CN118064094B - Single-component MS epoxy structural adhesive for new energy automobile and preparation method thereof - Google Patents
Single-component MS epoxy structural adhesive for new energy automobile and preparation method thereof Download PDFInfo
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- CN118064094B CN118064094B CN202410496892.2A CN202410496892A CN118064094B CN 118064094 B CN118064094 B CN 118064094B CN 202410496892 A CN202410496892 A CN 202410496892A CN 118064094 B CN118064094 B CN 118064094B
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- 239000000853 adhesive Substances 0.000 title claims abstract description 54
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 54
- 239000004593 Epoxy Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000003822 epoxy resin Substances 0.000 claims abstract description 44
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 44
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 31
- 229920000570 polyether Polymers 0.000 claims abstract description 31
- -1 polysiloxane Polymers 0.000 claims abstract description 28
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 27
- 229920005989 resin Polymers 0.000 claims abstract description 21
- 239000011347 resin Substances 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910000077 silane Inorganic materials 0.000 claims abstract description 13
- 239000004014 plasticizer Substances 0.000 claims abstract description 12
- 239000006235 reinforcing carbon black Substances 0.000 claims abstract description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011575 calcium Substances 0.000 claims abstract description 9
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 9
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 8
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 8
- 239000007822 coupling agent Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002516 radical scavenger Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 18
- 239000012948 isocyanate Substances 0.000 claims description 12
- 150000002513 isocyanates Chemical class 0.000 claims description 12
- 150000001412 amines Chemical class 0.000 claims description 11
- 229920005862 polyol Polymers 0.000 claims description 11
- 150000003077 polyols Chemical class 0.000 claims description 11
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 229920001451 polypropylene glycol Polymers 0.000 claims description 9
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 8
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 8
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 8
- 239000004115 Sodium Silicate Substances 0.000 claims description 7
- 239000010433 feldspar Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- LCPNYLRZLNERIG-ZETCQYMHSA-N (2S)-6-amino-2-[2-(oxomethylidene)hydrazinyl]hexanoyl isocyanate Chemical compound NCCCC[C@H](NN=C=O)C(=O)N=C=O LCPNYLRZLNERIG-ZETCQYMHSA-N 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- RYUJRXVZSJCHDZ-UHFFFAOYSA-N 8-methylnonyl diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(OCCCCCCCC(C)C)OC1=CC=CC=C1 RYUJRXVZSJCHDZ-UHFFFAOYSA-N 0.000 claims description 2
- ZVFDTKUVRCTHQE-UHFFFAOYSA-N Diisodecyl phthalate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC(C)C ZVFDTKUVRCTHQE-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 claims description 2
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 235000012773 waffles Nutrition 0.000 claims 1
- 238000010276 construction Methods 0.000 abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 8
- 239000006229 carbon black Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229960001124 trientine Drugs 0.000 description 5
- 239000000758 substrate Substances 0.000 description 4
- 239000000428 dust Substances 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 238000010009 beating Methods 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 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 2
- 230000036541 health Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 description 1
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 1
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 description 1
- KMBMQZQZBOLJHN-UHFFFAOYSA-N 2-methyloxirane;oxolane Chemical compound CC1CO1.C1CCOC1 KMBMQZQZBOLJHN-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- DNEHKUCSURWDGO-UHFFFAOYSA-N aluminum sodium Chemical compound [Na].[Al] DNEHKUCSURWDGO-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 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 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical group CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 238000009778 extrusion testing Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- MBAUOPQYSQVYJV-UHFFFAOYSA-N octyl 3-[4-hydroxy-3,5-di(propan-2-yl)phenyl]propanoate Chemical compound OC1=C(C=C(C=C1C(C)C)CCC(=O)OCCCCCCCC)C(C)C MBAUOPQYSQVYJV-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 239000004590 silicone sealant Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to the technical field of MS adhesives, in particular to a single-component MS epoxy structural adhesive for a new energy automobile and a preparation method thereof, wherein the preparation raw materials at least comprise the following components in parts by weight: 30-50 parts of silane end-capped polyether resin, 3-15 parts of plasticizer, 5-20 parts of polysiloxane modified epoxy resin, 5-50 parts of nano calcium, 1-5 parts of reinforcing carbon black, 0.1-1 part of antioxidant, 0.1-2 parts of water scavenger, 0.1-2 parts of coupling agent and 0.01-1 part of catalyst, and the preparation of stable single-component MS structural adhesive is realized by introducing the self-prepared polysiloxane modified epoxy resin into an MS structural adhesive system, and meanwhile, the strength and bonding strength of the adhesive body are effectively improved, and the application requirements of convenient construction can be met.
