CN117757400A - Low-temperature quick-curing type epoxy splice adhesive and preparation method thereof - Google Patents
Low-temperature quick-curing type epoxy splice adhesive and preparation method thereof Download PDFInfo
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- CN117757400A CN117757400A CN202410006786.1A CN202410006786A CN117757400A CN 117757400 A CN117757400 A CN 117757400A CN 202410006786 A CN202410006786 A CN 202410006786A CN 117757400 A CN117757400 A CN 117757400A
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- 239000004593 Epoxy Substances 0.000 title claims abstract description 58
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 54
- 239000000853 adhesive Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 64
- 229920005989 resin Polymers 0.000 claims abstract description 40
- 239000011347 resin Substances 0.000 claims abstract description 40
- 239000003822 epoxy resin Substances 0.000 claims abstract description 29
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 29
- 238000003756 stirring Methods 0.000 claims description 38
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 35
- 239000007822 coupling agent Substances 0.000 claims description 26
- 239000013008 thixotropic agent Substances 0.000 claims description 24
- 239000000843 powder Substances 0.000 claims description 22
- 239000010453 quartz Substances 0.000 claims description 22
- -1 3, 5-di-tert-butyl-4-hydroxyphenyl Chemical group 0.000 claims description 21
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 21
- 230000000694 effects Effects 0.000 claims description 18
- 239000013530 defoamer Substances 0.000 claims description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 14
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 14
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 13
- 239000006229 carbon black Substances 0.000 claims description 13
- 239000003085 diluting agent Substances 0.000 claims description 13
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 12
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 12
- 239000003963 antioxidant agent Substances 0.000 claims description 11
- 230000003078 antioxidant effect Effects 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- 229920001296 polysiloxane Polymers 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- 125000002723 alicyclic group Chemical group 0.000 claims description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000004842 bisphenol F epoxy resin Substances 0.000 claims description 9
- 229910021485 fumed silica Inorganic materials 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 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 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 7
- 229920000459 Nitrile rubber Polymers 0.000 claims description 7
- 239000012745 toughening agent Substances 0.000 claims description 7
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000002518 antifoaming agent Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229920000570 polyether Polymers 0.000 claims description 6
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- 239000001038 titanium pigment Substances 0.000 claims description 6
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 5
- ADAHGVUHKDNLEB-UHFFFAOYSA-N Bis(2,3-epoxycyclopentyl)ether Chemical compound C1CC2OC2C1OC1CCC2OC21 ADAHGVUHKDNLEB-UHFFFAOYSA-N 0.000 claims description 5
- FUIQBJHUESBZNU-UHFFFAOYSA-N 2-[(dimethylazaniumyl)methyl]phenolate Chemical compound CN(C)CC1=CC=CC=C1O FUIQBJHUESBZNU-UHFFFAOYSA-N 0.000 claims description 4
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 claims description 4
- 229920002396 Polyurea Polymers 0.000 claims description 4
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 claims description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 4
- 229920001971 elastomer Polymers 0.000 claims description 4
- 229920001021 polysulfide Polymers 0.000 claims description 4
- 239000005077 polysulfide Substances 0.000 claims description 4
- 150000008117 polysulfides Polymers 0.000 claims description 4
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 claims description 3
- MZWXWSVCNSPBLH-UHFFFAOYSA-N 3-(3-aminopropyl-methoxy-methylsilyl)oxypropan-1-amine Chemical compound NCCC[Si](C)(OC)OCCCN MZWXWSVCNSPBLH-UHFFFAOYSA-N 0.000 claims description 3
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 claims description 3
- 239000000440 bentonite Substances 0.000 claims description 3
- 229910000278 bentonite Inorganic materials 0.000 claims description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 3
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000000049 pigment Substances 0.000 claims description 3
- 239000004250 tert-Butylhydroquinone Substances 0.000 claims description 3
- 235000019281 tert-butylhydroquinone Nutrition 0.000 claims description 3
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 claims description 2
- QNYBOILAKBSWFG-UHFFFAOYSA-N 2-(phenylmethoxymethyl)oxirane Chemical compound C1OC1COCC1=CC=CC=C1 QNYBOILAKBSWFG-UHFFFAOYSA-N 0.000 claims description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 2
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003921 oil Substances 0.000 claims description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical group CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 1
- 239000000454 talc Substances 0.000 claims 1
- 229910052623 talc Inorganic materials 0.000 claims 1
- 235000012222 talc Nutrition 0.000 claims 1
- 230000009257 reactivity Effects 0.000 abstract description 7
- 230000009974 thixotropic effect Effects 0.000 abstract description 4
- 238000013461 design Methods 0.000 abstract description 2
- 230000002787 reinforcement Effects 0.000 abstract description 2
- 238000001723 curing Methods 0.000 description 75
- 230000032683 aging Effects 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000010276 construction Methods 0.000 description 9
