CN113801486B - Epoxy asphalt material and preparation method thereof - Google Patents
Epoxy asphalt material and preparation method thereof Download PDFInfo
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- CN113801486B CN113801486B CN202010552144.3A CN202010552144A CN113801486B CN 113801486 B CN113801486 B CN 113801486B CN 202010552144 A CN202010552144 A CN 202010552144A CN 113801486 B CN113801486 B CN 113801486B
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- polyphosphoric acid
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- modified
- asphalt
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- 239000010426 asphalt Substances 0.000 title claims abstract description 127
- 239000004593 Epoxy Substances 0.000 title claims abstract description 71
- 239000000463 material Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 31
- 239000003822 epoxy resin Substances 0.000 claims abstract description 26
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 26
- 239000002002 slurry Substances 0.000 claims abstract description 20
- 238000004523 catalytic cracking Methods 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 74
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 62
- 238000010008 shearing Methods 0.000 claims description 53
- 238000006243 chemical reaction Methods 0.000 claims description 46
- 238000003756 stirring Methods 0.000 claims description 33
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 31
- 239000002893 slag Substances 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 26
- 230000002829 reductive effect Effects 0.000 claims description 23
- 238000004821 distillation Methods 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 14
- 150000008064 anhydrides Chemical class 0.000 claims description 11
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 7
- 229920001187 thermosetting polymer Polymers 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000000084 colloidal system Substances 0.000 claims description 6
- 239000004952 Polyamide Substances 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 5
- 229920002647 polyamide Polymers 0.000 claims description 5
- 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 4
- 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 4
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 claims description 4
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 claims description 3
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 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
- 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 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
- 150000008065 acid anhydrides Chemical group 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 claims description 2
- 229920000141 poly(maleic anhydride) Polymers 0.000 claims description 2
- 229920005652 polyisobutylene succinic anhydride Polymers 0.000 claims description 2
- 238000003723 Smelting Methods 0.000 claims 2
- 239000000126 substance Substances 0.000 abstract description 9
- 229910000831 Steel Inorganic materials 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 3
- 238000010276 construction Methods 0.000 abstract description 3
- 239000010959 steel Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 19
- 239000003921 oil Substances 0.000 description 16
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 15
- 238000012360 testing method Methods 0.000 description 14
- 238000004321 preservation Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 239000003208 petroleum Substances 0.000 description 9
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 7
- 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 description 6
- 238000003860 storage Methods 0.000 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 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 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 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000012745 toughening agent Substances 0.000 description 3
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- -1 compatilizer Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- 239000002383 tung oil Substances 0.000 description 2
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000001814 pectin Substances 0.000 description 1
- 235000010987 pectin Nutrition 0.000 description 1
- 229920001277 pectin Polymers 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000010998 test method 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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/56—Amines together with other curing agents
- C08G59/58—Amines together with other curing agents with polycarboxylic acids or with anhydrides, halides, or low-molecular-weight esters thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/329—Phosphorus containing acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Landscapes
- 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)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses an epoxy asphalt material and a preparation method thereof. The modified blended asphalt is used as a raw material, and epoxy resin, two curing agents and an accelerator are added, wherein the modified blended asphalt comprises two components of modified vacuum residue and catalytic cracking slurry oil. The epoxy asphalt prepared by the preparation method has high compatibility and good flexibility, and does not need additional chemical additives such as a compatilizer, a flexibilizer and the like. The prepared epoxy asphalt material is suitable for road and bridge construction, and is particularly suitable for paving a large-span steel bridge deck.
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, great efforts are put into the research and development of epoxy asphalt materials by road workers, but the problems of poor compatibility and poor flexibility of epoxy asphalt are not well solved.
The physical and chemical properties of petroleum asphalt and epoxy resin are greatly different, and if the petroleum asphalt and the epoxy resin are directly mixed, the petroleum asphalt and the epoxy resin are easy to separate. Both physicsAnd the difference of chemical properties is mainly reflected in polarity, density and the like. The petroleum asphalt is a very complex mixture with chemical components, the dielectric constant of the petroleum asphalt is 2.5 to 3.0, the petroleum asphalt belongs to nonpolar or low-polarity substances, and the dielectric constant of the more common epoxy resin is about 3.9, and the petroleum asphalt belongs to polar substances. After the petroleum asphalt and the resin are mixed, the non-polar asphalt and the polar resin are difficult to form a homogeneous phase and cannot achieve the integral uniformity, the asphalt is separated out after the epoxy resin is cured, the thermoplasticity of the asphalt is not changed by a curing system, and the integral related performance of the material is poor. The density of the petroleum asphalt is about 0.98 to 1.01g/cm 3 The density of the common epoxy resin is about 1.15 to 1.20g/cm 3 And the two are easy to biologically settle and delaminate after being mixed. 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 to be taken into consideration while ensuring compatibility.
