Asphalt regeneration agent and preparation method thereof

Abstract

The present invention relates to the technical field of asphalt regeneration, specifically to an asphalt regeneration agent and a preparation method thereof, which comprises, by weight, 60 to 80 parts of base oil, 2 to 6 parts of rosin-modified phenolic resin, 10 to 30 parts of silicone-modified epoxy resin, 5 to 10 parts of halloysite nanotubes, and 0.5 to 2 parts of plasticizer. The asphalt regeneration agent of the present invention can effectively restore four major indicators of asphalt and can effectively improve the comprehensive road performance of aged asphalt.

Description

Technical Field

[0001] The invention relates to the technical field of asphalt regeneration, and in particular to an asphalt regeneration agent and a preparation method thereof. Background Art

[0002] Asphalt pavement will gradually age under the influence of heat, oxygen and pressure after long-term use, and will suffer from cracks, looseness and other defects. In order to restore the pavement performance and maintain a certain road service level, maintenance and repair measures must be taken for the old asphalt pavement. In the reconstruction of old roads, asphalt recycling technology can effectively utilize waste pavement materials, reduce production costs, improve efficiency, and is also beneficial to environmental protection and emission reduction. It has obvious economic and social benefits and is increasingly widely used in engineering.

[0003] When regenerating asphalt, a certain proportion of asphalt regeneration agent is often added to restore the performance of aged asphalt. Although domestic and foreign scholars have conducted a lot of research and development work on asphalt regeneration agents, the existing asphalt regeneration technology generally has the problem of insufficient performance after regeneration. Summary of the invention

[0004] Purpose of the invention: In view of the above technical problems, the present invention proposes an asphalt regeneration agent and a preparation method thereof.

[0005] The technical solutions adopted are as follows:

[0006] An asphalt regeneration agent, comprising, by weight:

[0007] 60-80 parts of base oil, 2-6 parts of rosin-modified phenolic resin, 10-30 parts of silicone-modified epoxy resin, 5-10 parts of halloysite nanotubes, and 0.5-2 parts of plasticizer.

[0008] Furthermore, the base oil is any one or more combinations of 60N base oil, 100N base oil, 150N base oil, bright oil 150BS, and aromatic oil.

[0009] Furthermore, the preparation method of the rosin-modified phenolic resin is as follows:

[0010] After heating and melting phenol, formaldehyde is added, and the pH value of the reaction system is adjusted to 1-3 with acid solution. The temperature is raised to reflux, and the reaction is kept warm for 2-4 hours. The temperature is then raised to 120-135°C to evaporate water to obtain a prepolymer. Liquid rosin is added to the prepolymer, and the temperature is raised to 230-270°C, and the reaction is kept warm for 3-5 hours. Unreacted products are removed by vacuum distillation, and the softening point is controlled to be 90-98°C, which is the end point.

[0011] Furthermore, the acid solution is any one or more combinations of sulfuric acid, hydrochloric acid, phosphoric acid, and oxalic acid.

[0012] Furthermore, the preparation method of the organosilicon-modified epoxy resin is as follows:

[0013] Heat the bisphenol A epoxy resin to 70-80°C, add an organic tin catalyst, dimethoxysilane and a trace amount of water, stir evenly, heat to 90-100°C, stir and react for 6-8 hours, then return to room temperature.

[0014] Furthermore, the halloysite nanotubes are modified with long-chain silane.

[0015] Further, the modification method is as follows:

[0016] Add halloysite nanotubes into ethanol aqueous solution, disperse them evenly by ultrasonic oscillation, add long-chain silane, raise the temperature to reflux, continue stirring for 2 to 4 hours, return to room temperature, filter, wash and dry.

[0017] Furthermore, the long-chain silane is any one or more combinations of dodecyltrimethoxysilane, tridecyltrimethoxysilane, tetradecyltrimethoxysilane, pentadecyltrimethoxysilane and hexadecyltrimethoxysilane.

[0018] Furthermore, the plasticizer is dioctyl sebacate and / or trioctyl trimellitate.

[0019] The present invention also provides a method for preparing an asphalt regeneration agent:

[0020] Add halloysite nanotubes to base oil and stir evenly, perform ultrasonic dispersion and three-roll grinding, heat to 130-140°C, add rosin-modified phenolic resin, silicone-modified epoxy resin and plasticizer, shear at a rate of 1000-2000 r / min for 20-40 min, then shear at a rate of 4000-5000 r / min for 10-20 min, and return to room temperature.

