CN112210221B - Epoxy asphalt material and preparation method thereof - Google Patents
Epoxy asphalt material and preparation method thereof Download PDFInfo
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- CN112210221B CN112210221B CN201910618899.6A CN201910618899A CN112210221B CN 112210221 B CN112210221 B CN 112210221B CN 201910618899 A CN201910618899 A CN 201910618899A CN 112210221 B CN112210221 B CN 112210221B
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- asphalt
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- 239000010426 asphalt Substances 0.000 title claims abstract description 158
- 239000000463 material Substances 0.000 title claims abstract description 75
- 239000004593 Epoxy Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 33
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000011593 sulfur Substances 0.000 claims abstract description 33
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 33
- 239000003822 epoxy resin Substances 0.000 claims abstract description 29
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 29
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 28
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 25
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003999 initiator Substances 0.000 claims abstract description 16
- 150000001412 amines Chemical class 0.000 claims abstract description 14
- 239000003607 modifier Substances 0.000 claims abstract description 8
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 117
- 238000006243 chemical reaction Methods 0.000 claims description 58
- 238000010008 shearing Methods 0.000 claims description 57
- 238000010438 heat treatment Methods 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 19
- 239000011261 inert gas Substances 0.000 claims description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 13
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 125000004018 acid anhydride group Chemical group 0.000 claims description 10
- 238000011049 filling Methods 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 10
- 239000011159 matrix material Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 239000001116 FEMA 4028 Substances 0.000 claims description 8
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims description 8
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims description 8
- 229960004853 betadex Drugs 0.000 claims description 8
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 8
- 239000000084 colloidal system Substances 0.000 claims description 8
- 229920006395 saturated elastomer Polymers 0.000 claims description 8
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 7
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 239000000498 cooling water Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 7
- 239000000376 reactant Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 claims description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 6
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 6
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 5
- 239000004952 Polyamide Substances 0.000 claims description 5
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 5
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 claims description 5
- 229920002647 polyamide Polymers 0.000 claims description 5
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 claims description 4
- 229920001450 Alpha-Cyclodextrin Polymers 0.000 claims description 4
- 238000005698 Diels-Alder reaction Methods 0.000 claims description 4
- HFHDHCJBZVLPGP-RWMJIURBSA-N alpha-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO HFHDHCJBZVLPGP-RWMJIURBSA-N 0.000 claims description 4
- 229940043377 alpha-cyclodextrin Drugs 0.000 claims description 4
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 4
- WVRNUXJQQFPNMN-VAWYXSNFSA-N 3-[(e)-dodec-1-enyl]oxolane-2,5-dione Chemical compound CCCCCCCCCC\C=C\C1CC(=O)OC1=O WVRNUXJQQFPNMN-VAWYXSNFSA-N 0.000 claims description 3
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- 229920000141 poly(maleic anhydride) Polymers 0.000 claims description 3
- 229920005652 polyisobutylene succinic anhydride Polymers 0.000 claims description 3
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims description 2
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 2
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 claims description 2
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 claims description 2
- GDSRMADSINPKSL-HSEONFRVSA-N gamma-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO GDSRMADSINPKSL-HSEONFRVSA-N 0.000 claims description 2
- 229940080345 gamma-cyclodextrin Drugs 0.000 claims description 2
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 claims description 2
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 2
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 2
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- 239000002383 tung oil Substances 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims 2
- 230000008018 melting Effects 0.000 claims 2
- CUXYLFPMQMFGPL-UHFFFAOYSA-N (9Z,11E,13E)-9,11,13-Octadecatrienoic acid Natural products CCCCC=CC=CC=CCCCCCCCC(O)=O CUXYLFPMQMFGPL-UHFFFAOYSA-N 0.000 claims 1
- 229920002732 Polyanhydride Polymers 0.000 claims 1
- CUXYLFPMQMFGPL-SUTYWZMXSA-N all-trans-octadeca-9,11,13-trienoic acid Chemical compound CCCC\C=C\C=C\C=C\CCCCCCCC(O)=O CUXYLFPMQMFGPL-SUTYWZMXSA-N 0.000 claims 1
- 238000010276 construction Methods 0.000 abstract description 6
- 239000003085 diluting agent Substances 0.000 description 10
- 230000014759 maintenance of location Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000012745 toughening agent Substances 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Classifications
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Civil Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses an epoxy asphalt material and a preparation method thereof. The epoxy asphalt material comprises the following raw materials: the modified asphalt comprises maleic anhydride modified blended asphalt, epoxy resin, a performance regulator, cyclodextrin, an initiator, an amine curing agent and an anhydride curing agent, wherein the performance regulator comprises free sulfur and a sulfur prepolymer; the weight portion of the material is as follows: maleic anhydride modified blended asphalt: 100 parts of (A); epoxy resin: 35 to 64 parts; performance modifier: 4 to 25 parts; cyclodextrin: 1 to 7 parts; initiator: 0.1 to 0.9 part; amine curing agent: 5 to 20 parts; acid anhydride curing agent: 20 to 45 portions. The epoxy asphalt material has long construction operation time, good flexibility after curing and excellent overall performance.
Description
Technical Field
The invention relates to a material for road and bridge construction and a preparation method thereof, in particular to an epoxy asphalt material and a preparation method thereof.
Background
Thermosetting epoxy asphalt is an excellent material for paving a long-span steel bridge deck, and road workers put a great deal of effort on the research and development of epoxy asphalt materials, but the problems of short retention time and poor flexibility of epoxy asphalt are not well solved, so that the large-range application of the epoxy asphalt materials is influenced.
