A method for preparing functional modified asphalt based on alcoholysis by-products

Abstract

The present invention provides a method for preparing functional modified asphalt based on polyester alcoholysis byproducts, comprising the following steps: S1) mixing porous boron nitride, layered double metal hydroxide, crown ether and water, freeze-drying after deposition to obtain a self-assembled solid material, ball-milling the self-assembled solid material to obtain a potassium ion metal shielding material; S2) subjecting the polyester alcoholysis byproducts, the potassium ion metal shielding material, carboxylic acid organic matter and ultraviolet light absorber to esterification reaction, and then to polymerization reaction to obtain a modified resin; S3) mixing a grafting agent and a compatibilizer, reacting after heating to obtain a reactive compatibilizer; S4) heating the asphalt to melt, adding the modified resin and the reactive compatibilizer, and reacting to obtain a functional modified asphalt. The functional modified asphalt prepared by the present application has the advantages of good storage stability and anti-ultraviolet aging performance, and can meet the road performance requirements.

Description

Technical Field

[0001] The invention relates to the technical field of asphalt, and in particular to a method for preparing functional modified asphalt based on alcoholysis by-products. Background Art

[0002] Asphalt is a dark brown complex mixture of hydrocarbons of different molecular weights and their non-metallic derivatives. It has low cost and good mechanical properties and is widely used in road engineering. Asphalt used for road surface is subject to repeated loads from wheels and erosion from natural conditions, and is prone to problems such as rutting, potholes and cracking, which have a great impact on the comfort and safety of road driving. In recent years, with the development of society, the substantial increase in vehicle load and number has put forward higher requirements on road performance, so it is necessary to further modify road asphalt to meet the needs of use.

[0003] Polyethylene terephthalate (PET) is a good asphalt modification material with good chemical stability and high strength. However, with the increase in polyester production and the continuous expansion of its application fields, the stock of waste polyester in my country continues to grow. The recycling of waste polyester has important economic and practical significance. Among many chemical recycling methods, ethylene glycol alcoholysis effectively depolymerizes waste PET into bis(hydroxyethyl) terephthalate (BHET). The reaction conditions are mild, the safety is good, and the product yield is high, making it one of the key technologies for recycling waste PET. However, during the alcoholysis of waste polyester ethylene glycol, a series of alcoholysis by-products with low polymerization degree will be produced. In addition, potassium carbonate, as an economical, environmentally friendly, low-toxic and efficient catalyst, has been widely used in depolymerization reactions, but due to its easy solubility in alcohol depolymerization liquids, it will remain in the depolymerization by-products in small amounts. When these depolymerization by-products are used as raw materials to prepare recycled resins, the residual potassium carbonate will seriously inhibit the molecular chain viscosity-increasing reaction, making it difficult for a large number of depolymerization by-products to be recycled.

[0004] Introducing alcoholysis byproducts into the field of road engineering can effectively improve the recycling rate of depolymerization byproducts and the performance of asphalt. However, since modified asphalt prepared from alcoholysis byproducts with low polymerization degree often undergoes phase separation, it cannot meet the technical standards of storage stability and is difficult to be applied to road engineering. Therefore, in order to better utilize alcoholysis byproducts, it is urgent to provide a new material and method to achieve the selective removal of potassium ions and the efficient polymerization modification of alcoholysis byproducts, which will be of great significance to protecting the environment and improving the performance of asphalt. Summary of the invention

[0005] The technical problem solved by the present invention is to provide a method for preparing functional modified asphalt based on polyester alcoholysis by-products. The method provided in this application can utilize polyester alcoholysis by-products to modify asphalt, thereby realizing the recycling of polyester alcoholysis by-products and improving the performance of asphalt.

[0006] In view of this, the present application provides a method for preparing functional modified asphalt based on polyester alcoholysis byproducts, comprising the following steps:

[0007] S1) mixing porous boron nitride, layered double metal hydroxide, crown ether and water, freeze-drying after deposition to obtain a self-assembled solid material, and ball-milling the self-assembled solid material to obtain a potassium ion metal shielding material;

[0008] S2) subjecting the polyester alcoholysis byproduct, the potassium ion metal shielding material, the carboxylic acid organic matter and the ultraviolet light absorber to an esterification reaction, and then subjecting the resultant to a polymerization reaction to obtain a modified resin;

[0009] S3) mixing the grafting agent and the compatibilizer, heating and reacting them to obtain a reactive compatibilizer;

[0010] S4) After heating the asphalt until it is melted, a modified resin and a reactive compatibilizer are added, and functional modified asphalt is obtained after the reaction.

[0011] Preferably, in step S1), the mass ratio of the porous boron nitride, the layered double hydroxide and the crown ether is 10:(5-10):(3-8).

[0012] Preferably, the crown ether includes one or more of 18-crown-6, dibenzo-18-crown-6, dibenzo-30-crown-10, 15-crown-5 and cyclohexanedo-18-crown-6; and / or, the carboxylic acid organic compound includes one or more of terephthalic acid, adipic acid, isophthalic acid, 4-bromophthalic acid, phthalic anhydride, p-hydroxybenzoic acid and succinic acid; and / or, the ultraviolet absorber includes one or more of bisbenzoxazole stilbene, salicylic benzoate, benzotriazole and 2-hydroxy-4-methoxybenzophenone.

[0013] Preferably, in step S1), the mass ratio of the grinding beads in the ball mill is 2.5:10:14:15:55, and the corresponding quantity ratio is (14-16):(9-11):(4-6):(4-6):(2-4); the ball milling time is 10-30 h, and the rotation speed is 300-500 r / min.

[0014] Preferably, in step S2), the mass ratio of the polyester alcoholysis by-product, the potassium ion metal shielding material, the carboxylic acid organic matter and the ultraviolet light absorber is (5-70): (1-15): (1-25): (1-10); and / or the temperature of the esterification reaction is 100-250°C and the time is 2-5h; and / or the vacuum degree of the polymerization reaction is 40-100 Pa, the temperature is 250-300°C, and the time is 3-10h.

[0015] Preferably, the grafting agent includes maleic anhydride, the compatibilizer includes one or more of 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, polyphenylmethane polyisocyanate and hexamethylene diisocyanate, and the asphalt includes one or more of petroleum asphalt, coal asphalt and rock asphalt; and / or, the mass ratio of the compatibilizer and the grafting agent is 100:(5~25); and / or, the mass ratio of the asphalt, the modified resin and the reactive compatibilizer is 100:(5~70):(1~20).

[0016] Preferably, in step S3), the heating temperature is 50-100° C., stirring is performed while heating, the stirring rate is 200-500 r / min, and the time is 5-20 min.

[0017] Preferably, in step S4), the reaction is carried out under stirring conditions, the stirring rate is 1500-5000 r / min, and the time is 30-120 min.

[0018] Preferably, the preparation method of the porous boron nitride is specifically as follows:

[0019] A boron source, a nitrogen source, a pore former and water are mixed and heated to obtain a boron nitride precursor;

[0020] calcining the boron nitride precursor to obtain porous boron nitride;

[0021] And / or, the preparation method of the layered double metal hydroxide is specifically:

[0022] The divalent metal salt, the trivalent metal salt and the alkaline reagent are mixed, subjected to hydrothermal reaction and then freeze-dried to obtain a layered double metal hydroxide.