Description
Technical Field
The invention relates to the technical field of MS adhesives, in particular to a single-component MS epoxy structural adhesive for a new energy automobile and a preparation method thereof.
Background
The bonding strength of the conventional single-component MS structural adhesive to metal substrates (such as 6-series aluminum and 3-series aluminum) of the new energy automobile is 2-3MPa, such as domestic mainstream products of white cloud chemical SMP590, jitai chemical AT-369, and Huitian MS 7931. If the automobile host factory needs higher strength (such as 4-6 MPa), the prior art basically adopts filling high-proportion (more than or equal to 15 wt%) reinforcing carbon black to improve the adhesive strength of colloid, such as a commercial product of white cloud chemical SMP592, jitai chemical AT-366, boundary Han 1065 and the like. Although the adhesive strength of the adhesive to a metal substrate can reach 4-6MPa or even higher, the adhesive is difficult to produce (the dispersibility of the carbon black is poor and dust is easy to pollute a production workshop) because the adhesive is filled with high-proportion carbon black, the adhesive particles are obvious, the adhesive is thick, the adhesive is hard to perform on site construction (according to the national standard GB/T13477 extrusion test, 40-60 g/min), and the cost is high, so that the market popularization and the application of single-component MS structural adhesive are greatly limited. In order to solve the above problems, the prior art improves the bonding strength of the product by combining an MS system with an acrylic system, an epoxy system and a polyurethane system, such as an acrylic modified MS sealant and a preparation method thereof disclosed in chinese patent (publication No. CN 114672274A), a two-component modified epoxy adhesive for bonding passenger car skin and a preparation method thereof disclosed in chinese patent (publication No. CN115746769 a), a one-component epoxy modified silicone sealant and a preparation method thereof disclosed in chinese patent (publication No. CN 106590501B), and an epoxy modified MS sealant disclosed in chinese patent (publication No. CN 109880569B), wherein epoxy resin or acrylic resin is introduced into the MS system, but the one-component system cannot be stored for a long time, and the two-component system is inconvenient to use. Therefore, the high-strength (4-6 MPa) single-component MS glue has important production application significance.
Disclosure of Invention
In order to solve the problems, the invention provides the single-component MS glue with high strength (more than 4 MPa), which is simple and convenient to produce (high-proportion reinforcing carbon black is not required to be added), is thinner, convenient to construct and low in cost, and meets the actual application requirements of the field of new energy automobiles.
The invention provides a single-component MS epoxy structural adhesive for a new energy automobile, which comprises the following preparation raw materials in parts by weight: 30-50 parts of silane end capped polyether resin, 3-15 parts of plasticizer, 5-20 parts of polysiloxane modified epoxy resin, 5-50 parts of nano calcium, 1-5 parts of reinforcing carbon black, 0.1-1 part of antioxidant, 0.1-2 parts of water scavenger, 0.1-2 parts of coupling agent and 0.01-1 part of catalyst.
As a preferable technical scheme, the single-component MS epoxy structural adhesive for the new energy automobile comprises the following raw materials in parts by weight: 35-40 parts of silane end capped polyether resin, 5-10 parts of plasticizer, 10-15 parts of polysiloxane modified epoxy resin, 40-45 parts of nano calcium, 1-2 parts of reinforcing carbon black, 0.5-1 part of antioxidant, 0.5-1 part of water scavenger, 0.5-1 part of coupling agent and 0.3-0.5 part of catalyst.
As a preferred embodiment, the silane-terminated polyether resin includes at least a silane-terminated polyether resin having hydrolyzable end groups.
Preferably, the silane terminated polyether resin is selected from at least one of brillouin chemistry SAX750, brillouin chemistry SAX400, brillouin chemistry SAX260, wake chemistry E10, wake chemistry E35, wake chemistry E925, rayoco-A350A, rayoco-A350D, rayoco-A3012.
Preferably, the silane-terminated polyether resin is a combination of a brillouin chemistry SAX750 and a Wake chemistry E35, and the mass ratio of the brillouin chemistry SAX750 to the Wake chemistry E35 is (20-30): (10-15), preferably 25: (10-15).
