CN117164296B - Rapid repair material applied to underwater concrete repair and preparation method and application thereof - Google Patents
Rapid repair material applied to underwater concrete repair and preparation method and application thereof Download PDFInfo
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- CN117164296B CN117164296B CN202310965010.8A CN202310965010A CN117164296B CN 117164296 B CN117164296 B CN 117164296B CN 202310965010 A CN202310965010 A CN 202310965010A CN 117164296 B CN117164296 B CN 117164296B
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- 239000000463 material Substances 0.000 title claims abstract description 121
- 230000008439 repair process Effects 0.000 title claims abstract description 117
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000003822 epoxy resin Substances 0.000 claims abstract description 130
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 130
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 108
- 239000004568 cement Substances 0.000 claims abstract description 67
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims description 48
- 238000006243 chemical reaction Methods 0.000 claims description 47
- 238000002156 mixing Methods 0.000 claims description 37
- 239000000203 mixture Substances 0.000 claims description 30
- 239000002002 slurry Substances 0.000 claims description 29
- 239000000178 monomer Substances 0.000 claims description 28
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- 239000003795 chemical substances by application Substances 0.000 claims description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 239000002243 precursor Substances 0.000 claims description 24
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 22
- 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 21
- 239000004576 sand Substances 0.000 claims description 19
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 18
- 229930185605 Bisphenol Natural products 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 15
- 230000001105 regulatory effect Effects 0.000 claims description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 12
- 238000010521 absorption reaction Methods 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 10
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 claims description 9
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 9
- 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 9
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 claims description 9
- DMBHHRLKUKUOEG-UHFFFAOYSA-N N-phenyl aniline Natural products C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- SSJXIUAHEKJCMH-UHFFFAOYSA-N cyclohexane-1,2-diamine Chemical compound NC1CCCCC1N SSJXIUAHEKJCMH-UHFFFAOYSA-N 0.000 claims description 9
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- 229960001124 trientine Drugs 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 8
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 8
- DGUJJOYLOCXENZ-UHFFFAOYSA-N 4-[2-[4-(oxiran-2-ylmethoxy)phenyl]propan-2-yl]phenol Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C1=CC=C(O)C=C1 DGUJJOYLOCXENZ-UHFFFAOYSA-N 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 6
- 229910021538 borax Inorganic materials 0.000 claims description 6
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 6
- 239000004328 sodium tetraborate Substances 0.000 claims description 6
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 6
- 239000004575 stone Substances 0.000 claims description 6
- 239000011975 tartaric acid Substances 0.000 claims description 6
- 235000002906 tartaric acid Nutrition 0.000 claims description 6
- CBOCVOKPQGJKKJ-UHFFFAOYSA-L Calcium formate Chemical compound [Ca+2].[O-]C=O.[O-]C=O CBOCVOKPQGJKKJ-UHFFFAOYSA-L 0.000 claims description 5
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- 239000004281 calcium formate Substances 0.000 claims description 5
- 235000019255 calcium formate Nutrition 0.000 claims description 5
- 229940044172 calcium formate Drugs 0.000 claims description 5
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 5
- 235000012907 honey Nutrition 0.000 claims description 5
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 5
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 5
- 235000011151 potassium sulphates Nutrition 0.000 claims description 5
- 239000004317 sodium nitrate Substances 0.000 claims description 5
- 235000010344 sodium nitrate Nutrition 0.000 claims description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 5
- 235000011152 sodium sulphate Nutrition 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 4
- 235000015165 citric acid Nutrition 0.000 claims description 4
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 claims description 3
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 3
- RBNPOMFGQQGHHO-UWTATZPHSA-N D-glyceric acid Chemical compound OC[C@@H](O)C(O)=O RBNPOMFGQQGHHO-UWTATZPHSA-N 0.000 claims description 3
- 239000005819 Potassium phosphonate Substances 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- YXXXKCDYKKSZHL-UHFFFAOYSA-M dipotassium;dioxido(oxo)phosphanium Chemical compound [K+].[K+].[O-][P+]([O-])=O YXXXKCDYKKSZHL-UHFFFAOYSA-M 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 235000011007 phosphoric acid Nutrition 0.000 claims description 3
- OQZCJRJRGMMSGK-UHFFFAOYSA-M potassium metaphosphate Chemical compound [K+].[O-]P(=O)=O OQZCJRJRGMMSGK-UHFFFAOYSA-M 0.000 claims description 3
- 239000004323 potassium nitrate Substances 0.000 claims description 3
- 235000010333 potassium nitrate Nutrition 0.000 claims description 3
- 235000019828 potassium polyphosphate Nutrition 0.000 claims description 3
- 235000019830 sodium polyphosphate Nutrition 0.000 claims description 3
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 239000011398 Portland cement Substances 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 7
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- 125000000129 anionic group Chemical group 0.000 abstract description 2
- 125000002091 cationic group Chemical group 0.000 abstract description 2
- 238000005189 flocculation Methods 0.000 abstract description 2
- 230000016615 flocculation Effects 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 20
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
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- 239000004593 Epoxy Substances 0.000 description 9
- 239000011414 polymer cement Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000003469 silicate cement Substances 0.000 description 8
- 238000005265 energy consumption Methods 0.000 description 7
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- 125000000524 functional group Chemical group 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 125000002723 alicyclic group Chemical group 0.000 description 4
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 229920002492 poly(sulfone) Polymers 0.000 description 4
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- 239000004721 Polyphenylene oxide Substances 0.000 description 3
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
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Landscapes
- Epoxy Resins (AREA)
Abstract
The invention provides a rapid repair material applied to underwater concrete repair, and a preparation method and application thereof. The rapid repair material comprises the following components: 20-50 parts of quick-hardening cement, 5-20 parts of quick-hardening water-borne epoxy resin, 30-100 parts of aggregate, 1-5 parts of setting component and 3-20 parts of water. The fast hardening water-based epoxy resin is a hyperbranched water-based polymer, can stably exist in a cationic environment and an anionic environment, has high solubility and no flocculation, and can form an ion barrier in a super-early-strength material. The quick repair material can be quickly hardened under water, can form effective bonding on a wet interface, has high strength and durability under the marine service environment, and has the advantages of high fracture resistance, strong bonding, impact resistance and adjustable setting time. The method has wide application prospect in maintenance and rush repair of hydraulic engineering and marine infrastructure such as marine coast structures, reservoirs, hydropower stations, bridges, culverts, sewage treatment facilities, submarine oil and gas pipelines, underwater communication facilities and the like.
Description
Technical Field
The invention belongs to the technical field of underwater concrete repair, and particularly relates to a rapid repair material applied to underwater concrete repair, and a preparation method and application thereof.
