A modified asphalt ductile agent and its preparation method, and modified asphalt.

Abstract

This invention relates to the field of asphalt additives technology, and particularly to a modified asphalt ductile agent and its preparation method, as well as modified asphalt. The modified asphalt ductile agent provided by this invention comprises the following components in weight percentages: 70%–94% vegetable oil; 1%–5% epoxidized fatty acid methyl ester; and 5%–25% fatty alcohol ether phosphate ester. The ductile agent provided by this invention exhibits synergistic effects among its components, improving the ductility index of asphalt before and after aging while also enhancing the thermal stability of asphalt. Furthermore, the components of the ductile agent prepared by this invention are inexpensive and readily available, and are environmentally friendly, non-toxic, and harmless, conforming to the concept of green and sustainable development of additives.

Description

Technical Field

[0001] This invention relates to the field of asphalt additives technology, and in particular to a modified asphalt ductile agent and its preparation method, as well as modified asphalt. Background Technology

[0002] The performance of asphalt directly determines the quality and service life of road surfaces. Ordinary asphalt is sensitive to temperature; it tends to flow at high temperatures and hardens and becomes brittle at low temperatures, leading to frequent problems such as cracks, ruts, loosening, and subsidence in asphalt pavements. Therefore, it is necessary to improve the performance and quality of asphalt to meet the current requirements of highways.

[0003] Modified asphalt is a type of asphalt whose properties are improved by adding modifiers. It can compensate for some of the defects in the base asphalt's properties, such as high-temperature performance, but its low-temperature performance often fails to meet standards. During production, a small amount of ductility enhancer needs to be added to improve ductility and slow down the aging process caused by oxidation during storage, thus reducing the rate of ductility degradation. However, existing ductility enhancers are not very effective in improving the ductility and thermal stability of modified asphalt after aging. Summary of the Invention

[0004] In view of this, the present invention provides a ductility modifier for modified asphalt, a method for preparing the same, and modified asphalt. The modified asphalt provided by the present invention can improve the ductility index of asphalt before and after aging, and also enhance the thermal stability of asphalt.

[0005] This invention provides a modified asphalt ductile agent, the raw materials of which comprise the following components by mass percentage:

[0006] Vegetable oil 70%–94%;

[0007] Epoxy fatty acid methyl esters 1%–5%;

[0008] Fatty alcohol ether phosphate 5%–25%.

[0009] Preferably, the vegetable oil is a vegetable oil whose main components include glycerides, fatty acids and oleic acid, and has a carbon number of 16 to 21.

[0010] Preferably, the vegetable oil is at least one selected from soybean oil, peanut oil, rapeseed oil, palm oil, flaxseed oil, sesame oil, and corn oil.

[0011] Preferably, the fatty alcohol ether phosphate is lauryl alcohol ether phosphate.

[0012] Preferably, the lauryl ether phosphate is lauryl ether phosphate MOA-3P.

[0013] Preferably, the amounts of each component are as follows:

[0014] Vegetable oil 82%–87%;

[0015] Epoxy fatty acid methyl esters 3%–5%;

[0016] Fatty alcohol ether phosphate 7%–18%.

[0017] The present invention also provides a method for preparing the modified asphalt ductile agent described in the above technical solution, comprising the following steps:

[0018] Vegetable oil, epoxy fatty acid methyl ester, and fatty alcohol ether phosphate ester are mixed and heated to obtain a elastomeric agent.

[0019] Preferably, the heating temperature is 80–110°C.

[0020] This invention also provides a modified asphalt, the raw materials for which include the following components:

[0021] Base asphalt;

[0022] The modifier is used at a concentration of 3.5% to 4.5% of the base asphalt.

[0023] The elastomeric agent is used at a concentration of 2.0% to 4.0% of the base asphalt.

[0024] A stabilizer, used at a concentration of 0.21% to 0.29% of the base asphalt;

[0025] The ductile agent is either the modified asphalt ductile agent described in the above technical solution or the ductile agent prepared by the preparation method described in the above technical solution.

[0026] Preferably, the modifier is an SBS modifier.

