CN118185532B - High-adhesive-strength epoxy adhesive capable of being rapidly cured at room temperature and preparation method thereof - Google Patents
High-adhesive-strength epoxy adhesive capable of being rapidly cured at room temperature and preparation method thereof Download PDFInfo
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- CN118185532B CN118185532B CN202410378801.5A CN202410378801A CN118185532B CN 118185532 B CN118185532 B CN 118185532B CN 202410378801 A CN202410378801 A CN 202410378801A CN 118185532 B CN118185532 B CN 118185532B
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- 229920006332 epoxy adhesive Polymers 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000003822 epoxy resin Substances 0.000 claims abstract description 51
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 51
- 229920000728 polyester Polymers 0.000 claims abstract description 47
- 239000007822 coupling agent Substances 0.000 claims abstract description 24
- 239000013530 defoamer Substances 0.000 claims abstract description 20
- RVEZZJVBDQCTEF-UHFFFAOYSA-N sulfenic acid Chemical compound SO RVEZZJVBDQCTEF-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000013008 thixotropic agent Substances 0.000 claims abstract description 18
- 239000000945 filler Substances 0.000 claims abstract description 16
- 239000003085 diluting agent Substances 0.000 claims abstract description 13
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003086 colorant Substances 0.000 claims abstract description 10
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims abstract description 10
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims abstract description 5
- 238000001723 curing Methods 0.000 claims description 65
- 238000003756 stirring Methods 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 230000001070 adhesive effect Effects 0.000 claims description 21
- 229920006335 epoxy glue Polymers 0.000 claims description 20
- 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 19
- 239000000853 adhesive Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- -1 glycidyl ester Chemical class 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 10
- 238000007259 addition reaction Methods 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 9
- 239000012745 toughening agent Substances 0.000 claims description 9
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 8
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 8
- 239000003292 glue Substances 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000002518 antifoaming agent Substances 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 6
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 5
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000002390 rotary evaporation Methods 0.000 claims description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 4
- YQMXOIAIYXXXEE-UHFFFAOYSA-N 1-benzylpyrrolidin-3-ol Chemical compound C1C(O)CCN1CC1=CC=CC=C1 YQMXOIAIYXXXEE-UHFFFAOYSA-N 0.000 claims description 4
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 claims description 4
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 claims description 4
- PLDLPVSQYMQDBL-UHFFFAOYSA-N 2-[[3-(oxiran-2-ylmethoxy)-2,2-bis(oxiran-2-ylmethoxymethyl)propoxy]methyl]oxirane Chemical compound C1OC1COCC(COCC1OC1)(COCC1OC1)COCC1CO1 PLDLPVSQYMQDBL-UHFFFAOYSA-N 0.000 claims description 4
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 4
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 claims description 4
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 4
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 4
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 claims description 4
- 239000012467 final product Substances 0.000 claims description 4
- 150000002460 imidazoles Chemical class 0.000 claims description 4
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 4
- QNYBOILAKBSWFG-UHFFFAOYSA-N 2-(phenylmethoxymethyl)oxirane Chemical compound C1OC1COCC1=CC=CC=C1 QNYBOILAKBSWFG-UHFFFAOYSA-N 0.000 claims description 3
- IMKMEPLAEXUGBU-UHFFFAOYSA-N 3-[3-aminopropyl(diethoxy)silyl]oxybutan-1-ol Chemical compound NCCC[Si](OCC)(OCC)OC(C)CCO IMKMEPLAEXUGBU-UHFFFAOYSA-N 0.000 claims description 3
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims description 3
- 238000000526 short-path distillation Methods 0.000 claims description 3
- 239000013466 adhesive and sealant Substances 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 31
- 239000003795 chemical substances by application Substances 0.000 description 31
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 26
- 239000000203 mixture Substances 0.000 description 17
- 239000011258 core-shell material Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- 239000004593 Epoxy Substances 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 229910002027 silica gel Inorganic materials 0.000 description 9
- 239000000741 silica gel Substances 0.000 description 9
- 229910021487 silica fume Inorganic materials 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical group SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 229910021485 fumed silica Inorganic materials 0.000 description 6
- 229920006295 polythiol Polymers 0.000 description 6
- 239000004721 Polyphenylene oxide Substances 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 229920000570 polyether Polymers 0.000 description 5
- 229920001296 polysiloxane Polymers 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- JOBBTVPTPXRUBP-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS JOBBTVPTPXRUBP-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 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 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 150000003573 thiols Chemical class 0.000 description 3
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000004359 castor oil Substances 0.000 description 2
- 235000019438 castor oil Nutrition 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000010835 comparative analysis Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000000269 nucleophilic effect Effects 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 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 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- CWTBRJLMUOHWQG-UHFFFAOYSA-N 3-phenyl-3h-dithiole Chemical class C1=CSSC1C1=CC=CC=C1 CWTBRJLMUOHWQG-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- YQGOJNYOYNNSMM-UHFFFAOYSA-N eosin Chemical compound [Na+].OC(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C(O)=C(Br)C=C21 YQGOJNYOYNNSMM-UHFFFAOYSA-N 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000013035 low temperature curing Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/66—Mercaptans
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Epoxy Resins (AREA)
Abstract
The invention belongs to the field of adhesives and sealants, and relates to a high-bonding-strength epoxy adhesive capable of being rapidly cured at room temperature and a preparation method thereof. The high-bonding strength epoxy adhesive capable of being rapidly cured at room temperature comprises a component A: 85-95 parts of epoxy resin, 5-6 parts of diluent, 10-12 parts of flexibilizer, 60-70 parts of filler, 1-5 parts of thixotropic agent, 1-10 parts of coupling agent, 0.5-3 parts of defoamer and 0.1-1 part of colorant; component B: 90 to 100 parts of polyester modified beta hydroxyl mercaptan, 1.5 to 2.5 parts of accelerator, 60 to 70 parts of filler, 1 to 5 parts of thixotropic agent, 1 to 10 parts of coupling agent and 0.5 to 3 parts of defoamer. The polyester modified beta hydroxyl mercaptan is prepared from trimethylolpropane, epsilon-caprolactone, epichlorohydrin and sodium hydrosulfide. The invention effectively improves the curing speed and the bonding strength, has good wet heat resistance and low smell, and ensures that the electronic component can be used in a high-humidity and hot environment to have excellent bonding performance.
Description
Technical Field
The invention belongs to the field of adhesives and sealants, and particularly relates to a high-bonding-strength epoxy adhesive capable of being rapidly cured at room temperature and a preparation method thereof.