[0021] Beneficial effects of the present invention:

[0022] The present invention provides an asphalt regeneration agent, wherein the polar epoxy groups of the epoxy resin can chemically react with asphaltene to weaken the strong attraction between asphaltene molecules, thereby causing the condensed asphaltene in the aged asphalt to be redissolved and dispersed in the asphalt colloid system, thereby destroying the spatial network structure formed by the agglomeration of asphaltene, weakening the barrier of the asphaltene spatial network structure to the penetration of the regeneration agent molecules, thereby improving and accelerating the penetration ability of the regeneration agent;

[0023] After modification with silicone, flexible Si-O-Si segments are introduced into the epoxy resin structure, thereby reducing the internal stress of the epoxy resin and lowering its viscosity, enabling more complete infiltration of asphaltene and accelerating regeneration;

[0024] Phenolic resin can be used as a curing agent for epoxy resin. The molecular flexibility of phenolic resin modified with rosin is improved, and it forms a cross-linked network with epoxy resin, which can penetrate well into aged asphalt and improve various properties of asphalt.

[0025] As a natural nanomaterial, halloysite nanotubes can improve the high-temperature performance and anti-aging performance of asphalt. After being modified with long-chain silane, the lipophilicity is improved. With its large specific surface area and good compatibility, it can reduce the surface energy of the macromolecular asphaltene molecules in the aged asphalt that were originally curled up due to aging aggregation, which is beneficial to the stretching of the macromolecular asphaltene. Together with the base oil and plasticizer, it can achieve the purpose of restoring the colloidal structure and various physical properties of the aged asphalt, and at the same time improve the anti-aging performance of the regeneration agent and the asphalt obtained after adding the regeneration agent.

[0026] The asphalt regeneration agent of the present invention can effectively restore the four major indicators of asphalt and can effectively improve the comprehensive road performance of aged asphalt. DETAILED DESCRIPTION

[0027] If the specific conditions are not specified in the examples, the experiments were carried out under conventional conditions or the conditions recommended by the manufacturer. If the manufacturer of the reagents or instruments is not specified, they are all conventional products that can be purchased commercially. The techniques not mentioned in the present invention are all referenced to the prior art. Unless otherwise specified, the following examples and comparative examples are parallel experiments, using the same processing steps and parameters.

[0028] Embodiment 1:

[0029] An asphalt regeneration agent, comprising, by weight:

[0030] 70 parts of 100N base oil, 3 parts of rosin-modified phenolic resin, 20 parts of silicone-modified epoxy resin, 8 parts of long-chain silane-modified halloysite nanotubes, and 1 part of trioctyl trimellitate.

[0031] Wherein, the preparation method of rosin modified phenolic resin is as follows:

[0032] In a 500mL round-bottom flask equipped with mechanical stirring, reflux condenser and temperature control, add 94.1g of phenol, heat to melt it, then add 79.6mL of 37% formaldehyde aqueous solution, adjust the pH of the reaction system to 2.2 with oxalic acid, heat to boiling reflux, keep the temperature for reaction for 3h, then heat to 130℃ to evaporate the water to obtain a prepolymer, add 48g of liquid rosin to the prepolymer, stir and heat to 260℃, keep the temperature for reaction for 5h, remove the unreacted products by vacuum distillation, and control the softening point to 98℃ as the end point.

[0033] The preparation method of silicone modified epoxy resin is as follows:

[0034] In a 500mL round-bottom flask equipped with a mechanical stirrer, a reflux condenser and a constant pressure dropping funnel, heat 100g of epoxy resin E-51 to 75°C, then add 0.5g of organotin catalyst, 9g of methylvinyldimethoxysilane and a trace amount of water. Stir evenly and heat to 95°C for 8h, then return to room temperature.

[0035] The preparation method of long-chain silane-modified halloysite nanotubes is as follows:

[0036] 100 g of halloysite nanotubes were added into 500 mL of ethanol aqueous solution (V 乙醇 :V 水 =19:1), ultrasonically oscillate for 30 min to make it evenly dispersed, add 10 g of dodecyltrimethoxysilane, heat to reflux, continue stirring for 2 h, return to room temperature and filter, wash with ethanol and water in turn, and dry at 80°C for 24 h.