[0023] The present application also provides a functional modified asphalt, which is prepared from a grafting agent, a compatibilizer, asphalt and a modified resin;

[0024] The preparation method of the modified resin comprises the following steps:

[0025] S1) mixing porous boron nitride, layered double metal hydroxide, crown ether and water, freeze-drying after deposition to obtain a self-assembled solid material, and ball-milling the self-assembled solid material to obtain a potassium ion metal shielding material;

[0026] S2) subjecting the polyester alcoholysis byproduct, the potassium ion metal shielding material, the carboxylic acid organic matter and the ultraviolet light absorber to an esterification reaction, and then to a polymerization reaction to obtain a modified resin.

[0027] The present application provides a method for preparing functional modified asphalt based on alcoholysis by-products, which firstly uses porous boron nitride, layered double metal hydroxides and crown ethers for self-assembly to obtain potassium ion metal shielding materials, then esterifies polyester alcoholysis by-products, potassium ion metal shielding materials, carboxylic acid organic matter and ultraviolet light absorbers, and then performs polymerization reaction to obtain modified resin; then, a grafting agent and a compatibilizer are mixed, heated and reacted to obtain a reactive compatibilizer, and finally, the asphalt is heated to be melted, and the modified resin and the reactive compatibilizer are added to obtain functional modified asphalt after the reaction; in this process, the potassium ion metal shielding material prepared by porous boron nitride, layered double metal hydroxides and crown ethers has a strong potassium ion shielding function, and has good catalytic activity for the polymer reaction of alcoholysis by-products and carboxylic acid organic matter, and at the same time, potassium ions in the modified resin are basically removed, and the introduction of a compatibilizer and an ultraviolet light absorber can improve the performance of the asphalt, and finally the softening point, needle penetration and ductility of the functional modified asphalt prepared by the present application are improved, which can meet the road performance requirements. DETAILED DESCRIPTION

[0028] In order to further understand the present invention, preferred embodiments of the present invention are described below in conjunction with examples. However, it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention, rather than limiting the claims of the present invention.

[0029] In view of the requirements for recycling and utilization of waste polyester alcoholysis byproducts and asphalt performance in the prior art, the present application provides a method for preparing functional modified asphalt based on waste polyester alcoholysis byproducts, which introduces potassium ion metal shielding materials to reduce the end-capping effect of potassium ions on the asphalt reaction system and promote the polymerization reaction of alcoholysis byproducts, and at the same time adds compatibilizers and ultraviolet light absorbers to improve the performance of asphalt. The asphalt finally prepared has the advantages of good storage stability and anti-ultraviolet aging performance, meeting the road performance requirements of asphalt. Specifically, the present invention first discloses a method for preparing functional modified asphalt based on polyester alcoholysis byproducts, comprising the following steps:

[0030] S1) mixing porous boron nitride, layered double metal hydroxide, crown ether and water, freeze-drying after deposition to obtain a self-assembled solid material, and ball-milling the self-assembled solid material to obtain a potassium ion metal shielding material;

[0031] S2) subjecting the polyester alcoholysis byproduct, the potassium ion metal shielding material, the carboxylic acid organic matter and the ultraviolet light absorber to an esterification reaction, and then subjecting the resultant to a polymerization reaction to obtain a modified resin;

[0032] S3) mixing the grafting agent and the compatibilizer, heating and reacting them to obtain a reactive compatibilizer;

[0033] S4) After heating the asphalt until it is melted, a modified resin and a reactive compatibilizer are added, and functional modified asphalt is obtained after the reaction.

[0034] In the preparation method of functional modified asphalt, the present application first mixes porous boron nitride, layered double metal hydroxide, crown ether and water, and freeze-dries after deposition to obtain a self-assembled solid material; in this process, the porous boron nitride is preferably porous boron nitride micropowder, and the layered double metal hydroxide is a hydroxide composed of two or more metal elements and having a hydrotalcite layer and a crystal structure. Specifically, the preparation method of the porous boron nitride includes the following steps:

[0035] A boron source, a nitrogen source, a pore former and water are mixed and heated to obtain a boron nitride precursor;

[0036] The boron nitride precursor is calcined to obtain porous boron nitride.

[0037] In the preparation process of the porous boron nitride, the boron source includes one or more of boric acid, ammonia borane, metaboric acid, boron chloride, boron oxide, boron sulfide and sodium borohydride. Specifically, the boron source is selected from one of boric acid, ammonia borane, metaboric acid, boron chloride, boron oxide, boron sulfide and sodium borohydride. The nitrogen source includes one or more of urea, melamine, sodium azide, dicyandiamide and sodium amide. Specifically, the nitrogen source is selected from one of urea, melamine, sodium azide, dicyandiamide and sodium amide. The pore-forming agent includes one or more of zinc acetate, nickel sulfate, cobalt sulfate, iron sulfate, copper sulfate and zinc sulfate. Specifically, the pore-forming agent is selected from one of zinc acetate, nickel sulfate, cobalt sulfate, iron sulfate, copper sulfate and zinc sulfate. The mass ratio of the boron source to the nitrogen source is 10: (3-8), specifically, the mass ratio of the boron source to the nitrogen source is (1.125-2.00): 1, more specifically, the mass ratio of the boron source to the nitrogen source is (1.25-1.80): 1, more specifically, the mass ratio of the boron source to the nitrogen source is (1.35-1.70): 1, more specifically, the mass ratio of the boron source to the nitrogen source is (1.37-1.60): 1. The mass ratio of the nitrogen source to the pore-forming agent is (15-21): 1, specifically, the mass ratio of the nitrogen source to the pore-forming agent is (18-20): 1. The heating temperature is 80-120° C., specifically, the heating temperature is 95-110° C. The heating is performed to evaporate the water to obtain a white boron nitride (BN) precursor.

[0038] Then the BN precursor is ground and calcined to obtain porous BN powder. In this process, the grinding is a grinding method well known to those skilled in the art and is not particularly limited here; the calcination temperature is 500-1500°C and the time is 3-10 hours; the calcination is carried out under a protective atmosphere, and the protective atmosphere includes one of nitrogen and argon; specifically, the calcination temperature is 700-900°C and the time is 3.5-6 hours, more specifically, the calcination temperature is 750-850°C and the time is 4-5 hours. The present application prepares porous BN powder by combining a pore-forming agent with a calcination process.

[0039] The preparation method of the layered double metal hydroxide comprises the following steps:

[0040] The divalent metal salt, the trivalent metal salt and the alkaline reagent are mixed, subjected to hydrothermal reaction and then freeze-dried to obtain a layered double metal hydroxide.

