A composite amine cured epoxy asphalt material, its preparation method and application

Abstract

The present application relates to a kind of composite amine cured epoxy asphalt material and its preparation method and application, including asphalt 40-60 parts, epoxy resin 13-16 parts, long carbon chain oil amine 8-10 parts, alicyclic amine 0.1-0.4 parts, amino-terminated butyronitrile rubber 1.2-1.5 parts and cashew phenol glycidyl ether 0.6-0.9 parts.Long carbon chain oil amine as main curing agent improves the compatibility of epoxy resin and asphalt by long carbon chain structure;Alicyclic amine as co-curing agent introduces aliphatic ring rigid node in curing network;Amino-terminated butyronitrile rubber as co-curing agent introduces butyronitrile rubber segment to improve material ductility;Cashew phenol glycidyl ether as reactive dilution compatibilizing component, through epoxy group participates in curing reaction and improves the compatibility with asphalt by cashew phenol long chain.Compared with prior art, the present application realizes the synchronous improvement of tensile strength and elongation at break of epoxy asphalt material by the synergistic effect of ternary composite curing system and reactive compatibilizing component.

Description

Technical Field

[0001] This invention relates to the field of epoxy asphalt materials technology, and in particular to a composite amine-cured epoxy asphalt material, its preparation method, and its application. Background Technology

[0002] Epoxy asphalt is composed of asphalt, epoxy resin and curing agent. After curing, it can form a three-dimensional cross-linked network, which has good high temperature stability, deformation resistance and durability. It can be used in engineering scenarios such as steel bridge deck paving, heavy-duty roads and airport pavement.

[0003] In existing oleylamine-cured epoxy asphalt systems, oleylamine molecules contain long carbon chain structures, exhibiting good compatibility with asphalt and significantly improving the flexibility and elongation at break of epoxy asphalt. However, the high proportion of flexible segments and insufficient rigid nodes in single oleylamine-cured systems result in low crosslinking density of the epoxy curing network, making it easy for the material to have insufficient tensile strength and thus difficult to simultaneously meet the requirements of high ductility and high strength.

[0004] Existing technologies include schemes that use long-chain amines compounded with a small amount of cyclic amine compounds and introduce coupling agents or rubber additives to improve the flexibility of epoxy asphalt. However, these schemes typically use cyclic amines as modifiers for long-chain curing agents, mainly emphasizing improvements in curing reactivity, viscosity, and low-temperature performance; the rubber component usually exists as an additive toughening phase, with limited integration into the epoxy curing network. For epoxy asphalt systems with oleylamine as the main curing agent, it is still necessary to construct new composite curing networks from the perspectives of active hydrogen equivalent substitution, synergistic effects between rigid and flexible segments, and reactive compatibilization and viscosity reduction.

[0005] In the prior art, there are existing research and patent reports on epoxy-modified asphalt materials. For example, Chinese invention patent application CN106977966A discloses a cold-mix, cold-lay epoxy-modified asphalt material and its preparation method. This material is formulated with epoxy resin, asphalt, toughening agent, active compatibilizer, flexible curing agent, and alicyclic amine curing agent to improve the cold-mix workability, crack resistance, and road performance of steel bridge deck pavement maintenance and repair materials. The focus of this technical solution is on the cold-mix, cold-lay construction system and the compatibilization and softening modification approach. Although it lists amine curing agents such as isophorone diamine, the above technical solution does not use long-chain aliphatic amines as the main curing agent, nor does it construct a composite amine curing network around the compatibility between long-chain aliphatic amines and the asphalt phase. Furthermore, it does not quantitatively design the synergistic curing relationship between long-chain aliphatic amines, terminal aminobutadiene nitrile rubber, and the rigid nodes of alicyclic amines. For high-ductility epoxy asphalt materials, while a single long-chain aliphatic amine curing system is beneficial for improving asphalt compatibility and elongation at break, the cured network strength is insufficient. Terminally aminobutadiene nitrile rubber can introduce flexible rubber segments and improve energy dissipation, but excessive use can reduce the effective crosslinking density. Cycloalicylic amine curing agents can improve network stiffness and tensile strength, but direct, excessive addition may lead to embrittlement and decreased compatibility. Therefore, how to simultaneously improve the strength and network stability of epoxy asphalt while maintaining high ductility remains a problem that existing technologies need to address. Therefore, there is an urgent need to develop a high-ductility epoxy asphalt material that uses long-chain oleylamines to ensure asphalt compatibility, alicyclic amines to increase crosslinking density, ATBN to provide reactive elastic segments, and cashew phenol glycidyl ether (CGE) to improve compatibility and workability. Summary of the Invention

[0006] The purpose of this invention is to overcome the defects of the prior art by providing a composite amine-cured epoxy asphalt material, its preparation method, and its application, so as to solve the problems of insufficient strength of single oil-amine cured epoxy asphalt, easy reduction of strength by simple flexible modification, and insufficient compatibility and ductility of ordinary small molecule amine modified systems.

