Road aged asphalt regenerant and preparation method thereof

Abstract

The invention discloses a road aged asphalt regenerant and a preparation method thereof, and relates to the technical field of high-molecular compound composition asphalt repair. The road aged asphalt regenerant is prepared from the following components in parts by mass: 30-50 parts of a petroleum softening agent, 10-25 parts of a vegetable oil derivative, 5-15 parts of a polymer modifier, 3-10 parts of a penetrant, 1-5 parts of an antioxidant, 2-8 parts of tackifying resin and 1-4 parts of a compatible stabilizer. According to the invention, through a multi-functional group synergistic mechanism (such as capturing free radicals by imino groups, absorbing ultraviolet rays by aromatic rings and chelating metal ions by carbonyl groups) of the specific antioxidant and in combination with a physical cross-linked network of the polymer modifier, high-efficiency resistance to composite aging is realized. Therefore, the continuous degradation of the asphalt colloid structure is inhibited, and the service life of the regenerated pavement is remarkably prolonged.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of polymer compound composition asphalt repair, in particular to a road aging asphalt regenerant and a preparation method thereof. BACKGROUND

[0002] The asphalt pavement is subjected to the combined action of ultraviolet radiation, oxygen thermal aging, moisture erosion and traffic load in the long-term service process, and is prone to irreversible aging phenomena such as component migration and molecular chain rupture, resulting in an increase in asphalt content and an imbalance in colloidal structure, which manifests as pavement hardening and embrittlement, a decrease in crack resistance and a loss of self-healing ability. The traditional regenerant mainly restores the ductility of asphalt by supplementing light oil components, but there are two technical bottlenecks: one is that the short-term effect is significant but the long-term weather resistance is insufficient, and the regenerated asphalt is prone to secondary aging under environmental stress, so it usually needs to be repaired repeatedly within 1-2 years, which greatly increases the maintenance cost; the other is that the component compatibility is poor, and the molecular polarity difference between the regenerant and the aging asphalt easily leads to phase separation, which aggravates the migration and loss of effective components under temperature cycling, and a stable colloidal system cannot be formed.

[0003] The current industry has an increasingly urgent demand for long-acting performance of the regenerant, especially in harsh climate regions such as high temperature, heavy rain and strong ultraviolet radiation, and heavy traffic sections. Although the existing technology attempts to improve durability by adding a polymer modifier or an antioxidant, it is still difficult to simultaneously solve key problems such as thermal oxygen stability, ultraviolet degradation resistance and water damage resistance due to the lack of systematic component synergistic design. For example: a single polymer modifier is prone to chain scission failure under the action of heat and oxygen; conventional antioxidants have a fast migration speed and are difficult to stay in the asphalt phase for a long time; and small molecule softening agents are easily volatile or exuded under the influence of temperature fluctuations. These defects make it difficult for the regenerated pavement to achieve a stable service period of more than 5 years, which restricts the large-scale application of the regeneration technology.

[0004] Therefore, it is urgent to develop a road aging asphalt regenerant with long-acting weather resistance, which needs to break through key technologies such as molecular polarity reconstruction, anti-migration retention and multi-mechanism aging inhibition, to achieve persistent regeneration of the asphalt colloidal structure through the synergistic effect of components, and meet the long-term service requirements in complex environments. SUMMARY

[0005] In view of the technical defects of the existing regenerant, such as poor weather resistance and easy migration and loss of effective components leading to secondary aging, the present application provides a road aging asphalt regenerant and a preparation method thereof. Through the synergistic effect of specific components (containing an antioxidant), the stability of the asphalt colloidal structure is reconstructed at the molecular level, achieving the following core objectives: resisting ultraviolet / oxygen thermal / water damage complex aging, extending the service life of the regenerated pavement to more than 5 years; inhibiting the exudation and loss of key components such as softening agents and antioxidants in temperature cycling; and simultaneously restoring the ductility, self-healing property and bonding strength of the aging asphalt.