In the using process of the epoxy asphalt, in order to enable the epoxy asphalt and stone materials to be conveniently mixed and paved, certain construction time, namely holding time, needs to be reserved. The viscosity is measured primarily as the time to reach a certain value after mixing of the two components A, B, usually expressed as a time to reach 1000mPa.s for more than 50 minutes or a time to reach 5000mPa.s for more than 30 minutes. However, it is very difficult to control the curing time on the premise of ensuring the qualified mechanical properties after curing. At present, the epoxy asphalt is generally too high in strength after being cured, insufficient in flexibility and poor in deformation coordination with a steel bridge deck. And under low temperature conditions, a large temperature stress is generated, and fatigue cracks are generated. Therefore, flexibility is considered while ensuring the retention time.
At present, the retention time of the epoxy asphalt is usually improved by adding a diluent into the system, and the addition of excessive diluent can forcibly reduce the viscosity and increase the retention time, but the mechanical property of the curing system is affected, and the method is not a two-in-one method. The addition of the long-chain flexible additive is one of the common methods for toughening, but the added toughening material often reacts with epoxy resin to accelerate the curing reaction process, so that the retention time is shortened.
CN103194070A discloses an epoxy asphalt material, and a preparation method and a use method thereof. The method reduces the viscosity of a curing system by adding a reactive diluent or a non-reactive diluent into an epoxy system, thereby prolonging the construction time. However, the addition of the additional diluent influences the final curing performance of the system, the compatibility of the diluent and asphalt is poor, and the added diluent is easy to volatilize, so that the environmental pollution is caused.
CN107151419A discloses a high-toughness cold-mix epoxy asphalt binder and a preparation method thereof, and the method takes a toughening agent, epoxy resin and a diluent as a component A to toughen and reduce viscosity of epoxy asphalt. But the toughening agent and the epoxy resin as the same component can react prematurely, the compatibility of the toughening agent and the component B containing the asphalt is poor, and meanwhile, the added diluent is easy to volatilize and only physically reduces the viscosity, and the curing reaction speed is not reduced.
In conclusion, the prior art has different defects in solving the problems of retention time and flexibility of the epoxy asphalt, and the additional diluent is easy to volatilize, has the problem of environmental pollution and can influence the final curing performance. The added toughening agent not only has the problem of poor compatibility with asphalt, but also can improve the curing reaction speed and reduce the retention time.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an epoxy asphalt material and a preparation method thereof. The epoxy asphalt material has long construction operation time, good flexibility after curing and excellent overall performance.
The invention provides an epoxy asphalt material, which comprises the following raw materials: the modified asphalt comprises maleic anhydride modified blended asphalt, epoxy resin, a performance regulator, cyclodextrin, an initiator, an amine curing agent and an anhydride curing agent, wherein the performance regulator comprises free sulfur and sulfur prepolymer; the weight portion of the material is as follows:
maleic anhydride modified blended asphalt: 100 parts of (A);
epoxy resin: 35 to 64 parts, preferably 51 to 61 parts;
performance modifier: 4 to 25 parts, preferably 8 to 20 parts;
cyclodextrin: 1 to 7, preferably 2 to 6 parts;
initiator: 0.1 to 0.9 part, preferably 0.2 to 0.6 part;
amine curing agent: 5 to 20 parts;
acid anhydride curing agent: 10 to 30 portions.
The maleic anhydride modified asphalt is obtained by the Diels-Alder reaction of a substance with an acid anhydride group and modified harmonic asphalt. The modified blended asphalt comprises the following components in parts by weight:
base asphalt I:20 to 70 parts, preferably 30 to 65 parts;
matrix asphalt II:30 to 80 parts, preferably 35 to 70 parts;
modifying agent: 0.03 to 0.5 part, preferably 0.05 to 0.4 part.
The modifier is polyphosphoric acid (PPA).
The matrix asphalt I: the aromatic asphalt comprises, by mass, 20-30% of a saturated component, 25-35% of an aromatic component, 30-45% of a colloid and 0.1-2% of an asphaltene.
The matrix asphalt II: the aromatic asphalt comprises, by mass, 15-30% of saturated components, 20-40% of aromatic components, 10-20% of colloid and 15-30% of asphaltene.
The substance with acid anhydride group is one or more of maleic anhydride, polyisobutylene succinic anhydride, methyl nadic anhydride, modified methyl nadic anhydride, dodecenyl succinic anhydride, eleostearic anhydride, polyazelaic anhydride, polyglutamic anhydride, polyazelaic anhydride or hydrolyzed polymaleic anhydride, and preferably maleic anhydride.
The cyclodextrin is one or more of alpha-cyclodextrin, beta-cyclodextrin and gamma-cyclodextrin, and is preferably alpha-cyclodextrin and/or beta-cyclodextrin.
The initiator is one or more of dicumyl peroxide, tert-butyl hydroperoxide, benzoyl peroxide and sodium metabisulfite.
The weight of the sulfur prepolymer is 40-80% of the total weight of the performance regulator, and the number of sulfur atoms on a molecular chain of the sulfur prepolymer is more than 108.
The epoxy resin is at least one of E-44 bisphenol A type epoxy resin and E-51 bisphenol A type epoxy resin, and preferably E-51 bisphenol A type epoxy resin.
The amine curing agent is one or more of low molecular polyamide 651, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, low molecular polyamide 650, diethylaminopropylamine, N-aminoethyl piperazine and isophorone diamine.
The anhydride curing agent is one or more of maleic anhydride, polyisobutylene succinic anhydride, methyl nadic anhydride, modified methyl nadic anhydride, dodecenyl succinic anhydride, methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, elaeostearic anhydride, polyazelaic anhydride, polyglutamic anhydride, polyacetic anhydride or hydrolyzed polymaleic anhydride, and preferably one or more of methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride and elaeostearic anhydride.
The epoxy asphalt material also comprises 0.04 to 0.6 part by weight of an accelerant. The promoter is one or more of DMP-30, triethylamine, triethanolamine, benzyl triethyl ammonium chloride, resorcinol and m-cresol.
