Double-component epoxy resin self-repairing microcapsule material for asphalt pavement, and preparation method and use method thereof

文档序号：501799 发布日期：2021-05-28 浏览：22次中文

阅读说明：本技术 沥青路面用双组份环氧树脂自修复微胶囊材料、其制备方法及使用方法 (Double-component epoxy resin self-repairing microcapsule material for asphalt pavement, and preparation method and use method thereof ) 是由郑木莲田艳娟刘侠刘珊于 2020-12-30 设计创作，主要内容包括：本发明公开了一种沥青路面用双组份环氧树脂自修复微胶囊材料、其制备方法及使用方法,沥青路面用双组份环氧树脂自修复微胶囊材料包括壳体以及包裹于壳体内的微胶囊芯材,其中,微胶囊芯材由氢化双酚A型环氧树脂及季戊四醇四-3-巯基丙酸酯组成,该微胶囊材料能够实现沥青路面裂缝修复,提高沥青路面的机械性能及耐老化性能,并且制备方法简单,使用也较为方便。(The invention discloses a double-component epoxy resin self-repairing microcapsule material for an asphalt pavement, a preparation method and a use method thereof.)

1. The double-component epoxy resin self-repairing microcapsule material for the asphalt pavement is characterized by comprising a shell and a microcapsule core material wrapped in the shell, wherein the microcapsule core material is composed of hydrogenated bisphenol A epoxy resin and pentaerythritol tetra-3-mercaptopropionate.

2. The two-component epoxy resin self-repairing microcapsule material for the asphalt pavement according to claim 1, wherein the mass ratio of the shell to the microcapsule core material is 1.2-1.5:1, and the mass ratio of the hydrogenated bisphenol A epoxy resin to pentaerythritol tetra-3-mercaptopropionate is 2: 1.

3. The two-component epoxy resin self-repairing microcapsule material for the asphalt pavement according to claim 1, wherein the shell is made of melamine formaldehyde resin or melamine urea formaldehyde resin.

4. A preparation method of a two-component epoxy resin self-repairing microcapsule material is characterized by comprising the following steps:

1) mixing urea, formaldehyde and melamine, adding triethanolamine to adjust the pH value to 8-9, heating and stirring to obtain a mixture A;

2) mixing sodium dodecyl benzene sulfonate and distilled water, stirring and fully dissolving, and then adjusting the pH value to be neutral to obtain a mixture B, wherein the concentration of the mixture B is 0.5-0.75%.

3) Respectively adding hydrogenated bisphenol A epoxy resin and pentaerythritol tetra-3-mercaptopropionate into the mixture B, and stirring and emulsifying to obtain O/W emulsion;

4) adding the mixture A into O/W emulsion according to the mass ratio of the shell to the microcapsule core material of 1.2-1.5:1, and then uniformly stirring to obtain a mixture C;

5) and adjusting the pH value of the mixture C to 3-5 by using an acidic regulator, adding a catalyst, heating for curing, washing, filtering and drying to obtain the double-component epoxy resin self-repairing microcapsule material.

5. The preparation method of the two-component epoxy resin self-repairing microcapsule material according to claim 4, wherein in the step 1), the molar ratio of urea to the mixture of formaldehyde and melamine is 2.5; the heating temperature is 70 ℃, the stirring speed is 400r/min, and the stirring time is 1 h;

the stirring speed in the step 2) is 200r/min, and the stirring time is 10 minutes;

the stirring time in the step 3) is 1 h;

the stirring time in the step 4) is 30 min;

the temperature rise in the step 5) is 65 ℃, and the curing time is 2 h.

6. The preparation method of the two-component epoxy resin self-repairing microcapsule material according to claim 4, wherein the acidity regulator is citric acid or hydrochloric acid.

7. The use method of the two-component epoxy resin self-repairing microcapsule material of claim 1 is characterized by comprising the following steps:

the two-component epoxy resin self-repairing microcapsule material is added into asphalt and then is uniformly stirred to obtain a mixture of the two-component epoxy resin self-repairing microcapsule material and the asphalt, and then the mixture of the two-component epoxy resin self-repairing microcapsule material and the asphalt is laid, wherein the addition amount of the two-component epoxy resin self-repairing microcapsule material is 2% -4% of the mass of the asphalt.

