An anti-aging organophosphate zirconium / polymer modified asphalt and its preparation method

Abstract

The present invention discloses an anti-aging organophosphoric acid zirconium / polymer modified asphalt and its preparation method. The raw materials of the anti-aging organophosphoric acid zirconium / polymer modified asphalt include organophosphoric acid zirconium, polymer modifier, matrix asphalt, solubilizer and sulfur. Compared with traditional polymer modified asphalt, the anti-aging organophosphoric acid zirconium / polymer modified asphalt of the present invention uses organophosphoric acid zirconium as a cross-linking agent to participate in the formation of the polymer cross-linking network, obtaining a novel zirconium phosphate-polymer cross-linking network. The addition of organophosphoric acid zirconium increases the density of the polymer cross-linking network and alleviates the segregation problem of modified asphalt caused by the relatively low density of traditional polymers. At the same time, this novel network structure enables the uniform dispersion of zirconium phosphate in asphalt, avoiding the agglomeration phenomenon of inorganic particles. In addition, the layered-structured zirconium phosphate is uniformly dispersed in the modified asphalt, which can reduce the oxidation of organic molecules in asphalt and thus improve the anti-aging performance of asphalt.

Description

Technical Field

[0001] The present invention relates to the technical field of building material preparation, and particularly relates to an anti-aging organophosphorus zirconate / polymer modified asphalt and a preparation method thereof. Background Art

[0002] Polymer modified asphalt has been more and more widely used in road engineering due to its excellent performance. However, the polymer modified asphalt pavement is prone to aging during service, resulting in a decline in its performance. The aged material will cause pavement problems such as loosening, peeling, cracking, potholes, etc., which seriously affect the service performance and driving safety of the polymer modified asphalt pavement, significantly increasing the pavement maintenance cost and reducing the service life of the pavement. In addition, the small density of the polymer makes the traditional polymer modified asphalt prone to segregation, which seriously affects the storage stability of the polymer modified asphalt. Therefore, the research and development of anti-aging polymer modified asphalt materials with good storage stability has extremely important engineering significance for building high-quality and long-life pavements.

[0003] Adding anti-aging agents is an important way to improve the anti-aging performance of asphalt. Adding UV531, alkaline lignin, carbon black, inorganic nanomaterials, layered double hydroxides, etc. to polymer modified asphalt can improve the anti-aging ability of polymer modified asphalt. In order to improve the modification effect of inorganic nanomaterials and layered double hydroxides, surface modification is also carried out on them. In recent years, the research on inorganic nanomaterials, layered double hydroxides, or surface modification products of both as asphalt anti-aging agents has received more and more attention. However, in the prior art, inorganic nanomaterials, layered double hydroxides, or surface modification products of both are simply physically blended with polymer modifiers and asphalt. The modified asphalt prepared in this way still has some problems. For example, the polymer modifier will segregate from the asphalt due to its low density, and surface modification cannot completely solve the agglomeration phenomenon of inorganic nanomaterials and layered double hydroxides, which will lead to poor storage stability of the modified asphalt. The agglomeration phenomenon of inorganic nanomaterials and layered double hydroxides will affect the improvement of the anti-aging performance of asphalt.

[0004] Combined with the research status of polymer modified asphalt, the present invention proposes a new idea for preparing anti-aging polymer modified asphalt with good storage stability. Summary of the Invention

[0005] The purpose of the present invention is to provide an anti-aging organophosphorus zirconate / polymer modified asphalt and a preparation method thereof to solve the problems existing in the above prior art.

[0006] To achieve the above purpose, the present invention provides the following solutions:

[0007] One of the technical solutions of the present invention: an aging-resistant organic zirconium phosphate / polymer modified asphalt, the raw materials of which include, by weight: 2 to 6 parts of organic zirconium phosphate, 3 to 10 parts of polymer modifier, 100 parts of base asphalt, 1 to 3 parts of solubilizer, and 0.02 to 0.05 parts of sulfur.

[0008] Compared with traditional polymer modified asphalt, the aging-resistant organic zirconium phosphate / polymer modified asphalt of the present invention adopts organic zirconium phosphate as a cross-linking agent to participate in the formation of the polymer cross-linking network, and obtains a new cross-linking network of zirconium phosphate-polymer. The addition of organic zirconium phosphate increases the density of the polymer cross-linking network, and alleviates the segregation problem of modified asphalt caused by the low density of traditional polymers. At the same time, this new network structure makes the zirconium phosphate evenly dispersed in the asphalt, avoiding the agglomeration of inorganic particles. In addition, the zirconium phosphate with a layered structure is evenly dispersed in the modified asphalt, which can reduce the oxidation of organic molecules in the asphalt, thereby improving the anti-aging performance of the asphalt, which is conducive to extending the life of the asphalt pavement. Moreover, sulfur can be used as a cross-linking agent to participate in the cross-linking reaction of organic zirconium phosphate and polymer, improve the cross-linking density of the polymer cross-linking network, thereby further improving the physical rheological properties of the asphalt.