Background
Along with the extension of the service time, the safety and the durability of the building structure are deteriorated year by year, a large number of concrete structures have cracks, denudation and other diseases, and if measures are not taken in time, the mussel is endless. The high-performance rapid repair material is urgently required for maintenance and rush repair of marine coastal structures such as seawall wharfs, reservoirs, hydropower stations, bridges, culverts, sewage treatment facilities, submarine oil and gas pipelines, underwater communication facilities and other hydraulic engineering and marine infrastructure. At present, various repairing materials such as common cement repairing mortar and polymer repairing mortar are applied and have good effects. In recent years, the aqueous epoxy-cement-based repair material stands out from cement-based repair materials, polymer repair materials, clay-based repair materials and other underwater repair materials, and has good underwater adhesion capability, excellent water resistance, stronger mechanical property and better construction performance than solvent-based epoxy. However, the curing time of the aqueous epoxy-cement-based rapid repair material is long, and the curing time can be several hours or more to reach the required strength, so that the requirements of rapid repair and rush repair are difficult to meet. The solvent type epoxy repair material is not resistant to long-term exposure to underwater environment, is easy to explode and gather in large-volume construction, has poor operability, can be quickly separated and isolated when being mixed with a cement system, and is difficult to realize cooperative work. Therefore, the materials are difficult to meet the engineering requirements for quick repair and rush repair of hydraulic and marine infrastructures.
The quick hardening cement has higher early strength, chemical erosion resistance and micro-expansibility, and has advantages in repair and construction engineering needing quick recovery. But the tensile strength is low, the brittleness is high, the dispersion resistance is poor, and the underwater adhesion is insufficient, so that the expected repairing effect is difficult to achieve when the underwater construction is directly carried out. The aqueous epoxy resin system uses water to replace organic solvent as a novel epoxy resin system of a disperse phase, has the advantages of being mutually soluble with water in any proportion, good in flexibility, low in toxicity, long in application period, capable of being cured at normal temperature, and the like, and has the defects of long curing period, insignificant interpenetrating network effect and the like. If the water-based epoxy is subjected to molecular modification to realize quick curing, the water-based epoxy is hardened to be cooperated with the high-alumina cement. The advantages of the two materials are fully utilized, an inorganic-organic ductile material system can be formed, and the quick repair material for the underwater concrete structure, which can be quickly hardened underwater, effectively bonded and high-strength durable, has wide application prospect in maintenance and rush repair of hydraulic and marine infrastructure such as marine coastal structures, reservoirs and hydropower stations, bridges and culverts, sewage treatment facilities, submarine oil and gas pipelines, underwater communication facilities and the like.
Accordingly, there is a need to provide an improved solution to the above-mentioned deficiencies of the prior art.
Disclosure of Invention
Aiming at the problems of low strength, insufficient underwater adhesion, long curing period and the like of the existing repair material, the invention aims to provide a rapid repair material applied to underwater concrete repair and a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a rapid repair material applied to underwater concrete repair, which comprises the following components in parts by weight: 20-50 parts of quick-hardening cement, 5-20 parts of quick-hardening water-borne epoxy resin, 30-100 parts of aggregate, 1-5 parts of setting component and 3-20 parts of water.
Preferably, the preparation method of the quick-hardening water-based epoxy resin comprises the following steps:
step 1, mixing 2,4, 6-tris (dimethylaminomethyl) phenol, polyetheramine D230 and N, N-dimethylformamide, heating to raise the temperature, stirring for reaction, and then distilling under reduced pressure to obtain a monomer A for later use;
step 2, mixing bisphenol glycidyl ether, 4 '-sulfonyl diphenylamine, 4' -oxydianiline, N-dimethylbenzylamine and polyetheramine D230, heating, stirring, reacting, decompressing and distilling to obtain monomer B for standby,
step 3, mixing the monomer A, the monomer B, the 1, 6-hexamethylenediamine, the 1, 2-cyclohexanediamine, triethylene tetramine and deionized water, and uniformly stirring to obtain a quick-hardening aqueous epoxy resin curing agent for later use;
step 4, mixing bisphenol glycidyl ether, 1,3, 5-triglycidyl-S-triazinetrione and 1, 4-butanediol diglycidyl ether, heating to raise the temperature, stirring for reaction, and then distilling under reduced pressure to obtain a fast-hardening aqueous epoxy resin precursor for later use;
and 5, mixing the rapid hardening water-based epoxy resin curing agent with the rapid hardening water-based epoxy resin precursor, and curing to obtain the rapid hardening water-based epoxy resin.
Preferably, in step 1, the molar ratio of 2,4,6 tris (dimethylaminomethyl) phenol, polyetheramine D230 and N, N-dimethylformamide is 1:3:1;
in the step 2, the mol ratio of bisphenol glycidyl ether, 4 '-sulfonyl diphenylamine, 4' -oxydianiline, N-dimethylbenzylamine and polyetheramine D230 is 1:1:1:1:1;
in the step 3, the mol ratio of the monomer A to the monomer B to the 1, 6-hexamethylenediamine to the 1, 2-cyclohexanediamine to the triethylene tetramine to the deionized water is 5:5:1:1:1:10;
in the step 4, the mol ratio of bisphenol glycidyl ether, 1,3, 5-triglycidyl-S-triazinetrione and 1, 4-butanediol diglycidyl ether is 7:1:1;
in the step 5, the molar ratio of the rapid hardening water-based epoxy resin curing agent to the rapid hardening water-based epoxy resin precursor is 1.2:1-1.4:1.
Preferably, the step 1 is carried out in a reaction vessel equipped with a thermometer, a stirring device, a nitrogen protection, a reflux and a gas absorption device, the stirring speed is 100-500rpm, the reaction temperature is 100-140 ℃, and the reaction time is 2-5 hours;
step 2, the reaction is carried out in a reaction vessel provided with a thermometer, a stirring device, a nitrogen protection device, a reflux device and a gas absorption device, the stirring speed is 100-500rpm, the reaction temperature is 100-140 ℃, and the reaction time is 2-5h;
step 4, the reaction is carried out in a reaction vessel provided with a thermometer, a stirring device, a nitrogen protection device, a reflux device and a gas absorption device, the stirring speed is 100-500rpm, the reaction temperature is 100-140 ℃, and the reaction time is 2-5h;
the curing time of the step 5 is 1-2h.
Preferably, in step 1 and step 4, the bisphenol glycidyl ether is any one or a mixture of several of bisphenol A glycidyl ether, bisphenol S glycidyl ether and bisphenol F glycidyl ether.
Preferably, the mass ratio of the quick hardening cement to the quick hardening water-based epoxy resin is 6:1-1:1.
Preferably, the rapid hardening cement is any one or a mixture of a plurality of rapid hardening silicate cement, sulphoaluminate cement and high-alumina cement; the aggregate is any one or a mixture of a plurality of river sand, sea sand, machine-made sand and broken stone.
Preferably, the condensation regulating component is any one or a mixture of a plurality of lithium carbonate, lithium sulfate, lithium oxalate, sodium sulfate, potassium sulfate, sodium nitrate, potassium nitrate, calcium nitrate, sodium phosphite, potassium phosphite, sodium polyphosphate, potassium polyphosphate, calcium formate, tartaric acid, phosphoric acid, oxalic acid, glyceric acid, borax, citric acid, succinic acid and honey.