Technical Field

The invention belongs to the technical field of preventive maintenance of asphalt pavements, and relates to a two-component epoxy resin self-repairing microcapsule material for an asphalt pavement, and a preparation method and a use method thereof.

Background

Under the action of load or temperature stress, the microcracks in the pavement structure are subjected to high stress concentration phenomenon to generate crack propagation, so that the cracking of the asphalt pavement is caused. The micro cracks are expanded and communicated, so that the width of the cracks is continuously increased, and then the micro cracks are developed into macro cracks. Although the micro cracks do not influence the vehicle passing, under the stress of temperature and the load of the vehicle, the moisture of the road surface permeates into the micro cracks, and the damage process of the road surface performance is accelerated. The pavement still has stronger mechanical strength in the stage of microcrack initiation, and can meet the use requirement; when the microcracks further propagate into macrocracks, the pavement performance is greatly deteriorated.

When the micro cracks develop into obvious macro cracks, the maintenance and the repair of the pavement are carried out, which not only increases the economic cost of the pavement in the operation period, but also causes resource waste. If the micro cracks and micro damages of the pavement are treated or repaired in time, the service life of the pavement can be effectively prolonged. When the temperature shrinkage crack is initiated, namely the pavement generates low-temperature micro cracks, if the temperature shrinkage crack is not interfered, the asphalt has self-repairing performance, and the cracks can be automatically closed by the asphalt when the temperature is raised. This presupposes that the bitumen is not aged and that the bitumen and aggregate properties are not severely deteriorated. However, in fact, under the combined action of external factors, the light components of the asphalt are continuously reduced, and aging phenomena such as oxidation reaction and the like occur. Asphalt aging accelerates crack propagation and causes macro cracks before the asphalt self-heals the cracks. If the self-repairing microcapsules are premixed in the asphalt mixture, the microcapsules crack to release the repairing agent when micro cracks are generated in the initial stage of low-temperature cracking. After the temperature rises again, the asphalt matrix is toughened, the impact resistance is effectively improved, and the performance of the aged asphalt is repaired. After the self-repairing performance of the asphalt is repaired or improved, the probability and time of next cracking can be delayed.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provides a two-component epoxy resin self-repairing microcapsule material for an asphalt pavement, a preparation method and a use method thereof.

In order to achieve the purpose, the double-component epoxy resin self-repairing microcapsule material for the asphalt pavement comprises a shell and a microcapsule core material wrapped in the shell, wherein the microcapsule core material is composed of hydrogenated bisphenol A epoxy resin and pentaerythritol tetra-3-mercaptopropionate.

The mass ratio of the shell to the microcapsule core material is 1.2-1.5:1, and the mass ratio of the hydrogenated bisphenol A epoxy resin to the pentaerythritol tetra-3-mercaptopropionate is 2: 1.

The shell is made of melamine formaldehyde resin or melamine urea formaldehyde resin.

The preparation method of the double-component epoxy resin self-repairing microcapsule material comprises the following steps:

1) mixing urea, formaldehyde and melamine, adding triethanolamine to adjust the pH value to 8-9, heating and stirring to obtain a mixture A;

3) Respectively adding hydrogenated bisphenol A epoxy resin and pentaerythritol tetra-3-mercaptopropionate into the mixture B, and stirring and emulsifying to obtain O/W emulsion;

4) adding the mixture A into O/W emulsion according to the mass ratio of the shell to the microcapsule core material of 1.2-1.5:1, and then uniformly stirring to obtain a mixture C;

In the step 1), the molar ratio of the urea to the mixture of formaldehyde and melamine is 2.5; the heating temperature is 70 ℃, the stirring speed is 400r/min, and the stirring time is 1 h;

the stirring speed in the step 2) is 200r/min, and the stirring time is 10 minutes;

the stirring time in the step 3) is 1 h;

the stirring time in the step 4) is 30 min;

the temperature rise in the step 5) is 65 ℃, and the curing time is 2 h.

The acidity regulator is citric acid or hydrochloric acid.

