Aging sbs modified asphalt reaction regenerant and preparation method thereof

Abstract

The application provides an aging SBS modified asphalt reaction regenerant, raw materials of which include component A and component B, wherein the component A includes isocyanate prepolymer 6-25 parts; the component B includes: asphalt component reducing agent 5-20 parts, common crosslinking agent 0.2-1.8 parts, dynamic crosslinking agent 0.4-4.2 parts, catalyst 0.01-0.1 parts, anti-aging agent 1.0-4.5 parts and hydrolysis stabilizer 0.1-0.8 parts. The application also provides a preparation method of the aging SBS modified asphalt reaction regenerant. In conclusion, the application can construct a residual SBS crosslinking structure-reaction reconstruction SBS crosslinking structure-polyurethane crosslinking structure multi-level flexible dynamic crosslinking network in the reaction regenerated SBS modified asphalt, so that the performance of the aging SBS modified asphalt is comprehensively recovered.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of road engineering materials, and particularly relates to an aging SBS modified asphalt reaction regenerant and a preparation method thereof. BACKGROUND

[0002] SBS modified asphalt has been widely used in high-grade highway construction in recent years due to its significant low-temperature anti-cracking and high-temperature anti-rutting properties. During the service of asphalt pavement, SBS modified asphalt will be affected by environmental factors such as heat, ultraviolet light and oxygen, and will be aged, which will reduce its performance and cause the asphalt pavement to be prone to cracks, peeling, potholes and ruts and other diseases, and the service life will be greatly shortened. At present, as the SBS modified asphalt pavement gradually reaches the service life, in order to ensure the driving safety of the SBS modified asphalt pavement, the pavement needs to be repaired and reconstructed, and a large amount of waste SBS modified asphalt mixture will be generated during the period. The recycling and reuse of waste SBS modified asphalt mixture is of great significance to the environment, society and economy. The difficulty of effective recycling and reuse of waste SBS modified asphalt mixture lies in how to effectively restore the performance of aged SBS modified asphalt.

[0003] SBS modified asphalt is a new material formed by adding SBS molecules to base asphalt. During the aging process of base asphalt, the saturated aromatic fraction decreases, the resin and asphaltene increases, the softening point of the asphalt increases, and the penetration decreases. The main method for recycling and reusing aged base asphalt is to add light component regenerant rich in aromatic components to restore the chemical composition and colloidal structure of the aged asphalt, and then restore its performance. This technology is now relatively mature. The recycling of aged SBS modified asphalt not only needs to restore the colloidal structure of the aged asphalt, but also needs to restore the destroyed SBS crosslinked network structure in the aged SBS modified asphalt, which is of great significance to the comprehensive recovery of the performance of the aged SBS modified asphalt.

[0004] In order to effectively restore the performance of aged SBS modified asphalt, Chinese patent application (patents CN112143244B, CN103819912B and CN104231640B) discloses related technical means. These technical solutions can restore the structure of SBS molecules to a certain extent. However, since the selected SBS molecular structure restorer is a small molecule reaction compound, its restoration ability for the molecular weight and structure of aged SBS is limited, and the small molecule reaction compound introduces a large number of hard segment structures for the reconstruction of aged SBS, which reduces the flexibility of SBS molecular chain. Thus, the ability of regenerated modified asphalt to eliminate internal stress through SBS molecular chain and its crosslinked network conformation adjustment is greatly weakened, which leads to limited performance recovery effect of aged SBS modified asphalt in ductility and low-temperature anti-cracking, which greatly reduces the recycling value of waste SBS modified asphalt mixture. SUMMARY

[0005] Therefore, the application provides an aging SBS modified asphalt reaction regenerant and a preparation method thereof, which can not only restore the component balance of the aging asphalt, but also reconstruct the SBS structure in the aging SBS modified asphalt, introduce dynamic covalent bonds, and construct a new polyurethane crosslinking network structure, so as to construct a multi-level flexible dynamic crosslinking network of residual SBS crosslinking structure-reaction reconstructed SBS crosslinking structure-polyurethane crosslinking structure in the reaction regenerated SBS modified asphalt, so as to solve the problems of the prior art, comprehensively restore the performance of the aging SBS modified asphalt, and help to realize the high-performance recycling of the aging SBS modified asphalt.

[0006] The technical scheme of the application is as follows:

[0007] In a first aspect, the application provides an aging SBS modified asphalt reaction regenerant, which comprises components A and B in a weight ratio, wherein,

[0008] The component A comprises 6-25 parts of isocyanate prepolymer.

[0009] The component B comprises 5-20 parts of asphalt component restorer, 0.2-1.8 parts of ordinary crosslinking agent, 0.4-4.2 parts of dynamic crosslinking agent, 0.01-0.1 parts of catalyst, 1.0-4.5 parts of anti-aging agent, and 0.1-0.8 parts of hydrolysis stabilizer.

[0010] Preferably, the isocyanate prepolymer is added in excess, that is, after the reaction of the isocyanate prepolymer and the active end groups of the aging SBS, there is residual isocyanate prepolymer, and the residual isocyanate prepolymer continues to react with the ordinary crosslinking agent or the dynamic crosslinking agent.

[0011] The isocyanate prepolymer is one or more of a diisocyanate prepolymer and a polyisocyanate prepolymer, and the diisocyanate prepolymer is preferred.