[0041] In the preparation process of layered double metal hydroxides, in the preparation process of regenerated resin, the present application first prepares layered double metal hydroxides (LDHs), that is, a divalent metal salt, a trivalent metal salt and an alkaline reagent are mixed, and freeze-dried after a hydrothermal reaction to obtain a layered double metal hydroxide (LDHs); in this process, the metal cations in the divalent metal salt include Fe 2+ 、Ni 2+ , Cu 2+ 、Zn 2+ and Mg 2+ Specifically, the metal cation in the divalent metal salt is selected from Fe 2+ 、Ni 2+ , Cu 2+ 、Zn 2+ and Mg 2+ The metal cation in the trivalent metal salt includes Ni 3+ , Fe 3+ 、Al 3+ and Ti 3+ Specifically, the metal salt ion in the trivalent metal salt is selected from Ni 3+ , Fe 3+ 、Al 3+ and Ti 3+ The anions of the divalent metal salt and the trivalent metal salt are independently selected from SO 4 2- 、NO 3 - , CO 3 2- and Cl -Specifically, the anions of the divalent metal salt and the trivalent metal salt are independently selected from SO 4 2- and Cl - One or two of the above. The alkaline reagent includes one of urea, ammonia water and sodium hydroxide. The mass ratio of the divalent metal salt to the trivalent metal salt is (1-5):1. Specifically, the mass ratio of the divalent metal salt to the trivalent metal salt is (1.25-3):1. Specifically, the mass ratio of the divalent metal salt to the trivalent metal salt is (1.3-2.3):1. The ratio of the total mass of the divalent metal salt and the trivalent metal salt to the mass of the alkaline reagent is 1:(0.5-5). Specifically, the ratio of the total mass of the divalent metal salt and the trivalent metal salt to the mass of the alkaline reagent is 1:(0.8-3). Specifically, the ratio of the total mass of the divalent metal salt and the trivalent metal salt to the mass of the alkaline reagent is 1:(0.9-2.3). The reaction temperature is 50-100°C and the time is 10-25h; specifically, the reaction temperature is 60-95°C and the time is 12-20h. The freeze drying time is 10-15 hours. The present application synthesizes layered LDHs by combining hydrothermal method with freeze drying process.

[0042] The crown ether includes one or more of 18-crown-6, dibenzo-18-crown-6, dibenzo-30-crown-10, 15-crown-5 and cyclohexaned-18-crown-6. Specifically, the crown ether is selected from one of 18-crown-6, dibenzo-18-crown-6, N,N,N',N'-tetramethyl-4,4'-diaminodiphenyl-18-crown-6, dibenzo-30-crown-10, 15-crown-5 and cyclohexaned-18-crown-6. The mass ratio of the porous boron nitride, the layered double metal hydroxide and the crown ether is 10:(5~10):(3~8). Specifically, the mass ratio of the porous boron nitride, the layered double metal hydroxide and the crown ether is 10:(6~8):(4~7). The deposition temperature is 20-50°C, the time is 1-5 hours, specifically, the deposition temperature is 30-40°C, the time is 2-4 hours. The freeze-drying time is 20-50 hours, specifically, the freeze-drying time is 30-40 hours.

[0043] The present application then ball-mills the self-assembled solid material to obtain a potassium ion metal shielding material; the mass ratio of the grinding beads of the ball mill is 2.5:10:14:15:55, and the corresponding number ratio is (14-16): (9-11): (4-6): (4-6): (2-4), specifically, the corresponding number ratio is 15:10:5:5:3; the ball milling time is 10-30 hours, the rotation speed is 300-500r / min, specifically, the ball milling time is 15-25 hours, and the rotation speed is 350-400r / min. In the preparation of the potassium ion metal shielding material, the mixing of the raw materials allows the crown ether to be uniformly adsorbed and deposited on the surface of the porous BN and LDHs mixture, ensuring that the initial deposition of the crown ether is fully mixed with each component, and its structure is stabilized by freeze-drying. Finally, the ball milling method is used to add a chemical effect to refine the material particles while enhancing the interfacial bonding between the porous BN, LDHs and the crown ether, so that it has a strong potassium ion shielding function.

[0044] According to the present invention, the polyester alcoholysis byproduct, the potassium ion metal shielding material, the carboxylic acid organic matter and the ultraviolet light absorber are then subjected to an esterification reaction, and then a polymerization reaction is carried out to obtain a modified resin; in this process, the potassium ion metal shielding material is used to remove potassium ions in the polyester alcoholysis byproduct, and the polymerization reaction of the polyester alcoholysis byproduct is promoted. In the present application, the polyester alcoholysis byproduct is preferably a waste polyester alcoholysis byproduct, and the waste polyester alcoholysis byproduct is specifically a byproduct obtained by alcoholysis of waste polyester, ethylene glycol and catalyst potassium carbonate, wherein the waste polyester is selected from one or more of waste polyester fibers, waste polyester plastics and waste polyester films; the alcoholysis reaction is an alcoholysis process well known to those skilled in the art, and will not be described in detail here. The carboxylic acid organic compound includes one or more of terephthalic acid, adipic acid, isophthalic acid, 4-bromophthalic acid, phthalic anhydride, p-hydroxybenzoic acid and succinic acid. Specifically, the carboxylic acid organic compound is selected from one of terephthalic acid, adipic acid, isophthalic acid, 4-bromophthalic acid, phthalic anhydride, p-hydroxybenzoic acid and succinic acid. More specifically, the carboxylic acid organic compound is selected from terephthalic acid. The ultraviolet absorber includes one or more of bisbenzoxazole stilbene, salicylic benzoate, benzotriazole and 2-hydroxy-4-methoxybenzophenone. Specifically, the ultraviolet absorber is selected from one of bisbenzoxazole stilbene, salicylic benzoate, benzotriazole and 2-hydroxy-4-methoxybenzophenone. The mass ratio of the polyester alcoholysis by-product, the potassium ion metal shielding material, the carboxylic acid organic matter and the ultraviolet light absorber is (5-70): (1-15): (1-25): (1-10). Specifically, the mass ratio of the polyester alcoholysis by-product, the potassium ion metal shielding material, the carboxylic acid organic matter and the ultraviolet light absorber is (10-60): (3-10): (5-20): (3-8). More specifically, the mass ratio of the polyester alcoholysis by-product, the potassium ion metal shielding material, the carboxylic acid organic matter and the ultraviolet light absorber is (20-50): (5-8): (8-15): (4-7). In a specific embodiment, the mass ratio of the polyester alcoholysis by-product, the potassium ion metal shielding material, the carboxylic acid organic matter and the ultraviolet light absorber is 70:10:15:5. The temperature of the esterification reaction is 100~250°C, and the time is 2~5h. Specifically, the temperature of the esterification reaction is 135~200°C, and the time is 3~4h. The vacuum degree of the polymerization reaction is 40~100Pa, the temperature is 250~300°C, and the time is 3~10h. Specifically, the vacuum degree of the polymerization reaction is 50~80Pa, the temperature is 260~280°C, and the time is 4~8h.

[0045] In the present application, the preparation of the modified resin is specifically as follows:

[0046] The alcoholysis by-product, potassium ion metal shielding material, carboxylic acid organic matter and ultraviolet light absorber are put into a reactor for esterification reaction, and distilled water and ethylene glycol are cut off from the top of the reactor. After the esterification reaction is completed, the temperature is raised under vacuum conditions with stirring until a polymerization reaction begins, and the temperature is kept until the polymerization reaction is completed to obtain a modified resin.