[0007] The objective of this invention can be achieved through the following technical solutions: The first aspect of this invention provides a composite amine-cured epoxy asphalt material, comprising the following components: 40-60 parts by weight of asphalt; 13-16 parts by weight of epoxy resin; 8-10 parts by weight of long-chain oleylamine, wherein the long-chain oleylamine is used as the main curing agent, and its long-chain structure is used to improve the compatibility between epoxy resin and asphalt. 0.1 to 0.4 parts by weight of alicyclic amine, wherein the alicyclic amine is used as a co-curing agent to introduce alicyclic rigid nodes in the curing network formed by epoxy resin and the long-chain oleylamine; 1.2 to 1.5 parts by weight of amino-terminated nitrile rubber, wherein the amino-terminated nitrile rubber is used as a co-curing agent to introduce nitrile rubber segments into the curing network to improve the ductility of the material; The reactive diluent compatibilizer is 0.6 to 0.9 parts by weight. The reactive diluent compatibilizer is cashew phenol glycidyl ether. The cashew phenol glycidyl ether participates in the curing reaction through its epoxy group and improves the compatibility with asphalt through its long cashew phenol chain.

[0008] Furthermore, the alicyclic amine is isophorone diamine or modified isophorone diamine.

[0009] Furthermore, the amino-terminated nitrile rubber is an amino-terminated liquid nitrile rubber.

[0010] Furthermore, the asphalt is one or more of the following: base asphalt, SBS modified asphalt, rubber modified asphalt, and high viscosity modified asphalt.

[0011] Furthermore, based on the active hydrogen equivalent provided by the long-chain oleylamine, the active hydrogen equivalent provided by the alicyclic amine replaces 3% to 10% of the active hydrogen equivalent of the long-chain oleylamine.

[0012] Furthermore, based on the active hydrogen equivalent provided by the long-chain oleylamine, the active hydrogen equivalent provided by the terminal amino-butadiene nitrile rubber replaces 2% to 8% of the active hydrogen equivalent of the long-chain oleylamine.

[0013] Furthermore, the mass of the reactive diluent compatibilizer is 3% to 20% of the mass of the epoxy resin.

[0014] Furthermore, the cashew phenol glycidyl ether, as a reactive dilution and compatibilizing component, is preferably 5% to 15%.

[0015] Furthermore, the long-chain oleylamine, alicyclic amine, and amino-terminated butadiene nitrile rubber together form a composite curing agent system, and the sum of the active hydrogen equivalents provided by the composite curing agent system matches the sum of the epoxy equivalents provided by the epoxy resin and the reactive diluent compatibilizer.

[0016] A second aspect of the present invention provides a method for preparing a composite amine-cured epoxy asphalt material as described above, comprising the following steps: Asphalt is heated to 130℃~170℃ to obtain asphalt in a fluid state; The epoxy resin is mixed with a reactive diluent compatibilizer to obtain an epoxy resin system; The epoxy resin system is added to flowing asphalt and sheared and mixed at 1000-5000 r / min for 5-60 minutes at 140℃-170℃ to obtain an epoxy resin-asphalt composite system. A composite curing agent system is obtained by mixing long-chain oleylamine, alicyclic amine, and amino-terminated butadiene nitrile rubber. The composite curing agent system is added to the epoxy resin-asphalt composite system, mixed evenly, and then cured to obtain the epoxy asphalt material.

[0017] Furthermore, the mixing temperature after adding the composite curing agent system is 120℃~160℃, and the stirring time is 3~15 minutes; The curing process includes pre-curing at 150°C for 3 hours and then curing at 60°C for 4 days.

[0018] The third aspect of this invention provides the application of the composite amine-cured epoxy asphalt material as described above in steel bridge deck paving materials, heavy-duty traffic road paving materials, airport pavement paving materials, fatigue-resistant asphalt mixtures, high-ductility asphalt binders, and high-elasticity recovery asphalt binders.

[0019] Compared with the prior art, the present invention has the following beneficial effects: This invention overcomes the technical bottlenecks of insufficient strength in single oleylamine curing systems and the inability of existing physical blending modifications to simultaneously achieve strength and ductility. It creatively constructs a ternary composite curing system with long-chain oleylamine as the main curing agent, alicyclic amine as the rigid co-curing agent, and amino-terminated nitrile butadiene rubber (ATBN) as the flexible co-curing agent. The long-chain oleylamine, through its long-chain structure, ensures excellent compatibility and basic flexibility between the epoxy resin and the asphalt phase. The alicyclic amine participates in curing according to the principle of active hydrogen equivalent substitution, precisely introducing alicyclic rigid nodes into the crosslinking network, significantly improving the network crosslinking density and tensile strength. ATBN also participates in the curing reaction through active hydrogen substitution, embedding the energy-consuming segments of reactive nitrile butadiene rubber into the curing network through chemical bonds, greatly improving the material's elongation at break and elastic recovery. The synergistic effect of these three components ensures that the final epoxy asphalt material has a tensile strength of no less than 2.0 MPa at 23°C, while maintaining an elongation at break of over 300%, achieving simultaneous optimization of strength and high ductility.