[0012] The preparation process of the diisocyanate prepolymer is as follows: the vacuum-dewatered hydroxyl-terminated oligomer is heated to 70-80℃, and then a diisocyanate compound (5%-15% of the mass of the hydroxyl-terminated oligomer) is added, and the diisocyanate prepolymer is obtained after stirring and reacting for 1.5-2 h under a nitrogen atmosphere.

[0013] On the basis of the above technical solutions, preferably, the terminal hydroxyl group oligomer is one or more of terminal hydroxyl butadiene, terminal hydroxyl butadiene-acrylonitrile, and polyether polyol with an average molecular weight of 1000-4000 g / mol; in order to improve the low-temperature performance of the regenerated SBS modified asphalt, the terminal hydroxyl group oligomer is preferably terminal hydroxyl butadiene-acrylonitrile or terminal hydroxyl butadiene; further preferably, the raw material of the aging SBS modified asphalt reaction regenerant further comprises sulfur, and the addition amount of sulfur is 0.01-0.1 parts.

[0014] On the basis of the above technical solutions, preferably, the asphalt component reducing agent is cashew nut shell oil or soft asphalt (aromatic content > 60%), used to restore the composition and performance of the aged asphalt and improve the anti-aging performance of the regenerated SBS modified asphalt, since the cashew nut shell oil contains a certain amount of phenol-resistant structure, which is beneficial to improving the anti-aging performance of the asphalt, and the cashew nut shell oil can be preferably selected.

[0015] On the basis of the above technical solutions, preferably, the ordinary crosslinking agent is a multi-functional compound capable of reacting with isocyanate groups, including one or more of polyols, polyamines, and polyacids. Since a single type of functional group is not good for adjusting the crosslinking density, in order to realize the regulation of the performance of the regenerated SBS modified asphalt by adjusting the crosslinking density, the ordinary crosslinking agent selected by the present application includes di-functional, tri-functional, and tetra-functional compounds, wherein preferably multiple types of trimethylolpropane, pentaerythritol, di-o-chloro-diphenylamine methane, hexanediamine, diethanolamine, or triethanolamine are selected.

[0016] On the basis of the above technical solutions, preferably, the dynamic crosslinking agent is a double / multi-active end group compound containing a dynamic bond, or a multi-functional compound capable of generating a dynamic bond group by reacting with isocyanate groups. The active end group can be a hydroxyl group, a carboxyl group, or an amine group. Since the triggering mechanism and applicable conditions of different dynamic covalent bonds are different, in order to be applicable to the temperature (-15℃-60℃) under the service condition of the road surface, the dynamic crosslinking agent is selected, and at least one of butanedione oxime, diaminodiphenyl disulfide, dithiodipropionic acid, seleno-cystamine, cystine, and 2,2'-(1,4-phenylene)-bis[4-mercapto-1,3,2-dioxaborolane] is preferably selected for reacting with isocyanate prepolymers to crosslink and introduce dynamic covalent bonds.

[0017] On the basis of the above technical solutions, preferably, the catalyst is N,N-dimethylbenzylamine, triethylenediamine, or dibutyltin dilaurate catalyst, used to accelerate the reaction process.

[0018] On the basis of the above technical solutions, preferably, the anti-aging agent is one or more of N,N'-di-sec-octyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, triphenyl phosphite, and tris(nonylphenyl) phosphite, used to improve the anti-aging performance of the regenerated asphalt and prolong its service life.

[0019] Preferably, the hydrolysis stabilizer is N,N-di(2,6-diisopropylphenyl)carbodiimide, which is used to improve the water stability of the reclaimed asphalt mixture.

[0020] In the first aspect, the application also provides a preparation method of the reclaimed agent for aged SBS modified asphalt, which comprises the following steps:

[0021] S1: preparing the raw material asphalt component reducing agent, ordinary crosslinking agent, dynamic crosslinking agent, catalyst, anti-aging agent and hydrolysis stabilizer according to the mass ratio;

[0022] S2: heating the asphalt component reducing agent to 120-150 DEG C, then adding the raw materials according to the mass ratio into the asphalt component reducing agent, and stirring at a constant temperature of 400-500 rpm for 15-20 min to obtain the reaction reclaimed agent B component, which is ready for use;

[0023] S3: storing the A component isocyanate prepolymer and the B component separately at room temperature, avoiding moisture and light, and preparing them according to the proportion when used, which is used for the regeneration of the aged SBS modified asphalt base material.

[0024] In the third aspect, the application also provides an application method of the reclaimed agent for aged SBS modified asphalt, which comprises the following steps: adding the prepared B component into the aged SBS modified asphalt, stirring at a speed of 500-1000 rpm for 5-10 min at 150-170 DEG C, then adding the A component and sulfur, and continuing to stir for 25-35 min, so as to obtain the reclaimed SBS modified asphalt.

[0025] The reclaimed agent for aged SBS modified asphalt has the following beneficial effects compared with the prior art:

[0026] 1. In the aging process of SBS modified asphalt, the polybutadiene (PS) flexible chain segment in the SBS molecule is easily oxidized, which causes the oxidation degradation of the SBS modifier. In the application, the isocyanate prepolymer is selected as the structural reaction repair agent for the aged SBS modifier, which restores the molecular structure of the aged SBS and reconstructs the crosslinking structure of the SBS in the asphalt by reacting with the active end groups (hydroxyl group / carboxyl group) of the aged and degraded SBS. Compared with the ordinary small molecule reaction repair agent, the isocyanate prepolymer can effectively make up for the large loss of the PS chain segment of the SBS modifier due to aging, which helps to improve the flexibility of the reclaimed SBS molecular chain and is more conducive to the comprehensive recovery of the performance of the aged SBS modified asphalt.