CN1837290A discloses a thermosetting epoxy asphalt material for roads and bridges and a preparation method thereof. The preparation method improves the compatibility of the epoxy resin and the matrix asphalt by carrying out the maleic anhydrization modification on the matrix asphalt, although the compatibility is improved to a certain degree, the conversion rate in the maleic anhydrization process is very low, and a large amount of acid mist can appear during the heating of the asphalt to influence the safety and the environmental protection; the presence of unconverted anhydride monomer in the asphalt causes the cured system to exhibit many voids, affecting the strength and tensile properties of the final cured system, which is undesirable in this way.
CN101255276A discloses an epoxy asphalt material for roads and bridges and a preparation method thereof, which mainly solves the problem of improving compatibility by maleic anhydride modification, and neutralizes and converts unreacted maleic anhydride monomers by adding organic alcohol substances, thereby preventing the pollution of volatilization of the maleic anhydride to the environment. However, the method has the defects of more reactions, difficult control of reaction process, difficult complete conversion of the maleic anhydride monomer and influence on the strength of a later-period curing system due to excessive addition of organic alcohols.
CN107603248A discloses an epoxy tung oil thermosetting asphalt compatibilizer, modified thermosetting epoxy asphalt and a preparation method thereof. But the compatibility of the compatibilizer prepared by the method with epoxy resin and asphalt is improved mainly through physical action, and the effect is not great; and the prepared compatibilizer contains epoxy groups, so that a curing agent cannot be contacted with the compatibilizer in advance, and the using process becomes complicated.
In conclusion, in the prior art, an asphalt maleic anhydride modification process is mainly adopted for solving the compatibility problem of the epoxy asphalt, the maleic anhydride has high requirement on the property of the matrix asphalt, the conversion rate is low, the extensibility of the product is adversely affected, and the generated acid mist is harmful to human bodies and the environment. The toughening agent added for improving the flexibility increases the usage amount of chemical agents, and further increases the production cost of the epoxy asphalt.
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 prepared by the invention has high compatibility and good flexibility, does not need additional chemical additives such as compatilizer, toughening agent and the like, and has lower overall cost.
The invention provides an epoxy asphalt material which comprises the following raw materials in parts by weight:
modified mixed asphalt: 100 parts of a binder;
epoxy resin: 35 to 64 parts, preferably 40 to 55 parts;
curing agent A:5 to 25 parts, preferably 5 to 20 parts;
curing agent B:20 to 45 parts, preferably 20 to 40 parts;
accelerator (b): 0.04 to 0.6 part, preferably 0.04 to 0.3 part.
Further, the modified blended asphalt comprises the following components in parts by weight:
modified vacuum residue: 20 to 60 parts, preferably 30 to 50 parts; catalytic cracking slurry oil: 40 to 80 parts, preferably 50 to 70 parts.
The modified vacuum residue preferably comprises the following components in parts by weight:
slag frequent generation: 100 parts of a binder;
polyphosphoric acid: 0.2 to 4 parts, preferably 0.4 to 3.6 parts;
initiator: 0.04 to 0.2 part, preferably 0.08 to 0.2 part.
The properties of the normal slag comprise: the flash point is 246 to 258 ℃, the sulfur content is 2.77 to 3.63wt%, and the saturation content accounts for 26.1 to 37.7 percent, the aroma content accounts for 20.2 to 34.5 percent, the colloid accounts for 18.3 to 24.8 percent, the asphaltene accounts for 21.3 to 30.1 percent, and the asphaltene accounts for preferably 21.3 to 25.0 percent in terms of mass fraction.
The normal slag also has the following basic properties: the carbon residue value is 19 to 28 weight percent, the total content of nickel and vanadium is 310 to 365 mu g/g, and the condensation index CI is 0.22 to 0.30.
The normal slag can be tower river normal slag or other normal slag meeting the properties. The normal slag is a fraction with an initial boiling point of more than 350 ℃.
The polyphosphoric acid comprises a first polyphosphoric acid and a second polyphosphoric acid, wherein the first polyphosphoric acid is a polyphosphoric acid with a high phosphoric acid content, the second polyphosphoric acid is a polyphosphoric acid with a low phosphoric acid content, and the polyphosphoric acid with the high phosphoric acid content accounts for 50-80% of the total mass of the polyphosphoric acid. The polyphosphoric acid with low phosphoric acid content accounts for 20-50% of the total mass of the polyphosphoric acid.
The high phosphoric acid content polyphosphoric acid refers to phosphoric acid (as H) contained in polyphosphoric acid 3 PO 4 Measured), the mass content is 130-145%, preferably 130-140%.
The low-phosphoric-acid-content polyphosphoric acid refers to phosphoric acid (as H) contained in polyphosphoric acid 3 PO 4 Calculated) is 105-125 percent, preferably 110-120 percent.
The properties of the catalytic cracking slurry oil comprise: the density (20 ℃) is 1.151 to 1.1634g/cm 3 The carbon residue value is 15.07-20.31 wt%, and the wax content is 1.1-1.7 wt%. The weight percentage of the aromatic hydrocarbon oil is 7.14-11.43 percent of saturated component, 66.43-72.18 percent of aromatic component, 16.39-26.43 percent of colloid and 0 percent of asphaltene.