- 230000035882 stress Effects 0.000 description 7
- 150000001412 amines Chemical class 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000306 component Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229920006332 epoxy adhesive Polymers 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- WAPNOHKVXSQRPX-UHFFFAOYSA-N 1-phenylethanol Chemical compound CC(O)C1=CC=CC=C1 WAPNOHKVXSQRPX-UHFFFAOYSA-N 0.000 description 1
- CUGZWHZWSVUSBE-UHFFFAOYSA-N 2-(oxiran-2-ylmethoxy)ethanol Chemical compound OCCOCC1CO1 CUGZWHZWSVUSBE-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 1
- 238000013035 low temperature curing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 238000009417 prefabrication Methods 0.000 description 1
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Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Epoxy Resins (AREA)
Abstract
The invention relates to the technical field of concrete reinforcement, in particular to a low-temperature rapid-curing type epoxy splice adhesive and a preparation method thereof, which are used for solving the problem that epoxy resin is easy to crystallize at low temperature and improving the reactivity of the resin system on the one hand from the resin system; on the other hand, from the design of the curing agent system, the inertness of the curing agent at low temperature or ultralow temperature is improved, and the epoxy splicing adhesive capable of being rapidly cured in a low-temperature environment is prepared by means of the low-temperature reactivity and low-temperature thixotropic property of the resin and the curing agent system.
Description
Technical Field
The invention relates to the technical field of concrete reinforcement, in particular to a low-temperature rapid-curing epoxy splice adhesive and a preparation method thereof.
Background
The prefabricated segment splicing technology has the advantages of convenience, rapidness, durability, energy conservation and the like, has rapidly developed in recent years, and is widely applied to engineering fields such as industrial and civil buildings, roads and bridges, underground structures, wind power towers and the like. The joints among the sections are key stress parts of the whole prefabrication splicing technology and are the weakest parts in the whole components, so that the selection of splicing materials is important, and the performance of the splicing materials can directly influence the safety and the reliability of the structure and the service life of the structure. At present, the joint of the prefabricated sections is made of epoxy splicing glue, and the main function of the epoxy splicing glue is to realize waterproof sealing, adhesive riveting and rapid splicing.
The epoxy splice adhesive is used as one of epoxy adhesives, and has excellent mechanical, bonding and ageing resistance, so that the epoxy splice adhesive plays an important role in the field of splicing engineering structures. However, with the application requirements of winter construction, the use of epoxy splice adhesives presents greater challenges, and low-temperature splice adhesives are relatively less studied. Patent CN 108300393B and CN 110484181A both disclose an epoxy splice adhesive at normal temperature and a preparation method thereof, and a property of the epoxy splice adhesive at normal temperature is explored. Patent CN 110144185A discloses a high temperature resistant epoxy splice adhesive, which mainly solves the problem of one property of the splice adhesive at high temperature; the patent CN 105368269A discloses a low-temperature curing liquid epoxy resin anticorrosive paint and a manufacturing method thereof, wherein the main means is that active carbon double bonds and hydroxyl groups in a styrene alcohol molecule can react with a thiol amine curing agent at a low temperature, so that the reaction of the epoxy resin and the thiol amine curing agent is initiated, the reactivity of the epoxy resin is increased, but the existence of the double bonds can also obviously influence the ageing resistance (humidity resistance, fatigue stress resistance, long-term stress action resistance and the like) of the material; in addition, the patent is a coating, the structure is not involved, the difference of the used raw materials is large, and the matching degree with the patent is not high.
Meanwhile, the literature finds that the epoxy curing agents such as aliphatic amine, alicyclic amine, polyether amine and the like which are commonly used at present are difficult to realize effective crosslinking and curing after being mixed with resin at the temperature lower than 5 ℃; curing agents such as phenolic amine and polythiol can realize curing at low temperature, but the curing and crosslinking degree is limited, and the mechanical properties are poor; and when the temperature is lower than-5 ℃, it is often difficult to achieve better curing properties with the above curing agents. In addition, the existing common resin system often generates crystallization hardening in the field environment with the temperature less than or equal to 0 ℃, can not be mixed and stirred with a curing agent, seriously influences the construction efficiency and increases the difficulty of field construction.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides the low-temperature rapid-curing type epoxy splice adhesive and the preparation method thereof, which are used for solving the problem that epoxy resin is easy to crystallize at low temperature and improving the reactivity of the resin system on one hand; on the other hand, from the design of the curing agent system, the inertness of the curing agent at low temperature or ultralow temperature is improved, and the epoxy splicing adhesive capable of being rapidly cured in a low-temperature environment is prepared by means of the low-temperature reactivity and low-temperature thixotropic property of the resin and the curing agent system.