[0020] This invention utilizes cashew phenol glycidyl ether (CGE) as a reactive diluent and compatibilizer. The long-chain structure of cashew phenol in the CGE molecule is naturally compatible with asphalt components, further enhancing the uniform dispersion and interfacial bonding of the epoxy resin system in the asphalt phase. Its epoxy groups directly participate in the amine-epoxy curing reaction, becoming part of the cross-linked network after curing. This fundamentally avoids the material performance degradation and environmental health risks caused by the migration and volatilization of traditional inert diluents (such as phthalates) during use. Simultaneously, the low viscosity of CGE effectively reduces the initial operating viscosity of the epoxy resin system, significantly improving the workability of the mixture and extending the workable time window. This provides crucial support for the widespread application of epoxy asphalt materials in large-area, long-process construction scenarios such as long-span steel bridge deck paving. Attached Figure Description

[0021] Figure 1 This is a flowchart illustrating the preparation method of the composite amine-cured epoxy asphalt material in this embodiment of the invention. Detailed Implementation

[0022] Explanation of English abbreviations: CA-HEA: refers to the high-ductility epoxy asphalt material cured with composite amine in this invention.

[0023] IPDA: refers to isophorone diamine, which is used as an alicyclic co-curing agent to introduce rigid nodes in a cured network.

[0024] ATBN: Aminonitrile finger rubber, used as a reactive flexible co-curing agent in epoxy curing reactions to introduce energy-consuming rubber segments.

[0025] CGE: refers to cashew phenol glycidyl ether, which participates in curing as a reactive diluent and compatibilizer and improves the compatibility between epoxy resin and asphalt.

[0026] E51: refers to liquid bisphenol A type epoxy resin, used as a matrix component of epoxy resin.

[0027] SBS: refers to styrene-butadiene-styrene block copolymer, used as an asphalt modifier or asphalt base material for epoxy asphalt materials.

[0028] LNBR: refers to liquid nitrile rubber, which is a non-reactive rubber used in comparative examples to verify the role of reactive terminal amino groups.

[0029] This invention proposes an oleylamine-terminated aminobutyronitrile rubber-isophorone diamine or modified alicyclic amine composite curing system. Oleylamine provides a long-chain compatible flexible structure, aminobutyronitrile rubber introduces energy-consuming rubber segments, and isophorone diamine or modified alicyclic amine serves as a rigid reinforcing node. Simultaneously, the substitution ratio of aminobutyronitrile rubber and isophorone diamine or modified alicyclic amine is controlled according to the active hydrogen equivalent, thereby achieving synergistic regulation of epoxy asphalt strength, ductility, and compatibility.

[0030] The present invention adopts the following technical solution: a composite amine-cured high-ductility epoxy asphalt material, comprising asphalt, E51 epoxy resin, long-chain oleylamine, alicyclic amine, amino-terminated butadiene nitrile rubber (ATBN), and cashew phenol glycidyl ether (CGE).

[0031] The oleylamine, as the primary curing agent, uses its long carbon chain structure to improve the compatibility between the epoxy resin system and the asphalt phase. The alicyclic amine, as an alicyclic co-curing agent, replaces 3%–10% of the active hydrogen in oleylamine with an equivalent of active hydrogen, introducing alicyclic rigid nodes into the curing network to improve crosslinking density and tensile strength. The ATBN, as a reactive flexible co-curing agent, replaces 2%–8% of the active hydrogen in oleylamine with an equivalent of active hydrogen at the terminal amino group, embedding flexible nitrile rubber segments into the curing network to improve the material's ductility and elastic recovery. The CGE, as a reactive diluent and compatibilizer, improves asphalt compatibility through its long alkyl chain and participates in the amine-epoxy curing reaction through its epoxy groups.

[0032] In this invention, neither alicyclic amines nor ATBN are added as ordinary external additives, but rather participate in the curing agent system design according to the principle of active hydrogen equivalent substitution. Let E be the total epoxy equivalent provided by E51 and CGE, RI be the ratio of active hydrogen equivalent of alicyclic amine replacing oleylamine, and RA be the ratio of active hydrogen equivalent of ATBN replacing oleylamine. Then the active hydrogen equivalent ratio provided by oleylamine is 1-RI-RA. By controlling RI to 3%–10% and RA to 2%–8%, the epoxy network strength and deformation recovery ability can be improved while ensuring the compatibility contribution of oleylamine.

