CN118027692A - Self-healing high-performance polyurethane modified asphalt at normal temperature and preparation method thereof - Google Patents
Self-healing high-performance polyurethane modified asphalt at normal temperature and preparation method thereof Download PDFInfo
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- CN118027692A CN118027692A CN202410103887.0A CN202410103887A CN118027692A CN 118027692 A CN118027692 A CN 118027692A CN 202410103887 A CN202410103887 A CN 202410103887A CN 118027692 A CN118027692 A CN 118027692A
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- 150000004985 diamines Chemical class 0.000 claims description 2
- 125000005442 diisocyanate group Chemical group 0.000 claims description 2
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides a preparation method of self-healing high-performance polyurethane modified asphalt at normal temperature, which comprises the following steps: firstly, dehydrating polyol, and then polymerizing the polyol with isophorone diisocyanate/hexamethylene diisocyanate to obtain a prepolymer; polymerizing the prepolymer with isophorone diamine, and constructing supermolecule multiple hydrogen bond polyurethane in a low-temperature environment; and shearing and mixing the polyurethane serving as a modifier with matrix asphalt in a molten state, and solidifying to obtain modified asphalt. The polyurethane prepared by the invention has multiple dynamic reversible hydrogen bonds, so that the polyurethane has self-healing characteristics, and is beneficial to realizing crack self-healing of corresponding modified asphalt at normal temperature; in addition, the multiple hydrogen bonds can also endow polyurethane with higher strength, so that the rutting resistance and the deformation recovery capability of the polyurethane modified asphalt are improved.
Description
Technical Field
The invention belongs to the technical field of road engineering material preparation, and particularly relates to a preparation method of self-healing high-performance polyurethane modified asphalt at normal temperature.
Background
During long-term service, the asphalt pavement can generate cracks under the influence of external environment changes, traffic loads and other factors, and the service life and running safety of the asphalt pavement are seriously influenced. Fatigue cracking and rutting are typical diseases of asphalt pavement and are also main causes of loose asphalt pavement layers, pits and base layer damage.
In recent years, microcapsule, fiber reinforcement, modified asphalt, long-life pavement structure and electromagnetic induction, microwave heating and other passive healing methods are adopted to enhance the crack resistance of the asphalt pavement for pavement cracking at home and abroad, but the methods can only inhibit or delay the generation of asphalt pavement cracks and have the defects of poor durability, unstable pavement structure after repair, higher repair cost, higher construction requirement, inapplicability to high flow and expressways and the like. Compared with the passive healing methods, the intrinsic self-healing material can be added to carry out self-healing by means of the self-structure, and the method has the characteristics of high self-healing speed, high efficiency, repeatable process and the like.
The Polyurethane (PU) has both soft segment comprising oligomer polyol and hard segment comprising isocyanate, and may be used in modifying asphalt to regulate the high and low temperature performance balance of the material flexibly, so as to realize intrinsic self-healing of asphalt road. The molecular structure design in the PU in-situ polymerization process is flexible, and the change of a reversible structure can be introduced in the polymerization process to realize the intrinsic self-healing, thereby playing an important role in the research field of self-healing modified asphalt. Hydrogen bonding is a weak dynamic reversible non-covalent bond, the bond energy of which is only one tenth of that of a carbon-carbon covalent bond (400 kJ/mol), and is easy to break and recombine at room temperature, so that the polymer containing the hydrogen bonding has room temperature self-healing property. The hydrogen bonds in polyurethanes are mainly formed by self-assembly of proton donors (N-H) and proton acceptors (c=o) in urethane or urea groups. The multiple hydrogen bonds build strong acting force, provide rich crosslinking points for the polymer network, and can be quickly recombined between material fracture interfaces to realize the reconstruction of the polymer network. Although the reversible structure of self-healing polyurethane has been reported in a large number, in the research of self-healing polyurethane modified asphalt, mainly focused on the introduction of dynamic covalent bonds, the related research is not yet sufficient.