[0047] According to the present invention, the grafting agent and the compatibilizer are then mixed, heated and reacted to obtain a reactive compatibilizer; in this process, the grafting agent includes maleic anhydride; the compatibilizer includes one or more of 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, polyphenylmethane polyisocyanate and hexamethylene diisocyanate, specifically, the compatibilizer is selected from 2,4' -diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, polyphenylmethane polyisocyanate and hexamethylene diisocyanate. More specifically, the compatibilizer is selected from 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,6-toluene diisocyanate, polyphenylmethane polyisocyanate or hexamethylene diisocyanate. The heating temperature is 50-100°C, and the heating is stirred at the same time. The stirring rate is 200-500r / min for 5-20min; specifically, the heating temperature is 65-85°C, the stirring rate is 250-350r / min for 6-15min. During this process, the maleic anhydride in the grafting agent and the isocyanate in the compatibilizer will react to form an amide bond, and the reactivity and compatibility of the two will be used to improve the binding properties of asphalt and modified polyester.

[0048] The present application finally heats the asphalt until it is melted, then adds the modified resin and the reactive compatibilizer, and obtains the functional modified asphalt after the reaction; in this process, the melting temperature is 150-300°C, specifically, the melting temperature is 180-240°C; the reaction is carried out under stirring conditions, the stirring rate is 1500-5000r / min, the time is 30-120min, specifically, the stirring rate is 1800-3200r / min, and the time is 50-70min. In the preparation process of functional modified asphalt, the modified resin does not contain residual potassium carbonate, and the polyester alcoholysis by-product is introduced into the preparation of functional modified asphalt, realizing the reuse of alcoholysis by-products while ensuring the performance of asphalt.

[0049] Furthermore, the present application also provides a functional modified asphalt, which is prepared from a grafting agent, a compatibilizer, asphalt and a modified resin;

[0050] The preparation method of the modified resin comprises the following steps:

[0051] S1) mixing porous boron nitride, layered double metal hydroxide, crown ether and water, freeze-drying after deposition to obtain a self-assembled solid material, and ball-milling the self-assembled solid material to obtain a potassium ion metal shielding material;

[0052] S2) subjecting the polyester alcoholysis byproduct, the potassium ion metal shielding material, the carboxylic acid organic matter and the ultraviolet light absorber to an esterification reaction, and then to a polymerization reaction to obtain a modified resin.

[0053] The preparation method of the functional modified asphalt provided in the present application first prepares a potassium ion metal shielding material, which not only has a strong potassium ion shielding function, but also has good catalytic activity for the polymerization reaction of depolymerization by-products and carboxylic acid organic matter. This catalytic applicability makes the material show great application potential in promoting the recycling of waste polyester by-products, which can effectively improve the recycling rate of by-products and reduce solid waste accumulation. The alcoholysis by-product modified asphalt of the present invention creatively uses alcoholysis by-products and asphalt as main raw materials, which can not only effectively realize the recycling of by-products after depolymerization, but also improve the use performance of asphalt, thereby promoting the green resource utilization of waste polyester.

[0054] In order to further understand the present invention, the method for preparing functional modified asphalt based on alcoholysis by-products provided by the present invention is described in detail below in conjunction with examples, and the protection scope of the present invention is not limited by the following examples.

[0055] Example 1

[0056] This embodiment provides a method for preparing functional modified asphalt based on alcoholysis byproducts, comprising the following raw materials: asphalt, alcoholysis byproducts, porous BN powder, layered MgAl-LDHs, 18-crown-6, maleic anhydride, 2,4'-diphenylmethane diisocyanate, terephthalic acid and bisbenzoxazole diphenylethylene, and the preparation method comprises the following steps:

[0057] (1) Porous BN powder, layered MgAl-LDHs and 18-crown-6 were mixed and dispersed in ultrapure water at a mass ratio of 10:5:3. The mixed dispersion was subjected to ultrasonic dispersion treatment for 40 min and then placed in a 30°C constant temperature shaker for hydrothermal shaking precipitation for 4 h. The mixture was then freeze-dried for 30 h to obtain a self-assembled solid powder material. The obtained solid powder material was placed in a ball mill and ball-milled at a speed of 400 r / min for 15 h to obtain a potassium ion metal shielding material.

[0058] (2) The alcoholysis byproduct, potassium ion metal shielding material, terephthalic acid and dibenzoxazole diphenylethylene were transported to the transesterification reactor at a mass ratio of 70:10:15:5, slowly stirred and heated to 135 °C under a nitrogen environment to carry out the transesterification reaction, during which water and ethylene glycol were continuously distilled off; after the esterification reaction for 3 hours, the temperature was raised to 250 °C for vacuum pre-condensation, and ethylene glycol was distilled off at the same time. After a period of reaction, the temperature was raised to 280 °C, and polymerization and viscosity enhancement were carried out for 4.5 hours. Finally, after extrusion, cooling and crystallization, the modified resin system A was obtained;

[0059] (3) 2,4'-diphenylmethane diisocyanate and maleic anhydride were mixed in a mass ratio of 100:5, heated to 70 °C and kept at a constant temperature, and stirred at 300 r / min for 10 min to obtain a reactive compatibilizer; petroleum asphalt was first heated to 180 °C to melt, and then system A and reactive compatibilizer were added, stirred at a rate of 1800 r / min~3200 r / min for 60 min, and cooled at room temperature to obtain functional modified asphalt.

[0060] Example 2

[0061] This embodiment provides a method for preparing functional modified asphalt based on alcoholysis byproducts, comprising the following raw materials: asphalt, alcoholysis byproducts, porous BN powder, layered MgAl-LDHs, 18-crown-6, maleic anhydride, 2,4'-diphenylmethane diisocyanate, terephthalic acid and salicylic benzoate, and the preparation method comprises the following steps:

[0062] (1) Porous BN powder, layered MgAl-LDHs and 18-crown-6 were mixed and dispersed in ultrapure water at a mass ratio of 10:5:3. The mixed dispersion was subjected to ultrasonic dispersion treatment for 40 min and then placed in a 30°C constant temperature shaker for hydrothermal shaking precipitation for 4 h. The mixture was then freeze-dried for 30 h to obtain a self-assembled solid powder material. The obtained solid powder material was placed in a ball mill and ball-milled at a speed of 400 r / min for 15 h to obtain a potassium ion metal shielding material.

[0063] (2) The alcoholysis byproduct, potassium ion metal shielding material, terephthalic acid and salicylic benzoate were transported to the transesterification reactor in a mass ratio of 70:10:15:5, slowly stirred and heated to 135 °C under a nitrogen environment to carry out the transesterification reaction, during which water and ethylene glycol were continuously distilled off; after the esterification reaction for 3 hours, the temperature was raised to 250 °C for vacuum pre-condensation, and ethylene glycol was distilled off at the same time. After a period of reaction, the temperature was raised to 280 °C, and polymerization and viscosity enhancement were carried out for 4.5 hours. Finally, after extrusion, cooling and crystallization, the modified resin system A was obtained;

[0064] (3) 2,4'-diphenylmethane diisocyanate and maleic anhydride were mixed in a mass ratio of 100:5, heated to 70 °C and kept at a constant temperature, and stirred at 300 r / min for 10 min to obtain a reactive compatibilizer; petroleum asphalt was first heated to 180 °C to melt, and then system A and reactive compatibilizer were added, stirred at a rate of 1800 r / min~3200 r / min for 60 min, and cooled at room temperature to obtain functional modified asphalt.