The epoxy resin is one or more of E-44 bisphenol A type epoxy resin and E-51 bisphenol A type epoxy resin, and E-51 bisphenol A type epoxy resin is preferred.
The curing agent A is an amine curing agent, and specifically 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 curing agent B is an anhydride curing agent, specifically 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, polyazelaic anhydride or hydrolyzed polymaleic anhydride, and preferably one or more of methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride and elaeostearic anhydride.
The accelerant is one or more of DMP-30, triethylamine, triethanolamine, benzyltriethylammonium chloride, resorcinol and m-cresol.
The initiator is one or more of dicumyl peroxide, tert-butyl hydroperoxide, benzoyl peroxide, sodium metabisulfite, azobisisobutyronitrile, azobisisoheptonitrile and cumene hydroperoxide.
The invention also provides a preparation method of the epoxy asphalt material, which comprises the following steps:
(1) Preparing modified blended asphalt;
(2) Pouring the modified blended asphalt prepared in the step (1) into a high-pressure reaction kettle, stirring, adding the curing agent B, and continuing stirring;
(3) And (3) mixing the material obtained in the step (2) with epoxy resin, a curing agent A and an accelerator, and shearing to obtain the thermosetting epoxy asphalt.
The method for preparing the modified blended asphalt in the step (1) comprises the following steps:
(a) Adding the normal slag heated to flow state and the first polyphosphoric acid into a reaction kettle for reaction;
(b) Adding a second polyphosphoric acid and an initiator into the material obtained in the step (a), uniformly stirring, and then shearing;
(c) Carrying out reduced pressure distillation on the sheared material in the step (b) to obtain modified slag;
(d) And (c) mixing the modified slag-reduced asphalt obtained in the step (c) with catalytic cracking slurry oil, and shearing to obtain the modified blended asphalt.
In the step (a), the reaction kettle is a high-pressure reaction kettle, and the initial temperature of the reaction kettle is adjusted to be 100 to 120 ℃. The first polyphosphoric acid added is polyphosphoric acid having a high phosphoric acid content (referred to as phosphoric acid (in terms of H) contained in polyphosphoric acid) 3 PO 4 Calculated) is 130-145 percent, preferably 130-140 percent), and the adding amount is 50-80 percent of the total mass of the polyphosphoric acid. Adding the normal slag and the first polyphosphoric acid into a reaction kettle, and stirring at the stirring speed of 600 to 900r/min. In the reaction process, heating to the reaction temperature by adopting a temperature programming mode, wherein the temperature programming rate is 1-3 ℃/min, and the temperature is raised to 130-150 ℃, preferably 135-150 ℃. The reaction is carried out in the presence of a protective gas, wherein the protective gas is inert gas and/or N 2 The amount of the shielding gas is such that the pressure in the reaction vessel is maintained at 0.2 to 0.9MPa, preferably 0.3 to 0.8MPa. The reaction time is 3 to 6 hours. And (3) carrying out heat preservation treatment after the reaction, wherein the heat preservation treatment condition is that the heat preservation is carried out for 8-12h at the temperature of 80-110 ℃.
In the step (b), the second polyphosphoric acid added is polyphosphoric acid having a low phosphoric acid content (which means phosphoric acid contained in polyphosphoric acid as H 3 PO 4 Calculated) is 105-125 percent, preferably 110-120 percent, and the adding amount is 20-50 percent of the total mass of the polyphosphoric acid. The shearing rate is 2000 to 4000 r/min, the shearing time is 40 to 100min, and the temperature required by shearing is 130 to 150 ℃.
In the step (c), the reduced pressure distillation is carried out in a reduced pressure distillation kettle. The reduced pressure distillation conditions are as follows: the temperature of the bottom of the reduced pressure distillation kettle is controlled to be more than 400 ℃ (the atmospheric temperature after conversion), the final temperature of reduced pressure distillation is 425 to 440 ℃, and the rotation speed of an inner rotor of the reduced pressure distillation kettle is 100 to 300 r/min in the reduced pressure distillation process.
In the step (d), the shearing temperature of the modified slag-reducing slurry and the catalytic cracking slurry is 120 to 140 ℃, the shearing speed is 3000 to 4000 r/min, the shearing time is 40 to 60min, and after the shearing is finished, the modified slag-reducing slurry and the catalytic cracking slurry are placed in an oven at the temperature of 100 to 120 ℃ for heat preservation for 2 to 4h for later use.
The method for preparing the epoxy asphalt material comprises the following steps: in the step (2), the temperature in the high-pressure reaction kettle is adjusted to be 100-120 ℃ after the modified mixed asphalt is poured into the high-pressure reaction kettle, and the curing agent B is preferably added within 0.5-1.5 h when the curing agent B is added. And adding the curing agent B, and then carrying out temperature programming at the temperature programming rate of 0.5-1 ℃/min to 130-160 ℃, preferably 135-150 ℃. The stirring speed is 200 to 400r/min, and the stirring time is 0.5 to 2.0 hours. The stirring process is carried out under a certain pressure by using inert gas, preferably N 2 The inert gas is charged in an amount such that the pressure in the reactor is 0.2 to 0.8MPa, preferably 0.4 to 0.8MPa.