As a preferable technical scheme, the plasticizer is at least one selected from diisononyl phthalate, diisodecyl phthalate, diphenyl isodecyl phosphate and polyoxypropylene glycol. Preferably, the plasticizer is a polyoxypropylene glycol, preferably a combination of PPG2000 and PPG3000, and the mass ratio of PPG2000 to PPG3000 is (1.5-3): (3.5-7).
As a preferable technical scheme, the preparation raw materials of the polysiloxane modified epoxy resin at least comprise: low viscosity epoxy resins, isocyanates, amine catalysts, silicates, polyether polyols.
As a preferable technical scheme, the preparation method of the polysiloxane modified epoxy resin at least comprises the following steps:
(1) Adding low-viscosity epoxy resin and isocyanate into a reaction kettle, controlling the temperature to be 65-95 ℃ under the protection of nitrogen, adding an amine catalyst, stirring and reacting to obtain an intermediate, discharging and sealing for later use;
(2) And (3) performing prepolymerization reaction on the intermediate and silicate at a controlled temperature, and then adding polyether polyol, mixing and stirring to obtain the polysiloxane modified epoxy resin.
Preferably, the low viscosity epoxy resin has a viscosity (25 ℃) of 4000 to 8000cps, preferably NPEL to 127L (south Asia) and a viscosity of 7000 to 8000cps.
Preferably, the isocyanate is at least one selected from TDI, IPDI (isophorone diisocyanate), MDI, HMDI (dicyclohexylmethane-4, 4' -diisocyanate), HDI (hexamethylene diisocyanate) and LDI (L-lysine diisocyanate), preferably the combination of TDI (toluene diisocyanate) and MDI (diphenylmethane diisocyanate), and the mass ratio of TDI and MDI is 1:1.
Preferably, the amine catalyst is at least one selected from ethylenediamine, triethylenetetramine, diethylenetriamine and 2-amino terephthalic acid, preferably a combination of ethylenediamine and triethylenetetramine, and the mass ratio of ethylenediamine to triethylenetetramine is 1:1.
Preferably, the silicate is at least one selected from sodium silicate, sodium polysilicate, sodium aluminum silicate, potassium silicate, mica, talcum powder, kaolin and feldspar powder, preferably a combination of sodium silicate and feldspar powder, and the mass ratio of the sodium silicate to the feldspar powder is 2:1.
Preferably, the polyether polyol is selected from at least one of polyoxypropylene glycol (PPG), polytetrahydrofuran glycol (PTHF), tetrahydrofuran-propylene oxide copolyglycol, polyether triol, polyether tetraol, preferably polyoxypropylene glycol, further preferably a combination of PPG2000 and PPG3000, the mass ratio of PPG2000 and PPG3000 being 1: (2-5), preferably 1:3.
Preferably, the mass ratio of the low-viscosity epoxy resin to the isocyanate to the amine catalyst is (6-9): (1-3): (0.1-1), preferably 7:2:0.5.
Preferably, the mass ratio of the intermediate to the silicate to the polyether polyol is 10: (1-2): (1-3), preferably 10:1.2:2.
Preferably, in the step (2), the temperature is controlled to be 80-150 ℃, and the time of the prepolymerization reaction is 1-10 hours; preferably, in the step (2), the temperature is controlled to be 80-100 ℃, and the time of the prepolymerization reaction is 1-3 h.
As a preferable technical scheme, the addition amount of the polysiloxane modified epoxy resin is 25-50wt%, preferably 40-50wt% of the addition amount of the silane-terminated polyether resin.
According to the invention, the preparation of stable single-component MS structural adhesive is realized by introducing the prepared polysiloxane modified epoxy resin into an MS structural adhesive system, and meanwhile, the strength and bonding strength of the adhesive body are effectively improved, and the application requirements of convenient construction can be met. The inventors analyzed the cause may be: in the prior art, an epoxy-MS colloid system obtained by simply mixing MS resin and epoxy resin cannot be stored for a long time due to poor compatibility, layering phenomenon occurs after long-term storage, mechanical property and bonding property after curing are reduced, and practical application requirements cannot be met.
Furthermore, the invention effectively balances the bonding strength and the workability of the product by controlling the addition amount of polysiloxane modified epoxy resin in the single-component MS epoxy structural adhesive to be 25-50wt% of the addition amount of silane end-capped polyether resin, and ensures that the extrusion performance is more than 150g/min while the tensile shear strength of 6-series aluminum is more than 5MPa and the tensile shear strength of 3-series aluminum is more than 6 MPa.
