Polyurethane / epoxy resin composite modified bio-oil asphalt and preparation method thereof

Abstract

The invention provides polyurethane / epoxy resin composite modified bio-oil asphalt. The polyurethane / epoxy resin composite modified bio-oil asphalt is prepared from raw materials in parts by mass as follows: 10-60 parts of bio-oil, 40-90 parts of matrix asphalt, 5-20 parts of isocyanate, 10-30 parts of a chain extender, 10-50 parts of epoxy resin, 10-50 parts of a curing agent and 5-10 parts of a compatilizer, according to the polyurethane / epoxy resin composite modified bio-oil asphalt, the defect that the bio-oil asphalt is poor in high-temperature performance is overcome, meanwhile, polyurethane can replace part of epoxy resin to provide strength, the dosage of the epoxy resin is reduced, and the cost of the modified bio-oil asphalt is reduced.

Description

Technical Field

[0001] The present invention relates to the technical field of asphalt preparation, and in particular to a polyurethane / epoxy resin composite modified bio-oil asphalt and a preparation method thereof. Background Art

[0002] Petroleum asphalt is a non-renewable resource and is showing signs of depletion. Bio-oil, as an environmentally friendly material, can partially replace non-renewable petroleum asphalt. However, the addition of bio-oil weakens petroleum asphalt's high-temperature deformation resistance and can lead to segregation during storage. These drawbacks significantly hinder the application of bio-oil in pavement engineering.

[0003] Polyurethane is an organic polymer composed of a mosaic of hard and soft segments. The difference in polarity between the hard and soft segments and the inherent crystallinity of the hard segments make them incompatible, resulting in a two-phase separation structure similar to that of SBS. However, the ratio of hard and soft segments in polyurethane can be adjusted as needed, with the hard segments providing strength and the soft segments providing flexibility. Furthermore, the isocyanate groups in polyurethane react chemically with active hydrogen, effectively improving the compatibility of composite materials. Epoxy resin is a high-performance thermosetting polymer widely used in coatings, adhesives, composite materials, and electronic packaging materials. It exhibits excellent adhesion, mechanical strength, and chemical resistance. During the curing process, epoxy resin and curing agent form a cross-linked network, imparting high strength and wear resistance to the material. This property gives epoxy resin composites exceptional resistance to deformation at high temperatures.

[0004] Patent CN 117004240 A describes a polyurethane-modified epoxy cold-mix asphalt. Epoxy resin is modified with polyurethane, and the flexible chain segments in the polyurethane are grafted and cross-linked into the epoxy resin. This polyurethane-epoxy resin composite modified cold-mix asphalt combines the advantages of epoxy resin, such as high strength, good high-temperature performance, and low shrinkage, with the good ductility, excellent flexibility, and anti-aging properties of polyurethane.

[0005] Patent CN 112322055 A discloses an asphalt based on water-based epoxy resin and a preparation method thereof. The modified water-based epoxy resin peptizing agent is prepared by reacting polypropylene glycol and diphenylmethane diisocyanate to obtain a polyurethane prepolymer, which is then chain-extended with a modified filler under the action of a chain extender, 1,4-butanediol. The prepolymer is then mixed with a water-based epoxy resin emulsion and a toughening filler to obtain a modified water-based epoxy resin peptizing agent. After mixing with an asphalt matrix, the toughness of the asphalt is greatly enhanced. Summary of the Invention

[0006] In response to the above-mentioned shortcomings of bio-oil asphalt in the existing technology, such as segregation and poor high-temperature deformation resistance, the present invention provides a polyurethane / epoxy resin composite modified bio-oil asphalt and a preparation method thereof. By designing a polyurethane material with a certain ratio of soft and hard segments and composite epoxy resin modified bio-oil asphalt, the storage stability and high-temperature rutting resistance of bio-oil asphalt can be improved, thereby promoting the sustainable development of the road engineering industry.

[0007] A polyurethane / epoxy resin composite modified bio-oil asphalt, comprising the following raw materials in parts by mass:

[0008]

[0009] The bio-oil is any one of plant oil, animal oil, waste oil, and microalgae oil, or a mixture of two or more of the above in any proportion.

[0010] The matrix asphalt is selected from any one of petroleum asphalt 70#, petroleum asphalt 90#, petroleum asphalt 110#, or a mixture of two or more of them in any proportion.