[0006] To achieve the above object, the technical scheme adopted by the present application is as follows: a road aging asphalt regenerant is prepared from the following components by mass fraction: petroleum softener 30-50 parts, plant oil derivative 10-25 parts, polymer modifier 5-15 parts, penetrating agent 3-10 parts, antioxidant 1-5 parts, tackifying resin 2-8 parts, and compatible stabilizer 1-4 parts.

[0007] The antioxidant is a compound shown in formula 1:

[0008] Formula 1:

[0009] R1 in formula 1 is selected from trifluoromethyl or carbonyl;

[0010] R2 in formula 1 is selected from any one of hydrogen, methoxy, fluorine, and methyl.

[0011] Further, the petroleum softener is selected from aromatic oil or liquid paraffin.

[0012] Further, the plant oil derivative is selected from epoxy soybean oil.

[0013] Further, the polymer modifier is selected from styrene-isoprene block copolymer with a diblock content of 50.0±3.0.

[0014] Further, the penetrating agent is selected from fatty alcohol polyoxyethylene ether.

[0015] Further, it is any one of the compounds shown in the following structures:

[0016]

[0017]

[0018] Further, the tackifying resin is selected from C5 petroleum resin or glycerol abietate.

[0019] Further, the compatible stabilizer is selected from zinc octoate or zinc naphthenate.

[0020] A preparation method of a road aging asphalt regenerant, comprising the following steps:

[0021] S1. Heating petroleum softener, plant oil derivative, and antioxidant to 100-110℃, stirring and mixing for 20-40 minutes to obtain material A;

[0022] S2. Adding polymer modifier to the material A, heating to 120-140℃, stirring and dispersing for 1-2 hours until completely dispersed and uniform to obtain material B;

[0023] S3. The temperature of the material B is reduced to 90-100 DEG C, the penetrant, tackifying resin are added in turn, constant temperature stirring for 40-60 minutes, the compatible stabilizer is added, continue stirring for 30 minutes, after cooling to room temperature, a road aging asphalt regenerant is obtained.

[0024] Further, the stirring and dispersing speed in S2 is 800-1000 rpm.

[0025] The application of a road aging asphalt regenerant in the regeneration and repair of aging asphalt pavement.

[0026] Further, the road aging asphalt regenerant can be used as a non-metallic additive material.

[0027] The antioxidant of the application can effectively block the aging process of asphalt and improve the regeneration effect through a multi-functional synergistic mechanism. First, the imino group directly captures the free radicals generated by the oxidation of asphalt to form stable amino radicals, and catalyzes the decomposition of hydroperoxide to interrupt the free radical chain reaction to solve the problem of thermal oxidative aging. Secondly, the hydroxyl group is closely connected with the polar components (such as asphaltene, colloid) in asphalt through hydrogen bond anchoring, significantly inhibits the migration and loss of the antioxidant, and synergistically enhances the free radical quenching ability of the imino group, thereby improving the long-term weather resistance and overcoming the long-term weather resistance and component migration bottleneck of traditional regenerants. The aromatic ring can efficiently absorb ultraviolet rays in the 290-400 nm band through the conjugated structure, convert them into heat energy to inhibit the photo-oxidation reaction, and form aryloxy radicals by stabilizing the free radical energy through the conjugated system, thereby significantly improving the anti-ultraviolet aging performance. The carbonyl group can block the catalytic oxidation activity of metal ions introduced into the asphalt by water erosion through chelation, and can optimize the compatibility and dispersity of the antioxidant in the aging asphalt colloid system through polarity adjustment, thereby solving the problems of poor component compatibility and imbalance of colloid structure. In the preparation process, step (S1) co-heats the antioxidant with a petroleum-based softening agent and a plant oil derivative at 100-110 DEG C to pre-form a complex anchored in the oil phase: this design not only ensures the uniform dispersion of the antioxidant in the subsequent high-temperature polymer addition stage (S2, 120-140 DEG C), but also avoids thermal inactivation through hydrogen bond / polarity pre-assembly, so that the regenerant has the ability to "in-situ anti-aging" in the deep aging asphalt layer.