In addition, the invention improves the mechanical property of the single-component MS epoxy structural adhesive and simultaneously contributes to the improvement of the extrusion property of the product by preferably adopting a silane end-capped polyether resin system and a plasticizer system, in particular adopting two MS resin combinations of Brillouin chemistry SAX750 and Wake chemistry E35 to be matched with the introduction of a certain amount of polyoxypropylene glycol.
As a preferable technical scheme, the oil absorption value of the nano calcium (nano calcium carbonate) is less than or equal to 32+/-1 mL/100g, and the average grain diameter is less than or equal to 100nm; the nano calcium is preferably at least one of CCS-18, CCS-25 and CCS-25I, CCS-27.
As a preferable technical scheme, the reinforcing carbon black is Li Anlong TH05 and/or cabot M570.
As a preferred embodiment, the antioxidant is at least one selected from IRGANOX1010, IRGANOX1135, IRGANOX 245.
As a preferable technical scheme, the water scavenger is vinyl trimethoxy silane.
As a preferred technical scheme, the coupling agent is selected from at least one of gamma-aminopropyl trimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyl methyl dimethoxy silane, gamma-glycidoxypropyl trimethoxysilane and methacryloxypropyl trimethoxysilane, preferably KBM603 (N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane), KH540 (gamma-aminopropyl trimethoxysilane) and KH560 (gamma-glycidoxypropyl trimethoxysilane), and the mass ratio of KBM603, KH540 and KH560 is (1-3): 1:1, preferably 2:1:1.
Based on the system of the invention, by simultaneously introducing the-aminopropyl trimethoxysilane, the N-beta- (aminoethyl) -gamma-aminopropyl trimethoxysilane and the gamma-glycidol ether oxypropyl trimethoxysilane,
As a preferred embodiment, the catalyst is at least one selected from stannous octoate, dibutyltin dilaurate and di-n-butylbis (acetylacetonato) tin, preferably, dado chemical U220H.
The single-component MS epoxy structural adhesive provided by the invention can directly replace a high carbon black product system in the market, is convenient to construct (easy and labor-saving in adhesive beating), is friendly to human body and environment (free of high-proportion carbon black, free of dust during production, free of damage to human body health and pollution to workshop environment, difficult to clean), simple in production process and easy to realize large-scale industrialized popularization and application.
The invention also provides a preparation method of the single-component MS epoxy structural adhesive for the new energy automobile, which at least comprises the following steps:
S1, sequentially adding silane end-capped polyether resin, plasticizer, polysiloxane modified epoxy resin, nano calcium, reinforcing carbon black and antioxidant into a stirring kettle according to parts by weight, stirring for 20-30min at 20-30 ℃, heating to 100-120 ℃, keeping the vacuum degree at-0.1 MPa, and stirring and dehydrating at a constant temperature and high speed for 2-3h to obtain a dehydrated material;
s2, cooling the dehydrated material to 20-30 ℃, adding a water removing agent, a coupling agent and a catalyst, stirring, mixing, vacuumizing and defoaming to obtain the single-component MS epoxy structural adhesive for the new energy automobile.
Advantageous effects
1. The invention provides a high-strength (more than 4 MPa) single-component MS (MS) adhesive, which is simple and convenient to produce (high-proportion reinforcing carbon black is not required to be added), is thinner, convenient to construct and low in cost, and meets the actual application requirements of the field of new energy automobiles.
2. According to the invention, the preparation of stable single-component MS structural adhesive is realized by introducing the prepared polysiloxane modified epoxy resin into an MS structural adhesive system, and meanwhile, the strength and bonding strength of the adhesive body are effectively improved, and the application requirements of convenient construction can be met.
3. According to the invention, the addition amount of polysiloxane modified epoxy resin in the single-component MS epoxy structural adhesive is controlled to be 25-50wt% of the addition amount of silane end-capped polyether resin, so that the bonding strength and the workability of the product are effectively balanced, the tensile shear strength of 6-series aluminum is more than 5MPa, the tensile shear strength of 3-series aluminum is more than 6MPa, and meanwhile, the extrudability is more than 150g/min.
4. The invention improves the mechanical property of the single-component MS epoxy structural adhesive and simultaneously contributes to the improvement of the extrusion property of the product by adopting a silane end-capped polyether resin system and a plasticizer system, in particular to adopting a combination of two MS resins of Brillouin chemistry SAX750 and Wake chemistry E35 to match with the introduction of a certain amount of polyoxypropylene diol.