The invention also provides a preparation method of the epoxy asphalt material, which comprises the following steps:
(1) Preparing maleic anhydride modified blended asphalt;
(2) Preparing a performance regulator;
(3) Heating the maleic anhydrization modified blended asphalt prepared in the step (1) to a flowing state, pouring the heated asphalt into a high-pressure reaction kettle, adjusting the temperature in the kettle, stirring, adding cyclodextrin, carrying out programmed heating, and continuing stirring; adding an initiator into a high-pressure reaction kettle, stirring, and filling inert gas for reaction;
(4) Shearing the material reacted in the step (3) at a certain temperature, mixing the sheared material with the preheated amine curing agent, the preheated anhydride curing agent and the preheated accelerator, and continuously shearing;
(5) And (4) mixing the mixture obtained in the step (4) with the preheated epoxy resin, uniformly stirring at a certain temperature, adding the performance regulator, and continuously stirring to obtain the epoxy asphalt material.
Wherein, the maleic anhydride modified blended asphalt prepared in the step (1) can be prepared by the following method: preheating the base asphalt I and the base asphalt II to a flowing state, mixing, and stirring under a heating condition to obtain mixed asphalt; then adding polyphosphoric acid, continuing to heat and stir to obtain modified blended asphalt; adding the heated and melted modified harmonic asphalt into a reactor, controlling the reaction temperature and pressure, and carrying out Diels-Alder reaction with the substance with the acid anhydride group in the inert gas atmosphere to obtain the modified harmonic asphalt with the acid anhydride group.
In the method for preparing the modified blended asphalt, the heating temperature is 100 to 180 ℃, preferably 120 to 160 ℃, the stirring time is 1 to 6 hours, preferably 3 to 6 hours, and the stirring speed is 200 to 500 r/min when preparing the mixed asphalt. After the polyphosphoric acid is added, the heating temperature is 120 to 170 ℃, preferably 135 to 170 ℃, the stirring time is 4 to 10h, and the stirring speed is 300 to 600r/min.
The weight ratio of the substance with the acid anhydride group to the modified harmonic asphalt is (1 to 10): 100, preferably (2 to 6): 100, respectively; the inert gas being N 2 The reaction time is 3 to 6 hours, the reaction temperature is 120 to 160 ℃, and the reaction pressure is 0.2 to 0.7MPa, preferably 0.25 to 0.5MPa.
Wherein, the performance regulator in the step (2) can be prepared by the following method: heating dried sulfur to 130-160 ℃, introducing inert gas after the sulfur is melted into liquid, keeping the pressure at 0.8-2.6 MPa, continuously raising the temperature to 220-380 ℃ by programming, and reacting for 2-4 h under a stirring state; and (3) quickly cooling the material after the reaction is finished by using cold water, separating out the cooling water, drying and crushing the reactant to obtain a mixture of the sulfur prepolymer and the free sulfur, namely the performance regulator, and storing the performance regulator at the temperature of 0-5 ℃ for later use.
In the step (3), the temperature in the kettle is adjusted to be 100-120 ℃, the cyclodextrin is added within 0.5-1.5 h, the temperature programming rate is 0.5-1 ℃/min, and the temperature programming is carried out to 130-160 ℃, preferably 135-150 ℃. The stirring speed is 200 to 400r/min before the initiator is added, and the stirring time is 0.5 to 2.0 hours.
In the step (3), the stirring speed after the initiator is added is 500 to 800r/min. The inert gas is preferably N 2 The amount of the inert gas is 0.2 to 0.8MPa, preferably 0.4 to 0.8MPa, and the reaction time is 3 to 9 hours, preferably 5 to 8 hours.
In the step (4), the shearing temperature before the materials are mixed is 110-120 ℃, the shearing time is 0.5-1.0 h, and the shearing speed is 800-1200 r/min. The preheating temperature of the amine curing agent, the anhydride curing agent and the accelerator is 115 to 125 ℃, the shearing temperature of all the materials after mixing is 120 ℃, the shearing time is 0.5 to 1.5 hours, and the shearing speed is 600 to 1000r/min.
In the step (5), the preheating temperature of the epoxy resin is 60 to 75 ℃, the stirring speed before the performance regulator is added is 500 to 900r/min, the stirring time is 15 to 30min, and the stirring temperature is 115 to 125 ℃; the stirring speed after the performance regulator is added is 800 to 1100r/min, the stirring time is 10 to 25min, and the stirring temperature is 100 to 120 ℃.
Compared with the prior art, the epoxy asphalt material and the preparation method thereof have the following advantages:
(1) The invention selects the modified blended asphalt to carry out anhydrization, and the anhydrization modified blended asphalt can be better matched with a curing agent, an accelerant, epoxy resin and the like subsequently under the action of cyclodextrin, thereby being beneficial to carrying out chemical reaction with a performance regulator in the curing process and preparing the thermosetting epoxy asphalt with long holding time and good flexibility.
(2) The performance regulator is introduced into the epoxy system, and a stabilizer is not required to be added in the preparation process, so that the process is simple; the performance regulator has a linear long-chain molecular structure, and can obviously increase the flexibility of a system and improve the tensile property of an epoxy asphalt cured product when being filled in a three-dimensional grid structure.
(3) The performance regulator introduced by the invention has special double-end free radicals, and the existence of the free radicals enables the performance regulator to be decomposed into elemental sulfur under the heating condition, and the instability of thermal decomposition is unfavorable for a curing system. However, the special system of the cis-anhydrization epoxy asphalt modified by the cyclodextrin can fully utilize the characteristics, free radicals in the epoxy system can react with free radicals at two ends of the performance regulator, and the performance regulator losing the free radicals is changed from a high active state to a stable state to exist in a curing system for a long time. Meanwhile, the performance regulator consumes free radicals generated in the curing process, so that the curing process is slowed, namely the viscosity of the epoxy asphalt is increased slowly in the early stage, the holding time is prolonged, and more time is provided for construction.