[0027] 2. After the isocyanate prepolymer reacts with the active end groups of aged SBS, there is residual isocyanate prepolymer. The residual isocyanate prepolymer reacts with a crosslinking agent (ordinary crosslinking agent or dynamic crosslinking agent) to construct a new polyurethane crosslinking network, including: the SBS crosslinking network remaining in the pre-recycled aged SBS modified asphalt that has not been aged and degraded, the SBS crosslinking network reconstructed by the reaction of the damaged aged SBS in the aged SBS modified asphalt with the isocyanate prepolymer, and the polyurethane crosslinking network structure constructed by the reaction of excess isocyanate prepolymer with the crosslinking agent. Finally, a multi-level crosslinking network of residual SBS crosslinking structure - reaction-reconstructed SBS crosslinking structure - polyurethane crosslinking structure is formed, which is beneficial to improving the high-temperature performance of recycled SBS modified asphalt.

[0028] 3. Furthermore, in order to improve the low-temperature performance of recycled SBS modified asphalt, this invention selects terminal hydroxyl oligomers with better molecular chain flexibility, such as terminal hydroxyl butadiene-acrylonitrile or terminal hydroxyl butadiene, when preparing the isocyanate prepolymer, so that the recycled SBS modified asphalt has better low-temperature performance.

[0029] 4. The use of hydroxyl-terminated oligomers such as hydroxyl-terminated butadiene-acrylonitrile and hydroxyl-terminated butadiene can improve the low-temperature performance of recycled SBS modified asphalt. However, since hydroxyl-terminated butadiene-acrylonitrile and hydroxyl-terminated butadiene contain carbon-carbon double bonds, they are prone to oxidation and breakage during service. To improve their stability, when hydroxyl-terminated butadiene-acrylonitrile and hydroxyl-terminated butadiene are used as raw materials, a certain amount of sulfur needs to be added to the raw materials of the aged SBS modified asphalt reaction regenerator. The sulfur reacts with the carbon-carbon double bonds to eliminate the double bonds and increase the crosslinking density, thereby improving the high-temperature performance of recycled SBS modified asphalt. At the same time, a certain amount of disulfide / polysulfide bonds can be introduced during the reaction. These are dynamic covalent bonds, which can also improve the low-temperature performance of recycled SBS modified asphalt.

[0030] 5. To further improve the low-temperature performance of recycled SBS modified asphalt, the crosslinking agent contains a dynamic crosslinking agent. During the reaction and regeneration process of aged SBS modified asphalt, dynamic covalent bonds can be introduced into the crosslinked structure of the reconstructed SBS and the newly formed polyurethane. With the help of the reversible fracture-reconstruction characteristics of dynamic covalent bonds, it helps to improve the conformational regulation ability of the reconstructed crosslinking network and eliminate stress concentration. In addition, the use of dynamic crosslinking agents helps to construct a dynamic crosslinking network structure. All of these are beneficial to improving the low-temperature performance of recycled SBS modified asphalt. Attached Figure Description

[0031] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0032] Figure 1 Schematic diagram of SBS crosslinking structure-reaction reconstruction SBS crosslinking structure-polyurethane crosslinking structure multi-level dynamic crosslinking network of the present application. DETAILED DESCRIPTION

[0033] The technical solutions in the embodiments of the present application will be clearly and completely described below in combination with the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than 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 scope of protection of the present application.

[0034] The reaction regenerated SBS modified asphalt prepared in each embodiment of the present application is subjected to physical performance testing according to the “Highway Engineering Asphalt and Asphalt Mixture Test Regulations” (JTJE20-2011), and the test results are shown in Table 1.

[0035] Preparation of aged SBS modified asphalt: SBS modified asphalt (5℃ ductility of 33.0 cm, softening point of 74.5℃) is placed in a film oven (RTFOT) and aged at a temperature of 163℃ for 85 minutes to simulate short-term aging in the mixing and paving process of the mixture; then it is placed in a pressure aging vessel (PAV) at 100℃ and a pressure of 2.1 MPa for 20 hours to simulate long-term aging in the process of use on the road surface; finally, aged SBS modified asphalt (5℃ ductility of 2.0 cm, softening point of 66.0℃) is obtained. The aged SBS modified asphalt prepared in the following described embodiments is prepared in this way.

[0036] Example 1:

[0037] The preparation process of the B component is as follows: the asphalt component reducing agent cashew nut shell oil 20g, the ordinary crosslinking agent 1.8g (trimethylolpropane 0.6g, pentaerythritol 0.7g, hexanediamine 0.5g), the dynamic crosslinking agent butanedione oxime 4.2g, the catalyst dibutyltin dilaurate 0.1g, the anti-aging agent N,N'-di-sec-octyl-p-phenylenediamine 4.5g, and the hydrolysis stabilizer N,N-di(2,6-diisopropylphenyl)carbodiimide 0.8g are prepared according to the mass ratio; then the asphalt component reducing agent is heated to 135℃, the above raw materials are added into the asphalt component reducing agent according to the mass ratio, and the B component of the reaction regenerating agent is obtained after constant temperature stirring at 500rpm for 15 minutes.