The invention provides a preparation method of the rapid repair material, which comprises the following steps:
(1) Weighing the raw materials of each component according to the proportion for standby;
(2) Uniformly mixing the quick-hardening cement, the aggregate and the setting regulating component to obtain a dry material;
(3) Mixing the quick-hardening aqueous epoxy resin with water, adding the dry material, and uniformly stirring and mixing to form slurry.
The invention provides an application of the rapid repair material in underwater concrete repair.
The beneficial effects are that:
(1) The quick repair material is compounded by adopting quick-hardening aqueous epoxy resin and super-early-strength material. First, in the slurry, the hydration reaction of the quick setting cement is an exothermic process, and the released heat accelerates the setting rate of the cement. Because the hydration reaction speed is high, a large amount of heat can be released in a short time, so that the fast-hardening cement is quickly hardened to form a hardening product: hydration reactions of the rapid hardening cement produce hardened products including sulphoaluminate hydration products, calcium silicate hydration products, and the like. These products form a strong crystalline structure in the cement matrix, allowing rapid hardening of the fast hardening cement and having a certain strength. Secondly, the quick-hardening aqueous epoxy resin has the co-soluble functional groups and chain segments of the aqueous epoxy resin and the oily epoxy resin, so that the compatibility of the aqueous epoxy resin and the oily epoxy resin can be enhanced, the interaction between the quick-hardening aqueous epoxy resin and the oily epoxy resin can be generated on a molecular level, and the interaction force between the quick-hardening aqueous epoxy resin and the oily epoxy resin is reduced, so that the mixing and the compatibility are promoted, and the water-hardening aqueous epoxy resin and the cement have the miscibility and the high solid content and the high reactivity of the oily epoxy resin. In addition, the rapid hardening water-based epoxy resin forms a flexible polymer three-dimensional net membranous structure in the gelled super-early-strength material slurry, fills the pores and improves the flexibility of the rapid repair material.
(2) The invention reasonably adjusts the mixing mass ratio of the quick hardening cement and the quick hardening water-based epoxy resin, wherein the content of the quick hardening cement has direct influence on the setting speed and the early strength. The increase of the dosage of the quick hardening cement can accelerate the setting and improve the early strength. The amount and size of aggregate can affect the compressive strength and flowability of the material. A proper amount of fine aggregate is advantageous for obtaining high strength. The setting component can adjust setting time, and control the plastic time and setting speed of the material. Waterborne epoxy resins are binding materials and the amount thereof can affect the binding and compressive strength, flowability and early strength of the material. The synergistic or antagonistic action exists among different components, and the balance is achieved by comprehensively adjusting.
(3) The quick-hardening aqueous epoxy resin is a hyperbranched aqueous polymer, can stably exist in a cationic environment and an anionic environment, has high solubility and no flocculation, and can form an ion barrier in a super-early-strength material: functional groups such as amino groups, hydroxyl groups and ether chains of the fast-hardening water-based epoxy resin and hyperbranched side chains can adsorb free ions of cement hydration, prevent underwater water flow scouring to realize dispersion resistance, and the functionality and structure of the set-up water-based resin can be changed by adjusting the composition of bisphenol chain segments with bisphenol structures, namely the molar ratio of the fast-hardening water-based epoxy resin curing agent to the fast-hardening water-based epoxy resin precursor, so that the setting-up time of the ultra-early-strength material can be adjusted as the functionality is larger and the retarding capacity is stronger as the branched chain is longer.
(4) The quick hardening aqueous epoxy resin combines the following advantages of aqueous resin and oily resin:
low polarity characteristics: the quick hardening aqueous epoxy resin of the invention takes alicyclic and aliphatic micromolecules as diluents, and the organic solvents have lower polarity. The low polarity nature of the resin in an underwater environment makes it better resistant to water penetration and wetting, thereby maintaining curing and adhesion capabilities.
Good water resistance: the quick-hardening water-based epoxy resin has good water resistance and can be kept stable in water for a long time. They have a low water absorption rate and a high moisture barrier capability, are not easily reacted or decomposed with moisture, and thus can maintain a good curing ability and adhesion ability.
Chemical reaction: the rapid hardening aqueous epoxy resin curing agent can be subjected to chemical reaction with a rapid hardening aqueous epoxy resin precursor in an underwater environment to form a crosslinked structure, so that curing is realized. The chemical reaction can be carried out in an underwater environment and is not influenced by the existence of water, so that the oily epoxy resin has strong underwater curing capability.
Physical adhesion: the quick hardening water-based epoxy resin can generate stronger physical adhesion force in the curing process, so that the quick hardening water-based epoxy resin can be firmly attached to the surface of an underwater substrate. This physical adhesion results from the interaction and bonding forces of the resin with the substrate surface during curing.
(5) The quick repair material can be quickly hardened under water, can form effective bonding on wet interfaces, has high strength and durability in a marine service environment, wherein the compressive strength is 35-65MPa, the flexural strength is 6-12MPa, the tensile strength is 4-9MPa, the bonding strength can reach 2-4MPa, the porosity is 1-5%, the axial-tensile toughness ratio is 1.5-3.5, the initial setting time is 0.1-0.3h, the final setting time is 0.7-1.3h, the single impact energy consumption is 30-45J, and the freezing resistance and durability index is 97-100%. The method has wide application prospect in maintenance and rush repair of hydraulic engineering and marine infrastructure such as marine coast structures, reservoirs, hydropower stations, bridges, culverts, sewage treatment facilities, submarine oil and gas pipelines, underwater communication facilities and the like.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. Wherein:
FIG. 1 is an infrared spectrum of a fast hardening aqueous epoxy resin prepared in example 1 of the present invention.
Wherein, (1): a fast hardening aqueous epoxy resin curing agent; (2) the method comprises the following steps A fast hardening aqueous epoxy resin precursor; (3) the method comprises the following steps Fast hardening water-based epoxy resins.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which are derived by a person skilled in the art based on the embodiments of the invention, fall within the scope of protection of the invention.
The present invention will be described in detail with reference to examples. It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
Aiming at the existing problems, the invention provides a rapid repair material applied to underwater concrete repair, which comprises the following components in parts by weight: 20-50 parts (e.g., 20 parts, 30 parts, 40 parts, or 50 parts), 5-20 parts (e.g., 5 parts, 10 parts, 15 parts, or 20 parts) of quick-setting cement, 30-100 parts (e.g., 30 parts, 50 parts, 70 parts, 80 parts, or 100 parts) of aggregate, 1-5 parts (e.g., 1 part, 2 parts, 3 parts, 4 parts, or 5 parts) of set-adjusting component, and 3-20 parts (e.g., 3 parts, 5 parts, 10 parts, 15 parts, or 20 parts) of water.
The quick repair material can be quickly hardened under water, can effectively bond a wet interface, has high strength and durability under the marine service environment, and has the advantages of high fracture resistance, strong bonding, impact resistance and adjustable setting time.
