CN116426138A - Polyurethane modified asphalt material containing dynamic covalent bond structure and preparation method thereof - Google Patents
Polyurethane modified asphalt material containing dynamic covalent bond structure and preparation method thereof Download PDFInfo
- Publication number
- CN116426138A CN116426138A CN202310343863.8A CN202310343863A CN116426138A CN 116426138 A CN116426138 A CN 116426138A CN 202310343863 A CN202310343863 A CN 202310343863A CN 116426138 A CN116426138 A CN 116426138A
- Authority
- CN
- China
- Prior art keywords
- modified asphalt
- polyurethane modified
- dynamic
- covalent bond
- hydroxyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000010426 asphalt Substances 0.000 title claims abstract description 135
- 239000004814 polyurethane Substances 0.000 title claims abstract description 72
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 72
- 239000000463 material Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 56
- 239000012948 isocyanate Substances 0.000 claims abstract description 34
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 34
- 239000011159 matrix material Substances 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 52
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 34
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 19
- 229910052717 sulfur Inorganic materials 0.000 claims description 19
- 239000011593 sulfur Substances 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 18
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 17
- 229920000570 polyether Polymers 0.000 claims description 17
- YCLSOMLVSHPPFV-UHFFFAOYSA-N 3-(2-carboxyethyldisulfanyl)propanoic acid Chemical compound OC(=O)CCSSCCC(O)=O YCLSOMLVSHPPFV-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- 229920000459 Nitrile rubber Polymers 0.000 claims description 7
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- JGUQDUKBUKFFRO-CIIODKQPSA-N dimethylglyoxime Chemical compound O/N=C(/C)\C(\C)=N\O JGUQDUKBUKFFRO-CIIODKQPSA-N 0.000 claims description 6
- LEVWYRKDKASIDU-QWWZWVQMSA-N D-cystine Chemical compound OC(=O)[C@H](N)CSSC[C@@H](N)C(O)=O LEVWYRKDKASIDU-QWWZWVQMSA-N 0.000 claims description 4
- 229960003067 cystine Drugs 0.000 claims description 4
- -1 diisocyanate compound Chemical class 0.000 claims description 4
- 229920005862 polyol Polymers 0.000 claims description 4
- 150000003077 polyols Chemical class 0.000 claims description 4
- FDKWRPBBCBCIGA-REOHCLBHSA-N (2r)-2-azaniumyl-3-$l^{1}-selanylpropanoate Chemical compound [Se]C[C@H](N)C(O)=O FDKWRPBBCBCIGA-REOHCLBHSA-N 0.000 claims description 2
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims description 2
- FDKWRPBBCBCIGA-UWTATZPHSA-N D-Selenocysteine Natural products [Se]C[C@@H](N)C(O)=O FDKWRPBBCBCIGA-UWTATZPHSA-N 0.000 claims description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 229920000768 polyamine Polymers 0.000 claims description 2
- 150000007519 polyprotic acids Polymers 0.000 claims description 2
- ZKZBPNGNEQAJSX-UHFFFAOYSA-N selenocysteine Natural products [SeH]CC(N)C(O)=O ZKZBPNGNEQAJSX-UHFFFAOYSA-N 0.000 claims description 2
- 229940055619 selenocysteine Drugs 0.000 claims description 2
- 235000016491 selenocysteine Nutrition 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- 150000005846 sugar alcohols Polymers 0.000 claims 1
- 230000035876 healing Effects 0.000 abstract description 3
- 230000008929 regeneration Effects 0.000 abstract 1
- 238000011069 regeneration method Methods 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 28
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 26
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 21
- 239000012975 dibutyltin dilaurate Substances 0.000 description 21
- 230000002441 reversible effect Effects 0.000 description 17
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 15
- 229910052742 iron Inorganic materials 0.000 description 14
- 238000004321 preservation Methods 0.000 description 14
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 13
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 13
- 238000004132 cross linking Methods 0.000 description 12
- 125000005442 diisocyanate group Chemical group 0.000 description 12
- 239000005058 Isophorone diisocyanate Substances 0.000 description 7
- 230000006378 damage Effects 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 7
- 239000004971 Cross linker Substances 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 239000003094 microcapsule Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical group O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- DDRPCXLAQZKBJP-UHFFFAOYSA-N furfurylamine Chemical compound NCC1=CC=CO1 DDRPCXLAQZKBJP-UHFFFAOYSA-N 0.000 description 4
- 229920003192 poly(bis maleimide) Polymers 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 230000005674 electromagnetic induction Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000008707 rearrangement Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000012492 regenerant Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C08G18/3228—Polyamines acyclic
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/4825—Polyethers containing two hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A30/00—Adapting or protecting infrastructure or their operation
- Y02A30/30—Adapting or protecting infrastructure or their operation in transportation, e.g. on roads, waterways or railways
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Civil Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides a polyurethane modified asphalt material containing a dynamic covalent bond structure, which comprises the raw material components of 70-90 parts of matrix asphalt, 8-29 parts of isocyanate prepolymer, 0.5-5.0 parts of dynamic cross-linking agent, 0.3-1.5 parts of common cross-linking agent and 0.01-0.1 part of catalyst; the dynamic cross-linking agent is a double/multiple active end group compound containing dynamic bonds or a multifunctional group compound which reacts with isocyanate groups to generate dynamic bond groups. The invention also provides a preparation method of the polyurethane modified asphalt material with the dynamic covalent bond structure. In summary, the polyurethane modified asphalt material containing the dynamic covalent bond structure has excellent low-temperature performance and fatigue resistance, active healing capacity and good regeneration performance.