5. The single-component MS epoxy structural adhesive provided by the invention can directly replace a high carbon black product system in the market, is convenient to construct (easy and labor-saving in adhesive beating), is friendly to human body and environment (free of high-proportion carbon black, free of dust during production, free of damage to human body health and pollution to workshop environment, difficult to clean), simple in production process and easy to realize large-scale industrialized popularization and application.
Drawings
FIG. 1 shows an infrared spectrum (b) of a polysiloxane-modified epoxy resin and an infrared spectrum (a) of a low-viscosity epoxy resin prepared in the example of the present invention.
Detailed Description
Examples 1 to 3, comparative examples 1 to 4
Examples 1-3 and comparative examples 1-4 of the present invention provide a single-component MS epoxy structural adhesive for new energy automobiles, and the preparation raw materials are shown in Table 1.
TABLE 1
In table 1: the polysiloxane modified epoxy resin is prepared from the following raw materials: low viscosity epoxy resins, isocyanates, amine catalysts, silicates, polyether polyols.
The preparation method of the polysiloxane modified epoxy resin comprises the following steps:
(1) Adding low-viscosity epoxy resin and isocyanate into a reaction kettle, controlling the temperature to be 80 ℃ under the protection of nitrogen, adding an amine catalyst, stirring and reacting to obtain an intermediate, discharging and sealing for later use;
(2) And (3) performing prepolymerization reaction on the intermediate and silicate at a controlled temperature, and then adding polyether polyol, mixing and stirring to obtain the polysiloxane modified epoxy resin.
The low-viscosity epoxy resin is NPEL-127L (Nanya) and the viscosity is 7000-8000cps.
The isocyanate is a combination of TDI (toluene diisocyanate) and MDI (diphenylmethane diisocyanate), and the mass ratio of the TDI to the MDI is 1:1.
The amine catalyst is a combination of ethylenediamine and triethylene tetramine, and the mass ratio of the ethylenediamine to the triethylene tetramine is 1:1.
The silicate is a combination of sodium silicate and feldspar powder, and the mass ratio of the sodium silicate to the feldspar powder is 2:1.
The polyether polyol is polyoxypropylene glycol, specifically a combination of PPG2000 and PPG3000, and the mass ratio of the PPG2000 to the PPG3000 is 1:3.
The mass ratio of the low-viscosity epoxy resin to the isocyanate to the amine catalyst is 7:2:0.5.
The mass ratio of the intermediate to the silicate to the polyether polyol is 10:1.2:2.
In the step (2), the temperature is controlled to be 85 ℃, and the time of the prepolymerization reaction is 2 hours.
The invention provides a preparation method of a single-component MS epoxy structural adhesive for a new energy automobile, which comprises the following steps of:
S1, sequentially adding silane end-capped polyether resin, plasticizer, polysiloxane modified epoxy resin, nano calcium, reinforcing carbon black and antioxidant into a stirring kettle according to parts by weight, stirring for 25min at 25 ℃, heating to 110 ℃, keeping the vacuum degree at-0.1 MPa, and stirring and dehydrating at a constant temperature and high speed for 2.5h to obtain a dehydrated material;
S2, cooling the dehydrated material to 25 ℃, adding the water scavenger, the coupling agent and the catalyst, stirring, mixing, vacuumizing and defoaming to obtain the single-component MS epoxy structural adhesive for the new energy automobile.
Performance test method
1. The single-component MS epoxy structural adhesives prepared in examples 1-3 and comparative examples 1-4 were tested according to national standard GB/T7124-2008 adhesive-determination of tensile shear strength (rigid material vs. rigid material), and the substrates were tested: 6 series aluminum material, 3 series aluminum material, bonding area: 25mm×12.5mm, glue layer thickness: 0.2mm, number of samples: 2 for each substrate and see table 2 for test results.
2. The single-component MS epoxy structural adhesive prepared in examples 1-3 and comparative examples 1-4 is tested according to the national standard GB/T13477 extrudability, and the caliber of the adhesive nozzle is as follows: 4mm, sizing pressure: 0.3MPa, test time: 1min, see Table 2 for test results.