In the step (3), substances added before mixing are preferably preheated, wherein the epoxy resin, the curing agent A and the accelerator are preheated at the preheating temperature of 50-75 ℃, preferably 55-70 ℃, and the material after reaction in the step (2) is preheated at the preheating temperature of 105-130 ℃, preferably 115-125 ℃. The shearing temperature after mixing is 110 to 120 ℃, the shearing time is 10 to 30min, preferably 15 to 30min, and the shearing speed is 4000 to 8000r/min, preferably 6000 to 8000r/min.
Compared with the prior art, the epoxy asphalt material and the preparation method thereof have the following advantages:
(1) The invention adopts the inferior normal slag with special properties as the raw material, such as the tower and river normal slag with high asphaltene content, special existing form and extremely poor comprehensive performance, utilizes polyphosphoric acid, initiator and the like to adjust the structure composition, asphaltene form, component polarity and the like of the normal slag to prepare the modified vacuum residue oil, and the modified vacuum residue oil is matched with catalytic cracking slurry oil with proper density and polarity to obtain the modified blended asphalt, thereby improving the compatibility with epoxy resin and inhibiting the component separation of the epoxy asphalt.
(2) The modified blended asphalt provided by the invention contains components with low viscosity and high ductility in a high proportion, the flexibility of the epoxy asphalt can be improved without adding a toughening agent on the premise of ensuring good compatibility with epoxy resin, the low viscosity also prolongs the retention time, and the construction difficulty is reduced.
(3) The polyphosphoric acid is added in two times, and the types and reaction conditions of the polyphosphoric acid are different in different adding periods, so that the asphaltene cluster in the residual oil is subjected to targeted adjustment, the asphaltene dispersion size is reduced, the polarity of the residual oil is improved, and the compatibility of the residual oil with catalytic cracking slurry oil, epoxy resin, a curing agent and the like is better.
(4) The epoxy asphalt provided by the invention adopts two curing agents with different curing conditions and curing time, and the dual curing components enable the cured epoxy asphalt to have better tensile strength and elongation at break. The whole preparation process has the advantages of less application of chemical reagents, simpler process, easily controlled reaction conditions, high boiling point of most additives, no volatilization and no harm to human bodies and environment. The slag reduction and the catalytic cracking slurry oil in the raw materials are cheap byproducts in a refinery, so that the production cost of the epoxy asphalt is greatly reduced.
Detailed Description
The technical solution of the present invention is further described by the following examples, which are not intended to limit the scope of the present invention, and the wt% is referred to as mass fraction.
Example 1
(1) (a) adding 100 parts of the tower river slag (properties shown in Table 1) heated to a flowing state into a high-pressure reaction kettle at a temperature of 110 ℃, stirring, and adding 0.4 part of phosphoric acid (as H) 3 PO 4 Calculated) 135 percent of polyphosphoric acid is slowly added into the reaction kettle (the addition is finished within 3 min), the temperature is raised to 140 ℃ according to the speed program of 2 ℃/min at the stirring speed of 600r/min, and N is added after the temperature rise is finished 2 Carrying out reaction in the atmosphere, wherein the pressure in the reaction kettle is maintained at 0.5MPa, and the reaction time is 4h; after the reaction is finished, the mixture is placed in an oven for heat preservation, the heat preservation temperature is 100 ℃, and the heat preservation time is 8 hours.
(b) 0.2 part of phosphoric acid (in terms of H) 3 PO 4 Calculated) 110 percent polyphosphoric acid is added into the tower river slag reacted in the step (a), 0.06 part of dicumyl peroxide and 0.02 part of azobisisobutyronitrile are added after uniform stirring, and the mixed system is sheared at high speed and shearing speed4000 r/min, the shearing time is 50min, and the heating temperature is 140 ℃ during shearing.
(c) And (3) putting the mixture into a reduced pressure distillation kettle for reduced pressure distillation, adjusting the rotation speed of the rotor in the kettle to 300 r/min, and ending the reduced pressure distillation to 430 ℃ (normal pressure temperature after conversion) to obtain the modified slag-reducing product.
(d) 50 parts of modified slag reduction and 50 parts of catalytic cracking slurry oil (the density (20 ℃) is 1.151g/cm 3 The carbon residue value is 18.07wt%, the wax content is 1.4wt%, and the mass fraction of the wax accounts for 11.43% of the saturated fraction, 72.18% of the aromatic fraction, 16.39% of the colloid fraction and 0% of the asphaltene fraction. ) Mixing and shearing, wherein the shearing temperature is 140 ℃, the shearing rate is 4000 r/min, the shearing time is 40min, and after shearing is finished, standing in a 120 ℃ drying oven for heat preservation for 2h to obtain the modified blended asphalt.