[0009] Furthermore, the organic zirconium phosphate is obtained by surface-modifying zirconium phosphate with an organic surface modifier; the organic surface modifier is one of ethyl isocyanate acrylate, isocyanoethyl methacrylate, vinyltrimethoxysilane and 1,2,2,6,6-pentamethyl-4-(vinyldiethoxysilyloxy)piperidine (PMVP).

[0010] The organic zirconium phosphate obtained by surface modification (surface grafting modification) of zirconium phosphate with an organic surface modifier carries reaction sites (the organic surface modifier grafted on the surface of zirconium phosphate provides the reaction sites), which can react with polymer modifiers to form a new cross-linked network structure, thereby improving the performance of asphalt. The layered structure of zirconium phosphate itself can also effectively prevent the oxidation of asphalt molecules.

[0011] The isocyanate in isocyanate ethyl acrylate and isocyanoethyl methacrylate can react with the hydroxyl group on the surface of zirconium phosphate to achieve surface modification. Vinyl trimethoxysilane and 1,2,2,6,6-pentamethyl-4-(vinyl diethoxysilyloxy) piperidine (PMVP) rely on the reaction of silyl groups with hydroxyl groups after hydrolysis. The double bonds contained in the structures of the four organic surface modifiers can achieve cross-linking with the polymer structure.

[0012] Further, the organic surface modifier is one of ethyl isocyanate acrylate and isocyanatoethyl methacrylate. The preparation steps of the organic zirconium phosphate include: mixing zirconium phosphate (ZrP) and toluene to obtain a zirconium phosphate-toluene mixture; adding the organic surface modifier and a catalyst to the zirconium phosphate-toluene mixture, and refluxing at a temperature of 80-120 °C for 4-8 h to obtain the organic zirconium phosphate;

[0013] Alternatively, the organic surface modifier is one of vinyltrimethoxysilane and 1,2,2,6,6-pentamethyl-4-(vinyldiethoxysiloxy)piperidine. The preparation steps of the organic zirconium phosphate include: performing hydroxyl modification on zirconium phosphate to obtain hydroxylated zirconium phosphate; dispersing the hydroxylated zirconium phosphate in water, then adding a methanol solution of the organic surface modifier, and stirring and reacting for 2-4 h to obtain the organic zirconium phosphate.

[0014] When the organic surface modifier is one of ethyl isocyanate acrylate and isocyanatoethyl methacrylate, toluene is selected as the reaction solvent during the surface modification process because toluene is an inert solvent relative to the isocyanate group, and common solvents such as water and alcohols can react with the isocyanate group, affecting the surface grafting of zirconium phosphate. When the organic surface modifier is one of vinyltrimethoxysilane and 1,2,2,6,6-pentamethyl-4-(vinyldiethoxysiloxy)piperidine, water is selected as the reaction solvent during the surface modification process because the siloxy group can be grafted onto the surface of zirconium phosphate only after hydrolysis.

[0015] Further, the catalyst is dibutyltin dilaurate, stannous octoate or lead octoate.

[0016] Further, the mass ratio of the zirconium phosphate, toluene, organic surface modifier and catalyst is 3:270-330:1.5-2.5:0.01;

[0017] Alternatively, the mass ratio of the hydroxylated zirconium phosphate, water and the methanol solution of the organic surface modifier is 1:8-12:8-12, and the concentration of the methanol solution of the organic surface modifier is 30-50 wt%.

[0018] Further, after the reflux ends, it also includes the steps of filtration, toluene washing and vacuum drying.

[0019] Further, the rotation speed of the stirring reaction is 1000-2000 rpm; after the stirring reaction ends, it also includes the steps of filtration, washing and drying.

[0020] Further, the step of mixing zirconium phosphate and toluene to obtain a zirconium phosphate-toluene mixture includes: mixing zirconium phosphate and toluene, performing ultrasonic treatment for 15 to 30 minutes, and then refluxing at a temperature of 80 to 120 °C for 20 to 40 minutes to obtain the zirconium phosphate-toluene mixture.

[0021] Further, the step of subjecting zirconium phosphate to hydroxyl modification to obtain hydroxylated zirconium phosphate includes: mixing zirconium phosphate and water, adjusting the pH of the mixed solution to 9 to 11, and then stirring for 8 to 10 hours to obtain the hydroxylated zirconium phosphate.

[0022] Subjecting zirconium phosphate to hydroxyl modification can make the hydroxyl groups on the surface of zirconium phosphate more active and improve the surface modification efficiency.

[0023] When using ethyl isocyanate acrylate or isocyanatoethyl methacrylate as the surface modifier, since the reaction activity between isocyanate groups and hydroxyl groups is very strong, good modification efficiency can be achieved without hydroxyl modification of zirconium phosphate.

[0024] Further, the mass ratio of zirconium phosphate to water is 1:8 to 12.

[0025] Further, after the stirring is completed, it also includes the steps of suction filtration, washing until the filtrate is neutral, and drying.

[0026] Further, the polymer modifier is a polymer containing double bonds in its structure.

[0027] Further preferably, the polymer modifier includes one or more of SBS (styrene-butadiene-styrene triblock copolymer), SBR (styrene-butadiene copolymer), and rubber powder (all are polymers containing double bonds in their structures).