Description
Technical Field
The invention relates to the technical field of road engineering materials, in particular to a polyurethane modified asphalt material containing a dynamic covalent bond structure and a preparation method thereof.
Background
Along with the gradual entering of new times of maintenance and rising of road construction in China, how to improve the maintenance level and the road surface traffic capacity are the subjects facing each other. Cracking is one of the major forms of failure of asphalt pavement, which can severely reduce the traffic capacity of the pavement over time. Therefore, research on how to inhibit the initiation of microcracks on asphalt pavement and reduce the propagation rate of the microcracks is of great significance in improving the maintenance efficiency of roads and prolonging the service life of roads. The self-repairing property of the asphalt material can endow the asphalt pavement with certain damage recovery capability, the asphalt material can keep enough intermittent time under the condition of no external load, and the self-repairing capability of the asphalt material can gradually heal cracks. However, asphalt materials have a weak ability to self-repair under service conditions and are not sufficiently resistant to crack initiation and propagation.
Current research focuses on the use of thermal induction techniques and microcapsule techniques to facilitate the self-healing process of asphalt. The heat induction technology is based on the temperature dependence characteristic of asphalt flow rate, and the temperature of asphalt is increased in an electromagnetic induction or microwave heating mode, so that asphalt flow to microcracks is accelerated, and the rapid healing of pavement cracks is realized. The microcapsule technology is to mix microcapsule containing regenerant into asphalt, and the microcapsule breaks under the action of crack tip stress to flow out the regenerant to repair the microcracks of asphalt pavement. These self-repairing techniques are all external assistance self-repairing techniques, which require electromagnetic/microwave generating devices and external doping electromagnetic induction materials or external doping microcapsules, have poor timeliness and can adversely affect the performance of asphalt itself. These problems limit their popularization and application in practical asphalt pavement.
In addition, a preparation method of a high-temperature self-repairing hot-mix epoxy asphalt material is disclosed in a patent with publication number CN112852109A, the basic principle of the technology is transesterification, and dynamic bonds in epoxy glass polymer materials can only undergo transesterification at a high temperature (more than 180 ℃), so that the toughening and self-healing properties of the material are improved. In the technical scheme, a dynamic bond is a thermal reversible dynamic bond (DA reaction), and the condition of the forward and reverse reaction of the epoxy resin is temperature change, and the recyclable epoxy asphalt can be realized by heating to 120 ℃.
Disclosure of Invention
In view of the above, the invention provides a polyurethane modified asphalt material containing a dynamic covalent bond structure and a preparation method thereof, which introduces the dynamic covalent bond into the polyurethane modified asphalt molecular structure from the aspect of the material molecular structure, constructs a dynamic reversible polyurethane crosslinking structure in asphalt, and gives the asphalt excellent self-repairing capability and good renewable performance while improving the physical-rheological performance of the asphalt, thereby realizing efficient active healing and high-quality recycling of polyurethane modified asphalt damaged cracks.
The technical scheme of the invention is realized as follows:
in the first aspect, the invention provides a polyurethane modified asphalt material with a dynamic covalent bond structure, which comprises the following raw materials, by weight, 70-90 parts of matrix asphalt, 8-29 parts of isocyanate prepolymer, 0.5-5.0 parts of dynamic cross-linking agent, 0.3-1.5 parts of common cross-linking agent and 0.01-0.1 part of catalyst.
Based on the technical scheme, preferably, the dynamic cross-linking agent is a double/multiple active end group compound containing dynamic bonds or a multifunctional group compound which can react with isocyanate groups to generate dynamic bond groups; the reactive end groups may be hydroxyl groups or carboxyl groups or amine groups. Because of the difference between the trigger mechanisms of different dynamic covalent bonds and the applicable conditions, in order to be suitable for the temperature (-15 ℃ to 60 ℃) under the service condition of the pavement, the dynamic cross-linking agent is screened, and preferably at least one of dimethylglyoxime, diaminodiphenyl disulfide, dithiodipropionic acid, selenocysteine, cystine, 2' - (1, 4-phenylene) -bis [ 4-mercapto-1, 3, 2-dioxaborane ], and the dynamic cross-linking agent is used for reacting and cross-linking with isocyanate prepolymer, and the dynamic covalent bonds are introduced through the dynamic cross-linking agent.