[0011] The isocyanate is selected from the group consisting of toluene diisocyanate, isophorone diisocyanate, and diphenylmethane diisocyanate, or a mixture of two or more of the two or more in any proportion. Excessive isocyanate content results in high material strength but insufficient toughness, while insufficient isocyanate content leads to the opposite effect.

[0012] The epoxy resin is selected from any one of bisphenol A epoxy resin, bisphenol F epoxy resin and resorcinol epoxy resin, or a mixture of two or more of them in any proportion.

[0013] The above-mentioned chain extender is any one of 4,4'-methylenebis(2-chloroaniline)4,4'-methylenebis(2-chloroaniline) (MOCA), 1,4-butanediol, 1,6-hexanediol or ethylenediamine, or a mixture of two or more in any proportion; the above-mentioned curing agent is any one of aliphatic amine curing agents, alicyclic amine curing agents, aromatic amine curing agents, and low molecular weight polyamide, or a mixture of two or more in any proportion; the above-mentioned compatibilizer is any one of epoxy fatty acid methyl ester, epoxy butyl stearate, epoxy soybean oil and epoxy linseed oil ester, or a mixture of two or more in any proportion.

[0014] This polyurethane / epoxy resin composite modified bio-oil asphalt material is prepared by in-situ polymerization of an isocyanate and a chain extender within the bio-oil asphalt. The resulting soft segment molecular chains provide flexibility. The epoxy resin and curing agent form a cured cross-linked network within the bio-oil asphalt, providing strength.

[0015] A method for preparing polyurethane / epoxy resin composite modified bio-oil asphalt comprises the following steps:

[0016] (1) adding molten matrix asphalt and bio-oil into a reactor and stirring to obtain bio-oil asphalt;

[0017] (2) adding isocyanate and chain extender into a reactor and stirring to obtain a polyurethane-modified bio-oil asphalt sample, and then lowering the temperature of the reactor to 80-120° C.;

[0018] (3) placing the polyurethane-modified bio-oil asphalt sample in a reactor at 80-120°C for 1-2 hours to obtain the polyurethane-modified bio-oil asphalt product;

[0019] (4) Add epoxy resin, curing agent, and compatibilizer into a reactor and stir to obtain polyurethane / epoxy resin composite modified bio-oil asphalt.

[0020] In the above step (1), the stirring temperature is 140-180° C., the stirring speed is 1000-3000 r / min, and the stirring time is 0.5-1 h.

[0021] In the above step (2), the stirring temperature is 140-180° C., the stirring speed is 4000-6000 r / min, and the stirring time is 1-2 h.

[0022] In the above step (4), the stirring temperature is 160-180° C., the stirring speed is 600-1500 r / min, and the stirring time is 1-2 h.

[0023] The specific steps of step (1) are as follows: placing the matrix asphalt in a blast drying oven at a temperature of 140°C to 160°C for 2 to 3 hours until it becomes a molten state, then adding petroleum asphalt and bio-oil into a reactor according to a certain mass ratio, and stirring the mixture at a high speed of 1000 to 3000 r / min at a temperature of 140 to 180°C for 0.5 to 1 hour, and obtaining bio-oil asphalt after stirring.

[0024] The specific steps of step (2) are as follows: then, isocyanate and chain extender are added to the reactor together according to a certain mass ratio, and high-speed shear mechanical stirring is performed at a temperature of 140-180° C. and a speed of 4000-6000 r / min for 1-2 hours. After the stirring is completed, a polyurethane-modified bio-oil asphalt sample is obtained, and then the temperature of the reactor is reduced to 80-120° C.

[0025] The specific steps of step (4) are: raising the temperature of the reactor to 160-180° C., adding epoxy resin, curing agent, and compatibilizer together into the reactor containing the polyurethane-modified bio-oil asphalt product according to a certain mass ratio, and mechanically stirring at a temperature of 160-180° C. and a speed of 600-1500 r / min for 1-2 hours. After the stirring is completed, a high-strength and high-toughness polyurethane / epoxy resin composite modified bio-oil asphalt product is obtained.

[0026] Compared with the prior art, this application has the following advantages:

[0027] (1) The polyurethane / epoxy resin composite modified bio-oil asphalt described in the present invention has excellent mechanical properties and good toughness (high strength and high toughness), and is widely applicable to various application scenarios.