[0028] SBS, SBR, and rubber powder have good modification effects on asphalt. Both the polymer and organic zirconium phosphate have double bonds in their structures, and the two crosslink to form a denser crosslinked network, which is beneficial to alleviating the segregation phenomenon of polymer-modified asphalt and improving the storage stability of polymer-modified asphalt.

[0029] Further, the solubilizer is a waste plastic degradation product; the preparation steps of the waste plastic degradation product include: mixing waste plastics, triethylenetetramine, and zinc acetate, and performing condensation reflux at a temperature of 160 to 200 °C for 2 to 3 hours to obtain the waste plastic degradation product.

[0030] The addition of the waste plastic degradation product can improve the compatibility between the new network structure and asphalt, and further improve the storage stability of the modified asphalt.

[0031] Further, the condensation reflux is carried out under nitrogen protection.

[0032] Further, the mass ratio of the waste plastic, triethylenetetramine, and zinc acetate is 1:5-9:0.01.

[0033] Further, the waste plastic is waste PET plastic.

[0034] Further, after the condensation reflux is completed, the steps of filtration, washing, and drying are further included.

[0035] The second technical solution of the present invention: The preparation method of the above-mentioned aging-resistant organophosphoric acid zirconium / polymer modified asphalt includes the following steps:

[0036] Preheat the matrix asphalt to 160-180°C, then add the polymer modifier and the solubilizer, and perform high-speed shearing at a temperature of 175-195°C for 50-70 min; then add the organophosphoric acid zirconium and sulfur, and perform high-speed shearing at a temperature of 175-195°C for 40-60 min; then cool down to 165-185°C and perform low-speed stirring for 40-60 min to obtain the aging-resistant organophosphoric acid zirconium / polymer modified asphalt.

[0037] Further, the rotation speed of the high-speed stirring is 4000-5000 rpm; the rotation speed of the low-speed stirring is 1000-2000 rpm.

[0038] The present invention discloses the following technical effects:

[0039] (1) The present invention uses organophosphoric acid zirconium to react with the polymer to form a new cross-linked network structure. Compared with the traditional polymer cross-linked network, the new cross-linked network has a higher density, which is beneficial to alleviating the segregation phenomenon of the polymer modified asphalt. At the same time, the zirconium phosphate is evenly distributed in the network structure, avoiding the agglomeration phenomenon of inorganic particles. Therefore, the aging-resistant organophosphoric acid zirconium / polymer modified asphalt prepared by the present invention has excellent storage stability.

[0040] (2) The zirconium phosphate is evenly distributed in the new cross-linked network, and its layered structure can produce a certain barrier effect on ultraviolet radiation and oxygen, thereby reducing the oxidation of organic molecules in the asphalt, and further improving the anti-ultraviolet aging ability of the polymer modified asphalt, which is beneficial to extending the service life of the asphalt pavement.

[0041] (3) The present invention uses the degradation product of waste plastic as a solubilizer to participate in asphalt modification. During the decomposition process of waste plastic, the ratio of waste plastic to the decomposing agent can be changed according to needs, and the molecular weight of the decomposition product of waste plastic can be adjusted, thereby regulating the solubilization effect. Using the decomposition product of waste plastic as a solubilizer conforms to the concept of sustainable development and provides a new idea for the treatment of waste plastic. Specific embodiments

[0042] The various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and implementation schemes of the present invention.

[0043] It should be understood that the terms used in the present invention are only for describing specific embodiments and are not used to limit the present invention. Additionally, for the numerical ranges in the present invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Any intermediate value within any stated value or stated range, as well as each smaller range between any other stated value or intermediate value within the stated range, is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded from the range.

[0044] Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the art to which the present invention pertains. Although the present invention only describes preferred methods and materials, any methods and materials similar or equivalent to those described herein can also be used in the implementation or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials related to the said documents. In case of conflict with any incorporated document, the content of this specification shall prevail.

[0045] Without departing from the scope or spirit of the present invention, various improvements and changes can be made to the specific embodiments of the present invention specification, which are obvious to those skilled in the art. Other embodiments obtained from the specification of the present invention are obvious to those skilled in the art. The specification and examples of the present invention are merely exemplary.

[0046] Regarding the use of "comprising", "including", "having", "containing", etc. in this article, they are all open-ended terms, meaning including but not limited to.

[0047] As a first aspect of the present invention, the present invention provides an anti-aging organophosphate zirconium / polymer modified asphalt. By mass, the raw materials include: 2 - 6 parts of organophosphate zirconium, 3 - 10 parts of polymer modifier, 100 parts of matrix asphalt, 1 - 3 parts of solubilizer, and 0.02 - 0.05 parts of sulfur.

[0048] As an embodiment of the present invention, the organophosphate zirconium is obtained by surface modification of zirconium phosphate with an organic surface modifier; the organic surface modifier is one of isocyanate ethyl acrylate, isocyanatoethyl methacrylate, vinyltrimethoxysilane, and 1,2,2,6,6-pentamethyl-4-(vinyldiethoxysiloxy)piperidine (PMVP).