By introducing dynamic covalent bonds, a dynamic reversible cross-linked network structure is constructed in the asphalt, which has excellent structural rearrangement and conformation adjustment capability, and the dynamic reversible cross-linked network structure has adjustability, so that the fatigue resistance of the polyurethane modified asphalt can be greatly improved. The dynamic covalent bond is introduced into the polyurethane modified asphalt crosslinking structure, and due to the reversible cracking-exchange reaction characteristic of the dynamic covalent bond, when the material is damaged and microcracked, the self-repairing of the material can be realized through the reversible chemical interaction between interface molecules, and the long-acting and repeated self-repairing can be realized. Because the reversible cracking-exchange reaction rate of the dynamic covalent bond has temperature dependence, the reversible reaction rate can be accelerated at high temperature, so the dynamic reversible crosslinking polyurethane modified asphalt has high-temperature active viscosity reduction property, and the construction temperature of the polyurethane modified asphalt mixture is hopefully reduced.
On the basis of the above technical solutions, it is preferable that the common crosslinking agent includes one or more of a polyol, a polyamine, and a polybasic acid. Since a single kind of functional group has poor effect on adjusting the crosslinking density, in order to realize the adjustment and control of the properties of polyurethane modified asphalt by adjusting the crosslinking density, the common crosslinking agent screened out by the invention comprises difunctional, trifunctional and tetrafunctional compounds, wherein a plurality of compounds selected from trimethylolpropane, pentaerythritol, di-o-chlorodiphenylamine methane, hexamethylenediamine, diethanolamine or triethanolamine are preferred.
On the basis of the above technical solution, preferably, the matrix asphalt is road petroleum asphalt, wherein one of 90# asphalt and 70# asphalt is preferable.
Based on the technical scheme, the catalyst is preferably one of N, N-dimethylbenzylamine, triethylenediamine or dibutyltin dilaurate, and the catalyst is used for accelerating the reaction process.
On the basis of the technical scheme, the preparation method of the isocyanate prepolymer is preferable to be as follows: firstly heating the hydroxyl-terminated oligomer dehydrated in vacuum to 70-80 ℃, then adding the diisocyanate compound, and stirring and reacting for 1.5-2 h under the nitrogen atmosphere to obtain the isocyanate prepolymer.
It is further preferred that the hydroxyl-terminated oligomer used for preparing the isocyanate prepolymer is one or more of hydroxyl-terminated butadiene, hydroxyl-terminated butadiene-acrylonitrile, polyether polyol having an average molecular weight of 1000 to 4000g/mol, preferably hydroxyl-terminated butadiene-acrylonitrile, hydroxyl-terminated butadiene in order to improve the low temperature properties of the polyurethane modified asphalt. Further preferably, the polyurethane modified asphalt material further comprises sulfur, and the addition amount of the sulfur in the polyurethane modified asphalt material is 0.01 to 0.1 part.
It is further preferable that the amount of the diisocyanate compound added is 5% to 15% by mass of the polyol.
Further preferably, the diisocyanate compound is one of isophorone diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, or diphenylmethane diisocyanate.
In a second aspect, the present invention also provides a method for preparing the polyurethane modified asphalt material containing the dynamic covalent bond structure according to the first aspect of the present invention, which includes the following steps:
s1, heating matrix asphalt to 120-140 ℃, adding a dynamic cross-linking agent, a common cross-linking agent and a catalyst according to the proportion, and stirring for 5-10 minutes at the speed of 400-500 rpm;
s2, adding isocyanate prepolymer and sulfur, and stirring for 25-30min at 140-150 ℃;
and S3, finally, preserving heat for 1.5-2.5 hours at the temperature of 100-110 ℃ to obtain the polyurethane modified asphalt.
Compared with the prior art, the polyurethane modified asphalt material containing the dynamic covalent bond structure has the following beneficial effects:
1. the dynamic reversible cross-linked network structure is built in the asphalt by introducing the dynamic covalent bond, has excellent structural rearrangement and conformation adjustment capability, and has adjustability, so that the low-temperature performance and fatigue resistance of the polyurethane modified asphalt can be greatly improved; in addition, in order to further improve the low temperature resistance of the polyurethane modified asphalt material containing the dynamic covalent bond structure, when the isocyanate prepolymer is prepared, the hydroxyl-terminated oligomer selects hydroxyl-terminated butadiene-acrylonitrile or hydroxyl-terminated butadiene with better molecular chain flexibility, so that the low temperature performance of the polyurethane modified asphalt material is further improved.