[0065] Example 3

[0066] This embodiment provides a method for preparing functional modified asphalt based on alcoholysis byproducts, comprising the following raw materials: asphalt, alcoholysis byproducts, porous BN powder, layered MgAl-LDHs, 18-crown-6, maleic anhydride, 2,4'-diphenylmethane diisocyanate, terephthalic acid and benzotriazole, and the preparation method comprises the following steps:

[0067] (1) Porous BN powder, layered MgAl-LDHs and 18-crown-6 were mixed and dispersed in ultrapure water at a mass ratio of 10:5:3. The mixed dispersion was subjected to ultrasonic dispersion treatment for 40 min and then placed in a 30 ℃ constant temperature shaker for hydrothermal shaking precipitation for 4 h. The mixture was then freeze-dried for 30 h to obtain a self-assembled solid powder material. The obtained solid powder material was placed in a ball mill and ball-milled at 400 r / min for 15 h to obtain a potassium ion metal shielding material.

[0068] (2) The alcoholysis byproduct, potassium ion metal shielding material, terephthalic acid and benzotriazole were transported to the transesterification reactor at a mass ratio of 70:10:15:5, slowly stirred and heated to 135 °C under a nitrogen environment to carry out the transesterification reaction, during which water and ethylene glycol were continuously distilled off; after the esterification reaction for 3 hours, the temperature was raised to 250 °C for vacuum pre-condensation, and ethylene glycol was distilled off at the same time. After a period of reaction, the temperature was raised to 280 °C, and polymerization and viscosity enhancement were carried out for 4.5 hours. Finally, after extrusion, cooling and crystallization, the modified resin system A was obtained;

[0069] (3) 2,4'-diphenylmethane diisocyanate and maleic anhydride were mixed in a mass ratio of 100:5, heated to 70 °C and kept at a constant temperature, and stirred at 300 r / min for 10 min to obtain a reactive compatibilizer; petroleum asphalt was first heated to 180 °C to melt, and then system A and reactive compatibilizer were added, stirred at a rate of 1800 r / min~3200 r / min for 60 min, and cooled at room temperature to obtain functional modified asphalt.

[0070] Example 4

[0071] This embodiment provides a method for preparing functional modified asphalt based on alcoholysis byproducts, comprising the following raw materials: asphalt, alcoholysis byproducts, porous BN powder, layered MgAl-LDHs, dibenzo-18-crown-6, maleic anhydride, 2,4'-diphenylmethane diisocyanate, terephthalic acid and 2-hydroxy-4-methoxybenzophenone, and the preparation method comprises the following steps:

[0072] (1) Porous BN powder, layered MgAl-LDHs and dibenzo-18-crown-6 were mixed and dispersed in ultrapure water at a mass ratio of 10:5:3. The mixed dispersion was subjected to ultrasonic dispersion treatment for 40 min and then placed in a 30 ℃ constant temperature shaker for hydrothermal shaking precipitation for 4 h. The mixture was then freeze-dried for 30 h to obtain a self-assembled solid powder material. The obtained solid powder material was placed in a ball mill and ball-milled at 400 r / min for 15 h to obtain a potassium ion metal shielding material.

[0073] (2) The alcoholysis byproduct, potassium ion metal shielding material, terephthalic acid and 2-hydroxy-4-methoxybenzophenone were transported to the transesterification reactor at a mass ratio of 70:10:15:5, slowly stirred and heated to 135°C under a nitrogen environment to carry out the transesterification reaction, during which water and ethylene glycol were continuously distilled off; after the esterification reaction for 3 hours, the temperature was raised to 250°C for vacuum pre-condensation, and ethylene glycol was distilled off at the same time. After a period of reaction, the temperature was raised to 280°C, and polymerization and viscosity enhancement were carried out for 4.5 hours. Finally, after extrusion, cooling and crystallization, the modified resin system A was obtained;

[0074] (3) 2,4'-diphenylmethane diisocyanate and maleic anhydride were mixed in a mass ratio of 100:5, heated to 70 °C and kept at a constant temperature, and stirred at 300 r / min for 10 min to obtain a reactive compatibilizer; petroleum asphalt was first heated to 180 °C to melt, and then system A and reactive compatibilizer were added, stirred at a rate of 1800 r / min-3200 r / min for 60 min, and cooled at room temperature to obtain functional modified asphalt.

[0075] Example 5

[0076] This embodiment provides a method for preparing functional modified asphalt based on alcoholysis byproducts, comprising the following raw materials: asphalt, alcoholysis byproducts, porous BN powder, layered MgAl-LDHs, dibenzo-18-crown-6, maleic anhydride, 2,2'-diphenylmethane diisocyanate, terephthalic acid and bisbenzoxazole diphenylethylene, and the preparation method comprises the following steps:

[0077] (1) Porous BN powder, layered MgAl-LDHs and dibenzo-18-crown-6 were mixed and dispersed in ultrapure water at a mass ratio of 10:5:3. The mixed dispersion was subjected to ultrasonic dispersion treatment for 40 min and then placed in a 30 ℃ constant temperature shaker for hydrothermal shaking precipitation for 4 h. The mixture was then freeze-dried for 30 h to obtain a self-assembled solid powder material. The obtained solid powder material was placed in a ball mill and ball-milled at 400 r / min for 15 h to obtain a potassium ion metal shielding material.

[0078] (2) The alcoholysis byproduct, potassium ion metal shielding material, terephthalic acid and dibenzoxazole diphenylethylene were transported to the transesterification reactor at a mass ratio of 70:10:15:5, slowly stirred and heated to 135 °C under a nitrogen environment to carry out the transesterification reaction, during which water and ethylene glycol were continuously distilled off; after the esterification reaction for 3 hours, the temperature was raised to 250 °C for vacuum pre-condensation, and ethylene glycol was distilled off at the same time. After a period of reaction, the temperature was raised to 280 °C, and polymerization and viscosity enhancement were carried out for 4.5 hours. Finally, after extrusion, cooling and crystallization, the modified resin system A was obtained;

[0079] (3) 2,2'-diphenylmethane diisocyanate and maleic anhydride were mixed in a mass ratio of 100:5, heated to 70 °C and kept at a constant temperature, and stirred at 300 r / min for 10 min to obtain a reactive compatibilizer; petroleum asphalt was first heated to 180 °C to melt, and then system A and reactive compatibilizer were added, stirred at a rate of 1800 r / min-3200 r / min for 60 min, and cooled at room temperature to obtain functional modified asphalt.