(4) The unconverted sulfur can react with cyclane and aromatic hydrocarbon in the asphalt to improve the polarity of the asphalt, thereby reducing the polarity difference between the epoxy resin and the asphalt to a certain extent and improving the compatibility of the epoxy resin and the asphalt. In addition, the unreacted sulfur is melted into liquid under the heating condition, the viscosity is low, the asphalt is diluted to a certain degree, and the holding time is prolonged.
(5) At present, a large amount of sulfur as a byproduct of a refinery does not have a reasonable utilization scheme, the comprehensive property of the epoxy asphalt is improved by introducing the sulfur modifier, and the problems of excessive sulfur capacity and low added value of the refinery are solved to a certain extent.
Detailed Description
The technical solution of the present invention is further described below by way of examples, but these examples are not intended to limit the present invention, and wt% referred to is mass fraction.
Example 1
(1) Preheating 60 parts by weight of base asphalt I (saturated component accounting for 27.0wt%, aromatic component accounting for 28.9wt%, colloid accounting for 43.9wt%, and asphaltene accounting for 0.2 wt%) and 40 parts by weight of base asphalt II (saturated component accounting for 28.0wt%, aromatic component accounting for 36.4wt%, colloid accounting for 19.2wt%, and asphaltene accounting for 16.4 wt%) to a flowing state, mixing, and stirring at 130 ℃ for 4 hours at a stirring speed of 300 r/min to obtain mixed asphalt; then slowly adding 0.2 part by weight of polyphosphoric acid, continuously heating to 150 ℃, adjusting the stirring speed to be 500 r/min, and stirring for 6 hours to obtain modified blended asphalt; mixing the modified mixed asphalt with 5 weight portions of maleic anhydride in N 2 Then maleic anhydride modification is carried out, the reaction time is 4h, the reaction temperature is 150 ℃, and the reaction pressure is 0.3 MPa, so that the maleic anhydride modified and blended asphalt a1 is obtained.
(2) Placing dry sulfur powder in a high-pressure reaction kettle, heating to 150 ℃, and filling N 2 The pressure is up to 1.5MPa, and the pressure is maintained for 1 hour to ensure that the sulfur powder is fully liquefied. And continuously heating to enable the temperature in the kettle to reach 280 ℃, reacting for 3 hours under a stirring state, quickly cooling by cold water after the reaction is finished, separating out cooling water, drying and crushing reactants to obtain the performance regulator, wherein the weight of the sulfur prepolymer is 60 percent of the total weight of the performance regulator, and placing the performance regulator in an environment of 5 ℃ for later use.
(3) Pouring 100 parts by weight of the maleic anhydrization modified blended asphalt a1 heated to a flowing state into a high-pressure reaction kettle, adjusting the temperature in the kettle to be 110 ℃, keeping the stirring at the speed of 300 r/min, and continuing stirring for 0.5h after the temperature is constant; slowly adding 4 parts by weight of beta-cyclodextrin into a reaction kettle within 1 hour, raising the temperature to 135 ℃ at a speed of 0.5 ℃/min, keeping stirring at a speed of 300 r/min in the adding process, and continuing stirring for 0.5 hour after the temperature is constant; slowly adding 0.4 weight part of dicumyl peroxide into the reaction kettle, readjusting the stirring speed to 600r/min after the addition is finished, and filling N into the reaction kettle when the pressure in the reaction kettle is kept unchanged 2 Keeping the pressure constant at 0.5MPa, and reacting for 5 hours under the condition;
(4) And (4) slowly releasing pressure after the reaction is finished, pouring out the material reacted in the step (3), shearing the material at a high speed by a shearing machine, wherein the shearing temperature is 120 ℃, the shearing time is 60min, the shearing speed is 1000r/min, mixing the material with 8 parts by weight of m-phenylenediamine, 40 parts by weight of methyltetrahydrophthalic anhydride and 0.25 part by weight of triethanolamine which are heated to 120 ℃, and shearing the material by the high-speed shearing machine for 30min, wherein the shearing temperature is 120 ℃ and the shearing speed is 800r/min.
(5) Preheating the mixture obtained in the step (4) to 120 ℃, mixing and stirring the mixture with 53 parts by weight of epoxy resin preheated to 65 ℃, wherein the stirring time is 600r/min and is 20min. And (3) after stirring, adding 10 parts by weight of the performance regulator prepared in the step (2), continuously mixing and stirring at the stirring speed of 1000r/min, the stirring temperature of 120 ℃ and the stirring time of 20min to obtain the final epoxy asphalt material A1.
Example 2
(1) Preheating 45 parts by weight of base asphalt I (saturated component accounting for 28.0wt%, aromatic component accounting for 31.8wt%, colloid accounting for 39.6wt%, and asphaltene accounting for 0.6 wt%) and 55 parts by weight of base asphalt II (saturated component accounting for 24.4wt%, aromatic component accounting for 35.0wt%, colloid accounting for 18.6wt%, and asphaltene accounting for 22.0 wt%) to a flowing state, mixing, and stirring at 150 ℃ for 4 hours at a stirring speed of 300 r/min to obtain mixed asphalt; then slowly adding 0.3 part by weight of polyphosphoric acid, continuously heating to 165 ℃, adjusting the stirring speed to 500 r/min, and stirring for 5 hours to obtain modified blended asphalt; mixing the modified mixed asphalt with 6 weight portions of maleic anhydride in N 2 Then maleic anhydride modification is carried out, the reaction time is 4h, the reaction temperature is 150 ℃, and the reaction pressure is 0.3 MPa, so that maleic anhydride modified and blended asphalt a2 is obtained.
(2) Placing dry sulfur powder in a high-pressure reaction kettle, heating to 160 ℃, and filling N 2 The pressure is up to 1.3MPa, and the pressure is maintained for 1 hour to ensure that the sulfur powder is fully liquefied. And continuously heating to ensure that the temperature in the kettle reaches 300 ℃, reacting for 3 hours under a stirring state, quickly cooling by cold water after the reaction is finished, separating out cooling water, drying and crushing reactants to obtain the performance regulator, wherein the weight of the sulfur prepolymer is 55 percent of the total weight of the performance regulator, and placing the performance regulator in an environment of 5 ℃ for later use.