The invention patent CN116426138A discloses a polyurethane modified asphalt material containing a dynamic covalent bond structure and a preparation method thereof, wherein a dynamic reversible cross-linked network structure is constructed in asphalt by introducing a dynamic covalent bond, so that the asphalt has excellent structural rearrangement and conformation adjustment capability, and the fatigue resistance of the polyurethane modified asphalt is improved. The invention patent CN116285397A provides a polyurethane modified asphalt based on DA thermal reversible dynamic covalent bond and a preparation method thereof, which utilizes the thermal reversibility of DA bond, fully utilizes the adjustability of the composition and the crosslinking degree, decomposes into smaller oligomer molecular chains at high temperature, is easier to move, enhances the interaction with matrix asphalt under the high-speed shearing action, increases the compatibility with the matrix asphalt, and ensures that DA undergoes positive reaction after the matrix asphalt is reduced to a certain temperature, and the oligomers are reconstructed into macromolecular polyurethane modified asphalt with a certain network structure in the matrix asphalt.
In addition, the mixing temperature of the polyurethane modified asphalt related to the patent is about 130-150, the temperature is high, the energy consumption is high, and only the self-healing is realized through the rupture and recombination of the reversible dynamic bonds, but the healing mechanism of the reversible dynamic non-covalent bonds (such as hydrogen bonds) is not intensively studied. In addition, the related patent and literature are also silent about the self-healing properties of multi-hydrogen bond polyurethane modified asphalt. Therefore, the design of the polyurethane modified asphalt material capable of realizing self-healing at normal temperature has important significance for improving road safety and saving energy.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides the self-healing high-performance polyurethane modified asphalt at normal temperature and the preparation method thereof, wherein the mechanical properties of the material are regulated and controlled by utilizing more flexible molecular structure design in the polyurethane in-situ polymerization process, meanwhile, the intrinsic self-healing is realized by introducing reversible structure change in the polymerization process, and a loose hard segment structure is constructed by utilizing the unique asymmetric aliphatic ring structure of isophorone diisocyanate and isophorone diamine, so that the high-efficiency self-repairing capability of the polyurethane is stimulated. The hard segments formed by the asymmetric alicyclic structure are highly disordered, impeding the formation of crystals. Under the excitation of temperature, the structure can be moderately relaxed, and the mobility of the molecular chain is enlarged. On the other hand, the numerous repeat units formed by isophorone diisocyanate and isophorone diamine build up a continuous hydrogen bond array, forming stable supramolecular interactions. In addition, the soft segment polytetrahydrofuran ether glycol/noncrystalline polypropylene glycol with stronger order not only increases the bonding energy between molecular chains, but also provides a carrier for hydrogen bonds. The prepared multi-hydrogen bond polyurethane has excellent mechanical strength and good self-healing efficiency due to the organic combination of the structures. The self-healing polyurethane with multiple hydrogen bonds is added into matrix asphalt as a modifier, so that the excellent self-healing capability and good renewable performance are provided for asphalt while the rutting resistance and deformation recovery capability of the asphalt are improved, and efficient active healing and high-quality recycling of the damaged cracks of the multi-hydrogen bond polyurethane modified asphalt are realized.
In order to achieve the above purpose, the present invention adopts the following scheme: the preparation method of the self-healing high-performance polyurethane modified asphalt at normal temperature comprises the following steps:
(1) Firstly, dehydrating polyalcohol, and then polymerizing the polyalcohol with isophorone diisocyanate/hexamethylene diisocyanate in a nitrogen atmosphere to obtain a prepolymer;
(2) Polymerizing the prepolymer with isophorone diamine, and constructing supermolecule multiple hydrogen bond polyurethane in a vacuum low-temperature environment;
(3) Crushing the multi-hydrogen bond polyurethane by a high-speed multifunctional crusher to obtain a rice-grain-sized multi-hydrogen bond polyurethane material, and then mixing the multi-hydrogen bond polyurethane material with matrix asphalt to obtain a reaction mixture;
(4) And heating and curing the reaction mixture to obtain the self-healing high-performance polyurethane modified asphalt material at normal temperature.