[0033] The superior comprehensive performance of the epoxy asphalt material of this invention stems from the precise matching and synergistic effect of rigid and flexible segments at the molecular scale in its cured network, without being bound by specific theories. During the curing process, the aliphatic long chains of long-chain oleylamines form the basic flexible framework of the network, providing the basic ability for the movement and deformation of macromolecular segments, thus endowing the material with high ductility. When the material is subjected to tensile stress, the flexible segments dissipate energy through conformational changes; while the alicyclic rigid nodes introduced by the alicyclic amines act as anchor points, uniformly distributed within the flexible network, effectively limiting irreversible slippage between molecular chains and improving the overall load-bearing capacity and deformation resistance of the network. At the same time, the ATBN nitrile rubber segments embedded in the network through terminal amino chemical bonds can form nanoscale microphase separation structures due to the difference in solubility parameters between them and epoxy substances. These reactive rubber microregions can act as stress concentration points under external forces, inducing a large number of crazes and shear yielding, efficiently absorbing and dissipating external energy, thereby significantly improving the ductility and elastic recovery ability of the material while strengthening it. By quantitatively controlling the ratio of active hydrogen equivalent substitution, the three curing agents achieve integrated construction and synergistic stress distribution of the flexible skeleton, rigid anchor points, and energy-consuming micro-regions in the same network, fundamentally solving the contradiction between strength and ductility in traditional solutions.

[0034] This invention addresses the compatibility and interfacial stability challenges between epoxy resin and asphalt through two synergistic mechanisms. First, the long alkyl chains of long-chain oleylamines have similar Hansen solubility parameters to the saturated and aromatic components in asphalt. When introduced into the crosslinking network in large quantities as the primary curing agent, they effectively reduce the surface energy of the epoxy resin-rich phase, thermodynamically favoring uniform and stable submicron-level dispersion within the continuous asphalt phase, thus preventing macroscopic phase separation. Second, CGE, as a reactive compatibilizer, has its long cashew phenol chains acting as interfacial anchors during the mixing stage, directionally adsorbing and penetrating into the asphalt phase, while its epoxy groups at the other end are anchored in the epoxy resin phase and participate in the curing reaction. After curing, CGE molecules covalently bond the epoxy resin crosslinking network to the asphalt phase interface, forming a stable chemically bridged interfacial layer. Compared to traditional physical adsorption or simple interpenetration interfaces, this chemically bonded interfacial layer exhibits significantly higher resistance to shear exfoliation and water damage, ensuring the long-term durability of epoxy asphalt materials under harsh service conditions such as high temperature, heavy load, and rain immersion.

[0035] The present invention will now be described in detail with reference to the accompanying drawings and specific embodiments. Any preparation methods, materials, structures, or composition ratios not explicitly described in this technical solution are considered common technical features disclosed in the prior art or existing commercial products.

[0036] In all the following embodiments and comparative examples, unless otherwise specified, the sources and specifications of the raw materials used are shown in Table A below.

[0037] Table A: Raw Material List and Specifications Example 1 This embodiment provides a composite amine-cured, highly ductile epoxy asphalt material, the formulation and preparation process of which are as follows.

[0038] Formulation Design Principle: The composite curing agent system ratio is designed according to the principle of active hydrogen equivalent substitution. Let E be the total epoxy equivalent provided by E51 epoxy resin and CGE, RI = 8% for the active hydrogen equivalent of long-chain oleylamine replaced by alicyclic amine (IPDA), and RA = 4% for the active hydrogen equivalent of long-chain oleylamine replaced by amino-terminated nitrile rubber (ATBN). Then, the proportion of active hydrogen equivalent provided by long-chain oleylamine is 1 - RI - RA = 88%. Calculations ensure that the total active hydrogen equivalent provided by the composite curing agent system (oleylamine, IPDA, ATBN) is equal to the total epoxy equivalent provided by the epoxy resin system (E51, CGE) (deviation controlled within ±2%).

[0039] The specific proportions of this embodiment, based on parts by weight, are as follows: 70 base bitumen: 25.00 parts E-51 epoxy resin: 14.25 parts Long-chain oleylamines: 9.10 parts Alicyclic amine (IPDA): 0.26 parts Amino-terminated nitrile butadiene rubber (ATBN): 1.38 parts Cashew phenol glycidyl ether (CGE): 0.68 parts For the preparation method of this embodiment, please refer to [link / reference]. Figure 1 The detailed steps are as follows: S1: Place the reaction vessel containing No. 70 base asphalt in an oil bath and heat it to 150±2℃. Start mechanical stirring and maintain the stirring speed at 200 rpm until the asphalt is completely melted and exhibits a uniform flow state. This process takes approximately 30 minutes. Sufficient preheating of the asphalt is a prerequisite for ensuring the uniform dispersion of the epoxy resin subsequently.