[0080] Example 6

[0081] This embodiment provides a method for preparing functional modified asphalt based on alcoholysis byproducts, comprising the following raw materials: asphalt, alcoholysis byproducts, porous BN powder, layered MgAl-LDHs, 18-crown-6, maleic anhydride, 2,4-toluene diisocyanate, terephthalic acid and bisbenzoxazole diphenylethylene, and the preparation method thereof comprises the following steps:

[0082] (1) Porous BN powder, layered MgAl-LDHs and 18-crown-6 were mixed and dispersed in ultrapure water at a mass ratio of 10:5:3. The mixed dispersion was subjected to ultrasonic dispersion treatment for 40 min and then placed in a 30 ℃ constant temperature shaker for hydrothermal shaking precipitation for 4 h. The mixture was then freeze-dried for 30 h to obtain a self-assembled solid powder material. The obtained solid powder material was placed in a ball mill and ball-milled at 400 r / min for 15 h to obtain a potassium ion metal shielding material.

[0083] (2) The alcoholysis byproduct, potassium ion metal shielding material, terephthalic acid and dibenzoxazole diphenylethylene were transported to the transesterification reactor at a mass ratio of 70:10:15:5, slowly stirred and heated to 135 °C under a nitrogen environment for transesterification reaction, during which water and ethylene glycol were continuously distilled off; after esterification reaction for 3 hours, the temperature was raised to 250 °C for vacuum pre-condensation, and ethylene glycol was distilled off at the same time. After a period of reaction, the temperature was raised to 280 °C, and polymerization and viscosity enhancement were carried out for 4.5 hours. Finally, after extrusion, cooling and crystallization, the modified resin system A was obtained;

[0084] (3) 2,4-Toluene diisocyanate and maleic anhydride were mixed in a mass ratio of 100:5, heated to 70 °C and kept at a constant temperature, and stirred at 300 r / min for 10 min to obtain a reactive compatibilizer; petroleum asphalt was first heated to 180 °C to melt, and then system A and reactive compatibilizer were added, stirred at a rate of 1800 r / min-3200 r / min for 60 min, and cooled at room temperature to obtain functional modified asphalt.

[0085] Example 7

[0086] This embodiment provides a method for preparing functional modified asphalt based on alcoholysis byproducts, comprising the following raw materials: asphalt, alcoholysis byproducts, porous BN powder, layered MgAl-LDHs, dibenzo-30-crown-10, maleic anhydride, 2,6-toluene diisocyanate, terephthalic acid and bisbenzoxazole diphenylethylene, and the preparation method comprises the following steps:

[0087] (1) Porous BN powder, layered MgAl-LDHs and dibenzo-30-crown-10 were mixed and dispersed in ultrapure water at a mass ratio of 10:5:3. The mixed dispersion was subjected to ultrasonic dispersion treatment for 40 min and then placed in a 30 ℃ constant temperature shaker for hydrothermal shaking precipitation for 4 h. The mixture was then freeze-dried for 30 h to obtain a self-assembled solid powder material. The obtained solid powder material was placed in a ball mill and ball-milled at 400 r / min for 15 h to obtain a potassium ion metal shielding material.

[0088] (2) The alcoholysis byproduct, potassium ion metal shielding material, terephthalic acid and dibenzoxazole diphenylethylene were transported to the transesterification reactor at a mass ratio of 70:10:15:5, slowly stirred and heated to 135 °C under a nitrogen environment to carry out the transesterification reaction, during which water and ethylene glycol were continuously distilled off; after the esterification reaction for 3 hours, the temperature was raised to 250 °C for vacuum pre-condensation, and ethylene glycol was distilled off at the same time. After a period of reaction, the temperature was raised to 280 °C, and polymerization and viscosity enhancement were carried out for 4.5 hours. Finally, after extrusion, cooling and crystallization, the modified resin system A was obtained;

[0089] (3) Mix 2,6-toluene diisocyanate and maleic anhydride in a mass ratio of 100:5, heat to 70 °C and keep the temperature constant, and stir at 300 r / min for 10 min to obtain a reactive compatibilizer. Add asphalt, system A and reactive compatibilizer in a mass ratio of 100:60:10. First, heat petroleum asphalt to 180 °C to melt, then add system A and reactive compatibilizer, stir at 1800 r / min~3200 r / min for 60 min, and cool at room temperature to obtain functional modified asphalt.

[0090] Example 8

[0091] This embodiment provides a method for preparing functional modified asphalt based on alcoholysis byproducts, comprising the following raw materials: asphalt, alcoholysis byproducts, porous BN powder, layered MgAl-LDHs, 15-crown-5, maleic anhydride, polyphenylmethane polyisocyanate, terephthalic acid and bisbenzoxazole diphenylethylene, and the preparation method thereof comprises the following steps:

[0092] (1) Porous BN powder, layered MgAl-LDHs and 15-crown-5 were mixed and dispersed in ultrapure water at a mass ratio of 10:5:3. The mixed dispersion was subjected to ultrasonic dispersion treatment for 40 min and then placed in a 30 ℃ constant temperature shaker for hydrothermal shaking precipitation for 4 h. The mixture was then freeze-dried for 30 h to obtain a self-assembled solid powder material. The obtained solid powder material was placed in a ball mill and ball-milled at 400 r / min for 15 h to obtain a potassium ion metal shielding material.

[0093] (2) The alcoholysis byproduct, potassium ion metal shielding material, terephthalic acid and dibenzoxazole diphenylethylene were transported to the transesterification reactor at a mass ratio of 70:10:15:5, slowly stirred and heated to 135 °C under a nitrogen environment to carry out the transesterification reaction, during which water and ethylene glycol were continuously distilled off; after the esterification reaction for 3 hours, the temperature was raised to 250 °C for vacuum pre-condensation, and ethylene glycol was distilled off at the same time. After a period of reaction, the temperature was raised to 280 °C, and polymerization and viscosity enhancement were carried out for 4.5 hours. Finally, after extrusion, cooling and crystallization, the modified resin system A was obtained;

[0094] (3) Polyphenylmethane polyisocyanate and maleic anhydride were mixed in a mass ratio of 100:5, heated to 70 °C and kept at a constant temperature, and stirred at 300 r / min for 10 min to obtain a reactive compatibilizer. The asphalt, system A and reactive compatibilizer were added in a mass ratio of 100:60:10. First, the petroleum asphalt was heated to 180 °C to melt, and then the system A and reactive compatibilizer were added. The mixture was stirred at a rate of 1800 r / min-3200 r / min for 60 min and cooled at room temperature to obtain a functional modified asphalt.

[0095] Example 9

[0096] This embodiment provides a method for preparing functional modified asphalt based on alcoholysis byproducts, comprising the following raw materials: asphalt, alcoholysis byproducts, porous BN powder, layered MgAl-LDHs, 15-crown-5, maleic anhydride, hexamethylene diisocyanate, terephthalic acid and bisbenzoxazole diphenylethylene, and the preparation method comprises the following steps:

[0097] (1) Porous BN powder, layered MgAl-LDHs and 15-crown-5 were mixed and dispersed in ultrapure water at a mass ratio of 10:5:3. The mixed dispersion was subjected to ultrasonic dispersion treatment for 40 min and then placed in a 30 ℃ constant temperature shaker for hydrothermal shaking precipitation for 4 h. The mixture was then freeze-dried for 30 h to obtain a self-assembled solid powder material. The obtained solid powder material was placed in a ball mill and ball-milled at 400 r / min for 15 h to obtain a potassium ion metal shielding material.