Background
The epoxy resin adhesive is epoxy adhesive or epoxy adhesive for short, and mainly comprises epoxy resin and a curing agent, and comprises components such as a toughening agent, an accelerator, a stabilizer, a diluent and the like for improving the application performance of the epoxy resin adhesive. Epoxy resins (generically referred to as Epoxy resins) are structures containing two or more epoxy groups and having an aliphatic, alicyclic or aromatic organic compound as a skeleton. The epoxy resin itself is a thermoplastic linear structure, cannot be directly used as an adhesive, and needs to be added with a curing agent and subjected to curing and crosslinking reaction under certain conditions. Curing agents are extremely important components in the application process of epoxy resin, and generally include amines, anhydrides, polythiols, imidazoles and the like.
The process of gluing epoxy resins with curing agents and other additives is a very complex physical and chemical change. The epoxy resin adhesive is of various types, and can be matched with a proper curing agent according to different use situations to exert the best performance of the epoxy resin system. Since many electronic components are relatively temperature sensitive and cannot withstand high temperatures, the epoxy adhesives used need to have lower cure temperatures and faster cure speeds. The epoxy resin adhesive is quickly cured at room temperature, so that the operation environment is simpler, the construction time is shortened, the cost is effectively reduced, and the energy-saving effect is achieved. However, at present, an aliphatic polyamine curing agent is generally used as a room temperature curing agent, and has the advantages of low curing speed, high toxicity, strong irritation to human skin, high heat release amount due to reaction with epoxy resin and poor flexibility of a cured product.
Thiol is an important variety of epoxy resin curing agents, and is widely applied in the field of low-temperature curing. Due to the structural characteristics of polythiol, the heat resistance and the moisture resistance of the polythiol are poor, and the cured product of the adhesive can have the problems of colloid cracking, greatly reduced strength, water absorption, electrical property damage and the like when the cured product is exposed to a high-humidity environment for a long time. Therefore, it is a continuous object to improve the moisture resistance of low-temperature-curable epoxy adhesives. Patent CN 114989757B discloses a low-temperature fast-curing moisture-heat-resistant epoxy adhesive, a preparation method and application thereof, wherein the adhesive comprises the following raw materials: epoxy resin, blocked isocyanate, polythiol curing agent, curing accelerator, filler, pigment and auxiliary agent; the polythiol curing agent is prepared by reacting phenyl dithiol compounds and diisocyanate silane compounds, the epoxy adhesive can be cured at 50-60 ℃ for 20-40min, and the shearing strength of the adhesive substrate PC8600 slice after curing at room temperature is 22-26.1MPa.
Above, the application effect and the application requirement of the prior art still have a certain gap, so the improvement of the low-temperature rapid curing and the moisture and heat resistance of the epoxy adhesive has important significance for further expanding the application of the epoxy adhesive.
Disclosure of Invention
The first purpose of the invention is to develop a double-component room-temperature-curable epoxy adhesive which has stronger bonding performance and can still maintain higher bonding strength in a damp-heat environment aiming at electronic components which are sensitive to temperature and cannot bear high temperature;
the second purpose is to provide a high-bonding strength epoxy adhesive which is quickly cured at room temperature, and a preparation method and application thereof.
Specifically, the invention provides a high-adhesive-strength epoxy adhesive which is quickly cured at room temperature, comprising a component A and a component B;
The component A comprises the following raw materials in parts by weight: 85-95 parts of epoxy resin, 5-6 parts of diluent, 10-12 parts of flexibilizer, 60-70 parts of filler, 1-5 parts of thixotropic agent, 1-10 parts of coupling agent, 0.5-3 parts of defoamer and 0.1-1 part of colorant;
The component B comprises the following raw materials in parts by weight: 90 to 100 parts of polyester modified beta hydroxyl mercaptan, 1.5 to 2.5 parts of accelerator, 60 to 70 parts of filler, 1 to 5 parts of thixotropic agent, 1 to 10 parts of coupling agent and 0.5 to 3 parts of defoamer.
Optionally, the polyester modified beta hydroxythiol has a structure according to formula (i):
Wherein n is a positive integer from 1 to 4.
Optionally, the preparation method of the polyester modified beta hydroxyl mercaptan comprises the following steps:
(1) Ring-opening polymerization: adding trimethylolpropane, epsilon-caprolactone and a first catalyst into a reaction vessel, and heating to react under the protection of inert gas to obtain a ring-opening polymerization product.
(2) Addition reaction: mixing, stirring and heating the ring-opening polymerization product, the second catalyst and epichlorohydrin, and distilling off the epichlorohydrin to obtain an addition reaction product.
(3) Nucleophilic substitution: and (3) dissolving the addition reaction product in a solvent, dropwise adding a sodium hydrosulfide aqueous solution, after the stirring reaction is finished, dropwise adding hydrochloric acid into the reaction solution to neutralize to pH=6-7, removing the solvent by rotary evaporation, and purifying by short-path distillation to obtain the final product polyester modified beta-hydroxyl mercaptan.
Alternatively, the molar ratio of trimethylolpropane to epsilon-caprolactone is 1 (3-12).
Optionally, the first catalyst comprises tin tetrachloride, stannous octoate; the second catalyst comprises one or more of boron trifluoride diethyl etherate and tin tetrachloride.
Optionally, the reaction temperature in the step (1) of the preparation method of the polyester modified beta hydroxyl mercaptan is 100-130 ℃ and the reaction time is 12-36h;
The reaction temperature in the step (2) of the preparation method of the polyester modified beta-hydroxyl mercaptan is 80-120 ℃ and the reaction time is 2-4h;
the reaction temperature in the step (3) of the preparation method of the polyester modified beta-hydroxyl mercaptan is 50-60 ℃ and the reaction time is 12-24h.
Alternatively, the epoxy resin includes one or more combinations of bisphenol a type epoxy resin, bisphenol F type epoxy resin, glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, and alicyclic epoxy resin.
Optionally, the diluent comprises one or more combinations of 1, 4-butanediol diglycidyl ether, polypropylene glycol diglycidyl ether, carbon ten-to-tetradecyl diglycidyl ether, benzyl glycidyl ether, 1, 4-cyclohexanedimethanol diglycidyl ether, pentaerythritol tetraglycidyl ether, dicyclopentadiene type diglycidyl ether.
Optionally, the first coupling agent comprises one or more combinations of vinyltris (2-methoxyethoxy) silane, gamma- (methacryloyloxy) propyl trimethoxysilane, gamma-glycidoxypropyl trimethoxysilane; the second coupling agent comprises one or more of gamma-aminopropyl triethoxysilane, gamma-mercaptopropyl triethoxysilane, beta-hydroxyethyl-gamma-aminopropyl triethoxysilane.