[0028] (2) The polyurethane / epoxy resin composite modified bio-oil asphalt of the present invention has a simple preparation process and excellent storage stability.

[0029] (3) The polyurethane / epoxy resin composite modified bio-oil asphalt described in the present invention not only solves the shortcoming of poor high-temperature performance of bio-oil asphalt, but also polyurethane can replace part of the epoxy resin to provide strength, thereby reducing the amount of epoxy resin used and lowering the cost of modified bio-oil asphalt. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 The results of the rutting test and low-temperature beam test of the embodiments and comparative examples of the present application are shown in FIG.

[0031] Figure 2 These are the storage stability test results of Example 1 and Comparative Example 1 of the present application. DETAILED DESCRIPTION

[0032] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0033] Example 1

[0034] (1): The matrix asphalt is placed in a blast drying oven and heated at 140°C for 2 hours until it becomes molten. Then, 90 parts of 70# petroleum asphalt and 10 parts of vegetable oil are added to the reactor according to the mass ratio. The mixture is mechanically stirred at 140°C and a speed of 1000 r / min for 0.5 hours. After the stirring is completed, the bio-oil asphalt is obtained.

[0035] (2): Then, 5 parts of toluene diisocyanate and 10 parts of 4,4'-methylenebis(2-chloroaniline) were added into the reactor according to the mass ratio, and high-speed shear stirring was carried out at a speed of 4000 r / min at a temperature of 180°C for 1 hour. After the stirring was completed, the polyurethane-modified bio-oil asphalt sample was obtained, and then the temperature of the reactor was reduced to 80°C.

[0036] (3): The polyurethane modified bio-oil asphalt sample is placed in an 80°C reactor for development for 2 hours to obtain the polyurethane modified bio-oil asphalt finished product.

[0037] (4): Raise the temperature of the reactor to 160°C, add 10 parts of bisphenol A epoxy resin, 10 parts of fatty amine curing agent, and 5 parts of epoxy fatty acid methyl ester into the reactor containing the polyurethane modified bio-oil asphalt product according to a certain mass ratio, and mechanically stir at a temperature of 160°C and a speed of 600r / min for 2h. After stirring, the polyurethane / epoxy resin composite modified bio-oil asphalt product is obtained.

[0038] Example 2

[0039] (1): The matrix asphalt is placed in a blast drying oven and heated at 150°C for 3 hours until it becomes molten. Then, 70# to 80 parts of petroleum asphalt and 20 parts of animal oil are added to the reactor according to the mass ratio. The mixture is mechanically stirred at 150°C and a speed of 2000 r / min for 1 hour. After the stirring is completed, the bio-oil asphalt is obtained.

[0040] (2): Then, 10 parts of diphenylmethane diisocyanate and 30 parts of 1,4-butanediol were added to the reactor according to the mass ratio, and the high-speed shearing machine was used at a speed of 5000 r / min at a temperature of 150°C for 2 hours. After stirring, the polyurethane-modified bio-oil asphalt sample was obtained, and then the temperature of the reactor was reduced to 90°C.

[0041] (3): The polyurethane modified bio-oil asphalt sample is placed in a reactor at 90°C for development for 1.5 hours to obtain the polyurethane modified bio-oil asphalt finished product.

[0042] (4): Raise the temperature of the reactor to 170°C, add 20 parts of bisphenol F epoxy resin, 20 parts of alicyclic amine curing agent, and 6 parts of epoxy butyl stearate into the reactor containing the polyurethane modified bio-oil asphalt product according to a certain mass ratio, and mechanically stir at a speed of 800 r / min at a temperature of 170°C for 2 hours. After stirring, a high-strength and high-toughness polyurethane / epoxy resin composite modified bio-oil asphalt product is obtained.

[0043] Example 3

[0044] (1): Petroleum asphalt 110# is placed in a forced air drying oven and heated at 160°C for 2.5 hours until it becomes molten. Then, 70 parts of petroleum asphalt 110# and 30 parts of waste oil are added to a reactor according to the mass ratio. The mixture is mechanically stirred at 160°C at a speed of 3000 r / min for 0.5 hours. After the stirring is completed, bio-oil asphalt is obtained.

[0045] (2): Then, 15 parts of isophorone diisocyanate and 20 parts of 1,6-hexanediol were added to the reactor according to the mass ratio, and high-speed shear stirring was carried out at a speed of 6000 r / min at a temperature of 160°C for 2 hours. After the stirring was completed, the polyurethane-modified bio-oil asphalt sample was obtained, and then the temperature of the reactor was reduced to 100°C.