[0038] The preparation process of the diisocyanate prepolymer is as follows: 76 g of hydroxyl-terminated butadiene is added to a three-necked glass flask, heated to 70-80 °C, vacuum dehydrated for 3 h under reduced pressure, then 12.6 g of isophorone diisocyanate and 0.05 g of dibutyltin dilaurate as a catalyst are added, and the reaction is stirred for 1.5-2 h under a nitrogen atmosphere to obtain the reaction rejuvenator component A for standby.

[0039] The aged SBS modified asphalt heated to 150 °C is weighed into an iron stirring tank, then the prepared B component is added, stirred at a stirring speed of 500 rpm for 5 min, then 25 g of the diisocyanate prepolymer A component and 0.1 g of sulfur are added, and the stirring is continued for 30 min to prepare the reaction rejuvenated SBS modified asphalt.

[0040] Example 2:

[0041] The preparation process of the B component is as follows: the asphalt component reducing agent cashew nut shell oil 5 g, the general crosslinking agent 0.2 g (trimethylolpropane 0.6 g, pentaerythritol 0.7 g, hexanediamine 0.5 g), the dynamic crosslinking agent butanedione oxime 0.4 g, the catalyst dibutyltin dilaurate 0.01 g, the anti-aging agent N,N'-di-sec-octyl-p-phenylenediamine 1.0 g, and the hydrolysis stabilizer N,N-di(2,6-diisopropylphenyl)carbodiimide 0.1 g are prepared according to the mass ratio; then the asphalt component reducing agent is heated to 135 °C, the above raw materials are added to the asphalt component reducing agent according to the mass ratio, and the constant temperature stirring is carried out at 500 rpm for 15 min to obtain the reaction rejuvenator B component for standby.

[0042] The preparation process of the diisocyanate prepolymer is as follows: 76 g of hydroxyl-terminated butadiene is added to a three-necked glass flask, heated to 70-80 °C, vacuum dehydrated for 3 h under reduced pressure, then 12.6 g of isophorone diisocyanate and 0.05 g of dibutyltin dilaurate as a catalyst are added, and the reaction is stirred for 1.5-2 h under a nitrogen atmosphere to obtain the reaction rejuvenator component A for standby.

[0043] The aged SBS modified asphalt heated to 150 °C is weighed into an iron stirring tank, then the prepared B component is added, stirred at a stirring speed of 500 rpm for 5 min, then 25 g of the diisocyanate prepolymer A component and 0.1 g of sulfur are added, and the stirring is continued for 30 min to prepare the reaction rejuvenated SBS modified asphalt.

[0044] Example 3:

[0045] The preparation process of B component is as follows: the asphalt component reducing agent cashew nut shell oil 15 g, common crosslinking agent 0.9 g (trimethylolpropane 0.6 g, pentaerythritol 0.7 g, hexanediamine 0.5 g), dynamic crosslinking agent butanedione oxime 3.1 g, catalyst dibutyltin dilaurate 0.06 g, anti-aging agent N,N'-di-sec-octyl-p-phenylenediamine 3.0 g, hydrolysis stabilizer N,N-di(2,6-diisopropylphenyl)carbodiimide 0.5 g are prepared according to the mass ratio; then the asphalt component reducing agent is heated to 135 ℃, and the above raw materials are added into the asphalt component reducing agent according to the mass ratio, and the reaction regenerant B component is obtained after constant temperature stirring at 500 rpm for 15 min.

[0046] The preparation process of the diisocyanate prepolymer is as follows: 76 g of hydroxyl-terminated butadiene is taken into a three-necked glass flask, heated to 70-80 ℃, and vacuum dehydrated under reduced pressure for 3 h; then isophorone diisocyanate 12.6 g and catalyst dibutyltin dilaurate 0.05 g are added, and the reaction regenerant A component is obtained after stirring under nitrogen atmosphere for 1.5-2 h.

[0047] The aged SBS modified asphalt heated to 150 ℃ is weighed into an iron stirring tank, then the prepared B component is added, stirred at a stirring speed of 500 rpm for 5 min, then the diisocyanate prepolymer A component 12 g and sulfur 0.05 g are added, and the reaction regenerated SBS modified asphalt is prepared after continuous stirring for 30 min.

[0048] Example 4 (A component is diphenylmethane diisocyanate):

[0049] The preparation process of B component is as follows: the asphalt component reducing agent cashew nut shell oil 15 g, common crosslinking agent 0.9 g (trimethylolpropane 0.6 g, pentaerythritol 0.7 g, hexanediamine 0.5 g), dynamic crosslinking agent butanedione oxime 3.1 g, catalyst dibutyltin dilaurate 0.06 g, anti-aging agent N,N'-di-sec-octyl-p-phenylenediamine 3.0 g, hydrolysis stabilizer N,N-di(2,6-diisopropylphenyl)carbodiimide 0.5 g are prepared according to the mass ratio; then the asphalt component reducing agent is heated to 135 ℃, and the above raw materials are added into the asphalt component reducing agent according to the mass ratio, and the reaction regenerant B component is obtained after constant temperature stirring at 500 rpm for 15 min.

[0050] The aged SBS modified asphalt heated to 150 ℃ is weighed into an iron stirring tank, then the prepared B component is added, stirred at a stirring speed of 500 rpm for 5 min, then the diisocyanate prepolymer A component 12 g and sulfur 0.05 g are added, and the reaction regenerated SBS modified asphalt is prepared after continuous stirring for 30 min.