The dynamic covalent bond is introduced into the polyurethane modified asphalt crosslinking structure, and due to the reversible cracking-exchange reaction characteristic of the dynamic covalent bond, when damage microcracks appear on the material, the material can be self-repaired through reversible chemical interaction among interface molecules at normal temperature, and long-acting and repeated self-repair can be realized, so that the polyurethane modified asphalt is endowed with excellent self-repair capability.
Because the reversible cracking-exchange reaction rate of the dynamic covalent bond has temperature dependence, the reversible reaction rate can be accelerated at high temperature, so that the dynamic reversible crosslinking polyurethane modified asphalt has high-temperature active viscosity reduction property, and the construction temperature of the polyurethane modified asphalt mixture is hopeful to be reduced.
Thermosetting polyurethane modified asphalt is difficult to melt at high temperature, so that effective reclaimed asphalt is difficult to obtain; the invention introduces a large number of dynamic covalent bonds into the thermosetting polyurethane crosslinked network through the dynamic crosslinking agent, and greatly improves the renewable property of the thermosetting polyurethane modified asphalt by utilizing the reversible fracture reconstruction property of the dynamic bonds.
2. The hydroxyl-terminated oligomer is preferably hydroxyl-terminated butadiene-acrylonitrile and hydroxyl-terminated butadiene, so that the low temperature and fatigue resistance of the polyurethane modified asphalt material can be further improved, but the hydroxyl-terminated butadiene-acrylonitrile and the hydroxyl-terminated butadiene are easily subjected to oxidative fracture in the service process, so that the performance of the polyurethane modified asphalt material is unstable; meanwhile, a certain amount of disulfide bonds/polysulfide bonds can be introduced in the reaction process, which belongs to dynamic covalent bonds, and the low-temperature toughness, fatigue resistance and self-healing capacity of the polyurethane modified asphalt can be improved.
3. After double bonds are eliminated by adding sulfur and the crosslinking density is improved, the crosslinking density is further regulated by a common crosslinking agent, and the single functional group is selected to have poor crosslinking density regulating effect, so that the common crosslinking agent screened by the invention covers di-functional group, tri-functional group and tetra-functional group compounds, is favorable for regulating the crosslinking density of polyurethane, and can realize the regulation and control of the performance of the polyurethane modified asphalt better.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of the self-healing principle of damage cracks of the dynamic cross-linked polyurethane modified asphalt.
FIG. 2 is a schematic diagram of the loading mode of the dynamic shear rheometer for self-healing performance test of the sample.
Detailed Description
The following description of the embodiments of the present invention will clearly and fully describe the technical aspects of the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, are intended to fall within the scope of the present invention.
Example 1:
preparation of isocyanate prepolymer: 76g of hydroxyl-terminated butadiene is added into a three-neck glass flask, heated to 110 ℃, decompressed, dehydrated in vacuum for 3 hours, cooled to 75 ℃, added with 12.6g of isophorone diisocyanate and 0.05g of dibutyltin dilaurate serving as a catalyst, and reacted for 1.5 hours at a stirring speed of 500rpm in a nitrogen atmosphere, thus obtaining the diisocyanate prepolymer.
Then 70g of 70# matrix asphalt is heated to 130 ℃, 70g of the 70# matrix asphalt is poured into an iron stirring tank, then 0.3g of common cross-linking agent (comprising 0.15g of trimethylolpropane, 0.05g of pentaerythritol and 0.10g of hexamethylenediamine), 0.5g of dynamic cross-linking agent dimethylglyoxime and 0.01g of catalyst dibutyltin dilaurate are added, stirring is carried out for 5 minutes at the speed of 500rpm to uniformly disperse, then 8g of diisocyanate prepolymer (wherein hydroxyl-terminated oligomer is hydroxyl-terminated butadiene) and 0.01g of sulfur are added, and the temperature is raised to 150 ℃ and stirring is continued for 28 minutes; and then transferring the asphalt into a heat preservation oven, and preserving heat for 2 hours at 105 ℃ to obtain the polyurethane modified asphalt.
Example 2:
the isocyanate prepolymer was prepared as in example 1.
Heating 70# matrix asphalt to 130 ℃, pouring 80g into an iron stirring tank, adding 0.9g of common cross-linking agent (comprising 0.3g of trimethylolpropane, 0.45g of pentaerythritol and 0.15g of hexamethylenediamine), 3.5g of dynamic cross-linking agent dithiodipropionic acid and 0.05g of catalyst dibutyltin dilaurate, stirring at 500rpm for 5 minutes to uniformly disperse, adding 15g of diisocyanate prepolymer (wherein the hydroxyl-terminated oligomer is hydroxyl-terminated butadiene) and 0.03g of sulfur, heating to 150 ℃, and continuously stirring for 28 minutes; and then transferring the asphalt into a heat preservation oven, and preserving heat for 2 hours at 105 ℃ to obtain the polyurethane modified asphalt.
