An anti-aging modified asphalt and its preparation method

Abstract

An anti-aging modified asphalt and its preparation method, wherein the raw materials include matrix asphalt, limestone aggregate, polytrimethylphenylsiloxane-modified halloysite nanotubes, perfluororubber, maleic anhydride-grafted ethylene vinyl acetate copolymer, epoxy soybean oil, and nano-titanium dioxide. By modifying halloysite nanotubes with polytrimethylphenylsiloxane, the present invention can not only avoid the agglomeration of raw materials such as nano-titanium dioxide, but also improve the compatibility of components, thereby significantly improving the anti-ultraviolet aging performance; moreover, the present invention improves the mechanical properties of the modified asphalt by modifying halloysite nanotubes with polytrimethylphenylsiloxane. At the same time, the synergistic effect between polytrimethylphenylsiloxane-modified halloysite nanotubes, perfluororubber, and maleic anhydride-grafted ethylene vinyl acetate copolymer can significantly improve the mechanical properties of the matrix asphalt and extend its service life.

Description

Technical Field

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

[0002] Asphalt is a material commonly used in the preparation of paving and roofing materials. In the road construction and road paving industries, a mature and practical method is to use hot fluid asphalt to coat aggregate materials such as sand, gravel, crushed stone or mixtures thereof, spread the coated material as a uniform layer on the roadbed or a previously constructed road while it is still hot, and compact the uniform layer by rolling with a heavy roller to form a road with a smooth surface. Asphalt concrete pavements have the advantages of high flatness, good skid resistance, low noise, less dust, and easy maintenance, and have become the mainstream choice for the pavement paving of long and large tunnels.

[0003] However, under the influence of ultraviolet radiation, water erosion, and vehicle loads, asphalt pavements are prone to cracks and ruts, affecting the flatness of the road surface and the service life of asphalt roads.

[0004] Therefore, in view of the deficiencies of the prior art, it is very necessary to provide an anti-aging modified asphalt and a preparation method thereof to solve the deficiencies of the prior art. Summary of the Invention

[0005] One of the purposes of the present invention is to avoid the deficiencies of the prior art and provide a preparation method of an anti-aging modified asphalt. The preparation method of the anti-aging modified asphalt can improve the anti-ultraviolet aging performance and mechanical strength, and can effectively extend the service life.

[0006] The above object of the present invention is achieved by the following technical measures:

[0007] Provide a preparation method of an anti-aging modified asphalt, the raw materials containing matrix asphalt, limestone ore, polytri-methylphenylsiloxane modified halloysite nanotubes, perfluororubber, maleic anhydride grafted ethylene vinyl acetate copolymer, epoxy soybean oil, and nano-titanium dioxide.

[0008] Comprising the following steps:

[0009] S1. Stir the polytri-methylphenylsiloxane modified halloysite nanotubes, epoxy soybean oil, and nano-titanium dioxide to obtain an intermediate;

[0010] S2. Add perfluororubber, maleic anhydride grafted ethylene vinyl acetate copolymer, limestone ore, and the intermediate to the matrix asphalt, and stir to obtain a modified asphalt.

[0011] By weight,

[0012] Matrix asphalt: 100 parts;

[0013] Limestone aggregate: 20 to 30 parts by weight;

[0014] Polymethylphenylsiloxane modified halloysite nanotubes: 5 to 12 parts by weight;

[0015] Perfluororubber: 10 to 15 parts by weight;

[0016] Maleic anhydride grafted ethylene vinyl acetate copolymer: 10 to 15 parts by weight;

[0017] Epoxidized soybean oil: 5 to 8 parts by weight;

[0018] Nano-titanium dioxide: 3 to 8 parts by weight.

[0019] Furthermore, by weight:

[0020] Matrix asphalt: 100 parts by weight;

[0021] Limestone aggregate: 25 to 28 parts by weight;

[0022] Polymethylphenylsiloxane modified halloysite nanotubes: 8 to 10 parts by weight;

[0023] Perfluororubber: 12 to 13 parts by weight;

[0024] Maleic anhydride grafted ethylene vinyl acetate copolymer: 12 to 13 parts by weight;

[0025] Distearyl pentaerythritol diphosphite: 2 to 3 parts by weight;

[0026] Epoxidized soybean oil: 6 to 7 parts by weight;

[0027] Nano-titanium dioxide: 5 to 6 parts by weight.

[0028] Even further, by weight:

[0029] Matrix asphalt: 100 parts by weight;

[0030] Limestone aggregate: 25.8 parts by weight;

[0031] Polymethylphenylsiloxane modified halloysite nanotubes: 8.6 parts by weight;

[0032] Perfluororubber: 12.7 parts by weight;

[0033] Maleic anhydride grafted ethylene vinyl acetate copolymer: 12.5 parts by weight;

[0034] Epoxidized soybean oil: 6.5 parts by weight;

[0035] Nano-titanium dioxide: 5.6 parts by weight.