[0037] Preparation method of the above asphalt regeneration agent:

[0038] The long-chain silane-modified halloysite nanotubes were added to 100N base oil and stirred evenly. After ultrasonic dispersion and three-roll grinding, the mixture was heated to 135°C. Rosin-modified phenolic resin, silicone-modified epoxy resin and trioctyl trimellitate were added. The mixture was sheared at a rate of 1800 r / min for 30 min and then at a rate of 5000 r / min for 15 min, and then returned to room temperature.

[0039] Embodiment 2:

[0040] An asphalt regeneration agent, comprising, by weight:

[0041] 80 parts of 100N base oil, 6 parts of rosin-modified phenolic resin, 30 parts of silicone-modified epoxy resin, 10 parts of long-chain silane-modified halloysite nanotubes, and 2 parts of trioctyl trimellitate.

[0042] The preparation methods of rosin-modified phenolic resin, silicone-modified epoxy resin and long-chain silane-modified halloysite nanotubes are the same as those in Example 1.

[0043] Preparation method of the above asphalt regeneration agent:

[0044] The long-chain silane-modified halloysite nanotubes were added to 100N base oil and stirred evenly. After ultrasonic dispersion and three-roll grinding, the mixture was heated to 140°C. Rosin-modified phenolic resin, silicone-modified epoxy resin and trioctyl trimellitate were added. The mixture was sheared at a rate of 2000 r / min for 40 min and then at a rate of 5000 r / min for 20 min, and then returned to room temperature.

[0045] Embodiment 3:

[0046] An asphalt regeneration agent, comprising, by weight:

[0047] 60 parts of 100N base oil, 2 parts of rosin-modified phenolic resin, 10 parts of silicone-modified epoxy resin, 5 parts of long-chain silane-modified halloysite nanotubes, and 0.5 parts of trioctyl trimellitate.

[0048] The preparation methods of rosin-modified phenolic resin, silicone-modified epoxy resin and long-chain silane-modified halloysite nanotubes are the same as those in Example 1.

[0049] Preparation method of the above asphalt regeneration agent:

[0050] The long-chain silane-modified halloysite nanotubes were added to 100N base oil and stirred evenly. After ultrasonic dispersion and three-roll grinding, the mixture was heated to 130°C. Rosin-modified phenolic resin, silicone-modified epoxy resin and trioctyl trimellitate were added. The mixture was sheared at a rate of 1000 r / min for 20 min and then at a rate of 4000 r / min for 10 min, and then returned to room temperature.

[0051] Embodiment 4:

[0052] An asphalt regeneration agent, comprising, by weight:

[0053] 80 parts of 100N base oil, 2 parts of rosin-modified phenolic resin, 30 parts of silicone-modified epoxy resin, 5 parts of long-chain silane-modified halloysite nanotubes, and 2 parts of trioctyl trimellitate.

[0054] The preparation methods of rosin-modified phenolic resin, silicone-modified epoxy resin and long-chain silane-modified halloysite nanotubes are the same as those in Example 1.

[0055] Preparation method of the above asphalt regeneration agent:

[0056] The long-chain silane-modified halloysite nanotubes were added to 100N base oil and stirred evenly. After ultrasonic dispersion and three-roll grinding, the mixture was heated to 130°C. Rosin-modified phenolic resin, silicone-modified epoxy resin and trioctyl trimellitate were added. The mixture was sheared at a rate of 2000 r / min for 20 min and then at a rate of 5000 r / min for 10 min, and then returned to room temperature.

[0057] Embodiment 5:

[0058] An asphalt regeneration agent, comprising, by weight:

[0059] 60 parts of 100N base oil, 6 parts of rosin-modified phenolic resin, 10 parts of silicone-modified epoxy resin, 10 parts of long-chain silane-modified halloysite nanotubes, and 0.5 parts of trioctyl trimellitate.

[0060] The preparation methods of rosin-modified phenolic resin, silicone-modified epoxy resin and long-chain silane-modified halloysite nanotubes are the same as those in Example 1.

[0061] Preparation method of the above asphalt regeneration agent:

[0062] The long-chain silane-modified halloysite nanotubes were added to 100N base oil and stirred evenly. After ultrasonic dispersion and three-roll grinding, the mixture was heated to 140°C. Rosin-modified phenolic resin, silicone-modified epoxy resin and trioctyl trimellitate were added. The mixture was sheared at a rate of 1000 r / min for 40 min and then at a rate of 4000 r / min for 20 min, and then returned to room temperature.

[0063] Comparative Example 1:

[0064] The method is substantially the same as Example 1, except that commercially available phenolic resin is used instead of the rosin-modified phenolic resin.