[0049] As an embodiment of the present invention, the organic surface modifier is one of ethyl isocyanate acrylate and isocyanatoethyl methacrylate. The preparation steps of the organic zirconium phosphate include: mixing zirconium phosphate and toluene, ultrasonic treating for 15 - 30 min, and then refluxing at a temperature of 80 - 120 °C for 20 - 40 min to obtain a zirconium phosphate - toluene mixture; adding an organic surface modifier and a catalyst to the zirconium phosphate - toluene mixture, and refluxing at a temperature of 80 - 120 °C for 4 - 8 h to obtain the organic zirconium phosphate;

[0050] Or, the organic surface modifier is one of vinyltrimethoxysilane and 1,2,2,6,6 - pentamethyl - 4 - (vinyldiethoxysiloxy)piperidine. The preparation steps of the organic zirconium phosphate include: performing hydroxyl modification on zirconium phosphate to obtain hydroxylated zirconium phosphate; dispersing the hydroxylated zirconium phosphate in water, and then adding a methanol solution of the organic surface modifier, and stirring and reacting for 2 - 4 h to obtain the organic zirconium phosphate.

[0051] As a preferred embodiment of the present invention, the organic surface modifier is one of ethyl isocyanate acrylate and isocyanatoethyl methacrylate. The more specific preparation steps of the organic zirconium phosphate include: adding 3 parts of zirconium phosphate (ZrP) to 270 - 330 parts of toluene, ultrasonicating for 15 - 30 min, and refluxing at 80 - 120 °C for 20 - 40 min to obtain a zirconium phosphate - toluene mixture; adding 1.5 - 2.5 parts of ethyl isocyanate acrylate or isocyanatoethyl methacrylate to the zirconium phosphate - toluene mixture, and dropwise adding 0.01 part of a catalyst (dibutyltin dilaurate, stannous octoate or lead octoate, preferably dibutyltin dilaurate), refluxing at 80 - 120 °C for 4 - 8 h, filtering, washing with toluene, and drying in vacuo to obtain the organic zirconium phosphate;

[0052] Or, the organic surface modifier is one of vinyltrimethoxysilane and 1,2,2,6,6 - pentamethyl - 4 - (vinyldiethoxysiloxy)piperidine. The more specific preparation steps of the organic zirconium phosphate include: placing 10 parts of zirconium phosphate in a beaker, adding 80 - 120 parts of water, and then gradually dropwise adding an aqueous sodium hydroxide solution (the concentration of the aqueous sodium hydroxide solution is not required) until the pH of the solution reaches 9 - 11, stirring at room temperature (rotation speed of 1000 - 2000 rpm) for 8 - 10 h, then filtering and washing until the filtrate is neutral, and drying to obtain hydroxylated zirconium phosphate; dispersing 10 parts of hydroxylated zirconium phosphate in 80 - 120 parts of water, and then dropwise adding 80 - 120 parts of a methanol solution of vinyltrimethoxysilane or PMVP (concentration of 30 - 50 wt%), stirring (rotation speed of 1000 - 2000 rpm) for 2 - 4 h, filtering, washing, and drying to obtain the organic zirconium phosphate.

[0053] As an embodiment of the present invention, the polymer modifier is a polymer containing double bonds in its structure.

[0054] As a preferred embodiment of the present invention, the polymer modifier includes one or more of SBS, SBR, and rubber powder.

[0055] As an embodiment of the present invention, the solubilizer is a waste plastic degradation product; the preparation steps of the waste plastic degradation product include: mixing waste plastics, triethylenetetramine, and zinc acetate, and carrying out condensation reflux at a temperature of 160 - 200°C for 2 - 3 h to obtain the waste plastic degradation product.

[0056] As a preferred embodiment of the present invention, after the condensation reflux, the steps of filtration, washing, and drying are further included.

[0057] As a preferred embodiment of the present invention, the condensation reflux is carried out under nitrogen protection.

[0058] As an embodiment of the present invention, the mass ratio of the waste plastics, triethylenetetramine, and zinc acetate is 1:5 - 9:0.01.

[0059] As a preferred embodiment of the present invention, the waste plastics are waste PET plastics.

[0060] As the second aspect of the present invention, the present invention provides a method for preparing the above-mentioned aging-resistant organic phosphazene zirconium / polymer modified asphalt, including the following steps:

[0061] Preheat the base asphalt to 160 - 180°C, then add the polymer modifier and the solubilizer, and carry out high-speed (4000 - 5000 rpm) shearing at a temperature of 175 - 195°C for 50 - 70 min; then add the organic phosphazene zirconium and sulfur, and carry out high-speed (4000 - 5000 rpm) shearing at a temperature of 175 - 195°C for 40 - 60 min; then cool down to 165 - 185°C and carry out low-speed (1000 - 2000 rpm) stirring for 40 - 60 min to obtain the aging-resistant organic phosphazene zirconium / polymer modified asphalt.

[0062] The following further illustrates the aging-resistant organic phosphazene zirconium / polymer modified asphalt and its preparation method of the present invention in conjunction with specific embodiments.

[0063] The room temperature involved in the specific embodiments of the present invention specifically refers to 20 - 30°C.