[0046] (3): The polyurethane modified bio-oil asphalt sample is placed in a reactor at 100°C for development for 1 hour to obtain the polyurethane modified bio-oil asphalt finished product.

[0047] (4): Raise the temperature of the reactor to 180°C, add 30 parts of resorcinol epoxy resin, 30 parts of aromatic amine curing agent, and 7 parts of epoxy soybean oil into the reactor containing the polyurethane-modified bio-oil asphalt product according to a certain mass ratio, and mechanically stir at a temperature of 180°C and a speed of 1000 r / min for 3 hours. After stirring, a high-strength and high-toughness polyurethane / epoxy resin composite modified bio-oil asphalt product is obtained.

[0048] Example 4

[0049] (1): Petroleum asphalt 70# is placed in a forced air drying oven and heated at 145°C for 2 hours until it becomes molten. Then, 60 parts of petroleum asphalt 70# and 40 parts of microalgae oil are added to the reactor according to the mass ratio. The mixture is mechanically stirred at 145°C and a speed of 1500 r / min for 1 hour. After the stirring is completed, bio-oil asphalt is obtained.

[0050] (2): Then, 12 parts of toluene diisocyanate and 18 parts of ethylenediamine were added to the reactor according to the mass ratio, and high-speed shear stirring was carried out at a speed of 4500 r / min at a temperature of 175°C for 2 hours. After the stirring was completed, the polyurethane-modified bio-oil asphalt sample was obtained, and then the temperature of the reactor was reduced to 110°C.

[0051] (3): The polyurethane modified bio-oil asphalt sample is placed in a reactor at 110°C for development for 0.5h to obtain the polyurethane modified bio-oil asphalt finished product.

[0052] (4): Raise the temperature of the reactor to 165°C, add 40 parts of bisphenol A epoxy resin, 40 parts of aromatic amine curing agent, and 8 parts of epoxy soybean oil into the reactor containing the polyurethane-modified bio-oil asphalt product according to a certain mass ratio, and mechanically stir at a temperature of 165°C and a speed of 1200 r / min for 2 hours. After the stirring is completed, a high-strength and high-toughness polyurethane / epoxy resin composite modified bio-oil asphalt product is obtained.

[0053] Example 5

[0054] (1): Petroleum asphalt 90# is placed in a forced air drying oven and heated at 155°C for 3 hours until it becomes molten. Then, 50 parts of petroleum asphalt 90# and 50 parts of vegetable oil are added to the reactor according to the mass ratio. The mixture is mechanically stirred at 155°C at a speed of 2500 r / min for 0.5 hours. After the stirring is completed, bio-oil asphalt is obtained.

[0055] (2): Then, 12 parts of diphenylmethane diisocyanate and 12 parts of 1,6-hexanediol were added to the reactor according to the mass ratio, and high-speed shear stirring was carried out at a speed of 5500 r / min at a temperature of 195°C for 2 hours. After the stirring was completed, the polyurethane-modified bio-oil asphalt sample was obtained, and then the temperature of the reactor was reduced to 120°C.

[0056] (3): The polyurethane modified bio-oil asphalt sample is placed in a reactor at 120°C for development for 0.2h to obtain the polyurethane modified bio-oil asphalt finished product.

[0057] (4): Raise the temperature of the reactor to 175°C, add 50 parts of bisphenol F epoxy resin, 50 parts of alicyclic amine curing agent, and 9 parts of epoxy butyl stearate into the reactor containing the polyurethane modified bio-oil asphalt product according to a certain mass ratio, and mechanically stir at a temperature of 175°C and a speed of 1400 r / min for 2.5 hours. After the stirring is completed, the high-strength and high-toughness polyurethane / epoxy resin composite modified bio-oil asphalt product is obtained.

[0058] Example 6

[0059] (1): Petroleum asphalt 110# is placed in a forced air drying oven and heated at 160°C for 2 hours until it becomes molten. Then, 40 parts of petroleum asphalt 110# and 60 parts of waste oil are added to a reactor according to the mass ratio. The mixture is mechanically stirred at 160°C at a speed of 3000 r / min for 1 hour. After the stirring is completed, bio-oil asphalt is obtained.