Specifically, the low-temperature rapid-curing type epoxy splicing adhesive consists of a resin system and a curing agent system.
Preferably, the resin system comprises modified bisphenol A type epoxy resin, alicyclic epoxy resin, bisphenol F type epoxy resin, reactive diluent, toughening agent, epoxy coupling agent, defoamer, thixotropic agent, talcum powder, quartz powder and titanium pigment.
Preferably, the curing agent system comprises a Mannich base curing agent, a thiourea-amine curing agent, an activity promoter, an amino coupling agent, a defoaming agent, a thixotropic agent, talcum powder, quartz powder and carbon black.
Preferably, the low-temperature rapid-curing type epoxy splicing adhesive consists of a resin system and a curing agent system according to the mass ratio of 2.5-3:1,
wherein the resin system consists of the following raw materials in parts by weight:
70-85 parts of modified bisphenol A epoxy resin, 5-10 parts of alicyclic epoxy resin, 5-20 parts of bisphenol F epoxy resin, 5-15 parts of reactive diluent, 1-3 parts of epoxy coupling agent, 0.5-2 parts of flexibilizer, 0.1-1 part of defoamer, 0.5-4 parts of thixotropic agent, 150-200 parts of talcum powder, 80-120 parts of quartz powder and 1-3 parts of titanium pigment,
the curing agent system consists of the following raw materials in parts by weight:
50-70 parts of Mannich base curing agent, 20-50 parts of thiourea-amine curing agent, 5-15 parts of activity promoter, 1-3 parts of amino coupling agent, 0.5-2 parts of antioxidant, 0.1-1 part of defoamer, 0.5-3 parts of thixotropic agent, 100-150 parts of silica micropowder, 50-100 parts of quartz powder and 0.005-0.01 part of carbon black,
the modified bisphenol A type epoxy resin is obtained by modifying E-51 with dihydric alcohol, and the epoxy value of the modified bisphenol A type epoxy resin is 0.45-0.48.
The invention relates to a low-temperature quick-curing type epoxy splice adhesive, which is characterized in that a flexible polyol chain segment is utilized to modify common bisphenol A resin, so that the viscosity, activity and crystallinity of the epoxy splice adhesive at low temperature are improved; meanwhile, a small amount of alicyclic epoxy resin and bisphenol F epoxy resin are compounded, so that the purity of the liquid bisphenol A epoxy resin is further reduced, and the resin system is further ensured not to crystallize in a low-temperature environment of-20-0 ℃; in addition, the polyfunctional glycidyl ether and the epoxy coupling agent are introduced, so that the viscosity is continuously reduced, and the reactivity of the system is increased. Secondly, based on the special low-temperature high-reactivity of the modified Mannich base curing agent, a staged curing system is constructed by matching with the thiourea modified amine curing agent which can be cured at low temperature. The thiourea modified amine curing agent reacts with epoxy groups at low temperature by virtue of the high reactivity of a-CS bond, and the temperature of the system is initially raised; then, the modified Mannich base curing agent can realize further crosslinking and curing with the epoxy group under the catalysis of the activity promoter by virtue of the low-temperature reaction characteristic of the modified Mannich base curing agent, so that the system temperature is further increased, the crosslinking and curing of the system are further promoted, and the splice adhesive can be normally cured and quickly strengthened in an environment of-20-0 ℃.
Preferably, the glycol has a molecular weight of 52 (ethylene glycol), 105 (diethylene glycol), 200, 300 or 400. The resin is a core component in the epoxy splice adhesive, and in terms of the construction performance and mechanical property, the diol with the molecular weight of 105 (diethylene glycol) and 200 and 300 is further preferred to be modified in consideration of the influence of the viscosity and mechanical property of the system. The molecular structure of the modified bisphenol A type epoxy resin is shown as follows:
preferably, the cycloaliphatic epoxy resin is one or a combination of bis (2, 3-epoxycyclopentyl) ether, 2, 3-epoxycyclopentyl ether; the bisphenol F type epoxy resin is REF-170 bisphenol F type epoxy resin. The two types of epoxy can participate in the curing reaction and simultaneously reduce the purity of the liquid bisphenol A type epoxy resin, thereby ensuring that the resin system is not crystallized in a low-temperature environment.
