High-elasticity crack-resistant crack filling adhesive and preparation method thereof

Abstract

The invention belongs to the technical field of polymer materials, and discloses a high-elasticity crack-resistant crack filling adhesive and a preparation method thereof, and the high-elasticity crack-resistant crack filling adhesive comprises the following raw materials: asphalt, a thermoplastic elastomer, a metallocene polyolefin elastomer, a plasticizer, lead peroxide, a silane coupling agent and a stabilizer. The preparation method comprises the following steps: heating the asphalt to 180-200 DEG C, then adding the thermoplastic elastomer, the metallocene polyolefin elastomer, the plasticizer, the stabilizer, the lead peroxide and the silane coupling agent, stirring, mixing and dispersing uniformly, continuously keeping the temperature, stirring and reacting, and cooling to room temperature, thereby obtaining the crack filling adhesive. The crack filling adhesive disclosed by the invention contains the metallocene polyolefin elastomer, the plasticizer and the lead peroxide, and the obtained crack filling adhesive has excellent aging resistance, low-temperature performance, adhesion and permeability by utilizing the synergistic interaction among the metallocene polyolefin elastomer, the plasticizer and the lead peroxide.

Description

Technical Field

[0001] The present invention belongs to the technical field of asphalt materials, and in particular relates to a highly elastic and crack-resistant crack filling adhesive and a preparation method thereof. Background Art

[0002] Asphalt pavement, the primary form of pavement structure for highways and urban roads, boasts mature construction technology, comfortable and safe driving, and easy maintenance and repair. It plays a vital role in people's daily lives and economic activities. However, due to the long-term impact of vehicle loads and natural environmental factors, roads inevitably develop various defects, among which cracks are the most common and harmful.

[0003] The appearance of road cracks can undermine the integrity and smoothness of the road surface. Rainwater, snow, and other substances can penetrate through the cracks into the road base, softening the base material and reducing its load-bearing capacity. This can lead to potholes, mud pumping, and other road defects, seriously shortening the road's service life. Furthermore, cracks can affect driving comfort and safety. Driving on cracked roads can cause bumps and vibrations, increasing tire wear and potentially causing accidents.

[0004] The common treatment methods for road cracks are grouting and taping. Commonly used grouting glue for asphalt pavement contains additives such as rubber powder and SBS. Although this type of grouting glue has certain effects, some problems may occur during use. For example, the grouting glue does not have good permeability, that is, the fluidity is poor after the grouting glue is heated to 180°C, which is reflected in the high rotational viscosity at 180°C. It cannot penetrate into the cracks in the pavement and accumulates on the surface of the cracks, resulting in insufficient grouting depth and failure to fill the cracks. The grouting glue has poor adhesion to the pavement. Dust or moisture on the pavement will cause poor adhesion between the grouting glue and the original pavement, and it is easy to be carried away by the wheels during vehicle movement. The grouting glue has poor aging resistance. Usually, the grouting glue can maintain a good condition within half a year after the pavement cracks are grouted. After half a year, the grouting glue ages and becomes brittle, and cracks appear in the grouting glue at the cracks. The grouting glue is easy to deform in summer and be crushed by wheels.

[0005] Based on this, the problem that the present invention needs to solve is: how to prepare a highly elastic and crack-resistant crack filling glue with excellent all-round performance such as aging resistance, low temperature performance, adhesion and permeability. Summary of the Invention

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

[0007] At the same time, the present invention also provides a preparation method of the crack filling glue.

[0008] To achieve the above object, the present invention provides the following technical solutions:

[0009] A highly elastic and crack-resistant crack filling adhesive, comprising 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 the present invention, metallocene polyolefin is an ethylene-octene copolymer made using a constrained geometry catalytic technology. It has a very narrow molecular weight distribution and short chain branching distribution, and thus has excellent physical properties (high elasticity, high strength and high elongation) and good low-temperature performance. At the same time, its molecular chain is saturated, and therefore also has excellent heat aging resistance and UV aging resistance. Adding metallocene polyolefin can significantly improve the aging resistance of asphalt. Lead peroxide is used as a cross-linking agent for metallocene polyolefin and needs to be used in combination with metallocene polyolefin. It can react specifically with metallocene polyolefin to convert metallocene olefin from a plasticizer to an elastomer, thereby improving metallocene polyolefin from aspects such as mechanical properties, rheological properties, and aging resistance, thereby further improving the performance of crack filling glue. Plasticizer can further improve the low-temperature performance of crack filling glue. The present invention is based on the synergistic effect of the three components of metallocene polyolefin elastomer, plasticizer, and lead peroxide, and achieves a qualitative improvement in the performance of crack filling glue.

[0012] Preferably, the thermoplastic elastomer is at least one of styrene-butadiene-styrene triblock copolymer (SBS) and styrene-ethylene-butylene-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-methacrylate propyltrimethoxysilane and γ-glycidoxypropyltrimethoxysilane.