[0036] Preferably, the raw materials for the above-mentioned polytrimethylphenylsiloxane-modified halloysite nanotubes include halloysite nanotubes, polytrimethylphenylsiloxane, glycerol, NaOH, and water.

[0037] Preferably, the preparation method of the above-mentioned polytrimethylphenylsiloxane-modified halloysite nanotubes is to add halloysite nanotubes to an aqueous solution of NaOH for hydroxylation of the halloysite nanotubes, and then add the hydroxylated halloysite nanotubes to glycerol and add polytrimethylphenylsiloxane to obtain polytrimethylphenylsiloxane-modified halloysite nanotubes.

[0038] In the polytrimethylphenylsiloxane-modified halloysite nanotubes, by weight, halloysite nanotubes: 10 parts;

[0039] Polytrimethylphenylsiloxane: 0.05 parts to 0.1 parts;

[0040] Glycerol: 50 parts to 100 parts;

[0041] 30 wt% aqueous NaOH solution: 40 parts to 80 parts.

[0042] Furthermore, in the polytrimethylphenylsiloxane-modified halloysite nanotubes, by weight,

[0043] Halloysite nanotubes: 10 parts;

[0044] Polytrimethylphenylsiloxane: 0.08 parts;

[0045] Glycerol: 60 parts;

[0046] 30 wt% aqueous NaOH solution: 60 parts.

[0047] Preferably, the preparation method of the above-mentioned polytrimethylphenylsiloxane-modified halloysite nanotubes is obtained by the following steps:

[0048] A1. Add halloysite nanotubes to a 30 wt% aqueous NaOH solution, stir ultrasonically for 30 min to 60 min, and then stir at 40°C to 50°C for 30 min to 60 min to carry out hydroxylation of the halloysite nanotubes, filter and dry to obtain hydroxylated halloysite nanotubes;

[0049] A2. Add the hydroxylated halloysite nanotubes to glycerol and stir, and then add them to polytrimethylphenylsiloxane and stir at 80°C to 100°C for 60 min to 120 min to obtain polytrimethylphenylsiloxane-modified halloysite nanotubes.

[0050] Preferably, the above-mentioned S2 is specifically to add perfluororubber, maleic anhydride-grafted ethylene vinyl acetate copolymer, limestone aggregate, and intermediate to the matrix asphalt heated to 105 - 110°C, and stir for 120 min to 150 min to obtain modified asphalt.

[0051] Another object of the present invention is to provide a modified asphalt to avoid the deficiencies of the prior art. The modified asphalt has high anti-ultraviolet aging performance and mechanical strength, and has a long service life.

[0052] The above object of the present invention is achieved by the following technical measures:

[0053] Provide an anti-aging modified asphalt prepared by the preparation method of the above anti-aging modified asphalt.

[0054] An anti-aging modified asphalt and its preparation method of the present invention, wherein the raw materials include matrix asphalt, limestone aggregate, polytrimethylphenylsiloxane-modified halloysite nanotubes, peroxyfluororubber, maleic anhydride-grafted ethylene vinyl acetate copolymer, epoxy soybean oil and nano-titanium dioxide. It includes the following steps: S1. Stir polytrimethylphenylsiloxane-modified halloysite nanotubes, epoxy soybean oil and nano-titanium dioxide to obtain an intermediate; S2. Add peroxyfluororubber, maleic anhydride-grafted ethylene vinyl acetate copolymer, limestone aggregate and the intermediate to the matrix asphalt and stir to obtain the modified asphalt. By modifying the halloysite nanotubes with polytrimethylphenylsiloxane in the present invention, not only can the agglomeration of raw materials such as nano-titanium dioxide be avoided, but also the compatibility of components can be improved, and the anti-ultraviolet aging performance can be significantly improved; moreover, the mechanical properties of the modified asphalt are improved by modifying the halloysite nanotubes with polytrimethylphenylsiloxane in the present invention. At the same time, the synergistic effect between polytrimethylphenylsiloxane-modified halloysite nanotubes, peroxyfluororubber and maleic anhydride-grafted ethylene vinyl acetate copolymer can significantly improve the mechanical properties of the matrix asphalt and extend the service life. Specific embodiments

[0055] The technical solution of the present invention will be further described in conjunction with the following embodiments. Unless otherwise specified in the following embodiments, the raw materials used in each embodiment are commercially available products. The peroxyfluororubber used in the present invention is a binary peroxyfluororubber with the brand name FE2603, purchased from Shandong Dongyue Shenzhou New Materials Co., Ltd. Halloysite nanotubes are purchased from Xi'an Ruixi Biotechnology Co., Ltd., and the model of polytrimethylphenylsiloxane is DC556, purchased from Dow Corning Corporation, USA.