[0064] All raw materials used in the specific embodiments of the present invention are ordinary commercially available products. Among them, the CAS number of ethyl isocyanate acrylate is 13641-96-8, the CAS number of isocyanatoethyl methacrylate is 30674-80-7, the CAS number of vinyltrimethoxysilane is 2768-02-7, and the CAS number of 1,2,2,6,6-pentamethyl-4-(vinyldiethoxysiloxy)piperidine (PMVP) is 14380-75-7. The matrix asphalt is specifically 70# matrix asphalt. The waste PET plastic flakes are derived from waste PET plastic bottles.

[0065] Example 1

[0066] A weather-resistant organophosphate zirconium / polymer modified asphalt, by mass, the raw material composition is: 4 parts of organophosphate zirconium, 7 parts of SBS, 100 parts of matrix asphalt, 2 parts of waste plastic degradation product, and 0.03 parts of sulfur.

[0067] The preparation method of the weather-resistant organophosphate zirconium / polymer modified asphalt is as follows:

[0068] S1. Preparation of organophosphate zirconium: Weigh 3 parts of zirconium phosphate and add it to 300 parts of toluene, ultrasonicate for 20 min, reflux at 100 °C for 30 min to obtain a zirconium phosphate-toluene mixture; add 2 parts of ethyl isocyanate acrylate to the zirconium phosphate-toluene mixture, and dropwise add 0.01 part of dibutyltin dilaurate, reflux at 100 °C for 6 h, then filter, wash with toluene, and vacuum dry to obtain organophosphate zirconium;

[0069] S2. Preparation of waste plastic degradation product: Add waste PET plastic flakes, triethylenetetramine, and zinc acetate with a mass ratio of 1:7:0.01 to a round-bottom flask under nitrogen protection, condense and reflux the mixture at 180 °C for 2 h, then filter, wash, and dry to obtain the waste plastic degradation product;

[0070] S3. Preparation of weather-resistant organophosphate zirconium / polymer modified asphalt: Preheat the matrix asphalt to 170 °C, then add SBS and the waste plastic degradation product in proportion, shear at a high speed (rotation speed of 4500 rpm) at 180 °C for 60 min; then add organophosphate zirconium and sulfur in proportion, shear at a high speed (rotation speed of 4500 rpm) at 180 °C for 40 min; then cool down to 170 °C and stir at a low speed (rotation speed of 1500 rpm) for 60 min to obtain the weather-resistant organophosphate zirconium / polymer modified asphalt.

[0071] Example 2

[0072] Same as Example 1, the difference is only that the number of parts of organophosphate zirconium in the weather-resistant organophosphate zirconium / polymer modified asphalt component is 2.

[0073] Example 3

[0074] Same as Example 1, the only difference is that the amount of zirconium organophosphate in the aging-resistant zirconium organophosphate / polymer modified asphalt component is 6 parts.

[0075] Example 4

[0076] An aging-resistant zirconium organophosphate / polymer modified asphalt, by mass, the raw material composition is: 4 parts of zirconium organophosphate, 7 parts of SBS, 100 parts of matrix asphalt, 2 parts of waste plastic degradation product, and 0.03 part of sulfur.

[0077] The preparation method of the aging-resistant zirconium organophosphate / polymer modified asphalt is as follows:

[0078] S1. Preparation of zirconium organophosphate: Weigh 10 parts of zirconium phosphate and place it in a beaker, add 100 parts of deionized water, and then gradually add sodium hydroxide aqueous solution until the pH of the solution reaches 10. Stir at room temperature (rotation speed of 1500 rpm) for 10 h, then filter and wash until the filtrate is neutral, and dry to obtain hydroxylated zirconium phosphate; take 10 parts of hydroxylated zirconium phosphate and disperse it in 100 parts of deionized water, then dropwise add 100 parts of a methanol solution (40 wt%) of vinyltrimethoxysilane, stir (rotation speed of 1500 rpm) for 3 h, filter, wash, and dry to obtain zirconium organophosphate;

[0079] S2. Preparation of waste plastic degradation product: Under nitrogen protection, add waste PET plastic flakes, triethylenetetramine, and zinc acetate with a mass ratio of 1:7:0.01 to a round-bottom flask, reflux the mixture under condensation at 180 °C for 2 h, then filter, wash, and dry to obtain the waste plastic degradation product;

[0080] S3. Preparation of aging-resistant zirconium organophosphate / polymer modified asphalt: Preheat the matrix asphalt to 170 °C, then add SBS and the waste plastic degradation product in proportion, and shear at a high speed (rotation speed of 4500 rpm) at 180 °C for 60 min; then add zirconium organophosphate and sulfur in proportion, and shear at a high speed (rotation speed of 4500 rpm) at 180 °C for 40 min; then cool down to 170 °C and stir at a low speed (rotation speed of 1500 rpm) for 60 min to obtain the aging-resistant zirconium organophosphate / polymer modified asphalt.

[0081] Example 5

[0082] Same as Example 4, the only difference is that the amount of zirconium organophosphate in the aging-resistant zirconium organophosphate / polymer modified asphalt component is 2 parts.

[0083] Example 6

[0084] Same as Example 4, the only difference is that the amount of zirconium organophosphate in the aging-resistant zirconium organophosphate / polymer modified asphalt component is 6 parts.