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

[0016] In addition, the present 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°C, add the thermoplastic elastomer, metallocene polyolefin elastomer and plasticizer in sequence, and stir to melt;

[0018] Step 2: The melted polymer is mixed and dispersed evenly using a high-speed shearing machine, and then a stabilizer, lead peroxide and a silane coupling agent are added and stirred for reaction to prepare the crack filling adhesive.

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

[0020] Preferably, the shear rate of the high-speed shearing machine for uniform mixing and dispersion in step 2 is 4000-5000 r / min, and the shearing time is 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 present invention has the following beneficial effects:

[0023] In the present invention, the metallocene polyolefin is an ethylene-octene copolymer made using a constrained geometry catalytic technology. It has a very narrow molecular weight distribution and short chain branching distribution, and thus has excellent physical properties and good low-temperature performance. At the same time, its molecular chain is saturated, and therefore also has excellent heat aging resistance and UV aging resistance. Adding metallocene polyolefin can significantly improve the aging resistance of asphalt. Lead peroxide is used as a cross-linking agent for metallocene polyolefin and needs to be used in combination with metallocene polyolefin. It can react specifically with metallocene polyolefin to convert metallocene olefin from a plasticizer to an elastomer, thereby improving metallocene polyolefin from aspects such as mechanical properties, rheological properties, and aging resistance, thereby further improving the performance of crack filling glue. The plasticizer can further improve the low-temperature performance of the crack filling glue. The present invention is based on the synergistic effect of the three components of metallocene polyolefin elastomer, plasticizer, and lead peroxide, and effectively improves the performance of the crack filling glue. DETAILED DESCRIPTION

[0024] The following will clearly and completely describe the technical solutions of the present invention in conjunction with the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0025] Product Information:

[0026] Asphalt: Singapore ESSO70# base asphalt;

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

[0028] Metallocene polyolefin elastomer: POE8452 produced by Du Pont Dow Elastomers, USA;

[0029] Ethylene-propylene copolymer: EPDM J-4045 produced by PetroChina Jilin Petrochemical Company, with an ethylene content of 5.5%;

[0030] Ethylene-butene copolymer: POE 9061 produced by Kraton Corporation of the United States;

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

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

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

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

[0035] The following examples and comparative examples are prepared as follows:

[0036] Step 1: Heat the asphalt to 190°C, 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 rate of 800 r / min;

[0037] Step 2: After the polymer is melted, it is sheared for 30 minutes using a high-speed shearing machine at a shear rate of 4500 r / min, and then the temperature is raised to 195°C, and a sulfur stabilizer is slowly added; then the temperature is lowered to 180°C, and lead peroxide and a silane coupling agent are added in sequence, and stirred for 1 hour at a stirring rate of 900 r / min to produce the crack filling glue.

[0038] The formula table of each embodiment and comparative example is shown in Table 1;

[0039] Table 1 Crack filling glue formula (mass parts)

[0040]

[0041] Among them, the plasticizer of Example 4 is substance ①: ethylene-butene copolymer, the plasticizer of Example 5 is substance ②: ethylene-vinyl acetate copolymer, and the rest are ethylene-propylene copolymers; the silane coupling agent of Example 6 is substance ③: γ-glycidyloxypropyltrimethoxysilane, and the rest are γ-methacrylate propyltrimethoxysilane; Comparative Example 4 replaces lead peroxide with substance ④: diisopropylbenzene peroxide, and Comparative Example 5 replaces lead peroxide with substance ⑤: light magnesium oxide.

[0042] Example 7

[0043] The method is substantially the same as Example 1, except that the preparation steps are as follows:

[0044] Step 1: Heat the asphalt to 190°C, 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 rate of 600 r / min;

[0045] Step 2: After the polymer is melted, it is sheared for 45 minutes using a high-speed shearing machine at a shear rate of 4000 r / min, and then the temperature is raised to 200°C, and a sulfur stabilizer is slowly added; then the temperature is lowered to 180°C, and lead peroxide and a silane coupling agent are added in sequence, and stirred for 2 hours at a stirring rate of 800 r / min to produce the crack filling glue.

[0046] Example 8

[0047] The method is substantially the same as Example 1, except that the preparation steps are as follows:

[0048] Step 1: Heat the asphalt to 200°C, 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 rate of 1000 r / min;

[0049] Step 2: After the polymer is melted, it is sheared for 15 minutes using a high-speed shearing machine at a shear rate of 5000 r / min, and then a sulfur stabilizer is slowly added; after the temperature is lowered to 180°C, lead peroxide and a silane coupling agent are added in sequence, and stirred for 0.5 hours at a stirring rate of 1000 r / min to prepare the crack filling adhesive.

[0050] Performance testing

[0051] Refer to the specification "Test Procedures for Asphalt and Asphalt Mixtures in Highway Engineering" JTGE20-2011, among which:

[0052] 5℃ elongation: T 0605-2011;

[0053] Softening point: T 0606-2011;

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

[0055] 180℃ rotational viscosity: T0625-2011;

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

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

[0058] The pull-out test is conducted at 25°C according to the American standard AASHTO T361-16 (2020) BBS Test.