[0028] Based on the bottleneck of road aging asphalt regeneration technology, the multi-component synergistic system is creatively constructed: the petroleum softener supplements the light component to quickly restore the ductility, the plant oil derivative realizes the polarity reconstruction by the reaction of epoxy group with carboxyl / hydroxyl group of the aging asphalt, and the compatible stabilizer catalyzes the crosslinking reaction to promote the recombination of asphaltene-soft asphaltene into a stable colloidal structure, and completely inhibits the phase separation. In terms of long-acting, the polymer modifier provides the physical crosslinking network locking small molecule components through the styrene segment and the elastic deformation capacity through the isoprene segment; the antioxidant anchors the anti-leakage by means of the hydrogen bond of hydroxyl / imino, absorbs ultraviolet rays by the aromatic ring conjugated system, and blocks the catalytic oxidation by the metal ion chelation of carbonyl. The anti-aging synergy is realized by the penetration agent to reduce the surface tension to promote the penetration of micro-cracks, the tackifying resin to enhance the cohesive force, and the oxygen / water barrier of the polymer modifier and the free radical capture / hydrogen peroxide decomposition capacity of the antioxidant, so that a multi-level aging inhibition chain is formed. The synergistic effect of each component ensures the retention of the activity of each component, and finally realizes the in-situ anti-aging and long-term service of the regenerated asphalt system.

[0029] Compared with the prior art, the beneficial effects of the present application are:

[0030] 1. Significantly improve long-term weather resistance: the regenerant in the prior art is prone to secondary aging under the action of environmental stress (such as ultraviolet rays, oxygen heat, water loss), which leads to the shortening of the service life of the pavement. The present application realizes the efficient resistance to composite aging through the multi-functional group synergistic mechanism of the specific antioxidant (such as imino radical capture, aromatic ring ultraviolet absorption, metal ion chelation of carbonyl) and the physical crosslinking network of the polymer modifier. This not only inhibits the continuous deterioration of the asphalt colloidal structure, but also significantly prolongs the service life of the regenerated pavement.

[0031] 2. Effectively inhibit the migration and loss of components: the prior art is prone to the migration and loss of the regenerant components (such as softener, antioxidant) due to the difference in molecular polarity and temperature fluctuation, which aggravates the phase separation. The present application reconstructs the asphaltene-soft asphaltene colloidal structure through the catalytic crosslinking effect of the compatible stabilizer, and forms a stable molecular level locking by the hydroxyl anchoring effect of the antioxidant and the polarity matching of the plant oil derivative. This synergistic design reduces the migration of key components from the source, ensuring the durability and stability of the regeneration effect.

[0032] 3. Fully restore and maintain the core performance of asphalt: the prior art can short-term restore the ductility of asphalt, but it is difficult to simultaneously improve the self-healing and bonding strength, and it is prone to repeated failure due to aging. The present application realizes the simultaneous optimization of ductility, self-healing and bonding strength through the penetration agent to promote micro-crack repair, the tackifying resin to enhance cohesive force, and the polymer modifier to provide elastic deformation capacity. The final regenerated asphalt system can still maintain balanced performance in harsh environments, avoiding the need for secondary repair. BRIEF DESCRIPTION OF DRAWINGS

[0033] Figure 1NMR chart of the antioxidant 1 described in the present application. DETAILED DESCRIPTION

[0034] The technical solutions of the present application will be described clearly and completely below in combination with the drawings in the present application. Obviously, the described embodiments are only some of the embodiments of the present application, but not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the protection scope of the present application.