[0056] Example 1

[0057] A preparation method of an anti-aging modified asphalt, the raw materials include matrix asphalt, limestone aggregate, polytrimethylphenylsiloxane-modified halloysite nanotubes, peroxyfluororubber, maleic anhydride-grafted ethylene vinyl acetate copolymer, epoxy soybean oil and nano-titanium dioxide.

[0058] By weight,

[0059] Matrix asphalt: 100 parts;

[0060] Limestone aggregate: 30 parts;

[0061] Polytri-methylphenylsiloxane modified halloysite nanotubes: 12 parts;

[0062] Perfluororubber: 15 parts;

[0063] Maleic anhydride grafted ethylene vinyl acetate copolymer: 12 parts;

[0064] Epoxidized soybean oil: 5 parts;

[0065] Nano-titanium dioxide: 8 parts.

[0066] Due to the extremely high surface energy of nano-titanium dioxide, it is prone to agglomeration after being added to the asphalt composition, thus limiting the anti-ultraviolet effect of nano-titanium dioxide. Halloysite nanotubes are a kind of tubular nano-material formed by the natural curling of silicate. The tubular structure enables nano-titanium dioxide to be uniformly dispersed on the surface and inside the tubular structure, having good dispersibility for it and improving the anti-ultraviolet effect of titanium dioxide. Moreover, in the present invention, halloysite nanotubes are modified by polytri-methylphenylsiloxane, so that a space network cross-linked structure is formed between polytri-methylphenylsiloxane halloysite nanotubes, matrix asphalt, maleic anhydride grafted ethylene vinyl acetate copolymer and perfluororubber, improving the mechanical properties of the asphalt.

[0067] The preparation method of this anti-aging modified asphalt includes the following steps:

[0068] S1. Stir polytri-methylphenylsiloxane modified halloysite nanotubes, epoxidized soybean oil and nano-titanium dioxide for 120 min to obtain an intermediate;

[0069] S2. Add perfluororubber, maleic anhydride grafted ethylene vinyl acetate copolymer, limestone aggregate and the intermediate to the matrix asphalt heated to 110 °C, and stir for 150 min to obtain the modified asphalt.

[0070] The raw materials of the polytri-methylphenylsiloxane modified halloysite nanotubes contain halloysite nanotubes, polytri-methylphenylsiloxane, glycerol, NaOH and water.

[0071] In the polytri-methylphenylsiloxane modified halloysite nanotubes, by weight,

[0072] Halloysite nanotubes: 10 parts;

[0073] Polytri-methylphenylsiloxane: 0.1 part;

[0074] Glycerol: 100 parts;

[0075] 30 wt% NaOH aqueous solution: 40 parts.

[0076] The preparation method of polytrimethylphenylsiloxane modified halloysite nanotubes is obtained by the following steps:

[0077] A1. Add halloysite nanotubes to 30 wt% NaOH aqueous solution, stir ultrasonically for 30 min, and then stir at 50 °C for 60 min to hydroxylate the halloysite nanotubes. Filter and dry to obtain hydroxylated halloysite nanotubes;

[0078] A2. Add the hydroxylated halloysite nanotubes to glycerol and stir, then add them to polytrimethylphenylsiloxane and stir at 100 °C for 60 min to obtain polytrimethylphenylsiloxane modified halloysite nanotubes.

[0079] Example 2

[0080] A preparation method of aging-resistant modified asphalt, the raw materials of which include matrix asphalt, limestone aggregate, polytrimethylphenylsiloxane modified halloysite nanotubes, perfluororubber, maleic anhydride grafted ethylene vinyl acetate copolymer, epoxy soybean oil and nano-titanium dioxide.

[0081] By weight,

[0082] Matrix asphalt: 100 parts;

[0083] Limestone aggregate: 25 parts;

[0084] Polytrimethylphenylsiloxane modified halloysite nanotubes: 10 parts;

[0085] Perfluororubber: 12 parts;

[0086] Maleic anhydride grafted ethylene vinyl acetate copolymer: 13 parts;

[0087] Epoxy soybean oil: 8 parts;

[0088] Nano-titanium dioxide: 3 parts.

[0089] The preparation method of the aging-resistant modified asphalt includes the following steps:

[0090] S1. Stir the polytrimethylphenylsiloxane modified halloysite nanotubes, epoxy soybean oil and nano-titanium dioxide for 120 min to obtain an intermediate;

[0091] S2. Add perfluororubber, maleic anhydride grafted ethylene vinyl acetate copolymer, limestone aggregate and the intermediate to the matrix asphalt heated to 105 °C, and stir for 120 min to obtain the modified asphalt.

[0092] Among them, the raw materials of the polytrimethylphenylsiloxane modified halloysite nanotubes include halloysite nanotubes, polytrimethylphenylsiloxane, glycerol, NaOH and water.

