A high rutting resistance asphalt mixture additive and a preparation method thereof

Abstract

This invention discloses a high-rutting-resistant asphalt mixture additive and its preparation method. The additive includes a heat-reactive modified component; it also includes a matrix, additives, compatibilizers, and oils. Adding the high-rutting-resistant asphalt mixture additive prepared according to this invention to asphalt can significantly improve the high-temperature stability of asphalt mixtures and provides flexible and convenient construction. This high-rutting-resistant asphalt mixture additive fundamentally solves the problem of poor rutting resistance in asphalt pavements while improving the overall road performance of asphalt mixtures.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of highway engineering, and particularly relates to a preparation method of asphalt mixture additive. BACKGROUND

[0002] With the development of social economy, the traffic activities are increasingly active, and the traffic volume borne by the highway gradually increases. Influenced by this, the rutting, flying and other diseases occur in the service process of the asphalt pavement, especially in the special road sections such as the intersection, the bus lane, the port and mining area road, and the long and large longitudinal slope. The rutting-dominant diseases of the asphalt pavement are more serious, which causes adverse effects on the driving comfort and safety, and must be solved.

[0003] In order to solve the rutting-dominant diseases of the asphalt pavement, the road technical personnel has carried out a series of attempts, and the main method is to modify the asphalt, usually using the polymer modification, the anti-rutting agent (high modulus) and other methods. Among them, the polymer modified asphalt refers to adding the polymer modifier such as SBS and SBR into the base asphalt, so that the asphalt has the special properties of the polymer, and the high and low temperature performance of the asphalt is improved. However, the practical results show that the polymer modification mechanism is mainly physical modification, so the method of using the polymer modification can only improve the high temperature performance of the modified asphalt mixture to the medium level, such as the dynamic stability of about 5000 times / mm which represents the anti-rutting ability. When facing the special road sections, it is still difficult to prevent the rutting from occurring. The anti-rutting agent refers to an additive prepared from PE, hard asphalt and other raw materials, and is also called high modulus agent in some occasions. When used, the high modulus agent is directly added into the asphalt mixture, and the hard component is used to adjust the asphalt component, so as to improve the high temperature stability of the asphalt mixture. However, the improvement range is still limited, and when the special road sections are faced, the serious rutting occurs in a very short time. In addition, according to the related research, the high modulus modification still belongs to the category of physical reaction. According to the mechanism, the high temperature performance and the low temperature performance obtained by the physical blending are contradictory. The better the high temperature performance is, the worse the low temperature performance is. When the high temperature performance is improved, the low temperature performance is lost, and the low temperature cracking phenomenon is prone to occur in the service effect of the pavement.

[0004] Therefore, when facing the special road sections, the existing modification technology system of the asphalt still has deficiencies, and it is necessary to adopt the asphalt material with higher anti-rutting ability and excellent comprehensive performance, such as the chemical modification material of the epoxy modified asphalt.

[0005] Epoxy modified asphalt refers to adding epoxy resin and curing agent into asphalt respectively, and significantly improving the high temperature stability of asphalt through curing reaction. Meanwhile, due to the three-dimensional network structure formed by epoxy curing reaction, it is recognized as one of the best asphalt modification methods at present, but its disadvantage is that the process is complicated, and the main agent and curing agent need to be stored separately, and then mixed during mixing, otherwise the curing will be accelerated and the normal mixing and use will be affected. At present, this method is used in the field of bridge deck asphalt paving. With the development of technology, the latent epoxy curing technology is proposed (Research Progress of Latent Epoxy Curing Agent, Xu Wu et al.), and has been applied in other industries. The so-called latent curing technology is an epoxy technology that has a certain storage stability at room temperature, but can be quickly cured under heating conditions. However, the existing latent curing technology is mostly low-temperature (≤160℃) curing, and the curing time is short, which cannot meet the needs of asphalt mixture mixing: the asphalt mixture often needs to be mixed at a high temperature of 170℃-200℃, and at this temperature, the epoxy component is invalid, and the weather resistance is poor during use. In addition, the asphalt mixture needs about 2h-5h from mixing to paving and rolling, and the existing technology has a storage time of less than 1h, which leads to the curing of asphalt before it is transported to the construction site. SUMMARY

[0006] The present application provides a high anti-rutting asphalt mixture additive which can significantly improve the high temperature stability of asphalt mixture and has excellent comprehensive performance and flexible and convenient construction, and a preparation method thereof. The core of the present application is to provide a latent epoxy asphalt modification technology which is used in combination with SBS and has high reaction temperature and long curing time.

[0007] To achieve the above-mentioned purpose, the present application provides an asphalt mixture additive, which comprises a thermal inversion modification component.

[0008] The thermal inversion modification component comprises epoxy resin and curing agent.

[0009] In particular, the thermal inversion modification component comprises epoxy resin, curing agent and curing aid.

[0010] In particular, the thermal inversion modification component is prepared from epoxy resin, curing agent and curing aid.

[0011] The thermal inversion modification component is the key component of the additive of the present application, which can exist stably at room temperature, meeting the needs of storage and transportation of the additive. When heated at a specific temperature (170℃-200℃) during mixing, the curing activity is excited, and the performance of the asphalt mixture is improved. At the same time, the curing time is as high as 5h or more, meeting the requirements of asphalt pavement construction.

[0012] The mass ratio of the epoxy resin, the curing agent and the curing aid in the thermal inversion modification component is 100:(10-50):(5-25), preferably 100:(10-40):(5-20), and further preferably 100:(15-30):(8-15).