[0035] Preparation Example 1

[0036] Synthesis of the antioxidant 1:

[0037]

[0038] Under the continuous nitrogen flow, 15 g of the raw material 1, 14.22 g of the raw material 2, 1.18 g of methane sulfonic acid (2-dicyclohexylphosphino-2', 4', 6'-tri-isopropyl-1, 1'-biphenyl) (2'-amino-1, 1'-biphenyl-2-yl) palladium (II) and 19.71 g of K3PO4 were sequentially added into the reaction system, which were dissolved in 200 ml of toluene. Then it was stirred at 120℃ for 10 hours. The obtained reaction mixture was cooled at room temperature, and then three extraction processes were carried out using water to obtain the organic layer. The organic layer was dried using magnesium sulfate, concentrated and purified using silica gel column chromatography (using a mixed solution of petroleum ether and ethyl acetate as the eluent), and rotary dried to obtain 18.55 g of the synthesized intermediate 1, with the purity of 99.8% shown by HPLC.

[0039]

[0040] Under the continuous nitrogen flow, 18.55 g of the intermediate 1, 7.64 g of the pivalic anhydride and 250 ml of toluene were sequentially added into the reaction system, and after being stirred to be uniformly dispersed, 9.86 g of the raw material 3 was added, and the temperature was increased to 50℃ for reaction for 4 hours. Subsequently, the pH of the system was adjusted to neutral using 1 mol / L sodium bicarbonate solution, the organic phase was washed with saturated brine, dried with anhydrous sodium sulfate, the solvent was removed by rotary evaporation, and purified using silica gel column chromatography (using a mixed solution of petroleum ether and ethyl acetate as the eluent), and rotary dried to finally obtain 21.83 g of the synthesized antioxidant 1. The purity was 99.8% shown by HPLC detection.

[0041] Structure identification of the synthesized product:

[0042] Mass spectrum of the intermediate 1, using MS+H + The test was carried out, and the test data were as follows: 498;

[0043] Mass spectrometry of antioxidant 1 was performed using MS+H + The test was conducted, and the test data was 700.

[0044] Antioxidant 1 1 HNMR (deuterated chloroform, Figure 1 )δ8.83(s,2H),8.24(d,1H),8.13-8.02(m,1H),7.81-7.63(m,4H),7.42-7.18(m,4H),7.05(d,1H),6.73-6.63(m,2H),5.90 (s,1H),5.27(m,1H),4.25(m,1H),3.68-3.49(m,1H),2.93(d,1H),1.89-1.35(m,4H),1.31-1.17(m,6H),1.00-0.87(m,6H).

[0045] Preparation Examples 2-6

[0046] In Preparation Examples 2-6, antioxidants 2-6 were prepared according to the preparation method of Preparation Example 1, replacing raw material 1, and the rest remained the same as in Preparation Example 1. For details, please refer to Table 1.

[0047] Table 1.

[0048]

[0049]

[0050] Example 1

[0051] Preparation of a road aging asphalt recycling agent:

[0052] 1. Raw material components:

[0053] Petroleum-based softener: 40 parts, selected from aromatic oils, viscosity: 50-80 mm. 2 / s, purchased from: Shandong Zhuyou Lubrication Technology Co., Ltd.;

[0054] Vegetable oil derivatives: 18 parts, selected from: epoxidized soybean oil, epoxy value 5.5%, purchased from: Shandong Baolilai Plastic Additives Co., Ltd.;

[0055] Polymer modifier: 8 parts, selected from: styrene-isoprene block copolymer, diblock content is 50.0±3.0, purchased from: Zibo Luhua Hongjin New Material Group Co., Ltd.;

[0056] Penetrant: 6 parts, selected from: fatty alcohol polyoxyethylene ether, hydroxyl value 86±3mgKOH / g, purchased from: Shanghai Banggao Chemical Co., Ltd.;

[0057] Antioxidant: 3 parts, selected from: antioxidant 1 synthesized in preparation example 1;

[0058] Tackifying resin: 5 parts, selected from: C5 petroleum resin, softening point: 95-100℃, purchased from: Henan You Nai Di Chemical Co., Ltd.

[0059] Compatibility stabilizer: 3 parts, selected from: zinc octoate, purchased from: Jiangsu Pengxiang Biological Medicine Co., Ltd.

