CN115124957B - Single-component epoxy resin adhesive easy to store and preparation method thereof - Google Patents
Single-component epoxy resin adhesive easy to store and preparation method thereof Download PDFInfo
- Publication number
- CN115124957B CN115124957B CN202210986604.2A CN202210986604A CN115124957B CN 115124957 B CN115124957 B CN 115124957B CN 202210986604 A CN202210986604 A CN 202210986604A CN 115124957 B CN115124957 B CN 115124957B
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- Prior art keywords
- epoxy resin
- accelerator
- parts
- microcapsule
- resin adhesive
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 261
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 261
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 126
- 239000000853 adhesive Substances 0.000 title claims abstract description 124
- 238000002360 preparation method Methods 0.000 title description 33
- 239000003094 microcapsule Substances 0.000 claims abstract description 121
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 95
- 239000000463 material Substances 0.000 claims abstract description 85
- 239000011162 core material Substances 0.000 claims abstract description 78
- 238000002844 melting Methods 0.000 claims abstract description 48
- 230000008018 melting Effects 0.000 claims abstract description 48
- 238000010438 heat treatment Methods 0.000 claims abstract description 34
- 239000000243 solution Substances 0.000 claims description 50
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical group NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 36
- 238000002156 mixing Methods 0.000 claims description 35
- 239000012071 phase Substances 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 32
- 150000004658 ketimines Chemical class 0.000 claims description 31
- 229920006295 polythiol Polymers 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 30
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- 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 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000011259 mixed solution Substances 0.000 claims description 20
- 239000007764 o/w emulsion Substances 0.000 claims description 18
- 229920000084 Gum arabic Polymers 0.000 claims description 13
- 241000978776 Senegalia senegal Species 0.000 claims description 13
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 13
- 235000010489 acacia gum Nutrition 0.000 claims description 13
- 239000000205 acacia gum Substances 0.000 claims description 13
- 229920001223 polyethylene glycol Polymers 0.000 claims description 13
- 239000002202 Polyethylene glycol Substances 0.000 claims description 12
- 239000008346 aqueous phase Substances 0.000 claims description 12
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 12
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 12
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 12
- 239000003995 emulsifying agent Substances 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 230000001804 emulsifying effect Effects 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- 238000009210 therapy by ultrasound Methods 0.000 claims description 9
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims 1
- 230000009471 action Effects 0.000 abstract description 5
- 238000003860 storage Methods 0.000 abstract description 5
- 238000012545 processing Methods 0.000 abstract description 3
- 239000000945 filler Substances 0.000 description 48
- 230000000052 comparative effect Effects 0.000 description 47
- 239000006087 Silane Coupling Agent Substances 0.000 description 37
- 239000013022 formulation composition Substances 0.000 description 34
- 238000011056 performance test Methods 0.000 description 33
- -1 imidazole compound Chemical class 0.000 description 32
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 30
- 239000002518 antifoaming agent Substances 0.000 description 20
- 229920006332 epoxy adhesive Polymers 0.000 description 18
- 239000003921 oil Substances 0.000 description 18
- 239000002245 particle Substances 0.000 description 18
- 239000013008 thixotropic agent Substances 0.000 description 18
- 239000000843 powder Substances 0.000 description 16
- 239000004202 carbamide Substances 0.000 description 15
- 239000004927 clay Substances 0.000 description 14
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 13
- 125000002723 alicyclic group Chemical group 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 11
- 229910021485 fumed silica Inorganic materials 0.000 description 10
- 230000002209 hydrophobic effect Effects 0.000 description 10
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 9
- 238000001694 spray drying Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 125000003700 epoxy group Chemical group 0.000 description 8
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 7
- ZWOULFZCQXICLZ-UHFFFAOYSA-N 1,3-dimethyl-1-phenylurea Chemical compound CNC(=O)N(C)C1=CC=CC=C1 ZWOULFZCQXICLZ-UHFFFAOYSA-N 0.000 description 6
- 239000002775 capsule Substances 0.000 description 6
- 239000007822 coupling agent Substances 0.000 description 6
- 229920002689 polyvinyl acetate Polymers 0.000 description 6
- 239000011118 polyvinyl acetate Substances 0.000 description 6
- 150000003141 primary amines Chemical class 0.000 description 6
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 4
- 239000004844 aliphatic epoxy resin Substances 0.000 description 4
- 239000004359 castor oil Substances 0.000 description 4
- 235000019438 castor oil Nutrition 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000004845 glycidylamine epoxy resin Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 150000003512 tertiary amines Chemical class 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 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 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000000930 thermomechanical effect Effects 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 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 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 125000005474 octanoate group Chemical group 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 229910021487 silica fume Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000012205 single-component adhesive Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- CXZMPNCYSOLUEK-UHFFFAOYSA-N triethyl propyl silicate Chemical compound CCCO[Si](OCC)(OCC)OCC CXZMPNCYSOLUEK-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 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
- C08G59/68—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 catalysts used
-
- 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
- C08G59/68—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 catalysts used
- C08G59/686—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 catalysts used containing nitrogen
-
- 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
- C08G59/68—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 catalysts used
- C08G59/687—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 catalysts used containing sulfur
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses a single-component epoxy resin adhesive easy to store, which comprises, by weight, 80-100 parts of epoxy resin, 5-15 parts of a latent curing agent and 1-10 parts of a microcapsule accelerator, wherein the microcapsule accelerator comprises a wall material with a melting point of 50-70 ℃ and an accelerator core material. The epoxy resin and the latent curing agent can exist independently and stably at normal temperature, and the microcapsule accelerator has less material occupation, is easy to uniformly disperse in a plurality of components and is surrounded and protected by other components, so that the storage and transportation are convenient, and when the temperature is increased to 50-70 ℃, the wall material of the microcapsule accelerator is melted, the accelerator is released, so that the epoxy resin and the latent curing agent start to react and cure under the action of the accelerator, the heating operation is simple, and the processing and curing during heating are simple.
Description
Technical Field
The invention belongs to the technical field of adhesives, and particularly relates to a single-component epoxy resin adhesive easy to store and a preparation method thereof.
Background
The epoxy resin adhesive has the advantages of good adhesive property, high strength, low curing shrinkage rate and the like, and is widely applied to various fields of industrial production and resident life. Typical applications are: 1. structural bonding between various parts generally requires a certain thixotropic property, high bonding strength and the like; 2. the encapsulation of electronic components generally requires low viscosity, slightly longer operable time, thermal conduction and insulation, and the like; 3. the interior decoration is filled with seam, also called as seam beautifying agent, and mainly requires good thixotropy, good elasticity, strong water resistance and the like.
At present, the epoxy resin adhesive circulated in the market mainly comprises two components, namely an epoxy resin main agent and a curing agent, wherein the main agent mainly comprises: epoxy resin, diluent, filler, other auxiliary agents and the like; the curing agent mainly comprises: curing agent, diluent, filler, other group auxiliary agents and the like. The using process comprises the following steps: firstly, uniformly mixing a main agent and a curing agent according to a required proportion, and then performing sizing or filling operation. In order to reduce the glue mixing flow and improve the construction efficiency, single-component epoxy resin adhesives are also available on the market, namely epoxy resin, curing agent, filler, auxiliary agent and the like are put in one package, and when the single-component epoxy resin adhesive is used, the single-component epoxy resin adhesive is directly extruded and used, but occupies less weight, mainly because the curing agent used by the single-component epoxy resin is generally a latent curing agent, has poor storage stability, and is easy to cause viscosity increase and glue solution curing phenomenon; in addition, one-part epoxy resin curing agents generally require high temperature (typically 150 degrees or more) curing.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a single-component epoxy resin adhesive easy to store and a preparation method thereof, so that the epoxy resin can be stored for a long time at room temperature, and the epoxy resin can be cured and used in a certain time by directly slightly heating without on-site batching and high-temperature curing.
In order to achieve the above purpose, the invention provides a single-component epoxy resin adhesive easy to store, which comprises, by weight, 80-100 parts of epoxy resin, 5-15 parts of a latent curing agent and 1-10 parts of a microcapsule accelerator, wherein the microcapsule accelerator comprises a wall material with a melting point of 50-70 ℃ and an accelerator core material.