Further, the mass ratio of the matrix asphalt to the multi-hydrogen bond polyurethane is 100:1-50. Thus, the density of the polyurethane with multiple hydrogen bonds is different from that of the matrix asphalt to a certain extent, and the excessive doping amount easily causes uneven dispersion of the polyurethane in the matrix asphalt, so that the preparation difficulty is increased; too little blending amount can not effectively improve the high and low temperature performance and the self-healing performance of asphalt.
Preferably, in the step (1), the polyol is one of polytetramethylene ether glycol, polypropylene glycol, polyethylene glycol, hydroxyl-terminated butadiene acrylonitrile or polycaprolactone.
Preferably, in the step (1), the polyol is heated to 100-120 ℃ under vacuum condition for dehydration for 4-8 hours, then cooled to less than 60 ℃ and added with isophorone diisocyanate/hexamethylene diisocyanate, and after sufficient stirring, the temperature is raised to 80 ℃ for reaction for 4 hours, thus obtaining the prepolymer.
Preferably, in step (1), the molar ratio of isocyanate groups in the two diisocyanates to hydroxyl groups in the polyol is 1:0.5 to 1.
Preferably, in step (2), the molar ratio of diamine roots in the isophorone diamine to hydroxyl groups in the polyol is 1:0.1 to 0.5.
Preferably, in the step (2), the mass ratio of the multi-hydrogen bond polyurethane to the asphalt is 3:7-7:3.
Preferably, in the step (3), the temperature of the heating and curing is 80-100, and the time of the heating and curing is 6-48 hours.
Preferably, the matrix asphalt is 70# or 90# matrix asphalt.
Based on the same technical conception, the invention also provides a preparation method of the self-healing high-performance polyurethane modified asphalt at normal temperature, which is obtained by the preparation method, and comprises the following steps of:
(1) Heating matrix asphalt to 70-100 ℃ for softening;
(2) Taking a plurality of cured multi-hydrogen bond polyurethane, and obtaining the multi-hydrogen bond polyurethane material with the size of rice grains for standby by a high-speed multifunctional crusher;
(3) And (3) adding the multi-hydrogen bond polyurethane prepared in the step (2) into matrix asphalt to obtain a mixture, heating to 80-120 ℃, starting constant-temperature low-speed stirring, and then shearing the mixture at the same temperature at a high speed to obtain the self-healing high-performance polyurethane modified asphalt material at normal temperature. Wherein, the hot-mixing temperature of the multi-hydrogen bond polyurethane and the asphalt is obviously lower than that of the traditional modified asphalt, and the energy consumption in the production process is reduced.
Further, the stirring speed in the step (3) is 500-1000 rpm, and the stirring time is 30-60 min.
Further, the rotating speed of shearing in the step (3) is 5000-20000 rpm, and the shearing time is 0.5-3 h.
The invention also aims at providing the self-healing asphalt, and the active ingredients comprise the high-performance polyurethane which heals at normal temperature or the modified asphalt prepared by the method.
Compared with the prior art, the invention has the following beneficial effects:
1. The invention adopts high-performance polyurethane with self-healing capability at normal temperature as an asphalt modifier. The multi-hydrogen bond polyurethane interacts with asphaltene to form a three-dimensional network, so that the viscosity, high-temperature performance and deformation resistance of asphalt are obviously improved. On the other hand, the invention researches to introduce the multi-hydrogen bond polyurethane with in-situ polymerization capability into asphalt so as to enhance the healing capability of the multi-hydrogen bond polyurethane, and realizes the self-healing at normal temperature (25), thereby reducing the safety problems of cracking, rutting and the like of asphalt pavement in long-term service to a certain extent, improving the high-temperature rutting resistance and elasticity of the modified asphalt to a greater extent and improving the self-healing efficiency of the modified asphalt.