[0060] 2. Preparation method:

[0061] S1. Under a nitrogen atmosphere, add petroleum softener, vegetable oil derivative and antioxidant into the reaction kettle, heat to 105℃, constant temperature stirring at 400 rpm for 30 minutes, make the components pre-assembled into a complex, and obtain material A;

[0062] S2. Add polymer modifier to material A, heat to 130℃, stir and disperse at 600 rpm for 1.5 hours to complete uniformity, form a stable colloidal network, and obtain material B;

[0063] S3. Under a nitrogen atmosphere, cool material B to 100℃, add penetrant and tackifying resin in turn, constant temperature stirring for 50 minutes; then add compatibility stabilizer, continue stirring for 30 minutes, and cool to room temperature to obtain a homogeneous paste of a road aging asphalt regenerant.

[0064] Examples 2-6

[0065] A road aging asphalt regenerant was prepared according to the preparation method of Example 1, wherein the antioxidant was replaced by antioxidant 2-antioxidant 6 in turn, and the rest was the same as Example 1.

[0066] Comparative Example 1

[0067] A road aging asphalt regenerant was prepared according to the preparation method of Example 1, wherein the antioxidant was replaced by antioxidant 2-antioxidant 6 in turn, and the rest was the same as Example 1. (anti-aging agent 44PD), and the rest was the same as Example 1.

[0068] Comparative Example 2

[0069] A road aging asphalt regenerant was prepared according to the preparation method of Example 1, wherein the antioxidant was replaced by antioxidant 1010 (CAS: 6683-19-8), and the rest was the same as Example 1.

[0070] Comparative Example 3

[0071] A road aging asphalt regenerant was prepared according to the preparation method of Example 1, wherein the antioxidant was not added, and the rest was the same as Example 1.

[0072] Comparative Example 4

[0073] A road aging asphalt rejuvenator was prepared according to the preparation method of Example 1, except that the polymer modifier therein was not added, and the rest was kept the same as Example 1.

[0074] Comparative Example 5

[0075] A road aging asphalt rejuvenator was prepared according to the preparation method of Example 1, except that the penetrating agent therein was not added, and the rest was kept the same as Example 1.

[0076] Comparative Example 6

[0077] A road aging asphalt rejuvenator was prepared according to the preparation method of Example 1, except that the compatibility stabilizer therein was not added, and the rest was kept the same as Example 1.

[0078] Performance test:

[0079] 1. Sample preparation: The road aging asphalt rejuvenator provided by the present application was used to restore the performance of the asphalt after long-term aging. The road aging asphalt rejuvenators prepared in the examples and comparative examples were added to the aged asphalt at a mixing amount of 6%, mixed at 145℃, and stirred at a speed of 600 rpm for 15 min. Among them, the aged asphalt was 70# base asphalt aged in a rotary oven at 163℃ for 5h, and then heated in a pressure aging vessel at 100℃ and 2.1Mpa for 20h.

[0080] 2. The prepared samples were tested for penetration, ductility, softening point, and 135℃ viscosity according to the corresponding test methods in JTGE202011 "Highway Engineering Asphalt and Asphalt Mixture Test Procedures", respectively. The test results are shown in Table 2.

[0081] 3. The regenerated asphalt was simulated aged by thin film oven aging method, the aging temperature was 165℃, and the aging time was 20h; the performances of the simulated aged asphalt were tested, and the results are shown in Table 3.

[0082] Table 2.

[0083]

[0084] Table 3.

[0085]

[0086] The data in Table 2 reflect the effects of aging, rejuvenation treatment, and different formulations on asphalt performance. The aging process significantly reduces the flexibility and flowability of asphalt, as evidenced by the substantial decrease in penetration and ductility, while increasing the softening point and viscosity, which is consistent with the typical degradation characteristics of asphalt after long-term service. After rejuvenation treatment, the examples using the inventive formulation exhibit excellent recovery: the penetration and ductility quickly rise to near the levels of the original asphalt, indicating that the flexibility and ductility are effectively restored by the rejuvenator; the softening point also decreases significantly, tending toward the original state, while the viscosity drops substantially, improving the flow performance, which highlights the high efficiency of component synergy in reversing the effects of aging. In contrast, the comparative examples have poorer rejuvenation effects: the recovery of penetration and ductility is limited, the improvement in softening point and viscosity is small, suggesting the inadequacy of traditional formulations in long-term stability. Overall, the performance trends are consistent among the examples, indicating that different antioxidant variants can maintain stable recovery effects, while the performance fluctuations of the comparative examples highlight the advantages of the present invention in inhibiting secondary aging and improving durability.