(2) Pouring 100 parts by weight of modified mixed asphalt heated to a flowing state into a high-pressure reaction kettle, adjusting the temperature in the kettle to be 110 ℃, keeping the stirring at a speed of 300 r/min, and continuing stirring for 0.5h after the temperature is constant; slowly adding 30 parts by weight of methyl tetrahydrophthalic anhydride into a reaction kettle within 1h, raising the temperature to 135 ℃ at a speed of 0.5 ℃/min, stirring at a speed of 300 r/min in the adding process, continuously stirring for 0.5h after the temperature is constant, and using N in the whole process 2 Maintaining a pressure of 0.5 MPa.
(3) And (3) preheating the mixed material obtained in the step (2) to 120 ℃, mixing and shearing 50 parts of E-51 bisphenol A epoxy resin, 10 parts of m-phenylenediamine and 0.1 part of triethanolamine which are preheated to 70 ℃, wherein the shearing temperature is 115 ℃, the shearing time is 20min, the shearing speed is 6000r/min, and the epoxy asphalt material A11 is obtained after shearing.
TABLE 1 Properties of the Tahe slag used in the examples and comparative examples
| Density (20 ℃ C.)/(g/cm) 3 ） | 1.0211 |
| Carbon residue value/wt% | 24.1 |
| Flash point (open)/° c | 248 |
| Carbon content/wt% | 87.02 |
| Hydrogen content/wt% | 8.67 |
| Sulfur content/wt.% | 2.86 |
| Fraction of saturation/%) | 29.8 |
| Fraction of aroma/%) | 28.7 |
| Percent of pectin | 19.4 |
| Asphaltene/% | 22.1 |
| Nickel content/(μ g/g) | 43.8 |
| Vanadium content/(μ g/g) | 271.1 |
| Kinematic viscosity (80 ℃ C.)/(mm) 2 /s） | ＞20000 |
| Kinematic viscosity (100 ℃)/(mm) 2 /s） | 6596 |
| Condensation index CI | 0.23 |
Example 2
(1) A modified asphalt blend was prepared as in example 1, except that 1 part of polyphosphoric acid was used in step (1) (a) and 0.3 part of polyphosphoric acid was used in step (1) (b).
(2) Pouring 100 parts by weight of modified mixed asphalt heated to a flowing state into a high-pressure reaction kettle, adjusting the temperature in the kettle to be 100 ℃, keeping the stirring at the speed of 200 r/min, and continuing stirring for 0.5h after the temperature is constant; slowly adding 20 parts by weight of methylhexahydrophthalic anhydride into a reaction kettle within 1h, raising the temperature to 140 ℃ at the speed of 1 ℃/min, stirring at the speed of 200 r/min in the adding process, continuing stirring for 1h after the temperature is constant, and using N in the whole process 2 The pressure of 0.6MPa is maintained.
(3) And (3) preheating the mixed material obtained in the step (2) to 115 ℃, mixing and shearing 50 parts of E-51 bisphenol A epoxy resin, 5 parts of diaminodiphenylmethane and 0.1 part of DMP-30 which are preheated to 55 ℃, wherein the shearing temperature is 110 ℃, the shearing time is 30min, the shearing speed is 8000r/min, and the epoxy asphalt material A22 is obtained after the shearing is finished.
Example 3
(1) (a) adding 100 parts of the tower river slag (properties shown in Table 1) heated to a flowing state into a high-pressure reaction kettle at 120 ℃ for stirring, and adding 2 parts of phosphoric acid (in terms of H) to obtain a mixture 3 PO 4 Calculated) 135 percent of polyphosphoric acid is slowly added into the reaction kettle (the addition is finished within 3 min), the temperature is raised to 150 ℃ according to the speed program of 2 ℃/min at the stirring speed of 900r/min, and N is added after the temperature rise is finished 2 Carrying out reaction in the atmosphere, wherein the pressure in the reaction kettle is maintained at 0.3 MPa, and the reaction time is 6h; after the reaction is finished, placing the mixture into a drying oven for heat preservation, wherein the heat preservation temperature isThe heat preservation time is 10h at 80 ℃.
(b) 0.8 part of phosphoric acid (in terms of H) 3 PO 4 Calculated) 110% polyphosphoric acid is added into the tower and river normal slag reacted in the step (a), 0.06 part of benzoyl peroxide and 0.02 part of azodiisobutyronitrile are added after uniform stirring, the mixed system is subjected to high-speed shearing, the shearing speed is 2000 r/min, the shearing time is 80min, and the heating temperature during shearing is 130 ℃.
(c) And (3) putting the mixture into a reduced pressure distillation kettle for reduced pressure distillation, adjusting the rotation speed of a rotor in the kettle to be 200 r/min, and ending the reduced pressure distillation to 440 ℃ (normal pressure temperature after conversion) to obtain modified slag-reducing.
(d) 30 parts of modified slag reduction and 70 parts of catalytic cracking slurry oil (the density (20 ℃) is 1.155g/cm 3 The carbon residue value is 17.07wt%, the wax content is 1.5wt%, and the mass fraction of the wax accounts for 8.63% of saturation fraction, 70.47% of aroma fraction, 20.9% of colloid fraction and 0% of asphaltene fraction. ) Mixing and shearing, wherein the shearing temperature is 120 ℃, the shearing speed is 3000 r/min, the shearing time is 50min, and after shearing, standing in a 110 ℃ oven for heat preservation for 3h to obtain the modified blended asphalt.