In a preferred embodiment of the invention, the preparation method of the quick-hardening aqueous epoxy resin comprises the following steps:
step 1, mixing 2,4, 6-tris (dimethylaminomethyl) phenol, polyetheramine D230 and N, N-dimethylformamide, heating to raise the temperature, stirring for reaction, and then distilling under reduced pressure to obtain a monomer A for later use;
step 2, mixing bisphenol glycidyl ether, 4 '-sulfonyl diphenylamine, 4' -oxydianiline, N-dimethylbenzylamine and polyetheramine D230, heating, stirring, reacting, decompressing and distilling to obtain monomer B for standby,
step 3, mixing the monomer A, the monomer B, the 1, 6-hexamethylenediamine, the 1, 2-cyclohexanediamine, triethylene tetramine and deionized water, and uniformly stirring to obtain a quick-hardening aqueous epoxy resin curing agent for later use;
step 4, mixing bisphenol glycidyl ether, 1,3, 5-triglycidyl-S-triazinetrione and 1, 4-butanediol diglycidyl ether, heating to raise the temperature, stirring for reaction, and then distilling under reduced pressure to obtain a fast-hardening aqueous epoxy resin precursor for later use;
and 5, mixing the rapid hardening water-based epoxy resin curing agent with the rapid hardening water-based epoxy resin precursor, and curing to obtain the rapid hardening water-based epoxy resin.
The quick-hardening aqueous epoxy resin curing agent is a self-emulsifying star-branched polymer, is a hyperbranched polymer, and has a multi-branched central molecule and a plurality of linear branched molecules in molecular configuration. Compared with linear polymers with the same molecular weight, the molecular configuration of the quick-hardening aqueous epoxy resin is highly branched, has more single-molecule reaction sites and is more dispersed, and has lower viscosity, higher solubility and better film forming property and crosslinking degree. With the polymerization expansion of the central molecular chain segment, the branch chain segment is uniformly dispersed and extended in a three-dimensional scale, and the density of surface functional groups is increased, so that the quick-hardening inorganic cementing material can macroscopically show better network crosslinking capability and underwater dispersion resistance, and is compatible with the expansion stress of inorganic components to resist the solidification shrinkage of the material.
On the other hand, by grafting polysulfone segments in the aqueous epoxy curing agent, the aqueous epoxy consolidation body is endowed with better thermal stability: the thermal decomposition temperature is generally above 300 ℃, and can bear high temperature, high pressure and extreme working conditions; stronger mechanical properties: the polysulfone structure has excellent mechanical strength and rigidity, and has high tensile strength and impact strength and good fatigue resistance; excellent chemical stability: polysulfone structures have corrosion resistance to most chemicals and have high resistance to acids, bases, organic solvents, and the like; stronger abrasion resistance: the polysulfone structure has excellent wear resistance and good resistance to abrasion and friction.
Finally, the self-emulsifying aqueous epoxy resin curing agent and the aqueous epoxy resin precursor system respectively introduce aliphatic chain and alicyclic chain small molecules (with small molecular weight), so that the system solubility parameter is regulated, and meanwhile, the whole system is endowed with stronger low-temperature reaction activity, and the pollution of the use of a diluent and a solvent to a water body is avoided. Meanwhile, the oil-bias chain segments can realize the self-drainage high-adhesion capacity at an underwater repair interface. Moreover, it has the following advantages:
lower viscosity: the lower molecular weight aqueous epoxy resins generally have lower viscosities, making them easier to process and construct. The low viscosity aids in the flowability and coatability of the repair material, allows for more uniform application of the coating, and allows for better filling and wetting of the substrate.
Better permeability: due to the smaller molecular weight, the aqueous epoxy resin is able to penetrate more easily into the micropores and capillaries of the substrate. This allows the repair material to better contact the substrate under water and provide better bond strength and adhesion.
Faster cure speed: waterborne epoxy resins of lower molecular weight generally have faster cure speeds. This helps to increase the production efficiency, shorten the drying time of the coating, thereby reducing the production cycle time and improving the production capacity.
In a preferred embodiment of the present invention, in step 1, the molar ratio of 2,4,6 tris (dimethylaminomethyl) phenol, polyetheramine D230 and N, N-dimethylformamide is 1:3:1; in the step 2, the mol ratio of bisphenol glycidyl ether, 4 '-sulfonyl diphenylamine, 4' -oxydianiline, N-dimethylbenzylamine and polyetheramine D230 is 1:1:1:1:1; in the step 3, the mol ratio of the monomer A to the monomer B to the 1, 6-hexamethylenediamine to the 1, 2-cyclohexanediamine to the triethylene tetramine to the deionized water is 5:5:1:1:1:10; in the step 4, the mol ratio of bisphenol glycidyl ether, 1,3, 5-triglycidyl-S-triazinetrione and 1, 4-butanediol diglycidyl ether is 7:1:1; in the step 5, the molar ratio of the fast-hardening aqueous epoxy resin curing agent to the fast-hardening aqueous epoxy resin precursor is 1.2:1 to 1.4:1 (e.g., 1.2:1, 1.3:1, or 1.4:1), if too high results in a reaction that is too fast to be applied and strength is reduced, too low results in a significant reduction in reaction rate and cure of the consolidated body is difficult to complete.
In a preferred embodiment of the present invention, step 1 is carried out in a reaction vessel equipped with a thermometer, stirring means, nitrogen protection, reflux and gas absorbing means, stirring rate of 100-500rpm (e.g., 100rpm, 200rpm, 300rpm, 400rpm or 500 rpm), reaction temperature of 100-140 ℃ (e.g., 100 ℃, 110 ℃, 120 ℃, 130 ℃, or 140 ℃), reaction time of 2-5 hours (e.g., 2 hours, 3 hours, 4 hours, or 5 hours); step 2 is performed in a reaction vessel equipped with a thermometer, stirring means, nitrogen protection, reflux and gas absorbing means, stirring rate of 100-500rpm (e.g., 100rpm, 200rpm, 300rpm, 400rpm or 500 rpm), reaction temperature of 100-140 ℃ (e.g., 100 ℃, 110 ℃, 120 ℃, 130 ℃, or 140 ℃), reaction time of 2-5 hours (e.g., 2 hours, 3 hours, 4 hours, or 5 hours); step 4 is performed in a reaction vessel equipped with a thermometer, stirring means, nitrogen protection, reflux and gas absorbing means at a stirring rate of 100-500rpm (e.g., 100rpm, 200rpm, 300rpm, 400rpm or 500 rpm), a reaction temperature of 100-140 ℃ (e.g., 100 ℃, 110 ℃, 120 ℃, 130 ℃, or 140 ℃), and a reaction time of 2-5 hours (e.g., 2 hours, 3 hours, 4 hours, or 5 hours). The curing time of step 5 is 1-2 hours (e.g., 1 hour, 1.5 hours, or 2 hours).
In the preferred embodiment of the present invention, in step 1 and step 4, the bisphenol glycidyl ether is any one or a mixture of several of bisphenol a glycidyl ether, bisphenol S glycidyl ether, bisphenol F glycidyl ether.