Example 3:
the isocyanate prepolymer was prepared as in example 1.
Heating 70# matrix asphalt to 130 ℃, pouring 90g into an iron stirring tank, adding 1.5g of a common cross-linking agent (comprising 0.45g of trimethylolpropane, 0.35g of pentaerythritol and 0.7g of hexamethylenediamine), 5g of dynamic cross-linking agent cystine and 0.1g of catalyst dibutyltin dilaurate, stirring at 500rpm for 5 minutes to uniformly disperse, adding 29g of binary isocyanate prepolymer (wherein the hydroxyl-terminated oligomer is hydroxyl-terminated butadiene) and 0.03g of sulfur, and heating to 150 ℃ to continuously stir for 28 minutes; and then transferring the asphalt into a heat preservation oven, and preserving heat for 2 hours at 105 ℃ to obtain the polyurethane modified asphalt.
Example 4 (hydroxyl terminated oligomer is polyether triol):
preparation of isocyanate prepolymer: 76g of polyether triol is added into a three-neck glass flask, heated to 110 ℃, decompressed, dehydrated in vacuum for 3 hours, cooled to 75 ℃, then 12.6g of isophorone diisocyanate and 0.05g of catalyst dibutyltin dilaurate are added, and the reaction is carried out for 1.5 hours at a stirring speed of 500rpm in a nitrogen atmosphere, thus obtaining the diisocyanate prepolymer.
Then 70g of 70# matrix asphalt is heated to 130 ℃, 70g of the 70# matrix asphalt is poured into an iron stirring tank, then 0.3g of common cross-linking agent (comprising 0.15g of trimethylolpropane, 0.05g of pentaerythritol and 0.10g of hexamethylenediamine), 0.5g of dynamic cross-linking agent dimethylglyoxime and 0.01g of catalyst dibutyltin dilaurate are added, stirring is carried out at the speed of 500rpm for 5 minutes to uniformly disperse, then 8g of diisocyanate prepolymer (wherein hydroxyl-terminated oligomer is polyether triol) and 0.01g of sulfur are added, and the temperature is raised to 150 ℃ and stirring is continued for 28 minutes; and then transferring the asphalt into a heat preservation oven, and preserving heat for 2 hours at 105 ℃ to obtain the polyurethane modified asphalt.
Example 5 (no sulfur added):
the isocyanate prepolymer was prepared as in example 1.
Heating 70# matrix asphalt to 130 ℃, pouring 80g into an iron stirring tank, adding 0.9g of a common crosslinking agent (comprising 0.3g of trimethylolpropane, 0.45g of pentaerythritol and 0.15g of hexamethylenediamine), 3.5g of dynamic crosslinking agent dithiodipropionic acid and 0.05g of catalyst dibutyltin dilaurate, stirring at 500rpm for 5 minutes to uniformly disperse, adding 15g of diisocyanate prepolymer (wherein hydroxyl-terminated oligomer is hydroxyl-terminated butadiene), and heating to 150 ℃ for continuous stirring for 28 minutes; and then transferring the asphalt into a heat preservation oven, and preserving heat for 2 hours at 105 ℃ to obtain the polyurethane modified asphalt.
Example 6 (common crosslinker is a single kind of functional group):
the isocyanate prepolymer was prepared as in example 1.
Heating 70# matrix asphalt to 130 ℃, pouring 90g into an iron stirring tank, adding 1.5g of trimethylolpropane as a common crosslinking agent, 5g of cystine as a dynamic crosslinking agent and 0.1g of dibutyltin dilaurate as a catalyst, stirring at a speed of 500rpm for 5 minutes to uniformly disperse, adding 29g of binary isocyanate prepolymer (wherein hydroxyl-terminated oligomer is hydroxyl-terminated butadiene) and 0.03g of sulfur, and heating to 150 ℃ for continuous stirring for 28 minutes; and then transferring the asphalt into a heat preservation oven, and preserving heat for 2 hours at 105 ℃ to obtain the polyurethane modified asphalt.
Example 7 (without dynamic cross-linker):
the isocyanate prepolymer was prepared as in example 1.
Then 70g of 70# matrix asphalt is heated to 130 ℃, 70g of the 70# matrix asphalt is poured into an iron stirring tank, then 0.3g of common cross-linking agent (comprising 0.15g of trimethylolpropane, 0.05g of pentaerythritol and 0.10g of hexamethylenediamine) and 0.01g of catalyst dibutyltin dilaurate are added, stirring is carried out at the speed of 500rpm for 5 minutes to uniformly disperse, then 8g of binary isocyanate prepolymer (wherein hydroxyl-terminated oligomer is hydroxyl-terminated butadiene) and 0.01g of sulfur are added, and stirring is continued until the temperature reaches 150 ℃; and then transferring the asphalt into a heat preservation oven, and preserving heat for 2 hours at 105 ℃ to obtain the polyurethane modified asphalt.