Optionally, the accelerator comprises one or more of 2,4, 6-tris (dimethylaminomethyl) phenol, benzyl dimethylamine, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole and modified imidazole in combination.
Optionally, the toughening agent comprises one or a combination of more of polyurethane modified epoxy resin, organosilicon modified epoxy resin, carboxyl terminated nitrile rubber and core shell rubber.
Optionally, the thixotropic agent comprises one or more of modified castor oil, organobentonite, polyamide wax, fumed silica, in combination.
Optionally, the defoamer comprises one or more of a silicone defoamer, a polyether defoamer, a mineral oil defoamer.
Optionally, the colorant is carbon black.
On the other hand, the invention also provides a preparation method of the epoxy glue with high bonding strength, which is rapidly cured at room temperature, and comprises the following preparation steps:
(1) And (3) preparation of a component A: respectively adding epoxy resin, a diluent, a toughening agent, a filler, a thixotropic agent, a coupling agent, a defoaming agent and a colorant into a stirring kettle according to weight proportion, and stirring in vacuum until the components are completely and uniformly dispersed; and (3) placing the stirred glue solution in a planetary homogenizer for mixing and defoaming, and obtaining the component A after the defoaming is completed.
(2) And (3) preparing a component B: respectively adding a curing agent, an accelerator, a filler, a thixotropic agent, a coupling agent and a defoaming agent into a stirring kettle according to the weight proportion, and stirring until the materials are completely dispersed uniformly; and (3) placing the stirred glue solution in a planetary homogenizer for mixing and defoaming, and obtaining the component B after the defoaming is completed.
The defoaming in the steps (1) and (2) is divided into three sections, wherein the first section is 600 rpm-800 rpm/60 s-120 s, the second section is 1000 rpm-1200 rpm/120 s-240 s, the third section is 600 rpm-800 rpm/60 s-120 s, and the vacuum degree is 5 kPa-10 kPa.
The beneficial effects of the invention are as follows:
(1) The invention prepares the polyester modified beta hydroxyl mercaptan as the curing agent of the epoxy glue, and as a plurality of polyester groups with larger polarity are introduced into the structure of the curing agent, the cured epoxy glue has excellent adhesive property; the longer carbon chain in the molecular chain of the curing agent has good hydrophobicity, so that the moisture and heat resistance is better.
(2) The polyester modified beta hydroxyl mercaptan is used as a curing agent of epoxy glue, and because hydroxyl is introduced into beta position of mercaptan in the structure of the curing agent, the electronegativity of sulfur atoms of the mercaptan is increased through the conduction of carbon chains, hydrogen atoms are easier to leave, the nucleophilic ability of the mercaptan is increased, the curing agent has stronger reactivity, can react at room temperature, and has higher speed in the curing process of the epoxy glue.
(3) The double-component epoxy adhesive adopted by the invention effectively improves the curing speed and the bonding strength under the reasonable matching of the component A and the component B, and simultaneously has good wet heat resistance and low smell, so that the electronic component can be used in a high-humidity and hot environment, and an excellent bonding effect is achieved.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects solved by the invention more clear, the invention is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The invention provides a high-bonding strength epoxy adhesive which is quickly cured at room temperature, comprising a component A and a component B;
The component A comprises the following raw materials in parts by weight: 85 to 95 parts of epoxy resin, such as 85, 87, 90, 92, 95 parts by weight or any value therebetween; 5 to 6 parts of diluent, such as 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6 parts by weight or any value therebetween; 10 to 12 parts of toughening agent, such as 10, 10.5, 11, 11.5, 12 parts by weight or any value in between; 60 to 70 parts of filler, such as 60, 62, 64, 66, 68, 70 parts by weight or any value therebetween; 1 to 5 parts, such as 1,2, 3,4, 5 parts by weight or any value therebetween, of a thixotropic agent; 1 to 10 parts of coupling agent, such as 1,2, 3,4, 5,6, 7, 8, 9, 10 parts by weight or any value in between; 0.5 to 3 parts of defoamer, such as 0.5, 1, 1.5, 2, 2.5, 3 parts by weight or any value in between; 0.1 to 1 part of a colorant, such as 0.1, 0.3, 0.5, 0.7, 1 part by weight or any value therebetween;
The component B comprises the following raw materials in parts by weight: 90 to 100 parts, such as 90, 92, 94, 96, 98, 100 parts by weight or any value therebetween, of polyester modified beta hydroxythiol; 1.5 to 2.5 parts of accelerator, such as 1.5, 1.7, 2.0, 2.3, 2.5 parts by weight or any value in between; 60 to 70 parts of filler, such as 60, 62, 64, 66, 68, 70 parts by weight or any value therebetween; 1 to 5 parts, such as 1,2, 3, 4, 5 parts by weight or any value therebetween, of a thixotropic agent; 1 to 10 parts of a coupling agent, such as 1,2, 4, 6, 8, 10 parts by weight or any value therebetween; 0.5 to 3 parts of defoamer, such as 0.1, 0.3, 0.5, 0.7, 1 part by weight or any value in between.
The prepared polyester modified beta hydroxyl mercaptan is used as a curing agent of the epoxy adhesive, and a plurality of ester bonds with larger polarity and beta hydroxyl groups are introduced into the structure of the curing agent, so that the cured epoxy adhesive has excellent adhesive property; the longer carbon chain in the molecular chain of the curing agent has good hydrophobicity, so that the moisture and heat resistance is better.
The prepared polyester modified beta hydroxyl mercaptan is used as a curing agent of epoxy glue, and as hydroxyl is introduced into beta position of mercaptan in the structure of the curing agent, the electronegativity of sulfur atoms of the mercaptan is increased through conduction of carbon chains, hydrogen atoms are easier to leave, the nucleophilic ability of the mercaptan is increased, the curing agent has stronger reactivity, can react at room temperature, and has higher speed in the curing process of the epoxy glue.
The adopted bi-component epoxy adhesive effectively improves the curing speed and the bonding strength under the reasonable matching of the component A and the component B, and simultaneously has good wet heat resistance and low smell, so that the electronic component can be used in a high-humidity and hot environment, and an excellent bonding effect is achieved.
In some embodiments of the invention, the polyester modified β -hydroxythiol has a structure according to formula (i):
Where n is a positive integer from 1 to 4, such as 1, 2,3, 4, etc., but are not limited to the recited values, combinations not recited in this range are equally applicable.