[0040] S2: Accurately weigh E-51 epoxy resin and CGE in a separate glass container. Since E-51 epoxy resin has a high viscosity at room temperature (approximately 12000 mPa·s), place the container in an oven and heat to 90°C and hold for 15 minutes to reduce its viscosity to below approximately 500 mPa·s. Then, manually stir for 5 minutes to ensure the epoxy resin and CGE are fully miscible, forming a transparent and homogeneous reactive epoxy resin system. The addition of CGE not only acts as a reactive diluent to reduce the system viscosity, but its long-chain cashew phenol structure also contributes to its affinity for asphalt.

[0041] S3: While maintaining the flowable asphalt obtained in step S1 at 150±2℃ and 500rpm, slowly add the reactive epoxy resin system prepared in step S2 dropwise into the hot asphalt over 5 minutes using a constant-pressure dropping funnel. Immediately after the addition is complete, replace the agitator with a high-shear dispersing emulsifier (FLUKO FA25 type), increasing the shear speed to 3000r / min for high-speed shear mixing for 10 minutes. During the shearing process, the material temperature is maintained stable using an oil bath. After shearing, a uniform epoxy resin-asphalt composite system without macroscopic particles is obtained, with a uniform dark brown color.

[0042] S4: In another glass container, long-chain oleylamine, IPDA, and ATBN were mixed according to the specified ratio. Due to the high viscosity of ATBN (approximately 150,000 mPa·s), to ensure uniform mixing of the three amine curing agents, the mixture was placed in an 80°C water bath and stirred for 5 minutes at 300 rpm to obtain a clear, homogeneous oleylamine / IPDA / ATBN composite curing agent system. The three curing agents each play a specific role: oleylamine acts as the main curing agent, providing long-chain compatibility and a basic flexible network; IPDA introduces alicyclic rigid nodes; and ATBN introduces reactive nitrile rubber energy-dissipating segments.

[0043] S5: Re-stabilize the temperature of the epoxy resin-asphalt composite system obtained in step S3 to 150±2℃. While continuously stirring (500 rpm), rapidly add the composite curing agent system prepared in step S4 in one go. Then immediately increase the stirring speed to 800 rpm and stir vigorously for 10 minutes to ensure that the composite curing agent is highly uniformly dispersed in the epoxy resin-asphalt system. The uniformity of curing agent dispersion directly affects the integrity of the cured network and the consistency of the final material properties.

[0044] S6: Quickly pour the uniformly mixed material from step S5 into a preheated PTFE dumbbell-shaped mold at 150°C. Place the mold in a forced-air oven and pre-cur at 150°C for 3 hours to allow the epoxy resin and amine curing agent to fully undergo a ring-opening crosslinking reaction, forming a preliminary three-dimensional network structure. Then, turn off the oven heating and allow the specimen to slowly cool to room temperature (approximately 25°C) to avoid internal defects caused by thermal stress. Afterward, transfer the specimen to another constant-temperature oven and continue curing at 60°C for 4 days to ensure the curing reaction is complete and the epoxy group conversion rate is maximized. After curing, demold to obtain the final composite amine-cured high-ductility epoxy asphalt material specimen.

[0045] Example 2 This embodiment is basically the same as Example 1, except that the proportion of active hydrogen equivalent of alicyclic amine (IPDA) replacing long carbon chain oleylamine is adjusted to 5% (the active hydrogen provided by alicyclic amine accounts for 5% of the total active hydrogen provided by oleylamine, IPDA and ATBN), and the amount of each component is adjusted accordingly to maintain the balance of active equivalent.

[0046] The specific proportions, by weight, are as follows: 70 base bitumen: 25.00 parts E-51 epoxy resin: 14.13 parts Long-chain oleylamines: 9.34 parts Alicyclic amine (IPDA): 0.16 parts Amino-terminated nitrile butadiene rubber (ATBN): 1.37 parts Cashew phenol glycidyl ether (CGE): 0.70 parts The preparation method is exactly the same as in Example 1.

[0047] Example 3 This embodiment is basically the same as Example 1, except that the proportion of alicyclic amine (IPDA) replacing the active hydrogen equivalent of long-chain oleylamine is adjusted to the upper limit of 10%, and the amount of each component is adjusted accordingly.

[0048] The specific proportions, by weight, are as follows: 70 base bitumen: 25.00 parts E-51 epoxy resin: 14.33 parts Long-chain oleylamines: 8.95 parts Alicyclic amine (IPDA): 0.33 parts Amino-terminated nitrile butadiene rubber (ATBN): 1.39 parts Cashew phenol glycidyl ether (CGE): 0.71 parts The preparation method is exactly the same as in Example 1.

[0049] Example 4 This embodiment is basically the same as Embodiment 1, except that the proportion of amino-terminated butadiene nitrile rubber (ATBN) replacing the active hydrogen equivalent of long-chain oleylamine is adjusted to the upper limit of 8%, while the IPDA replacement ratio is kept at 8%, and the dosage of each component is adjusted accordingly.