(3) Pouring 100 parts by weight of maleic anhydrization modified harmonic asphalt a2 heated to a flowing state into a high-pressure reaction kettleRegulating the temperature in the kettle to 110 ℃, keeping the stirring speed at 300 r/min, and continuing stirring for 0.5h after the temperature is constant; slowly adding 5 parts by weight of beta-cyclodextrin into a reaction kettle within 1 hour, raising the temperature to 135 ℃ at a speed of 0.5 ℃/min, stirring at a speed of 300 r/min in the adding process, and continuing stirring for 0.5 hour after the temperature is constant; slowly adding 0.4 weight part of benzoyl peroxide into the reaction kettle, readjusting the stirring speed to 600r/min after the addition is finished, and filling N when the pressure in the kettle is kept constant 2 Keeping the pressure constant at 0.5MPa, and reacting for 6h under the condition;
(4) And (3) slowly releasing pressure after the reaction is finished, pouring out the material reacted in the step (3), shearing the material at a high speed by a shearing machine, wherein the shearing temperature is 120 ℃, the shearing time is 45min, and the shearing speed is 1000r/min, mixing the material with 8 parts by weight of low molecular polyamide 651, 40 parts by weight of methylhexahydrophthalic anhydride and 0.25 part by weight of triethylamine which are heated to 120 ℃, and shearing the material for 30min by the high-speed shearing machine, wherein the shearing temperature is 120 ℃, and the shearing speed is 800r/min.
(5) Preheating the mixture obtained in the step (4) to 120 ℃, mixing and stirring the mixture with 53 parts by weight of epoxy resin preheated to 65 ℃, wherein the stirring time is 800r/min and is 20min. And (3) after stirring, adding 12 parts by weight of the performance regulator prepared in the step (2), continuously mixing and stirring at the stirring speed of 1000r/min, the stirring temperature of 120 ℃ and the stirring time of 25min to obtain the final epoxy asphalt material A2.
Example 3
(1) Preheating 40 parts by weight of matrix asphalt I (same as example 2) and 60 parts by weight of matrix asphalt II (same as example 2) to a flowing state, mixing, and stirring at 150 ℃ for 4h at a stirring speed of 300 r/min to obtain mixed asphalt; then slowly adding 0.3 part by weight of polyphosphoric acid, continuously heating to 170 ℃, adjusting the stirring speed to be 500 r/min, and stirring for 6 hours to obtain modified blended asphalt; mixing the modified mixed asphalt with 6 weight portions of maleic anhydride in N 2 Then maleic anhydride modification is carried out, the reaction time is 4h, the reaction temperature is 150 ℃, and the reaction pressure is 0.3 MPa, so that the maleic anhydride modified and blended asphalt a3 is obtained.
(2) Will be driedPlacing sulfur powder in a high-pressure reaction kettle, heating to 160 ℃, and filling N 2 The pressure is up to 1.5MPa, and the pressure is maintained for 1 hour to ensure that the sulfur powder is fully liquefied. And continuously heating to ensure that the temperature in the kettle reaches 320 ℃, reacting for 2 hours under a stirring state, quickly cooling by cold water after the reaction is finished, separating out cooling water, drying and crushing reactants to obtain the performance regulator, wherein the weight of the sulfur prepolymer is 48 percent of the total weight of the performance regulator, and placing the performance regulator in an environment of 5 ℃ for later use.
(3) Pouring 100 parts by weight of the maleic anhydrization modified and blended asphalt a3 heated to a flowing state into a high-pressure reaction kettle, adjusting the temperature in the kettle to be 110 ℃, keeping the stirring at the speed of 300 r/min, and continuing stirring for 0.5h after the temperature is constant; slowly adding 5 parts by weight of beta-cyclodextrin into a reaction kettle within 1 hour, raising the temperature to 135 ℃ at a speed of 0.5 ℃/min, stirring at a speed of 300 r/min in the adding process, and continuing stirring for 0.5 hour after the temperature is constant; slowly adding 0.4 weight part of dicumyl peroxide into the reaction kettle, readjusting the stirring speed to be 500 r/min after the addition is finished, and filling N into the reaction kettle when the pressure in the reaction kettle is kept unchanged 2 Keeping the pressure constant at 0.6 MPa, and reacting for 6h under the condition;
(4) And (3) slowly releasing pressure after the reaction is finished, pouring out the material reacted in the step (3), shearing the material at a high speed by a shearing machine, wherein the shearing temperature is 120 ℃, the shearing time is 60min, and the shearing speed is 1000r/min, mixing the material with 8 parts by weight of m-phenylenediamine, 40 parts by weight of elaeostearic anhydride and 0.26 part by weight of DMP-30 which are heated to 120 ℃, and shearing the material for 30min by a high-speed shearing machine, wherein the shearing temperature is 120 ℃, and the shearing speed is 800r/min.
(5) Preheating the mixture obtained in the step (4) to 120 ℃, and mixing and stirring the mixture with 55 parts by weight of epoxy resin preheated to 65 ℃, wherein the stirring time is 800r/min and is 20min. And (3) after stirring, adding 13 parts by weight of the performance regulator prepared in the step (2), continuously mixing and stirring at the stirring speed of 1000r/min, the stirring temperature of 120 ℃ and the stirring time of 20min to obtain the final epoxy asphalt material A3.