In some embodiments of the invention, the polyester modified beta hydroxythiol is prepared by:
(1) Ring-opening polymerization: adding trimethylolpropane, epsilon-caprolactone and a first catalyst into a reaction vessel, and heating to react under the protection of inert gas to obtain a ring-opening polymerization product.
(2) Addition reaction: mixing, stirring and heating the ring-opening polymerization product, the second catalyst and epichlorohydrin, and distilling off the epichlorohydrin to obtain an addition reaction product.
(3) Nucleophilic substitution: and (3) dissolving the addition reaction product in a solvent, dropwise adding a sodium hydrosulfide aqueous solution, after the stirring reaction is finished, dropwise adding hydrochloric acid into the reaction solution to neutralize to pH=6-7, removing the solvent by rotary evaporation, and purifying by short-path distillation to obtain the final product polyester modified beta-hydroxyl mercaptan.
In some embodiments of the invention, the first catalyst comprises tin tetrachloride, stannous octoate; the second catalyst comprises one or more of boron trifluoride diethyl etherate and tin tetrachloride.
In some embodiments of the invention, the molar ratio of trimethylolpropane to epsilon-caprolactone is from 1 (3 to 12), such as 1: 4. 1: 8. 1: 12. 1:16, etc., but are not limited to the recited values, combinations not recited in this range are equally applicable.
In some embodiments of the present invention, the reaction temperature in step (1) of the process for preparing a polyester-modified beta-hydroxythiol is 100 ℃ to 130 ℃, such as 100 ℃, 110 ℃, 120 ℃, 130 ℃, etc., but is not limited to the recited values, and combinations not recited in this range are equally applicable; the reaction time is 12-36h, such as 12h, 18h, 24h, 36h, etc., but is not limited to the recited values, and combinations not recited in this range are equally applicable;
The reaction temperature in step (2) of the process for producing a polyester-modified beta-hydroxythiol is 80℃to 120℃such as 80℃90℃100℃110℃120℃and the like, but not limited to the values recited, and combinations not recited in the range are equally applicable; the reaction time is 2 to 4 hours, such as 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, etc., but is not limited to the recited values, and combinations not recited in the range are equally applicable;
The reaction temperature in step (3) of the process for producing a polyester-modified β -hydroxythiol is 50 to 60 ℃, such as 50 ℃, 52 ℃, 54 ℃, 56 ℃, 58 ℃, 60 ℃, etc., but not limited to the values recited, and combinations not recited in the range are equally applicable; the reaction time is 12 to 24 hours, such as 12 hours, 16 hours, 20 hours, 24 hours, etc., but is not limited to the recited values, and combinations not recited in this range are equally applicable.
In some embodiments of the invention, the epoxy resin comprises one or more combinations of bisphenol a type epoxy resin, bisphenol F type epoxy resin, glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, and cycloaliphatic epoxy resin.
In a preferred embodiment, the epoxy resin is a bisphenol a epoxy resin.
In some embodiments of the invention, the diluent comprises one or more of 1, 4-butanediol diglycidyl ether, polypropylene glycol diglycidyl ether, carbon ten-to-tetradecyl diglycidyl ether, benzyl diglycidyl ether, 1, 4-cyclohexanedimethanol diglycidyl ether, pentaerythritol tetraglycidyl ether, dicyclopentadiene type diglycidyl ether.
In a preferred embodiment, the diluent is dicyclopentadiene type diglycidyl ether; still further, the dicyclopentadiene type diglycidyl ether is preferably EP-4088S.
In some embodiments of the invention, the coupling agent comprises a combination of one or more of gamma-aminopropyl triethoxysilane, vinyl tris (2-methoxyethoxy) silane, gamma-glycidoxypropyl trimethoxysilane.
In some embodiments of the invention, the first coupling agent comprises one or more of vinyltris (2-methoxyethoxy) silane, gamma- (methacryloyloxy) propyl trimethoxysilane, gamma-glycidoxypropyl trimethoxysilane; the second coupling agent comprises one or more of gamma-aminopropyl triethoxysilane, gamma-mercaptopropyl triethoxysilane, beta-hydroxyethyl-gamma-aminopropyl triethoxysilane.
In a preferred embodiment, the first coupling agent is gamma-glycidoxypropyl trimethoxysilane and the second coupling agent is gamma-mercaptopropyl triethoxysilane.
In some embodiments of the invention, the accelerator comprises a combination of one or more of 2,4, 6-tris (dimethylaminomethyl) phenol, benzyl dimethylamine, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, and modified imidazole.
In a preferred embodiment, the accelerator is 2,4, 6-tris (dimethylaminomethyl) phenol.
In some embodiments of the invention, the toughening agent comprises one or more of a polyurethane modified epoxy, a silicone modified epoxy, a carboxyl terminated nitrile rubber, a core shell rubber.
In a preferred embodiment, the toughening agent is a core shell rubber; still further, the core shell rubber is MX-125.
In some embodiments of the invention, the thixotropic agent comprises a combination of one or more of modified castor oil, organobentonite, polyamide wax, fumed silica.
In a preferred embodiment, the thixotropic agent is fumed silica.
In some embodiments of the invention, the defoamer comprises one or more of a silicone defoamer, a polyether defoamer, a mineral oil defoamer.
In a preferred embodiment, the defoamer is a silicone defoamer; still further, the silicone defoamer is BYK-066N.
In some embodiments of the invention, the colorant is carbon black.
The invention also provides a preparation method of the moisture-heat resistant two-component epoxy adhesive with high room temperature rapid curing and high adhesive strength, which comprises the following preparation steps:
(1) And (3) preparation of a component A: respectively adding epoxy resin, a diluent, a toughening agent, a filler, a thixotropic agent, a coupling agent, a defoaming agent and a colorant into a stirring kettle according to weight proportion, and stirring in vacuum until the components are completely and uniformly dispersed; and (3) placing the stirred glue solution in a planetary homogenizer for mixing and defoaming, and obtaining the component A after the defoaming is completed.
(2) And (3) preparing a component B: respectively adding a curing agent, an accelerator, a filler, a thixotropic agent, a coupling agent and a defoaming agent into a stirring kettle according to the weight proportion, and stirring until the materials are completely dispersed uniformly; and (3) placing the stirred glue solution in a planetary homogenizer for mixing and defoaming, and obtaining the component B after the defoaming is completed.
The defoaming in the steps (1) and (2) is divided into three sections, wherein the first section is 600 rpm-800 rpm/60 s-120 s, the second section is 1000 rpm-1200 rpm/120 s-240 s, the third section is 600 rpm-800 rpm/60 s-120 s, and the vacuum degree is 5 kPa-10 kPa.