2. The modified asphalt prepared by the invention is prepared by directly adding the cured multi-hydrogen bond polyurethane into the matrix asphalt, heating and stirring, equipment transformation is not needed for modified asphalt processing enterprises, and compared with the traditional modified asphalt or the modified asphalt doped with the rutting resistant agent, the modified asphalt has low hot-stirring temperature and low preparation temperature (120 ℃), reduces energy consumption in the production process, promotes energy conservation and emission reduction, lightens environmental and resource pressure, and opens up a new way for developing green low-carbon economic asphalt pavement materials.
Drawings
FIG. 1 is a schematic diagram of the self-healing principle of a self-healing high-performance polyurethane modified asphalt at normal temperature.
FIG. 2 is a self-healing test of the modified asphalt prepared in comparative examples 1 to 2 and examples 1 to 4 at normal temperature (25 ℃ C.) over time.
FIG. 3 is a graph showing the composite modulus G-frequency dependence at 60℃of the modified asphalt prepared in comparative examples 1 to 2 and examples 1 to 4.
FIG. 4 is a plot of delta-frequency of phase angle at 60℃for the modified asphalt prepared in comparative examples 1-2 and examples 1-4.
FIG. 5 is a graph showing the infrared test results of the modified asphalt prepared in comparative examples 1 to 2 and examples 1 to 4.
FIG. 6 is a microstructure view of the modified asphalt prepared in comparative examples 1 to 2 and examples 1 to 4 under an optical microscope.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
1. A preparation method of self-healing high-performance polyurethane modified asphalt at normal temperature.
Example 1
The self-healing high-performance polyurethane modified asphalt at normal temperature is prepared by the following method:
(1) 14g of polytetrahydrofuran ether glycol is dehydrated, 45ml of N, N-dimethylacetamide solvent is added, and then the mixture is polymerized with 3.336g of isophorone diisocyanate and 1.284g of hexamethylene diisocyanate for 4 hours under the nitrogen atmosphere, so as to obtain a prepolymer;
(2) Polymerizing the prepolymer with 2.55g of isophorone diamine, reacting for 30min in a vacuum low-temperature environment (0 ℃), reacting for 24h at 60 ℃, taking out, and curing for 12h at 80 ℃ to obtain multiple hydrogen bond polyurethane;
(3) Crushing the multi-hydrogen bond polyurethane in the step (2) by a high-speed multifunctional crusher to obtain a multi-hydrogen bond polyurethane material with the size of rice grains, adding the multi-hydrogen bond polyurethane material into matrix asphalt, heating the matrix asphalt to 120 ℃, and starting high-speed shearing at 5000rpm for 0.5h to obtain a reaction mixture;
(4) And heating and curing the reaction mixture to obtain the self-healing high-performance polyurethane modified asphalt at normal temperature, wherein the self-healing high-performance polyurethane modified asphalt comprises the following raw materials in parts by weight: 100 parts of 70# matrix asphalt and 25 parts of multiple hydrogen bond polyurethane.
Example 2
The self-healing high-performance polyurethane modified asphalt at normal temperature is prepared by the following method:
(1) Firstly, dehydrating 21g of polypropylene glycol, adding 45ml of N, N-dimethylacetamide solvent, and then heating to 80 ℃ with 3.336g of isophorone diisocyanate and 2.568g of hexamethylene diisocyanate under nitrogen atmosphere for polymerization for 4 hours to obtain a prepolymer;
(2) Polymerizing the prepolymer with 3.835g of isophorone diamine, reacting for 30min in a vacuum low-temperature environment (0 ℃), reacting for 24h at 60 ℃, taking out, and curing for 12h at 80 ℃ to obtain multi-hydrogen bond polyurethane;
(3) Crushing the multi-hydrogen bond polyurethane in the step (2) by a high-speed multifunctional crusher to obtain a multi-hydrogen bond polyurethane material with the size of rice grains, adding the multi-hydrogen bond polyurethane material into matrix asphalt, heating the matrix asphalt to 120 ℃, and starting high-speed shearing at 5000rpm for 0.5h to obtain a reaction mixture;
(4) And heating and curing the reaction mixture to obtain the self-healing high-performance polyurethane modified asphalt at normal temperature, wherein the self-healing high-performance polyurethane modified asphalt comprises the following raw materials in parts by weight: 100 parts of 70# matrix asphalt and 25 parts of multiple hydrogen bond polyurethane.