By adopting the technical scheme, the epoxy resin and the latent curing agent can independently and stably exist at normal temperature, when the temperature is increased to 50-70 ℃, the wall material of the microcapsule accelerator is melted, and the accelerator is released, so that the epoxy resin and the latent curing agent start to react and cure under the action of the accelerator. The microcapsule accelerator is used, the microcapsule accelerator takes up less material, is used as a small amount of components and can be easily and uniformly dispersed in a large amount of components, the dispersibility is good, the processing and solidification during heating are facilitated, the accelerator overflow can be realized only by reaching the melting point temperature of the capsule wall during heating, the latent curing agent and the epoxy resin are promoted to react, the heating operation is simple, and the heating requirement of 50-70 ℃ is easy to realize. In addition, the microcapsule accelerator as a small component is easily surrounded and protected by a large component, so that each phase exists independently and stably at normal temperature, and the storage and transportation of the epoxy resin are facilitated. Compared with the microcapsule curing agent directly used, the microcapsule curing agent disclosed by the invention has the advantages that the dosage of the microcapsule curing agent is far lower than that of the microcapsule curing agent, so that the dispersibility of the microcapsule curing agent in a material is better, the operation of both a heating process and a mixing process is simpler and easier when the microcapsule curing agent is required to be cured, and finally, the curing effect is better because no complicated operation steps such as higher temperature control, longer heating time and more adding and mixing steps are adopted.
Further, the latent curing agent is dicyandiamide, and the average granularity of the dicyandiamide is 1-2 mu m. The dicyandiamide is used as a curing agent, and four active hydrogens and one cyano group which are formed by molecules of the dicyandiamide can react with an epoxy group to enable the dicyandiamide to open a loop, but the hydrogen bond in the dicyandiamide is relatively stable and is not easy to break, so that the curing temperature of the dicyandiamide is relatively high, and the dicyandiamide is also relatively long in storage time due to high stability, so that the purpose of long-term storage can be achieved. Under normal temperature conditions, dicyandiamide has low solubility in epoxy resin, and after heating to a melting point, the solubility gradually increases, and a curing reaction occurs. The high melting point temperature of about 200 ℃ results in a high curing temperature when used as an epoxy resin curing agent, and the curing temperature when used alone for curing an epoxy resin is generally about 160 ℃. The curing temperature can be reduced, the curing speed can be slowed down, and sufficient bonding time can be provided by using an accelerator. The dicyandiamide has an average granularity of 1-2 mu m, has good dispersibility in epoxy resin and is uniformly dispersed. Since the size of the dicyandiamide particle size can affect the reaction of dicyandiamide in epoxy resin, the smaller the particle size is, the larger the contact area between dicyandiamide and epoxy resin is, the more uniform the dispersion of dicyandiamide in epoxy resin is, and the more sufficient the curing reaction is.
Further, the accelerator core material is one or more of ketimine, polythiol, stannous octoate, imidazole compounds and urea compounds. After the accelerator core material is contacted with the latent curing agent and the epoxy resin, each raw material shows higher reactivity, can be cured at moderate temperature (the epoxy resin is cured at the moderate temperature of 50-110 ℃ generally, and the curing temperature is about 70-80 ℃), and has chemical action or stronger physical action with a matrix to be bonded after the latent curing agent is polymerized with the epoxy resin so as to achieve good bonding effect.
Still further, the accelerator core material is a mixture of ketimine, polythiol, stannous octoate. The polythiol can directly enable the epoxy resin to be quickly cured at room temperature, and a large amount of heat is released during curing, so that the toughness of the epoxy resin can be further improved when the polythiol is used in the epoxy resin. The presence of polythiols can provide curing heat for dicyandiamide, reducing the heat released from curing. The ketimine needs to generate primary amine with active hydrogen after water absorption and decomposition under the condition of high humidity or water existence, and the primary amine can enable the epoxy resin to be directly cured at room temperature, and the curing speed is not too high due to the water absorption and decomposition process. The ketimine is characterized in that primary amine with high activity is provided, the active hydrogen on the amino group is enabled to initiate a small amount of epoxy group ring-opening reaction to obtain hydroxyl by controlling the amount of the primary amine, nitrogen atoms and hydroxyl groups in a primary amine reaction product can also be enabled to initiate the epoxy group ring-opening reaction to obtain hydroxyl, the hydroxyl is bonded with a curing agent, the crosslinking degree of a polymer can be greatly improved, the molecular weight of the polymer is increased, and therefore the mechanical property, the temperature resistance and the ageing resistance of the material are improved.
Further, the mass ratio of ketimine, polythiol and stannous octoate in the mixture is (3-5): 10. The ketimine content needs to be moderate because it needs to be decomposed by water absorption to crosslink and cure, and when it is the component, it can just absorb the corresponding water to perform a curing reaction with proper temperature and proper time, avoiding that when the content is too much, it cannot be fully contacted with air to absorb enough water to hydrolyze, and also avoiding that too little of it is insufficient to generate enough primary amine to affect the final curing effect.
Furthermore, the accelerator core material is an imidazole compound, and the imidazole compound is 2-methylimidazole. The curing reaction of 2-methylimidazole and epoxy resin is carried out in two steps, wherein the first step is that tertiary amine nitrogen atoms in 3 positions react with epoxy groups to generate an addition product of 1:1, and secondary amine nitrogen in imidazole is converted into tertiary amine nitrogen after H + on secondary amine nitrogen atoms are transferred; in the second step, the nitrogen atom of secondary amine in the 1-position reacts with epoxy group to generate 1:2 addition compound, and the curing reaction is completed in a chain reaction mode. The 2-methylimidazole is used as an accelerator, so that the curing temperature can be reduced, the curing time can be shortened, the curing speed can be increased, and the use amount of the 2-methylimidazole can be increased when the temperature is lower, so that the curing speed of the epoxy resin can be increased.
Further, the accelerator core material is urea compound, and the urea compound is phenyl dimethyl urea. In the curing reaction, the urea compound is decomposed to form dimethylamine, the dimethylamine reacts with the epoxy resin to form tertiary amine, and the tertiary amine further catalyzes the reaction of the epoxy resin with dicyandiamide. The urea compound can reduce the curing temperature and shorten the curing time.
Further, the wall material is polyethylene glycol or polyvinyl acetate. Polyethylene glycol with molecular weight over 4000 has melting point over 50 deg.c. The melting point of the polyvinyl acetate is about 60 ℃. Therefore, the two materials can exist stably at room temperature, have good compatibility with epoxy resin, have good tightness and can bear certain external force action after being coated with the accelerator, and the prior art can realize a capsule wall which is thin enough to ensure that the microcapsule has higher core content under the condition of small granularity. When the temperature rises to above 50 ℃, polyethylene glycol or polyvinyl acetate capsule wall melts and cracks, and the accelerator overflows to promote the epoxy resin to be solidified under the action of the latent curing agent. The polyethylene glycol with molecular weight 4000, 6000 and 8000 is preferably used as the wall material, the melting point is between 52 ℃ and 63 ℃, the preparation process is mature as the capsule wall material, the stable separation effect on the latent curing agent and the accelerator can be well achieved, and the polyethylene glycol capsule wall can be well compatible with other components due to the nonionic property after being melted, so that the components are mutually dispersed and crosslinked and wound.
Further, the mass ratio of the wall material to the accelerator core material is 1:1-3.
Further, the epoxy resin is an aqueous epoxy resin.
Further, the epoxy resin is one or more of glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, linear aliphatic epoxy resin and alicyclic epoxy resin.
Further, the epoxy resin is alicyclic epoxy resin which is synergistically modified by methyltrimethoxysilane and phenol.
The epoxy resin and the phenol are firstly subjected to ring-opening polymerization of phenolic hydroxyl groups and epoxy groups, the epoxy resin is grafted in a chemical copolymerization mode, benzene rings are introduced into the epoxy resin, silicon atoms are also introduced into the macromolecular structure of the epoxy resin, the modified epoxy resin containing epoxy group long molecular chains in the molecular structure is prepared, the toughness of the epoxy resin is improved due to the flexibility of the epoxy group long molecular chains and the organosilicon, and the temperature resistance of the epoxy resin is improved due to the silicon-oxygen bonds with higher bond energy and the Wen Guan-group benzene rings.
Further, the epoxy resin adhesive also comprises 1-20 parts of filler. The filler can reduce the consumption of epoxy resin and reduce the cost.
Further, the filler is one or more of nano silicon dioxide, silicon micropowder, nano calcium carbonate, nano aluminum oxide, nano aluminum hydroxide, kaolin or clay powder. Preferably, nano aluminum oxide and nano aluminum hydroxide are used as fillers, so that the heat release can be increased to provide curing heat during the curing reaction. Or ceramic powder is preferably used as filler to increase the temperature resistance. The filler may be selected for the adhesive properties.