[0013] In particular, the mass ratio of the epoxy resin, the curing agent and the curing aid in the thermal inversion modification component is 100:(10-50):(5-20), preferably 100:10:5.

[0014] In particular, the epoxy resin is a bisphenol A type epoxy resin in solid or liquid form, which is a polycondensation product of epichlorohydrin and bisphenol A, and preferably is a bisphenol A type epoxy resin in solid form.

[0015] In particular, when the epoxy resin is in liquid form, the epoxy equivalent weight is not less than 100 g / mol; and when the epoxy resin is in solid form, the epoxy equivalent weight is not less than 200 g / mol.

[0016] The curing agent is selected from one or more of aromatic polyamine, methyl end methine tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, amino resin, dicyandiamide and adipic diacyl hydrazide.

[0017] In particular, when the curing agent is composed of aromatic polyamine, methyl end methine tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, amino resin, dicyandiamide and adipic diacyl hydrazide, the mass ratio is (0-5):(0-5):(0-5):(0-5):(0-5):(0-5), preferably (1-5):(1-5):(1-5):(1-5):(1-5):(1-5), and further preferably (2-3):(2-3):(2-3):(2-3):(2-3):(2-3).

[0018] In particular, the aromatic polyamine is 4,4'-diaminodiphenyl sulfone (DDS) or 4,4'-diaminodiphenyl methane (DDM); the amino resin is polyamide polyamine epichlorohydrin resin or cationic polyacrylamide resin; and the dicyandiamide is dicyandiamide (DCD).

[0019] In particular, when the curing agent is composed of methyl end methine tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, amino resin and dicyandiamide, the mass ratio is 5:2:2:2; when the curing agent is composed of aromatic polyamine, methyl tetrahydrophthalic anhydride, dicyandiamide and adipic diacyl hydrazide, the mass ratio is 5:3:2:3; and when the curing agent is composed of aromatic polyamine, methyl end methine tetrahydrophthalic anhydride, amino resin, dicyandiamide and adipic diacyl hydrazide, the mass ratio is 5:1:2:2:3.

[0020] In order to improve the curing effect, a curing accelerator (i.e. curing aid) is added in the thermal reaction component of the epoxy resin and curing agent.

[0021] The curing aid is selected from one or more of the following: tertiary amine salt, phenol, imidazole, metal acetylacetone complex, metal carboxylate, preferably tertiary amine salt, phenol or imidazole.

[0022] In particular, the curing accelerator is composed of tertiary amine salt, phenol, imidazole, metal acetylacetone complex and metal carboxylate.

[0023] In particular, the mass ratio of the tertiary amine salt, phenol, imidazole, metal acetylacetone complex and metal carboxylate is (0-10):(0-10):(0-10):(0-10):(0-10), preferably (1-10):(1-10):(1-10):(1-10):(1-10); further preferably (1-8):(2-8):(2-8):(2-8):(2-8), and more preferably 1:8:2:2:4.

[0024] In particular, the tertiary amine salt is dodecyl tertiary amine salt (BS-12) or octadecyl tertiary amine salt; the metal acetylacetone complex is aluminum acetylacetone or calcium acetylacetone; and the metal carboxylate is zinc stearate, zinc naphthenate or zinc octanoate.

[0025] In particular, when the curing aid is composed of tertiary amine salt, phenol, metal acetylacetone complex and metal carboxylate, the mass ratio is 8:5:1:5; when the curing aid is composed of tertiary amine salt, imidazole and metal carboxylate, the mass ratio is 6:3:6; and when the curing aid is composed of phenol, imidazole and metal acetylacetone complex, the mass ratio is 2:3:4.

[0026] The inventor has found through a large number of experiments that the thermal modification component composed of the above-mentioned epoxy resin, curing agent and curing aid can exist stably at room temperature without curing reaction, meeting the needs of additives in factory production, transportation and storage at the use site. Once put into the mixing plant, the curing reaction can occur at a specific temperature of mixing, thereby modifying the asphalt. The selected curing agent can stimulate the reactivity within the required temperature range of mixing, and the curing aid can adjust the tolerance time of curing, so that the construction process can be carried out smoothly.

[0027] Another aspect of the present application provides an asphalt mixture additive, which comprises the following raw materials: thermal modification component, base, aid, compatibilizer and oil product.

[0028] The weight ratio of the raw materials is as follows:

[0029]

[0030] In particular, the weight ratio of the raw materials is preferably as follows:

[0031]

[0032]

[0033] In particular, the weight ratio of the raw materials is further preferably as follows:

[0034]

[0035] The matrix is a styrene-butadiene-styrene block copolymer (SBS).

[0036] The matrix SBS is a product after physical and mechanical crushing. The addition of the matrix can increase the high and low temperature, water stability and fatigue resistance of the asphalt to the level of SBS modified asphalt, and further improve the high temperature rutting resistance of the asphalt mixture.

[0037] According to specific conditions, SBS can be omitted, and only the thermal anti-modification component is added, which is pure epoxy modified asphalt.

[0038] In particular, the particle size of the crushed SBS is 10-2000 μm. The SBS can be a mixture of one or both of linear and star types. The SBS is the matrix of the present high rutting resistance asphalt mixture additive, which can exert a certain SBS modification effect. The addition of SBS can exert a certain composite modification effect.