[0027] The ductile agent provided by this invention is prepared by combining vegetable oil, epoxy fatty acid methyl ester, and fatty alcohol ether phosphate in a certain proportion. The vegetable oil used can interact chemically with the polar groups such as hydroxyl and phenolic groups in the asphaltenes and gums of asphalt, thereby improving the anti-aging properties of asphalt and its compatibility with modifiers such as SBS, and improving the thermal storage stability of asphalt. At the same time, the introduction of epoxy fatty acid methyl ester can prolong the aging time of asphalt and improve the ductility index of asphalt after aging, and is environmentally friendly. The introduction of specific fatty alcohol ether phosphate can promote the compatibility of asphalt with modifiers such as SBS, reduce the surface tension of the two-phase interface, and enhance the stability of modified asphalt. The synergistic effect among the components of this ductile agent improves the ductility index of asphalt before and after aging while also enhancing the thermal stability of asphalt. In addition, the components of the ductile agent prepared by this invention are inexpensive and readily available, and are environmentally friendly, non-toxic, and harmless, which is in line with the concept of green and sustainable development of additives. Detailed Implementation

[0028] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.

[0029] In this article, the technical features described in an open-ended manner include both closed technical solutions composed of the listed features and open technical solutions that include the listed features.

[0030] In this document, numerical ranges are referred to as continuous unless otherwise specified, and include the minimum and maximum values ​​of the range, as well as every value between the minimum and maximum values. Furthermore, when a range refers to an integer, it includes every integer between the minimum and maximum values ​​of the range. Additionally, when multiple ranges are provided to describe a feature or characteristic, the ranges may be combined. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges to which they are incorporated.

[0031] In this article, when referring to units for data ranges, if the unit is only followed by the right endpoint, it means that the units for the left and right endpoints are the same. For example, 80~110℃ means that the units for the left endpoint "80" and the right endpoint "110" are both in ℃.

[0032] This document only specifically discloses some numerical ranges. However, any lower limit can be combined with any upper limit to form an unspecified range; and any lower limit can be combined with other lower limits to form an unspecified range, just as any upper limit can be combined with any other upper limit to form an unspecified range. Furthermore, each individually disclosed point or single value can itself serve as a lower or upper limit and be combined with any other point or single value or with other lower or upper limits to form an unspecified range.

[0033] This invention provides a modified asphalt ductile agent, the raw materials of which comprise the following components by mass percentage:

[0034] Vegetable oil 70%–94%;

[0035] Epoxy fatty acid methyl esters 1%–5%;

[0036] Fatty alcohol ether phosphate 5%–25%.

[0037] In this invention, the vegetable oil is preferably a vegetable oil whose main components include glycerides, fatty acids, and oleic acid, and whose carbon number is between 16 and 21; more preferably, it is at least one of soybean oil, peanut oil, rapeseed oil, palm oil, linseed oil, sesame oil, and corn oil. Compared with traditional heavy oil components, the above-mentioned vegetable oil can generate physicochemical interactions with polar groups such as hydroxyl and phenolic groups in asphalt and gums, thereby improving the anti-aging properties of asphalt and its compatibility with modifiers such as SBS, and improving the thermal storage stability of asphalt; at the same time, it is widely available and inexpensive, which can effectively solve the problems of environmental pollution and high costs caused by resource scarcity resulting from heavy oil components. This invention does not have special restrictions on the source of the vegetable oil, as long as it is a commercially available product. In this invention, the amount of vegetable oil used is 70% to 94%, specifically 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, and more preferably 82% to 87%.

[0038] In this invention, the epoxy fatty acid methyl ester differs from the dioctyl phthalate (DOP) and dioctyl adipate (DOA) plasticizers added to conventional ductile agents. It can extend the aging time of asphalt, improve the ductility index of aged asphalt, and is more environmentally friendly. This invention does not have special restrictions on the source of the epoxy fatty acid methyl ester; it can be a commercially available product. In this invention, the amount of epoxy fatty acid methyl ester used is 1% to 5%, specifically 1%, 2%, 3%, 4%, or 5%, more preferably 3% to 5%.

[0039] In this invention, the fatty alcohol ether phosphate is preferably lauryl alcohol ether phosphate, more preferably lauryl alcohol ether phosphate MOA-3P, which can be provided by Haian Petrochemical Co., Ltd. of Jiangsu Province. This invention introduces the above-mentioned fatty alcohol ether phosphate, whose molecular structure consists of the association of fatty alcohol chains with ethylene oxide (EO) or propylene oxide (PO) chains. It can act as a surfactant and stabilizing dispersant, promoting the compatibility of asphalt with modifiers such as SBS, reducing the surface tension at the interface between the two phases, and enhancing the stability of modified asphalt. In this invention, the amount of the fatty alcohol ether phosphate is 5% to 25%, specifically 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, preferably 7% to 18%.