[0098] (2) The alcoholysis byproduct, potassium ion metal shielding material, terephthalic acid and dibenzoxazole diphenylethylene were transported to the transesterification reactor at a mass ratio of 70:10:15:5, slowly stirred and heated to 135 °C under a nitrogen environment to carry out the transesterification reaction, during which water and ethylene glycol were continuously distilled off; after the esterification reaction for 3 hours, the temperature was raised to 250 °C for vacuum pre-condensation, and ethylene glycol was distilled off at the same time. After a period of reaction, the temperature was raised to 280 °C, and polymerization and viscosity enhancement were carried out for 4.5 hours. Finally, after extrusion, cooling and crystallization, the modified resin system A was obtained;

[0099] (3) Hexamethylene diisocyanate and maleic anhydride were mixed in a mass ratio of 100:5, heated to 70 °C and kept at a constant temperature, and stirred at 300 r / min for 10 min to obtain a reactive compatibilizer. The asphalt, system A and reactive compatibilizer were added in a mass ratio of 100:60:10. First, the petroleum asphalt was heated to 180 °C to melt, and then the system A and reactive compatibilizer were added. The mixture was stirred at a rate of 1800 r / min-3200 r / min for 60 min and cooled at room temperature to obtain a functional modified asphalt.

[0100] Example 10

[0101] This embodiment provides a method for preparing functional modified asphalt based on alcoholysis byproducts, comprising the following raw materials: asphalt, alcoholysis byproducts, porous BN powder, layered MgAl-LDHs, cyclohexanedio-18-crown-6, maleic anhydride, 2,4'-diphenylmethane diisocyanate, terephthalic acid and bisbenzoxazole diphenylethylene, and the preparation method comprises the following steps:

[0102] (1) Porous BN powder, layered MgAl-LDHs and cyclohexane-18-crown-6 were mixed and dispersed in ultrapure water at a mass ratio of 10:5:3. The mixed dispersion was subjected to ultrasonic dispersion treatment for 40 min and then placed in a 30 ℃ constant temperature shaker for hydrothermal shaking precipitation for 4 h. The mixture was then freeze-dried for 30 h to obtain a self-assembled solid powder material. The obtained solid powder material was placed in a ball mill and ball-milled at 400 r / min for 15 h to obtain a potassium ion metal shielding material.

[0103] (2) The alcoholysis byproduct, potassium ion metal shielding material, terephthalic acid and dibenzoxazole diphenylethylene were transported to the transesterification reactor at a mass ratio of 60:10:20:10, slowly stirred and heated to 135 °C under a nitrogen environment to carry out the transesterification reaction, during which water and ethylene glycol were continuously distilled off; after the esterification reaction for 3 hours, the temperature was raised to 250 °C for vacuum pre-condensation, and ethylene glycol was distilled off at the same time. After a period of reaction, the temperature was raised to 280 °C, and polymerization and viscosity enhancement were carried out for 4.5 hours. Finally, after extrusion, cooling and crystallization, the modified resin system A was obtained;

[0104] (3) 2,4'-diphenylmethane diisocyanate and maleic anhydride were mixed in a mass ratio of 100:5, heated to 70 °C and kept at a constant temperature, and stirred at 300 r / min for 10 min to obtain a reactive compatibilizer. The asphalt, system A and reactive compatibilizer were added in a mass ratio of 100:60:10. First, petroleum asphalt was heated to 180 °C to melt, and then system A and reactive compatibilizer were added. The mixture was stirred at a rate of 1800 r / min-3200 r / min for 60 min and cooled at room temperature to obtain functional modified asphalt.

[0105] Comparative Example 1

[0106] This comparative example provides a method for preparing functional modified asphalt based on alcoholysis byproducts, comprising the following raw materials: asphalt, alcoholysis byproducts, porous BN powder, layered MgAl-LDHs, 18-crown-6, terephthalic acid and bisbenzoxazole diphenylethylene, and the preparation method thereof comprises the following steps:

[0107] (1) Porous BN powder, layered MgAl-LDHs and 18-crown-6 were mixed and dispersed in ultrapure water at a mass ratio of 10:5:3. The mixed dispersion was subjected to ultrasonic dispersion treatment for 40 min and then placed in a 30 ℃ constant temperature shaker for hydrothermal shaking precipitation for 4 h. The mixture was then freeze-dried for 30 h to obtain a self-assembled solid powder material. The obtained solid powder material was placed in a ball mill and ball-milled at 400 r / min for 15 h to obtain a potassium ion metal shielding material.

[0108] (2) The alcoholysis byproduct, potassium ion metal shielding material, terephthalic acid and dibenzoxazole diphenylethylene were transported to the transesterification reactor at a mass ratio of 70:10:15:5, slowly stirred and heated to 135 °C under a nitrogen environment to carry out the transesterification reaction, during which water and ethylene glycol were continuously distilled off; after the esterification reaction for 3 hours, the temperature was raised to 250 °C for vacuum pre-condensation, and ethylene glycol was distilled off at the same time. After a period of reaction, the temperature was raised to 280 °C, and polymerization and viscosity enhancement were carried out for 4.5 hours. Finally, after extrusion, cooling and crystallization, the modified resin system A was obtained;

[0109] (3) The asphalt and system A were added in a mass ratio of 100:60. The petroleum asphalt was first heated to 180 °C to melt, and then system A was added. The mixture was stirred at a rate of 2400 r / min for 60 min and cooled at room temperature to obtain functional modified asphalt.

[0110] Comparative Example 2

[0111] This comparative example provides a method for preparing functional modified asphalt based on alcoholysis byproducts, comprising the following raw materials: asphalt, alcoholysis byproducts, maleic anhydride, 2,4'-diphenylmethane diisocyanate, terephthalic acid and bisbenzoxazole diphenylethylene, and the preparation method thereof comprises the following steps:

[0112] (1) The alcoholysis byproduct, terephthalic acid and dibenzoxazole diphenylethylene were transported to the transesterification reactor at a mass ratio of 70:15:5, slowly stirred and heated to 135 °C under a nitrogen environment to carry out the transesterification reaction, during which water and ethylene glycol were continuously distilled off; after the esterification reaction for 3 hours, the temperature was raised to 250 °C for vacuum pre-condensation, and ethylene glycol was distilled off at the same time. After a period of reaction, the temperature was raised to 280 °C, and polymerization and viscosity enhancement were carried out for 4.5 hours. Finally, after extrusion, cooling and crystallization, the modified resin system A was obtained;

[0113] (2) 2,4'-diphenylmethane diisocyanate and maleic anhydride were mixed in a mass ratio of 100:5, heated to 70 °C and kept at a constant temperature, and stirred at 300 r / min for 10 min to obtain a reactive compatibilizer; asphalt, system A and reactive compatibilizer were added in a mass ratio of 100:60:10. First, the oil asphalt was heated to 180 °C to melt, and then system A and reactive compatibilizer were added. The mixture was stirred at 2400 r / min for 60 min and cooled at room temperature to obtain functional modified asphalt.