[0093] In the polytrimethylphenylsiloxane-modified halloysite nanotubes, by weight parts,

[0094] Halloysite nanotubes: 10 parts;

[0095] Polytrimethylphenylsiloxane: 0.05 parts;

[0096] Glycerol: 50 parts;

[0097] 30 wt% NaOH aqueous solution: 80 parts.

[0098] The preparation method of the polytrimethylphenylsiloxane-modified halloysite nanotubes is obtained by the following steps:

[0099] A1. Add the halloysite nanotubes to the 30 wt% NaOH aqueous solution, stir ultrasonically for 60 min, and then stir at 40 °C for 30 min to hydroxylate the halloysite nanotubes, and filter and dry to obtain hydroxylated halloysite nanotubes;

[0100] A2. Add the hydroxylated halloysite nanotubes to glycerol and stir, then add them to polytrimethylphenylsiloxane and stir at 80 °C for 120 min to obtain polytrimethylphenylsiloxane-modified halloysite nanotubes.

[0101] Example 3

[0102] A preparation method of aging-resistant modified asphalt, the raw materials include matrix asphalt, limestone aggregate, polytrimethylphenylsiloxane-modified halloysite nanotubes, perfluororubber, maleic anhydride-grafted ethylene vinyl acetate copolymer, epoxy soybean oil and nano-titanium dioxide.

[0103] By weight parts,

[0104] Matrix asphalt: 100 parts;

[0105] Limestone aggregate: 28 parts;

[0106] Polytrimethylphenylsiloxane-modified halloysite nanotubes: 8 parts;

[0107] Perfluororubber: 10 parts;

[0108] Maleic anhydride-grafted ethylene vinyl acetate copolymer: 10 parts;

[0109] Epoxy soybean oil: 6 parts;

[0110] Nano-titanium dioxide: 6 parts.

[0111] The preparation method of the aging-resistant modified asphalt includes the following steps:

[0112] S1. Stir the polytrimethylphenylsiloxane-modified halloysite nanotubes, epoxy soybean oil and nano-titanium dioxide for 120 min to obtain an intermediate;

[0113] S2. Add perfluororubber, maleic anhydride grafted ethylene vinyl acetate copolymer, limestone aggregate and intermediate to the matrix asphalt heated to 107 °C, and stir for 140 min to obtain modified asphalt.

[0114] Among them, the raw materials for polytrimethylphenylsiloxane modified halloysite nanotubes contain halloysite nanotubes, polytrimethylphenylsiloxane, glycerol, NaOH and water.

[0115] In the polytrimethylphenylsiloxane modified halloysite nanotubes, by weight:

[0116] Halloysite nanotubes: 10 parts;

[0117] Polytrimethylphenylsiloxane: 0.08 part;

[0118] Glycerol: 80 parts;

[0119] 30 wt% NaOH aqueous solution: 50 parts.

[0120] The preparation method of polytrimethylphenylsiloxane modified halloysite nanotubes is obtained by the following steps:

[0121] A1. Add halloysite nanotubes to 30 wt% NaOH aqueous solution, stir ultrasonically for 45 min, and then stir at 45 °C for 45 min to hydroxylate halloysite nanotubes, and filter and dry to obtain hydroxylated halloysite nanotubes;

[0122] A2. Add the hydroxylated halloysite nanotubes to glycerol and stir, then add them to polytrimethylphenylsiloxane and stir at 88 °C for 130 min to obtain polytrimethylphenylsiloxane modified halloysite nanotubes.

[0123] Example 4

[0124] A preparation method of anti-aging modified asphalt, the raw materials contain matrix asphalt, limestone aggregate, polytrimethylphenylsiloxane modified halloysite nanotubes, perfluororubber, maleic anhydride grafted ethylene vinyl acetate copolymer, epoxy soybean oil and nano titanium dioxide.

[0125] By weight:

[0126] Matrix asphalt: 100 parts;

[0127] Limestone aggregate: 20 parts;

[0128] Polytrimethylphenylsiloxane modified halloysite nanotubes: 5 parts;

[0129] Perfluororubber: 13 parts;

[0130] Maleic anhydride grafted ethylene vinyl acetate copolymer: 15 parts;

[0131] Epoxidized soybean oil: 7 parts;

[0132] Nano titanium dioxide: 5 parts.

[0133] The preparation method of the anti-aging modified asphalt comprises the following steps:

[0134] S1. Stir polytrimethylphenylsiloxane modified halloysite nanotubes, epoxidized soybean oil and nano titanium dioxide for 120 min to obtain an intermediate;

[0135] S2. Add perfluororubber, maleic anhydride grafted ethylene vinyl acetate copolymer, limestone aggregate and the intermediate to the matrix asphalt heated to 107 °C, and stir for 130 min to obtain the modified asphalt.

[0136] The raw materials of the polytrimethylphenylsiloxane modified halloysite nanotubes contain halloysite nanotubes, polytrimethylphenylsiloxane, glycerol, NaOH and water.