[0050] The specific proportions, by weight, are as follows: 70 base bitumen: 25.00 parts E-51 epoxy resin: 13.72 parts Long-chain oleylamines: 8.37 parts Alicyclic amine (IPDA): 0.25 parts Amino-terminated nitrile butadiene rubber (ATBN): 2.66 parts Cashew phenol glycidyl ether (CGE): 0.68 parts The preparation method is exactly the same as in Example 1.

[0051] Example 5 This embodiment is basically the same as Embodiment 1, except that the proportion of amino-terminated butadiene nitrile rubber (ATBN) replacing the active hydrogen equivalent of long-chain oleylamine is adjusted to the lower limit of 2%, while the IPDA replacement ratio is kept at 8%, and the dosage of each component is adjusted accordingly.

[0052] The specific proportions, by weight, are as follows: 70 base bitumen: 25.00 parts E-51 epoxy resin: 14.53 parts Long-chain oleylamines: 9.50 parts Alicyclic amine (IPDA): 0.27 parts Amino-terminated nitrile butadiene rubber (ATBN): 0.71 parts Cashew phenol glycidyl ether (CGE): 0.73 parts The preparation method is exactly the same as in Example 1.

[0053] Example 6 This embodiment is basically the same as Embodiment 1, except that the amount of CGE is increased to 20% of the mass of E-51 epoxy resin, and the substitution ratio of IPDA and ATBN is kept consistent with that in Embodiment 1. At the same time, the amount of E-51 epoxy resin is adjusted to balance the epoxy equivalent.

[0054] The specific proportions, by weight, are as follows: 70 base bitumen: 25.00 parts E-51 epoxy resin: 14.25 parts Long-chain oleylamines: 9.10 parts Alicyclic amine (IPDA): 0.26 parts Amino-terminated nitrile butadiene rubber (ATBN): 1.38 parts Cashew phenol glycidyl ether (CGE): 2.92 parts The preparation method is basically the same as in Example 1, except that in step S2, the proportion of CGE is significantly increased (its viscosity at room temperature is extremely low, only about 30 mPa·s). After mixing with E-51 epoxy resin, the overall viscosity is greatly reduced, so preheating to 90°C is unnecessary. A homogeneous and transparent reactive epoxy resin system can be obtained by stirring at room temperature (about 25°C) for 10 minutes. This indicates that the addition of CGE can effectively reduce the initial operating viscosity of the system and significantly improve its applicability in construction.

[0055] Example 7 This embodiment is basically the same as Embodiment 1, except that SBS modified asphalt is used instead of No. 70 base asphalt, and the composite curing agent ratio of Embodiment 1 is adopted.

[0056] The specific proportions, by weight, are as follows: SBS modified bitumen: 25.00 parts E-51 epoxy resin: 14.25 parts Long-chain oleylamines: 9.10 parts Alicyclic amine (IPDA): 0.26 parts Amino-terminated nitrile butadiene rubber (ATBN): 1.38 parts Cashew phenol glycidyl ether (CGE): 0.70 parts In the preparation method, step S1 requires raising the heating temperature of the SBS modified asphalt to 160±2℃ because its viscosity is higher than that of the base asphalt, and a higher temperature is needed to ensure a uniform flow state. The remaining steps are exactly the same as in Example 1.

[0057] Comparative Example 1 This comparative example uses a common oleylamine-cured epoxy asphalt material, which, by weight, comprises 25.00 parts of No. 70 base asphalt, 13.70 parts of E51 epoxy resin, 11.30 parts of oleylamine, and 0.68 parts of CGE, without the addition of IPDA and ATBN. The oleylamine acts as the sole curing agent in the curing reaction with the E51 epoxy resin.

[0058] Its preparation method is as follows: S1: Heat No. 70 base asphalt to 150℃ to make it reach a uniform flow state; S2: E51 epoxy resin is heated to 80-110℃ and then added to hot asphalt. It is sheared at 3000r / min for 10min to obtain an epoxy resin-asphalt composite system. S3: Add oleylamine to the epoxy resin-asphalt composite system, stir at 150℃ for 10 min, pre-cur at 150℃ for 3 h, and cure at 60℃ for 4 d to obtain ordinary oleylamine-cured epoxy asphalt material.

[0059] Comparative Example 2 This comparative example is an IPDA-modified oleylamine-cured epoxy asphalt material, which, by weight, comprises 25.00 parts of No. 70 base asphalt, 14.67 parts of E51 epoxy resin, 9.73 parts of oleylamine, 0.27 parts of IPDA, and 0.78 parts of CGE, without the addition of ATBN. The proportion of IPDA replacing the active hydrogen equivalent of oleylamine is 8%.

[0060] Its preparation method is as follows: S1: Heat No. 70 base asphalt to 150℃ to make it reach a uniform flow state; S2: E51 epoxy resin is heated to 80-110℃ and then added to hot asphalt. It is sheared at 3000r / min for 10min to obtain an epoxy resin-asphalt composite system. S3: Mix oleylamine and IPDA according to the active hydrogen equivalent ratio, and stir at 80°C for 5 min to obtain an oleylamine / IPDA composite curing agent system; S4: Add the oleylamine / IPDA composite curing agent system to the epoxy resin-asphalt composite system, stir at 150℃ for 10 min, pre-cur at 150℃ for 3 h, and cure at 60℃ for 4 d to obtain IPDA modified oleylamine cured epoxy asphalt material.