Example 3
The self-healing high-performance polyurethane modified asphalt at normal temperature is prepared by the following method:
(1) 14g of polytetrahydrofuran ether glycol is dehydrated, 45ml of N, N-dimethylacetamide solvent is added, and then the mixture is polymerized with 3.336g of isophorone diisocyanate and 1.284g of hexamethylene diisocyanate for 4 hours under the nitrogen atmosphere, so as to obtain a prepolymer;
(2) Polymerizing the prepolymer with 1.275g of isophorone diamine, reacting for 30min in a vacuum low-temperature environment (0 ℃), reacting for 24h at 60 ℃, taking out, and curing for 12h at 80 ℃ to obtain multiple hydrogen bond polyurethane;
(3) Crushing the multi-hydrogen bond polyurethane in the step (2) by a high-speed multifunctional crusher to obtain a multi-hydrogen bond polyurethane material with the size of rice grains, adding the multi-hydrogen bond polyurethane material into matrix asphalt, heating the matrix asphalt to 120 ℃, and starting high-speed shearing at 5000rpm for 0.5h to obtain a reaction mixture;
(4) And heating and curing the reaction mixture to obtain the self-healing high-performance polyurethane modified asphalt at normal temperature, wherein the self-healing high-performance polyurethane modified asphalt comprises the following raw materials in parts by weight: 100 parts of 70# matrix asphalt and 25 parts of multiple hydrogen bond polyurethane.
Example 4
(1) Firstly, dehydrating 21g of polypropylene glycol, adding 45ml of N, N-dimethylacetamide solvent, and then heating to 80 ℃ with 3.336g of isophorone diisocyanate and 1.284g of hexamethylene diisocyanate under nitrogen atmosphere for polymerization for 4 hours to obtain a prepolymer;
(2) Polymerizing the prepolymer with 2.55g of isophorone diamine, reacting for 30min in a vacuum low-temperature environment (0 ℃), reacting for 24h at 60 ℃, taking out, and curing for 12h at 80 ℃ to obtain multiple hydrogen bond polyurethane;
(3) Crushing the multi-hydrogen bond polyurethane in the step (2) by a high-speed multifunctional crusher to obtain a multi-hydrogen bond polyurethane material with the size of rice grains, adding the multi-hydrogen bond polyurethane material into matrix asphalt, heating the matrix asphalt to 120 ℃, and starting high-speed shearing at 5000rpm for 0.5h to obtain a reaction mixture;
(4) And heating and curing the reaction mixture to obtain the self-healing high-performance polyurethane modified asphalt at normal temperature, wherein the self-healing high-performance polyurethane modified asphalt comprises the following raw materials in parts by weight: 100 parts of 70# matrix asphalt and 25 parts of multiple hydrogen bond polyurethane.
Comparative example 1
The modified asphalt consists of the following raw materials in parts by weight: 100 parts of 70# matrix asphalt, 4 parts of SBS (styrene-butadiene-styrene block copolymer); the preparation method comprises the following steps:
(1) Heating the 70# matrix asphalt to 100 ℃ for softening;
(2) Adding SBS into matrix asphalt, heating to 180 ℃, starting constant temperature low-speed stirring at 500rpm for 30min, and further shearing the asphalt at the same temperature at 5000rpm for 2h to obtain the modified asphalt.