Further, the epoxy resin adhesive also comprises 1-10 parts of silane coupling agent. The addition of the coupling agent can enhance the connection between inorganic and organic interfaces and improve the connection stability of the material.
Further, the silane coupling agent is one or more of gamma-glycidyl ether oxypropyl trimethoxy silane, vinyl siloxane coupling agent, gamma-epoxidation propoxy triethoxy silane or polysiloxane coupling agent.
Further, the epoxy resin adhesive also comprises 2-5 parts of thixotropic agent, wherein the thixotropic agent is hydrophobic fumed silica or hydrogenated castor oil. The thixotropic agent can increase the molding stability of the material, so that the molded shape can be well maintained after molding, and the periphery is not polluted.
Further, the epoxy resin adhesive also comprises 0.2-0.5 part of defoaming agent, wherein the defoaming agent is an organosilicon defoaming agent. Eliminate the internal bubble of the adhesive, avoid the bubble to exist to influence the pasting performance and the service life.
In order to further achieve the above purpose, the invention also provides a preparation method of the single-component epoxy resin adhesive, which comprises the following steps:
A preparation method of a single-component epoxy resin adhesive easy to store comprises the following steps:
S1, dissolving a dispersing agent and an emulsifying agent in deionized water, and stirring to obtain a water phase solution;
s2, mixing, heating and melting the accelerator core material and the wall material according to a proportion, then dissolving the mixture in dichloromethane, and obtaining an oil phase mixed solution after ultrasonic treatment;
s3, mixing the oil phase mixed solution and the aqueous phase solution in proportion, and emulsifying in a high-speed homogenizer to obtain an oil-in-water emulsion;
S4, adding the oil-in-water emulsion into 0.01g/mL PVA solution, stirring and heating to volatilize the organic solvent, and forming microcapsule solution;
s5, placing the microcapsule solution into a centrifuge, separating and extracting by adopting 8500r/min, and drying to obtain the microcapsule accelerator;
S6, mixing the microcapsule accelerator, the epoxy resin, the latent curing agent and other raw materials according to different proportions, stirring and dispersing, and removing bubbles in vacuum to obtain the epoxy resin adhesive.
Further, in the step S1, the dispersing agent is polyvinylpyrrolidone, the emulsifying agent is a mixed emulsifying agent of sodium dodecyl sulfate and gum arabic, and the mass ratio of the polyvinylpyrrolidone, the sodium dodecyl sulfate and the gum arabic is 1 (0.1-0.5) to 0.5-0.9. When the emulsifier is a mixed emulsifier of sodium dodecyl sulfate and gum arabic, the microcapsule surface is smooth and compact, and the agglomeration is less.
Further, in the step S2, the mixing mass ratio of the accelerator core material and the wall material is (2-5): 1.
Further, in the step S3, the mixing volume ratio of the oil phase mixed solution to the aqueous phase solution is 1 (1.5-3).
Further, in the step S4, the stirring speed is 500-1500r/min. The size of the microcapsules increases with increasing stirring speed. Preferably, the stirring speed is 800r/min.
Further, in step S5, the drying is spray drying, and the drying temperature is 40 ℃. The microcapsule obtained by spray drying has the advantages of large particle size, large core material content, simplicity, low cost and high productivity.
The invention has the following beneficial effects:
1. the epoxy resin adhesive is a single-component adhesive, can be directly heated to medium temperature for curing, does not need to be added with the mixture ratio of two components, has no component regulation and control problem, has good gluing and curing effects, does not need to be cured at high temperature, and is easy to realize and operate in heating and curing.
2. The epoxy resin adhesive can be stored for a long time at normal temperature, has good stability, uses a microcapsule accelerator, has small material occupation, is easily surrounded and protected by a large amount of components, ensures that each phase exists independently and stably at normal temperature, and is convenient for storing and transporting epoxy resin. And because the material occupies less weight, the dispersibility of the material in the epoxy resin is good, the material is convenient for processing and curing during heating, and the accelerator overflow can be realized only by reaching the melting point temperature of the capsule wall during heating to promote the reaction of the latent curing agent and the epoxy resin, so that the heating operation is simple, and the heating requirement temperature is easy to realize.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a single-component epoxy resin adhesive easy to store, which comprises, by weight, 80-100 parts of epoxy resin, 5-15 parts of a latent curing agent and 1-10 parts of a microcapsule accelerator, wherein the microcapsule accelerator comprises a wall material with a melting point of 50-70 ℃ and an accelerator core material.
Specifically, in some embodiments, the latent curing agent is dicyandiamide having an average particle size of 1-2 μm.
Specifically, in some embodiments, the accelerator core material is one or more of ketimine, polythiol, stannous octoate, imidazole-based compounds, urea-based compounds.
Specifically, in some embodiments, the accelerator core is a mixture of ketimines, polythiols, stannous octoates.
Specifically, in some embodiments, the mass ratio of ketimine, polythiol, stannous octoate in the mixture is (3-5): 10.
Specifically, in some embodiments, the accelerator core is an imidazole compound, and the imidazole compound is 2-methylimidazole.
Specifically, in some embodiments, the accelerator core is a urea compound, and the urea compound is phenyl dimethyl urea.
Specifically, in some embodiments, the wall material is polyethylene glycol or polyvinyl acetate. Polyethylene glycols having molecular weights of 4000, 6000, 8000 are preferably used.
Specifically, in some embodiments, the mass ratio of wall material to accelerator core material is 1:1-3.
Specifically, in some embodiments, the epoxy resin is an aqueous epoxy resin.
Specifically, in some embodiments, the epoxy resin is one or more of a glycidyl ether epoxy resin, a glycidyl ester epoxy resin, a glycidyl amine epoxy resin, a linear aliphatic epoxy resin, and an alicyclic epoxy resin.
Specifically, in some embodiments, the epoxy resin is a cycloaliphatic epoxy resin that is synergistically modified with methyltrimethoxysilane and phenol.
Specifically, in some embodiments, the epoxy adhesive further includes 1-20 parts of a filler.
Specifically, in some embodiments, the filler is one or more of nano-silica, micro-silica powder, nano-calcium carbonate, nano-alumina, nano-aluminum hydroxide, kaolin, or clay powder.
Specifically, in some embodiments, the epoxy adhesive further comprises 1-10 parts of a silane coupling agent.
Specifically, in some embodiments, the silane coupling agent is one or more of gamma-glycidoxypropyl trimethoxysilane, vinyl siloxane coupling agents, gamma-epoxypropoxy triethoxysilane, or polysiloxane coupling agents.
Specifically, in some embodiments, the epoxy adhesive further comprises 2-5 parts of a thixotropic agent, which is a hydrophobic fumed silica or hydrogenated castor oil.
Specifically, in some embodiments, the epoxy adhesive further comprises 0.2-0.5 parts of an antifoaming agent, which is an organosilicon antifoaming agent.
Specifically, the preparation method of the single-component epoxy resin adhesive in each embodiment comprises the following steps:
S1, dissolving a dispersing agent and an emulsifying agent in deionized water, and stirring to obtain a water phase solution;
s2, mixing, heating and melting the accelerator core material and the wall material according to a proportion, then dissolving the mixture in dichloromethane, and obtaining an oil phase mixed solution after ultrasonic treatment;
s3, mixing the oil phase mixed solution and the aqueous phase solution in proportion, and emulsifying in a high-speed homogenizer to obtain an oil-in-water emulsion;
S4, adding the oil-in-water emulsion into 0.01g/mL PVA solution, stirring and heating to volatilize the organic solvent, and forming microcapsule solution;
s5, placing the microcapsule solution into a centrifuge, separating and extracting by adopting 8500r/min, and drying to obtain the microcapsule accelerator;
S6, mixing the microcapsule accelerator, the epoxy resin, the latent curing agent and other raw materials according to different proportions, stirring and dispersing, and removing bubbles in vacuum to obtain the epoxy resin adhesive.
In some embodiments, in step S1, the dispersing agent is polyvinylpyrrolidone, the emulsifying agent is a mixed emulsifying agent of sodium dodecyl sulfate and gum arabic, and the mass ratio of polyvinylpyrrolidone, sodium dodecyl sulfate and gum arabic is 1 (0.1-0.5): 0.5-0.9.
In some embodiments, in step S2, the mass ratio of the core material to the wall material is (2-5): 1.
In some embodiments, in step S3, the mixing volume ratio of the oil phase mixture to the aqueous phase solution is 1 (1.5-3).
In some embodiments, in step S4, the stirring speed is 500-1500r/min. Preferably, the stirring speed is 800r/min.