The defoaming in the steps (1) and (2) is divided into three sections, wherein the first section is 600rpm to 800rpm/60s to 120s, such as 600rpm/60s, 600rpm/120s, 700rpm/60s, 700rpm/120s, 800rpm/60s, 800rpm/120s and the like, but the defoaming method is not limited to the recited values, and the non-recited combinations in the range are equally applicable; the second stage is 1000rpm to 1200rpm/120s to 240s, such as 1000rpm/120s, 1000rpm/240s, 1100rpm/120s, 1100rpm/240s, 1200rpm/120s, 1200rpm/240s, etc., but not limited to the recited values, combinations not recited in this range are equally applicable; ; the third stage is 600rpm to 800rpm/60s to 120s, such as 600rpm/60s, 600rpm/120s, 700rpm/60s, 700rpm/120s, 800rpm/60s, 800rpm/120s, etc., but not limited to the recited values, combinations not recited in this range are equally applicable; the vacuum degree is 5kPa to 10kPa, such as 5kPa, 6kPa, 7kPa, 8kPa, 9kPa, 10kPa, etc., but not limited to the values recited, and combinations not recited in the ranges are equally applicable.
The raw materials and sources used in the following examples and comparative examples are as follows:
Trimethylolpropane, from Perstorp corporation; epsilon-caprolactone derived from japanese macroxylonite; sn (Oct) 2, a new material; epichlorohydrin is derived from mountain eastern sea chemical industry; boron trifluoride etherate solution, from the company Zitengchi; methyl ethyl ketone, derived from boyou chemical industry; sodium hydrosulfide, derived from the hundred-gold chemical industry; hydrochloric acid, derived from aledine.
Epoxy resin, bisphenol a type epoxy, brand No. YL980, from mitsubishi chemistry; diluents, type DCPDM, brand EP-4088S, from ADEKA; toughening agent, core-shell rubber with MX-125, derived from Japanese Brillouin; filler, silica micropowder derived from ya Dou Ma; thixotropic agent, fumed silica, brand R-202, derived from win origins; the coupling agent, gamma-glycidoxypropyl trimethoxysilane, has the brand of KH-560, gamma-mercaptopropyl triethoxysilane, has the brand of KH-580, and is derived from Nanjing eosin; a defoamer, brand BYK-066N, from Pick chemistry; a colorant, carbon black derived from cabot; a curing agent, trimethylolpropane tri (3-mercaptopropionic acid) ester, with the brand TMPMP; pentaerythritol tetrakis (3-mercaptopropionate), PETMP, is available from Bruno Bock; polyether thiols, brand Capcure-3800, polyether thiols, brand GPM-800, all derived from Huntsman; the accelerator, 2,4, 6-tris (dimethylaminomethyl) phenol, is named DMP-30 and originates from the mountain of Changzhou.
Preparation example 1
The preparation method of the polyester modified beta hydroxyl mercaptan A1 comprises the following steps:
13.4g of trimethylolpropane, 34.2g of epsilon-caprolactone and a catalytic amount of Sn (Oct) 2 are added into a thoroughly dried sealed reactor, the mixture is vacuumized, replaced by filling nitrogen for three times, and the mixture is heated to 120 ℃ for stirring reaction for 24 hours; adding 0.002g of boron trifluoride diethyl etherate solution, dropwise adding 27.8g of epichlorohydrin to the mixture at room temperature under stirring, heating to 100 ℃ and stirring for reaction for 6h, and then removing excessive epichlorohydrin by distillation; adding 500ml of methyl ethyl ketone, stirring and dissolving uniformly, slowly dripping 33.6g of NaSH aqueous solution (50 wt%) into the mixture, heating to 55 ℃ and stirring and reacting for 12h, and slowly dripping 36wt% of hydrochloric acid into the mixture to neutralize the mixture until the pH value is reduced to 7; finally, the solvent was distilled off by rotary evaporation, and the mixture was purified by short-path vacuum distillation at 50℃under reduced pressure (0.01 mmHg) to obtain 70.4g of polyester-modified-. Beta.hydroxythiol A1.
Preparation example 2
The preparation method of the polyester modified beta hydroxyl mercaptan A2 comprises the following steps:
13.4g of trimethylolpropane, 68.4g of epsilon-caprolactone and a catalytic amount of Sn (Oct) 2 are added into a thoroughly dried sealed reactor, the mixture is vacuumized, replaced by filling nitrogen for three times, and the mixture is heated to 120 ℃ for stirring reaction for 24 hours; adding 0.004g of boron trifluoride diethyl etherate solution, dropwise adding 27.8g of epoxy chloropropane into the mixture at room temperature under stirring, heating to 100 ℃ and stirring for reaction for 6 hours, and then distilling off excessive epoxy chloropropane; adding 500ml of methyl ethyl ketone, stirring and dissolving uniformly, slowly dripping 33.6g of NaSH aqueous solution (50 wt%) into the mixture, heating to 55 ℃ and stirring and reacting for 12h, and slowly dripping 36wt% of hydrochloric acid into the mixture to neutralize the mixture until the pH value is reduced to 7; finally, the solvent is removed by rotary evaporation, and short-path vacuum distillation purification is carried out under the conditions of 50 ℃ and reduced pressure (0.01 mmHg) to obtain the final product polyester modified beta-hydroxyl mercaptan A2.
Example 1
Preparation of high-adhesive-strength epoxy glue capable of being rapidly cured at room temperature:
90.7 parts of bisphenol A epoxy, 5.3 parts of EP-4088S, 10.7 parts of core-shell silica gel, 64 parts of silica powder, 3 parts of fumed silica, 5 parts of KH-560, 2 parts of BYK-066N and 0.5 part of carbon black are respectively added into a stirring kettle according to the weight proportion, and the rotating speed is 800rpm, and the stirring is carried out until the components are completely dispersed uniformly; placing the stirred glue solution into a planetary homogenizer for mixing and defoaming, wherein the defoaming process is divided into three sections: the first section is 600rpm/60s, the second section is 1200rpm/120s, the third section is 600rpm/60s, and the vacuum degree is 5kPa; and after the defoaming is finished, the component A can be obtained.