[0137] In the polytrimethylphenylsiloxane modified halloysite nanotubes, by weight,

[0138] Halloysite nanotubes: 10 parts;

[0139] Polytrimethylphenylsiloxane: 0.08 part;

[0140] Glycerol: 60 parts;

[0141] 30 wt% aqueous NaOH solution: 60 parts.

[0142] The preparation method of the polytrimethylphenylsiloxane modified halloysite nanotubes is obtained by the following steps:

[0143] A1. Add halloysite nanotubes to 30 wt% aqueous NaOH solution, ultrasonically stir for 45 min, and then stir at 45 °C for 45 min to hydroxylate the halloysite nanotubes, and filter and dry to obtain hydroxylated halloysite nanotubes;

[0144] A2. Add the hydroxylated halloysite nanotubes to glycerol and stir, then add them to polytrimethylphenylsiloxane and stir at 88 °C for 100 min to obtain polytrimethylphenylsiloxane modified halloysite nanotubes.

[0145] Example 5

[0146] A preparation method of anti-aging modified asphalt, the raw materials of which contain matrix asphalt, limestone aggregate, polytrimethylphenylsiloxane modified halloysite nanotubes, perfluororubber, maleic anhydride grafted ethylene vinyl acetate copolymer, epoxidized soybean oil and nano titanium dioxide.

[0147] By weight,

[0148] Matrix asphalt: 100 parts;

[0149] Limestone aggregate: 25.8 parts;

[0150] Polytrimethylphenylsiloxane-modified halloysite nanotubes: 8.6 parts;

[0151] Perfluororubber: 12.7 parts;

[0152] Maleic anhydride-grafted ethylene vinyl acetate copolymer: 12.5 parts;

[0153] Epoxidized soybean oil: 6.5 parts;

[0154] Nano-titanium dioxide: 5.6 parts.

[0155] The preparation method of the anti-aging modified asphalt comprises the following steps:

[0156] S1. Stir the polytrimethylphenylsiloxane-modified halloysite nanotubes, epoxidized soybean oil and nano-titanium dioxide for 120 min to obtain an intermediate;

[0157] S2. Add perfluororubber, maleic anhydride-grafted ethylene vinyl acetate copolymer, limestone aggregate and the intermediate to the matrix asphalt heated to 106 °C, and stir for 130 min to obtain the modified asphalt.

[0158] Among them, the raw materials and preparation method of the polytrimethylphenylsiloxane-modified halloysite nanotubes are the same as those in Example 4.

[0159] Comparative Example 1

[0160] A preparation method of an anti-aging modified asphalt, the raw materials of which include matrix asphalt, limestone aggregate, polytrimethylphenylsiloxane-modified halloysite nanotubes, perfluororubber, maleic anhydride-grafted ethylene vinyl acetate copolymer, epoxidized soybean oil and nano-titanium dioxide.

[0161] By weight,

[0162] Matrix asphalt: 100 parts;

[0163] Limestone aggregate: 25.8 parts;

[0164] Polytrimethylphenylsiloxane-modified halloysite nanotubes: 3 parts;

[0165] Perfluororubber: 5 parts;

[0166] Maleic anhydride-grafted ethylene vinyl acetate copolymer: 20 parts;

[0167] Epoxidized soybean oil: 6.5 parts;

[0168] Nano-titanium dioxide: 5.6 parts.

[0169] The preparation method of the anti-aging modified asphalt is the same as that of Example 5, and the raw materials and preparation method of the polytrimethylphenylsiloxane-modified halloysite nanotubes are the same as those of Example 4.

[0170] Comparative Example 2

[0171] A preparation method of anti-aging modified asphalt, the raw materials of which include matrix asphalt, limestone aggregate, polytrimethylphenylsiloxane-modified halloysite nanotubes, peroxyfluororubber, maleic anhydride-grafted ethylene vinyl acetate copolymer, epoxy soybean oil and nano-titanium dioxide.

[0172] By weight,

[0173] Matrix asphalt: 100 parts;

[0174] Limestone aggregate: 25.8 parts;

[0175] Polytrimethylphenylsiloxane-modified halloysite nanotubes: 20 parts;

[0176] Peroxyfluororubber: 20 parts;

[0177] Maleic anhydride-grafted ethylene vinyl acetate copolymer: 3 parts;

[0178] Epoxy soybean oil: 6.5 parts;

[0179] Nano-titanium dioxide: 5.6 parts.

[0180] The preparation method of the anti-aging modified asphalt is the same as that of Example 5, and the raw materials and preparation method of the polytrimethylphenylsiloxane-modified halloysite nanotubes are the same as those of Example 4.