[0039] After the addition of the matrix, in order to accelerate the performance of the matrix in the asphalt mixture, an additive, a compatibilizer and an oil product can also be added.

[0040] The additive is one or more of sulfur, metal oxide, thiuram, thiazole, dithiocarbamate or fatty acid.

[0041] In particular, the additive is composed of sulfur, metal oxide, thiuram, thiazole, dithiocarbamate and fatty acid, wherein the mass ratio of sulfur, metal oxide, thiuram, thiazole, dithiocarbamate (Dithiocarbamates, (C4H6N2S4Zn)x) and fatty acid is 10:(0-5):(0-4):(0-6):(0-5):(0-6), preferably 10:(1-5):(1-4):(1-6):(1-5):(1-6); further preferably 10:(1-5):(1-4):(1-6):(1-5):(1-5); more preferably 10:(2-4):(2-3):(1-3):(1-3):(1-3).

[0042] In particular, the auxiliary agent consists of sulfur, metal oxide, thiuram, thiazole, dithiocarbamate and fatty acid, wherein the mass ratio of sulfur, metal oxide, thiuram, thiazole, dithiocarbamate (Dithiocarbamates, (C4H6N2S4Zn)x) and fatty acid is 10:(1-5):(1-4):(2-6):(2-5):(2-6).

[0043] In particular, the auxiliary agent consists of sulfur, metal oxide, thiuram, thiazole, dithiocarbamate and fatty acid, wherein the mass ratio of sulfur, metal oxide, thiuram, thiazole, dithiocarbamate (Dithiocarbamates, (C4H6N2S4Zn)x) and fatty acid is 10:(1-5):(1-4):(2-6):(2-5):(2-6).

[0044] In particular, the metal oxide is one or more of iron oxide, zinc oxide, magnesium oxide, aluminum oxide or copper oxide; the fatty acid is one or more of stearic acid, ricinoleic acid or hydroxystearic acid.

[0045] The auxiliary agent is added to initiate and promote the cross-linking reaction of SBS of the matrix to improve the modification effect.

[0046] The compatible agent is one or more of Fischer-Tropsch wax, polyethylene wax or sasobit, or one or more of wax-containing materials containing Fischer-Tropsch wax, polyethylene wax, sasobit or similar components, or one or more of Fischer-Tropsch wax, polyethylene wax, sasobit or wax-containing materials.

[0047] In particular, the wax-containing material is a material containing one or more of Fischer-Tropsch wax, polyethylene wax or sasobit or similar components. If more than one is used, they can be mixed in any ratio.

[0048] In particular, the compatible agent is a mixture of any two of Fischer-Tropsch wax, polyethylene wax or sasobit (Sasolbit), and the mass ratio of any two of them in the mixture is in any ratio, preferably 1:1.

[0049] In particular, the compatible agent is a mixture of Fischer-Tropsch wax and polyethylene wax, which can be mixed in any ratio, preferably 1:1; the compatible agent is a mixture of Fischer-Tropsch wax and sasobit, which can be mixed in any ratio, preferably 1:1.

[0050] The addition of the compatibilizer can reduce the viscosity of the system, lubricate the asphalt and the mineral aggregate during mixing, and maintain normal mixing state when a large amount of SBS is added. It should be noted that the same modification effect can also be achieved even without the addition of the compatibilizer, and the appearance and workability of the mixture can be improved by increasing the mixing temperature, increasing the oil-stone ratio, etc. Therefore, the compatibilizer can also be selected not to be added.

[0051] The oil product is one or more of side-cut oil obtained by petroleum distillation, extracted oil obtained by refining the side-cut oil through furfural extraction, and FCC oil slurry byproduct of a catalytic cracking device. The addition of the oil product can pre-dissolve the SBS particles, reduce the asphalt-SBS two-phase interface effect, and further accelerate the melting effect. On the other hand, the oil product can also play a role in component blending, and improve the low-temperature crack resistance of the asphalt.

[0052] The side-cut oil is a fraction obtained during the petroleum distillation process, other than the overhead and the bottom of the distillation column.

[0053] The extracted oil is a non-ideal component of lubricating oil separated after the extraction process during furfural extraction.

[0054] The FCC oil slurry is a product obtained after cracking and condensation reactions of residual oil and wax oil.

[0055] The side-cut oil, the extracted oil, and the FCC oil slurry are mature products and can be purchased from the market.

[0056] In particular, the oil product is a mixture of any two of the side-cut oil, the extracted oil, and the FCC oil slurry, and the mass ratio of the mixture of any two is any ratio, and preferably 1:1.

[0057] In particular, the oil product is a mixture of the side-cut oil and the extracted oil, and the two can be mixed in any ratio, and preferably 1:1. The compatibilizer is a mixture of the side-cut oil and the FCC oil slurry, and the two can be mixed in any ratio, and preferably 1:1.

[0058] In another aspect, the application provides a preparation method of an asphalt mixture additive, which comprises uniformly mixing epoxy resin, curing agent, and curing aid in a certain proportion, wherein the mass ratio of the epoxy resin, the curing agent, and the curing aid is 100:(10-50):(5-25), preferably 100:(10-40):(5-20), and further preferably 100:(15-30):(8-15).

[0059] The epoxy resin is a bisphenol A type epoxy resin in solid or liquid form, which is a polycondensation product of epichlorohydrin and bisphenol A, and is preferably a bisphenol A type epoxy resin in solid form.