In some embodiments, in step S5, the drying is spray drying at a drying temperature of 40 ℃.
The following is a description of specific examples.
Example 1:
The one-component epoxy resin adhesive easy to store comprises, by weight, 100 parts of epoxy resin, 11 parts of a latent curing agent and 2 parts of a microcapsule accelerator, wherein the microcapsule accelerator comprises a wall material with a melting point of 50-70 ℃ and an accelerator core material.
Specifically, in this example, the latent curing agent was dicyandiamide, and the average particle size of dicyandiamide was 1. Mu.m.
Specifically, in this embodiment, the wall material is polyethylene glycol. The molecular weight is 4000.
Specifically, in this embodiment, the accelerator core material is a mixture of ketimine, polythiol, stannous octoate.
Specifically, in this embodiment, the mass ratio of ketimine, polythiol, stannous octoate in the mixture is 4:5:10.
Specifically, in this embodiment, the mass ratio of the wall material to the core material is 1:2.
Specifically, in this embodiment, the epoxy resin is an alicyclic epoxy resin that is synergistically modified with methyltrimethoxysilane and phenol.
Specifically, the preparation method of the single-component epoxy resin adhesive in the embodiment comprises the following steps:
s1, dissolving polyvinylpyrrolidone, sodium dodecyl sulfate and gum arabic in deionized water according to a mass ratio of 1:0.3:0.7, and stirring to obtain an aqueous phase solution;
S2, mixing, heating and melting the accelerator core material and the wall material according to the mass ratio of 3.5:1, then dissolving in dichloromethane, and carrying out ultrasonic treatment to obtain an oil phase mixed solution;
s3, mixing the oil phase mixed solution and the water phase solution according to the volume ratio of 1:2, and emulsifying in a high-speed homogenizer to obtain an oil-in-water emulsion;
S4, adding the oil-in-water emulsion into 0.01g/mL PVA solution, stirring at a speed of 800r/min, and heating to volatilize the organic solvent to form microcapsule solution;
S5, placing the microcapsule solution into a centrifuge, separating and extracting by adopting 8500r/min, and spray-drying at 40 ℃ to obtain the microcapsule accelerator;
And S6, mixing the microcapsule accelerator, the epoxy resin and the latent curing agent according to the component proportions, stirring and dispersing, and removing bubbles in vacuum to obtain the epoxy resin adhesive.
The specific formulation composition of the epoxy resin adhesive obtained in this example is shown in Table 1, and the performance test results are shown in Table 3.
Example 2:
The one-component epoxy resin adhesive easy to store comprises, by weight, 90 parts of epoxy resin, 6 parts of a latent curing agent and 4 parts of a microcapsule accelerator, wherein the microcapsule accelerator comprises a wall material with a melting point of 50-70 ℃ and an accelerator core material.
The difference from example 1 is that 90 parts of epoxy resin, 6 parts of latent curing agent and 4 parts of microcapsule accelerator are included, and the rest of the arrangement is the same as in example 1.
The preparation method is the same as in example 1.
The specific formulation composition of the epoxy resin adhesive obtained in this example is shown in Table 1, and the performance test results are shown in Table 3.
Example 3:
The one-component epoxy resin adhesive easy to store comprises, by weight, 80 parts of epoxy resin, 15 parts of a latent curing agent and 10 parts of a microcapsule accelerator, wherein the microcapsule accelerator comprises a wall material with a melting point of 50-70 ℃ and an accelerator core material.
The difference from example 1 is that 80 parts of epoxy resin, 15 parts of latent curing agent and 10 parts of microcapsule accelerator are included, and the rest of the arrangement is the same as in example 1.
The preparation method is the same as in example 1.
The specific formulation composition of the epoxy resin adhesive obtained in this example is shown in Table 1, and the performance test results are shown in Table 3.
Example 4:
The one-component epoxy resin adhesive easy to store comprises, by weight, 100 parts of epoxy resin, 11 parts of a latent curing agent and 2 parts of a microcapsule accelerator, wherein the microcapsule accelerator comprises a wall material with a melting point of 50-70 ℃ and an accelerator core material.
Specifically, in this example, the latent curing agent was dicyandiamide, and the average particle size of dicyandiamide was 1.5. Mu.m.
The difference from example 1 is that the dicyandiamide has an average particle size of 1.5. Mu.m, and the rest of the arrangement is the same as in example 1.
The preparation method is the same as in example 1.
The specific formulation composition of the epoxy resin adhesive obtained in this example is shown in Table 1, and the performance test results are shown in Table 3.
Example 5:
The one-component epoxy resin adhesive easy to store comprises, by weight, 100 parts of epoxy resin, 11 parts of a latent curing agent and 2 parts of a microcapsule accelerator, wherein the microcapsule accelerator comprises a wall material with a melting point of 50-70 ℃ and an accelerator core material.
Specifically, in this example, the latent curing agent was dicyandiamide, and the average particle size of dicyandiamide was 2. Mu.m.
The difference from example 1 is that the dicyandiamide has an average particle size of 2. Mu.m, and the rest of the arrangement is the same as in example 1.
The preparation method is the same as in example 1.
The specific formulation composition of the epoxy resin adhesive obtained in this example is shown in Table 1, and the performance test results are shown in Table 3.
Example 6:
The one-component epoxy resin adhesive easy to store comprises, by weight, 100 parts of epoxy resin, 11 parts of a latent curing agent and 2 parts of a microcapsule accelerator, wherein the microcapsule accelerator comprises a wall material with a melting point of 50-70 ℃ and an accelerator core material.
Specifically, in this embodiment, the wall material is polyvinyl acetate.
The difference from example 1 is that the wall material is polyvinyl acetate, and the rest is the same as example 1.
The preparation method is the same as in example 1.
The specific formulation composition of the epoxy resin adhesive obtained in this example is shown in Table 1, and the performance test results are shown in Table 3.
Example 7:
The one-component epoxy resin adhesive easy to store comprises, by weight, 100 parts of epoxy resin, 11 parts of a latent curing agent and 2 parts of a microcapsule accelerator, wherein the microcapsule accelerator comprises a wall material with a melting point of 50-70 ℃ and an accelerator core material.
Specifically, in this embodiment, the mass ratio of ketimine, polythiol, stannous octoate in the mixture is 3:5:10.
The difference from example 1 is that the mass ratio of ketimine, polythiol, stannous octoate in the mixture is 3:5:10, and the rest of the arrangement is the same as in example 1.
The preparation method is the same as in example 1.
The specific formulation composition of the epoxy resin adhesive obtained in this example is shown in Table 1, and the performance test results are shown in Table 3.
Example 8:
The one-component epoxy resin adhesive easy to store comprises, by weight, 100 parts of epoxy resin, 11 parts of a latent curing agent and 2 parts of a microcapsule accelerator, wherein the microcapsule accelerator comprises a wall material with a melting point of 50-70 ℃ and an accelerator core material.
Specifically, in this embodiment, the mass ratio of ketimine, polythiol, stannous octoate in the mixture is 5:5:10.
The difference from example 1 is that the mass ratio of ketimine, polythiol, stannous octoate in the mixture is 5:5:10, and the rest of the arrangement is the same as in example 1.
The preparation method is the same as in example 1.
The specific formulation composition of the epoxy resin adhesive obtained in this example is shown in Table 1, and the performance test results are shown in Table 3.
Example 9:
The one-component epoxy resin adhesive easy to store comprises, by weight, 100 parts of epoxy resin, 11 parts of a latent curing agent and 2 parts of a microcapsule accelerator, wherein the microcapsule accelerator comprises a wall material with a melting point of 50-70 ℃ and an accelerator core material.
Specifically, in this embodiment, the mass ratio of ketimine, polythiol, stannous octoate in the mixture is 5:4:10.
The difference from example 1 is that the mass ratio of ketimine, polythiol, stannous octoate in the mixture is 5:4:10, and the rest of the arrangement is the same as in example 1.
The preparation method is the same as in example 1.
The specific formulation composition of the epoxy resin adhesive obtained in this example is shown in Table 1, and the performance test results are shown in Table 3.
Example 10:
The one-component epoxy resin adhesive easy to store comprises, by weight, 100 parts of epoxy resin, 11 parts of a latent curing agent and 2 parts of a microcapsule accelerator, wherein the microcapsule accelerator comprises a wall material with a melting point of 50-70 ℃ and an accelerator core material.
Specifically, in this embodiment, the mass ratio of ketimine, polythiol, stannous octoate in the mixture is 5:3:10.