[0181] Comparative Example 3

[0182] A preparation method of anti-aging modified asphalt, the raw materials of which include matrix asphalt, limestone aggregate, polytrimethylphenylsiloxane-modified halloysite nanotubes, peroxyfluororubber, maleic anhydride-grafted ethylene vinyl acetate copolymer, epoxy soybean oil and nano-titanium dioxide.

[0183] By weight,

[0184] Matrix asphalt: 100 parts;

[0185] Limestone aggregate: 25.8 parts;

[0186] Polytrimethylphenylsiloxane-modified halloysite nanotubes: 8.6 parts;

[0187] Peroxyfluororubber: 12.7 parts;

[0188] Maleic anhydride grafted ethylene vinyl acetate copolymer: 12.5 parts;

[0189] Epoxidized soybean oil: 6.5 parts;

[0190] Nano-titanium dioxide: 5.6 parts.

[0191] The preparation method of this anti-aging modified asphalt is the same as that of Example 5.

[0192] Among them, the raw materials of the polytrimethylphenylsiloxane modified halloysite nanotubes contain halloysite nanotubes, polytrimethylphenylsiloxane, glycerol, NaOH and water.

[0193] In the polytrimethylphenylsiloxane modified halloysite nanotubes, by weight,

[0194] Halloysite nanotubes: 10 parts;

[0195] Polytrimethylphenylsiloxane: 1 part;

[0196] Glycerol: 60 parts;

[0197] 30wt% NaOH aqueous solution: 60 parts.

[0198] The preparation method of the polytrimethylphenylsiloxane modified halloysite nanotubes is obtained by the following steps:

[0199] A1. Add halloysite nanotubes to 30wt% NaOH aqueous solution, stir ultrasonically for 45 min, and then stir at 45 °C for 45 min to hydroxylate the halloysite nanotubes, filter and dry to obtain hydroxylated halloysite nanotubes;

[0200] A2. Add the hydroxylated halloysite nanotubes to glycerol and stir, then add them to polytrimethylphenylsiloxane and stir at 88 °C for 100 min to obtain polytrimethylphenylsiloxane modified halloysite nanotubes.

[0201] Comparative Example 4

[0202] A preparation method of anti-aging modified asphalt, the raw materials contain matrix asphalt, limestone aggregate, perfluororubber, maleic anhydride grafted ethylene vinyl acetate copolymer, epoxidized soybean oil and nano-titanium dioxide.

[0203] By weight,

[0204] Matrix asphalt: 100 parts;

[0205] Limestone aggregate: 25.8 parts;

[0206] Perfluororubber: 18.3 parts;

[0207] Maleic anhydride grafted ethylene vinyl acetate copolymer: 15.5 parts;

[0208] Epoxidized soybean oil: 6.5 parts;

[0209] Nano-titanium dioxide: 5.6 parts.

[0210] The preparation method of the anti-aging modified asphalt includes the following steps:

[0211] S1. Stir the epoxidized soybean oil and nano-titanium dioxide for 120 min to obtain an intermediate;

[0212] S2. Add perfluororubber, maleic anhydride grafted ethylene-vinyl acetate copolymer, limestone aggregate and the intermediate to the matrix asphalt heated to 106 °C, and stir for 130 min to obtain the modified asphalt.

[0213] Comparative Example 5

[0214] A preparation method of anti-aging modified asphalt, the raw materials of which include matrix asphalt, limestone aggregate, polytri-methylphenylsiloxane modified halloysite nanotubes, maleic anhydride grafted ethylene-vinyl acetate copolymer, epoxidized soybean oil and nano-titanium dioxide.

[0215] By weight,

[0216] Matrix asphalt: 100 parts;

[0217] Limestone aggregate: 25.8 parts;

[0218] Polytri-methylphenylsiloxane modified halloysite nanotubes: 10 parts;

[0219] Maleic anhydride grafted ethylene-vinyl acetate copolymer: 23.8 parts;

[0220] Epoxidized soybean oil: 6.5 parts;

[0221] Nano-titanium dioxide: 5.6 parts.

[0222] The preparation method of the anti-aging modified asphalt includes the following steps:

[0223] S1. Stir the polytri-methylphenylsiloxane modified halloysite nanotubes, epoxidized soybean oil and nano-titanium dioxide for 120 min to obtain an intermediate;

[0224] S2. Add maleic anhydride grafted ethylene-vinyl acetate copolymer, limestone aggregate and the intermediate to the matrix asphalt heated to 106 °C, and stir for 130 min to obtain the modified asphalt.

[0225] The raw materials and preparation method of the polytri-methylphenylsiloxane modified halloysite nanotubes are the same as those in Example 3.

[0226] Comparative Example 6

[0227] A preparation method of aging-resistant modified asphalt, the raw materials of which include matrix asphalt, limestone aggregate, polytrimethylphenylsiloxane-modified halloysite nanotubes, perfluororubber, epoxy soybean oil and nano-titanium dioxide.