96 Parts of polyester modified beta-hydroxyl mercaptan A1, 2.1 parts of 2,4, 6-tris (dimethylaminomethyl) phenol, 64 parts of silicon micropowder, 3 parts of fumed silica, 5 parts of KH-580 and 2 parts of BYK-066N are respectively added into a stirring kettle according to the weight proportion, and the rotating speed is 800rpm, and the mixture is stirred until the mixture is completely dispersed uniformly; placing the stirred glue solution into a planetary homogenizer for mixing and defoaming, wherein the defoaming process is divided into three sections: the first section is 600rpm/60s, the second section is 1200rpm/120s, the third section is 600rpm/60s, and the vacuum degree is 5kPa; and after the defoaming is finished, the component B can be obtained.
Example 2
A high bond strength epoxy adhesive which cures rapidly at room temperature was prepared as in example 1, except that 87.8 parts bisphenol A epoxy, 5.2 parts EP-4088S, 10.3 parts core-shell silica gel, 62 parts silica fume were added to the A component; 93 parts of polyester modified beta-hydroxyl mercaptan A1, 2.1 parts of 2,4, 6-tris (dimethylaminomethyl) phenol and 62 parts of silicon micropowder are added into the component B, and the rest conditions are the same as in the example 1.
Example 3
A high bond strength epoxy adhesive which cures rapidly at room temperature was prepared as in example 1, except that 85.0 parts bisphenol A epoxy, 5.0 parts EP-4088S, 10.0 parts core-shell silica gel, 60 parts silica fume were added to the A component; 90 parts of polyester modified beta-hydroxyl mercaptan A1, 2.0 parts of 2,4, 6-tris (dimethylaminomethyl) phenol and 60 parts of silica micropowder are added into the component B, and the rest conditions are the same as in the example 1.
Example 4
A high bond strength epoxy adhesive which cures rapidly at room temperature was prepared as in example 1, except that 92.6 parts bisphenol A epoxy, 5.4 parts EP-4088S, 10.9 parts core-shell silica gel, 65 parts silica fume were added to the A component; the component B was charged with 98 parts of polyester-modified beta-hydroxythiol A1, 2.2 parts of 2,4, 6-tris (dimethylaminomethyl) phenol, 65 parts of silica micropowder, and the other conditions were the same as in example 1.
Example 5
A high bond strength epoxy adhesive which cures rapidly at room temperature was prepared as in example 1, except that 94.4 parts bisphenol A epoxy, 5.6 parts EP-4088S, 11.1 parts core-shell silica gel, 67 parts silica fume were added to the A component; 100 parts of polyester modified beta-hydroxyl mercaptan A1, 2.2 parts of 2,4, 6-tris (dimethylaminomethyl) phenol and 67 parts of silica micropowder are added into the component B, and the rest conditions are the same as in the example 1.
Example 6
A high bond strength epoxy adhesive which cures rapidly at room temperature was prepared as in example 1, except that 86.9 parts bisphenol A epoxy, 5.1 parts EP-4088S, 10.2 parts core-shell silica gel, 61 parts silica fume were added to the A component; 92 parts of polyester modified beta-hydroxythiol A2, 2.0 parts of 2,4, 6-tris (dimethylaminomethyl) phenol and 61 parts of silica micropowder are added to the component B, and the conditions are the same as in example 1.
Example 7
A high bond strength epoxy adhesive which cures rapidly at room temperature was prepared as in example 1, except that 88.8 parts bisphenol A epoxy, 5.2 parts EP-4088S, 10.4 parts core-shell silica gel, 63 parts silica fume were added to the A component; 94 parts of polyester modified beta-hydroxythiol A2, 2.1 parts of 2,4, 6-tris (dimethylaminomethyl) phenol and 63 parts of silica micropowder are added to the component B, and the rest conditions are the same as in example 1.
Example 8
A high bond strength epoxy adhesive which cures rapidly at room temperature was prepared as in example 1, except that 91.6 parts bisphenol A epoxy, 5.4 parts EP-4088S, 10.8 parts core-shell silica gel, 65 parts silica fume were added to the A component; 97 parts of polyester modified beta-hydroxyl mercaptan A2, 2.2 parts of 2,4, 6-tris (dimethylaminomethyl) phenol and 65 parts of silica micropowder are added into the component B, and the rest conditions are the same as in the example 1.
Example 9
A high bond strength epoxy adhesive which cures rapidly at room temperature was prepared as in example 1, except that 93.5 parts bisphenol A epoxy, 5.5 parts EP-4088S, 11.0 parts core-shell silica gel, 66 parts silica fume were added to the A component; 99 parts of polyester modified beta-hydroxyl mercaptan A2, 2.2 parts of 2,4, 6-tris (dimethylaminomethyl) phenol and 66 parts of silicon micropowder are added into the component B, and the rest conditions are the same as in the example 1.
Comparative example 1
A room temperature fast curing two-component epoxy glue was prepared as in example 1, except that the polyester modified beta-hydroxythiol A1 was replaced with the same weight parts of TMPMP in the B component, with the remainder being the same as in example 1.
Comparative example 2
A room temperature fast curing two-component epoxy glue was prepared as in example 1, except that the polyester modified beta hydroxythiol A1 was replaced with the same weight parts of PETMP in the B component, with the remainder being the same as in example 1.
Comparative example 3
A two-component epoxy adhesive which was rapidly cured at room temperature was prepared as in example 1, except that the polyester-modified beta-hydroxythiol A1 was replaced with Capcure-3800 parts by weight in the B component, with the remaining conditions being the same as in example 1.
Comparative example 4
A two-component epoxy adhesive which was rapidly cured at room temperature was prepared as in example 1, except that the polyester-modified beta-hydroxythiol A1 was replaced with the same parts by weight of GPM-800 in the B component, with the remaining conditions being the same as in example 1.
Comparative example 5
A room temperature fast curing two-part epoxy glue was prepared as in example 1, except that 85 parts of polyester modified beta-hydroxythiol A1 was added to the B-part, with the remainder of the conditions being the same as in example 1.
Comparative example 6
A two-component epoxy adhesive which was rapidly cured at room temperature was prepared as in example 1, except that 105 parts of polyester-modified beta-hydroxythiol A1 was added to the B component, and the other conditions were the same as in example 1.
Test case
(1) Surface drying time:
Sample preparation: and uniformly mixing A, B components according to the mass ratio of 1:1, and extruding the mixture into a corresponding die to obtain the surface dry test sample.
The testing process comprises the following steps: the end of the finger was rubbed with absolute ethanol and gently contacted with three different areas of the sample surface, and the above procedure was repeated at appropriate intervals until no sample was adhered to the finger. The time elapsed after sample preparation was completed until the sample did not adhere to the finger was recorded.
