Table 2. The asphalt was then subjected to a simulated experiment under the high-temperature wake environment of an aircraft. After one cycle of testing, a pull-out test was performed, and the results are shown in Table 2.

[0051] Example 5

[0052] The anti-stripping and anti-aging agent obtained in Example 2 was added to petroleum asphalt (Zhenhai 70A) produced by Zhenhai Petrochemical Company, which had a penetration of 65 dmm at 25°C and had been melted at 174°C. The weight ratio of petroleum asphalt to anti-stripping and anti-aging agent was 97.5:2.5. The mixture was stirred at a constant temperature of 174°C for 74 minutes, followed by development at a constant temperature of 174°C for 8 hours to obtain anti-stripping and anti-aging asphalt.

[0053] The adhesion strength of the anti-stripping and aging-resistant asphalt was tested using a pull-out tester, and the results are shown in Table 2. The asphalt was then subjected to a simulated experiment under the high-temperature wake environment of an aircraft. After one cycle of testing, a pull-out test was performed, and the results are shown in Table 2.

[0054] Example 6

[0055] The anti-stripping and anti-aging agent obtained in Example 3 was added to petroleum asphalt (Zhenhai 70A) produced by Zhenhai Petrochemical Company, which had a penetration of 65 dmm at 25°C and had been melted at 165°C. The weight ratio of petroleum asphalt to anti-stripping and anti-aging agent was 98:2. The mixture was stirred at a constant temperature of 165°C for 60 minutes, followed by development at a constant temperature of 165°C for 6 hours to obtain anti-stripping and anti-aging asphalt.

[0056] The adhesion strength of the anti-stripping and aging-resistant asphalt was tested using a pull-out tester, and the results are shown in Table 2. The asphalt was then subjected to a simulated experiment under the high-temperature wake environment of an aircraft. After one cycle of testing, a pull-out test was performed, and the results are shown in Table 2.

[0057] Comparative Example 1

[0058] For comparison, the adhesion strength of 25℃ asphalt (Zhenhai 70A) with a penetration of 65dmm produced by Zhenhai Petrochemical Company was tested using a pull-out tester, and the results are listed in Table 2. Zhenhai 70A was also subjected to a simulated experiment under the high temperature wake environment of an aircraft. After one cycle of testing, a pull-out test was performed, and the results are shown in Table 2.

[0059] Comparative Example 2

[0060] For comparison, JW-AS1, a commercial anti-stripping agent produced by Shenzhen Jiashengwei, was added to petroleum asphalt (Zhenhai 70A) produced by Zhenhai Petrochemical Company, which had a penetration of 65 dmm at 25℃ and had been melted at 174℃. The weight ratio of petroleum asphalt to commercial anti-stripping agent was 97.5:2.5. The mixture was stirred at a constant temperature of 174℃ for 74 minutes, followed by development at a constant temperature of 174℃ for 8 hours to obtain anti-stripping asphalt.

[0061] The adhesion strength of the anti-stripping asphalt was tested using a pull-out tester, and the results are shown in Table 2. The anti-stripping asphalt was then subjected to a simulated experiment under the high-temperature wake environment of an aircraft. After one cycle of testing, a pull-out test was performed, and the results are shown in Table 2.

[0062] Table 1. Amount of raw materials used in the preparation of anti-stripping and anti-aging agents

[0063] Material weight / kg Example 1 Example 2 Example 3 Styrene-butadiene-styrene copolymer 20.0 80.0 50.0 Styrene-butadiene rubber 20.0 80.0 50.0 Polyethylene oxide 20.0 60.0 40.0 Styrified phenol 30.0 70.0 50.0 p-phenylenediamine compounds 20.0 70.0 45.5 Coupling agent 2.0 6.0 4.0 antioxidants 4.0 6.0 5.0

[0064] Table 2 Results of Asphalt Pull-out Test

[0065] Adhesion strength / psi Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 No simulation experiment was conducted. 552 570 588 391 441 After simulation experiment 592 611 626 328 453

[0066] As shown in Table 2, adding the anti-stripping and anti-aging agent of this invention to asphalt significantly improves the adhesion strength and anti-stripping performance of the asphalt. After one cycle of aircraft high-temperature wake simulation experiments, the adhesion strength of the asphalt with the added anti-stripping and anti-aging agent not only did not decrease but actually increased, indicating that the anti-stripping and anti-aging agent of this invention not only improves the anti-stripping performance of asphalt but also has strong aging resistance and strong adaptability to the high-temperature wake environment of aircraft. In contrast, the adhesion strength of the asphalt without the added anti-stripping and anti-aging agent decreased significantly after the simulation experiment. Compared with the anti-stripping and anti-aging agent of this invention, the addition of a commercially available anti-stripping agent resulted in a smaller improvement in adhesion strength, and the increase in adhesion strength after the simulation experiment was also smaller.