Example 4
(1) 65 parts by weight of base asphalt I (same as in example 2) and 35 parts by weight of base asphaltII (same as example 2), preheating to a flowing state, mixing, and stirring at the temperature of 150 ℃ for 4 hours at the stirring speed of 300 r/min to obtain mixed asphalt; then slowly adding 0.3 part by weight of polyphosphoric acid, continuously heating to 170 ℃, adjusting the stirring speed to be 500 r/min, and stirring for 6 hours to obtain modified blended asphalt; mixing the modified mixed asphalt with 6 weight portions of maleic anhydride in N 2 Then maleic anhydride modification is carried out, the reaction time is 4h, the reaction temperature is 150 ℃, and the reaction pressure is 0.3 MPa, so that maleic anhydride modified and blended asphalt a4 is obtained.
(2) Placing dry sulfur powder in a high-pressure reaction kettle, heating to 145 ℃, and filling N 2 The pressure is up to 1.2MPa, and the pressure is maintained for 1 hour to ensure that the sulfur powder is fully liquefied. And continuously heating to ensure that the temperature in the kettle reaches 300 ℃, reacting for 2.5 hours under a stirring state, quickly cooling by cold water after the reaction is finished, separating out the cooling water, drying and crushing the reactant to obtain the performance regulator, wherein the weight of the sulfur prepolymer is 65 percent of the total weight of the performance regulator, and placing the performance regulator in an environment of 5 ℃ for later use.
(3) Pouring 100 parts by weight of maleic anhydride modified blended asphalt a4 heated to a flowing state into a high-pressure reaction kettle, adjusting the temperature in the kettle to 110 ℃, keeping the stirring speed at 300 r/min, and continuing stirring for 0.5h after the temperature is constant; slowly adding 4 parts by weight of beta-cyclodextrin into a reaction kettle within 1 hour, raising the temperature to 135 ℃ at a speed of 0.5 ℃/min, keeping stirring at a speed of 300 r/min in the adding process, and continuing stirring for 0.5 hour after the temperature is constant; slowly adding 0.4 weight part of dicumyl peroxide into the reaction kettle, readjusting the stirring speed to 600r/min after the addition is finished, and filling N into the reaction kettle when the pressure in the reaction kettle is kept unchanged 2 Keeping the pressure constant at 0.5MPa, and reacting for 6 hours under the condition;
(4) And (3) slowly releasing pressure after the reaction is finished, pouring out the material reacted in the step (3), shearing the material at a high speed by a shearing machine, wherein the shearing temperature is 120 ℃, the shearing time is 60min, and the shearing speed is 1000r/min, mixing the material with 8 parts by weight of m-phenylenediamine, 40 parts by weight of tung oil anhydride and 0.30 part by weight of triethanolamine which are heated to 120 ℃, and shearing the material for 30min by a high-speed shearing machine, wherein the shearing temperature is 120 ℃, and the shearing speed is 800r/min.
(5) Preheating the mixture obtained in the step (4) to 120 ℃, mixing and stirring the mixture with 55 parts by weight of epoxy resin preheated to 70 ℃, wherein the stirring time is 800r/min and is 20min. And (3) after stirring, adding 10 parts by weight of the performance regulator prepared in the step (2), continuously mixing and stirring at the stirring speed of 1000r/min, the stirring temperature of 120 ℃ and the stirring time of 10min to obtain the final epoxy asphalt material A4.
Comparative example 1
100 parts by weight of base asphalt I (same as example 1) is heated to 120 ℃, mixed with 40 parts by weight of E-51 bisphenol A epoxy resin heated to 60 ℃, 8 parts by weight of m-phenylenediamine, 53 parts by weight of methyl tetrahydrophthalic anhydride and 0.25 part by weight of triethanolamine, and sheared for 30min by a high-speed shearing machine, wherein the shearing temperature is 120 ℃ and the shearing speed is 6000r/min, and a modified epoxy asphalt material B1 is obtained.
Comparative example 2
An epoxy asphalt material B2 was obtained in the same manner as in example 2 except that the performance modifier was not added in the preparation process.
Comparative example 3
100 parts by weight of base asphalt I (same as example 1) was heated to 120 ℃ and mixed with 53 parts by weight of E-51 bisphenol A epoxy resin heated to 60 ℃, 8 parts by weight of m-phenylenediamine, 40 parts by weight of methyltetrahydrophthalic anhydride, 10 parts by weight of a performance modifier and 0.25 part by weight of triethylamine, and the mixture was sheared with a high-speed shearing machine at 120 ℃ and a shearing speed of 6000r/min for 30 minutes to obtain an epoxy asphalt material B3.
Comparative example 4
The same as example 3, except that the anhydrified blend asphalt was not modified with cyclodextrin during the preparation, epoxy asphalt material B4 was obtained.
Test example
The epoxy asphalt materials obtained in the examples and comparative examples were subjected to tensile strength and elongation at break tests (according to "general technical conditions for epoxy asphalt materials for road and bridge pavement" GB/T30598-2014), and the holding times thereof were measured, and the test results are shown in Table 1.