Comparative example 2
A preparation method of self-healing polyurethane modified asphalt based on disulfide bonds comprises the following steps:
(1) 15.7g of polytetrahydrofuran ether glycol is put into a three-neck flask, put into a vacuum oven at 120 ℃ for drying and dewatering for 1h, and taken out and put into a water bath kettle at 80 ℃;
(2) Adding 5.4g of isophorone diisocyanate into a three-neck flask, dropwise adding 2 drops of dibutyltin dilaurate, and reacting at 80 ℃ for 2 hours to obtain an isocyanate-terminated prepolymer;
(3) 3.9g of 2, 2-diaminodiphenyl disulfide is added into isocyanate-terminated prepolymer after being melted at 120 ℃ to react for 3 hours at 80 ℃ to obtain polyurethane prepolymer, and the polyurethane prepolymer is put into a vacuum oven to be cured for 2 hours at 80 ℃ to obtain self-healing polyurethane;
(4) Melting 100g of matrix asphalt, putting into an oil bath pot at 120 ℃, shearing the self-healing polyurethane, adding the crushed self-healing polyurethane into the matrix asphalt, stirring for 20min, pouring into a polytetrafluoroethylene disc, and curing for 2h at 80 ℃ in an oven to obtain the self-healing polyurethane modified asphalt.
2. Performance detection
1. A self-healing test is carried out under the condition of natural normal temperature (25 ℃), healing changes are shown in figure 2, long strips with similar length and width are cut off from comparative examples 1-2 and examples 1-4 respectively, a blade is used for cutting off the long strips in the middle, the modified asphalt is uniformly placed in a room temperature environment (25 ℃) after being spliced, the modified asphalt is placed for 24 hours and 48 hours respectively, and the self-healing conditions are observed. As can be seen from FIG. 1, the healing degree of the multi-hydrogen bond polyurethane modified asphalt designed by the invention is superior to that of the traditional SBS modified asphalt, as the healing degree of the multi-hydrogen bond polyurethane modified asphalt is different from that of the traditional SBS modified asphalt after the multi-hydrogen bond polyurethane modified asphalt is placed for 24 hours, and the healing degree of the multi-hydrogen bond polyurethane modified asphalt is different from that of the traditional SBS modified asphalt; after the multi-hydrogen bond polyurethane modified asphalt is placed for 24 hours at normal temperature, further self-healing is found in each of the examples 1-4 and the comparative example 2, wherein the healing degree of the example 1 and the example 2 is the best, the surface incision is basically disappeared, but the incision does not obviously self-heal after the comparative example 1 is healed for 48 hours at room temperature, which indicates that the multi-hydrogen bond polyurethane modified asphalt designed by the invention is helpful for realizing the self-healing process of a heterogeneous system due to the directionality and reversibility of hydrogen bonds, can quickly repair damage, and consumes energy generated by strain as a weak dynamic bond. The self-healing ability of the asphalt can be further enhanced as a result of the composite network of the self-healing polyurethane modified asphalt formed by the interaction of the thermally reversible crosslinked network and the plurality of hydrogen bonds.
2. The modified asphalt prepared in comparative examples 1 to 2 and examples 1 to 4 was subjected to rheological property test using a Dynamic Shear Rheometer (DSR) at a temperature of 60, which is generally regarded as the highest temperature of the asphalt pavement, with strain fixed at 1%, and was subjected to dynamic frequency sweep in a frequency sweep range of 100 to 0.01rad/s from high frequency to low frequency, and the high temperature rheological properties of the modified asphalt were measured. The composite modulus G * can reflect the rutting resistance of the asphalt material, and the larger the G * value is, the better the rutting resistance is.
The phase angle δ reflects the viscoelasticity of the material, with values between 0 and 90 °, when δ=0°, the material exhibits pure elasticity, and when δ=90°, the material exhibits pure tackiness. For asphalt materials in high temperature conditions, an excessively high delta value results in tackiness of the pavement, and the lower the delta value is, the better the elasticity is, i.e., the greater the deformation recovery capability is, and the rut resistance is improved.
The complex modulus G * of different modified asphalt as a function of frequency is shown in fig. 3, and it can be found that the magnitude relation of G * values is satisfied over the entire scanning frequency range, example 1> example 2> example 3> example 4> comparative example 1> comparative example 2. As can be seen from the results of fig. 2, the G * values of the modified asphalt added with the multi-hydrogen bond polyurethane are higher than the G * values of the modified asphalt added with the SBS and the modified asphalt of the polyurethane with disulfide bonds, which indicates that the anti-rutting ability of the multi-hydrogen bond polyurethane modified asphalt designed by the invention is better, and the effect of improving the anti-rutting ability of the asphalt is better than that of the SBS, wherein the anti-rutting ability of the embodiment 1 is most prominent.