Claims

1. An anti-stripping and anti-aging agent, comprising, by weight parts: 1-9 parts styrene-butadiene-styrene copolymer, 1-9 parts styrene-butadiene rubber, 1-7 parts polyethylene oxide, 2-8 parts styrene-modified phenol, 1-8 parts p-phenylenediamine compound, 0.1-0.7 parts coupling agent, and 0.3-0.7 parts antioxidant; The p-phenylenediamine compounds are selected from one or more of N,N'-diphenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, and N-phenyl-N'-isopropyl-p-phenylenediamine; The coupling agent is selected from one or more of silane coupling agents, aluminate coupling agents, and titanate coupling agents; The antioxidant is selected from one or more of 2,6-di-tert-butyl-p-cresol, hydroquinone dibenzyl ether, dilaurate thiodipropionate, trinonylphenyl phosphite, octadecyl thiodipropionate, and poly(2,2,4-trimethyl-1,2-dihydroquinone).

2. The anti-stripping age resistor according to claim 1, characterized in that: By weight, it includes the following raw materials: 2-8 parts styrene-butadiene-styrene copolymer, 2-8 parts styrene-butadiene rubber, 2-6 parts polyethylene oxide, 3-7 parts styrene-modified phenol, 2-7 parts p-phenylenediamine compounds, 0.2-0.6 parts coupling agent, and 0.4-0.6 parts antioxidant.

3. The anti-stripping and anti-aging agent according to claim 1 or 2, characterized in that: The styrene-butadiene-styrene copolymer is linear or star-shaped, with an average relative molecular mass of 110,000 to 250,000.

4. The anti-stripping and anti-aging agent according to claim 1 or 2, characterized in that: The styrene-butadiene rubber contains 25wt% to 45wt% styrene by mass.

5. The anti-stripping and anti-aging agent according to claim 4, characterized in that: The particle size of the styrene-butadiene rubber is no greater than 20 mm.

6. The anti-stripping and anti-aging agent according to claim 1 or 2, characterized in that: The molecular weight of the polyoxyethylene is 150,000 to 4,000,000.

7. The anti-stripping and anti-aging agent according to claim 6, characterized in that: The molecular weight of the polyoxyethylene is between 160,000 and 3.9 million.

8. The anti-stripping and anti-aging agent according to claim 1 or 2, characterized in that: The anti-stripping and anti-aging agent is in granular form with a particle size of 2-5 mm.

9. A method for preparing the anti-stripping and anti-aging agent according to any one of claims 1-8, comprising the following steps: Styrene-butadiene-styrene copolymer, styrene-butadiene rubber, polyethylene oxide, styrene-modified phenol, p-phenylenediamine compounds, coupling agents, and antioxidants are mixed evenly, then kneaded and granulated to obtain an anti-peeling and anti-aging agent.

10. The preparation method according to claim 9, characterized in that, The mixing conditions are as follows: mixing temperature is 155℃~175℃, and mixing time is 45~75min; And / or, the granulation is carried out by extrusion granulation at a temperature of 155℃~175℃.

11. A spalling-resistant and aging-resistant asphalt, comprising: Petroleum asphalt and the anti-stripping and anti-aging agent according to any one of claims 1-8.

12. The anti-stripping and aging-resistant asphalt according to claim 11, characterized in that, The amount of the anti-stripping and anti-aging agent is 2% to 3% of the mass of the anti-stripping and anti-aging asphalt.

13. The anti-stripping and aging-resistant asphalt according to claim 11, characterized in that, In the anti-stripping and aging-resistant asphalt, the petroleum asphalt is at least one of straight-run asphalt, oxidized asphalt, blended asphalt, solvent-de-oiled asphalt, and polymer-modified asphalt.

14. A method for preparing the anti-stripping and aging-resistant asphalt according to any one of claims 11-13, comprising: First, the petroleum asphalt is heated and melted, then the anti-stripping and anti-aging agent is added, mixed evenly, and then developed to obtain the anti-stripping and anti-aging asphalt.

15. The preparation method according to claim 14, characterized in that, The heating and melting temperature of the petroleum asphalt is 155℃~175℃, the mixing temperature is 155℃~175℃, and the mixing time is 45~75min; the development temperature is 155℃~175℃, and the development time is 4~8 hours.

16. The application of the anti-stripping and anti-aging agent according to any one of claims 1-8 or the anti-stripping and anti-aging asphalt according to any one of claims 11-13 in airport runways.