TABLE 1 test data table for examples and comparative examples
| Test sample | A1 | A2 | A3 | A4 | B1 | B2 | B3 | B4 |
| Tensile strength (23 ℃)/MPa | 2.1 | 2.7 | 2.9 | 2.4 | 2.6 | 2.1 | 1.9 | 1.5 |
| Elongation at break (23 ℃)/% | 296 | 350 | 381 | 318 | 84 | 148 | 159 | 254 |
| Viscosity at 120 ℃ is increased to 1 pas time/min | 67 | 74 | 78 | 69 | 11 | 14 | 44 | 56 |
| Viscosity at 120 ℃ is increased to 5 pas/min | 85 | 91 | 90 | 88 | 24 | 30 | 58 | 70 |
Claims (22)
1. An epoxy asphalt material comprises the following raw materials: the modified asphalt comprises maleic anhydride modified blended asphalt, epoxy resin, a performance regulator, cyclodextrin, an initiator, an amine curing agent and an anhydride curing agent, wherein the performance regulator comprises free sulfur and a sulfur prepolymer; the weight portion of the material is as follows:
maleic anhydride modified blended asphalt: 100 parts of (A);
epoxy resin: 35 to 64 parts;
performance modifier: 4 to 25 parts;
cyclodextrin: 1 to 7 parts;
initiator: 0.1 to 0.9 part;
amine curing agent: 5 to 20 parts;
acid anhydride curing agent: 10 to 30 parts;
accelerator (b): 0.04 to 0.6 portion;
the maleic anhydrization modified blended asphalt is prepared by adopting the following preparation method: preheating the base asphalt I and the base asphalt II to a flowing state, mixing, and stirring under a heating condition to obtain mixed asphalt; then adding polyphosphoric acid, continuing to heat and stir to obtain modified blended asphalt; adding the heated and melted modified harmonic asphalt into a reactor, controlling the reaction temperature and pressure, and carrying out Diels-Alder reaction with the substance with the acid anhydride group in the inert gas atmosphere to obtain maleic anhydride modified harmonic asphalt; the matrix asphalt I: the weight percentage of the saturated component is 20% -30%, the weight percentage of the aromatic component is 25% -35%, the weight percentage of the colloid is 30% -45%, and the weight percentage of the asphaltene is 0.1% -2%; the matrix asphalt II: the aromatic asphalt comprises, by mass, 15-30% of saturated components, 20-40% of aromatic components, 10-20% of colloid and 15-30% of asphaltene;
the substance with the acid anhydride group is maleic anhydride;
the performance regulator is prepared by adopting the following preparation method: heating the dried sulfur to 130-160 ℃, melting the sulfur into liquid, introducing inert gas, keeping the pressure at 0.8-2.6 MPa, continuously raising the temperature to 220-380 ℃, and reacting for 2-4 h under a stirring state; quickly cooling the material after the reaction with cold water, separating out the cooling water, drying and crushing the reactant to obtain a mixture of a sulfur prepolymer and free sulfur, namely a performance regulator, and storing the mixture at 0-5 ℃ for later use;
the weight of the sulfur prepolymer is 40-80% of the total weight of the performance regulator, and the number of sulfur atoms on a molecular chain of the sulfur prepolymer is more than 108;
the accelerant is one or more of DMP-30, triethylamine, triethanolamine, benzyltriethylammonium chloride, resorcinol and m-cresol.
2. An epoxy asphalt material according to claim 1, characterized in that: the epoxy asphalt material comprises the following raw materials: the modified asphalt comprises maleic anhydride modified blended asphalt, epoxy resin, a performance regulator, cyclodextrin, an initiator, an amine curing agent and an anhydride curing agent, wherein the performance regulator comprises free sulfur and a sulfur prepolymer; the weight portion of the material is as follows:
maleic anhydride modified blended asphalt: 100 parts of (A);
epoxy resin: 51 to 61 parts;
performance regulator: 8 to 20 parts;
cyclodextrin: 2 to 6 parts;
initiator: 0.2 to 0.6 portion;
amine curing agent: 5 to 20 parts;
acid anhydride curing agent: 10 to 30 parts;
accelerator (b): 0.04 to 0.6 part.
3. An epoxy asphalt material according to claim 1, wherein: the maleic anhydride modified blended asphalt comprises the following components in parts by weight:
base asphalt I:20 to 70 parts;
matrix asphalt II:30 to 80 parts;
modifying agent: 0.03 to 0.5 portion;
the modifier is polyphosphoric acid.
4. An epoxy asphalt material according to claim 3, characterized in that: the maleic anhydride modified blended asphalt comprises the following components in parts by weight:
base asphalt I:30 to 65 parts;
matrix asphalt II:35 to 70 parts;
modifying agent: 0.05 to 0.4 part.
5. An epoxy asphalt material according to claim 1, wherein: the cyclodextrin is one or more of alpha-cyclodextrin, beta-cyclodextrin and gamma-cyclodextrin.
6. An epoxy asphalt material according to claim 5, characterized in that: the cyclodextrin is alpha-cyclodextrin and/or beta-cyclodextrin.
7. An epoxy asphalt material according to claim 1, wherein: the initiator is one or more of dicumyl peroxide, tert-butyl hydroperoxide, benzoyl peroxide and sodium metabisulfite.
8. An epoxy asphalt material according to claim 1, characterized in that: the epoxy resin is at least one of E-44 bisphenol A epoxy resin and E-51 bisphenol A epoxy resin.
9. An epoxy asphalt material according to claim 8, characterized in that: the epoxy resin is E-51 bisphenol A type epoxy resin.
10. An epoxy asphalt material according to claim 1, characterized in that: the amine curing agent is one or more of low molecular polyamide 651, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, low molecular polyamide 650, diethylaminopropylamine, N-aminoethyl piperazine and isophorone diamine; the anhydride curing agent is one or more of maleic anhydride, polyisobutylene succinic anhydride, methyl nadic anhydride, modified methyl nadic anhydride, dodecenyl succinic anhydride, methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, eleostearic acid anhydride, polyazelaic anhydride, polyglutamic anhydride, polyanhydride or hydrolyzed polymaleic anhydride.
11. The epoxy asphalt material according to claim 10, characterized in that: the anhydride curing agent is one or more of methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride and tung oil anhydride.
