Anti-stripping agent and preparation method and application thereof
Technical Field
The invention belongs to the fields of petroleum industry and basic material chemistry, and particularly relates to an anti-stripping agent and a preparation method thereof, which are particularly suitable for an airport asphalt runway.
Background
The material of the runway surface of the airport is divided into two types, namely cement concrete and asphalt concrete, wherein the former is mainly applied to branch airports, and the latter is mainly applied to asphalt concrete overlay of the cement runway surface by a trunk airport or the branch airports. In China, airports with more than ten million levels of passenger flow mainly adopt asphalt concrete materials as runway pavement materials. The working state of the asphalt concrete material for the airport runway is obviously different from that of the asphalt concrete material for the common highway, and the working state is mainly represented by the following two points: firstly, the high-temperature airflow ejected by the jet aircraft seriously influences the stability of the asphalt concrete material; secondly, after the oil content of the asphalt concrete material is reduced, the surface coarse aggregate is easy to loosen to form foreign invaders (FOD), and once the FOD is sucked into an aircraft engine, serious flight accidents can be caused. Therefore, the improvement of the high-temperature stability and the coarse aggregate shedding resistance of the asphalt concrete material is an important research direction for improving the safety of civil aviation operation. At present, airport runways in the world are generally paved by polymer modified asphalt with good high-temperature performance so as to deal with the problems of airplane wake baking and road surface deformation and threshing under high shear stress, but the effect is not ideal, and after the airport runway is used for a period of time, the road surface bulges and cracks and the aggregate falls frequently, so that huge flight potential safety hazards and maintenance cost are brought. Therefore, the development of a high-temperature-resistant and anti-stripping asphalt material suitable for being used on an airport runway is urgently needed, a special high-temperature-resistant and anti-stripping evaluation method for the airport asphalt is established, a complete set of systematic and scientific matching technology is formed, and the international and domestic requirements for high-quality asphalt materials in the next thirty years are met.
The problem of stone falling on an airport runway is different from the situation on the highway, the highway is mainly used for water damage, the airport runway mainly considers the sweeping effect of high-temperature wake flow of a jet plane, the temperature is high (850-900 ℃), the airflow is large, the airflow speed is high (180 m/s), the temperature of the runway surface is rapidly increased, the temperature of the plane is reduced after passing, the plane is always in frequent temperature fluctuation, and asphalt on the runway surface is easy to age, fatigue, damage and thresh. At present, no anti-stripping agent developed specially for solving the problem of asphalt concrete aggregate shedding caused by the influence of high-temperature wake flow of a jet plane on an airport runway exists.
Disclosure of Invention
The invention provides an anti-stripping agent and a preparation method and application thereof, aiming at the problem of aggregate shedding faced by an asphalt runway of an airport. When the anti-stripping agent is used for an asphalt runway of an airport, the anti-stripping performance of asphalt can be obviously improved.
The invention provides an anti-stripping agent which comprises the following raw materials in parts by mass:
5 to 15 portions of ethylene-vinyl acetate copolymer (EVA),
3 to 9 portions of polyethylene oxide,
3 to 10 parts of styrenated phenol,
3 to 9 parts of p-phenylenediamine compounds,
1.2 to 2.0 portions of coupling agent,
0.5 to 1.2 portions of hindered phenol compounds,
0.5 to 1.2 portions of aromatic oil.
Preferably, the anti-stripping agent comprises the following raw materials in parts by weight:
6 to 14 parts of ethylene-vinyl acetate copolymer (EVA),
4 to 8 parts of polyethylene oxide,
4 to 9 parts of styrenated phenol,
4 to 8 parts of p-phenylenediamine compounds,
1.3 to 1.9 portions of coupling agent
0.6 to 1.1 parts of hindered phenol compounds,
0.6 to 1.1 portions of aromatic oil.
In the EVA, the mass content of the combined vinyl acetate is 21-26 wt%, preferably 22-25 wt%.
The molecular weight of the polyethylene oxide is 14-500 ten thousand, and preferably 20-400 ten thousand.
The p-phenylenediamine compound is 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 one or more of silane coupling agent (at least one of types KH550, KH560 and KH 570), aluminate coupling agent and titanate coupling agent.
The hindered phenol compound comprises one or more of 2, 8-di-tert-butyl-4-methylphenol, tetra- [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid octadecyl alcohol ester and 1,3,5- (3, 5-di-tert-butyl-4-hydroxyphenyl) s-triazine-2, 4,6 (1H, 3H, 5H) trione.