[0040] In this invention, the total amount of the vegetable oil, epoxy fatty acid methyl ester and fatty alcohol ether phosphate is preferably 100%.

[0041] In this invention, the modified asphalt is asphalt modified with a modifier. Preferably, the modifier is SBS.

[0042] The present invention also provides a method for preparing the modified asphalt ductile agent described in the above technical solution, comprising the following steps: mixing vegetable oil, epoxy fatty acid methyl ester and fatty alcohol ether phosphate ester, heating to obtain the ductile agent.

[0043] The types and amounts of the vegetable oil, epoxy fatty acid methyl ester, and fatty alcohol ether phosphate ester are consistent with those described in the previous technical solution and will not be repeated here. There are no special restrictions on the mixing method; the above raw materials can be mixed evenly according to conventional mixing methods in the art. The preferred heating temperature is 80–110°C, specifically 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, and 110°C. In this invention, the heating process is preferably accompanied by stirring, i.e., stirring heating. There are no special restrictions on the heating time; it is sufficient to ensure that all components are completely and evenly mixed, generally 40–80 minutes, specifically 40 minutes, 45 minutes, 50 minutes, 55 minutes, 60 minutes, 65 minutes, 70 minutes, 75 minutes, and 80 minutes. After the above treatment, the elastomeric agent is obtained.

[0044] This invention also provides a modified asphalt, the raw materials for which include the following components:

[0045] Base asphalt;

[0046] The modifier is used at a concentration of 3.5% to 4.5% of the base asphalt.

[0047] The elastomeric agent is used at a concentration of 2.0% to 4.0% of the base asphalt.

[0048] A stabilizer, used at a concentration of 0.21% to 0.29% of the base asphalt;

[0049] The elastomeric agent is the elastomeric agent described in the above technical solution or the elastomeric agent prepared by the preparation method described in the above technical solution.

[0050] In this invention, there are no special restrictions on the type of base asphalt, and any conventional base asphalt in the art is acceptable, preferably 70# base asphalt.

[0051] In this invention, the modifier is preferably an SBS (styrene-butadiene-styrene block copolymer) modifier, and in some embodiments, it is SBS with model number YH-791H. In this invention, the amount of the modifier is preferably 3.5% to 4.5% of the mass of the base asphalt, specifically 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0%, 4.1%, 4.2%, 4.3%, 4.4%, and 4.5%.

[0052] In this invention, the elastomeric agent is the same as that described in the above technical solution, and will not be repeated here. In this invention, the preferred dosage of the elastomeric agent is 2.0% to 4.0% of the mass of the base asphalt, specifically 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, and 4.0%.

[0053] In this invention, the stabilizer is preferably Boyue stabilizer, model HMD, provided by Dongying Runfeng Boyue Petroleum Technology Co., Ltd. The preferred dosage of the stabilizer is 0.21% to 0.29% of the mass of the base asphalt, specifically 0.21%, 0.22%, 0.23%, 0.24%, 0.25%, 0.26%, 0.27%, 0.28%, and 0.29%.

[0054] The present invention also provides a method for preparing the modified asphalt described in the above technical solution, characterized in that it includes: mixing and heating a base asphalt and a modifier, then adding an elongating agent and a stabilizer, heating and stirring to obtain an asphalt material.

[0055] The types and amounts of the base asphalt, modifier, elastomeric agent, and stabilizer are consistent with those described in the preceding technical solution and will not be repeated here. The preferred temperature for heating the base asphalt and modifier mixture is 160–185°C, specifically 160°C, 165°C, 170°C, 175°C, 180°C, or 185°C, more preferably 175°C. The mixture can be heated and mixed in a heating jacket. Shearing is preferably performed during the heating process. The preferred heating time is 30–50 minutes, specifically 30 minutes, 35 minutes, 40 minutes, 45 minutes, or 50 minutes, more preferably 40 minutes. The preferred heating temperature after adding the elastomeric agent and stabilizer is 170–190°C, specifically 170°C, 175°C, 180°C, or 185°C, more preferably 185°C. The preferred heating and stirring time is 90–120 min, specifically 90 min, 95 min, 100 min, 105 min, 110 min, 115 min, or 120 min, and more preferably 100 min. After stirring and development, asphalt material is obtained.