[0228] By weight,

[0229] Matrix asphalt: 100 parts;

[0230] Limestone aggregate: 25.8 parts;

[0231] Polytrimethylphenylsiloxane-modified halloysite nanotubes: 10 parts;

[0232] Perfluororubber: 23.8 parts;

[0233] Epoxy soybean oil: 6.5 parts;

[0234] Nano-titanium dioxide: 5.6 parts.

[0235] The preparation method of the aging-resistant modified asphalt includes the following steps:

[0236] S1. Stir the polytrimethylphenylsiloxane-modified halloysite nanotubes, epoxy soybean oil and nano-titanium dioxide for 120 min to obtain an intermediate;

[0237] S2. Add perfluororubber, limestone aggregate and the intermediate to the matrix asphalt heated to 106 °C, and stir for 130 min to obtain modified asphalt.

[0238] The raw materials and preparation method of the polytrimethylphenylsiloxane-modified halloysite nanotubes are the same as those in Example 3.

[0239] Effect example

[0240] According to JTG E40-2011 "Test Procedures for Asphalt and Asphalt Mixtures in Highway Engineering", the performance tests of the modified asphalt prepared in Examples 1-5 and Comparative Examples 1-6 were carried out respectively, and the corresponding Tables 1 and 2 were obtained.

[0241] Table 1. Performance test results of the modified asphalt in Examples 1-5

[0242] Project Example 1 Example 2 Example 3 Example 4 Example 5 Penetration (25°C) (0.1 mm) 53 52 53 53 54 Ductility (5°C) (cm) 99 98 97 100 103 Toughness at 25°C (N.m) 27 26 26 28 29 Viscous toughness at 25°C (N.m) 41 40 39 41 40 <![CDATA[Cohesion (J / cm 2 )]]> 2.83 2.56 2.61 2.67 2.88

[0243] Table 2. Performance test results of the modified asphalt in Comparative Examples 1-6

[0244] Project Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Penetration (25°C, 0.1 mm) 51 53 50 50 52 52 Ductility (5°C, cm) 100 97 92 94 97 95 Toughness at 25°C (N.m) 23 26 25 25 24 26 Viscous toughness at 25°C (Nm) 36 35 38 33 36 34 <![CDATA[Cohesion (J / cm 2 )]]> 2.45 2.32 2.12 2.29 2.38 2.36

[0245] The present invention also continued to prepare pavement asphalt mixtures with the modified asphalt prepared in Examples 1 - 5 and Comparative Examples 1 - 6, and continued to conduct performance tests on the pavement asphalt mixtures and added polytri-methylphenylsiloxane to obtain Tables 3 and 4. The specific preparation method of the pavement asphalt mixture is as follows: Pump the modified asphalt into the hot bin containing aggregates and stir to obtain the modified asphalt mixture.

[0246] Table 3. Performance test results of the modified asphalt mixtures of Examples 1 - 5

[0247]

[0248] Table 4. Performance test results of the modified asphalt mixtures of Comparative Examples 1 - 6

[0249]

[0250] Among them, the flexural tensile failure strength was tested by preparing rutting plate specimens with a height of 35 mm, a length of 250 mm, and a width of 30 mm at a loading rate of 500 mm / min at a temperature of -10°C. The ultraviolet aging was carried out by placing the asphalt concrete specimens in an ultraviolet aging chamber with an ultraviolet intensity of 210 W / m 2 , an aging temperature of 60°C, and an aging time of 6 days.

[0251] From the data in Tables 1 - 4, it can be seen that the mechanical properties of the modified asphalt and pavement asphalt mixtures in Examples 1 - 5 are basically higher than those in Comparative Examples 1 to 6. Among them, the fatigue life of the pavement asphalt mixtures prepared with the modified asphalt of the present invention is greater than 1.99 million times, and the highest can reach 2,001,329 times. The flexural tensile failure strength is greater than 23 MPa, and the highest can reach 23.6 MPa. Moreover, after the ultraviolet aging treatment of the modified asphalt of the present invention, the dynamic stability of the 60°C rutting test is greater than 9,934 times / mm, and the highest reaches 10,165 times / mm. The dynamic stability of the 70°C rutting test is greater than 7,524 times / mm, and the highest reaches 8,118 times / mm.

[0252] It can be seen that the modified asphalt of the present invention has good anti-ultraviolet aging performance and is not prone to cracks and damage. The modified asphalt of the present invention has good mechanical properties and a longer service life. Moreover, from Comparative Examples 4 to 6 of the present invention, it can be seen that only when polytri-methylphenylsiloxane-modified halloysite nanotubes, perfluororubber, and maleic anhydride-grafted ethylene vinyl acetate copolymer exist simultaneously can the Marshall stability, dynamic stability of the rutting test, low-temperature bending failure strain, and flexural tensile failure strength be significantly improved. At the same time, the above data show that the present invention can further improve the above performance through the reasonable ratio of each component and appropriate preparation conditions.