(2) Pouring 100 parts by weight of modified mixed asphalt heated to a flowing state into a high-pressure reaction kettle, adjusting the temperature in the kettle to 120 ℃, keeping the stirring at the speed of 350 r/min, and continuing stirring for 1.5 hours after the temperature is constant; slowly adding 38 weight parts of tung oil acid anhydride into a reaction kettle within 1h, raising the temperature to 145 ℃ at a speed of 1 ℃/min, stirring at a speed of 350 r/min in the adding process, continuously stirring for 1.5h after the temperature is constant, and using N in the whole process 2 The pressure of 0.8MPa is maintained.
(3) And (3) preheating the mixed material obtained in the step (2) to 125 ℃, mixing and shearing 50 parts of E-51 bisphenol A epoxy resin, 15 parts of diethylaminopropylamine and 0.1 part of DMP-30 which are preheated to 60 ℃, wherein the shearing temperature is 120 ℃, the shearing time is 25min, the shearing speed is 6000r/min, and obtaining an epoxy asphalt material A33 after shearing.
Example 4
(1) A modified asphalt blend was prepared as in example 3, except that 1.5 parts of polyphosphoric acid was used in step (1) (b).
(2) Pouring 100 parts by weight of modified mixed asphalt heated to a flowing state into a high-pressure reaction kettle, adjusting the temperature in the kettle to be 115 ℃, keeping the stirring at a speed of 400r/min, and continuing stirring for 0.5h after the temperature is constant; slowly adding 35 weight parts of maleic anhydride into a reaction kettle within 0.5h, raising the temperature to 150 ℃ at a speed of 0.5 ℃/min, stirring at a speed of 400r/min in the adding process, continuously stirring for 2h after the temperature is constant, and using N in the whole process 2 The pressure was maintained at 0.4 MPa.
(3) And (3) preheating the mixed material obtained in the step (2) to 120 ℃, mixing and shearing 50 parts of E-51 bisphenol A epoxy resin preheated to 65 ℃, 20 parts of low molecular polyamide 651 and 0.15 part of DMP-30, wherein the shearing temperature is 110 ℃, the shearing time is 15min, the shearing speed is 7000r/min, and the epoxy asphalt material A44 is obtained after shearing.
Comparative example 1
In the same way as example 1, the normal slag is directly subjected to reduced pressure distillation in the preparation stage of the modified blended asphalt, and modifying agents such as polyphosphoric acid and the like are not added, so that the obtained reduced slag is not blended with catalytic cracking slurry oil and is directly used as a material for preparing the epoxy asphalt. Thus, epoxy asphalt B11 was obtained.
Comparative example 2
In the same way as example 1, only in the preparation stage of the modified blended asphalt, the obtained modified slag-reduced asphalt is not blended with the catalytic cracking slurry oil and is directly used as a material for preparing the epoxy asphalt. Thus, epoxy asphalt B22 was obtained.
Comparative example 3
In the same way as example 3, only the normal slag is directly distilled under reduced pressure in the preparation stage of the modified blended asphalt without adding modifiers such as polyphosphoric acid and the like. Thus, epoxy asphalt B33 was obtained.
Comparative example 4
The same as example 1, except that curing agent A was not used in the preparation of the epoxy asphalt. Epoxy asphalt B44 was obtained.
Comparative example 5
The same as example 1, except that curing agent B was not used in the preparation of the epoxy asphalt. Thus obtaining epoxy asphalt B55.
Comparative example 6
The same procedure as in example 1 is repeated, except that 0.2 part of polyphosphoric acid having a phosphoric acid content (calculated as H3PO 4) of 110%, 0.06 part of dicumyl peroxide and 0.02 part of azobisisobutyronitrile are not added during the preparation of the epoxy asphalt. Epoxy asphalt B66 was obtained.
Comparative example 7
Same as example 1, except that 0.4 part of phosphoric acid (in terms of H) was not added during the preparation of the epoxy asphalt 3 PO 4 Calculated) was 135% polyphosphoric acid. Thus, epoxy asphalt B77 was obtained.
Test example 1
This test example was used to test the compatibility of asphalt with epoxy resin: and (2) uniformly mixing the modified mixed asphalt obtained in the step (1) of preparing the embodiment and the comparative example with the epoxy resin according to the proportion shown in the table 2 to obtain corresponding compatibility samples A1-A4 and B1-B7 to be tested. And (3) carrying out storage stability tests on the obtained test samples at different times, and testing the softening point difference and the viscosity ratio of the upper and lower section samples after the tests are finished so as to represent the compatibility of the epoxy asphalt. (imitate the test procedure JTG E20-2011 of highway engineering asphalt and asphalt mixtures), and the comparison results are shown in Table 3.