[0056] The ductile agent provided by this invention is prepared by combining vegetable oil, epoxy fatty acid methyl ester, and fatty alcohol ether phosphate in a certain proportion. The vegetable oil used can interact chemically with the polar groups such as hydroxyl and phenolic groups in the asphaltenes and gums of asphalt, thereby improving the anti-aging properties of asphalt and its compatibility with modifiers such as SBS, and improving the thermal storage stability of asphalt. At the same time, the introduction of epoxy fatty acid methyl ester can prolong the aging time of asphalt and improve the ductility index of asphalt after aging, and is environmentally friendly. The introduction of specific fatty alcohol ether phosphate can promote the compatibility of asphalt with modifiers such as SBS, reduce the surface tension of the two-phase interface, and enhance the stability of modified asphalt. The synergistic effect among the components of this ductile agent improves the ductility index of asphalt before and after aging while also enhancing the thermal stability of asphalt. In addition, the components of the ductile agent prepared by this invention are inexpensive and readily available, and are environmentally friendly, non-toxic, and harmless, which is in line with the concept of green and sustainable development of additives.

[0057] To further understand the present invention, preferred embodiments of the present invention are described below in conjunction with examples. However, it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention, and not for limiting the scope of the claims of the present invention.

[0058] Unless otherwise stated, the raw materials and reagents used in the following examples are commercially available or can be prepared by known methods. Epoxy fatty acid methyl esters are from Tesco Chemicals. Lauryl ether phosphate MOA-3P is from Haian Petrochemical, Jiangsu Province.

[0059] Example 1

[0060] raw material:

[0061] Soybean oil 90%, epoxy fatty acid methyl ester 5%, lauryl ether phosphate MOA-3P 5%.

[0062] preparation:

[0063] Weigh the above raw materials according to the proportions, mix them evenly, and then stir and heat at 100℃ for 60 minutes to ensure that the components are completely mixed and homogeneous, thus obtaining the elastomeric agent.

[0064] Example 2

[0065] raw material:

[0066] Soybean oil 80%, epoxy fatty acid methyl ester 5%, lauryl ether phosphate MOA-3P 15%.

[0067] Preparation: Same as in Example 1.

[0068] Example 3

[0069] raw material:

[0070] 70% soybean oil, 5% epoxidized fatty acid methyl ester, 25% lauryl ether phosphate (MOA-3P).

[0071] Preparation: Same as in Example 1.

[0072] Example 4

[0073] raw material:

[0074] Soybean oil 82%, epoxy fatty acid methyl ester 1%, lauryl ether phosphate MOA-3P 17%.

[0075] Preparation: Same as in Example 1.

[0076] Example 5

[0077] raw material:

[0078] Soybean oil 30%, peanut oil 40%, epoxy fatty acid methyl ester 5%, lauryl ether phosphate MOA-3P 25%.

[0079] Preparation: Same as in Example 1.

[0080] Example 6

[0081] raw material:

[0082] Soybean oil 42%, palm oil 40%, epoxy fatty acid methyl ester 1%, lauryl ether phosphate MOA-3P 17%.

[0083] Preparation: Same as in Example 1.

[0084] Comparative Example 1

[0085] Traditional aromatic oil heavy component elastomeric agent originates from Shandong Furunda Chemical Co., Ltd., namely the modified asphalt elastomeric agent of Shandong Furunda Chemical Co., Ltd.

[0086] Effect test:

[0087] The effects of the ductile agents in Examples 1-6 and Comparative Example 1 on the performance of SBS modified asphalt were compared and tested, and the results are shown in Table 1. The specific preparation process of the modified asphalt is as follows: 550g of 70# base asphalt and 23.65g of modifier YH-791H SBS were mixed in a heating mantle at 175℃ and sheared for 40min. Then, 17.6g of ductile agent and 1.38g of Boyue stabilizer HMD were added, and the mixture was stirred at 185℃ for 100min to obtain the asphalt material.