[0060] In particular, the epoxy resin is a liquid epoxy resin, and the epoxy equivalent weight is not less than 100 g / mol; or the epoxy resin is a solid epoxy resin, and the epoxy equivalent weight is not less than 200 g / mol.

[0061] The curing agent is selected from one or more of aromatic polyamine, methyl end methine tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, amino resin, dicyandiamide, adipic diacid anhydride.

[0062] In particular, the curing aid is selected from one or more of tertiary ammonium salt, phenol, imidazole, metal acetylacetone complex, metal carboxylate salt, preferably tertiary ammonium salt, phenol or imidazole.

[0063] In particular, the curing aid is selected from one or more of tertiary ammonium salt, phenol, imidazole, metal acetylacetone complex, metal carboxylate salt, preferably tertiary ammonium salt, phenol or imidazole.

[0064] In another aspect, the present application provides a preparation method of the asphalt mixture additive, comprising the following steps:

[0065] 1) preparing raw materials according to the following weight ratio:

[0066]

[0067] 2) adding oil into the matrix and mixing uniformly to obtain a matrix-oil mixture;

[0068] 3) sequentially adding the thermal inversion modification component, the aid, and the compatibilizer into the matrix-oil mixture and mixing uniformly to obtain the asphalt mixture additive.

[0069] In step 1), the matrix is selected as SBS particles; the thermal inversion modification component comprises epoxy resin, curing agent, and curing aid.

[0070] In particular, the epoxy resin is a solid or liquid epoxy resin.

[0071] In particular, the solid epoxy resin has an epoxy equivalent weight of not less than 200 g / mol; and the liquid epoxy resin has an epoxy equivalent weight of not less than 100 g / mol.

[0072] In particular, the mass ratio of the epoxy resin, the curing agent, and the curing aid is 100:(10-50):(5-25), preferably 100:(10-40):(5-20), and further preferably 100:(15-30):(8-15).

[0073] In particular, the thermal inversion modification component is prepared by mixing the epoxy resin, the curing agent and the curing aid in a certain proportion, wherein the mass ratio of the epoxy resin, the curing agent and the curing aid is 100:(10-50):(5-25), preferably 100:(10-40):(5-20), and further preferably 100:(15-30):(8-15).

[0074] In particular, the method further comprises pulverizing the epoxy resin in solid form in the thermal inversion modification component into powder before mixing with the curing agent and the curing aid.

[0075] In particular, the particle size of the pulverized epoxy resin powder is 10-2000 μm.

[0076] In particular, the method further comprises pulverizing the SBS particles into SBS powder before adding the oil product and mixing.

[0077] In particular, the particle size of the pulverized SBS powder is 10-2000 μm.

[0078] In particular, the weight ratio of the raw materials in step 1) is preferably as follows:

[0079]

[0080] The equipment for pulverizing the SBS particles in dry state can adopt high-speed mechanical impact pulverizer, air flow pulverizer, vibration ball mill, planetary ball mill, stirring ball mill, high-pressure roller mill and other powder pulverizing equipment. The principle is to impact the SBS by the high-speed relative rotation of the rotary body or the grinding cylinder to generate impact force, and to obtain SBS powder with particle size of tens of microns through shearing, grinding and friction. Fresh air is forced to pass through the inside of the pulverizer for cooling. When pulverizing the SBS particles, in order to improve the pulverizing effect, 0.05-0.1% of CeO2 content greater than 40% of rare earth polishing powder can be added as an abrasive.

[0081] In particular, step 3) further comprises adding a curing accelerator and mixing uniformly.

[0082] Through extensive research, the inventors discovered that the thermally reactive epoxy resin system used, under the aforementioned formulation, can remain stable at low temperatures, with its curing reaction function in a latent state, thus meeting the needs of storage and transportation. During construction, once added to the mixing plant and reaching the mixing temperature (170℃-200℃), the latent activity is restored, allowing for rapid curing. The resulting three-dimensional network structure improves the properties of the asphalt. This invention creatively changes the previously used production method where dry-process SBS modifier, epoxy resin, and curing agent needed to be added to the mixing plant in three separate steps. By implementing a latent reaction treatment, a single material can replace all three, greatly simplifying the construction process and increasing flexibility.

[0083] Compared with the prior art, the present invention has the following advantages and benefits:

[0084] 1. The technology of this invention, through systematic research, obtains a latent epoxy resin technology by compounding epoxy resin, curing agent and curing aid. On the one hand, it can be stored stably at room temperature, and on the other hand, it has the characteristics of high curing temperature and long residence time, which meets the construction needs of asphalt mixture.

[0085] 2. This invention provides a method for preparing a composite modifier by technical processing of SBS modifier, epoxy resin and curing agent, which is then added to asphalt mixing plant as an external admixture, simplifying the construction process.

[0086] 3. The asphalt mixture additive of the present invention has excellent high-temperature stability, with a dynamic stability of >10,000 times / mm at 70℃ and 1.0MPa, which is more than twice that of the prior art.

[0087] 4. When the asphalt mixture additive of the present invention is used in the asphalt mixture mixing process, the epoxy component does not fail when the mixing is carried out at a relatively high temperature of 170℃-200℃. It has good weather resistance when used. Moreover, the asphalt mixture has a long retention time from mixing to paving and compaction, reaching more than 2 hours, or even more than 5 hours, which significantly extends the retention time (the existing retention time is less than 1 hour), thus meeting the requirements for asphalt pavement construction. Detailed Implementation

[0088] The present invention will be further described below with reference to specific embodiments, and the advantages and features of the present invention will become clearer as a result. However, these embodiments are merely exemplary and do not constitute any limitation on the scope of the present invention. Those skilled in the art should understand that modifications or substitutions can be made to the details and form of the technical solutions of the present invention without departing from the spirit and scope of the present invention, but all such modifications and substitutions fall within the protection scope of the present invention.