The use method of the two-component epoxy resin self-repairing microcapsule material comprises the following steps:

The invention has the following beneficial effects:

the invention relates to a two-component epoxy resin self-repairing microcapsule material for asphalt pavement, a preparation method and a using method thereof, during specific operation, the two-component epoxy resin self-repairing microcapsule is broken under the action of tip stress of low-temperature microcracks of asphalt, after released core material is fully diffused in the microcracks of the asphalt, the microcracks are closed by a three-dimensional network structure generated by curing and crosslinking actions of the two components, the crack is repaired in the real sense, asphalt molecules can be firmly locked, the probability of next cracking is reduced, the mechanical property and the aging resistance of an asphalt matrix are improved, thereby the pavement cracking is delayed and the pavement service life is prolonged, when in use, the microcapsule core material is only required to be mixed with the asphalt, and when in preparation, the microcapsule core material is obtained by hydrogenating common bisphenol A epoxy resin under the conditions of high temperature and high pressure, and has few unsaturated bonds, has good ultraviolet aging resistance and simple preparation method.

Drawings

FIG. 1a is a scanning electron micrograph of an epoxy component microcapsule;

FIG. 1b is a scanning electron microscope image of curing agent component microcapsules;

FIG. 2 is a view of a specimen with a precut;

FIG. 3 is a schematic diagram of the self-repairing rate SH1 of microcapsule asphalt under different blending amounts.

Detailed Description

The invention is described in further detail below with reference to the accompanying drawings:

example one

The invention relates to a bi-component epoxy resin self-repairing microcapsule material for an asphalt pavement, which is characterized by comprising a shell and a microcapsule core material wrapped in the shell, wherein the microcapsule core material is composed of hydrogenated bisphenol A epoxy resin and pentaerythritol tetra-3-mercaptopropionate.

The mass ratio of the shell to the microcapsule core material is 1.2:1, and the mass ratio of the hydrogenated bisphenol A epoxy resin to the pentaerythritol tetra-3-mercaptopropionate is 2: 1.

The shell is made of melamine formaldehyde resin.

Example two

The mass ratio of the shell to the microcapsule core material is 1.5:1, and the mass ratio of the hydrogenated bisphenol A epoxy resin to the pentaerythritol tetra-3-mercaptopropionate is 2: 1.

The shell is made of melamine urea-formaldehyde resin.

EXAMPLE III

The mass ratio of the shell to the microcapsule core material is 1.3:1, and the mass ratio of the hydrogenated bisphenol A epoxy resin to the pentaerythritol tetra-3-mercaptopropionate is 2: 1.

The shell is made of melamine formaldehyde resin.

Example four

The mass ratio of the shell to the microcapsule core material is 1.4:1, and the mass ratio of the hydrogenated bisphenol A epoxy resin to the pentaerythritol tetra-3-mercaptopropionate is 2: 1.

The shell is made of melamine urea-formaldehyde resin.

EXAMPLE five

The mass ratio of the shell to the microcapsule core material is 1.4:1, and the mass ratio of the hydrogenated bisphenol A epoxy resin to the pentaerythritol tetra-3-mercaptopropionate is 2: 1.

EXAMPLE six

The mass ratio of the shell to the microcapsule core material is 1.25:1, and the mass ratio of the hydrogenated bisphenol A epoxy resin to the pentaerythritol tetra-3-mercaptopropionate is 2: 1.

The shell is made of melamine urea-formaldehyde resin.

EXAMPLE seven

The preparation method of the two-component epoxy resin self-repairing microcapsule material comprises the following steps:

1) mixing urea, formaldehyde and melamine, adding triethanolamine to adjust the pH value to 8, heating and stirring to obtain a mixture A;

2) mixing sodium dodecyl benzene sulfonate and distilled water, stirring to fully dissolve, and adjusting the pH value to be neutral to obtain a mixture B, wherein the concentration of the mixture B is 0.5%.

3) Respectively adding hydrogenated bisphenol A epoxy resin and pentaerythritol tetra-3-mercaptopropionate into the mixture B, and stirring and emulsifying to obtain O/W emulsion;

4) adding the mixture A into O/W emulsion according to the mass ratio of the shell to the microcapsule core material of 1.2:1, and uniformly stirring to obtain a mixture C;

5) and adjusting the pH value of the mixture C to 3 by using an acidic regulator, adding a catalyst, heating for curing, washing, filtering and drying to obtain the double-component epoxy resin self-repairing microcapsule material.