Example 8 (dynamic cross-linker is bismaleimide and furfuryl amine):
the isocyanate prepolymer was prepared as in example 1.
Then 70g of 70# matrix asphalt is heated to 130 ℃, 70g of the 70# matrix asphalt is poured into an iron stirring tank, then 0.3g of common cross-linking agent (comprising 0.15g of trimethylolpropane, 0.05g of pentaerythritol and 0.10g of hexamethylenediamine), 0.5g of dynamic cross-linking agent (comprising 0.3g of bismaleimide and 0.2g of furfuryl amine) and 0.01g of catalyst dibutyltin dilaurate are added, the mixture is stirred at the speed of 500rpm for 5 minutes to be uniformly dispersed, then 8g of binary isocyanate prepolymer (wherein hydroxyl-terminated oligomer is hydroxyl-terminated butadiene) and 0.01g of sulfur are added, and the mixture is heated to 150 ℃ and stirred for 28 minutes continuously; and then transferring the asphalt into a heat preservation oven, and preserving heat for 2 hours at 105 ℃ to obtain the polyurethane modified asphalt.
Example 9 (without Sulfur, with a single functional group as a common crosslinker)
The isocyanate prepolymer was prepared as in example 1.
Heating 70# matrix asphalt to 130 ℃, pouring 80g into an iron stirring tank, adding 0.9g of pentaerythritol serving as a common crosslinking agent, 3.5g of dithiodipropionic acid serving as a dynamic crosslinking agent and 0.05g of dibutyltin dilaurate serving as a catalyst, stirring at a speed of 500rpm for 5 minutes to uniformly disperse, adding 15g of diisocyanate prepolymer (wherein hydroxyl-terminated oligomer is hydroxyl-terminated butadiene), and heating to 150 ℃ for continuous stirring for 28 minutes; and then transferring the asphalt into a heat preservation oven, and preserving heat for 2 hours at 105 ℃ to obtain the polyurethane modified asphalt.
Example 10 (the hydroxyl terminated oligomer is a polyether triol and the conventional crosslinker is a single type of functional group)
Preparation of isocyanate prepolymer: 76g of polyether triol is added into a three-neck glass flask, heated to 110 ℃, decompressed, dehydrated in vacuum for 3 hours, cooled to 75 ℃, then 12.6g of isophorone diisocyanate and 0.05g of catalyst dibutyltin dilaurate are added, and the reaction is carried out for 1.5 hours at a stirring speed of 500rpm in a nitrogen atmosphere, thus obtaining the diisocyanate prepolymer.
Then heating 70# matrix asphalt to 130 ℃, pouring 70g into an iron stirring tank, adding 0.3g of common cross-linking agent hexamethylenediamine, 0.5g of dynamic cross-linking agent dimethylglyoxime and 0.01g of catalyst dibutyltin dilaurate, stirring at 500rpm for 5 minutes to uniformly disperse, adding 8g of binary isocyanate prepolymer (wherein hydroxyl-terminated oligomer is polyether triol) and 0.01g of sulfur, and heating to 150 ℃ and continuously stirring for 28 minutes; and then transferring the asphalt into a heat preservation oven, and preserving heat for 2 hours at 105 ℃ to obtain the polyurethane modified asphalt.
Example 11 (hydroxyl terminated oligomer is polyether triol without Sulfur)
Preparation of isocyanate prepolymer: 76g of polyether triol is added into a three-neck glass flask, heated to 110 ℃, decompressed, dehydrated in vacuum for 3 hours, cooled to 75 ℃, then 12.6g of isophorone diisocyanate and 0.05g of catalyst dibutyltin dilaurate are added, and the reaction is carried out for 1.5 hours at a stirring speed of 500rpm in a nitrogen atmosphere, thus obtaining the diisocyanate prepolymer.
Then 70g of 70# matrix asphalt is heated to 130 ℃, 70g of the 70# matrix asphalt is poured into an iron stirring tank, then 0.3g of common cross-linking agent (comprising 0.15g of trimethylolpropane, 0.05g of pentaerythritol and 0.10g of hexamethylenediamine), 0.5g of dynamic cross-linking agent dimethylglyoxime and 0.01g of catalyst dibutyltin dilaurate are added, stirring is carried out for 5 minutes at the speed of 500rpm for uniform dispersion, then 8g of diisocyanate prepolymer (wherein hydroxyl-terminated oligomer is polyether triol) is added, and stirring is continued for 28 minutes after the temperature is raised to 150 ℃; and then transferring the asphalt into a heat preservation oven, and preserving heat for 2 hours at 105 ℃ to obtain the polyurethane modified asphalt.