The reaction equation of the quick hardening aqueous epoxy resin is shown as follows:
step 1: reacting 2,4, 6-tris (dimethylaminomethyl) phenol with polyetheramine D230 by using N, N-dimethylformamide as a solvent to obtain a monomer A;
step 2: bisphenol glycidyl ether, 4 '-sulfonyl diphenylamine, 4' -diphenyl oxide, N-dimethylbenzylamine and polyetheramine D230 react to obtain a monomer B; R1/R2 are each a molecular segment which may be grafted when random copolymerization occurs;
step 3: triethylene tetramine is used as a solvent, and monomer A, monomer B, 1, 6-hexamethylenediamine and 1, 2-cyclohexanediamine are mixed to obtain a quick-hardening aqueous epoxy resin curing agent; r is a molecular chain segment which can be grafted when random copolymerization is generated;
step 4: bisphenol glycidyl ether, 1,3, 5-triglycidyl-S-triazinetrione and 1, 4-butanediol diglycidyl ether are mixed and reacted to obtain a rapid hardening aqueous epoxy resin precursor;
step 5: and mixing the fast-hardening water-based epoxy resin curing agent with the fast-hardening water-based epoxy resin precursor to obtain the fast-hardening water-based epoxy resin (random copolymerization of the fast-hardening water-based epoxy resin curing agent and the fast-hardening water-based epoxy resin precursor).
In the preferred embodiment of the invention, the mass ratio of the quick hardening cement to the quick hardening water-based epoxy resin is 6:1 to 1:1 (e.g., 1:1, 2:1, 3:1, 4:1, 5:1, or 6:1), if too high results in insufficient rigidity of the repair material, and too low results in difficulty in forming an organic-inorganic network interpenetrating structure, the repair material is not flexible enough.
In a preferred embodiment of the invention, the rapid hardening cement is any one or a mixture of a plurality of rapid hardening silicate cement, sulphoaluminate cement and high alumina cement; the aggregate is any one or a mixture of a plurality of river sand, sea sand, machine-made sand and broken stone.
Wherein, aggregate: the river sand aggregate can reduce shrinkage and improve crack resistance. The sea sand contains salt, and can accelerate coagulation. The machine-made sand has neat particles, which is beneficial to improving the strength. The crushed stone aggregate can improve the compressive strength.
In a preferred embodiment of the present invention, the condensation regulating component is any one or a mixture of several of lithium carbonate, lithium sulfate, lithium oxalate, sodium sulfate, potassium sulfate, sodium nitrate, potassium nitrate, calcium nitrate, sodium phosphite, potassium phosphite, sodium polyphosphate, potassium polyphosphate, calcium formate, tartaric acid, phosphoric acid, oxalic acid, glyceric acid, borax, citric acid, succinic acid, and honey.
Wherein, the component for regulating coagulation: the lithium carbonate, the lithium sulfate and the like can shorten the coagulation time and accelerate the early strength. The phosphite, polyphosphate and the like can regulate and control the setting time, and prolong or shorten the plasticizing time. Borax, saccharides, tartaric acid, citric acid and the like have retarding and water-retaining effects, and can prolong the construction time.
The invention provides a preparation method of a rapid repair material, which comprises the following steps:
(1) Weighing the raw materials of each component according to the proportion for standby;
(2) Uniformly mixing the quick-hardening cement, the aggregate and the setting regulating component to obtain a dry material;
(3) Mixing the quick-hardening aqueous epoxy resin with water, adding the dry material, and uniformly stirring and mixing to form slurry.
In repair, the cured is carried out at a temperature of-5℃to 50 ℃ (e.g., -5 ℃, 0 ℃,5 ℃,10 ℃, 15 ℃, 25 ℃,30 ℃, 40 ℃ or 50 ℃) for 3 to 5 hours (e.g., 3 hours, 4 hours or 5 hours) to complete hardening.
The invention provides an application of a rapid repair material in underwater concrete repair.
The following describes in detail a rapid repair material for underwater concrete repair, a method for preparing the same and application thereof by means of specific examples.
Example 1
The embodiment provides a rapid repair material applied to underwater concrete repair, which comprises the following components in parts by weight: 50 parts of quick-setting cement, 20 parts of quick-setting water-based epoxy resin, 100 parts of aggregate, 5 parts of setting component and 20 parts of water (namely, the mass ratio of the quick-setting cement to the quick-setting water-based epoxy resin is 2.5:1).
Wherein, the quick hardening cement is the mixture of sulphoaluminate cement, quick hardening silicate cement and high alumina cement, and the quick hardening cement comprises the following components in parts by mass: 5 parts of sulphoaluminate cement, 1 part of rapid hardening silicate cement and 1 part of high-alumina cement; the condensation regulating component is a mixture of lithium carbonate, lithium sulfate and borax, and comprises the following components in parts by mass: 5 parts of lithium carbonate, 1 part of lithium sulfate and 1 part of borax; the aggregate is a mixture of river sand and broken stone, and comprises the following components in parts by mass: 2 parts of river sand and 3 parts of crushed stone.
The preparation method of the quick-hardening water-based epoxy resin comprises the following steps:
step 1, mixing 2,4, 6-tris (dimethylaminomethyl) phenol, polyetheramine D230 and N, N-dimethylformamide in a reaction vessel provided with a thermometer, a stirring device, a nitrogen protection, a reflux and gas absorption device, heating to 120 ℃ at a stirring speed of 300rpm, reacting for 3 hours, and then distilling under reduced pressure to obtain a monomer A for later use;
wherein, the mol ratio of the 2,4, 6-tri (dimethylaminomethyl) phenol, the polyetheramine D230 and the N, N-dimethylformamide is 1:3:1;
step 2, mixing bisphenol A glycidyl ether, 4 '-sulfonyl diphenylamine, 4' -oxydiphenylamine, N-dimethylbenzylamine and polyetheramine D230 in a reaction vessel equipped with a thermometer, a stirring device, a nitrogen protection, a reflux and a gas absorption device, heating to 120 ℃ at a stirring rate of 300rpm, reacting for 3 hours, then distilling under reduced pressure to obtain a monomer B for standby,
wherein, the mol ratio of bisphenol A glycidyl ether, 4 '-sulfonyl diphenylamine, 4' -oxydianiline, N-dimethylbenzylamine and polyetheramine D230 is 1:1:1:1:1;
step 3, mixing the monomer A, the monomer B, the 1, 6-hexamethylenediamine, the 1, 2-cyclohexanediamine, triethylene tetramine and deionized water, and stirring until all the components are dissolved into a uniform emulsion mixture to obtain a quick-hardening aqueous epoxy resin curing agent for later use;
wherein, the mol ratio of the monomer A to the monomer B to the 1, 6-hexamethylenediamine to the 1, 2-cyclohexanediamine to the triethylene tetramine to the deionized water is 5:5:1:1:1:10;
step 4, mixing bisphenol A glycidyl ether, 1,3, 5-triglycidyl-S-triazinetrione and 1, 4-butanediol diglycidyl ether in a reaction vessel equipped with a thermometer, a stirring device, a nitrogen protection, a reflux and gas absorption device, heating to 120 ℃ at a stirring rate of 500rpm, reacting for 3 hours, and then distilling under reduced pressure to obtain a rapid hardening aqueous epoxy resin precursor for later use;
wherein, the mol ratio of bisphenol A glycidyl ether, 1,3, 5-triglycidyl-S-triazinetrione and 1, 4-butanediol diglycidyl ether is 7:1:1;
and 5, mixing the rapid hardening water-based epoxy resin curing agent with the rapid hardening water-based epoxy resin precursor, wherein the molar ratio of the rapid hardening water-based epoxy resin curing agent to the rapid hardening water-based epoxy resin precursor is 1.2:1. After curing for 1.5 hours, a fast hardening aqueous epoxy resin was obtained.