12. A process for the preparation of an epoxy asphalt material according to any of claims 1 to 11, which comprises the steps of:
(1) Preparing maleic anhydrization modified blended asphalt;
(2) Preparing a performance regulator;
(3) Heating the maleic anhydrization modified blended asphalt prepared in the step (1) to a flowing state, pouring the heated asphalt into a high-pressure reaction kettle, adjusting the temperature in the kettle, stirring, adding cyclodextrin, carrying out programmed heating, and continuing stirring; adding an initiator into a high-pressure reaction kettle, stirring, and filling inert gas for reaction;
(4) Shearing the material reacted in the step (3) at a certain temperature, mixing the sheared material with the preheated amine curing agent and the preheated anhydride curing agent, and continuously shearing;
(5) Mixing the mixture obtained in the step (4) with the preheated epoxy resin, uniformly stirring at a certain temperature, adding a performance regulator, and continuously stirring to obtain an epoxy asphalt material;
adding an accelerator into the mixture in the step (4), wherein the accelerator is 0.04 to 0.6 part by weight, and the accelerator is one or more of DMP-30, triethylamine, triethanolamine, benzyltriethylammonium chloride, resorcinol and m-cresol;
the maleic anhydrization modified blended asphalt prepared in the step (1) adopts the following preparation method: preheating the base asphalt I and the base asphalt II to a flowing state, mixing, and stirring under a heating condition to obtain mixed asphalt; then adding polyphosphoric acid, continuing heating and stirring to obtain modified blended asphalt; adding the heated and melted modified harmonic asphalt into a reactor, controlling the reaction temperature and pressure, and carrying out Diels-Alder reaction with the substance with the acid anhydride group in the inert gas atmosphere to obtain maleic anhydride modified harmonic asphalt;
the performance regulator in the step (2) is prepared by the following method: heating the dried sulfur to 130-160 ℃, melting the sulfur into liquid, introducing inert gas, keeping the pressure at 0.8-2.6 MPa, continuously raising the temperature to 220-380 ℃, and reacting for 2-4 h under a stirring state; and (3) quickly cooling the material after the reaction is finished by using cold water, separating out the cooling water, drying and crushing the reactant to obtain a mixture of the sulfur prepolymer and free sulfur, namely the performance regulator, and storing the mixture at the temperature of 0-5 ℃ for later use.
13. The method of claim 12, wherein: the heating temperature for preparing the mixed asphalt is 100 to 180 ℃, the stirring time is 1 to 6 hours, and the stirring speed is 200 to 500 r/min; after the polyphosphoric acid is added, the heating temperature is 120 to 170 ℃, the stirring time is 4 to 10 hours, and the stirring speed is 300 to 600r/min.
14. The method of claim 13, wherein: the heating temperature for preparing the mixed asphalt is 120 to 160 ℃, the stirring time is 3 to 6 hours, and the stirring speed is 200 to 500 r/min; after the polyphosphoric acid is added, the heating temperature is 135 to 170 ℃, the stirring time is 4 to 10 hours, and the stirring speed is 300 to 600r/min.
15. The method of claim 12, wherein: the weight ratio of the substance with the acid anhydride group to the modified harmonic asphalt is (1 to 10): 100, respectively; the inert gas being N 2 The reaction time is 3 to 6 hours, the reaction temperature is 120 to 160 ℃, and the reaction pressure is 0.2 to 0.7 MPa.
16. The method of claim 15, wherein: the weight ratio of the substance with the acid anhydride group to the modified harmonic asphalt is (2 to 6): 100; the inert gas being N 2 The reaction time is 3 to 6 hours, the reaction temperature is 120 to 160 ℃, and the reaction pressure is 0.25 to 0.5MPa.
17. The method of claim 12, wherein: in the step (3), the temperature in the kettle is adjusted to be 100-120 ℃, the cyclodextrin is added within 0.5-1.5 h, the temperature programming rate is 0.5-1 ℃/min, and the temperature programming is carried out to 130-160 ℃; the stirring speed is 200 to 400r/min before the initiator is added, and the stirring time is 0.5 to 2.0 hours.
18. The method of claim 17, wherein: in the step (3), the temperature is programmed to 135-150 ℃.
19. The method of claim 12, wherein: in the step (3), the stirring speed after the initiator is addedThe degree is 500 to 800 r/min; the inert gas is N 2 The inert gas is filled in the kettle in an amount of 0.2 to 0.8MPa, and the reaction time is 3 to 9 hours.
20. The method of claim 19, wherein: in the step (3), the inert gas is filled in the reactor, so that the pressure in the reactor ranges from 0.4 to 0.8MPa, and the reaction time ranges from 5h to 8h.
21. The method of claim 12, wherein: in the step (4), the shearing temperature before the materials are mixed is 110-120 ℃, the shearing time is 0.5-1.0 h, and the shearing speed is 800-1200 r/min; the preheating temperature of the amine curing agent, the anhydride curing agent and the accelerator is 115-125 ℃, the shearing temperature of the mixed materials is 120 ℃, the shearing time is 0.5-1.5 h, and the shearing speed is 600-1000 r/min.
22. The method of claim 12, wherein: in the step (5), the preheating temperature of the epoxy resin is 60 to 75 ℃, the stirring speed is 500 to 900r/min before the performance regulator is added, the stirring time is 15 to 30min, and the stirring temperature is 115 to 125 ℃; the stirring speed is 800 to 1100r/min after the performance regulator is added, the stirring time is 10 to 25min, and the stirring temperature is 100 to 120 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201910618899.6A CN112210221B (en) | 2019-07-10 | 2019-07-10 | Epoxy asphalt material and preparation method thereof |
Applications Claiming Priority (1)
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| CN113416422A (en) * | 2021-05-19 | 2021-09-21 | 东南大学 | Epoxy asphalt caulking material and preparation method and application thereof |
| CN115433467B (en) * | 2021-06-01 | 2023-09-01 | 中国石油化工股份有限公司 | Cationic asphalt and preparation method thereof |
| CN115433466B (en) * | 2021-06-01 | 2024-02-02 | 中国石油化工股份有限公司 | Epoxy modified asphalt and preparation method thereof |
| CN115433465B (en) * | 2021-06-01 | 2024-01-09 | 中国石油化工股份有限公司 | Anhydride modified asphalt and preparation method thereof |
| CN115433553B (en) * | 2021-06-01 | 2024-02-09 | 中国石油化工股份有限公司 | Hydrophilic asphalt material and preparation method thereof |
| CN114539797A (en) * | 2022-04-08 | 2022-05-27 | 张华杰 | Waterproof corrosion-resistant asphalt and preparation method thereof |
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