The aromatic oil is a component rich in aromatic hydrocarbon, wherein the content of the aromatic hydrocarbon is more than 70 percent by mass fraction, and the aromatic hydrocarbon can be selected from one or a mixture of more of reduced tetra-line extract oil, furfural refined extract oil, phenol refined extract oil or catalytic cracking slurry oil.
The anti-shedding agent is a paste at normal temperature.
The invention provides a preparation method of the anti-stripping agent, which comprises the following steps:
uniformly mixing EVA, polyethylene oxide, styrenated phenol, p-phenylenediamine compounds, coupling agents, hindered phenol compounds and aromatic oil, and then mixing and extruding to obtain the anti-falling agent.
The mixing is realized by using a conventional mixing device, such as a kneader and a bottom self-carrying extrusion structure of the kneader. The mixing conditions were as follows: the mixing temperature is 130-160 ℃, and the mixing time is 60-90min.
The extrusion conditions were as follows: the extrusion temperature is 130-160 ℃.
In a third aspect, the present invention provides a pitch resistant to stripping, comprising: petroleum asphalt and the above anti-stripping agent.
In the anti-stripping asphalt, the dosage of the anti-stripping agent accounts for 2-3% of the mass of the anti-stripping asphalt.
In the anti-stripping asphalt, the petroleum asphalt can be conventional petroleum asphalt used for airport runways and is at least one of straight-run asphalt, oxidized asphalt, blended asphalt and solvent deoiled asphalt.
The fourth aspect of the invention provides a preparation method of the anti-falling asphalt, which comprises the following steps: heating and melting petroleum asphalt, adding the anti-stripping agent, and stirring until the anti-stripping agent is uniformly mixed to obtain the anti-stripping asphalt.
In the preparation method, the petroleum asphalt is heated to melt at 140-160 ℃, the stirring temperature is 130-160 ℃, and the stirring time can be 50-80min.
The anti-stripping agent is particularly suitable for being applied to asphalt of airport runways.
The anti-stripping asphalt provided by the invention is suitable for being used as asphalt for airfield runways.
The invention has the following advantages:
1. the anti-stripping agent provided by the invention not only can obviously improve the anti-stripping performance of asphalt, but also has strong adaptability to the high-temperature wake environment of an airplane, can improve the anti-stripping performance of an asphalt runway of an airport, reduces the stripping of aggregate, and can reduce the incidence rate of flight accidents.
2. The anti-stripping agent is pasty at normal temperature, development is not needed in the process of preparing the anti-stripping asphalt by using the anti-stripping agent, the production time of the anti-stripping asphalt is shortened, the working efficiency is improved, the adhesion strength of the asphalt can be further improved, the low-temperature elongation performance of the asphalt can be improved, and frost heaving and cracking of a pavement can be avoided.
3. In the preparation method of the anti-stripping agent, under the assistance of the coupling agent, the ethylene-vinyl acetate copolymer, the polyethylene oxide, the styrenated phenol, the p-phenylenediamine compound and the like are subjected to grafting reaction in a kneading machine and in the screw extrusion process, so that all substances can be quickly and well combined, the formed product has higher viscosity and flexibility and better polarity, and the anti-stripping agent can enable asphalt to have better high-temperature shedding resistance in a high-temperature environment. The addition of styrenated phenol improves the adhesion strength and the adaptability to the high-temperature wake environment of the airplane, so that the asphalt has stronger anti-falling capacity. The addition of hindered phenol compounds can improve the anti-aging capability of the substances containing unsaturated bonds, and further improve the anti-shedding agent and the heat aging resistance of asphalt. Under the action of aromatic oil, the components are easier to fuse, the reaction condition is reduced, the energy is saved, the low-temperature extensibility of the asphalt can be improved, and frost cracking of the pavement in winter is avoided. Therefore, the anti-shedding agent of the invention comprehensively strengthens the adhesion strength of asphalt to stone from multiple aspects and improves the high-temperature shedding resistance of asphalt in airports.
Detailed Description
The following examples are given to illustrate the technical aspects of the present invention in detail, but the present invention is not limited to the following examples. In the present invention, wt% is a mass fraction.