[0085] Comparative Example 1

[0086] A polymer-modified asphalt, by mass, the raw material composition is: 7 parts of SBS, 100 parts of matrix asphalt, 2 parts of waste plastic degradation product, and 0.03 part of sulfur.

[0087] The preparation method of the polymer-modified asphalt is as follows:

[0088] S1. Preparation of waste plastic degradation product: Add waste PET plastic flakes, triethylenetetramine, and zinc acetate with a mass ratio of 1:7:0.01 to a round-bottom flask under nitrogen protection. Condense and reflux the mixture at 180 °C for 2 h, then filter, wash, and dry to obtain the waste plastic degradation product;

[0089] S2. Preparation of polymer-modified asphalt: Preheat the matrix asphalt to 170 °C, then add SBS and the waste plastic degradation product in proportion, and shear at a high speed (rotation speed of 4500 rpm) at 180 °C for 60 min; then add sulfur in proportion and shear at a high speed (rotation speed of 4500 rpm) at 180 °C for 40 min; then cool down to 170 °C and stir at a low speed (rotation speed of 1500 rpm) for 60 min to obtain the polymer-modified asphalt.

[0090] Comparative Example 2

[0091] An aging-resistant organophosphazene / polymer-modified asphalt, by mass, the raw material composition is: 4 parts of organophosphazene, 7 parts of SBS, 100 parts of matrix asphalt, and 0.03 part of sulfur.

[0092] The preparation method of the aging-resistant organophosphazene / polymer-modified asphalt is as follows:

[0093] S1. Preparation of organophosphazene: Weigh 3 parts of phosphazene and add it to 300 parts of toluene, ultrasonicate for 20 min, and reflux at 100 °C for 30 min to obtain a phosphazene-toluene mixture; add 2 parts of isocyanate ethyl acrylate to the phosphazene-toluene mixture, and dropwise add 0.01 part of dibutyltin dilaurate, reflux at 100 °C for 6 h, then filter, wash with toluene, and vacuum dry to obtain organophosphazene;

[0094] S2. Preparation of aging-resistant organophosphazene / polymer-modified asphalt: Preheat the matrix asphalt to 170 °C, then add SBS in proportion, and shear at a high speed (rotation speed of 4500 rpm) at 180 °C for 60 min; then add organophosphazene and sulfur in proportion and shear at a high speed (rotation speed of 4500 rpm) at 180 °C for 40 min; then cool down to 170 °C and stir at a low speed (rotation speed of 1500 rpm) for 60 min to obtain the aging-resistant organophosphazene / polymer-modified asphalt.

[0095] Comparative Example 3

[0096] Same as Example 1, except that the amount of zirconium organophosphate in the anti-aging zirconium organophosphate / polymer modified asphalt component is 1 part.

[0097] Comparative Example 4

[0098] Same as Example 1, except that the amount of zirconium organophosphate in the anti-aging zirconium organophosphate / polymer modified asphalt component is 8 parts.

[0099] Comparative Example 5

[0100] Same as Example 4, except that the amount of zirconium organophosphate in the anti-aging zirconium organophosphate / polymer modified asphalt component is 1 part.

[0101] Comparative Example 6

[0102] Same as Example 4, except that the amount of zirconium organophosphate in the anti-aging zirconium organophosphate / polymer modified asphalt component is 8 parts.

[0103] Comparative Example 7

[0104] A zirconium phosphate / polymer modified asphalt, by mass, the raw material composition is: 4 parts of zirconium phosphate, 7 parts of SBS, 100 parts of matrix asphalt, 2 parts of waste plastic degradation product, 0.03 part of sulfur.

[0105] Preparation method of zirconium phosphate / polymer modified asphalt, the steps are as follows:

[0106] S1. Preparation of waste plastic degradation product: Add waste PET plastic flakes, triethylenetetramine, and zinc acetate with a mass ratio of 1:7:0.01 to a round-bottom flask under nitrogen protection, condense and reflux the mixture at 180 °C for 2 h, then filter, wash, and dry to obtain the waste plastic degradation product;

[0107] S2. Preparation of zirconium phosphate / polymer modified asphalt: Preheat the matrix asphalt to 170 °C, then add SBS and waste plastic degradation product in proportion, and shear at a high speed (rotation speed of 4500 rpm) at 180 °C for 60 min; then add zirconium phosphate and sulfur in proportion, and shear at a high speed (rotation speed of 4500 rpm) at 180 °C for 40 min; then cool down to 170 °C and stir at a low speed (rotation speed of 1500 rpm) for 60 min to obtain zirconium phosphate / polymer modified asphalt.

[0108] Comparative Example 8

[0109] An anti-aging organophosphoric acid zirconium / polymer modified asphalt, by mass fraction, the raw material composition is: 4 parts of organophosphoric acid zirconium, 7 parts of SBS, 100 parts of base asphalt, and 2 parts of waste plastic degradation product.