The difference from example 1 is that the mass ratio of ketimine, polythiol, stannous octoate in the mixture is 5:3:10, and the rest of the arrangement is the same as in example 1.
The preparation method is the same as in example 1.
The specific formulation composition of the epoxy resin adhesive obtained in this example is shown in Table 1, and the performance test results are shown in Table 3.
Example 11:
The one-component epoxy resin adhesive easy to store comprises, by weight, 100 parts of epoxy resin, 11 parts of a latent curing agent and 2 parts of a microcapsule accelerator, wherein the microcapsule accelerator comprises a wall material with a melting point of 50-70 ℃ and an accelerator core material.
Specifically, in this embodiment, the mass ratio of the wall material to the core material is 1:3.
The difference from example 1 is that the mass ratio of wall material to core material is 1:3, the rest of the settings are the same as in example 1.
Specifically, the preparation method of the single-component epoxy resin adhesive in the embodiment comprises the following steps:
s1, dissolving polyvinylpyrrolidone, sodium dodecyl sulfate and gum arabic in deionized water according to a mass ratio of 1:0.5:0.5, and stirring to obtain an aqueous phase solution;
s2, mixing, heating and melting the accelerator core material and the wall material according to the mass ratio of 5:1, then dissolving in dichloromethane, and carrying out ultrasonic treatment to obtain an oil phase mixed solution;
s3, mixing the oil phase mixed solution and the water phase solution according to the volume ratio of 1:3, and emulsifying in a high-speed homogenizer to obtain an oil-in-water emulsion;
S4, adding the oil-in-water emulsion into 0.01g/mL PVA solution, stirring at a speed of 1000r/min, and heating to volatilize the organic solvent to form microcapsule solution;
S5, placing the microcapsule solution into a centrifuge, separating and extracting by adopting 8500r/min, and spray-drying at 40 ℃ to obtain the microcapsule accelerator;
And S6, mixing the microcapsule accelerator, the epoxy resin and the latent curing agent according to the component proportions, stirring and dispersing, and removing bubbles in vacuum to obtain the epoxy resin adhesive.
The specific formulation composition of the epoxy resin adhesive obtained in this example is shown in Table 1, and the performance test results are shown in Table 3.
Example 12:
The one-component epoxy resin adhesive easy to store comprises, by weight, 100 parts of epoxy resin, 11 parts of a latent curing agent and 2 parts of a microcapsule accelerator, wherein the microcapsule accelerator comprises a wall material with a melting point of 50-70 ℃ and an accelerator core material.
Specifically, in this embodiment, the mass ratio of the wall material to the core material is 1:1.
The difference from example 1 is that the mass ratio of wall material to core material is 1:1, the rest of the settings are the same as in example 1.
Specifically, the preparation method of the single-component epoxy resin adhesive in the embodiment comprises the following steps:
S1, dissolving polyvinylpyrrolidone, sodium dodecyl sulfate and gum arabic in deionized water according to a mass ratio of 1:0.1:0.9, and stirring to obtain an aqueous phase solution;
S2, mixing, heating and melting the accelerator core material and the wall material according to the mass ratio of 2:1, then dissolving in dichloromethane, and carrying out ultrasonic treatment to obtain an oil phase mixed solution;
s3, mixing the oil phase mixed solution and the water phase solution according to the volume ratio of 1:3, and emulsifying in a high-speed homogenizer to obtain an oil-in-water emulsion;
S4, adding the oil-in-water emulsion into 0.01g/mL PVA solution, stirring at a speed of 500r/min, and heating to volatilize the organic solvent to form microcapsule solution;
S5, placing the microcapsule solution into a centrifuge, separating and extracting by adopting 8500r/min, and spray-drying at 40 ℃ to obtain the microcapsule accelerator;
And S6, mixing the microcapsule accelerator, the epoxy resin and the latent curing agent according to the component proportions, stirring and dispersing, and removing bubbles in vacuum to obtain the epoxy resin adhesive.
The specific formulation composition of the epoxy resin adhesive obtained in this example is shown in Table 1, and the performance test results are shown in Table 3.
Example 13:
The one-component epoxy resin adhesive easy to store comprises, by weight, 100 parts of epoxy resin, 11 parts of a latent curing agent and 2 parts of a microcapsule accelerator, wherein the microcapsule accelerator comprises a wall material with a melting point of 50-70 ℃ and an accelerator core material.
Specifically, in this embodiment, the accelerator core material is an imidazole compound, and the imidazole compound is 2-methylimidazole.
The difference from example 1 is that the accelerator core material is an imidazole compound, the imidazole compound is 2-methylimidazole, and the rest of the arrangement is the same as in example 1.
The preparation method is the same as in example 1.
The specific formulation composition of the epoxy resin adhesive obtained in this example is shown in Table 1, and the performance test results are shown in Table 3.
Example 14:
The one-component epoxy resin adhesive easy to store comprises, by weight, 100 parts of epoxy resin, 11 parts of a latent curing agent and 2 parts of a microcapsule accelerator, wherein the microcapsule accelerator comprises a wall material with a melting point of 50-70 ℃ and an accelerator core material.
Specifically, in this embodiment, the accelerator core material is a urea compound, and the urea compound is phenyldimethylurea.
The difference from example 1 is that the accelerator core material is urea compound, the urea compound is phenyldimethylurea, and the rest is the same as example 1.
The preparation method is the same as in example 1.
The specific formulation composition of the epoxy resin adhesive obtained in this example is shown in Table 1, and the performance test results are shown in Table 3.
Example 15:
The one-component epoxy resin adhesive easy to store comprises, by weight, 100 parts of epoxy resin, 11 parts of a latent curing agent and 2 parts of a microcapsule accelerator, wherein the microcapsule accelerator comprises a wall material with a melting point of 50-70 ℃ and an accelerator core material.
Specifically, in this embodiment, the epoxy resin is a glycidylamine epoxy resin.
The difference from example 1 is that the epoxy resin is a glycidylamine type epoxy resin, and the rest is the same as example 1.
The preparation method is the same as in example 1.
The specific formulation composition of the epoxy resin adhesive obtained in this example is shown in Table 1, and the performance test results are shown in Table 3.
Example 16:
The one-component epoxy resin adhesive easy to store comprises, by weight, 100 parts of epoxy resin, 11 parts of a latent curing agent and 2 parts of a microcapsule accelerator, wherein the microcapsule accelerator comprises a wall material with a melting point of 50-70 ℃ and an accelerator core material.
Specifically, in the present embodiment, the epoxy resin is a linear aliphatic epoxy resin and a glycidyl ether epoxy resin.
The difference from example 1 is that the epoxy resin is a linear aliphatic epoxy resin and a glycidyl ether epoxy resin, and the rest is the same as in example 1.
The preparation method is the same as in example 1.
The specific formulation composition of the epoxy resin adhesive obtained in this example is shown in Table 1, and the performance test results are shown in Table 3.
Example 17:
The one-component epoxy resin adhesive easy to store comprises, by weight, 80 parts of epoxy resin, 11 parts of a latent curing agent and 2 parts of a microcapsule accelerator, wherein the microcapsule accelerator comprises a wall material with a melting point of 50-70 ℃ and an accelerator core material.
Specifically, in this embodiment, the epoxy adhesive further includes 20 parts of filler. The filler is nano aluminium hydroxide.
Specifically, in this embodiment, the epoxy resin adhesive further includes 10 parts of a silane coupling agent. The silane coupling agent is gamma-glycidyl ether oxypropyl trimethoxy silane.
The difference from example 1 is that 80 parts of epoxy resin are included, 20 parts of filler are also included, the filler is nano aluminum hydroxide, 10 parts of silane coupling agent is gamma-glycidyl ether oxypropyl trimethoxy silane, and the rest of arrangement is the same as that of example 1.
Specifically, the preparation method of the single-component epoxy resin adhesive in the embodiment comprises the following steps:
s1, dissolving polyvinylpyrrolidone, sodium dodecyl sulfate and gum arabic in deionized water according to a mass ratio of 1:0.3:0.7, and stirring to obtain an aqueous phase solution;
S2, mixing, heating and melting the core material and the wall material according to the mass ratio of 3.5:1, then dissolving in dichloromethane, and carrying out ultrasonic treatment to obtain an oil phase mixed solution;
s3, mixing the oil phase mixed solution and the water phase solution according to the volume ratio of 1:2, and emulsifying in a high-speed homogenizer to obtain an oil-in-water emulsion;
S4, adding the oil-in-water emulsion into 0.01g/mL PVA solution, stirring at a speed of 800r/min, and heating to volatilize the organic solvent to form microcapsule solution;
S5, placing the microcapsule solution into a centrifuge, separating and extracting by adopting 8500r/min, and spray-drying at 40 ℃ to obtain the microcapsule accelerator;
And S6, mixing the microcapsule accelerator, the epoxy resin, the latent curing agent, the filler and the silane coupling agent according to the component proportions, stirring and dispersing, and removing bubbles in vacuum to obtain the epoxy resin adhesive.