The invention relates to an aircraft high-temperature wake flow simulation experiment method, which comprises the following steps: the tail part of the engine is linked with a straight cylinder type cylinder body made of high-temperature resistant materials with a heating function by using an airplane engine (such as a renewed engine). During the experiment, the asphalt to be tested is placed in a metal tray after being melted, and is spread flatly to form a film, wherein the thickness of the film is 3mm +/-0.3 mm. And (3) placing the tray filled with the asphalt film at the bottom in the cylinder body, and firmly fixing. The bottom of barrel has the heating function, guarantees that the pitch temperature in the tray maintains 60 degrees centigrade +/-20 ℃ (road surface temperature when simulation summer high temperature). And starting the engine to enable high-temperature tail gas of the engine to enter from one end of the straight cylinder and to be discharged from the other end of the straight cylinder, blowing the high-temperature tail gas above the asphalt film for 30 minutes and stopping for 10 minutes, and continuously repeating the steps for multiple times. One experimental period was 240 hours from the initial start of blowing. And then taking out the asphalt, analyzing various properties, and comparing the properties with the properties before the simulation experiment. Therefore, the condition of asphalt on the runway (especially the takeoff section) of the airport is simulated when the asphalt is subjected to high-temperature tail gas purging of an airplane for a long time, and the change of the asphalt property, especially the change of the anti-falling performance is inspected.
In the present invention, the adhesion strength of asphalt is measured by a pull tester. The instrument and test method are as follows:
instruments and equipment: the drawing tester with the model of Positest AT-A has the following parameters: a draw rate of 150psi/s; testing range 0-2000psi; the test method is as follows:
weighing 0.03g of asphalt on an experimental surface of a spindle; placing the spindle attached with the asphalt on an electric hot plate, after the asphalt is melted, uniformly coating the asphalt within 10s, simultaneously quickly transferring the preheated white steel plate to a horizontal operation table, buckling the spindle coated with the asphalt uniformly on the white steel plate, and standing and cooling to room temperature (about 1 h). The liquid asphalt is uniformly spread under the action of the gravity of the spindle, the spindle and the white steel plate are bonded after cooling, and the thickness of the asphalt film is about 0.1mm. The white steel plate and the spindle cooled to room temperature were placed in an environmental chamber (temperature: 20 ℃; relative humidity: 50 Rh%) and were taken out after constant temperature for 1 hour, and the adhesiveness was tested using a Positest AT-A tester. The value of the pull strength at the moment of separation of the spindle from the metal sheet is recorded. The anti-falling performance of the asphalt is characterized by the numerical value, and the larger the numerical value is, the better the anti-falling performance is.
Example 1
Weighing 61.0kg of ethylene-vinyl acetate copolymer with the combined vinyl acetate content of 22wt%, 41.0kg of polyethylene oxide with the molecular weight of 22 ten thousand, 41.0kg of styrenated phenol, 41.0kg of N, N' -diphenyl-p-phenylenediamine, 13.5kg of silane coupling agent (KH 560), 6.2kg of 2, 8-di-tert-butyl-4-methylphenol and 6.2kg of tetra-line drawing oil, placing the materials into a preheated kneader for mixing, wherein the mixing temperature is 135 ℃, and the mixing time is 60min; then extruding at 135 ℃ to obtain the anti-shedding agent. The proportions of the components are shown in Table 1.
Example 2
Weighing 100.0kg of ethylene-vinyl acetate copolymer with 25wt% of combined vinyl acetate content, 60.0kg of polyethylene oxide with the molecular weight of 400 ten thousand, 65.0 kg of styrenated phenol, 60.0kg of N-cyclohexyl-N' -phenyl-p-phenylenediamine, 16.0 kg of aluminate coupling agent, 8.5kg of tetra- [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 8.5kg of furfural refined extract oil, placing the materials into a pre-heated kneader for kneading at the kneading temperature of 158 ℃ for 88min; then extruding at 158 ℃ to obtain the anti-stripping agent. The distribution ratio of each component is shown in table 1.
Example 3
138.0kg of ethylene-vinyl acetate copolymer with 24wt% of combined vinyl acetate content, 78.0kg of polyethylene oxide with the molecular weight of 200 ten thousand, 88.0 kg of styrenated phenol, 78.0kg of N-phenyl-N' -isopropyl-p-phenylenediamine, 18.8kg of titanate coupling agent, 10.8kg of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate and 10.8kg of catalytic cracking slurry oil are weighed and placed in a pre-heated kneader for mixing, the mixing temperature is 145 ℃, and the mixing time is 75min; then extruded at an extrusion temperature of 145 ℃. Obtaining the anti-stripping agent. The distribution ratio of each component is shown in table 1.
Example 4
The anti-stripping agent obtained in example 1 was added to molten petroleum asphalt with a penetration of 70dmm at 25 ℃ (ziru 70) manufactured by ziru petrochemical company, petroleum asphalt: the weight ratio of the anti-stripping agent is 97:3. stirring at constant temperature of 132 deg.C for 52 min to obtain anti-drop asphalt.