[0110] The preparation method of the anti-aging organophosphoric acid zirconium / polymer modified asphalt is as follows:

[0111] S1. Preparation of organophosphoric acid zirconium: Weigh 3 parts of zirconium phosphate and add it to 300 parts of toluene, ultrasonicate for 20 min, reflux at 100 °C for 30 min to obtain a zirconium phosphate-toluene mixture; add 2 parts of isocyanate ethyl acrylate to the zirconium phosphate-toluene mixture, and dropwise add 0.01 part of dibutyltin dilaurate, reflux at 100 °C for 6 h, then filter, wash with toluene, and dry in vacuum to obtain organophosphoric acid zirconium;

[0112] S2. Preparation of waste plastic degradation product: Add waste PET plastic flakes, triethylenetetramine, and zinc acetate with a mass ratio of 1:7:0.01 to a round-bottom flask under nitrogen protection, reflux the mixture at 180 °C for 2 h, then filter, wash, and dry to obtain the waste plastic degradation product;

[0113] S3. Preparation of the anti-aging organophosphoric acid zirconium / polymer modified asphalt: Preheat the base asphalt to 170 °C, then add SBS and the waste plastic degradation product in proportion, shear at a high speed (rotation speed of 4500 rpm) at 180 °C for 60 min; then add the organophosphoric acid zirconium in proportion, shear at a high speed (rotation speed of 4500 rpm) at 180 °C for 40 min; then cool down to 170 °C and stir at a low speed (rotation speed of 1500 rpm) for 60 min to obtain the anti-aging organophosphoric acid zirconium / polymer modified asphalt.

[0114] Comparative Example 9

[0115] An anti-aging organophosphoric acid zirconium / polymer modified asphalt, by mass fraction, the raw material composition is: 4 parts of organophosphoric acid zirconium, 7 parts of SBS, 100 parts of base asphalt, 2 parts of waste plastic degradation product, and 0.03 part of sulfur.

[0116] The preparation method of the anti-aging organophosphoric acid zirconium / polymer modified asphalt is as follows:

[0117] S1. Preparation of organophosphoric acid zirconium: Take 10 parts of zirconium phosphate and disperse it in 100 parts of deionized water, then dropwise add 100 parts of a methanol solution (40 wt%) of vinyltrimethoxysilane, stir (rotation speed of 1500 rpm) for 3 h, filter, wash, and dry to obtain organophosphoric acid zirconium;

[0118] S2. Preparation of waste plastic degradation products: Add waste PET plastic flakes, triethylenetetramine, and zinc acetate with a mass ratio of 1:7:0.01 into a round-bottom flask under nitrogen protection. Condense and reflux the mixture at 180 °C for 2 h, then filter, wash, and dry to obtain waste plastic degradation products;

[0119] S3. Preparation of aging-resistant organophosphorus zirconium / polymer modified asphalt: Preheat the matrix asphalt to 170 °C, then add SBS and waste plastic degradation products in proportion, and shear at a high speed (rotation speed of 4500 rpm) at 180 °C for 60 min; then add organophosphorus zirconium and sulfur in proportion, and shear at a high speed (rotation speed of 4500 rpm) at 180 °C for 40 min; then cool down to 170 °C and stir at a low speed (rotation speed of 1500 rpm) for 60 min to obtain aging-resistant organophosphorus zirconium / polymer modified asphalt.

[0120] Test Example 1

[0121] To verify the anti-aging performance of the modified asphalt, conduct an asphalt segregation experiment on the modified asphalt in the above examples and comparative examples according to the "Specifications for Highway Engineering Asphalt and Asphalt Mixture Tests" (JTG E20-2011) to analyze the storage stability of the asphalt. Then conduct a short-term aging test (thin film oven test) on the modified asphalt samples according to the above specifications. On the basis of the short-term aging test, conduct an ultraviolet aging test (ultraviolet light intensity 800 w / m 2 , temperature 60 °C, aging time 3 days), and use a dynamic shear rheometer to conduct a temperature sweep experiment on the samples before and after aging, calculate the complex modulus aging index (CAI), and evaluate the anti-aging ability of the asphalt. The smaller the value of the complex modulus aging index, the stronger the anti-aging ability of the asphalt. The aging index calculation formula is as follows:

[0122]

[0123] In the formula: aging represents the index after aging, and origin represents the index before aging.

[0124] The test results of each performance are shown in Table 1:

[0125] Table 1

[0126]

[0127]

[0128] Among them, the softening point difference is the softening point difference between the upper layer and the lower layer after the asphalt segregation test. The larger the softening point difference, the worse the storage stability of the asphalt, and the smaller the better.

[0129] According to the experimental data recorded in Table 1, by comparing Example 1 with Comparative Examples 1 and 2, it can be seen that the crosslinking of zirconium organophosphate with polymers can significantly improve the storage stability of polymer-modified asphalt, and the addition of waste plastic degradation products further enhances the storage stability of asphalt. In addition, the addition of zirconium organophosphate greatly improves the anti-ultraviolet aging ability of asphalt.

[0130] By comparing Examples 1-3 with Comparative Examples 3 and 4 (Examples 4-6 and Comparative Examples 5-6 can also be compared), it can be obtained that the combination of zirconium organophosphate and polymers can improve the storage stability of asphalt and enhance the anti-ultraviolet aging ability of polymer-modified asphalt. During the preparation of modified asphalt, if the dosage of zirconium organophosphate is too low, the improvement of asphalt performance is limited; as the dosage of zirconium organophosphate increases, the improvement amplitude of asphalt performance gradually decreases. Considering the preparation cost, the dosage of zirconium organophosphate should not be too high either.