Preferably, the reactive diluent is one or a combination of butyl glycidyl ether, phenyl glycidyl ether, benzyl glycidyl ether, ethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether and trimethylolpropane triglycidyl ether. The reactive diluent can reduce the viscosity of the system, but also affects the reaction rate of the system and the mechanical properties of the cured product, and more preferably one or a combination of ethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, and trimethylolpropane triglycidyl ether.
Preferably, the epoxy coupling agent is glycidoxypropyl trimethoxy silane.
Preferably, the toughening agent is one or a combination of dibutyl phthalate, dioctyl phthalate, nitrile rubber and polysulfide rubber. The toughening agent is important for improving the toughness of the cured product, and is further preferably one or a combination of nitrile rubber and polysulfide rubber in view of whether the toughening agent participates in the system reaction and forms a crosslinked network.
Preferably, the activity promoter is one or a combination of triethylamine, triethanolamine, dimethylaminomethylphenol and tris (dimethylaminomethyl) phenol. The main function is to increase the curing reaction rate, and in view of the actual acceleration effect, one or a combination of dimethylaminomethylphenol and tris (dimethylaminomethyl) phenol is further preferable.
Preferably, the amino coupling agent is one or a combination of aminopropyl triethoxysilane, aminoethyl aminopropyl trimethoxysilane and aminoethyl aminopropyl methyl dimethoxysilane.
Preferably, the antioxidant is one or a combination of tert-butylhydroquinone and pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ]. The main function of the adhesive is to improve the ageing resistance of the splice adhesive, and tert-butylhydroquinone is further preferred in consideration of the synergistic reaction effect with a curing agent system.
Preferably, the defoamer is one or a combination of polysiloxanes, polyethers and oil. The main function of the adhesive is to reduce the content of air brought in the adhesive, improve the compactness and mechanical property of the adhesive, and further preferably select one or a combination of polysiloxanes and polyethers.
Preferably, the thixotropic agent is one or a combination of fumed silica, organic bentonite and polyurea thixotropic agent.
Preferably, the talcum powder is one or a combination of 325 meshes, 600 meshes and 800 meshes; the quartz powder is one or the combination of 100 meshes, 200 meshes and 400 meshes; the silicon micropowder is one or the combination of 200 meshes, 400 meshes and 600 meshes. The main function of the filler is to play a skeleton or filling role in the splice adhesive, so that the overall stability of the splice adhesive is improved.
Preferably, the titanium dioxide is rutile titanium dioxide; the carbon black is pigment carbon black. The main function of the adhesive is to serve as a functional pigment, so that the splice adhesive is closer to the color of the concrete.
The invention also relates to a preparation method of the low-temperature rapid-curing type epoxy splicing adhesive, which comprises the following steps:
(1) Preparation of the resin System
(1) The raw materials used in the resin system are respectively weighed according to the parts by weight;
(2) adding the weighed modified bisphenol A epoxy resin, cycloaliphatic epoxy resin, bisphenol F epoxy resin and epoxy coupling agent into a stirrer, mixing and stirring, and then adding an active diluent, a toughening agent, a defoaming agent, a thixotropic agent and titanium pigment for continuous stirring;
(3) slowly pouring the weighed talcum powder and quartz powder into a stirrer, firstly adding fine materials, then adding coarse materials, starting a vacuum system after the addition is finished, and continuing vacuum stirring;
(2) Preparation of the curing agent System
a, respectively weighing raw materials used in a curing agent system according to parts by weight;
b, adding the weighed Mannich base curing agent, thiourea-amine curing agent, activity promoter and amino coupling agent into a stirrer, mixing and stirring, and then adding an antioxidant, a defoaming agent, a thixotropic agent and carbon black for continuous stirring;
c, slowly pouring the weighed silicon micropowder and quartz powder into a planetary stirrer, firstly adding fine materials and then adding coarse materials, starting a vacuum system after the addition is finished, and continuing vacuum stirring.
The preparation process of the low-temperature rapid-curing type epoxy splice adhesive has the advantages of readily available raw materials, simple preparation method and simple operation, and has very important significance for expanding the application of the low-temperature/ultralow-temperature epoxy splice adhesive.
Preferably, the stirrer is a planetary stirrer.
Preferably, in the step (2), the mixture is stirred at 50-70 ℃ for 60-120min, and the stirring time is continued for 10-30min.
Preferably, in the step (3), the vacuum stirring is continued for 60-120min.
Preferably, in the step b, mixing and stirring are carried out at 30-50 ℃ for 60-90min, and the stirring time is continued for 10-30min.