[0089] Example 1

[0090] 1. Preparation of curing agent

[0091] DDS, methylmethylenetetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, polyamide polyamine epichlorohydrin, DCD, and adipate dihydrazide are mixed evenly to prepare a curing agent. The mass ratio of each component of the curing agent is as follows:

[0092]

[0093] 2. Preparation of curing aid

[0094] Octadecyl tertiary amine salt, phenol, imidazole, aluminum acetylacetonate, and zinc stearate are mixed evenly to prepare a curing aid. The mass ratios of each component of the curing aid are as follows:

[0095]

[0096]

[0097] 3. Preparation of epoxy resin powder

[0098] Solid epoxy resin (bisphenol A type solid epoxy resin E-12, Phoenix brand, Jiangsu Nantong Xingchen Company) is pulverized into epoxy resin powder with a particle size of 10-500μm using a high-speed mechanical impact pulverizer at room temperature, wherein the epoxy equivalent of the epoxy resin is 833g / mol (not less than 200g / mol).

[0099] 4. Preparation of asphalt mixture additives

[0100] The epoxy resin powder, curing agent, and curing aid are mixed evenly, wherein the mass ratio of epoxy resin powder, curing agent, and curing aid is 100:10:5.

[0101] In this embodiment of the invention, 100 kg of epoxy resin, 10 kg of curing agent, and 5 kg of curing aid are used.

[0102] Example 1A

[0103] Except for the absence of curing aids in the raw materials, everything else is the same as in Example 1.

[0104] Example 1B

[0105] Except that the curing agent in the raw materials is aliphatic polyamine EDA, everything else is the same as in Example 1.

[0106] Example 1C

[0107] Except for the fact that the curing agent in the raw materials is dicyandiamide, everything else is the same as in Example 1.

[0108] Example 2

[0109] 1. Preparation of curing agent

[0110] DDM, methylmethylenetetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, cationic polyacrylamide, DCD, and adipate dihydrazide are mixed evenly to prepare a curing agent. The mass ratio of each component of the curing agent is as follows:

[0111]

[0112]

[0113] 2. Preparation of curing aid

[0114] Dodecyl tertiary amine salt, phenol, imidazole, aluminum acetylacetonate, and zinc naphthenate are mixed evenly to prepare a curing aid. The mass ratios of each component of the curing aid are as follows:

[0115]

[0116] 3. Preparation of asphalt mixture additives

[0117] The epoxy resin (bisphenol A type liquid epoxy resin E-44, Phoenix brand, Jiangsu Nantong Xingchen Company), curing agent, and curing aid are mixed evenly, wherein the mass ratio of epoxy resin, curing agent, and curing aid is 100:50:20, and the epoxy equivalent of the epoxy resin is 227 g / mol (not less than 100 g / mol).

[0118] In this embodiment of the invention, 100 kg of epoxy resin, 50 kg of curing agent, and 20 kg of curing aid are used.

[0119] Example 3

[0120] 1. Preparation of curing agent

[0121] DDM, methylmethylenetetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, cationic polyacrylamide, DCD, and adipate dihydrazide are mixed evenly to prepare a curing agent. The mass ratio of each component of the curing agent is as follows:

[0122]

[0123] 2. Preparation of curing aid

[0124] Dodecyl tertiary amine salt, phenol, imidazole, calcium acetylacetonate, and zinc naphthenate are mixed evenly to prepare a curing aid. The mass ratios of each component of the curing aid are as follows:

[0125]

[0126] 3. Preparation of epoxy resin powder

[0127] Solid epoxy resin (bisphenol A type solid epoxy resin E-12, Phoenix brand, Jiangsu Nantong Xingchen Company) is pulverized into epoxy resin powder with a particle size of 10-100μm using a high-speed mechanical impact pulverizer at room temperature, wherein the epoxy equivalent of the epoxy resin is 833g / mol (not less than 200g / mol).

[0128] 4. Preparation of asphalt mixture additives

[0129] The epoxy resin powder, curing agent, and curing aid are mixed evenly, wherein the mass ratio of epoxy resin powder, curing agent, and curing aid is 100:30:5.

[0130] In this embodiment of the invention, 100 kg of epoxy resin, 30 kg of curing agent, and 5 kg of curing aid are used.

[0131] Example 4

[0132] 1. Prepare the raw materials according to the following weight ratio (×kg)

[0133]

[0134] The heat-reactive modified component is a mixture additive prepared in Example 1;

[0135] The matrix is ​​star-shaped SBS (SBS 4303, produced by Yanshan Petrochemical Company);

[0136] The additive is composed of sulfur, zinc oxide, thiuram, thiazole, dithiocarbamate, and stearic acid in a mass ratio of 10:5:4:6:5:6; the raw materials that make up the additive, namely sulfur, zinc oxide, thiuram, thiazole, dithiocarbamate, and stearic acid, are all commercially available products.

[0137] The compatibilizer is polyethylene wax, a commercially available product;

[0138] The oil product is extracted oil obtained from the reduced-density fraction of petroleum obtained through vacuum distillation in the atmospheric and vacuum refining process, followed by furfural extraction. It was purchased from CNOOC.