The preparation method of the rapid repair material comprises the following steps:
(1) Weighing the raw materials of each component according to the proportion for standby;
(2) Uniformly mixing the quick-hardening cement, the aggregate and the setting regulating component to obtain a dry material;
(3) And mixing the quick-hardening aqueous epoxy resin with water, adding the dry material, and uniformly stirring and mixing to form slurry, thus obtaining the quick-repairing material.
And pouring the quick repair material slurry into a test mold under water, and curing (25 ℃) the surface coating for 3 hours until the quick repair material slurry is completely hardened. And then detecting various performance indexes of the test paper. The performance of the polymer cement waterproof mortar is measured by referring to a standard JCT 984-2011:
compressive strength (3 hours) 45MPa, flexural strength (3 hours) 9.1MPa, tensile strength (3 hours) 5.1MPa, bonding strength (3 hours) 2.7MPa, porosity 2.2%, axial tensile toughness ratio 2.9, initial setting time 0.3 hours, final setting time 1.0 hours, single impact energy consumption 38.4J and freezing resistance durability index 99%.
The fast-hardening aqueous epoxy resin curing agent, the fast-hardening aqueous epoxy resin precursor and the fast-hardening aqueous epoxy resin (consolidated body) prepared in the invention are subjected to infrared spectrum test, so that an infrared spectrum shown in figure 1 is obtained.
As can be seen from FIG. 1, the fast-hardening aqueous epoxy resin curing agent (reference numeral (1)) is 2890cm -1 And 1240cm -1 Typical characteristic peaks for alicyclic, aliphatic and polyether exist at two places of wavenumber; the rapid hardening aqueous epoxy resin precursor (number (2)) is 897cm -1 And 865 to 810cm -1 (865～810cm -1 Out-of-plane C-H bending vibration) characteristic peaks of epoxy and benzene rings appear. Characteristic peaks corresponding to alicyclic rings, fat, hydroxyl groups, polyether and the like are found in the infrared spectrum of the consolidated fast-hardening water-based epoxy resin (reference numeral (3)), and the characteristic peaks of the epoxy almost disappear, which indicates that the epoxy is ring-opened to generate hydroxyl groups, and functional groups such as hydroxyl groups, ether and the like generated in the reaction can increase the water solubility of a final product. The results show that the due polyether chain, amine group and other water-based and reactive functional groups and the oil-soluble chain segment similar to bisphenol A are grafted according to the designed chemical structure and reaction steps.
Example 2
The rapid repair material for repairing underwater concrete provided by the embodiment comprises the following components in parts by weight:
20 parts of quick-setting cement, 10 parts of quick-setting water-based epoxy resin, 30 parts of aggregate, 1 part of setting component and 3 parts of water (namely, the mass ratio of the quick-setting cement to the quick-setting water-based epoxy resin is 2:1).
Wherein, the quick hardening cement is the mixture of sulphoaluminate cement, quick hardening silicate cement and high alumina cement, and the quick hardening cement comprises the following components in parts by mass: 1 part of sulphoaluminate cement, 4 parts of rapid hardening silicate cement and 1 part of high-alumina cement; the coagulation regulating component is a mixture of lithium oxalate, sodium sulfate, calcium formate and tartaric acid, and comprises the following components in parts by mass: 3 parts of lithium oxalate, 1 part of sodium sulfate, 1 part of calcium formate and 1 part of tartaric acid; the aggregate is a mixture of river sand and sea sand, and comprises the following components in parts by mass: 5 parts of river sand and 1 part of sea sand.
The preparation method of the fast hardening water-based epoxy resin is different from that of the example 1 only in that: in the step 1, the stirring speed is 100rpm, the temperature is raised to 140 ℃, the reaction is carried out for 3 hours, in the step 2, the stirring speed is 100rpm, the heating temperature is raised to 140 ℃, the reaction is carried out for 3 hours, in the step 4, the stirring speed is 200rpm, the heating temperature is raised to 140 ℃, and the reaction is carried out for 3 hours. Other steps and parameters were the same as in example 1.
The preparation method of the rapid repair material is the same as that of example 1. And pouring the quick repair material slurry into a test mold under water, and curing (25 ℃) the surface coating for 3 hours until the quick repair material slurry is completely hardened. And then detecting various performance indexes of the test paper. The performance of the polymer cement waterproof mortar is measured by referring to a standard JCT 984-2011:
the compressive strength (3 hours) is 65MPa, the flexural strength (3 hours) is 11.3MPa, the tensile strength (3 hours) is 5.7MPa, the bonding strength (3 hours) is 2.4MPa, the porosity is 4.2%, the axial tensile toughness ratio is 1.9, the initial setting time is 0.2 hours, the final setting time is 0.9 hours, the single impact energy consumption is 33.4J, and the freezing resistance durability index is 98%.
Example 3
The rapid repair material for repairing underwater concrete provided by the embodiment comprises the following components in parts by weight:
30 parts of quick-setting cement, 5 parts of quick-setting water-based epoxy resin, 50 parts of aggregate, 2 parts of setting component and 10 parts of water (namely, the mass ratio of the quick-setting cement to the quick-setting water-based epoxy resin is 6:1).
Wherein, the quick hardening cement is the mixture of sulphoaluminate cement, quick hardening silicate cement and high alumina cement, and the quick hardening cement comprises the following components in parts by mass: 3 parts of sulphoaluminate cement, 3 parts of rapid hardening silicate cement and 1 part of high-alumina cement; the coagulation regulating component is a mixture of lithium sulfate, sodium nitrate, potassium sulfate and honey, and comprises the following components in parts by mass: 4 parts of lithium sulfate, 2 parts of sodium nitrate, 1 part of potassium sulfate and 1 part of honey; the aggregate is a mixture of river sand and machine-made sand, and comprises the following components in parts by mass: 1 part of river sand and 4 parts of machine-made sand.
The preparation method of the fast hardening water-based epoxy resin is different from that of the example 1 only in that: in the step 1, the stirring speed is 200rpm, the temperature is raised to 120 ℃ by heating, the reaction is carried out for 3 hours, in the step 2, the stirring speed is 200rpm, the temperature is raised to 120 ℃ by heating, the reaction is carried out for 3 hours, in the step 4, the stirring speed is 300rpm, the temperature is raised to 120 ℃ by heating, and the reaction is carried out for 3 hours. Other steps and parameters were the same as in example 1.