The adhesion strength of the anti-drop asphalt was measured by a pull tester, and the results are shown in Table 2. The anti-dropping asphalt is subjected to a simulation experiment under the high-temperature wake environment of an airplane, and a drawing test is carried out after a period of test, and the result is shown in table 2.
Example 5
The anti-stripping agent obtained in example 2 was added to molten petroleum asphalt with a penetration of 70dmm at 25 ℃ (ziru 70) manufactured by ziru petrochemical company, petroleum asphalt: the weight ratio of the anti-stripping agent is 97.5:2.5. stirring at constant temperature of 158 ℃ for 78 min to obtain the anti-stripping asphalt.
The adhesion strength of the anti-dropping asphalt was measured by a drawing tester, and the results are shown in Table 2. The anti-dropping asphalt is subjected to a simulation experiment under the high-temperature wake environment of an airplane, and a drawing test is carried out after a period of test, and the result is shown in table 2.
Example 6
The anti-stripping agent obtained in example 3 was added to molten petroleum asphalt produced by the company ziru petrochemical having a penetration of 70dmm at 25 ℃ (ziru 70), and the ratio of petroleum asphalt: the weight ratio of the anti-stripping agent is 98:2. stirring at the constant temperature of 145 ℃ for 65 min to obtain the anti-stripping asphalt.
The adhesion strength of the anti-dropping asphalt was measured by a drawing tester, and the results are shown in Table 2. The anti-dropping asphalt is subjected to a simulation experiment under the high-temperature wake environment of an airplane, and a drawing test is carried out after a period of test, and the result is shown in table 2.
Comparative example 1
For comparison, the adhesion strength of a pull tester test of grade 70A bitumen (zilu 70) produced by zilu petrochemical company is also listed in table 2; 70A-grade asphalt (Qilu 70) produced by the Qilu petrochemical company is also subjected to a simulation experiment in the high-temperature wake environment of an airplane, and drawing experiments are respectively carried out after a period of experiment, and the results are shown in Table 2.
Comparative example 2
For comparison, commercial anti-sloughing agent PAVE192 from invitrogen corporation was added to molten petroleum asphalt from zipru petrochemical having a penetration of 70dmm at 25 ℃ (zilu 70A), petroleum asphalt: the weight ratio of the anti-stripping agent is 97.5:2.5. stirring at constant temperature of 158 ℃ for 78 min to obtain the anti-stripping asphalt.
The adhesion strength of the anti-drop asphalt was measured by a pull tester, and the results are shown in Table 2. The anti-drop asphalt is subjected to a simulation experiment under the high-temperature wake flow environment of an airplane, a drawing test is carried out after a period of test, and the result is shown in table 2.
TABLE 1 preparation of anti-stripping agent component ratios
Weight of material/kg
|
Example 1
|
Example 2
|
Example 3
|
Ethylene-vinyl acetate copolymer
|
61.0
|
100.0
|
138.0
|
Polyethylene oxide
|
41.0
|
60.0
|
78.0
|
Styrenated phenol
|
41.0
|
65.0
|
88.0
|
P-phenylenediamine compounds
|
41.0
|
60.0
|
78.0
|
Coupling agent
|
13.5
|
16.0
|
18.8
|
Hindered phenol compound
|
6.2
|
8.5
|
10.8
|
Aromatic oil
|
6.2
|
8.5
|
10.8 |
TABLE 2 Pitch Pull test results
Adhesion Strength/psi
|
Example 4
|
Example 5
|
Example 6
|
Comparative example 1
|
Comparative example 2
|
No simulation experiment was performed
|
498
|
526
|
537
|
380
|
430
|
After the simulation experiment
|
541
|
557
|
570
|
308
|
304 |
As can be seen from Table 2, the addition of the anti-stripping agent of the present invention to asphalt significantly improves the adhesion strength and anti-stripping performance of asphalt; after a period of airplane high-temperature wake simulation experiment, the adhesion strength of the asphalt added with the anti-stripping agent is not reduced but increased, which shows that the anti-stripping agent can improve the anti-stripping performance of the asphalt and has strong adaptability to airplane high-temperature wake environment. The adhesion strength of the asphalt without the anti-stripping agent is obviously reduced after a simulation experiment; after a certain commercially available antistripping agent is added, compared with the antistripping agent disclosed by the invention, the improvement range of the adhesive strength is smaller, and the adhesive strength is reduced after a simulation experiment.