[0139] 2. The dried SBS particles (SBS4303) are pulverized at room temperature using a high-speed mechanical impact pulverizer to produce SBS powder with a particle size of less than 2000μm.

[0140] To improve grinding efficiency, 0.1% of SBS powder and rare earth polishing powder with a CeO2 content greater than 40% can be added during the grinding process. When the grinding effect is excellent, rare earth polishing powder may not be added.

[0141] 3. Add the oil to the crushed SBS powder and mix well to obtain the SBS-oil mixture;

[0142] 4. Add the additives and compatibilizers sequentially to the SBS-oil mixture, mix thoroughly, and finally add the heat-reactive modified component prepared in Example 1 and mix thoroughly to obtain the high-rutting-resistant asphalt mixture additive.

[0143] In this embodiment, the thermally modified component prepared in Example 1 is used as an example. Other additives prepared in Examples 2-3 are also applicable. The thermally modified component (i.e., additive) made of epoxy resin, curing agent and curing aid of the present invention is also applicable.

[0144] Example 5

[0145] 1. Prepare the raw materials according to the following weight ratio (×kg)

[0146]

[0147] The heat-reactive modified component is the additive for the mixture prepared in Example 1;

[0148] The matrix is ​​linear SBS (YH791-H, SBS 1301-1 produced by Sinopec Baling Branch);

[0149] The compatibilizer is commercially available PE wax (polyethylene wax, Panjin Northern Asphalt Fuel Co., Ltd.); the oil is FCC slurry, produced by Sinopec.

[0150] The additive is composed of sulfur, aluminum oxide, thiazole, dithiocarbamate, and hydroxystearic acid in a mass ratio of 10:2:2:2:2; the raw materials that make up the additive, namely sulfur, aluminum oxide, thiazole, dithiocarbamate, and hydroxystearic acid, are all commercially available products.

[0151] 2. The dried SBS particles (YH791-H, SBS1301-1) are pulverized at room temperature using a high-speed mechanical impact pulverizer to produce SBS powder with a particle size of 10-100μm.

[0152] During the pulverization process, 0.1% of SBS powder and rare earth polishing powder with a CeO2 content greater than 40% are added.

[0153] 3. Add the oil to the crushed SBS powder and mix well to obtain the SBS-oil mixture;

[0154] 4. Add the additives and compatibilizers to the SBS-oil mixture in sequence, mix them evenly, and finally add the heat-reactive modified component prepared in Example 1 and mix them evenly to obtain the high rutting resistance asphalt mixture additive.

[0155] In this embodiment, the thermally modified component prepared in Example 1 is used as an example. Other additives prepared in Examples 2-3 are also applicable. The thermally modified component (i.e., additive) made of epoxy resin, curing agent and curing aid of the present invention is also applicable.

[0156] Example 6

[0157] 1. Prepare the raw materials according to the following weight ratio (×kg)

[0158]

[0159] The heat-modified component is the additive for the mixture prepared in Example 1; the matrix is ​​star-shaped SBS (SBS4303, produced by Yanshan Petrochemical Company);

[0160] The additive is composed of sulfur, magnesium oxide, thiuram, thiazole, dithiocarbamate, and ricinoleic acid in a mass ratio of 10:1:1:3:2:5. The raw materials that make up the additive, namely sulfur, magnesium oxide, thiuram, thiazole, dithiocarbamate, and ricinoleic acid, are all commercially available products.

[0161] The compatibilizer is Fischer-Tropsch wax and polyethylene wax, mixed in a 1:1 ratio; both are commercially available products.

[0162] The oil product is obtained by mixing side-stream oil and extracted oil in a 1:1 ratio, and both are produced by CNOOC.

[0163] 2. The dried SBS particles (SBS4303) are pulverized at room temperature using a high-speed mechanical impact pulverizer to produce SBS powder with a particle size of 10-1000μm.

[0164] During the pulverization process, 0.1% of rare earth polishing powder with a CeO2 content greater than 40% is added to the SBS powder. Utilizing its unique angular structure, it allows for repeated high-speed impact on the SBS particles during pulverization, further reducing the SBS particle size, resulting in excellent pulverization effect and high efficiency.

[0165] 3. Add the oil to the crushed SBS powder and mix well to obtain the SBS-oil mixture;

[0166] 4. Add the additives and compatibilizers to the SBS-oil mixture in sequence, mix them evenly, and finally add the heat-reactive modified component prepared in Example 1 and mix them evenly to obtain the high rutting resistance asphalt mixture additive.

[0167] In this embodiment, the thermally modified component prepared in Example 1 is used as an example. Other additives prepared in Examples 2-3 are also applicable. The thermally modified component (i.e., additive) made of epoxy resin, curing agent and curing aid of the present invention is also applicable.

[0168] Example 7

[0169] 1. Prepare the raw materials according to the following weight ratio (×kg)

[0170]

[0171] The heat-reactive modified component is the additive for the mixture prepared in Example 1;

[0172] The matrix is ​​linear SBS (YH791-H, SBS 1301-1 produced by Sinopec Baling Branch);

[0173] The additive is a mixture of sulfur, zinc oxide, thiuram, thiazole, dithiocarbamate, and stearic acid in a mass ratio of 10:2:2:2:2:2. The raw materials that make up the additive, namely sulfur, zinc oxide, thiuram, thiazole, dithiocarbamate, and stearic acid, are all commercially available products.