The preparation method of the rapid repair material is the same as that of example 1. And pouring the quick repair material slurry into a test mold under water, and curing (25 ℃) the surface coating for 3 hours until the quick repair material slurry is completely hardened. And then detecting various performance indexes of the test paper. The performance of the polymer cement waterproof mortar is measured by referring to a standard JCT 984-2011:
the compressive strength (3 hours) is 55MPa, the flexural strength (3 hours) is 10.1MPa, the tensile strength (3 hours) is 4.7MPa, the bonding strength (3 hours) is 2.6MPa, the porosity is 3.2%, the axial tensile toughness ratio is 2.2, the initial setting time is 0.3 hours, the final setting time is 1.1 hours, the single impact energy consumption is 31.4J, and the freezing resistance durability index is 98%.
Example 4
The difference between the quick repair material for repairing underwater concrete provided in this embodiment and the quick repair material in example 1 is that the mass ratio of the quick hardening cement to the quick hardening water-based epoxy resin in the raw material components of the quick repair material is 1:1, the other raw materials had the same composition as in example 1.
Namely, the rapid repair material comprises the following components in parts by weight:
20 parts of quick-hardening cement, 20 parts of quick-hardening water-based epoxy resin, 100 parts of aggregate, 5 parts of setting component and 20 parts of water.
The preparation method of the rapid hardening aqueous epoxy resin and the rapid repair material is the same as that of example 1.
And pouring the quick repair material slurry into a test mold under water, and curing (25 ℃) the surface coating for 3 hours until the quick repair material slurry is completely hardened. And then detecting various performance indexes of the test paper. The performance of the polymer cement waterproof mortar is measured by referring to a standard JCT 984-2011:
the compression strength (3 hours) is 35MPa, the flexural strength (3 hours) is 6.1MPa, the tensile strength (3 hours) is 4.1MPa, the bonding strength (3 hours) is 2.3MPa, the porosity is 1.2%, the axial tensile toughness ratio is 3.1, the initial setting time is 0.3 hours, the final setting time is 1.3 hours, the single impact energy consumption is 34.4J, and the freezing resistance durability index is 97%.
Example 5
The rapid repair material applied to underwater concrete repair provided in this embodiment is the same as the raw material components of the rapid repair material in embodiment 1 and the preparation method of the rapid repair material, and is different from the preparation method of the rapid hardening aqueous epoxy resin in embodiment 1.
The preparation method of the fast-hardening aqueous epoxy resin is different from that of the embodiment 1 only in that in the step 5, the molar ratio of the fast-hardening aqueous epoxy resin curing agent to the fast-hardening aqueous epoxy resin precursor is 1.3:1. other steps and parameters were the same as in example 1.
And pouring the quick repair material slurry into a test mold under water, and curing (25 ℃) the surface coating for 3 hours until the quick repair material slurry is completely hardened. And then detecting various performance indexes of the test paper. The performance of the polymer cement waterproof mortar is measured by referring to a standard JCT 984-2011:
the compressive strength (3 hours) is 47MPa, the flexural strength (3 hours) is 9.8MPa, the tensile strength (3 hours) is 7.2MPa, the bonding strength (3 hours) is 2.9MPa, the porosity is 1.8%, the axial tensile toughness ratio is 3.2, the initial setting time is 0.2 hours, the final setting time is 0.8 hours, the single impact energy consumption is 39.2J, and the freezing resistance durability index is 99%.
Example 6
The rapid repair material applied to underwater concrete repair provided in this embodiment is the same as the raw material components of the rapid repair material in embodiment 1 and the preparation method of the rapid repair material, and is different from the preparation method of the rapid hardening aqueous epoxy resin in embodiment 1.
The preparation method of the fast-hardening aqueous epoxy resin is different from that of the embodiment 1 only in that in the step 5, the molar ratio of the fast-hardening aqueous epoxy resin curing agent to the fast-hardening aqueous epoxy resin precursor is 1.4:1. other steps and parameters were the same as in example 1.
And pouring the quick repair material slurry into a test mold under water, and curing (25 ℃) the surface coating for 3 hours until the quick repair material slurry is completely hardened. And then detecting various performance indexes of the test paper. The performance of the polymer cement waterproof mortar is measured by referring to a standard JCT 984-2011:
the compressive strength (3 hours) is 49MPa, the flexural strength (3 hours) is 11.2MPa, the tensile strength (3 hours) is 8.1MPa, the bonding strength (3 hours) is 3.1MPa, the porosity is 1.9%, the axial tensile toughness ratio is 3.1, the initial setting time is 0.1 hour, the final setting time is 0.7 hour, the single impact energy consumption is 41.1J, and the freezing resistance durability index is 100%.
Comparative example 1
The present comparative example provides a repair material differing from example 1 only in that the raw material composition of the repair material does not involve a fast-setting aqueous epoxy resin, and the other raw material composition is the same as that of example 1.
The repairing material comprises the following components in parts by weight: 50 parts of quick hardening cement, 100 parts of aggregate, 5 parts of setting regulating component and 20 parts of water.
The preparation method of the rapid repair material comprises the following steps:
(1) Weighing the raw materials of each component according to the proportion for standby;
(2) Uniformly mixing the quick-hardening cement, the aggregate and the setting regulating component to obtain a dry material;
(3) And mixing the dry material with water, and uniformly stirring to form slurry, thus obtaining the repair material.
The repair material slurry is poured into a test mold under water, and the slurry is separated from the aggregate and cannot be molded because the slurry is obviously dispersed in water.
Comparative example 2
The present comparative example provided a repair material differing from example 1 only in that the quick-setting aqueous epoxy resin in the raw material composition of the repair material of example 1 was replaced with a commercially available ordinary aqueous epoxy resin, and the other raw material composition was the same as that of example 1.
The repairing material comprises the following components in parts by weight: 50 parts of quick hardening cement, 20 parts of commercial common aqueous epoxy resin, 100 parts of aggregate, 5 parts of setting regulating component and 20 parts of water.
The preparation method of the repair material is the same as that of example 1. And pouring the repair material slurry into a test mold under water, and curing (25 ℃) the surface coating for 3 hours until the repair material slurry is completely hardened. And then detecting various performance indexes of the test paper. The performance of the polymer cement waterproof mortar is measured by referring to a standard JCT 984-2011:
compressive strength (3 hours) 15MPa, flexural strength (3 hours) 2.1MPa, cohesive strength (3 hours) 0.2MPa, porosity 6.2%, axial-tensile toughness ratio 0.9, initial setting time 1.3 hours, and final setting time 4.1 hours. Because the common waterborne epoxy resin has long underwater curing period, the performance of the repair material is difficult to meet the underwater quick repair requirement.
Comparative example 3
The present comparative example provided a repair material differing from example 1 only in that the mass ratio of the rapid hardening cement to the rapid hardening aqueous epoxy resin in the raw material components of the repair material was 25:1, and the other raw material compositions were the same as in example 1.