[0131] By comparing Example 1 with Comparative Example 7, it can be seen that the organic treatment of zirconium phosphate is a necessary step to realize the combination of zirconium phosphate and polymers, which is beneficial to the improvement of the storage stability and anti-aging performance of modified asphalt.

[0132] By comparing Example 1 with Comparative Example 8, it can be seen that sulfur can increase the crosslinking density of polymers and also has a certain promoting effect on the improvement of the storage stability and anti-aging performance of modified asphalt.

[0133] By comparing Example 4 with Comparative Example 9, it can be seen that the hydroxylation treatment of zirconium phosphate is beneficial to improving the organic treatment effect of zirconium phosphate, facilitating the combination of zirconium phosphate and polymers, and thus enhancing the storage stability and anti-aging performance of asphalt.

[0134] The above-described embodiments are only descriptions of the preferred embodiments of the present invention and do not limit the scope of the present invention. Without departing from the design spirit of the present invention, various deformations and improvements made by those of ordinary skill in the art to the technical solutions of the present invention shall fall within the protection scope determined by the claims of the present invention.

Claims

1. An anti-aging organophosphate zirconium / polymer modified asphalt, characterized in that, By mass parts, the raw materials include: 2-6 parts of zirconium organic phosphate, 3-10 parts of polymer modifier, 100 parts of matrix asphalt, 1-3 parts of solubilizer, and 0.02-0.05 parts of sulfur; The zirconium organic phosphate is obtained by surface modification of zirconium phosphate with an organic surface modifier; the organic surface modifier is one of ethyl isocyanate acrylate, isocyanatoethyl methacrylate, vinyltrimethoxysilane, and 1,2,2,6,6-pentamethyl-4-(vinyldiethoxysiloxy)piperidine; When the organic surface modifier is one of ethyl isocyanate acrylate and isocyanatoethyl methacrylate, the preparation steps of the zirconium organic phosphate include: mixing zirconium phosphate and toluene to obtain a zirconium phosphate-toluene mixture; adding the organic surface modifier and a catalyst to the zirconium phosphate-toluene mixture, and refluxing at a temperature of 80-120 °C for 4-8 h to obtain the zirconium organic phosphate; When the organic surface modifier is one of vinyltrimethoxysilane and 1,2,2,6,6-pentamethyl-4-(vinyldiethoxysiloxy)piperidine, the preparation steps of the zirconium organic phosphate include: performing hydroxyl modification on zirconium phosphate to obtain hydroxylated zirconium phosphate; dispersing the hydroxylated zirconium phosphate in water, then adding a methanol solution of the organic surface modifier, and stirring and reacting for 2-4 h to obtain the zirconium organic phosphate; The polymer modifier includes one or more of SBS and SBR; The solubilizer is a waste plastic degradation product; The preparation steps of the waste plastic degradation product include: mixing waste PET plastic flakes, triethylenetetramine, and zinc acetate, and performing condensation reflux at a temperature of 160-200 °C for 2-3 h to obtain the waste plastic degradation product.

2. The anti-aging organophosphorus zirconium / polymer modified asphalt according to claim 1, wherein The mass ratio of the zirconium phosphate, toluene, organic surface modifier, and catalyst is 3:270-330:1.5-2.5:0.01; Or, the mass ratio of the hydroxylated zirconium phosphate, water, and the methanol solution of the organic surface modifier is 1:8-12:8-12, and the concentration of the methanol solution of the organic surface modifier is 30-50 wt%.

3. The anti-aging organophosphorus zirconate / polymer modified asphalt according to claim 1, wherein The mixing of zirconium phosphate and toluene to obtain a zirconium phosphate-toluene mixture includes: mixing zirconium phosphate and toluene, performing ultrasonic treatment for 15-30 min, and then refluxing at a temperature of 80-120 °C for 20-40 min to obtain the zirconium phosphate-toluene mixture.

4. The anti-aging organophosphorus zirconium / polymer modified asphalt according to claim 1, wherein, The performing of hydroxyl modification on zirconium phosphate to obtain hydroxylated zirconium phosphate includes: mixing zirconium phosphate and water, adjusting the pH of the mixed solution to 9-11, and then stirring for 8-10 h to obtain the hydroxylated zirconium phosphate.

5. The anti-aging organophosphorus zirconate / polymer modified asphalt according to claim 1, wherein The mass ratio of the waste PET plastic flakes, triethylenetetramine, and zinc acetate is 1:5-9:0.

01.

6. The preparation method of the anti-aging organophosphoric acid zirconium / polymer modified asphalt according to any one of claims 1 to 5, characterized in that, Comprising the following steps: Preheat the base asphalt to 160 - 180 °C, then add the polymer modifier and the solubilizer, and perform high-speed shearing at a temperature of 175 - 195 °C for 50 - 70 min; then add zirconium organophosphate and sulfur, and perform high-speed shearing at a temperature of 175 - 195 °C for 40 - 60 min; then cool down to 165 - 185 °C and perform low-speed stirring for 40 - 60 min to obtain the aging-resistant zirconium organophosphate / polymer modified asphalt.

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