Preferably, in step c, vacuum stirring is continued for 60-120min.
The invention has the following technical advantages:
(1) The construction performance is good: the resin component and the curing agent component have thixotropic property at the temperature of-20-0 ℃, can be normally mixed without heating, and can be bonded for more than or equal to 60 minutes.
(2) The low-temperature mechanical property is good: the normal crosslinking curing reaction can be carried out at the temperature of 20 ℃ below zero to 0 ℃, the compressive strength is more than or equal to 20MPa for 2 hours, the compressive strength is more than or equal to 80MPa for 24 hours, the compressive strength is more than or equal to 100MPa for 7 days, and the strength is not damaged after the reaction is placed in a low-temperature environment.
(3) The adhesive property is strong: the forward pulling bonding strength with concrete is more than or equal to 4.0MPa, the cohesive failure of the concrete is realized, and the tensile shear strength of steel to steel is more than or equal to 20.0MPa.
(4) Excellent durability: waterproof, corrosion-resistant, wet heat aging-resistant, freeze-thaw cycle-resistant, fatigue stress-resistant, long-term stress-resistant and the like.
(5) Easy production: the raw materials used for preparing the splice adhesive are common, the cost is low, and the production flow is simpler.
Detailed Description
In order to characterize the technical effect of the invention, the epoxy splice adhesive is prepared and the performance thereof is detected, wherein the mass ratio of the resin system to the curing agent system in the embodiment is 2.5:1.
Example 1
Resin system: 75 parts of modified bisphenol A epoxy resin (the E51 is modified by dihydric alcohol with the molecular weight of 200, the epoxy value is 0.47), 9 parts of alicyclic epoxy resin (2, 3-epoxy cyclopentyl ether), 16 parts of bisphenol F epoxy resin and 1.5 parts of epoxy coupling agent are added into a planetary mixer, and mixed and stirred for 100 minutes at the temperature of 60 ℃; then 8 parts of reactive diluent (neopentyl glycol diglycidyl ether), 1 part of flexibilizer (nitrile rubber), 0.3 part of defoamer (polysiloxane), 2 parts of thixotropic agent (fumed silica) and 1.5 parts of titanium dioxide are added and stirring is continued for 25min; finally 160 parts of talcum powder (325 meshes) and 100 parts of quartz powder (100 meshes) are slowly poured into a planetary stirrer, and vacuum stirring is continued for 90min.
Curing agent system: 62 parts of Mannich base curing agent, 38 parts of thiourea-amine curing agent, 10 parts of activity promoter (tris (dimethylaminomethyl) phenol) and 2 parts of amino coupling agent (aminopropyl triethoxysilane) are added into a planetary mixer, and mixed and stirred for 80min at 45 ℃; then adding 1 part of antioxidant, 0.2 part of defoamer (polysiloxane), 2 parts of thixotropic agent (fumed silica) and 0.006 part of carbon black, and continuously stirring for 25min; finally, 120 parts of weighed silicon micropowder (400 meshes) and 80 parts of quartz powder (200 meshes) are slowly poured into a planetary stirrer, and vacuum stirring is continued for 100min.
Example 2
Resin system: 80 parts of modified bisphenol A epoxy resin (the molecular weight 105 dihydric alcohol is modified for E51, the epoxy value is 0.46), 7 parts of alicyclic epoxy resin (bis (2, 3-epoxy cyclopentyl) ether), 13 parts of bisphenol F epoxy resin and 2 parts of epoxy coupling agent are added into a planetary mixer, and mixed and stirred for 80 minutes at 60 ℃; then 10 parts of reactive diluent (ethylene glycol glycidyl ether), 1.2 parts of flexibilizer (polysulfide rubber), 0.5 part of defoamer (polysiloxane), 3 parts of thixotropic agent (fumed silica) and 2 parts of titanium dioxide are added and stirring is continued for 20min; finally 160 parts of talcum powder (600 meshes) and 90 parts of quartz powder (200 meshes) are slowly poured into a planetary stirrer, and vacuum stirring is continued for 60 minutes.
Curing agent system: 55 parts of Mannich base curing agent, 45 parts of thiourea-amine curing agent, 8 parts of activity promoter (dimethylaminomethylphenol) and 1.5 parts of amino coupling agent (aminoethylaminopropyl trimethoxysilane) are added into a planetary mixer, and mixed and stirred for 70min at 35 ℃; then adding 1 part of antioxidant, 1.5 parts of defoamer (polysiloxane), 2 parts of thixotropic agent (organic bentonite) and 0.008 part of carbon black, and continuously stirring for 15min; finally, 110 parts of weighed silicon micropowder (600 meshes) and 90 parts of quartz powder (400 meshes) are slowly poured into a planetary stirrer, and vacuum stirring is continued for 70min.