Example 12 (hydroxyl terminated oligomer is polyether triol, free of dynamic covalent bonds)
Preparation of isocyanate prepolymer: 76g of polyether triol is added into a three-neck glass flask, heated to 110 ℃, decompressed, dehydrated in vacuum for 3 hours, cooled to 75 ℃, then 12.6g of isophorone diisocyanate and 0.05g of catalyst dibutyltin dilaurate are added, and the reaction is carried out for 1.5 hours at a stirring speed of 500rpm in a nitrogen atmosphere, thus obtaining the diisocyanate prepolymer.
Then 70g of 70# matrix asphalt is heated to 130 ℃, 70g of the 70# matrix asphalt is poured into an iron stirring tank, then 0.3g of common cross-linking agent (comprising 0.15g of trimethylolpropane, 0.05g of pentaerythritol and 0.10g of hexamethylenediamine) and 0.01g of catalyst dibutyltin dilaurate are added, stirring is carried out at the speed of 500rpm for 5 minutes to uniformly disperse, then 8g of binary isocyanate prepolymer (wherein hydroxyl-terminated oligomer is polyether triol) and 0.01g of sulfur are added, and stirring is continued for 28 minutes after the temperature is raised to 150 ℃; and then transferring the asphalt into a heat preservation oven, and preserving heat for 2 hours at 105 ℃ to obtain the polyurethane modified asphalt.
Example 13 (without dynamic Cross-linking agent, without Sulfur)
The isocyanate prepolymer was prepared as in example 1.
Then 70g of 70# matrix asphalt is heated to 130 ℃, 70g of the 70# matrix asphalt is poured into an iron stirring tank, then 0.3g of common cross-linking agent (comprising 0.15g of trimethylolpropane, 0.05g of pentaerythritol and 0.10g of hexamethylenediamine) and 0.01g of catalyst dibutyltin dilaurate are added, stirring is carried out at the speed of 500rpm for 5 minutes to uniformly disperse, then 8g of binary isocyanate prepolymer (wherein hydroxyl-terminated oligomer is hydroxyl-terminated butadiene) is added, and the temperature is raised to 150 ℃ and stirring is continued for 28 minutes; and then transferring the asphalt into a heat preservation oven, and preserving heat for 2 hours at 105 ℃ to obtain the polyurethane modified asphalt.
Example 14 (free of dynamic Cross-linking agent, hydroxyl terminated oligomer being polyether triol)
Preparation of isocyanate prepolymer: 76g of polyether triol is added into a three-neck glass flask, heated to 110 ℃, decompressed, dehydrated in vacuum for 3 hours, cooled to 75 ℃, then 12.6g of isophorone diisocyanate and 0.05g of catalyst dibutyltin dilaurate are added, and the reaction is carried out for 1.5 hours at a stirring speed of 500rpm in a nitrogen atmosphere, thus obtaining the diisocyanate prepolymer.
Then 70g of 70# matrix asphalt is heated to 130 ℃, 70g of the 70# matrix asphalt is poured into an iron stirring tank, then 0.3g of common cross-linking agent (comprising 0.15g of trimethylolpropane, 0.05g of pentaerythritol and 0.10g of hexamethylenediamine) and 0.01g of catalyst dibutyltin dilaurate are added, stirring is carried out at the speed of 500rpm for 5 minutes to uniformly disperse, then 8g of binary isocyanate prepolymer (wherein hydroxyl-terminated oligomer is polyether triol) is added, and the temperature is raised to 150 ℃ and stirring is continued for 28 minutes; and then transferring the asphalt into a heat preservation oven, and preserving heat for 2 hours at 105 ℃ to obtain the polyurethane modified asphalt.
In order to verify the related performance of the polyurethane modified asphalt material containing the dynamic covalent bond structure, the invention tests the low-temperature ductility of the sample by a dynamic rheometer under the condition of room temperature (20-30 ℃), and can analyze the low-temperature toughness of the sample; the samples were scanned in amplitude and frequency by dynamic shear rheometer and then analyzed by data to obtain fatigue life for the samples at different strains as shown in table 1.
Table 1 Low temperature ductility and fatigue resistance of samples
From the data in the table, it can be seen that the introduction of the dynamic covalent bond into the polyurethane crosslinked network through the dynamic crosslinking agent is helpful to improve the low-temperature performance and fatigue resistance of the polyurethane modified asphalt, and the dynamic crosslinking agent in the application is compared with the dynamic crosslinking agent in the prior art: the bismaleimide and the furfuryl amine have better effects of improving the low-temperature performance and the fatigue resistance of the polyurethane modified asphalt.