The specific formulation composition of the epoxy resin adhesive obtained in this example is shown in Table 2, and the performance test results are shown in Table 3.
Example 18:
The one-component epoxy resin adhesive easy to store comprises, by weight, 80 parts of epoxy resin, 11 parts of a latent curing agent and 2 parts of a microcapsule accelerator, wherein the microcapsule accelerator comprises a wall material with a melting point of 50-70 ℃ and an accelerator core material.
Specifically, in this embodiment, the epoxy adhesive further includes 20 parts of filler. The filler is nano aluminum oxide and nano aluminum hydroxide.
Specifically, in this embodiment, the epoxy resin adhesive further includes 10 parts of a silane coupling agent. The silane coupling agent is gamma-glycidyl ether oxypropyl trimethoxy silane.
The difference from example 1 is that 80 parts of epoxy resin is included, 20 parts of filler is also included, the filler is nano alumina and nano aluminum hydroxide, 10 parts of silane coupling agent is gamma-glycidyl ether oxypropyl trimethoxy silane, and the rest of the arrangement is the same as that of example 1.
The preparation method is the same as in example 17.
The specific formulation composition of the epoxy resin adhesive obtained in this example is shown in Table 2, and the performance test results are shown in Table 3.
Example 19:
The one-component epoxy resin adhesive easy to store comprises, by weight, 90 parts of epoxy resin, 11 parts of a latent curing agent and 2 parts of a microcapsule accelerator, wherein the microcapsule accelerator comprises a wall material with a melting point of 50-70 ℃ and an accelerator core material.
Specifically, in this embodiment, the epoxy adhesive further includes 10 parts of filler. The filler is clay powder.
Specifically, in this embodiment, the epoxy resin adhesive further includes 8 parts of a silane coupling agent. The silane coupling agent is gamma-epoxypropoxy triethoxysilane.
The difference from example 1 is that 90 parts of epoxy resin are included; and also comprises 10 parts of filler, wherein the filler is clay powder; and also comprises 8 parts of silane coupling agent, wherein the silane coupling agent is gamma-epoxypropoxy triethoxysilane; the rest of the arrangement is the same as in example 1.
The preparation method is the same as in example 17.
The specific formulation composition of the epoxy resin adhesive obtained in this example is shown in Table 2, and the performance test results are shown in Table 3.
Example 20:
The one-component epoxy resin adhesive easy to store comprises, by weight, 90 parts of epoxy resin, 11 parts of a latent curing agent and 2 parts of a microcapsule accelerator, wherein the microcapsule accelerator comprises a wall material with a melting point of 50-70 ℃ and an accelerator core material.
Specifically, in this embodiment, the epoxy adhesive further includes 10 parts of filler. The filler is clay powder.
Specifically, in this embodiment, the epoxy resin adhesive further includes 8 parts of a silane coupling agent. The silane coupling agent is gamma-epoxypropoxy triethoxysilane.
Specifically, in this embodiment, the epoxy adhesive further includes 3 parts of a thixotropic agent, which is hydrogenated castor oil.
The difference from example 1 is that 90 parts of epoxy resin are included; and also comprises 10 parts of filler, wherein the filler is clay powder; and also comprises 8 parts of silane coupling agent, wherein the silane coupling agent is gamma-epoxypropoxy triethoxysilane; and further comprises 3 parts of a thixotropic agent, wherein the thixotropic agent is hydrogenated castor oil; the rest of the arrangement is the same as in example 1.
Specifically, the preparation method of the single-component epoxy resin adhesive in the embodiment comprises the following steps:
s1, dissolving polyvinylpyrrolidone, sodium dodecyl sulfate and gum arabic in deionized water according to a mass ratio of 1:0.3:0.7, and stirring to obtain an aqueous phase solution;
S2, mixing, heating and melting the accelerator core material and the wall material according to the mass ratio of 3.5:1, then dissolving in dichloromethane, and carrying out ultrasonic treatment to obtain an oil phase mixed solution;
s3, mixing the oil phase mixed solution and the water phase solution according to the volume ratio of 1:2, and emulsifying in a high-speed homogenizer to obtain an oil-in-water emulsion;
S4, adding the oil-in-water emulsion into 0.01g/mL PVA solution, stirring at a speed of 800r/min, and heating to volatilize the organic solvent to form microcapsule solution;
S5, placing the microcapsule solution into a centrifuge, separating and extracting by adopting 8500r/min, and spray-drying at 40 ℃ to obtain the microcapsule accelerator;
s6, mixing the microcapsule accelerator, the epoxy resin, the latent curing agent, the filler, the silane coupling agent and the thixotropic agent according to the components, stirring and dispersing, and removing bubbles in vacuum to obtain the epoxy resin adhesive.
The specific formulation composition of the epoxy resin adhesive obtained in this example is shown in Table 2, and the performance test results are shown in Table 3.
Example 21:
The one-component epoxy resin adhesive easy to store comprises, by weight, 90 parts of epoxy resin, 11 parts of a latent curing agent and 2 parts of a microcapsule accelerator, wherein the microcapsule accelerator comprises a wall material with a melting point of 50-70 ℃ and an accelerator core material.
Specifically, in this embodiment, the epoxy adhesive further includes 10 parts of filler. The filler is clay powder.
Specifically, in this embodiment, the epoxy resin adhesive further includes 8 parts of a silane coupling agent. The silane coupling agent is gamma-epoxypropoxy triethoxysilane.
Specifically, in this embodiment, the epoxy adhesive further includes 2 parts of a thixotropic agent, which is a hydrophobic fumed silica.
The difference from example 1 is that 90 parts of epoxy resin are included; and also comprises 10 parts of filler, wherein the filler is clay powder; and also comprises 8 parts of silane coupling agent, wherein the silane coupling agent is gamma-epoxypropoxy triethoxysilane; and further comprises 2 parts of thixotropic agent, wherein the thixotropic agent is hydrophobic fumed silica; the rest of the arrangement is the same as in example 1.
The preparation method is the same as in example 20.
The specific formulation composition of the epoxy resin adhesive obtained in this example is shown in Table 2, and the performance test results are shown in Table 3.
Example 22:
The one-component epoxy resin adhesive easy to store comprises, by weight, 90 parts of epoxy resin, 11 parts of a latent curing agent and 2 parts of a microcapsule accelerator, wherein the microcapsule accelerator comprises a wall material with a melting point of 50-70 ℃ and an accelerator core material.
Specifically, in this embodiment, the epoxy adhesive further includes 10 parts of filler. The filler is clay powder.
Specifically, in this embodiment, the epoxy resin adhesive further includes 8 parts of a silane coupling agent. The silane coupling agent is gamma-epoxypropoxy triethoxysilane.
Specifically, in this embodiment, the epoxy adhesive further includes 2 parts of a thixotropic agent, which is a hydrophobic fumed silica.
Specifically, in this embodiment, the epoxy resin adhesive further includes 0.2 part of an antifoaming agent, which is an organosilicon antifoaming agent.
The difference from example 1 is that 90 parts of epoxy resin are included; and also comprises 10 parts of filler, wherein the filler is clay powder; and also comprises 8 parts of silane coupling agent, wherein the silane coupling agent is gamma-epoxypropoxy triethoxysilane; and further comprising 2 parts of a thixotropic agent, hydrophobic fumed silica; and also comprises 0.2 part of defoaming agent, wherein the defoaming agent is organic silicon defoaming agent; the rest of the arrangement is the same as in example 1.