[0253] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention rather than to limit the protection scope of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that the technical solutions of the present invention can be modified or equivalently replaced without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A method for preparing aging-resistant modified asphalt, characterized in that: The raw materials include base asphalt, limestone mineral material, polytrimethylphenylsiloxane modified halloysite nanotubes, peroxide fluororubber, maleic anhydride grafted ethylene vinyl acetate copolymer, epoxidized soybean oil and nano titanium dioxide; The following steps are involved: S1, stirring polytrimethylphenylsiloxane-modified halloysite nanotubes, epoxidized soybean oil and nano-titanium dioxide to obtain an intermediate; S2, adding fluoroperoxide rubber, maleic anhydride grafted ethylene vinyl acetate copolymer, limestone ore and intermediate into base asphalt, stirring to obtain modified asphalt; In parts by weight, Base asphalt: 100 parts; Limestone ore: 20 to 30 parts; Polytrimethylphenylsiloxane modified halloysite nanotubes: 5 to 12 parts; Fluororubber peroxide: 10 to 15 parts; Maleic anhydride grafted ethylene vinyl acetate copolymer: 10 to 15 parts; Epoxidized soybean oil: 5 to 8 parts; Nano titanium dioxide: 3 to 8 parts; The raw materials of the polytrimethylphenylsiloxane-modified halloysite nanotubes contain halloysite nanotubes, polytrimethylphenylsiloxane, glycerol, NaOH and water; The preparation method of the polytrimethylphenylsiloxane-modified halloysite nanotubes comprises adding the halloysite nanotubes to an aqueous solution of NaOH to hydroxylate the halloysite nanotubes, then adding the hydroxylated halloysite nanotubes to glycerol and adding polytrimethylphenylsiloxane to obtain the polytrimethylphenylsiloxane-modified halloysite nanotubes; In the polytrimethylphenylsiloxane modified halloysite nanotubes, in parts by weight, Halloysite nanotubes: 10 parts; Polytrimethylphenylsiloxane: 0.05 to 0.1 parts; Glycerol: 50 to 100 parts; 30wt% NaOH aqueous solution: 40 to 80 parts.

2. The method for preparing aging-resistant modified asphalt according to claim 1, characterized in that: In parts by weight, Base asphalt: 100 parts; Limestone ore: 25 to 28 parts; Polytrimethylphenylsiloxane modified halloysite nanotubes: 8 to 10 parts; Fluororubber peroxide: 12 to 13 parts; Maleic anhydride grafted ethylene vinyl acetate copolymer: 12 to 13 parts; Epoxidized soybean oil: 6-7 parts; Nano titanium dioxide: 5 to 6 parts.

3. The method for preparing aging-resistant modified asphalt according to claim 2, characterized in that: In parts by weight, Base asphalt: 100 parts; Limestone ore: 25.8 parts; Polytrimethylphenylsiloxane modified halloysite nanotubes: 8.6 parts; Fluororubber peroxide: 12.7 parts; Maleic anhydride grafted ethylene vinyl acetate copolymer: 12.5 parts; Epoxidized soybean oil: 6.5 parts; Nano titanium dioxide: 5.6 parts.

4. The method for preparing aging-resistant modified asphalt according to claim 1, characterized in that: In the polytrimethylphenylsiloxane modified halloysite nanotubes, in parts by weight, Halloysite nanotubes: 10 parts; Polytrimethylphenylsiloxane: 0.08 parts; Glycerol: 60 parts; 30wt% NaOH aqueous solution: 60 parts.

5. The method for preparing aging-resistant modified asphalt according to claim 1, characterized in that: The preparation method of the polytrimethylphenylsiloxane modified halloysite nanotubes is obtained by the following steps: A1, adding halloysite nanotubes to a 30wt% NaOH aqueous solution, stirring ultrasonically for 30min to 60min, stirring at 40°C to 50°C for 30min to 60min to hydroxylate the halloysite nanotubes, filtering and drying to obtain hydroxylated halloysite nanotubes; A2. Add hydroxylated halloysite nanotubes to propylene glycol and stir, then add to polytrimethylphenylsiloxane and stir at 80° C. to 100° C. for 60 min to 120 min to obtain polytrimethylphenylsiloxane-modified halloysite nanotubes.

6. The method for preparing the aging-resistant modified asphalt according to any one of claims 1 to 5, characterized in that: Specifically, the S2 is prepared by adding fluoroperoxide rubber, maleic anhydride grafted ethylene vinyl acetate copolymer, limestone ore and intermediates to a base asphalt heated to 105-110° C., and stirring for 120-150 minutes to obtain modified asphalt.

7. An aging-resistant modified asphalt, characterized in that: The asphalt is prepared by the method for preparing the aging-resistant modified asphalt as described in any one of claims 1 to 6.

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