TABLE 2 mixing ratio for compatibility testing of modified asphalt blend with epoxy resin
| Serial number | Modified mixed asphalt/weight portion | Epoxy resin/parts by weight | The obtained sample to be tested |
| 1 | Example 1 (1) preparation/100 | E-51 bisphenol A epoxy resin/50 | A1 |
| 2 | Example 2 (1) preparation/100 | E-44 bisphenol A epoxy resin/50 | A2 |
| 3 | Example 3 (1) preparation/100 | E-51 bisphenol A epoxy resin/50 | A3 |
| 4 | Example 4 (1) preparation/100 | E-51 bisphenol A epoxy resin/50 | A4 |
| 5 | Comparative example 1 (1) preparation/100 | E-51 bisphenol A epoxy resin/50 | B1 |
| 6 | Comparative example 2 (1) preparation/100 | E-51 bisphenol A epoxy resin/50 | B2 |
| 7 | Comparative example 3 (1) preparation/100 | E-51 bisphenol A epoxy resin/50 | B3 |
| 8 | Comparative example 4 (1) preparation/100 | E-51 bisphenol A epoxy resin/50 | B4 |
| 9 | Comparative example 5 (1) preparation/100 | E-51 bisphenol A epoxy resin/50 | B5 |
| 10 | Comparative example 6 (1) preparation/100 | E-51 bisphenol A epoxy resin/50 | B6 |
| 11 | Comparative example 7 (1) preparation/100 | E-51 bisphenol A epoxy resin/50 | B7 |
TABLE 3 compatibility testing of the examples and comparative examples epoxy bitumens
| Sample to be tested | Softening point difference/DEG C after 4h storage at 163 DEG C | Viscosity ratio of 120 ℃ after 4h storage at 163 ℃ | 163℃，Softening point difference/DEG C after 8h storage | Viscosity ratio of 120 ℃ after 8h storage at 163 ℃ |
| A1 | 0.04 | 1.0014 | 0.12 | 1.0371 |
| A2 | 0.02 | 1.0008 | 0.09 | 1.0048 |
| A3 | 0.07 | 1.0019 | 0.14 | 1.0054 |
| A4 | 0.10 | 1.0025 | 0.21 | 1.0082 |
| B1 | 5.72 | 1.6341 | 5.81 | 1.6913 |
| B2 | 1.35 | 1.1439 | 3.24 | 1.4691 |
| B3 | 1.41 | 1.1911 | 2.73 | 1.2129 |
| B4 | 0.05 | 1.0019 | 0.12 | 1.0081 |
| B5 | 0.06 | 1.0029 | 0.12 | 1.0097 |
| B6 | 1.31 | 1.1228 | 2.99 | 1.4177 |
| B7 | 1.37 | 1.1429 | 3.27 | 1.5106 |
Test example 2
Flexibility test of epoxy asphalt: the thermosetting epoxy asphalt obtained in the examples and the 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) to characterize the flexibility of the epoxy asphalt. The test results are shown in table 4.
TABLE 4 flexibility test of epoxy asphalt for examples and comparative examples
| Test sample | Tensile strength (23 ℃)/MPa | Elongation at break (23 ℃)/% |
| A11 | 2.3 | 256 |
| A22 | 2.1 | 291 |
| A33 | 2.4 | 246 |
| A44 | 2.1 | 287 |
| B11 | 2.4 | 83 |
| B22 | 2.1 | 105 |
| B33 | 1.9 | 169 |
| B44 | 1.7 | 204 |
| B55 | 1.6 | 199 |
| B66 | 2.1 | 217 |
| B77 | 2.0 | 229 |
Claims (21)
1. The epoxy asphalt material is characterized by comprising the following raw material components in parts by weight:
modified mixed asphalt: 100 parts of a binder;
epoxy resin: 35 to 64 parts;
curing agent A:5 to 25 parts;
curing agent B:20 to 45 parts;
accelerator (b): 0.04 to 0.6 portion;
the modified blended asphalt comprises the following components in parts by weight:
modified vacuum residue: 20 to 60 parts; catalytic cracking slurry oil: 40 to 80 parts;
the modified vacuum residue comprises the following components in parts by weight:
slag-smelting: 100 parts of (A);
polyphosphoric acid: 0.2 to 4 parts;
initiator: 0.04 to 0.2 part;
the properties of the normal slag comprise: the flash point is 246 to 258 ℃, the sulfur content is 2.77 to 3.63wt%, and the saturation component accounts for 26.1 to 37.7 percent, the aroma component accounts for 20.2 to 34.5 percent, the colloid accounts for 18.3 to 24.8 percent, and the asphaltene accounts for 21.3 to 30.1 percent in terms of mass fraction;
the polyphosphoric acid comprises a first polyphosphoric acid and a second polyphosphoric acid, the first polyphosphoric acid is polyphosphoric acid with high phosphoric acid content, the second polyphosphoric acid is polyphosphoric acid with low phosphoric acid content, the polyphosphoric acid with high phosphoric acid content accounts for 50% -80% of the total mass of the polyphosphoric acid, and the polyphosphoric acid with low phosphoric acid content accounts for 20% -50% of the total mass of the polyphosphoric acid.