Example 3
Resin system: 83 parts of modified bisphenol A epoxy resin (molecular 300 dihydric alcohol is used for modifying E51, the epoxy value is 0.48), 3 parts of alicyclic epoxy resin (bis (2, 3-epoxy cyclopentyl ether+2, 3-epoxy cyclopentyl ether) is added into 3 parts of +6 parts of bisphenol F epoxy resin, 8 parts of epoxy coupling agent and 3 parts of epoxy coupling agent, and the mixture is mixed and stirred for 90 minutes at 55 ℃; then adding 12 parts of reactive diluent (trimethylolpropane triglycidyl ether), 1.5 parts of flexibilizer (nitrile rubber), 0.8 part of defoamer (polyether), 3.5 parts of thixotropic agent (polyurea) and 2.5 parts of titanium pigment, and continuously stirring for 15min; finally, 150 parts of talcum powder (800 meshes) and 100 parts of quartz powder (100 meshes) are slowly poured into a planetary stirrer, and vacuum stirring is continued for 110min.
Curing agent system: adding 50 parts of a Mannich base curing agent, 50 parts of a thiourea-amine curing agent, 15 parts of an activity promoter (tris (dimethylaminomethyl) phenol) and 2.5 parts of an amino coupling agent (aminoethylaminopropyl methyl dimethoxy silane) into a planetary mixer, and mixing and stirring for 75min at 30 ℃; then adding 1.2 parts of antioxidant, 1 part of defoamer (polyether) and 3 parts of thixotropic agent (polyurea) and continuously stirring for 20min; finally, 120 parts of weighed silicon micropowder (400 meshes) and 100 parts of quartz powder (200 meshes) are slowly poured into a planetary stirrer, and vacuum stirring is continued for 110min.
Example 4
Resin system: 75 parts of common bisphenol A type epoxy resin (E51), 9 parts of alicyclic epoxy resin (2, 3-epoxy cyclopentyl ether), 16 parts of bisphenol F type epoxy resin and 1.5 parts of epoxy coupling agent are added into a planetary mixer, and mixed and stirred for 100 minutes at 60 ℃; then 8 parts of reactive diluent (neopentyl glycol diglycidyl ether), 1 part of flexibilizer (nitrile rubber), 0.3 part of defoamer (polysiloxane), 2 parts of thixotropic agent (fumed silica) and 1.5 parts of titanium dioxide are added and stirring is continued for 25min; finally 160 parts of talcum powder (325 meshes) and 100 parts of quartz powder (100 meshes) are slowly poured into a planetary stirrer, and vacuum stirring is continued for 90min.
Curing agent system: the same curing agent system as in example 1.
Example 5
Resin system: 100 parts of modified bisphenol A epoxy resin (the molecular weight 200 dihydric alcohol is used for modifying E51, the epoxy value is 0.47), 1.5 parts of epoxy coupling agent are added into a planetary mixer, and mixed and stirred for 100 minutes at 60 ℃; then 8 parts of reactive diluent (neopentyl glycol diglycidyl ether), 1 part of flexibilizer (nitrile rubber), 0.3 part of defoamer (polysiloxane), 2 parts of thixotropic agent (fumed silica) and 1.5 parts of titanium dioxide are added and stirring is continued for 25min; finally 160 parts of talcum powder (325 meshes) and 100 parts of quartz powder (100 meshes) are slowly poured into a planetary stirrer, and vacuum stirring is continued for 90min.
Curing agent system: the same curing agent system as in example 1.
Example 6
Resin system: the same resin system as in example 1.
Curing agent system: 100 parts of thiourea-amine curing agent, 10 parts of activity promoter (tris (dimethylaminomethyl) phenol) and 2 parts of amino coupling agent (aminopropyl triethoxysilane) are added into a planetary mixer, and mixed and stirred for 80 minutes at 45 ℃; then adding 1 part of antioxidant, 0.2 part of defoamer (polysiloxane), 2 parts of thixotropic agent (fumed silica) and 0.006 part of carbon black, and continuously stirring for 25min; finally, 120 parts of weighed silicon micropowder (400 meshes) and 80 parts of quartz powder (200 meshes) are slowly poured into a planetary stirrer, and vacuum stirring is continued for 100min.
Example 7
Resin system: the same resin system as in example 1.