The invention carries out self-healing performance test under the condition of room temperature (20-30 ℃), adopts a dynamic shear rheometer to carry out constant temperature and constant strain continuous loading on a sample until the complex shear modulus thereof is reduced to 80 percent (G) of the initial value b1 )、60％(G b2 )、40％(G b3 ) After stopping loading for 900 seconds, loading is resumed, the loading mode is shown in fig. 2, the self-repairing performance of the sample is evaluated by the degree of resumption of complex modulus before and after the gap (self-healing index evaluation), two self-healing index indexes are selected in the experiment to perform evaluation analysis, the specific formulas are shown in formulas (1) and (2), and the test results are shown in table 2.
Wherein: g b1 、G b2 、G b3 G respectively b2 80%,60%,40%.
TABLE 2 self-healing index of samples at different injury levels
As can be seen from the above table data, the introduction of the dynamic covalent bond into the polyurethane crosslinked network through the dynamic crosslinking agent is helpful to improve the self-healing index of the polyurethane modified asphalt under different damage degrees, and the improvement effect is more remarkable under the condition of serious damage degree (complex modulus decays to 40% of the initial value), for example, the improvement amount of example 1 is 34.4% ((57.8% -43%)/43% = 34.4%) compared with example 7. The method shows that the self-repairing capability of the polyurethane modified asphalt is remarkably improved by introducing dynamic bonds in the polyurethane modified asphalt, and the self-repairing capability after multiple damages is improved more obviously.
In addition, the dynamic crosslinking agent in the present application is compared with the dynamic crosslinking agent in the prior art: the bismaleimide and the furfuryl amine have better effect on improving the self-healing index of the polyurethane modified asphalt.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (10)
1. The polyurethane modified asphalt material containing the dynamic covalent bond structure is characterized by comprising the following raw materials, by weight, 70-90 parts of matrix asphalt, 8-29 parts of isocyanate prepolymer, 0.5-5.0 parts of dynamic cross-linking agent, 0.3-1.5 parts of common cross-linking agent and 0.01-0.1 part of catalyst;
the dynamic cross-linking agent is a double/multiple active end group compound containing dynamic bonds or a multifunctional group compound which reacts with isocyanate groups to generate dynamic bond groups.
2. The polyurethane modified asphalt material containing dynamic covalent bond structure according to claim 1, wherein: the active end group is hydroxyl, carboxyl or amino.
3. The polyurethane modified asphalt material containing dynamic covalent bond structure according to claim 1, wherein: the dynamic cross-linking agent comprises at least one of dimethylglyoxime, diaminodiphenyl disulfide, dithiodipropionic acid, selenocysteine, cystine, 2' - (1, 4-phenylene) -bis [ 4-mercapto-1, 3, 2-dioxaborane ].
4. The polyurethane modified asphalt material containing dynamic covalent bond structure according to claim 1, wherein: the common cross-linking agent comprises one or more of polyalcohol, polyamine and polybasic acid.
5. The polyurethane modified asphalt material containing dynamic covalent bond structure according to claim 4, wherein: the general crosslinking agents include difunctional, trifunctional and tetrafunctional compounds.
6. The polyurethane modified asphalt material containing dynamic covalent bond structure according to claim 1, wherein: the preparation method of the isocyanate prepolymer comprises the following steps: firstly heating the hydroxyl-terminated oligomer dehydrated in vacuum to 70-80 ℃, then adding the diisocyanate compound, and stirring and reacting for 1.5-2 h under the nitrogen atmosphere to obtain the isocyanate prepolymer.
7. The polyurethane modified asphalt material containing dynamic covalent bond structure according to claim 6, wherein: the hydroxyl-terminated oligomer is one or more of hydroxyl-terminated butadiene, hydroxyl-terminated butadiene-acrylonitrile and polyether polyol.
8. The polyurethane modified asphalt material containing dynamic covalent bond structure according to claim 7, wherein: the hydroxyl-terminated oligomer is hydroxyl-terminated butadiene-acrylonitrile or hydroxyl-terminated butadiene.
9. The polyurethane modified asphalt material containing dynamic covalent bond structure according to claim 1, wherein: also comprises 0.01 to 0.1 part of sulfur.
10. A preparation method of polyurethane modified asphalt material containing dynamic covalent bond structure is characterized in that: the method comprises the following steps:
s1, heating matrix asphalt to 120-140 ℃, adding a dynamic cross-linking agent, a common cross-linking agent and a catalyst according to the proportion, and stirring for 5-10 minutes at the speed of 400-500 rpm;
s2, adding isocyanate prepolymer and sulfur, and stirring for 25-30min at 140-150 ℃;
s3, finally, preserving heat for 1.5-2.5 hours at 100-110 ℃ to obtain the polyurethane modified asphalt.
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