[0051] Example 5 (without dynamic crosslinking agent):

[0052] The preparation process of B component is as follows: the asphalt component reducing agent cashew nut shell oil 20 g, common crosslinking agent 1.8 g (trimethylolpropane 0.6 g, pentaerythritol 0.7 g, hexanediamine 0.5 g), catalyst dibutyl tin dilaurate 0.1 g, anti-aging agent N,N'-di-sec-octyl-p-phenylenediamine 4.5 g, hydrolysis stabilizer N,N-di(2,6-diisopropylphenyl)carbodiimide 0.8 g are prepared according to the mass ratio; then the asphalt component reducing agent is heated to 135 ℃, and the above raw materials are added into the asphalt component reducing agent according to the mass ratio, and the reaction regenerating agent B component is obtained after constant temperature stirring at 500 rpm for 15 min.

[0053] The preparation process of the diisocyanate prepolymer is as follows: 76 g of hydroxyl-terminated butadiene is added to a three-necked glass flask, heated to 70-80 ℃, and vacuum dehydrated under reduced pressure for 3 h; then isophorone diisocyanate 12.6 g and catalyst dibutyl tin dilaurate 0.05 g are added, and the reaction regenerating agent A component is obtained after stirring under nitrogen atmosphere for 1.5-2 h.

[0054] The aged SBS modified asphalt heated to 150 ℃ 200 g is weighed in an iron stirring tank, then the prepared B component is added, stirred at a stirring speed of 500 rpm for 5 min, then A component diisocyanate prepolymer 25 g and sulfur 0.1 g are added, and the reaction regenerated SBS modified asphalt is prepared by continuing to stir for 30 min.

[0055] Example 6 (A component does not exceed):

[0056] The preparation process of B component is as follows: the asphalt component reducing agent cashew nut shell oil 20 g, common crosslinking agent 1.8 g (trimethylolpropane 0.6 g, pentaerythritol 0.7 g, hexanediamine 0.5 g), catalyst dibutyl tin dilaurate 0.1 g, anti-aging agent N,N'-di-sec-octyl-p-phenylenediamine 4.5 g, hydrolysis stabilizer N,N-di(2,6-diisopropylphenyl)carbodiimide 0.8 g are prepared according to the mass ratio; then the asphalt component reducing agent is heated to 135 ℃, and the above raw materials are added into the asphalt component reducing agent according to the mass ratio, and the reaction regenerating agent B component is obtained after constant temperature stirring at 500 rpm for 15 min.

[0057] The preparation process of the diisocyanate prepolymer is as follows: 76 g of hydroxyl-terminated butadiene is added to a three-necked glass flask, heated to 70-80 ℃, and vacuum dehydrated under reduced pressure for 3 h; then isophorone diisocyanate 12.6 g and catalyst dibutyl tin dilaurate 0.05 g are added, and the reaction regenerating agent A component is obtained after stirring under nitrogen atmosphere for 1.5-2 h.

[0058] Take 200g of aged SBS modified asphalt heated to 150°C in an iron mixing tank, then add the above prepared B component, stir at a stirring speed of 500 rpm for 5 min, then add the A component diisocyanate prepolymer 0.5g and sulfur 0.01g, continue to stir for 30 min, thus preparing the reaction regenerated SBS modified asphalt.

[0059] Example 7 (terminal hydroxyl oligomer is polyether diol):

[0060] The preparation process of B component is as follows: the asphalt component reducing agent cashew nut shell oil 5g, the ordinary crosslinking agent 0.2g (trimethylolpropane 0.6g, pentaerythritol 0.7g, hexanediamine 0.5g), dynamic crosslinking agent butanedione oxime 0.4g, catalyst dibutyltin dilaurate 0.01g, anti-aging agent N,N'-di-sec-octyl-p-phenylenediamine 1.0g, hydrolysis stabilizer N,N-di(2,6-diisopropylphenyl)carbodiimide 0.1g are prepared according to the mass ratio; then the asphalt component reducing agent is heated to 135°C, the above raw materials are added into the asphalt component reducing agent according to the mass ratio, and the reaction regenerator B component is obtained after constant temperature stirring at 500 rpm for 15 min.

[0061] The preparation process of diisocyanate prepolymer is as follows: take 76g of polyether diol into a three-necked glass flask, heat to 70-80°C, vacuum dehydration for 3h under reduced pressure, then add isophorone diisocyanate 12.6g and catalyst dibutyltin dilaurate 0.05g, stir for 1.5-2h under nitrogen atmosphere, then obtain the reaction regenerator A component for standby.

[0062] Take 200g of aged SBS modified asphalt heated to 150°C in an iron mixing tank, then add the above prepared B component, stir at a stirring speed of 500 rpm for 5 min, then add the A component diisocyanate prepolymer 6g and sulfur 0.01g, continue to stir for 30 min, thus preparing the reaction regenerated SBS modified asphalt.