Curing agent system: 100 parts of common amine curing agent, 10 parts of activity promoter (tris (dimethylaminomethyl) phenol) and 2 parts of amino coupling agent (aminopropyl triethoxysilane) are added into a planetary mixer, and mixed and stirred for 80 minutes at 45 ℃; then adding 1 part of antioxidant, 0.2 part of defoamer (polysiloxane), 2 parts of thixotropic agent (fumed silica) and 0.006 part of carbon black, and continuously stirring for 25min; finally, 120 parts of weighed silicon micropowder (400 meshes) and 80 parts of quartz powder (200 meshes) are slowly poured into a planetary stirrer, and vacuum stirring is continued for 100min.
The performance evaluations of examples 1 to 7 above were conducted in terms of workability (thixotropic property, mixability, bondability time), mechanical properties (compressive strength), bondability (forward tensile bond strength with concrete, tensile shear strength with steel to steel), aging resistance (resistance to damp heat, freeze thawing, fatigue stress, long-term stress), etc., and compared with products applied more on the market, and the specific results are shown in table 1.
Table 1 results of performance testing of different embodiments
By comparing the test results of the embodiment, the epoxy splice adhesive prepared by the invention has better low-temperature construction, mechanical, bonding and ageing resistance, and can meet the technical index requirements of the splice adhesive by comparing T/CECS 10080-2020 epoxy adhesive for prefabricated segment assembly.
As can be seen from comparative examples 1 and 4, the use of the conventional bisphenol a epoxy resin (E51) instead of the modified bisphenol a epoxy resin produced the splice gum resin system, which had a crystallization phenomenon at low temperature and a pseudo-curing phenomenon (the mixture was frozen instead of crosslinked) at low temperature, resulted in poor mechanical, adhesive and aging resistance properties of the splice gum. The common bisphenol A epoxy resin has high viscosity, is easy to crystallize at low temperature (less than or equal to 0 ℃), is a key component in a resin system and has high content, so that the problem of easy crystallization of the whole resin system is also caused; the modified resin has the advantages that the system viscosity is reduced, and meanwhile, the activity of the chain segment at low temperature is increased through grafting the flexible chain segment, so that good construction operability exists at low temperature, and the strength of the resin cannot be influenced.
As can be seen from comparative examples 1 and 5, after the alicyclic epoxy resin and bisphenol F type epoxy resin are removed from the resin system, the construction, mechanics, adhesion and aging resistance of the splice adhesive are reduced to different degrees. The alicyclic epoxy resin and the bisphenol F epoxy resin can participate in the crosslinking curing reaction while reducing the purity of the liquid bisphenol A epoxy resin and ensuring that the resin system is not crystallized at low temperature, and the rigid structure in the molecular chain can also improve the integral performance of the splice adhesive to a certain extent.
As can be seen from comparative examples 1 and 6, the curing speed, mechanical, adhesive and aging resistance of the splice adhesive are reduced to different degrees after the Mannich base curing agent is removed. This is because the use of thiourea-amine curing agents alone can provide the splice adhesive with low-temperature curability, but the strength of the splice adhesive itself is low after the thiourea-amine curing agents are crosslinked and cured with epoxy.
Comparative examples 1 and 7 show that the conventional amine-based curing agent is used instead of the Mannich base-based curing agent and the thiourea-amine-based curing agent, and that the mechanical properties, adhesion and aging resistance at low temperatures are poor. This is because the ordinary amine-based curing agent is substantially deactivated in a low-temperature environment, is difficult to crosslink and cure with the resin, and the test block is easily subjected to a phenomenon of pseudo-curing (the mixture is frozen instead of crosslinked).
The comparison examples 1-3 and the products on the market can obviously find that the splicing adhesive prepared by the invention has better construction, mechanical, bonding and ageing resistance at low temperature, and is superior to the comparison sample.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limited thereto; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features can be replaced with equivalents; such modifications and substitutions do not depart from the essence of the corresponding technical solutions from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A low-temperature quick-curing type epoxy splice adhesive is characterized by comprising a resin system and a curing agent system according to a mass ratio of 2.5-3:1,
wherein the resin system consists of the following raw materials in parts by weight:
70-85 parts of modified bisphenol A epoxy resin, 5-10 parts of alicyclic epoxy resin, 5-20 parts of bisphenol F epoxy resin, 5-15 parts of reactive diluent, 1-3 parts of epoxy coupling agent, 0.5-2 parts of flexibilizer, 0.1-1 part of defoamer, 0.5-4 parts of thixotropic agent, 150-200 parts of talcum powder, 80-120 parts of quartz powder and 1-3 parts of titanium pigment,
the curing agent system consists of the following raw materials in parts by weight:
50-70 parts of Mannich base curing agent, 20-50 parts of thiourea-amine curing agent, 5-15 parts of activity promoter, 1-3 parts of amino coupling agent, 0.5-2 parts of antioxidant, 0.1-1 part of defoamer, 0.5-3 parts of thixotropic agent, 100-150 parts of silica micropowder, 50-100 parts of quartz powder and 0.005-0.01 part of carbon black,
the modified bisphenol A type epoxy resin is obtained by modifying E-51 with dihydric alcohol, and the epoxy value of the modified bisphenol A type epoxy resin is 0.45-0.48.