(2) Adhesive strength:
Sample preparation: and uniformly mixing A, B components according to the mass ratio of 1:1, extruding the mixture on an iron sheet, pressing the other iron sheet, and curing at room temperature (25 ℃) for 24 hours to obtain the bonding test sample. When the sample is prepared, the two iron sheets are aligned as precisely as possible, and the thickness of the adhesive layer is uniform and consistent as much as possible. The bonding surface length of the test specimen was 12.5mm and the width was 25mm, and the thickness of the specimen was controlled to 0.2mm by a wire.
The testing process comprises the following steps: the sample was clamped symmetrically on the clamp at a distance of 50mm from the nearest bonding end. During clamping, the clamp and the sample do not move relatively, the long axis of the sample is kept consistent with the force application direction, and the long axis of the sample is kept consistent with the center line of the clamp. The stretching rate is 5mm/min during the test, in order to ensure the accuracy of the test result, the number of samples is not less than 3, and the average value is taken as the final result.
(3) Adhesive strength after high temperature and high humidity experiment:
Sample preparation: and (3) preparing a sample with the same bonding strength.
The treatment process comprises the following steps: and (3) placing the prepared sample into a high-temperature high-humidity test box, wherein the temperature of the test box is 85 ℃, the humidity is 85% RH, and the treatment time is 168 hours.
The testing process comprises the following steps: and testing the same adhesive strength.
Table 1 performance test data for the preparation examples and examples
① Testing for 60min, curing at room temperature, and heating for curing
From the data in the table it can be derived that:
By comparing and analyzing the comparative example 1, the comparative example 2 and the example 1, the curing agent of the two-component epoxy glue using the polyester modified beta-hydroxy thiol A1 can be cured at room temperature and has stronger bonding strength compared with the common commercial tri-functional and tetra-functional polythiol curing agents.
By comparing and analyzing the comparative example 3, the comparative example 4 and the example 1, the polyester modified beta-hydroxy mercaptan A1 is adopted as the curing agent of the bi-component epoxy glue, compared with the common commercial polyether mercaptan, the room temperature curing speed can be increased, the bonding strength after curing is improved, and the bonding strength after high temperature and high humidity experiments can reach 6.5MPa.
By comparative analysis and examples 1-9, it can be seen that the surface drying time is less than 3min, the bonding strength is greater than 15MPa, and the bonding strength after high-temperature and high-humidity experiments is greater than 5MPa by adopting the polyester modified beta hydroxyl mercaptan A1 as the curing agent of the bi-component epoxy adhesive.
From comparative analysis of comparative example 5, comparative example 6 and example 1, it can be seen that when the part of the curing agent is added beyond the range, the tack-free time reaches 4 minutes when 105 parts of polyester modified beta-hydroxythiol A1 is added, the adhesive strength is 12.6MPa, and the adhesive strength after high temperature and high humidity experiments is greatly reduced; when 85 parts of polyester modified beta hydroxyl mercaptan A1 is added, the surface drying time reaches 5min, the bonding strength is changed to 13.3MPa, and the bonding strength after high-temperature high-humidity experiments is greatly reduced;
In conclusion, the prepared polyester modified beta hydroxyl mercaptan A1 is used as a curing agent of the bi-component epoxy adhesive, the purpose of rapid curing can be achieved after the epoxy adhesive is cured, the adhesive strength is high, the adhesive strength after a high-temperature high-humidity experiment can also keep excellent adhesive strength, and the adhesive has high use value.
Example 10
A room temperature fast curing high bond strength epoxy adhesive was prepared as in example 1, except that bisphenol A type epoxy resin was replaced with the same parts by weight of bisphenol F type epoxy resin in the A component, and the remaining conditions were the same as in example 1.
Example 11
A room temperature fast curing high bond strength epoxy adhesive was prepared as in example 1, except that the bisphenol A type epoxy resin was replaced with the same parts by weight of the glycidyl ester type epoxy resin in the A component, and the remaining conditions were the same as in example 1.
Example 12
A room temperature fast curing high bond strength epoxy adhesive was prepared as in example 1, except that the bisphenol A type epoxy resin was replaced with the same parts by weight of glycidylamine type epoxy resin in the A component, and the remaining conditions were the same as in example 1.
Example 13
A room temperature fast curing high bond strength epoxy adhesive was prepared as in example 1, except that the bisphenol A type epoxy resin was replaced with the same parts by weight of the cycloaliphatic epoxy resin in the A component, with the remaining conditions being the same as in example 1.
Example 14
A room temperature fast curing high bond strength epoxy adhesive was prepared as in example 1, except that EP-4088S was replaced with the same parts by weight of 1, 4-butanediol diglycidyl ether in the A component, with the remainder of the conditions as in example 1.
Example 15
A room temperature fast curing high bond strength epoxy adhesive was prepared as in example 1, except that EP-4088S was replaced with the same parts by weight of polypropylene glycol diglycidyl ether in the A component, with the remainder of the conditions as in example 1.
Example 16
A room temperature fast curing high bond strength epoxy adhesive was prepared as in example 1, except that EP-4088S was replaced with the same parts by weight of a carbon ten-to-tetradecyl glycidyl ether in the A component, with the remaining conditions being the same as in example 1.
Example 17
A room temperature fast curing high bond strength epoxy adhesive was prepared as in example 1, except that EP-4088S was replaced with the same weight parts of benzyl glycidyl ether in the A component, with the remainder being the same as in example 1.
Example 18
A room temperature fast curing high bond strength epoxy adhesive was prepared as in example 1, except that EP-4088S was replaced with the same parts by weight of 1, 4-cyclohexanedimethanol diglycidyl ether in the A component, with the remainder of the conditions as in example 1.
Example 19
A room temperature fast curing high bond strength epoxy adhesive was prepared as in example 1, except that EP-4088S was replaced in the A component with the same parts by weight of pentaerythritol tetraglycidyl ether, with the remainder being the same as in example 1.
Example 20
A room temperature fast curing high bond strength epoxy adhesive was prepared as in example 1, except that 2,4, 6-tris (dimethylaminomethyl) phenol was replaced with the same parts by weight of benzyl dimethylamine in the A-component, with the remaining conditions being the same as in example 1.
Example 21
A room temperature fast cure high bond strength epoxy adhesive was prepared as in example 1 except that 2,4, 6-tris (dimethylaminomethyl) phenol was replaced with the same parts by weight of 2-methylimidazole in the A-component, with the remainder being the same as in example 1.
Example 22
A room temperature fast cure high bond strength epoxy adhesive was prepared as in example 1 except that 2,4, 6-tris (dimethylaminomethyl) phenol was replaced with the same parts by weight of 2-phenylimidazole in the A-component, with the remainder being the same as in example 1.