[0065] Comparative Example 2:

[0066] The method is basically the same as Example 1, except that epoxy resin E-51 is used instead of silicone-modified epoxy resin.

[0067] Comparative Example 3:

[0068] It is basically the same as Example 1, except that the halloysite nanotubes are not modified by long-chain silane.

[0069] Comparative Example 4:

[0070] The method is substantially the same as Example 1, except that the long-chain silane-modified halloysite nanotubes are not added.

[0071] Performance Test:

[0072] The recycled asphalt pavement material used in this test was taken from the upper layer of an asphalt pavement project in Hunan Province. The recycled asphalt was obtained according to the Test Procedure for Asphalt and Asphalt Mixtures in Highway Engineering (JTGE20) (hereinafter referred to as JTGE20) T0727;

[0073] The asphalt regeneration agent prepared in Examples 1 to 5 of the present invention and Comparative Examples 1 to 4 was added to the recovered asphalt at a dosage of 5%, and its penetration (25°C), softening point, ductility (5°C) and tensile strength were tested;

[0074] Among them, the needle penetration test method refers to T 0604-2011;

[0075] Softening point test method refers to T 0606-2011;

[0076] Ductility test method reference T 0605-2011;

[0077] The pull-out strength test method refers to AASHTO standard T 361-16 (15). The test results are shown in Table 1:

[0078] Table 1:

[0079]

[0080] It can be seen from Table 1 above that the asphalt regeneration agent of the present invention can effectively restore the four major indicators of asphalt and can effectively improve the comprehensive road performance of aged asphalt.

[0081] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that the technical solutions described in the aforementioned embodiments may still be modified, or some of the technical features may be replaced by equivalents. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. An asphalt regeneration agent, characterized in that: In parts by weight, it includes: 60-80 parts of base oil, 2-6 parts of rosin-modified phenolic resin, 10-30 parts of silicone-modified epoxy resin, 5-10 parts of halloysite nanotubes, and 0.5-2 parts of plasticizer; The preparation method of the rosin-modified phenolic resin is as follows: After heating and melting phenol, formaldehyde is added, and the pH of the reaction system is adjusted to 1-3 with acid solution, and the temperature is raised to reflux, and the temperature is kept for reaction for 2-4 hours, and then the temperature is raised to 120-135°C to evaporate the water to obtain a prepolymer, and liquid rosin is added to the prepolymer, and then the temperature is raised to 230-270°C, and the temperature is kept for reaction for 3-5 hours, and unreacted products are removed by reduced pressure distillation, and the softening point is controlled to be 90-98°C, which is the end point; The preparation method of the organosilicon-modified epoxy resin is as follows: Heat the bisphenol A epoxy resin to 70-80°C, add the organotin catalyst, methylvinyl dimethoxysilane and a small amount of water, stir evenly, heat to 90-100°C, stir and react for 6-8 hours, and return to room temperature; The halloysite nanotubes are modified by long-chain silane, and the modification method is as follows: Add the halloysite nanotubes to the ethanol aqueous solution, disperse them evenly by ultrasonic oscillation, add the long-chain silane, heat to reflux, continue stirring for 2 to 4 hours, return to room temperature, filter, wash and dry; The long-chain silane is any one or more combinations of dodecyltrimethoxysilane, tridecyltrimethoxysilane, tetradecyltrimethoxysilane, pentadecyltrimethoxysilane and hexadecyltrimethoxysilane.

2. The asphalt regeneration agent according to claim 1, characterized in that: The base oil is any one or more combinations of 60N base oil, 100N base oil, 150N base oil, bright oil 150BS, and aromatic oil.

3. The asphalt regeneration agent according to claim 1, characterized in that The acid solution is any one or more combinations of sulfuric acid, hydrochloric acid, phosphoric acid and oxalic acid.

4. The asphalt regeneration agent according to claim 1, characterized in that The plasticizer is dioctyl sebacate and / or trioctyl trimellitate.

5. A method for preparing an asphalt regeneration agent as claimed in any one of claims 1 to 4, characterized in that: Add halloysite nanotubes to base oil and stir evenly, perform ultrasonic dispersion and three-roll grinding, heat to 130-140°C, add rosin-modified phenolic resin, silicone-modified epoxy resin and plasticizer, shear at a rate of 1000-2000 r / min for 20-40 min, then shear at a rate of 4000-5000 r / min for 10-20 min, and return to room temperature.

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