The repairing material comprises the following components in parts by weight: 50 parts of quick hardening cement, 2 parts of quick hardening water-based epoxy resin, 100 parts of aggregate, 5 parts of setting regulating component and 20 parts of water.
The preparation method of the quick-hardening aqueous epoxy resin and the repair material is the same as that of the embodiment 1.
And pouring the repair material slurry into a test mold under water, and curing (25 ℃) the surface coating for 3 hours until the repair material slurry is completely hardened. And then detecting various performance indexes of the test paper. The performance of the polymer cement waterproof mortar is measured by referring to a standard JCT 984-2011:
compressive strength (3 hours) 14MPa, flexural strength (3 hours) 2.1MPa, adhesive strength (3 hours) 0.5MPa, axial tensile toughness ratio 2.0, porosity 5.2%, initial setting time 1.1 hours, and final setting time 1.9 hours. Because the content of the quick-hardening water-based epoxy resin is too small, an interpenetrating network structure is difficult to form, and partial repair materials are isolated under water, negative effects are caused on hardening of the materials, so that the compression resistance, the fracture resistance and the bonding strength are obviously reduced.
Comparative example 4
The repair material provided in this comparative example was the same as the raw material composition of the repair material in example 1 and the same as the preparation method of the repair material, and was different from the preparation method of the rapid hardening aqueous epoxy resin in example 1.
The preparation method of the fast-hardening aqueous epoxy resin is different from that of the embodiment 1 only in that in the step 5, the molar ratio of the fast-hardening aqueous epoxy resin curing agent to the fast-hardening aqueous epoxy resin precursor is 1.5:1. other steps and parameters were the same as in example 1.
And pouring the quick repair material slurry into a test mold under water, and curing (25 ℃) the surface coating for 3 hours until the quick repair material slurry is completely hardened. And then detecting various performance indexes of the test paper. Referring to the standard JCT 984-2011 polymer cement waterproof mortar, the quick hardening type water-based epoxy resin curing agent is too large in doping amount, and the initial setting time of the slurry is less than 0.1 hour, so that the repairing material is quickly cured and is difficult to construct.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. The quick repair material for repairing underwater concrete is characterized by comprising the following components in parts by weight:
20-50 parts of quick-hardening cement, 5-20 parts of quick-hardening water-borne epoxy resin, 30-100 parts of aggregate, 1-5 parts of setting component and 3-20 parts of water;
the preparation method of the quick-hardening water-based epoxy resin comprises the following steps:
step 1, mixing 2,4, 6-tris (dimethylaminomethyl) phenol, polyetheramine D230 and N, N-dimethylformamide, heating to raise the temperature, stirring for reaction, and then distilling under reduced pressure to obtain a monomer A for later use;
step 2, mixing bisphenol glycidyl ether, 4 '-sulfonyl diphenylamine, 4' -oxydianiline, N-dimethylbenzylamine and polyetheramine D230, heating, stirring, reacting, and then distilling under reduced pressure to obtain a monomer B for later use;
step 3, mixing the monomer A, the monomer B, the 1, 6-hexamethylenediamine, the 1, 2-cyclohexanediamine, triethylene tetramine and deionized water, and uniformly stirring to obtain a quick-hardening aqueous epoxy resin curing agent for later use;
step 4, mixing bisphenol glycidyl ether, 1,3, 5-triglycidyl-S-triazinetrione and 1, 4-butanediol diglycidyl ether, heating to raise the temperature, stirring for reaction, and then distilling under reduced pressure to obtain a fast-hardening aqueous epoxy resin precursor for later use;
step 5, mixing a rapid hardening water-based epoxy resin curing agent with a rapid hardening water-based epoxy resin precursor, and curing for 1-2 hours to obtain a rapid hardening water-based epoxy resin;
in step 1, the molar ratio of 2,4,6 tris (dimethylaminomethyl) phenol, polyetheramine D230 and N, N-dimethylformamide is 1:3:1;
in the step 2, the mol ratio of bisphenol glycidyl ether, 4 '-sulfonyl diphenylamine, 4' -oxydianiline, N-dimethylbenzylamine and polyetheramine D230 is 1:1:1:1:1;
in the step 3, the mol ratio of the monomer A to the monomer B to the 1, 6-hexamethylenediamine to the 1, 2-cyclohexanediamine to the triethylene tetramine to the deionized water is 5:5:1:1:1:10;
in the step 4, the mol ratio of bisphenol glycidyl ether, 1,3, 5-triglycidyl-S-triazinetrione and 1, 4-butanediol diglycidyl ether is 7:1:1;
in the step 5, the molar ratio of the rapid hardening water-based epoxy resin curing agent to the rapid hardening water-based epoxy resin precursor is 1.2:1-1.4:1;
step 1, the reaction is carried out in a reaction vessel provided with a thermometer, a stirring device, a nitrogen protection device, a reflux device and a gas absorption device, the stirring speed is 100-500rpm, the reaction temperature is 100-140 ℃, and the reaction time is 2-5h;
step 2, the reaction is carried out in a reaction vessel provided with a thermometer, a stirring device, a nitrogen protection device, a reflux device and a gas absorption device, the stirring speed is 100-500rpm, the reaction temperature is 100-140 ℃, and the reaction time is 2-5h;
step 4 is carried out in a reaction vessel equipped with a thermometer, a stirring device, a nitrogen protection device, a reflux device and a gas absorption device, the stirring speed is 100-500rpm, the reaction temperature is 100-140 ℃, and the reaction time is 2-5h.
2. The rapid repair material of claim 1, wherein in step 1 and step 4, the bisphenol glycidyl ether is any one or a mixture of bisphenol a glycidyl ether, bisphenol S glycidyl ether, bisphenol F glycidyl ether.
3. The rapid repair material of claim 1 or 2, wherein the mass ratio of the rapid hardening cement to the rapid hardening aqueous epoxy resin is 6:1 to 1:1.
4. The rapid repair material according to claim 3, wherein the rapid hardening cement is any one or a mixture of several of rapid hardening portland cement, sulphoaluminate cement and high alumina cement; the aggregate is any one or a mixture of a plurality of river sand, sea sand, machine-made sand and broken stone.
5. The rapid repair material of claim 4, wherein the set-adjusting component is any one or a mixture of several of lithium carbonate, lithium sulfate, lithium oxalate, sodium sulfate, potassium sulfate, sodium nitrate, potassium nitrate, calcium nitrate, sodium phosphite, potassium phosphite, sodium polyphosphate, potassium polyphosphate, calcium formate, tartaric acid, phosphoric acid, oxalic acid, glyceric acid, borax, citric acid, succinic acid, and honey.
6. A method of preparing a rapid repair material according to any one of claims 1 to 5, comprising the steps of:
(1) Weighing the raw materials of each component according to the proportion for standby;
(2) Uniformly mixing the quick-hardening cement, the aggregate and the setting regulating component to obtain a dry material;
(3) Mixing the quick-hardening aqueous epoxy resin with water, adding the dry material, and uniformly stirring and mixing to form slurry.
7. Use of the rapid repair material according to any one of claims 1 to 5 in underwater concrete repair.
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