[0174] The compatibilizer is Fischer-Tropsch wax and Sasobit, which are mixed in a 1:1 ratio and are both commercially available products.

[0175] The oil is a side-stream oil: it is obtained by mixing FCC oil slurry in a 1:1 ratio and is produced by CNOOC and Sinopec respectively.

[0176] 2. The dried SBS particles (YH791-H, SBS1301-1) are pulverized at room temperature using a high-speed mechanical impact pulverizer to produce SBS powder with a particle size of 20-100μm.

[0177] During the pulverization process, 0.1% of SBS powder and rare earth polishing powder with a CeO2 content greater than 40% are added.

[0178] 3. Add the oil to the crushed SBS powder and mix well to obtain the SBS-oil mixture;

[0179] 4. Add the additives and compatibilizers to the SBS-oil mixture in sequence, mix them evenly, and finally add the heat-reactive modified component prepared in Example 1 and mix them evenly to obtain the high rutting resistance asphalt mixture additive.

[0180] In this embodiment, the thermally modified component prepared in Example 1 is used as an example. Other additives prepared in Examples 2-3 are also applicable. The thermally modified component (i.e., additive) made of epoxy resin, curing agent and curing aid of the present invention is also applicable.

[0181] Compare with Example 1

[0182] Except for the absence of thermally modified components in the raw materials, the rest is the same as in Example 4.

[0183] Compare with Example 2

[0184] 1. Prepare the raw materials according to the following weight ratio (×kg)

[0185]

[0186] The matrix is ​​a 1:1 mixture of linear YH791H and star-shaped SBS 4303, produced by Sinopec Baling Branch and Yanshan Petrochemical Company respectively.

[0187] 2. At room temperature, the uniformly mixed and dried SBS (linear YH791H and star-shaped SBS 4303) particles are pulverized into SBS powder with a particle size of 20-50μm using a high-speed mechanical impact pulverizer.

[0188] During the pulverization process, 0.1% of SBS powder and rare earth polishing powder with a CeO2 content greater than 40% are added.

[0189] 3. Mix the crushed SBS powder evenly to obtain asphalt mixture additive.

[0190] Test case

[0191] Using the additives prepared in Examples 1-7, 1A, 1B, and Comparative Examples 1-2 as raw materials, and with AC-13 gradation, 70 # A mixture of base asphalt and limestone is prepared at 185°C, wherein the amount of additives added is 1% of the mass of the mixture.

[0192] Rutting tests were conducted on asphalt mixtures to evaluate their high-temperature performance. The test temperature was 70℃, the loading pressure was 960N±50N, and the contact pressure between the test wheel and the specimen was 1.0MPa±0.05MPa. The test results are shown in Table 1.

[0193] Low-temperature bending tests were conducted on asphalt mixtures at -10℃ to obtain the maximum bending tensile strain, which was used to evaluate the low-temperature performance. The test results are shown in Table 2.

[0194] Table 1 Comparison of vehicle rutting dynamic stability (higher values ​​indicate better stability)

[0195]

[0196]

[0197] Table 2 Maximum flexural tensile strain (the larger the value, the better the low-temperature crack resistance)

[0198] Asphalt mixture additive Maximum flexural tensile strain (με) Asphalt mixture additive Maximum flexural tensile strain (με) Example 1 1921 Example 4 2542 Example 1A 1872 Example 5 2610 Example 1B Modifier prematurely solidifies Example 6 2489 Example 1C 1432 Example 7 2852 Example 2 1952 Control 1 2711 Example 3 1921 Control 2 1901

[0199] A comparison of Examples 1 and 1A reveals that the high-temperature and low-temperature performance of Example 1 is significantly improved compared to Example 1A, indicating that adding curing aids can significantly enhance high-temperature performance.

[0200] A comparison of Examples 1 and 1B reveals that using a common curing agent will result in premature curing, while the unique curing agent can provide a good latent curing effect.

[0201] A comparison of Examples 1 and 1C reveals that the high and low temperatures of Example 1 are significantly higher than those of Example 1C, indicating that the curing effect is poor when using ordinary latent curing agents under high-temperature mixing.

[0202] A comparison of Examples 1 and 4-7 revealed that the addition of additives such as SBS slightly reduced the high-temperature performance, but improved the low-temperature performance to some extent.

[0203] Compared with Comparative Example 1, Examples 4-7 show that the high-temperature performance decreased significantly after removing the thermal reaction component, indicating that the thermal reaction component is a key component for improving high-temperature performance.

[0204] Comparing Comparative Example 1 and Comparative Example 2, it was found that the high-temperature performance and low-temperature performance were reduced after only adding SBS polymer, indicating that SBS can play a better role under unique conditions of additives, compatibilizers, and oils.

Claims

1. An additive for high rutting resistance asphalt mixtures, characterized in that, The heat-reversing modification component comprises an epoxy resin, a curing agent and a curing aid, wherein: The epoxy resin is a bisphenol A type epoxy resin in solid or liquid form, which is a polycondensation product of epichlorohydrin and bisphenol A, wherein the epoxy equivalent weight of the epoxy resin in liquid form is not less than 100 g / mol, and the epoxy equivalent weight of the epoxy resin in solid form is not less than 200 g / mol; The curing agent is composed of aromatic polyamine, methyl end methine tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, amino resin, dicyandiamide and adipic acid dihydrazide, and the mass ratio is (1-5):(1-5):(1-5):(1-5):(1-5):(1-5), wherein the aromatic polyamine is 4,4'-diamino diphenyl sulfone or 4,4'-diamino diphenyl methane; the amino resin is polyamide polyamine epichlorohydrin resin or cationic polyacrylamide resin; the dicyandiamide is dicyandiamide; The curing aid is composed of tertiary ammonium salt, phenol, imidazole, metal acetylacetone complex, metal carboxylate, and the mass ratio is (1-10):(1-10):(1-10):(1-10):(1-10).