[0063] Example 8 (without adding sulfur):

[0064] The preparation process of B component is as follows: the asphalt component reducing agent cashew nut shell oil 5g, the ordinary crosslinking agent 0.2g (trimethylolpropane 0.6g, pentaerythritol 0.7g, hexanediamine 0.5g), dynamic crosslinking agent butanedione oxime 0.4g, catalyst dibutyltin dilaurate 0.01g, anti-aging agent N,N'-di-sec-octyl-p-phenylenediamine 1.0g, hydrolysis stabilizer N,N-di(2,6-diisopropylphenyl)carbodiimide 0.1g are prepared according to the mass ratio; then the asphalt component reducing agent is heated to 135°C, the above raw materials are added into the asphalt component reducing agent according to the mass ratio, and the reaction regenerator B component is obtained after constant temperature stirring at 500 rpm for 15 min.

[0065] The preparation process of the diisocyanate prepolymer is as follows: 76 g of hydroxyl-terminated butadiene is added to a three-necked glass flask, heated to 70-80 °C, vacuum dehydrated for 3 h under reduced pressure, then 12.6 g of isophorone diisocyanate and 0.05 g of catalyst dibutyltin dilaurate are added, and stirred for 1.5-2 h under nitrogen atmosphere to obtain the reaction regenerator component A for standby.

[0066] The aged SBS modified asphalt heated to 150 °C is weighed into an iron stirring tank, then the prepared B component is added, stirred at a stirring speed of 500 rpm for 5 min, then 12 g of the diisocyanate prepolymer A component is added, and stirred for 30 min to prepare the reaction regenerated SBS modified asphalt.

[0067] Example 9 (A component is not excessive, and the hydroxyl-terminated oligomer is a polyether diol):

[0068] The preparation process of the B component is as follows: the asphalt component reducing agent cashew nut shell oil 5 g, the ordinary crosslinking agent 0.2 g (trimethylolpropane 0.6 g, pentaerythritol 0.7 g, hexanediamine 0.5 g), the dynamic crosslinking agent butanedione oxime 0.4 g, the catalyst dibutyltin dilaurate 0.01 g, the anti-aging agent N,N'-di-sec-octyl-p-phenylenediamine 1.0 g, and the hydrolysis stabilizer N,N-bis (2, 6-diisopropylphenyl) carbodiimide 0.1 g are prepared according to the mass ratio; then the asphalt component reducing agent is heated to 135 °C, the above raw materials are added into the asphalt component reducing agent according to the mass ratio, stirred at a constant temperature of 500 rpm for 15 min to obtain the reaction regenerator B component for standby.

[0069] The preparation process of the diisocyanate prepolymer is as follows: 76 g of polyether diol is added to a three-necked glass flask, heated to 70-80 °C, vacuum dehydrated for 3 h under reduced pressure, then 12.6 g of isophorone diisocyanate and 0.05 g of catalyst dibutyltin dilaurate are added, and stirred for 1.5-2 h under nitrogen atmosphere to obtain the reaction regenerator component A for standby.

[0070] The aged SBS modified asphalt heated to 150 °C is weighed into an iron stirring tank, then the prepared B component is added, stirred at a stirring speed of 500 rpm for 5 min, then 12 g of the diisocyanate prepolymer A component is added, and stirred for 30 min to prepare the reaction regenerated SBS modified asphalt.

[0071] Example 10 (A component is not excessive, and no sulfur is added):

[0072] The preparation process of B component is as follows: the asphalt component reducing agent cashew nut shell oil 5 g, common crosslinking agent 0.2 g (trimethylolpropane 0.6 g, pentaerythritol 0.7 g, hexanediamine 0.5 g), dynamic crosslinking agent butanedione oxime 0.4 g, catalyst dibutyltin dilaurate 0.01 g, anti-aging agent N,N'-di-sec-octyl-p-phenylenediamine 1.0 g, hydrolysis stabilizer N,N-di(2,6-diisopropylphenyl)carbodiimide 0.1 g are prepared according to the mass ratio; then the asphalt component reducing agent is heated to 135 DEG C, and the above raw materials are added into the asphalt component reducing agent according to the mass ratio, and the reaction regenerant B component is obtained after constant temperature stirring at 500 rpm for 15 min.

[0073] The preparation process of the binary isocyanate prepolymer is as follows: 76 g of hydroxyl-terminated butadiene is added into a three-necked glass flask, heated to 70-80 DEG C, and vacuum dehydrated for 3 h under reduced pressure, then isophorone diisocyanate 12.6 g and catalyst dibutyltin dilaurate 0.05 g are added, and the reaction regenerant A component is obtained after stirring and reaction for 1.5-2 h under nitrogen atmosphere.

[0074] The preparation process of the binary isocyanate prepolymer is as follows: 76 g of hydroxyl-terminated butadiene is added into a three-necked glass flask, heated to 70-80 DEG C, and vacuum dehydrated for 3 h under reduced pressure, then isophorone diisocyanate 12.6 g and catalyst dibutyltin dilaurate 0.05 g are added, and the reaction regenerant A component is obtained after stirring and reaction for 1.5-2 h under nitrogen atmosphere.

[0075] Example 11 (A component is not excessive, and does not contain dynamic crosslinking agent):

[0076] The preparation process of B component is as follows: the asphalt component reducing agent cashew nut shell oil 5 g, common crosslinking agent 0.2 g (trimethylolpropane 0.6 g, pentaerythritol 0.7 g, hexanediamine 0.5 g), catalyst dibutyltin dilaurate 0.01 g, anti-aging agent N,N'-di-sec-octyl-p-phenylenediamine 1.0 g, hydrolysis stabilizer N,N-di(2,6-diisopropylphenyl)carbodiimide 0.1 g are prepared according to the mass ratio; then the asphalt component reducing agent is heated to 135 DEG C, and the above raw materials are added into the asphalt component reducing agent according to the mass ratio, and the reaction regenerant B component is obtained after constant temperature stirring at 500 rpm for 15 min.