[0060] (2): Then, 20 parts of isophorone diisocyanate and 15 parts of 1,4-butanediol were added to the reactor according to the mass ratio, and high-speed shear stirring was carried out at a speed of 6000 r / min at a temperature of 180°C for 3 hours. After the stirring was completed, the polyurethane-modified bio-oil asphalt sample was obtained, and then the temperature of the reactor was reduced to 100°C.

[0061] (3): The polyurethane modified bio-oil asphalt sample is placed in a reactor at 100°C for development for 1 hour to obtain the polyurethane modified bio-oil asphalt finished product.

[0062] (4): Raise the temperature of the reactor to 180°C, add 35 parts of resorcinol epoxy resin, 35 parts of alicyclic amine curing agent, and 5 parts of epoxy fatty acid methyl ester into the reactor containing the polyurethane modified bio-oil asphalt product according to a certain mass ratio, and mechanically stir at a temperature of 180°C and a speed of 1500r / min for 3 hours. After stirring, a high-strength and high-toughness polyurethane / epoxy resin composite modified bio-oil asphalt product is obtained.

[0063] Example 7

[0064] (1): Petroleum asphalt 90# is placed in a forced air drying oven and heated at 150°C for 3 hours until it becomes molten. Then, 50 parts of petroleum asphalt 90# and 50 parts of animal oil are added to the reactor according to the mass ratio. The mixture is mechanically stirred at 160°C and a speed of 3000 r / min for 1 hour. After the stirring is completed, bio-oil asphalt is obtained.

[0065] (2): Then, 20 parts of toluene diisocyanate and 20 parts of 4,4'-methylenebis(2-chloroaniline) were added into the reactor according to the mass ratio, and high-speed shear stirring was carried out at a speed of 2500r / min at a temperature of 180℃ for 2h. After the stirring was completed, the polyurethane modified bio-oil asphalt sample was obtained, and then the temperature of the reactor was reduced to 120℃.

[0066] (3): The polyurethane modified bio-oil asphalt sample is placed in an 80°C reactor for development for 2 hours to obtain the polyurethane modified bio-oil asphalt finished product.

[0067] (4): Raise the temperature of the reactor to 180°C, add 25 parts of bisphenol A epoxy resin, 25 parts of low molecular weight polyamide, and 10 parts of epoxy linseed oil ester into the reactor containing the polyurethane modified bio-oil asphalt product according to a certain mass ratio, and mechanically stir at a temperature of 180°C and a speed of 1500r / min for 3h. After the stirring is completed, the high-strength and high-toughness polyurethane / epoxy resin composite modified bio-oil asphalt product is obtained.

[0068] Comparative Example 1

[0069] A bio-oil asphalt material and a preparation method thereof are as follows:

[0070] The matrix asphalt was placed in a blast drying oven and heated at 140°C for 2 hours until it became molten. Then, 90 parts of 70# petroleum asphalt and 10 parts of vegetable oil were added to the reactor according to the mass ratio. The mixture was mechanically stirred at a high speed of 1000 r / min at 140°C for 0.5 hours. After the stirring was completed, the finished bio-oil asphalt product was obtained.

[0071] Comparative Example 2

[0072] A polyurethane bio-oil asphalt material and its preparation method are as follows:

[0073] (1): The matrix asphalt is placed in a blast drying oven and heated at 140°C for 2 hours until it becomes molten. Then, 90 parts of 70# petroleum asphalt and 10 parts of vegetable oil are added to the reactor according to the mass ratio. The mixture is mechanically stirred at 140°C and a speed of 1000 r / min for 0.5 hours. After the stirring is completed, the bio-oil asphalt is obtained.

[0074] (2): Then, 5 parts of toluene diisocyanate and 10 parts of 4,4'-methylenebis(2-chloroaniline) were added into the reactor according to the mass ratio, and high-speed shear stirring was carried out at a speed of 4000 r / min at a temperature of 180°C for 1 hour. After the stirring was completed, the polyurethane-modified bio-oil asphalt sample was obtained, and then the temperature of the reactor was reduced to 80°C.

[0075] (3): The polyurethane modified bio-oil asphalt sample is placed in an 80°C reactor for development for 2 hours to obtain the polyurethane modified bio-oil asphalt finished product.