The phase angle delta of the different modified asphalt as a function of frequency is shown in fig. 4. In the low frequency scanning range, the magnitude relation of the δ value satisfies comparative example 2 to comparative example 1> embodiment 4> embodiment 3> embodiment 2> embodiment 1. As can be seen from the results of fig. 4, the delta values of the modified asphalt added with the multi-hydrogen bond polyurethane are lower than those of the modified asphalt added with the SBS, which indicates that the multi-hydrogen bond polyurethane modified asphalt designed by the invention has better rutting resistance, and the effect of improving the deformation resistance of the asphalt is better than that of the SBS and the polyurethane modified asphalt with disulfide bonds, wherein the deformation resistance of the modified asphalt of the example 1 is the most prominent, and the deformation resistance of the modified asphalt of the comparative example 1 is the worst.
The results of fig. 2 to 4 show that: the modified asphalt of example 1 has excellent high temperature rutting resistance and deformation resistance, most outstanding comprehensive properties, and is superior to the traditional SBS modified asphalt with the doping amount of 4%, and although the modified asphalt of comparative example 2 can realize self-healing at normal temperature, the self-healing capability is not outstanding, the mechanical strength is lowest, and the modified asphalt is lower than the multi-hydrogen bond polyurethane modified asphalt. Therefore, the multi-hydrogen bond polyurethane modified asphalt designed by the invention can be used as a substitute of the traditional asphalt modifier SBS by comprehensively considering the self-healing performance and the mechanical strength, effectively improves the high-temperature rutting resistance and the self-healing capacity of the asphalt, and can be prepared by simple mechanical crushing, and has simple process and low energy consumption.
3. The modified asphalt prepared in comparative examples 1 to 2 and examples 1 to 4 was characterized for functional groups, by fourier transform infrared spectroscopy (FTIR), with a wave number range of 400-4000cm -1, a resolution of 4cm -1, and all spectra were obtained in transmission mode.
As can be seen from FIG. 5, 3367cm -1 is a characteristic peak of-NH, the characteristic peaks of 2910cm -1 and 2854cm -1 occur due to the antisymmetric and symmetrical stretching vibrations of-CH 3 and-CH 2, respectively, the absorption peak at 1568cm -1 represents a bending vibration of-NH, the stretching vibration peak of the C-O-C group was located at 1107cm -1, the absorption peak at 1373cm -1 was due to stretching vibration of-CN, and the vibration signal of-NCO around 2270cm -1 disappeared, indicating that the polymerization reaction was complete, and the multiple hydrogen bond polyurethanes of examples 1 to 4 were prepared successfully.
4. The film samples of the modified asphalt prepared in examples 1 to 4 of comparative examples 1 to 2 were observed by using an optical microscope, and fig. 6 shows the microstructure of the modified asphalt prepared in examples 1 to 2 of comparative examples 1 to 4, respectively, in a light transmission mode.