[0114] The functional modified asphalt prepared in the above examples and comparative examples was characterized. Table 1 shows the performance results of the functional modified asphalt prepared in the examples and comparative examples of the present invention. The test method is as follows:

[0115] Penetration measurement: Tested according to GB / T2408-2008 standard, where the specific test conditions are: preheat the asphalt sample to 150~160 ℃, pour it into the container of the penetrometer, wait for a thin film to appear on the surface of the sample, insert the needle into the sample completely, hold for 5 seconds, and record the distance the needle descends;

[0116] Softening point measurement: Tested according to GB / T2408-2008 standard, where the specific test conditions are: put about 5 grams of asphalt sample into a conical cup, put the measuring cup into the softening point tester, and record the temperature value after the temperature stabilizes. Turn on the softening point tester heater and heat at a rate of 5°C per minute until the asphalt sample begins to soften; when the asphalt sample begins to soften, insert the thermometer into the measuring cup and observe the temperature value at which the asphalt sample begins to drop and touch the glass needle, which is the softening point; record the softening point temperature value, and perform necessary data processing and recording;

[0117] Elongation measurement: According to GB / T2408-2008 standard test, the specific test conditions are: the diameter of the sample is 25 mm, the height is 10 mm, the stretching speed for measuring the elongation is 5 cm / min, and the temperature during stretching is 5 ℃;

[0118] Ultraviolet radiation aging test: The asphalt material to be tested is made into a sample with a length of 20 cm × a width of 20 cm and a thickness of 3 cm, and placed in an ultraviolet radiation test box with a temperature range of 20-50 °C and a power of 300 W / m 2 The type of ultraviolet light is UV-B. After 500 h of ultraviolet radiation, the samples are taken out. The penetration, elongation and softening point of the aged samples are tested again to evaluate the anti-ultraviolet aging performance of asphalt.

[0119] Table 1 Test results of functional modified asphalt materials prepared in Examples and Comparative Examples

[0120]

[0121] From the above results, it can be seen that the functional modified asphalt prepared based on the alcoholysis product by selecting the formula of the present invention has excellent performance, and with the addition of potassium ion metal shielding material, the softening point, needle penetration and ductility properties are all improved, and the anti-ultraviolet aging ability is excellent.

[0122] The above embodiments are only used to help understand the method and core idea of ​​the present invention. It should be noted that, for those skilled in the art, several improvements and modifications can be made to the present invention without departing from the principles of the present invention, and these improvements and modifications also fall within the scope of protection of the claims of the present invention.

[0123] The above description of the disclosed embodiments enables one skilled in the art to implement or use the present invention. Various modifications to these embodiments will be apparent to one skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown herein, but rather to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A method for preparing functional modified asphalt based on polyester alcoholysis byproducts, comprising the following steps: S1) mixing porous boron nitride, layered double metal hydroxide, crown ether and water, freeze-drying after deposition to obtain a self-assembled solid material, and ball-milling the self-assembled solid material to obtain a potassium ion metal shielding material; S2) subjecting the polyester alcoholysis byproduct, the potassium ion metal shielding material, the carboxylic acid organic matter and the ultraviolet light absorber to an esterification reaction, and then subjecting the resultant to a polymerization reaction to obtain a modified resin; S3) mixing the grafting agent and the compatibilizer, heating and reacting them to obtain a reactive compatibilizer; S4) After heating the asphalt until it is melted, a modified resin and a reactive compatibilizer are added, and functional modified asphalt is obtained after the reaction.

2. The method according to claim 1, characterized in that In step S1), the mass ratio of the porous boron nitride, the layered double hydroxide and the crown ether is 10:(5-10):(3-8).

3. The method according to claim 1, characterized in that: The crown ether includes one or more of 18-crown-6, dibenzo-18-crown-6, dibenzo-30-crown-10, 15-crown-5 and cyclohexane-18-crown-6; and / or, the carboxylic acid organic substance includes one or more of terephthalic acid, adipic acid, isophthalic acid, 4-bromophthalic acid, phthalic anhydride, p-hydroxybenzoic acid and succinic acid; and / or, the ultraviolet absorber includes one or more of bisbenzoxazole stilbene, salicylic benzoate, benzotriazole and 2-hydroxy-4-methoxybenzophenone.

4. The method according to claim 1, characterized in that: In step S1), the mass ratio of the grinding beads in the ball mill is 2.5:10:14:15:55, and the corresponding quantity ratio is (14-16):(9-11):(4-6):(4-6):(2-4); the ball milling time is 10-30 hours, and the rotation speed is 300-500 r / min.

5. The method according to claim 1, characterized in that: In step S2), the mass ratio of the polyester alcoholysis by-product, the potassium ion metal shielding material, the carboxylic acid organic matter and the ultraviolet light absorber is (5-70): (1-15): (1-25): (1-10); and / or the temperature of the esterification reaction is 100-250°C and the time is 2-5h; and / or the vacuum degree of the polymerization reaction is 40-100 Pa, the temperature is 250-300°C, and the time is 3-10h.

6. The method according to claim 1, characterized in that The grafting agent includes maleic anhydride, the compatibilizer includes one or more of 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, polyphenylmethane polyisocyanate and hexamethylene diisocyanate, and the asphalt includes one or more of petroleum asphalt, coal asphalt and rock asphalt; and / or, the mass ratio of the compatibilizer and the grafting agent is 100: (5~25); and / or, the mass ratio of the asphalt, the modified resin and the reactive compatibilizer is 100: (5~70): (1~20).

7. The method according to claim 1, characterized in that In step S3), the heating temperature is 50-100° C., stirring is performed while heating, the stirring rate is 200-500 r / min, and the time is 5-20 min.

8. The method according to claim 1, characterized in that: In step S4), the reaction is carried out under stirring conditions, the stirring rate is 1500-5000 r / min, and the time is 30-120 min.

9. The method according to any one of claims 1 to 8, characterized in that: The preparation method of the porous boron nitride is specifically as follows: A boron source, a nitrogen source, a pore former and water are mixed and heated to obtain a boron nitride precursor; calcining the boron nitride precursor to obtain porous boron nitride; And / or, the preparation method of the layered double metal hydroxide is specifically: The divalent metal salt, the trivalent metal salt and the alkaline reagent are mixed, subjected to hydrothermal reaction and then freeze-dried to obtain a layered double metal hydroxide.

10. A functional modified asphalt prepared from a grafting agent, a compatibilizer, asphalt and a modified resin; The preparation method of the functional modified asphalt comprises the following steps: S1) mixing porous boron nitride, layered double metal hydroxide, crown ether and water, freeze-drying after deposition to obtain a self-assembled solid material, and ball-milling the self-assembled solid material to obtain a potassium ion metal shielding material; S2) subjecting the polyester alcoholysis byproduct, the potassium ion metal shielding material, the carboxylic acid organic matter and the ultraviolet light absorber to an esterification reaction, and then subjecting the resultant to a polymerization reaction to obtain a modified resin; S3) mixing the grafting agent and the compatibilizer, heating and reacting them to obtain a reactive compatibilizer; S4) After heating the asphalt until it is melted, a modified resin and a reactive compatibilizer are added, and functional modified asphalt is obtained after the reaction.

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