[0076] Comparative Example 3

[0077] (1): The matrix asphalt is placed in a blast drying oven and heated at 140°C for 2 hours until it becomes molten. Then, 90 parts of 70# petroleum asphalt and 10 parts of vegetable oil are added to the reactor according to the mass ratio. The mixture is mechanically stirred at 140°C and a speed of 1000 r / min for 0.5 hours. After the stirring is completed, the bio-oil asphalt is obtained.

[0078] (2): Raise the temperature of the reactor to 160°C, add 10 parts of bisphenol A epoxy resin, 10 parts of fatty amine curing agent, and 5 parts of epoxy fatty acid methyl ester into the reactor containing the bio-oil asphalt product according to a certain mass ratio, and mechanically stir at a temperature of 160°C and a speed of 600 r / min for 2 hours. After the stirring is completed, the epoxy resin modified bio-oil asphalt product is obtained.

[0079] Comparative Example 4

[0080] (1) 5 parts of toluene diisocyanate, 10 parts of 4,4'-methylenebis(2-chloroaniline) and 10 parts of bisphenol A epoxy resin were added into a reactor according to the mass ratio and mechanically stirred at 140°C and 1000 r / min for 0.5 h to obtain polyurethane grafted epoxy resin.

[0081] (2): Place the base asphalt in a blast drying oven and heat it at 140°C for 2 hours until it becomes molten. Raise the temperature of the reactor to 160°C. Add 100 parts of 70# petroleum asphalt, 20 parts of polyurethane grafted epoxy resin, 10 parts of fatty amine curing agent, and 5 parts of epoxy fatty acid methyl ester into the reactor. Mechanically stir at 160°C and 600 r / min for 2 hours. After stirring, the polyurethane / epoxy resin composite modified asphalt product is obtained.

[0082] Test Example 1:

[0083] According to the asphalt mixture rutting test method T0719-2011 and the asphalt mixture bending test method T0715-2011 in the "Test Procedure for Asphalt and Asphalt Mixtures in Highway Engineering" (JTG E20-2011), the asphalt-stone ratio is 5%, the aggregate is basalt, and the grading is AC-13. All modified asphalts in Examples 1 to 7 and Comparative Examples 1 to 4 are tested for high and low temperature road performance. The dynamic stability results and low temperature beam results are as follows: Figure 1 As shown, from Figure 1 It can be seen from the data that the dynamic stability of the polyurethane / epoxy resin composite modified bio-oil asphalt materials in the seven groups of examples all exceeded 15,000 times / mm, even exceeding the standard of 8,000 times / mm or more in the "General Technical Requirements for Epoxy Asphalt Materials for Road and Bridge Paving" GB / T30598-2014, indicating that the polyurethane / epoxy resin composite modified bio-oil asphalt material of the present invention has excellent high-temperature deformation resistance and high strength. Figure 1 Results from low-temperature beam bending tests show that the polyurethane / epoxy resin composite modified bio-oil asphalt material is significantly stronger than bio-oil asphalt, indicating that the addition of polyurethane and epoxy resin significantly improves the low-temperature crack resistance of bio-oil asphalt. Furthermore, test results for asphalt modified with either polyurethane or epoxy resin alone show that high- and low-temperature performance is not well coordinated.

[0084] According to the comparison of the results of each embodiment with that of comparative example 1, it can be seen that the polyurethane / epoxy resin composite modified bio-oil asphalt of the present application greatly improves the deformation resistance of bio-oil asphalt, and the low-temperature performance is also improved to a certain extent.

[0085] Compared with the results of Comparative Examples 2 and 3, the high and low temperature performance of the polyurethane / epoxy resin composite modified bio-oil asphalt of the present application are significantly improved, which shows that the composite modified bio-oil asphalt prepared by the technical route of the present invention is better than the bio-oil asphalt modified by polyurethane or epoxy resin alone.

[0086] Compared with the results of Comparative Example 4, the modified bio-oil asphalt prepared by the technical route of the present invention has the best effect on improving the anti-rutting performance and low-temperature cracking resistance of the bio-oil asphalt.

[0087] Test Example 2: Storage stability test

[0088] The storage stability test of Example 1 and Comparative Example 1 was carried out in accordance with the polymer modified asphalt segregation test standard of "Test Procedure for Asphalt and Asphalt Mixtures in Highway Engineering" (JTG E20-2011) T0601.