As can be seen from FIG. 6, comparative example 1 and comparative example 2 show sea-island structure in asphalt, and microphase separation phenomenon occurs, while the multiple hydrogen bond polyurethane part of the present invention is randomly dispersed in matrix asphalt, microphase separation does not occur, and overall mixing is relatively uniform. Because the parts of the multiple hydrogen bond polyurethane are randomly distributed, the constraint and the blocking effect can be generated on the materials, so that the relative sliding among the materials is reduced, and the effect similar to that of the reinforcing ribs is also the main reason that the multiple hydrogen bond polyurethane can effectively improve the composite modulus of the modified asphalt, namely the rutting resistance. On the one hand, a plurality of repeated units formed by the isophorone diisocyanate and the isophorone diamine construct a continuous hydrogen bond array to form stable supermolecular interaction, and the deformation resistance of the modified asphalt can be improved. In addition, the soft segment polytetrahydrofuran ether glycol/noncrystalline polypropylene glycol with stronger order not only increases the bonding energy between molecular chains, but also provides a carrier for hydrogen bonds, so that the self-healing polyurethane is used as a modifier, a polyurethane structure of a dynamic reversible hydrogen bond can be constructed in asphalt, the rutting resistance and elastic recovery capability of the asphalt are enhanced, meanwhile, the excellent self-healing capability is given to the asphalt, the efficient and active healing of polyurethane modified asphalt damaged cracks is realized, the glass transition temperature of the asphalt is reduced, and the self-healing at normal temperature can be realized. On the other hand, the structure can be rapidly dispersed in the material and adsorb asphalt under the high-temperature flow state of the matrix asphalt, so that the load borne by the composite material can be dispersed and transferred, the stress of the material is more uniform, and the deformation resistance of the composite material is further improved.
In summary, the multi-hydrogen bond modified asphalt of example 1 has excellent high temperature rutting resistance and deformation resistance, and also has excellent self-healing ability, and can realize self-healing under normal temperature conditions, and the comprehensive performance is most outstanding, and is superior to the traditional SBS modified asphalt and polyurethane modified asphalt with disulfide bonds.
Finally, it is noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the applicant has described the present invention in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention, and it is intended to be covered by the scope of the claims of the present invention.
Claims (10)
1. The preparation method of the self-healing high-performance polyurethane modified asphalt at normal temperature is characterized by comprising the following steps of:
(1) Firstly, dehydrating polyalcohol, and then polymerizing the polyalcohol with isophorone diisocyanate/hexamethylene diisocyanate in a nitrogen atmosphere to obtain a prepolymer;
(2) Polymerizing the prepolymer with isophorone diamine, and constructing supermolecule multiple hydrogen bond polyurethane in a vacuum low-temperature environment;
(3) Crushing the multi-hydrogen bond polyurethane by a high-speed multifunctional crusher to obtain a rice-grain-sized multi-hydrogen bond polyurethane material, and then carrying out melt mixing with matrix asphalt to obtain a reaction mixture;
(4) And heating and curing the reaction mixture to obtain the self-healing high-performance polyurethane modified asphalt material at normal temperature.
2. The method according to claim 1, wherein in the step (1), the polyol is one of polytetramethylene ether glycol, polypropylene glycol, polyethylene glycol, hydroxyl-terminated butadiene or hydroxyl-terminated butadiene-acrylonitrile.
3. The process according to claim 1, wherein in the step (1), the polyol is heated to 100 to 120 ℃ under vacuum to dehydrate for 4 to 8 hours, cooled to 60 ℃ or lower, and then isophorone diisocyanate/hexamethylene diisocyanate is added, and the mixture is stirred sufficiently and then heated to 80 ℃ to react for 4 hours to obtain the prepolymer.
4. The method of claim 1, wherein in step (1), the molar ratio of isocyanate groups in the two diisocyanates to hydroxyl groups in the polyol is 1:0.5 to 1.
5. The method according to claim 1, wherein in the step (2), the molar ratio of diamine roots in the isophorone diamine to hydroxyl groups in the polyol is 1:0.1 to 0.5.
6. The method according to claim 1, wherein in the step (3), the mass ratio of the multi-hydrogen bond polyurethane to the matrix asphalt is 3:7 to 7:3.
7. The high performance polyurethane modified asphalt of claim 1, wherein the matrix asphalt is 70# or 90# matrix asphalt.
8. The method according to claim 1, wherein in the step (3), the temperature of the melt-mixing is 80 to 120 ℃ and the mixing time is 0.5 to 3 hours.
9. The method according to claim 1, wherein in the step (4), the temperature of the heat curing is 80 to 100 ℃ and the time of the heat curing is 6 to 48 hours.
10. The high-performance polyurethane modified asphalt material self-healing at normal temperature obtained by the preparation method of any one of claims 1 to 9.
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