Specifically, the preparation method of the single-component epoxy resin adhesive in the embodiment comprises the following steps:
s1, dissolving polyvinylpyrrolidone, sodium dodecyl sulfate and gum arabic in deionized water according to a mass ratio of 1:0.3:0.7, and stirring to obtain an aqueous phase solution;
S2, mixing, heating and melting the accelerator core material and the wall material according to the mass ratio of 3.5:1, then dissolving in dichloromethane, and carrying out ultrasonic treatment to obtain an oil phase mixed solution;
s3, mixing the oil phase mixed solution and the water phase solution according to the volume ratio of 1:2, and emulsifying in a high-speed homogenizer to obtain an oil-in-water emulsion;
S4, adding the oil-in-water emulsion into 0.01g/mL PVA solution, stirring at a speed of 800r/min, and heating to volatilize the organic solvent to form microcapsule solution;
S5, placing the microcapsule solution into a centrifuge, separating and extracting by adopting 8500r/min, and spray-drying at 40 ℃ to obtain the microcapsule accelerator;
S6, mixing the microcapsule accelerator, the epoxy resin, the latent curing agent, the filler, the silane coupling agent, the thixotropic agent and the defoamer according to the proportion of the components, stirring and dispersing, and removing bubbles in vacuum to obtain the epoxy resin adhesive.
The specific formulation composition of the epoxy resin adhesive obtained in this example is shown in Table 2, and the performance test results are shown in Table 3.
Example 23:
The one-component epoxy resin adhesive easy to store comprises, by weight, 90 parts of epoxy resin, 11 parts of a latent curing agent and 2 parts of a microcapsule accelerator, wherein the microcapsule accelerator comprises a wall material with a melting point of 50-70 ℃ and an accelerator core material.
Specifically, in this embodiment, the epoxy adhesive further includes 10 parts of filler. The filler is clay powder.
Specifically, in this embodiment, the epoxy resin adhesive further includes 8 parts of a silane coupling agent. The silane coupling agent is gamma-epoxypropoxy triethoxysilane.
Specifically, in this embodiment, the epoxy adhesive further includes 2 parts of a thixotropic agent, which is a hydrophobic fumed silica.
Specifically, in this embodiment, the epoxy resin adhesive further includes 0.4 part of an antifoaming agent, which is an organosilicon antifoaming agent.
The difference from example 1 is that 90 parts of epoxy resin are included; and also comprises 10 parts of filler, wherein the filler is clay powder; and also comprises 8 parts of silane coupling agent, wherein the silane coupling agent is gamma-epoxypropoxy triethoxysilane; and further comprising 2 parts of a thixotropic agent, hydrophobic fumed silica; and also comprises 0.4 part of defoaming agent, wherein the defoaming agent is organic silicon defoaming agent; the rest of the arrangement is the same as in example 1.
The preparation method is the same as in example 22.
The specific formulation composition of the epoxy resin adhesive obtained in this example is shown in Table 2, and the performance test results are shown in Table 3.
Example 24:
The one-component epoxy resin adhesive easy to store comprises, by weight, 90 parts of epoxy resin, 11 parts of a latent curing agent and 2 parts of a microcapsule accelerator, wherein the microcapsule accelerator comprises a wall material with a melting point of 50-70 ℃ and an accelerator core material.
Specifically, in this embodiment, the epoxy adhesive further includes 10 parts of filler. The filler is clay powder.
Specifically, in this embodiment, the epoxy resin adhesive further includes 8 parts of a silane coupling agent. The silane coupling agent is gamma-epoxypropoxy triethoxysilane.
Specifically, in this embodiment, the epoxy adhesive further includes 2 parts of a thixotropic agent, which is a hydrophobic fumed silica.
Specifically, in this embodiment, the epoxy resin adhesive further includes 0.5 part of an antifoaming agent, which is an organosilicon antifoaming agent.
The difference from example 1 is that 90 parts of epoxy resin are included; and also comprises 10 parts of filler, wherein the filler is clay powder; and also comprises 8 parts of silane coupling agent, wherein the silane coupling agent is gamma-epoxypropoxy triethoxysilane; and further comprising 2 parts of a thixotropic agent, hydrophobic fumed silica; and also comprises 0.5 part of defoaming agent, wherein the defoaming agent is organic silicon defoaming agent; the rest of the arrangement is the same as in example 1.
The preparation method is the same as in example 22.
The specific formulation composition of the epoxy resin adhesive obtained in this example is shown in Table 2, and the performance test results are shown in Table 3.
Comparative example 1:
a single-component epoxy resin adhesive easy to store comprises, by weight, 100 parts of epoxy resin and 11 parts of latent curing agent.
Specifically, in this comparative example, the latent curing agent was dicyandiamide, and the average particle size of dicyandiamide was 1. Mu.m.
The specific formulation composition of the epoxy resin adhesive obtained in this example is shown in Table 1, and the performance test results are shown in Table 3.
Comparative example 2:
The one-component epoxy resin adhesive easy to store comprises, by weight, 100 parts of epoxy resin, 11 parts of a latent curing agent and 2 parts of a microcapsule accelerator, wherein the microcapsule accelerator comprises a wall material with a melting point of 50-70 ℃ and an accelerator core material.
Specifically, in this comparative example, the latent curing agent was dicyandiamide, and the average particle size of dicyandiamide was 3. Mu.m.
Specifically, in this comparative example, the wall material was polyethylene glycol. The molecular weight is 4000.
Specifically, in this comparative example, the accelerator core material is a mixture of ketimine, polythiol, stannous octoate. The mass ratio of ketimine, polythiol and stannous octoate in the mixture is 4:5:10.
Specifically, in this comparative example, the mass ratio of the wall material to the core material is 1:2.
Specifically, in this comparative example, the epoxy resin was an alicyclic epoxy resin in which methyltrimethoxysilane and phenol were synergistically modified.
The difference from example 1 is that the dicyandiamide has an average particle size of 3 μm and the rest is the same as in example 1.
The specific formulation composition of the epoxy resin adhesive obtained in this example is shown in Table 1, and the performance test results are shown in Table 3.
Comparative example 3:
The one-component epoxy resin adhesive easy to store comprises, by weight, 100 parts of epoxy resin, 11 parts of a latent curing agent and 2 parts of a microcapsule accelerator, wherein the microcapsule accelerator comprises a wall material with a melting point of 50-70 ℃ and an accelerator core material.
Specifically, in this comparative example, the latent curing agent was dicyandiamide, and the average particle size of dicyandiamide was 1. Mu.m.
Specifically, in this comparative example, the wall material was polyethylene glycol. The molecular weight is 10000.
Specifically, in this comparative example, the accelerator core material is a mixture of ketimine, polythiol, stannous octoate. The mass ratio of ketimine, polythiol and stannous octoate in the mixture is 4:5:10.
Specifically, in this comparative example, the mass ratio of the wall material to the core material is 1:2.
Specifically, in this comparative example, the epoxy resin was an alicyclic epoxy resin in which methyltrimethoxysilane and phenol were synergistically modified.
The difference from example 1 is that the wall material is polyethylene glycol, the molecular weight is 10000, and the rest is the same as example 1.
The specific formulation composition of the epoxy resin adhesive obtained in this example is shown in Table 1, and the performance test results are shown in Table 3.
Comparative example 4:
The one-component epoxy resin adhesive easy to store comprises, by weight, 100 parts of epoxy resin, 11 parts of a latent curing agent and 2 parts of a microcapsule accelerator, wherein the microcapsule accelerator comprises a wall material with a melting point of 50-70 ℃ and an accelerator core material.
Specifically, in this comparative example, the latent curing agent was dicyandiamide, and the average particle size of dicyandiamide was 1. Mu.m.
Specifically, in this comparative example, the wall material was polyethylene glycol. The molecular weight is 4000.
Specifically, in this comparative example, the accelerator core material is a mixture of ketimine, polythiol, stannous octoate. The mass ratio of ketimine, polythiol and stannous octoate in the mixture is 4:5:10.
Specifically, in this comparative example, the mass ratio of the wall material to the core material is 3:1.
Specifically, in this comparative example, the epoxy resin was an alicyclic epoxy resin in which methyltrimethoxysilane and phenol were synergistically modified.
The difference from example 1 is that the mass ratio of wall material to core material is 3:1, the rest of the settings are the same as in example 1.
The specific formulation composition of the epoxy resin adhesive obtained in this example is shown in Table 1, and the performance test results are shown in Table 3.
Comparative example 5:
the single-component epoxy resin adhesive easy to store comprises, by weight, 100 parts of epoxy resin, 11 parts of a latent curing agent and 2 parts of an accelerator, wherein the accelerator is an imidazole compound, and the imidazole compound is 2-methylimidazole.
Specifically, in this comparative example, the epoxy resin was an alicyclic epoxy resin in which methyltrimethoxysilane and phenol were synergistically modified.
The difference from example 1 is that the accelerator is directly an imidazole compound, the imidazole compound is 2-methylimidazole, and the rest is the same as example 1.
The specific formulation composition of the epoxy resin adhesive obtained in this example is shown in Table 1, and the performance test results are shown in Table 3.