Example 23
A room temperature fast cure high bond strength epoxy adhesive was prepared as in example 1 except that 2,4, 6-tris (dimethylaminomethyl) phenol was replaced with the same parts by weight of 2-ethyl-4-methylimidazole in the A component, with the remainder being the same as in example 1.
Although embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives, and variations may be made in the above embodiments by those skilled in the art without departing from the spirit and principles of the invention.
Claims (9)
1. The high-adhesive-strength epoxy adhesive capable of being quickly cured at room temperature comprises a component A and a component B, and is characterized in that,
The component A comprises the following raw materials in parts by weight: 85-95 parts of epoxy resin, 5-6 parts of diluent, 10-12 parts of flexibilizer, 60-70 parts of filler, 1-5 parts of thixotropic agent, 1-10 parts of first coupling agent, 0.5-3 parts of defoamer and 0.1-1 part of colorant;
The component B comprises the following raw materials in parts by weight: 90 to 100 parts of polyester modified beta hydroxyl mercaptan, 1.5 to 2.5 parts of accelerator, 60 to 70 parts of filler, 1 to 5 parts of thixotropic agent, 1 to 10 parts of second coupling agent and 0.5 to 3 parts of defoamer;
the polyester modified beta hydroxyl mercaptan has a structure shown in a general formula (I):
wherein n is a positive integer from 1 to 4, and n is not equal to 1.
2. The room temperature rapid curing high bond strength epoxy glue of claim 1, wherein the polyester modified beta hydroxyl mercaptan is prepared by the following steps:
(1) Ring-opening polymerization: adding trimethylolpropane, epsilon-caprolactone and a first catalyst into a reaction vessel, and heating and reacting under the protection of inert gas to obtain a ring-opening polymerization product;
(2) Addition reaction: mixing, stirring and heating the ring-opening polymerization product, the second catalyst and epichlorohydrin, and distilling to remove epichlorohydrin to obtain an addition reaction product;
(3) Nucleophilic substitution: and (3) dissolving the addition reaction product in a solvent, dropwise adding a sodium hydrosulfide aqueous solution, after the stirring reaction is finished, dropwise adding hydrochloric acid into the reaction solution to neutralize to pH=6-7, removing the solvent by rotary evaporation, and purifying by short-path distillation to obtain the final product polyester modified beta-hydroxyl mercaptan.
3. The room temperature fast cure high bond strength epoxy glue of claim 2, wherein the molar ratio of trimethylolpropane to epsilon-caprolactone is 1 (3-12).
4. The room temperature rapid curing high adhesive strength epoxy glue according to claim 2, wherein the reaction temperature in the step (1) of the preparation method of the polyester modified beta hydroxyl mercaptan is 100-130 ℃ and the reaction time is 12-36h;
The reaction temperature in the step (2) of the preparation method of the polyester modified beta-hydroxyl mercaptan is 80-120 ℃ and the reaction time is 2-4h;
the reaction temperature in the step (3) of the preparation method of the polyester modified beta-hydroxyl mercaptan is 50-60 ℃ and the reaction time is 12-24h.
5. The room temperature rapid cure high bond strength epoxy glue of claim 1, wherein the epoxy resin comprises one or more combinations of bisphenol a type epoxy resin, bisphenol F type epoxy resin, glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, cycloaliphatic epoxy resin.
6. The room temperature quick cure high bond strength epoxy adhesive of claim 1, wherein the diluent comprises one or more combinations of 1, 4-butanediol diglycidyl ether, polypropylene glycol diglycidyl ether, C 10 to C 14 alkyl glycidyl ether, benzyl glycidyl ether, 1, 4-cyclohexanedimethanol diglycidyl ether, pentaerythritol tetraglycidyl ether, dicyclopentadiene type diglycidyl ether.
7. The room temperature rapid cure high bond strength epoxy glue of claim 1, wherein the first coupling agent comprises one or more combinations of vinyl tris (2-methoxyethoxy) silane, gamma- (methacryloyloxy) propyl trimethoxysilane, gamma-glycidoxypropyl trimethoxysilane; the second coupling agent comprises one or more of gamma-aminopropyl triethoxysilane, gamma-mercaptopropyl triethoxysilane, beta-hydroxyethyl-gamma-aminopropyl triethoxysilane.
8. The room temperature rapid cure high bond strength epoxy glue of claim 1, wherein the accelerator comprises a combination of one or more of 2,4, 6-tris (dimethylaminomethyl) phenol, benzyl dimethylamine, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole and modified imidazole.
9. A method for preparing a room temperature fast curing high bond strength epoxy glue as defined in any one of claims 1 to 8, comprising:
(1) And (3) preparation of a component A: respectively adding epoxy resin, a diluent, a toughening agent, a filler, a thixotropic agent, a first coupling agent, a defoaming agent and a colorant into a stirring kettle according to weight proportion, and stirring in vacuum until the components are completely and uniformly dispersed; placing the stirred glue solution into a planetary homogenizer for mixing and defoaming, and obtaining a component A after the defoaming is completed;
(2) And (3) preparing a component B: adding polyester modified beta hydroxyl mercaptan, an accelerator, a filler, a thixotropic agent, a second coupling agent and a defoaming agent into a stirring kettle respectively according to the weight proportion, and stirring until the polyester modified beta hydroxyl mercaptan is completely dispersed uniformly; and (3) placing the stirred glue solution in a planetary homogenizer for mixing and defoaming, and obtaining the component B after the defoaming is completed.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01185319A (en) * | 1988-01-18 | 1989-07-24 | Matsushita Electric Works Ltd | Epoxy resin molding material |
| FR2912751A1 (en) * | 2007-02-16 | 2008-08-22 | Arkema France | PROCESS FOR THE PREPARATION OF POLYLACTONES AND POLYLACTAMES |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3021755B2 (en) * | 1990-04-19 | 2000-03-15 | 日本油脂株式会社 | Thermosetting composition, latent hydroxyl compound or latent thiol compound and method for producing the same |
| US9920006B2 (en) * | 2016-06-28 | 2018-03-20 | Prc-Desoto International, Inc. | Prepolymers exhibiting rapid development of physical properties |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01185319A (en) * | 1988-01-18 | 1989-07-24 | Matsushita Electric Works Ltd | Epoxy resin molding material |
| FR2912751A1 (en) * | 2007-02-16 | 2008-08-22 | Arkema France | PROCESS FOR THE PREPARATION OF POLYLACTONES AND POLYLACTAMES |
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