[0077] The preparation process of the binary isocyanate prepolymer is as follows: 76 g of hydroxyl-terminated butadiene is added into a three-necked glass flask, heated to 70-80 DEG C, and vacuum dehydrated for 3 h under reduced pressure, then isophorone diisocyanate 12.6 g and catalyst dibutyltin dilaurate 0.05 g are added, and the reaction regenerant A component is obtained after stirring and reaction for 1.5-2 h under nitrogen atmosphere.

[0078] Take 200g of aged SBS modified asphalt heated to 150°C in an iron mixing tank, then add the above prepared B component, stir at a stirring speed of 500 rpm for 5 min, then add 0.3g of isocyanate prepolymer and 0.01g of sulfur, continue to stir for 30 min, thus preparing the reaction regenerated SBS modified asphalt.

[0079] Example 12 (oligomer with terminal hydroxyl group is polyether diol, without sulfur):

[0080] The preparation process of B component is as follows: the asphalt component reducing agent cashew nut shell oil 15g, the ordinary crosslinking agent 0.9g (trimethylolpropane 0.6g, pentaerythritol 0.7g, hexanediamine 0.5g), dynamic crosslinking agent butanedione oxime 3.1g, catalyst dibutyltin dilaurate 0.06g, anti-aging agent N,N'-di-sec-octyl-p-phenylenediamine 3.0g, hydrolysis stabilizer N,N-di(2,6-diisopropylphenyl)carbodiimide 0.5g are prepared according to the mass ratio; then the asphalt component reducing agent is heated to 135°C, the above raw materials are added into the asphalt component reducing agent according to the mass ratio, and the reaction regenerant B component is obtained after constant temperature stirring at 500 rpm for 15 min.

[0081] The preparation process of isocyanate prepolymer is as follows: take 76g of polyether diol into a three-necked glass flask, heat to 70-80°C, vacuum dehydration for 3h under reduced pressure, then add isophorone diisocyanate 12.6g and catalyst dibutyltin dilaurate 0.05g, stir for 1.5-2h under nitrogen atmosphere, and then the reaction regenerant A component is obtained.

[0082] Take 200g of aged SBS modified asphalt heated to 150°C in an iron mixing tank, then add the above prepared B component, stir at a stirring speed of 500 rpm for 5 min, then add 12g of isocyanate prepolymer, continue to stir for 30 min, thus preparing the reaction regenerated SBS modified asphalt.

[0083] Example 13 (oligomer with terminal hydroxyl group is polyether diol, without dynamic crosslinking agent):

[0084] The preparation process of B component is as follows: the asphalt component reducing agent cashew nut shell oil 15g, the ordinary crosslinking agent 0.9g (trimethylolpropane 0.6g, pentaerythritol 0.7g, hexanediamine 0.5g), catalyst dibutyltin dilaurate 0.06g, anti-aging agent N,N'-di-sec-octyl-p-phenylenediamine 3.0g, hydrolysis stabilizer N,N-di(2,6-diisopropylphenyl)carbodiimide 0.5g are prepared according to the mass ratio; then the asphalt component reducing agent is heated to 135°C, the above raw materials are added into the asphalt component reducing agent according to the mass ratio, and the reaction regenerant B component is obtained after constant temperature stirring at 500 rpm for 15 min.

[0085] The preparation process of the diisocyanate prepolymer is as follows: 76 g of polyether diol is added to a three-necked glass flask, heated to 70-80 °C, vacuum dehydrated for 3 h under reduced pressure, then 12.6 g of isophorone diisocyanate and 0.05 g of dibutyltin dilaurate as catalyst are added, and stirred for 1.5-2 h under nitrogen atmosphere to obtain the reaction regenerant component A for standby.

[0086] The aged SBS modified asphalt heated to 150 °C is weighed into an iron stirring tank, then the prepared B component is added, stirred at a stirring speed of 500 rpm for 5 min, then 12 g of the diisocyanate prepolymer of component A and 0.05 g of sulfur are added, and stirred for another 30 min to prepare the reaction regenerated SBS modified asphalt.

[0087] Example 14 (without sulfur and without dynamic crosslinking agent):

[0088] The preparation process of the B component is as follows: the asphalt component reducing agent cashew nut shell oil 20 g, the ordinary crosslinking agent 1.8 g (trimethylolpropane 0.6 g, pentaerythritol 0.7 g, hexanediamine 0.5 g), the catalyst dibutyltin dilaurate 0.1 g, the anti-aging agent N,N'-di-sec-octyl-p-phenylenediamine 4.5 g, and the hydrolysis stabilizer N,N-di(2,6-diisopropylphenyl)carbodiimide 0.8 g are prepared according to the mass ratio; then the asphalt component reducing agent is heated to 135 °C, and the above raw materials are added into the asphalt component reducing agent according to the mass ratio, stirred at a constant temperature of 500 rpm for 15 min to obtain the reaction regenerant B component for standby.

[0089] The preparation process of the diisocyanate prepolymer is as follows: 76 g of hydroxyl-terminated butadiene is added to a three-necked glass flask, heated to 70-80 °C, vacuum dehydrated for 3 h under reduced pressure, then 12.6 g of isophorone diisocyanate and 0.05 g of dibutyltin dilaurate as catalyst are added, and stirred for 1.5-2 h under nitrogen atmosphere to obtain the reaction regenerant component A for standby.