2. The epoxy asphalt material according to claim 1, which comprises the following raw material components in parts by weight:
modified mixed asphalt: 100 parts of a binder;
epoxy resin: 40 to 55 parts;
curing agent A:5 to 20 parts;
curing agent B:20 to 40 parts;
accelerator (b): 0.04 to 0.3 part;
the modified blended asphalt comprises the following components in parts by weight: modified vacuum residue: 30 to 50 parts; catalytic cracking slurry oil: 50 to 70 portions.
3. The epoxy asphalt material according to claim 1, wherein the modified vacuum residue comprises the following components in parts by weight:
slag-smelting: 100 parts of a binder;
polyphosphoric acid: 0.4 to 3.6 parts;
initiator: 0.08 to 0.2 part.
4. The epoxy asphalt material according to claim 1, wherein the properties of the slag include: the asphaltene accounts for 21.3 to 25.0 percent.
5. The epoxy asphalt material according to claim 1, wherein the slag has the following properties: the carbon residue value is 19 to 28 weight percent, the total content of nickel and vanadium is 310 to 365 mu g/g, and the condensation index CI is 0.22 to 0.30.
6. The epoxy asphalt material according to claim 1, wherein the high phosphoric acid content polyphosphoric acid is phosphoric acid contained in polyphosphoric acid, and H is 3 PO 4 The mass content is 130% -145%; the polyphosphoric acid with low phosphoric acid content refers to phosphoric acid contained in polyphosphoric acid, and H is used as H 3 PO 4 The mass content is 105-125%.
7. The epoxy asphalt material according to claim 6, wherein the high phosphoric acid content polyphosphoric acid is H 3 PO 4 The mass content is 130% -140%; the low-phosphoric-acid-content polyphosphoric acid is H 3 PO 4 The mass content is 110-120%.
8. The epoxy asphalt material of claim 1, wherein the properties of the catalytic cracking slurry oil comprise: the density at 20 ℃ is 1.151 to 1.1634g/cm 3 The carbon residue value is 15.07wt% -20.31 wt%, and the wax content is 1.1wt% -1.7 wt%.
9. The epoxy asphalt material of claim 1, wherein the catalytic cracking slurry oil comprises, by mass, 7.14% -11.43% of saturated components, 66.43% -72.18% of aromatic components, 16.39% -26.43% of colloid components, and 0% of asphaltene components.
10. The epoxy asphalt material according to claim 1, wherein the curing agent a is an amine curing agent.
11. The epoxy asphalt material according to claim 10, wherein the curing agent a is one or more of low molecular polyamide 651, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, low molecular polyamide 650, diethylaminopropylamine, N-aminoethyl piperazine, isophorone diamine.
12. The epoxy asphalt material according to claim 1, wherein the curing agent B is an acid anhydride curing agent.
13. The epoxy asphalt material according to claim 12, wherein the curing agent B 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.
14. A process for the preparation of an epoxy asphalt material according to any of claims 1 to 13, characterized in that it comprises the following steps:
(1) Preparing modified blended asphalt;
(2) Pouring the modified blended asphalt prepared in the step (1) into a high-pressure reaction kettle, stirring, adding the curing agent B, and continuing stirring;
(3) And (3) mixing the material obtained in the step (2) with epoxy resin, a curing agent A and an accelerator, and shearing to obtain the thermosetting epoxy asphalt.
15. The method for preparing an epoxy asphalt material according to claim 14, wherein the method for preparing the modified tempered asphalt in the step (1) comprises:
(a) Adding the normal slag heated to flow state and the first polyphosphoric acid into a reaction kettle for reaction;
(b) Adding a second polyphosphoric acid and an initiator into the material obtained in the step (a), uniformly stirring, and then shearing;
(c) Carrying out reduced pressure distillation on the sheared material in the step (b) to obtain modified slag;
(d) And (d) mixing the modified slag-reducing obtained in the step (c) with catalytic cracking slurry oil, and shearing to obtain the modified blended asphalt.
16. The method for producing an epoxy asphalt material according to claim 15, wherein the first polyphosphoric acid in step (a) is a high-phosphoric-acid-content polyphosphoric acid, and phosphoric acid contained in the polyphosphoric acid is H 3 PO 4 The mass content is 130% -145%.
17. The method of claim 15, wherein the phosphoric acid contained in the first polyphosphoric acid in step (a) is H 3 PO 4 The mass content is 130% -140%.
18. The method for preparing an epoxy asphalt material according to claim 15 or 16, wherein the first polyphosphoric acid is added in an amount of 50-80% by mass of the total polyphosphoric acid in step (a).
19. The method of claim 15, wherein the second polyphosphoric acid in step (b) is polyphosphoric acid having a low phosphoric acid content, and the phosphoric acid contained in the polyphosphoric acid is H 3 PO 4 The mass content is 105-125%.
20. The method of claim 19, wherein the phosphoric acid contained in the second polyphosphoric acid in step (b) is H 3 PO 4 The mass content is 110-120%.
21. The method for preparing an epoxy asphalt material according to claim 15 or 19, wherein the second polyphosphoric acid is added in an amount of 20-50% by mass of the total polyphosphoric acid in step (b).
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Effective date of registration: 20231110 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |