A highly elastic and crack-resistant crack filler and its preparation method

Abstract

The application belongs to the technical field of polymer materials, and discloses a high-elasticity and anti-cracking crack filling glue and a preparation method thereof. The high-elasticity and anti-cracking crack filling glue comprises the following raw materials: asphalt, thermoplastic elastomer, metallocene polyolefin elastomer, plasticizer, lead peroxide, silane coupling agent and stabilizer. The preparation method is as follows: the asphalt is heated to 180-200 DEG C, and then the thermoplastic elastomer, metallocene polyolefin elastomer, plasticizer, stabilizer, lead peroxide and silane coupling agent are added and uniformly mixed and dispersed by stirring; after the reaction is continuously carried out under the condition of heat preservation and stirring, the crack filling glue is obtained by cooling to room temperature. The crack filling glue of the application contains metallocene polyolefin elastomer, plasticizer and lead peroxide, and the synergistic effect among the three is utilized, so that the obtained crack filling glue has excellent aging resistance, low-temperature performance, adhesion and permeability.

Description

Technical Field

[0001] This invention belongs to the field of asphalt material technology, specifically relating to a highly elastic and crack-resistant crack filler and its preparation method. Background Technology

[0002] Asphalt pavement, as the main form of road surface structure for highways and urban roads, has advantages such as mature construction technology, comfortable and safe driving, and convenient maintenance and management, playing a vital role in people's daily lives and economic activities. However, roads are subjected to vehicle loads and the influence of natural environmental factors over a long period of time, inevitably leading to various defects, among which cracks are the most common and damaging.

[0003] The appearance of road cracks can damage the integrity and smoothness of the road surface. On the one hand, rainwater and snowmelt can seep into the road base layer through the cracks, softening the base material and reducing its load-bearing capacity. This can lead to potholes, mud pumping, and other road defects, severely affecting the service life of the road. On the other hand, cracks can also affect driving comfort and safety. When vehicles drive on cracked roads, they will experience bumps and jolting, increasing tire wear and potentially causing traffic accidents.

[0004] For road cracks, common treatment methods include crack filling and caulking. Commonly used asphalt pavement crack fillers often contain additives such as rubber powder and SBS. While these fillers have some effectiveness, they also present several problems during use. For example, their permeability is insufficient; when heated to 180℃, their fluidity decreases, resulting in a high rotational viscosity that prevents them from penetrating the cracks, causing them to accumulate on the surface and resulting in insufficient filling depth. Furthermore, the filler has poor adhesion to the road surface; dust or moisture can cause poor bonding, making it easily carried away by vehicle wheels. The filler also has poor aging resistance; typically, it maintains good condition for up to six months after crack filling, but after that, it ages and becomes brittle, developing cracks at the cracks. Finally, the filler is prone to deformation in summer and damage from vehicle traffic.

[0005] Based on this, the problem that this invention needs to solve is: how to prepare a highly elastic and crack-resistant crack filler with excellent overall performance in terms of aging resistance, low-temperature performance, adhesion, and permeability. Summary of the Invention

[0006] The purpose of this invention is to provide a highly elastic and crack-resistant crack filler adhesive, which contains a metallocene polyolefin elastomer, a plasticizer, and lead peroxide. By utilizing the synergistic effect among the three, the aging resistance, low-temperature performance, adhesion, and permeability of the obtained crack filler adhesive are effectively improved.

[0007] In addition, the present invention also provides a method for preparing the crack-filling adhesive.

[0008] To achieve the above objectives, the present invention provides the following technical solution:

[0009] A highly elastic and crack-resistant crack filler is composed of the following raw materials: asphalt, thermoplastic elastomer, metallocene polyolefin elastomer, plasticizer, lead peroxide, silane coupling agent, and stabilizer.

[0010] The mass ratio of the asphalt, thermoplastic elastomer, metallocene polyolefin elastomer, plasticizer, lead peroxide, silane coupling agent, and stabilizer is 100:2~6:6~10:4~8:0.1~0.5:0.5~2:0.1~0.5.

[0011] In this invention, the metallocene polyolefin is an ethylene-octene copolymer produced using a defined geometry catalytic technology. It has a narrow molecular weight distribution and short branched chain distribution, thus exhibiting excellent physical properties (high elasticity, high strength, and high elongation) and good low-temperature performance. Simultaneously, its molecular chain is saturated, thus also possessing excellent heat aging resistance and UV aging resistance. The addition of metallocene polyolefin significantly improves the aging resistance of asphalt. Lead peroxide, as a crosslinking agent for metallocene polyolefin, needs to be used in combination with it. It can undergo a specific reaction with metallocene polyolefin, converting the metallocene olefin from a plastic to an elastomer, improving the metallocene polyolefin in terms of mechanical properties, rheological properties, and aging resistance, thereby further enhancing the performance of the crack filler. The plasticizer further improves the low-temperature performance of the crack filler. This invention, based on the synergistic effect of the three components—metallocene polyolefin elastomer, plasticizer, and lead peroxide—achieves a qualitative improvement in the performance of the crack filler.

[0012] Preferably, the thermoplastic elastomer is at least one of styrene-butadiene-styrene triblock copolymer (SBS) and styrene-ethylene-butene-styrene block copolymer (SEBS).

[0013] Preferably, the plasticizer is at least one of ethylene-propylene copolymer, ethylene-butene copolymer, and ethylene-vinyl acetate copolymer.

[0014] Preferably, the silane coupling agent is at least one of γ-propyl methacrylate trimethoxysilane and γ-glycidoxypropyl trimethoxysilane.

[0015] Preferably, the stabilizer is a sulfur-based stabilizer.

[0016] Furthermore, this invention also discloses a method for preparing the crack-filling adhesive as described above, comprising the following steps:

[0017] Step 1: Heat the asphalt to 180℃~200℃, and add thermoplastic elastomer, metallocene polyolefin elastomer and plasticizer in sequence while stirring to melt;

[0018] Step 2: Mix and disperse the melted polymer evenly using a high-speed shearing machine, then add stabilizer, lead peroxide and silane coupling agent and stir to react, thus preparing the crack filling adhesive.

[0019] Preferably, the stirring rate for melting in step 1 is 600-1000 r / min, and the stirring time is 15-60 min.

[0020] Preferably, the high-speed shearing machine in step 2 achieves uniform mixing and dispersion at a shearing rate of 4000–5000 r / min and a shearing time of 15–60 min.

[0021] Preferably, the stirring rate of the stirring reaction in step 2 is 800-1000 r / min, and the stirring reaction time is 0.5-2 h.

[0022] Compared with the prior art, the beneficial effects of the present invention are:

[0023] In this invention, the metallocene polyolefin is an ethylene-octene copolymer produced using a defined geometry catalytic technology. It exhibits a narrow molecular weight distribution and short branched chain distribution, resulting in excellent physical properties and good low-temperature performance. Furthermore, its saturated molecular chains contribute to excellent heat aging resistance and UV aging resistance. The addition of the metallocene polyolefin significantly improves the aging resistance of asphalt. Lead peroxide, acting as a crosslinking agent for the metallocene polyolefin, needs to be used in conjunction with it. It undergoes a specific reaction with the metallocene polyolefin, converting it from a plastic to an elastomer, thereby improving its mechanical properties, rheological properties, and aging resistance, thus further enhancing the performance of the crack filler. The plasticizer further improves the low-temperature performance of the crack filler. This invention effectively enhances the performance of the crack filler based on the synergistic effect of the metallocene polyolefin elastomer, plasticizer, and lead peroxide. Detailed Implementation

[0024] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0025] Product Information:

[0026] Asphalt: Singapore ESSO 70# base asphalt;

[0027] Thermoplastic elastomer: Sinopec Baling Petrochemical, YH791-H;

[0028] Metallocene polyolefin elastomer: POE8452 manufactured by DuPont Dow Elastomers, Inc., USA;

[0029] Ethylene-propylene copolymer: J-4045 ethylene-propylene rubber produced by PetroChina Jilin Petrochemical Company, in which the ethylene content accounts for 5.5%;

[0030] Ethylene-butene copolymer: POE 9061 manufactured by Kraton Pharmaceuticals, Inc., USA;

[0031] Ethylene-vinyl acetate copolymer: EV560 manufactured by Mitsui Chemicals, Japan;

[0032] Lead peroxide: Lead dioxide (lead peroxide) produced by Shenyang Congke Chemical Co., Ltd.

[0033] Silane coupling agent: KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd., Japan;

[0034] Stabilizer: Sulfur powder produced by Linyi Houpu Chemical Co., Ltd.

[0035] The preparation methods for the following examples and comparative examples are shown below;

[0036] Step 1: Heat the asphalt to 190°C, then add the thermoplastic elastomer styrene-butadiene-styrene triblock copolymer (SBS), metallocene polyolefin elastomer, and plasticizer in sequence, and stir for 30 minutes at a stirring speed of 800 r / min.

[0037] Step 2: After the polymer melts, shear it for 30 minutes using a high-speed shearing machine at a shearing rate of 4500 r / min. Then, raise the temperature to 195℃ and slowly add sulfur-based stabilizers. After lowering the temperature to 180℃, add lead peroxide and silane coupling agent in sequence, and stir for 1 hour at a stirring rate of 900 r / min to prepare the crack filler.

[0038] The formulations of each embodiment and comparative example are shown in Table 1;

[0039] Table 1. Crack Filler Formulation (parts by weight)

[0040]

[0041] In Example 4, the plasticizer was substance ①: ethylene-butene copolymer; in Example 5, the plasticizer was substance ②: ethylene-vinyl acetate copolymer; and the rest were ethylene-propylene copolymers. In Example 6, the silane coupling agent was substance ③: γ-glycidoxypropyltrimethoxysilane; and the rest were γ-propyl methacrylate-based trimethoxysilane. In Comparative Example 4, lead peroxide was replaced with substance ④: dicumyl peroxide; and in Comparative Example 5, lead peroxide was replaced with substance ⑤: light magnesium oxide.

[0042] Example 7

[0043] Generally the same as Example 1, except that the preparation steps are as follows:

[0044] Step 1: Heat the asphalt to 190°C, then add the thermoplastic elastomer styrene-butadiene-styrene triblock copolymer (SBS), metallocene polyolefin elastomer, and plasticizer in sequence, and stir for 45 minutes at a stirring speed of 600 r / min.

[0045] Step 2: After the polymer melts, shear it for 45 minutes using a high-speed shearing machine at a shearing rate of 4000 r / min. Then, raise the temperature to 200℃ and slowly add sulfur-based stabilizers. After lowering the temperature to 180℃, add lead peroxide and silane coupling agent in sequence, and stir for 2 hours at a stirring rate of 800 r / min to prepare the crack filler.

[0046] Example 8

[0047] Generally the same as Example 1, except that the preparation steps are as follows:

[0048] Step 1: Heat the asphalt to 200℃, add the thermoplastic elastomer styrene-butadiene-styrene triblock copolymer (SBS), metallocene polyolefin elastomer, and plasticizer in sequence, and stir for 15 minutes at a stirring speed of 1000 r / min.

[0049] Step 2: After the polymer melts, shear it for 15 minutes using a high-speed shearing machine at a shearing rate of 5000 r / min, and then slowly add sulfur-based stabilizers; after the temperature is reduced to 180℃, add lead peroxide and silane coupling agent in sequence, stir for 0.5 hours at a stirring rate of 1000 r / min, and the crack filling adhesive can be prepared.

[0050] Performance testing

[0051] Referring to the standard "Test Procedures for Asphalt and Asphalt Mixtures in Highway Engineering" JTGE20-2011, where:

[0052] Ductility at 5℃: T 0605-2011;

[0053] Softening point: T 0606-2011;

[0054] Dynamic viscosity at 60℃: T 0620-2000;

[0055] Rotational viscosity at 180°C: T0625-2011;

[0056] PAV aging test method: T 0630-2011;

[0057] Elastic recovery at 25℃: T 0662-2000;

[0058] The pull-out test was conducted at 25°C in accordance with the American standard AASHTO T361-16(2020) BBS Test.

[0059] The detection data for each embodiment and comparative example are shown in the table below;

[0060] Table 2 Crack Filler Test Data

[0061]

[0062] Note: For dynamic viscosity testing, the standard requires an upper limit of 580,000. Results exceeding 580,000 can be calculated theoretically based on the experiment.

[0063] Table 3 Long-term aging data of PAV crack filler

[0064]

[0065]

[0066] Analysis of the data in Tables 2 and 3 shows that:

[0067] The crack filler adhesives prepared in Examples 1-8 all showed significant improvements in various performance indicators. Among them, Example 3 exhibited the best performance indicators, with a ductility of 62.8 cm at 5°C, a softening point of 103.6°C, a dynamic viscosity of 1525800 Pa·s at 60°C, a rotational viscosity of 0.73 Pa·s at 180°C, a pull-out strength of 2.79 MPa, an elastic recovery rate of 98.7% after one PAV long-term aging, and an elastic recovery rate of 95.3% after three PAV long-term aging. This indicates that the technical solution of this invention innovatively employs metallocene polyolefin, lead peroxide, and plasticizer. These three components have a synergistic effect, which can significantly optimize the various performance indicators of the crack filler adhesive. Data from Examples 4-8 shows that in the technical solution of this invention, the optimal choice for plasticizer is ethylene-propylene copolymer, and the optimal choice for silane coupling agent is γ-propyl methacrylate trimethoxysilane. Furthermore, within the process parameter range of this invention, crack filler adhesives with excellent performance can be prepared.

[0068] Analysis of the data from Comparative Examples 1-5 shows that, in Comparative Example 1, the formulation without plasticizer significantly reduced the ductility at 5℃ to 31.6 cm, while the rotational viscosity at 180℃ increased to 3.62 Pa·s. This indicates that the lack of plasticizer affects both the low-temperature and high-temperature properties of the crack filler, especially the low-temperature performance. Comparative Example 2, lacking metallocene polyolefin and lead peroxide, exhibited a significant decrease in softening point, dynamic viscosity at 60℃, rotational viscosity at 180℃, elastic recovery rate after one PAV long-term aging, and elastic recovery rate after three PAV long-term aging. Its crack filler showed extremely poor high-temperature stability, high-temperature flowability, and elastic recovery rate. Comparative Example 3, lacking metallocene polyolefin, lead peroxide, and plasticizer, further reduced the various properties of its crack filler. Comparative Examples 4 and 5 replaced lead peroxide crosslinking agents with dicumyl peroxide and light magnesium oxide crosslinking agents, respectively, resulting in a decrease in the 5°C ductility of the crack filler adhesive; however, the decrease in elastic recovery rate was even greater. The elastic recovery rates after one PAV long-term aging were 88.1% and 85.9%, respectively, which were about 10% lower than those in Example 3; the elastic recovery rates after three PAV long-term aging were 79.4% and 72.3%, respectively, which were about 20% lower than those in Example 3.

[0069] In summary, the technical solution of this invention innovatively employs metallocene polyolefin, lead peroxide, and plasticizer. These three components are indispensable to achieve a synergistic effect and significantly optimize the various properties of the crack filler.

[0070] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, it is intended that all variations falling within the meaning and scope of equivalents of the claims be included within the present invention.

Claims

1. A high-elasticity anti-cracking crack-filling adhesive, characterized by comprising: Composed of the following raw materials: asphalt, thermoplastic elastomer, metallocene polyolefin elastomer, plasticizer, lead peroxide, silane coupling agent and stabilizer; The mass ratio of the asphalt, thermoplastic elastomer, metallocene polyolefin elastomer, plasticizer, lead peroxide, silane coupling agent and stabilizer is 100:2~6:6~10:4~8:0.1~0.5:0.5~2:0.1~0.

5.

2. The crack-filling glue according to claim 1, wherein The thermoplastic elastomer is at least one of styrene-butadiene-styrene triblock copolymer and styrene-ethylene-butylene-styrene block copolymer.

3. The crack-filling glue as claimed in claim 1, wherein The plasticizer is at least one of ethylene-propylene copolymer, ethylene-butene copolymer and ethylene-vinyl acetate copolymer.

4. The crack-filling glue as claimed in claim 1, wherein The silane coupling agent is at least one of γ-methacrylate propyl trimethoxysilane and γ-glycidyl ether oxygen propyl trimethoxysilane.

5. The crack-filling glue as claimed in claim 1, wherein The stabilizer is sulfur-based stabilizer.

6. A method for preparing the crack-filling glue according to any one of claims 1 to 5, characterized in that, Comprising the following steps: Step 1: heat the asphalt to 180~200℃, and then add the thermoplastic elastomer, metallocene polyolefin elastomer and plasticizer in sequence and stir to melt; Step 2: mix and disperse the melted polymer uniformly by using a high-speed shearing machine, and then add the stabilizer, lead peroxide and silane coupling agent and stir to react, thereby obtaining the crack filling adhesive.

7. The method of claim 6, wherein the crack-filling adhesive is prepared by the steps of: The stirring rate of the stirring and melting in step 1 is 600~1000r / min, and the stirring time is 15~60min.

8. The method of claim 6, wherein the crack-filling adhesive is prepared by the steps of: The shearing rate of the high-speed shearing machine in step 2 is 4000~5000r / min, and the shearing time is 15~60min.

9. The method of claim 6, wherein the crack-filling adhesive is prepared by the steps of: The stirring rate of the stirring and melting in step 1 is 600~1000r / min, and the stirring time is 15~60min. The stirring rate of the stirring and melting in step 1 is 600~1000r / min, and the stirring time is 15~60min.

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