[0061] Comparative Example 3 This comparative example is an ATBN-modified oleylamine-cured epoxy asphalt material, which, by weight, comprises 25.00 parts of No. 70 base asphalt, 13.98 parts of E51 epoxy resin, 9.67 parts of oleylamine, 1.36 parts of ATBN, and 0.70 parts of CGE, without the addition of IPDA. The proportion of ATBN replacing the active hydrogen equivalent of oleylamine is 5%.

[0062] Its preparation method is as follows: S1: Heat No. 70 base asphalt to 150℃ to make it reach a uniform flow state; S2: E51 epoxy resin is heated to 80-110℃ and then added to hot asphalt. It is sheared at 3000r / min for 10min to obtain an epoxy resin-asphalt composite system. S3: Mix oleylamine and ATBN according to the active hydrogen equivalent ratio, and stir at 80°C for 5 min to obtain an oleylamine / ATBN composite curing agent system; S4: Add the oleylamine / ATBN composite curing agent system to the epoxy resin-asphalt composite system, stir at 150℃ for 10 min, pre-cur at 150℃ for 3 h, and cure at 60℃ for 4 d to obtain ATBN modified oleylamine cured epoxy asphalt material.

[0063] Test Example 1 To verify the performance of the epoxy asphalt materials prepared in the various embodiments and comparative examples of the present invention, the following tests were conducted: Tensile strength and elongation at break at 23℃: The epoxy asphalt materials prepared in each example and comparative example were cast into standard dumbbell-shaped tensile specimens (total length 75mm, gauge length 25mm, thickness 2mm). After curing according to the established curing regime, the specimens were kept at 23±1℃ for no less than 2 hours. Using an electronic universal testing machine (METS CMT4104), the test was conducted at a tensile rate of 500mm / min according to GB / T 528-2009 "Determination of Tensile Stress-Strain Properties of Vulcanized Rubber or Thermoplastic Rubber". The maximum stress at specimen failure was recorded as the tensile strength at 23℃ (unit: MPa), and the elongation at break was recorded as the elongation at break at 23℃ (unit: %). No fewer than 5 specimens were tested in each group, and the average value was taken.

[0064] Elastic recovery rate test: The elastic recovery capability of some representative examples and comparative examples was evaluated. Tensile specimens were stretched to 100% of the set elongation at 23°C and held at that elongation for 1 minute. Then, the stress was rapidly released, allowing the specimens to recover freely at room temperature (23±1°C) for 10 minutes. The recovered gauge length was measured. The elastic recovery rate was calculated using the following formula: Elastic recovery rate (%) = [1 - (recovered gauge length - original gauge length) / original gauge length] × 100%. The average value of three specimens in each test group was taken.

[0065] Application suitability, i.e., initial viscosity test: The initial viscosity of each example and comparative material was tested immediately after the addition of the curing agent at 120°C using a Brookfield rotational viscometer to evaluate its workability and operability time window.

[0066] Performance Test Results and Analysis The mechanical properties and viscosity test results of each set of examples and comparative examples are shown in Table 1 below.

[0067] Table 1 Tensile properties of each embodiment and comparative example Table 1 shows that the single oleylamine curing system has a high elongation at break but low tensile strength, indicating that while long-chain oleylamine is beneficial for improving the flexibility and ductility of epoxy asphalt, its cured network strength is insufficient. When IPDA replaces part of the active hydrogen in oleylamine, the tensile strength of the material significantly increases, indicating that the alicyclic structure of IPDA can introduce rigid nodes into the flexible oleylamine curing network, increasing the crosslinking density and load-bearing capacity of the system, but simultaneously causing a decrease in elongation at break.

[0068] When ATBN alone replaces part of the active hydrogen in oleylamine, the elongation at break is higher than that of the IPDA-modified system alone, but the increase in tensile strength is limited. This indicates that ATBN mainly improves the material's ductility and elastic recovery through flexible nitrile rubber segments. In Examples 1-7, when IPDA and ATBN are used to replace part of the active hydrogen in oleylamine simultaneously, a high elongation at break can be maintained while improving tensile strength. This shows that the rigid reinforcing effect of IPDA and the flexible toughening effect of ATBN have a synergistic effect, achieving a balance between the strength and high ductility of epoxy asphalt.