In the step 1), the molar ratio of the urea to the mixture of formaldehyde and melamine is 2.5; the heating temperature is 70 ℃, the stirring speed is 400r/min, and the stirring time is 1 h;

the stirring speed in the step 2) is 200r/min, and the stirring time is 10 minutes;

the stirring time in the step 3) is 1 h;

the stirring time in the step 4) is 30 min;

the temperature rise in the step 5) is 65 ℃, and the curing time is 2 h.

The acidity regulator is citric acid.

Example eight

The preparation method of the two-component epoxy resin self-repairing microcapsule material comprises the following steps:

1) mixing urea, formaldehyde and melamine, adding triethanolamine to adjust the pH value to 9, heating and stirring to obtain a mixture A;

3) Respectively adding hydrogenated bisphenol A epoxy resin and pentaerythritol tetra-3-mercaptopropionate into the mixture B, and stirring and emulsifying to obtain O/W emulsion;

4) adding the mixture A into O/W emulsion according to the mass ratio of the shell to the microcapsule core material of 1.5:1, and uniformly stirring to obtain a mixture C;

5) and adjusting the pH value of the mixture C to 5 by using an acidic regulator, adding a catalyst, heating for curing, washing, filtering and drying to obtain the double-component epoxy resin self-repairing microcapsule material.

In the step 1), the molar ratio of the urea to the mixture of formaldehyde and melamine is 2.5; the heating temperature is 70 ℃, the stirring speed is 400r/min, and the stirring time is 1 h;

the stirring speed in the step 2) is 200r/min, and the stirring time is 10 minutes;

the stirring time in the step 3) is 1 h;

the stirring time in the step 4) is 30 min;

the temperature rise in the step 5) is 65 ℃, and the curing time is 2 h.

The acidity regulator is hydrochloric acid.

Example nine

The preparation method of the two-component epoxy resin self-repairing microcapsule material comprises the following steps:

1) mixing urea, formaldehyde and melamine, adding triethanolamine to adjust the pH value to 8.5, heating and stirring to obtain a mixture A;

3) Respectively adding hydrogenated bisphenol A epoxy resin and pentaerythritol tetra-3-mercaptopropionate into the mixture B, and stirring and emulsifying to obtain O/W emulsion;

4) adding the mixture A into O/W emulsion according to the mass ratio of the shell to the microcapsule core material of 1.35:1, and uniformly stirring to obtain a mixture C;

5) and adjusting the pH value of the mixture C to 4 by using an acidic regulator, adding a catalyst, heating for curing, washing, filtering and drying to obtain the double-component epoxy resin self-repairing microcapsule material.

In the step 1), the molar ratio of the urea to the mixture of formaldehyde and melamine is 2.5; the heating temperature is 70 ℃, the stirring speed is 400r/min, and the stirring time is 1 h;

the stirring speed in the step 2) is 200r/min, and the stirring time is 10 minutes;

the stirring time in the step 3) is 1 h;

the stirring time in the step 4) is 30 min;

the temperature rise in the step 5) is 65 ℃, and the curing time is 2 h.

The acidity regulator is citric acid.

Example ten

The preparation method of the two-component epoxy resin self-repairing microcapsule material comprises the following steps:

1) mixing urea, formaldehyde and melamine, adding triethanolamine to adjust the pH value to 8.2, heating and stirring to obtain a mixture A;

3) Respectively adding hydrogenated bisphenol A epoxy resin and pentaerythritol tetra-3-mercaptopropionate into the mixture B, and stirring and emulsifying to obtain O/W emulsion;

4) adding the mixture A into O/W emulsion according to the mass ratio of the shell to the microcapsule core material of 1.2.5:1, and uniformly stirring to obtain a mixture C;

5) and adjusting the pH value of the mixture C to 3.5 by using an acidic regulator, adding a catalyst, heating for curing, washing, filtering and drying to obtain the double-component epoxy resin self-repairing microcapsule material.

In the step 1), the molar ratio of the urea to the mixture of formaldehyde and melamine is 2.5; the heating temperature is 70 ℃, the stirring speed is 400r/min, and the stirring time is 1 h;

the stirring speed in the step 2) is 200r/min, and the stirring time is 10 minutes;

the stirring time in the step 3) is 1 h;

the stirring time in the step 4) is 30 min;

the temperature rise in the step 5) is 65 ℃, and the curing time is 2 h.