[0087] The example group (using the inventive antioxidant) in Table 3 shows excellent long-term weather resistance: the penetration residual ratio remains high overall, indicating stable anti-aging ability; the softening point increase value is generally low, reflecting weak temperature sensitivity; the ductility residual ratio consistently maintains a high level, demonstrating that the deterioration of ductility is effectively inhibited. The comparative example group, on the other hand, shows a clear deterioration trend: the penetration residual ratio decreases significantly, suggesting accelerated secondary aging; the softening point increase value is generally high, indicating insufficient high-temperature stability; the ductility residual ratio drops sharply, pointing to severe deterioration of ductility. The differences between the two groups highlight the synergistic advantages of the components of the present invention in inhibiting performance degradation and improving service life.

[0088] Although embodiments of the present application have been shown and described, it is to be understood that various modifications, substitutions, replacements and changes can be made to these embodiments without departing from the principles and spirit of the present application, and the scope of the present application is defined by the appended claims and their equivalents.

Claims

1. A road aging asphalt rejuvenator characterized by, Prepared from components comprising the following parts by mass: petroleum softener 30-50 parts, vegetable oil derivative 10-25 parts, polymer modifier 5-15 parts, penetrating agent 3-10 parts, antioxidant 1-5 parts, tackifying resin 2-8 parts, compatible stabilizer 1-4 parts; The antioxidant is a compound shown in formula 1: Formula 1: R1 in formula 1 is selected from trifluoromethyl or carbonyl; R2 in formula 1 is selected from any one of hydrogen, methoxy, fluorine, methyl.

2. The road aging asphalt rejuvenator as claimed in claim 1, wherein, The petroleum softener is selected from aromatic oil or liquid paraffin; The vegetable oil derivative is selected from epoxy soybean oil.

3. The road aging asphalt rejuvenator as claimed in claim 1, wherein, The polymer modifier is selected from styrene-isoprene block copolymer, diblock content is 50.0±3.

0.

4. The road aging asphalt rejuvenator as claimed in claim 1, wherein, The penetrating agent is selected from fatty alcohol polyoxyethylene ether.

5. The road aging asphalt rejuvenator as claimed in claim 1, wherein, The antioxidant is any one of the compounds shown in the following structure:

6. The road aging asphalt rejuvenator as claimed in claim 1, wherein, The tackifying resin is selected from C5 petroleum resin or glycerol ester of rosin.

7. The road aging asphalt rejuvenator as claimed in claim 1, wherein, The compatible stabilizer is selected from zinc octoate or zinc naphthenate.

8. A method of preparing a road aging asphalt rejuvenator according to any one of claims 1-7, characterized in that, Comprising the following steps: S1. Heat the petroleum softener, vegetable oil derivative and antioxidant to 100-110℃, stir and mix for 20-40 minutes to obtain material A; S2. Add the polymer modifier to the material A, heat to 120-140℃, stir and disperse for 1-2 hours until completely dispersed and uniform to obtain material B; S3. Reduce the temperature of the material B to 90-100℃, add the penetrating agent, tackifying resin in sequence, constant temperature stirring for 40-60 minutes, add the compatible stabilizer, continue stirring for 30 minutes, cool to room temperature to obtain a road aging asphalt regenerant.

9. A method for preparing a road aging asphalt rejuvenator according to claim 8, characterized in that, The stirring speed in S2 is 800-1000 rpm.

10. The application of a road aging asphalt regenerant according to any one of claims 1-7 in the regeneration and repair of aging asphalt pavement.

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