[0069] After constructing a composite curing system using oleylamine, IPDA, and ATBN, the tensile strength of Examples 1-7 is not less than 2.0 MPa, meeting the technical requirement of not less than 2.0 MPa for epoxy asphalt materials in the "Technical Specification for Design and Construction of Highway Steel Bridge Deck Pavement". Simultaneously, the elongation at break of Examples 1-7 remains above 300%, significantly exceeding the requirement of not less than 100% in the specification. This demonstrates that the composite amine-cured high-ductility epoxy asphalt material prepared by this invention not only meets the basic tensile strength requirements for steel bridge deck pavement but also possesses significantly higher ductility and deformation capacity and crack resistance potential, making it suitable for bridge deck pavement and heavy-load traffic pavement structures with high requirements for strength, flexibility, and deformation coordination.

[0070] The above description of the embodiments is provided to enable those skilled in the art to understand and use the invention. It will be apparent to those skilled in the art that various modifications can be made to these embodiments, and the general principles described herein can be applied to other embodiments without inventive effort. Therefore, the present invention is not limited to the above embodiments, and any improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the invention should be within the protection scope of the present invention.

Claims

1. A composite amine-cured epoxy asphalt material, characterized in that, It includes the following components: asphalt 40–60 parts by weight; 13-16 parts by weight of epoxy resin; 8-10 parts by weight of long-chain oleylamine, wherein the long-chain oleylamine is used as the main curing agent, and its long-chain structure is used to improve the compatibility between epoxy resin and asphalt. 0.1 to 0.4 parts by weight of alicyclic amine, wherein the alicyclic amine is used as a co-curing agent to introduce alicyclic rigid nodes in the curing network formed by epoxy resin and the long-chain oleylamine; 1.2 to 1.5 parts by weight of amino-terminated nitrile rubber, wherein the amino-terminated nitrile rubber is used as a co-curing agent to introduce nitrile rubber segments into the curing network to improve the ductility of the material; The reactive diluent compatibilizer is 0.6 to 0.9 parts by weight. The reactive diluent compatibilizer is cashew phenol glycidyl ether. The cashew phenol glycidyl ether participates in the curing reaction through its epoxy group and improves the compatibility with asphalt through its long cashew phenol chain.

2. The composite amine-cured epoxy asphalt material according to claim 1, characterized in that, The alicyclic amine is isophorone diamine or modified isophorone diamine; The amino-terminated nitrile rubber is an amino-terminated liquid nitrile rubber.

3. The composite amine-cured epoxy asphalt material according to claim 1, characterized in that, The asphalt is one or more of the following: base asphalt, SBS modified asphalt, rubber modified asphalt, and high viscosity modified asphalt.

4. The composite amine-cured epoxy asphalt material according to claim 1, characterized in that, Based on the active hydrogen equivalent provided by the long-chain oleylamine, the active hydrogen equivalent provided by the alicyclic amine replaces 3% to 10% of the active hydrogen equivalent of the long-chain oleylamine.

5. The composite amine-cured epoxy asphalt material according to claim 1, characterized in that, Based on the active hydrogen equivalent provided by the long-chain oleamide, the active hydrogen equivalent provided by the amino-terminated butadiene-acrylonitrile rubber replaces 2% to 8% of the active hydrogen equivalent of the long-chain oleamide.

6. The composite amine-cured epoxy asphalt material according to claim 1, characterized in that, The mass of the reactive dilution compatibilizer is 3% to 20% of the mass of the epoxy resin.

7. The composite amine-cured epoxy asphalt material according to claim 1, characterized in that, The long-chain oleylamine, alicyclic amine, and amino-terminated butadiene nitrile rubber together form a composite curing agent system. The sum of the active hydrogen equivalents provided by the composite curing agent system matches the sum of the epoxy equivalents provided by the epoxy resin and the reactive diluent compatibilizer.

8. A method for preparing a composite amine-cured epoxy asphalt material as described in any one of claims 1 to 7, characterized in that, Includes the following steps: Asphalt is heated to 130℃~170℃ to obtain asphalt in a fluid state; The epoxy resin is mixed with a reactive diluent compatibilizer to obtain an epoxy resin system; The epoxy resin system is added to flowing asphalt and sheared and mixed at 1000-5000 r / min for 5-60 minutes at 140℃-170℃ to obtain an epoxy resin-asphalt composite system. A composite curing agent system is obtained by mixing long-chain oleylamine, alicyclic amine, and amino-terminated butadiene nitrile rubber. The composite curing agent system is added to the epoxy resin-asphalt composite system, mixed evenly, and then cured to obtain the epoxy asphalt material.

9. The method for preparing the composite amine-cured epoxy asphalt material according to claim 8, characterized in that, The mixing temperature after adding the composite curing agent system is 120℃~160℃, and the stirring time is 3~15 minutes; The curing process includes pre-curing at 150°C for 3 hours and then curing at 60°C for 4 days.

10. The application of a composite amine-cured epoxy asphalt material as described in any one of claims 1 to 7 in steel bridge deck paving materials, heavy-duty traffic road paving materials, airport pavement paving materials, fatigue-resistant asphalt mixtures, high-ductility asphalt binders, and high-elasticity recovery asphalt binders.

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