[0059] The test data of each embodiment and comparative example are shown in the following table;

[0060] Table 2 Crack filling glue test data

[0061]

[0062] Note: For dynamic viscosity test, the specification requires the upper limit of the test range to be 580,000. Results exceeding 580,000 can be calculated through experimental theory.

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

[0064]

[0065]

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

[0067] The crack filling adhesives prepared in Examples 1-8 all showed significant improvements in various performance indicators. Among them, Example 3 achieved the best performance indicators, with an elongation of 62.8 cm at 5°C, a softening point of 103.6°C, a dynamic viscosity of 1,525,800 Pa·s at 60°C, a rotational viscosity of 0.73 Pa·s at 180°C, a pull-out strength of 2.79 MPa, a 1-pass PAV long-term aging elastic recovery of 98.7%, and a 3-pass PAV long-term aging elastic recovery of 95.3%. This demonstrates that the technical solution of the present invention innovatively utilizes metallocene polyolefin, lead peroxide, and a plasticizer. These three components exhibit a synergistic effect, significantly optimizing the various properties of the crack filling adhesive. The data from Examples 4-8 demonstrate that, in the technical solution of the present invention, the optimal plasticizer is ethylene-propylene copolymer, and the optimal silane coupling agent is γ-methacrylate-based trimethoxysilane. Furthermore, within the process parameter range of the technical solution of the present invention, crack filling adhesives with excellent performance can be prepared.

[0068] Analysis of the data of Comparative Examples 1-5 shows that no plasticizer is added to the formula of Comparative Example 1, and the 5°C elongation decreases significantly to 31.6 cm. At the same time, the 180°C rotational viscosity increases to 3.62 Pa·s, indicating that the lack of plasticizer affects both the low-temperature and high-temperature properties of the crack filling glue, especially the low-temperature performance; the formula of Comparative Example 2 lacks metallocene polyolefin and lead peroxide, and the softening point, 60°C dynamic viscosity, 180°C rotational viscosity, 1 PAV long-term aging elastic recovery rate, and 3 PAV long-term aging elastic recovery rate are greatly reduced. The high-temperature stability, high-temperature fluidity, and elastic recovery rate of its crack filling glue are extremely poor; the formula of Comparative Example 3 lacks three components: metallocene polyolefin, lead peroxide, and plasticizer, and the various performances of its crack filling glue are further reduced. Comparative Examples 4 and 5, in which the lead peroxide crosslinker was replaced by dicumyl peroxide and light magnesium oxide crosslinkers, respectively, showed a decrease in the 5°C ductility of the crack filling adhesives. The elastic recovery rate decreased even more significantly. The elastic recovery rates of the PAV after long-term aging were 88.1% and 85.9%, respectively, about 10% lower than that of Example 3. The elastic recovery rates of the PAV after long-term aging were 79.4% and 72.3%, respectively, about 20% lower than that of Example 3.

[0069] In summary, the technical solution of the present invention innovatively adopts metallocene polyolefin, lead peroxide and plasticizer. These three components are indispensable and can have a synergistic effect, which can significantly optimize the various properties of the crack filling glue.

[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 embodied 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 illustrative and non-restrictive, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations that come within the meaning and range of equivalents of the claims be embraced therein.

Claims

1. A highly elastic and crack-resistant crack filling adhesive, characterized in that: The invention is 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 adhesive according to claim 1, characterized in that The thermoplastic elastomer is at least one of styrene-butadiene-styrene triblock copolymer and styrene-ethylene-butylene-styrene block copolymer.

3. The crack filling adhesive according to claim 1, characterized in that The plasticizer is at least one of ethylene-propylene copolymer, ethylene-butene copolymer and ethylene-vinyl acetate copolymer.

4. The crack filling adhesive according to claim 1, characterized in that The silane coupling agent is at least one of gamma-methacrylate propyltrimethoxysilane and gamma-glycidyloxypropyltrimethoxysilane.

5. The crack filling adhesive according to claim 1, characterized in that: The stabilizer is a sulfur stabilizer.

6. A method for preparing the crack filling adhesive according to claims 1 to 5, characterized in that: The following steps are involved: Step 1: Heat the asphalt to 180-200°C, add the thermoplastic elastomer, metallocene polyolefin elastomer and plasticizer in sequence, and stir to melt; Step 2: The melted polymer is mixed and dispersed evenly using a high-speed shearing machine, and then a stabilizer, lead peroxide and a silane coupling agent are added and stirred for reaction to prepare the crack filling adhesive.

7. The method for preparing the crack filling adhesive according to claim 6, characterized in that: The stirring rate of the stirring and melting in step 1 is 600-1000 r / min, and the stirring time is 15-60 min.

8. The method for preparing the crack filling adhesive according to claim 6, characterized in that: The shear rate of the high-speed shearing machine for uniform mixing and dispersion in step 2 is 4000-5000 r / min, and the shearing time is 15-60 min.

9. The method for preparing the crack filling adhesive according to claim 6, wherein: 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.

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