The acidity regulator is hydrochloric acid.

EXAMPLE eleven

The preparation method of the two-component epoxy resin self-repairing microcapsule material comprises the following steps:

1) mixing urea, formaldehyde and melamine, adding triethanolamine to adjust the pH value to 8.7, heating and stirring to obtain a mixture A;

3) Respectively adding hydrogenated bisphenol A epoxy resin and pentaerythritol tetra-3-mercaptopropionate into the mixture B, and stirring and emulsifying to obtain O/W emulsion;

4) adding the mixture A into O/W emulsion according to the mass ratio of the shell to the microcapsule core material of 1.4:1, and uniformly stirring to obtain a mixture C;

5) and adjusting the pH value of the mixture C to 4.5 by using an acidic regulator, adding a catalyst, heating for curing, washing, filtering and drying to obtain the double-component epoxy resin self-repairing microcapsule material.

In the step 1), the molar ratio of the urea to the mixture of formaldehyde and melamine is 2.5; the heating temperature is 70 ℃, the stirring speed is 400r/min, and the stirring time is 1 h;

the stirring speed in the step 2) is 200r/min, and the stirring time is 10 minutes;

the stirring time in the step 3) is 1 h;

the stirring time in the step 4) is 30 min;

the temperature rise in the step 5) is 65 ℃, and the curing time is 2 h.

The acidity regulator is citric acid.

Example twelve

The preparation method of the two-component epoxy resin self-repairing microcapsule material comprises the following steps:

1) mixing urea, formaldehyde and melamine, adding triethanolamine to adjust the pH value to 8, heating and stirring to obtain a mixture A;

3) Respectively adding hydrogenated bisphenol A epoxy resin and pentaerythritol tetra-3-mercaptopropionate into the mixture B, and stirring and emulsifying to obtain O/W emulsion;

4) adding the mixture A into O/W emulsion according to the mass ratio of the shell to the microcapsule core material of 1.2:1, and uniformly stirring to obtain a mixture C;

In the step 1), the molar ratio of the urea to the mixture of formaldehyde and melamine is 2.5; the heating temperature is 70 ℃, the stirring speed is 400r/min, and the stirring time is 1 h;

the stirring speed in the step 2) is 200r/min, and the stirring time is 10 minutes;

the stirring time in the step 3) is 1 h;

the stirring time in the step 4) is 30 min;

the temperature rise in the step 5) is 65 ℃, and the curing time is 2 h.

The acidity regulator is hydrochloric acid.

EXAMPLE thirteen

The use method of the double-component epoxy resin self-repairing microcapsule material comprises the following steps:

Example fourteen

The use method of the double-component epoxy resin self-repairing microcapsule material comprises the following steps:

Example fifteen

The use method of the double-component epoxy resin self-repairing microcapsule material comprises the following steps:

Example sixteen

The use method of the double-component epoxy resin self-repairing microcapsule material comprises the following steps:

Example seventeen

1) Double-component epoxy resin self-repairing microcapsule

Firstly, preparing a prepolymer of melamine modified urea-formaldehyde resin (MUF), and secondly, emulsifying a core material; then, dropwise adding MUF prepolymer particles into the emulsion; dropwise adding an acid catalyst to adjust the pH value to 5, carrying out a curing reaction for 3 hours, washing and filtering the reaction solution for multiple times when the temperature is reduced to room temperature, and finally drying to obtain the microcapsule.

The technical requirements of the raw materials in the preparation process of the two-component epoxy resin self-repairing microcapsule are shown in table 1.

TABLE 1

Scanning electron micrographs of the prepared two-component epoxy resin self-repairing microcapsules are shown in fig. 1a and fig. 1b, and particle size grading is shown in table 2.