[0089] Figure 2 The storage stability test results of Example 1 and Comparative Example 1 show that the smaller the difference between the upper and lower softening points, the better the storage stability. The differences between the upper and lower softening points after 48 hours are 1.5°C and 7.2°C, respectively. This means that the polyurethane / polyurethane / epoxy resin composite modified bio-oil asphalt prepared by the present invention can significantly solve the segregation problem of bio-oil asphalt and has relatively excellent storage stability.

[0090] In summary, the polyurethane / epoxy resin composite modified bio-oil asphalt material of the present invention exhibits high strength and toughness, and its preparation method is highly advanced. The polyurethane / epoxy resin composite modified bio-oil asphalt material and its preparation method effectively address the problems of poor deformation resistance and segregation in bio-oil asphalt, while also improving its toughness, specifically its low-temperature crack resistance.

[0091] While embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions, and variations may be made to these embodiments without departing from the principles and spirit of the invention, and that the scope of the invention is defined by the appended claims and their equivalents.

Claims

1. A polyurethane / epoxy resin composite modified bio-oil asphalt, characterized in that: Including the following raw materials in parts by weight:

2. The polyurethane / epoxy resin composite modified bio-oil asphalt according to claim 1, characterized in that: The bio-oil is any one of plant oil, animal oil, waste oil, and microalgae oil, or a mixture of two or more of the above in any proportion.

3. The polyurethane / epoxy resin composite modified bio-oil asphalt according to claim 1, characterized in that: The matrix asphalt is selected from any one of petroleum asphalt 70#, petroleum asphalt 90#, petroleum asphalt 110#, or a mixture of two or more of them in any proportion.

4. The polyurethane / epoxy resin composite modified bio-oil asphalt according to claim 1, characterized in that: The isocyanate is any one of toluene diisocyanate, isophorone diisocyanate, and diphenylmethane diisocyanate, or a mixture of two or more of the above in any proportion.

5. The polyurethane / epoxy resin composite modified bio-oil asphalt according to claim 1, characterized in that: The epoxy resin is selected from any one of bisphenol A epoxy resin, bisphenol F epoxy resin and resorcinol epoxy resin, or a mixture of two or more of them in any proportion.

6. The polyurethane / epoxy resin composite modified bio-oil asphalt according to claim 1, characterized in that: The chain extender is any one of 4,4'-methylenebis(2-chloroaniline), 4,4'-methylenebis(2-chloroaniline), 4,4'-methylenebis(2-chloroaniline), 1,4-butanediol, 1,6-hexanediol or ethylenediamine, or a mixture of two or more in any proportion; the curing agent is any one of aliphatic amine curing agents, alicyclic amine curing agents, aromatic amine curing agents, and low molecular weight polyamide, or a mixture of two or more in any proportion; the compatibilizer is any one of epoxy fatty acid methyl ester, epoxy butyl stearate, epoxy soybean oil and epoxy linseed oil ester, or a mixture of two or more in any proportion.

7. The method for preparing a polyurethane / epoxy resin composite modified bio-oil asphalt according to any one of claims 1 to 6, characterized in that: The following steps are involved: (1) adding molten matrix asphalt and bio-oil into a reactor and stirring to obtain bio-oil asphalt; (2) adding isocyanate and chain extender into a reactor and stirring to obtain a polyurethane-modified bio-oil asphalt sample, and then lowering the temperature of the reactor to 80-120° C.; (3) placing the polyurethane-modified bio-oil asphalt sample in a reactor at 80-120°C for 1-2 hours to obtain the polyurethane-modified bio-oil asphalt product; (4) Add epoxy resin, curing agent, and compatibilizer into a reactor and stir to obtain polyurethane / epoxy resin composite modified bio-oil asphalt.

8. The method for preparing a polyurethane / epoxy resin composite modified bio-oil asphalt according to claim 7, characterized in that: In the step (1), the stirring temperature is 140-180° C., the stirring speed is 1000-3000 r / min, and the stirring time is 0.5-1 h.

9. The method for preparing a polyurethane / epoxy resin composite modified bio-oil asphalt according to claim 7, characterized in that: In the step (2), the stirring temperature is 140-180° C., the stirring speed is 4000-6000 r / min, and the stirring time is 1-2 h.

10. The method for preparing a polyurethane / epoxy resin composite modified bio-oil asphalt according to claim 7, characterized in that: In the step (4), the stirring temperature is 160-180° C., the stirring speed is 600-1500 r / min, and the stirring time is 1-2 h.

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