[0088] Table 1: Performance Test Results of Asphalt Materials

[0089] Performance indicators Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Needle penetration (25℃, 100g, 5s): 0.1mm 65.3 64.9 64.7 65.0 64.6 65.2 67.1 Softening point, ℃ 78 78.5 78.1 77.4 79.2 78.8 77.5 Ductility at 5℃, cm 42.7 41.8 42.5 41.2 42.1 42.6 30.9 5°C ductility after TFOT, cm 21.8 21.4 22.6 22.1 21.5 21.3 15.3 Residual penetration ratio, 25°C, % 65.1 64.5 65.6 64.6 64.3 65.0 61.3

[0090] Note: The conditions for the TFOT aging test are as follows: For each example product, three parallel samples of 50±0.5g are weighed and placed in a thin-film oven at 163±1℃ for aging. The total time shall not exceed 5.25h. The average value of the three parallel samples is then taken as the test result of the product of that example (the same applies to Comparative Example 1). The residual penetration ratio refers to the ratio of the penetration index before and after heating. In the table above, it specifically refers to the ratio of the penetration index before and after the TFOT thermal aging test. This index is a quality indicator used to evaluate the durability and atmospheric stability of asphalt; the higher the value, the better the quality.

[0091] As shown in Table 1, the ductility of Comparative Example 1 is 30.9 cm, while the ductility of Examples 1-6 is above 41 cm. After TFOT heat aging, the ductility of Comparative Example 1 decreases to 15.3 cm, while the ductility of Examples 1-6 is above 21 cm. This demonstrates that the ductility enhancer of the present invention can effectively improve the ductility index of asphalt before and after aging. Furthermore, the residual penetration ratio of Comparative Example 1 is 61.3%, while the residual penetration ratio of Examples 1-6 reaches over 64%, a significant improvement compared to Comparative Example 1, proving that the ductility enhancer of the present invention can effectively improve the thermal stability of asphalt materials. Therefore, the ductility enhancer of the present invention improves the ductility index of asphalt before and after aging while also enhancing the thermal stability of asphalt.

[0092] This document uses specific examples to illustrate the principles and implementation methods of the present invention. The descriptions of these embodiments are merely to aid in understanding the method and core ideas of the present invention, including the best mode, and to enable any person skilled in the art to practice the present invention, including manufacturing and using any device or system, and implementing any combined method. It should be noted that those skilled in the art can make various improvements and modifications to the present invention without departing from its principles, and these improvements and modifications also fall within the scope of protection of the claims. The scope of protection of this patent is defined by the claims and may include other embodiments that can be conceived by those skilled in the art. If these other embodiments have structural elements similar to those expressed in the claims, or if they include equivalent structural elements that are not substantially different from those expressed in the claims, then these other embodiments should also be included within the scope of the claims.

Claims

1. A modified asphalt elastomeric agent, characterized in that, Its preparation raw materials include the following components by mass percentage: Vegetable oil 70%~94%; Epoxy fatty acid methyl esters 1%~5%; Fatty alcohol ether phosphate 5%~25%.

2. The modified asphalt elastomeric agent according to claim 1, characterized in that, The vegetable oil is a vegetable oil whose main components include glycerides, fatty acids and oleic acid, and whose carbon number is between 16 and 21.

3. The modified bitumen elastomeric agent according to claim 1 or 2, characterized in that, The vegetable oil is at least one of soybean oil, peanut oil, rapeseed oil, palm oil, flaxseed oil, sesame oil, and corn oil.

4. The modified asphalt elastomeric agent according to claim 1, characterized in that, The fatty alcohol ether phosphate is lauryl alcohol ether phosphate.

5. The modified bitumen elastomeric agent according to claim 4, characterized in that, The lauryl alcohol ether phosphate is lauryl alcohol ether phosphate MOA-3P.

6. The modified asphalt elastomeric agent according to claim 1, characterized in that, The dosage of each component is as follows: Vegetable oil 82%~87%; Epoxy fatty acid methyl esters 3%~5%; Fatty alcohol ether phosphate 7%~18%.

7. A method for preparing a modified asphalt ductile agent according to any one of claims 1 to 6, characterized in that, Includes the following steps: Vegetable oil, epoxy fatty acid methyl ester, and fatty alcohol ether phosphate ester are mixed and heated to obtain a elastomeric agent.

8. The preparation method according to claim 7, characterized in that, The heating temperature is 80~110℃.

9. A modified asphalt, characterized in that, Its preparation raw materials include the following components: Base asphalt; The modifier is used at a concentration of 3.5% to 4.5% of the base asphalt. The elastomeric agent is used at a concentration of 2.0% to 4.0% of the base asphalt. A stabilizer, used at a concentration of 0.21% to 0.29% of the base asphalt; Wherein, the ductile agent is the modified asphalt ductile agent according to any one of claims 1 to 6 or the ductile agent prepared by the preparation method according to any one of claims 7 to 8; The modifier is an SBS modifier.