2. The low temperature rapid cure epoxy splice gum of claim 1, wherein the glycol has a molecular weight of 52, 105, 200, 300, or 400.
3. The low temperature rapid cure epoxy splice gum of claim 1, wherein the cycloaliphatic epoxy resin is one or a combination of bis (2, 3-epoxycyclopentyl) ether, 2, 3-epoxycyclopentyl ether; the bisphenol F type epoxy resin is REF-170 bisphenol F type epoxy resin; the reactive diluent is one or a combination of butyl glycidyl ether, phenyl glycidyl ether, benzyl glycidyl ether, ethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether and trimethylolpropane triglycidyl ether.
4. The low temperature rapid curing epoxy splice adhesive of claim 1, wherein the epoxy coupling agent is glycidoxypropyl trimethoxysilane; the toughening agent is one or a combination of dibutyl phthalate, dioctyl phthalate, nitrile rubber and polysulfide rubber.
5. The low temperature rapid curing epoxy splice adhesive of claim 1, wherein the activity promoter is one or a combination of triethylamine, triethanolamine, dimethylaminomethylphenol, tris (dimethylaminomethyl) phenol; the amino coupling agent is one or a combination of aminopropyl triethoxy silane, aminoethyl aminopropyl trimethoxy silane and aminoethyl aminopropyl methyl dimethoxy silane.
6. The low temperature rapid curing epoxy splice adhesive of claim 1, wherein the antioxidant is one or a combination of tert-butylhydroquinone and pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
7. The low-temperature rapid-curing type epoxy splice adhesive according to claim 1, wherein the defoaming agent is one or a combination of polysiloxanes, polyethers and oils; the thixotropic agent is one or a combination of fumed silica, organic bentonite and polyurea thixotropic agent.
8. The low temperature rapid curing epoxy splice gum of claim 1, wherein the talc is one or a combination of 325 mesh, 600 mesh, 800 mesh; the quartz powder is one or the combination of 100 meshes, 200 meshes and 400 meshes; the silicon micropowder is one or the combination of 200 meshes, 400 meshes and 600 meshes.
9. The low temperature rapid curing epoxy splice adhesive of claim 1, wherein the titanium dioxide is rutile titanium dioxide; the carbon black is pigment carbon black.
10. The method for preparing the low-temperature rapid-curing type epoxy splice adhesive according to any one of claims 1 to 9, comprising the following steps:
(1) Preparation of the resin System
(1) The raw materials used in the resin system are respectively weighed according to the parts by weight;
(2) adding the weighed modified bisphenol A epoxy resin, cycloaliphatic epoxy resin, bisphenol F epoxy resin and epoxy coupling agent into a stirrer, mixing and stirring, and then adding an active diluent, a toughening agent, a defoaming agent, a thixotropic agent and titanium pigment for continuous stirring;
(3) slowly pouring the weighed talcum powder and quartz powder into a stirrer, firstly adding fine materials, then adding coarse materials, starting a vacuum system after the addition is finished, and continuing vacuum stirring;
(2) Preparation of the curing agent System
a, respectively weighing raw materials used in a curing agent system according to parts by weight;
b, adding the weighed Mannich base curing agent, thiourea-amine curing agent, activity promoter and amino coupling agent into a stirrer, mixing and stirring, and then adding an antioxidant, a defoaming agent, a thixotropic agent and carbon black for continuous stirring;
c, slowly pouring the weighed silicon micropowder and quartz powder into a planetary stirrer, firstly adding fine materials and then adding coarse materials, starting a vacuum system after the addition is finished, and continuing vacuum stirring.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN118291071A (en) * | 2024-04-17 | 2024-07-05 | 佛山禾邦新材料科技有限公司 | Epoxy thermal conductive structural adhesive capable of realizing rapid positioning and curing at room temperature and preparation method thereof |
| CN118725696A (en) * | 2024-07-12 | 2024-10-01 | 北京浩明环保科技有限公司 | A fast-curing sound-insulating coating and preparation method thereof |
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