TABLE 2

In Table 2, D (0.5) represents a particle diameter in which the particle diameter distribution range is less than 50% by number of the total number, also referred to as an average particle diameter; d (0.1) represents a particle diameter in which the number of particles having a particle diameter distribution range smaller than this value accounts for 10% of the total number; d (0.9) represents particles having a particle size of less than this value representing 90% of the total number of particles; uniformity refers to the degree to which the particle size fraction of a population of particles deviates from a normal distribution. As can be seen from Table 2, the average particle size of the epoxy component microcapsules was 23.582 μm, and 90% or more of the particles had particle sizes of 87.440 μm or less; the average particle diameter of the curing agent component is 22.4 μm, and the particle diameters of more than 90% are below 63.2 μm. This is consistent with the results observed by scanning electron microscopy; the particle size grading diagram and the consistency result show that the particle size distribution of each sample is in a better normal distribution. This is consistent with the results of microscopic observation and scanning electron microscope observation. The average grain diameter is less than 50 μm, and the grain diameter meets the use requirement.

A performance verification test is carried out on the two-component epoxy resin self-repairing microcapsule, and the used asphalt is SK70# road petroleum asphalt.

2) Implementation effect of two-component epoxy resin self-repairing microcapsule

The aging test of SK70# road petroleum asphalt is carried out, and the aging asphalt is prepared by referring to a pressure aging container accelerated asphalt aging test (PAV) method described in T0630-2011 of road engineering asphalt and asphalt mixture test regulation (JTG E20-2011) of Ministry of transportation. The self-repairing performance of the asphalt sample is verified by a ductility test of the asphalt sample added with the microcapsule. The test is carried out on a force-measuring ductility instrument by using a ductility test piece with a notch. By bringing the interfaces on both sides of the cut into close contact, a clear, completely wetted, artificial crack interface is formed. Complete transient wetting can be considered when the two surfaces of the specimen cutout are in contact with each other. First, ductility test specimens were prepared according to the test protocol. And performing pre-slit processing on the prepared ductility test sample, and designing an artificial crack. The method comprises the following specific steps: two RMB are placed on two sides of the ductility test die, the central line of the sample is measured by a graduated scale, the blade is placed at the central line of the sample, and downward cutting is performed with force until the blade cuts the upper surface of the coin, as shown in figure 2. After heating and heat preservation are carried out for a certain time, a force measurement ductility test is carried out. Both sets of test specimens were subjected to a force ductility test at 5 ℃ at a tensile rate of 5cm/min (+ -5%) until the specimen fracture test was terminated. Asphalt has typical viscoelastic properties, which can achieve the same repairing effect both at low temperatures for long periods of time and at high temperatures for short periods of time. In order to examine the influence on the self-repairing effect after the microcapsules are added, the repairing temperature and time are respectively set to be 30 ℃ and 1 h. By adding the repair time and the given repair temperature in the test process, the tensile force of the microcapsule asphalt material and the mechanical property parameters after repair can be obtained so as to represent the self-repair capability of the microcapsule asphalt material.

And (3) measuring a ductility value corresponding to the peak tension through a force measurement ductility test, and calculating the tensile flexibility f according to the formula (1), wherein the tensile flexibility can well represent the deformation capacity of the asphalt. And (3) defining a formula (2) to calculate the low-temperature cracking self-repairing rate SH1 of the asphalt according to the relation of the tensile flexibility in the self-repairing test process.

Wherein f defines the compliance of each tensile specimen; p is the maximum tensile force in the stretching process, and d is the specimen ductility value corresponding to the maximum tensile force.

Wherein SH1 is the low-temperature cracking self-repairing rate of the microcapsule asphalt; f1 is the tensile flexibility of the test piece without cutting the seam; f2 is the tensile flexibility of the cutting seam without repair time; f3 is the tensile flexibility over time of repair after a slit tensile break.

The results of the experimental tests are plotted in figure 3.

Self-repairing rate SH of asphalt₁The self-repairing rate is maximized when the amount of the epoxy microcapsules is 4 percent. The more microcapsules added, the more microcapsules at the precut interface, and hence the more core repair agent that flows out. Under the action of molecular diffusion, the two components are fully cured in the repair time to bond the cuts around the capsule, so that the self-repair efficiency is gradually increased. Therefore, the self-repairing performance of the microcapsule system on low-temperature cracking of asphalt is remarkably improved.

Although the invention has been described in detail in this specification by way of general description and specific embodiments, it is apparent that modifications and improvements can be made thereto based on the invention. As will be apparent to those skilled in the art. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

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Double-component epoxy resin self-repairing microcapsule material for asphalt pavement, and preparation method and use method thereof

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