3. The infrared characterization is carried out on the polysiloxane modified epoxy resin prepared in the embodiment, and the infrared spectrogram (b) of the low-viscosity epoxy resin before modification and the infrared spectrogram (a) of the polysiloxane modified epoxy resin after modification are compared, so that the characteristic peak of the siloxane bond appears at 1072.20 in the infrared spectrogram (a) of the polysiloxane modified epoxy resin, and the polysiloxane modified epoxy resin is proved to be successfully prepared.
TABLE 2
As can be seen from the table above: the tensile shear strength of the single-component MS epoxy structural adhesive for the new energy automobile provided in the examples 1-3 to 6-series aluminum is more than 5MPa, the tensile shear strength of 3-series aluminum is more than 6MPa, and the extrudability is more than 150g/min; while comparative examples 1 to 4 cannot ensure both high tensile shear strength and extrudability.
Claims (8)
1. The single-component MS epoxy structural adhesive for the new energy automobile is characterized by comprising the following preparation raw materials in parts by weight: 30-50 parts of silane end capped polyether resin, 3-15 parts of plasticizer, 5-20 parts of polysiloxane modified epoxy resin, 5-50 parts of nano calcium, 1-5 parts of reinforcing carbon black, 0.1-1 part of antioxidant, 0.1-2 parts of water scavenger, 0.1-2 parts of coupling agent and 0.01-1 part of catalyst; the silane-terminated polyether resin is a combination of brillouin chemistry SAX750 and Wake chemistry E35; the polysiloxane modified epoxy resin is prepared from the following raw materials: a low viscosity epoxy resin, isocyanate, amine catalyst, silicate, polyether polyol, the viscosity of the low viscosity epoxy resin being 4000-8000cps; the silicate is a combination of sodium silicate and feldspar powder, and the mass ratio of the sodium silicate to the feldspar powder is 2:1; the addition amount of the polysiloxane modified epoxy resin is 25-50wt% of the addition amount of the silane end capped polyether resin; the preparation method of the polysiloxane modified epoxy resin at least comprises the following steps: (1) Adding low-viscosity epoxy resin and isocyanate into a reaction kettle, controlling the temperature to be 65-95 ℃ under the protection of nitrogen, adding an amine catalyst, stirring and reacting to obtain an intermediate, discharging and sealing for later use; (2) And (3) performing prepolymerization reaction on the intermediate and silicate at a controlled temperature, and then adding polyether polyol, mixing and stirring to obtain the polysiloxane modified epoxy resin.
2. The single-component MS epoxy structural adhesive for new energy automobiles according to claim 1, wherein the mass ratio of the brillouin chemistry SAX750 to the waffle chemistry E35 is (20-30): (10-15).
3. The single-component MS epoxy structural adhesive for new energy vehicles according to claim 1, wherein the plasticizer is at least one selected from diisononyl phthalate, diisodecyl phthalate, diphenyl isodecyl phosphate and polyoxypropylene glycol.
4. The single-component MS epoxy structural adhesive for new energy vehicles according to claim 1, wherein the isocyanate is at least one selected from toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane-4, 4' -diisocyanate, hexamethylene diisocyanate, and L-lysine diisocyanate.
5. The single-component MS epoxy structural adhesive for new energy automobiles according to claim 1, wherein the temperature is controlled to be 80-150 ℃ in the step (2), and the time of the prepolymerization is 1-10 h.
6. The single-component MS epoxy structural adhesive for new energy automobiles according to claim 1, wherein the mass ratio of the low-viscosity epoxy resin, isocyanate and amine catalyst is (6-9): (1-3): (0.1-1).
7. The single-component MS epoxy structural adhesive for new energy automobiles according to claim 1, wherein the mass ratio of the intermediate to the silicate to the polyether polyol is 10: (1-2): (1-3).
8. A method for preparing the single-component MS epoxy structural adhesive for new energy automobiles according to any one of claims 1 to 7, which is characterized by comprising at least the following steps:
S1, sequentially adding silane end-capped polyether resin, plasticizer, polysiloxane modified epoxy resin, nano calcium, reinforcing carbon black and antioxidant into a stirring kettle according to parts by weight, stirring for 20-30min at 20-30 ℃, heating to 100-120 ℃, keeping the vacuum degree at-0.1 MPa, and stirring and dehydrating at a constant temperature and high speed for 2-3h to obtain a dehydrated material;
s2, cooling the dehydrated material to 20-30 ℃, adding a water removing agent, a coupling agent and a catalyst, stirring, mixing, vacuumizing and defoaming to obtain the single-component MS epoxy structural adhesive for the new energy automobile.
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