[0090] The aged SBS modified asphalt heated to 150 °C is weighed into an iron stirring tank, then the prepared B component is added, stirred at a stirring speed of 500 rpm for 5 min, then 25 g of the diisocyanate prepolymer of component A is added, and stirred for another 30 min to prepare the reaction regenerated SBS modified asphalt.

[0091] Example 15 (component A is diphenylmethane diisocyanate, without dynamic crosslinking agent):

[0092] The preparation process of the B component is as follows: the asphalt component reducing agent cashew nut shell oil 20 g, the common crosslinking agent 1.8 g (trimethylolpropane 0.6 g, pentaerythritol 0.7 g, hexanediamine 0.5 g), the catalyst dibutyl tin dilaurate 0.1 g, the anti-aging agent N,N'-di-sec-octyl-p-phenylenediamine 4.5 g, and the hydrolysis stabilizer N,N-di(2,6-diisopropylphenyl)carbodiimide 0.8 g are prepared according to the mass ratio; then the asphalt component reducing agent is heated to 135 ℃, the above raw materials are added into the asphalt component reducing agent according to the mass ratio, and the reaction regenerant B component is obtained after constant temperature stirring at 500 rpm for 15 min.

[0093] The aged SBS modified asphalt heated to 150 ℃ 200 g is weighed in an iron stirring tank, then the prepared B component is added, the stirring speed is 500 rpm, and stirring is performed for 5 min, then diphenyl methane diisocyanate 25 g is added, and stirring is continuously performed for 30 min, thereby preparing the reaction regenerated SBS modified asphalt.

[0094] The performance test results of the reaction regenerated SBS modified asphalt in each example in table 1

[0095]

[0096]

[0097] It can be seen from the performance test results of the reaction regenerated SBS modified asphalt in the above examples that the use of isocyanate prepolymer is beneficial to the recovery of the performance of the aged SBS modified asphalt; and the reaction of the excess isocyanate prepolymer with the crosslinking agent to form a polyurethane crosslinking structure is beneficial to the comprehensive improvement of the high and low temperature performance of the regenerated SBS modified asphalt; at the same time, the introduction of the dynamic covalent bond is beneficial to the balanced and comprehensive recovery of the high and low temperature performance of the aged SBS modified asphalt.

[0098] The above only describes the preferred embodiments of the present application and is not used to limit the present application, and any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. An aging SBS modified asphalt reaction rejuvenator, characterized in that, By weight ratio, its raw materials include component A and component B, wherein, Component A includes 6-25 parts of isocyanate prepolymer; Component B includes: 5-20 parts of asphalt reducing agent, 0.2-1.8 parts of ordinary crosslinking agent, 0.4-4.2 parts of dynamic crosslinking agent, 0.01-0.1 parts of catalyst, 1.0-4.5 parts of anti-aging agent and 0.1-0.8 parts of hydrolysis stabilizer; After the isocyanate prepolymer reacts with the active end groups of aged SBS, there is a residual isocyanate prepolymer, which continues to react with a common crosslinking agent or a dynamic crosslinking agent. The reducing agent for the asphalt components is cashew nut shell oil or soft asphalt with an aromatic content greater than 60%. The common crosslinking agent is at least two of the following: trimethylolpropane, pentaerythritol, di-o-chlorodiphenylamine methane, hexamethylenediamine, diethanolamine, or triethanolamine; The dynamic crosslinking agent is at least one of dimethylglyoxime, diaminodiphenyl disulfide, dithiodipropionic acid, selenocysteine, cystine, and 2,2'-(1,4-phenylene)-bis[4-mercapto-1,3,2-dioxorane]. The isocyanate prepolymer is a diisocyanate prepolymer. The preparation process of the diisocyanate prepolymer is as follows: the vacuum-dehydrated terminal hydroxyl oligomer is heated to 70~80℃, then the diisocyanate compound is added, and the reaction is stirred under a nitrogen atmosphere for 1.5~2h to obtain the diisocyanate prepolymer. The hydroxyl-terminated oligomer is hydroxyl-terminated butadiene-acrylonitrile or hydroxyl-terminated butadiene; The raw materials for the aged SBS modified asphalt reactive regenerator also include sulfur; the amount of sulfur added is 0.01~0.1 parts.

2. The aged SBS-modified asphalt reaction rejuvenator of claim 1, wherein: The active end group is a hydroxyl, carboxyl, or amino group.

3. A method for preparing an aged SBS modified asphalt reactive rejuvenator as described in any one of claims 1 or 2, characterized in that: Includes the following steps: S1 is prepared by mixing raw material asphalt components, reducing agent, ordinary crosslinking agent, dynamic crosslinking agent, catalyst, anti-aging agent, and hydrolysis stabilizer according to the mass ratio; S2 heats the asphalt component reducing agent to 120~150℃, then adds the above raw materials to the asphalt component reducing agent according to the mass ratio, and stirs at 400~500 rpm for 15~20 minutes at a constant temperature to obtain the reactive regenerator component B, which is then set aside. S3 stores the isocyanate prepolymer (component A) and component B separately at room temperature, away from moisture and light, and then mixes them in proportion when needed for the regeneration of aged SBS modified bitumen-based materials.

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