2. The additive of claim 1, wherein The mass ratio of the epoxy resin, the curing agent and the curing aid is 100:(10-50):(5-25).

3. The additive of claim 1, wherein The mass ratio of the epoxy resin, the curing agent and the curing aid is 100:(10-40):(5-20).

4. The additive of claim 1, wherein The mass ratio of the epoxy resin, the curing agent and the curing aid is 100:(15-30):(8-15).

5. An additive for high rutting resistance asphalt mixtures, characterized in that, The raw materials comprise a heat-reversing modification component, a matrix, an aid, a compatibilizer and an oil product, wherein the heat-reversing modification component comprises an epoxy resin, a curing agent and a curing aid, The epoxy resin is a bisphenol A type epoxy resin in solid or liquid form, which is a polycondensation product of epichlorohydrin and bisphenol A, wherein the epoxy equivalent weight of the epoxy resin in liquid form is not less than 100 g / mol, and the epoxy equivalent weight of the epoxy resin in solid form is not less than 200 g / mol; The curing agent is composed of aromatic polyamine, methyl end methine tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, amino resin, dicyandiamide and adipic acid dihydrazide, and the mass ratio is (1-5):(1-5):(1-5):(1-5):(1-5):(1-5), wherein the aromatic polyamine is 4,4'-diamino diphenyl sulfone or 4,4'-diamino diphenyl methane; the amino resin is polyamide polyamine epichlorohydrin resin or cationic polyacrylamide resin; the dicyandiamide is dicyandiamide; The curing aid is composed of tertiary ammonium salt, phenol, imidazole, metal acetylacetone complex, metal carboxylate, and the mass ratio is (1-10):(1-10):(1-10):(1-10):(1-10). The matrix is a styrene-butadiene-styrene block copolymer.

6. The additive of claim 5, wherein The weight ratio of the raw materials is: 。 7. A method of preparing an additive for high rutting resistance asphalt mixtures, characterized in that, Mixing the epoxy resin, curing agent and curing aid uniformly, wherein the mass ratio of the epoxy resin, curing agent, curing aid is 100: (10-50): (5-25), wherein The epoxy resin is bisphenol A type epoxy resin existing in solid or liquid form, which is the polycondensation product of epichlorohydrin and bisphenol A, wherein the epoxy equivalent weight of the epoxy resin in liquid form is not less than 100 g / mol; the epoxy equivalent weight of the epoxy resin in solid form is not less than 200 g / mol; The curing agent is composed of aromatic polyamine, methyl end methine tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, amino resin, dicyandiamide and adipic acid dihydrazide, and the mass ratio is (1-5): (1-5): (1-5): (1-5): (1-5): (1-5), wherein the aromatic polyamine is 4,4'-diamino diphenyl sulfone or 4,4'-diamino diphenyl methane; the amino resin is polyamide polyamine epichlorohydrin resin or cationic polyacrylamide resin; the dicyandiamide is dicyandiamide; The curing aid is composed of tertiary ammonium salt, phenol, imidazole, metal acetylacetone complex, metal carboxylate, and the mass ratio is (1-10): (1-10): (1-10): (1-10): (1-10).

8. The production method according to claim 7, wherein the production method is characterized by, The mass ratio of the epoxy resin, curing agent, curing aid is 100: (10-40): (5-20).

9. The production method according to claim 7, wherein the production method is characterized by, The mass ratio of the epoxy resin, curing agent, curing aid is 100: (15-30): (8-15).

10. A method of making an additive for high rutting resistance asphalt mixtures, characterized in that, It comprises the following steps: 1) Prepare raw materials according to the following weight ratio: The hot reaction modification component includes epoxy resin, curing agent and curing aid, the epoxy resin is bisphenol A type epoxy resin existing in solid or liquid form, which is the polycondensation product of epichlorohydrin and bisphenol A, wherein the epoxy equivalent weight of the epoxy resin in liquid form is not less than 100 g / mol; the epoxy equivalent weight of the epoxy resin in solid form is not less than 200 g / mol; The curing agent is composed of aromatic polyamine, methyl end methine tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, amino resin, dicyandiamide and adipic acid dihydrazide, and the mass ratio is (1-5): (1-5): (1-5): (1-5): (1-5): (1-5), wherein the aromatic polyamine is 4,4'-diamino diphenyl sulfone or 4,4'-diamino diphenyl methane; the amino resin is polyamide polyamine epichlorohydrin resin or cationic polyacrylamide resin; the dicyandiamide is dicyandiamide; The curing aid is composed of tertiary ammonium salt, phenol, imidazole, metal acetylacetone complex, metal carboxylate, and the mass ratio is (1-10): (1-10): (1-10): (1-10): (1-10); 2) Add oil to the matrix and mix uniformly to obtain a matrix-oil mixture; 3) Add the hot reaction modification component, the aid, the compatibilizer to the matrix-oil mixture in turn, mix uniformly, and the asphalt mixture additive is obtained, wherein the matrix is styrene-butadiene-styrene block copolymer.

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