Comparative example 6:
The single-component epoxy resin adhesive easy to store comprises, by weight, 100 parts of epoxy resin, 11 parts of a latent curing agent and 2 parts of an accelerator, wherein the accelerator is a urea compound, and the urea compound is phenyl dimethyl urea.
Specifically, in this comparative example, the epoxy resin was an alicyclic epoxy resin in which methyltrimethoxysilane and phenol were synergistically modified.
The difference from example 1 is that the accelerator is directly urea compound, the urea compound is phenyl dimethyl urea, and the rest is the same as example 1.
The specific formulation composition of the epoxy resin adhesive obtained in this example is shown in Table 1, and the performance test results are shown in Table 3.
Comparative example 7:
The one-component epoxy resin adhesive easy to store comprises, by weight, 100 parts of epoxy resin, 11 parts of a latent curing agent and 2 parts of an accelerator, wherein the accelerator is ketimine.
Specifically, in this comparative example, the epoxy resin was an alicyclic epoxy resin in which methyltrimethoxysilane and phenol were synergistically modified.
The difference from example 1 is that the accelerator is directly a ketimine and the rest is the same as in example 1.
The specific formulation composition of the epoxy resin adhesive obtained in this example is shown in Table 1, and the performance test results are shown in Table 3.
Comparative example 8:
The one-component epoxy resin adhesive easy to store comprises, by weight, 100 parts of epoxy resin, 11 parts of a latent curing agent and 2 parts of an accelerator, wherein the accelerator is polythiol.
Specifically, in this comparative example, the epoxy resin was an alicyclic epoxy resin in which methyltrimethoxysilane and phenol were synergistically modified.
The difference from example 1 is that the accelerator is directly a polythiol, the rest of the arrangement being the same as in example 1.
The specific formulation composition of the epoxy resin adhesive obtained in this example is shown in Table 1, and the performance test results are shown in Table 3.
Comparative example 9:
The one-component epoxy resin adhesive easy to store comprises, by weight, 100 parts of epoxy resin, 11 parts of a latent curing agent and 2 parts of an accelerator, wherein the accelerator is stannous octoate.
Specifically, in this comparative example, the epoxy resin was an alicyclic epoxy resin in which methyltrimethoxysilane and phenol were synergistically modified.
The difference from example 1 is that the accelerator is directly stannous octoate, the rest of the arrangement is the same as example 1.
The specific formulation composition of the epoxy resin adhesive obtained in this example is shown in Table 1, and the performance test results are shown in Table 3.
The epoxy adhesives of the examples and comparative examples of the present invention were tested as follows:
(1) Curing reaction temperature: determining an optimum curing temperature for curing using a DSC thermo-mechanical analyzer;
(2) Curing reaction speed: determining the curing reaction time at 75 ℃ with a DSC thermo-mechanical analyzer;
(3) Tensile strength: preparing a resin sheet with the thickness of 20 x 40 x 2mm, and testing the tensile strength by using a universal tester;
(4) Viscosity test: viscosity at 25℃was measured according to the standard GB/T22314-2008 method for measuring viscosity of Plastic epoxy resins.
Table 1 formulation composition tables of examples 1 to 16 and comparative examples 1 to 9
Table 2 formulation tables of examples 17 to 24
Table 3 tables of test data for examples 1-24 and comparative examples 1-9
| Project | Optimal curing temperature/. Degree.C | Curing time/min at 75 DEG C | 25 ℃ And 60-day viscosity change rate | Tensile Strength/MPa |
| Example 1 | 83 | 96 | 8％ | 38 |
| Example 2 | 79 | 79 | 5％ | 42 |
| Example 3 | 75 | 68 | 10％ | 43 |
| Example 4 | 86 | 107 | 6％ | 39 |
| Example 5 | 91 | 136 | 5％ | 41 |
| Example 6 | 85 | 102 | 9％ | 28 |
| Example 7 | 87 | 114 | 7％ | 39 |
| Example 8 | 79 | 81 | 10％ | 34 |
| Example 9 | 88 | 119 | 7％ | 33 |
| Example 10 | 94 | 144 | 6％ | 31 |
| Example 11 | 78 | 72 | 9％ | 40 |
| Example 12 | 87 | 115 | 6％ | 35 |
| Example 13 | 105 | 198 | 7％ | 33 |
| Example 14 | 127 | 237 | 6％ | 26 |
| Example 15 | 99 | 158 | 8％ | 34 |
| Example 16 | 96 | 150 | 7％ | 40 |
| Example 17 | 74 | 64 | 6％ | 45 |
| Example 18 | 72 | 62 | 7％ | 41 |
| Example 19 | 83 | 68 | 9％ | 43 |
| Example 20 | 85 | 79 | 6％ | 42 |
| Example 21 | 86 | 90 | 5％ | 43 |
| Example 22 | 88 | 102 | 6％ | 44 |
| Example 23 | 87 | 99 | 5％ | 43 |
| Example 24 | 90 | 107 | 4％ | 42 |
| Comparative example 1 | 163 | ～ | 5％ | 20 |
| Comparative example 2 | 132 | ～ | 9％ | 35 |
| Comparative example 3 | 121 | 226 | 6％ | 47 |
| Comparative example 4 | 106 | 203 | 4％ | 43 |
| Comparative example 5 | 102 | 181 | 15％ | 27 |
| Comparative example 6 | 131 | 303 | 17％ | 23 |
| Comparative example 7 | 145 | 134 | 25％ | 26 |
| Comparative example 8 | 123 | 119 | 31％ | 30 |
| Comparative example 9 | 130 | 124 | 28％ | 23 |
As can be seen from Table 3, the epoxy resin adhesives obtained in examples 1 to 24 using the formulation of the present invention have a preferred minimum curing temperature of 72℃and a minimum curing time of 62 minutes at 75℃and a 60-day viscosity change rate of not more than 10% at 25℃and a tensile strength of not less than 26MPa. Compared with comparative example 1 without the microcapsule accelerator, the optimal curing temperature is obviously reduced, the maximum reduction is about 100 ℃, the applicability and the energy-saving effect are greatly improved, and the heating requirement of about 80 ℃ can be generally achieved. Compared with comparative examples 5-9, in which the accelerator was directly used without the microcapsule accelerator, the 60-day viscosity change rate at 25℃was significantly improved, and the stability was significantly improved. Compared with comparative example 2 using a large-particle-size latent curing agent, the optimum curing temperature is reduced to be close to 60 ℃, and the tensile strength is slightly improved, so that it is seen that the excessively large particle size of the latent curing agent directly affects the curing temperature, and finally, more energy is consumed for liquefying due to the large particle size, so that the curing temperature is obviously increased, but the latent curing agent is finally crosslinked and polymerized with the epoxy resin in a liquid state, so that the toughness after the final crosslinking and polymerization is not greatly changed under the condition that other conditions are unchanged as long as the addition amount of the latent curing agent is the same or similar. The high molecular weight or high content of the wall material resulted in an increase in the optimum cure temperature compared to comparative example 3 using a high molecular weight wall material and comparative example 4 using a high content of the wall material, but the tensile strength of the material also became stronger, probably due to the increased cross-linking polymerization of the wall material with the matrix after melting, as can be seen from the relative decrease in the promoter core material at 25 c for a 60 day rate of change of viscosity, the relative increase of the wall material resulted in a more stable phases. In addition, it can also be confirmed from the results of table 3: 1. the results of examples 1,2 and 3 show that when the amount of the epoxy resin is gradually reduced, the latent curing agent is gradually increased, and the microcapsule accelerator is gradually increased, the optimal curing temperature is gradually reduced, the curing time is gradually shortened, and the speed is increased; 2. the particle size of the latent curing agent has an effect on the optimal curing temperature, and the results of examples 1,4 and 5 show that the larger the particle size is, the higher the optimal curing temperature is; 3. when the accelerator core material is a mixture of ketimine, polythiol and stannous octoate, the results of examples 1, 7 and 8 show that the optimal curing temperature gradually decreases with increasing ketimine component, but the curing time gradually increases, and the results of examples 8, 9 and 10 show that the optimal curing temperature gradually decreases and the curing time gradually shortens with increasing polythiol component, so that proper component preparation is needed to ensure that the curing time is moderate, not fast and slow, and not only sufficient bonding time is available, but also rapid curing is available; 4. the higher the content of the accelerator core material, the faster the curing time and the lower the curing temperature, as can be seen from comparison of the results of examples 1, 11 and 12, but it should be noted that the higher the content of the accelerator core material, the stability of the microcapsules may affect the stability of the adhesive; 5. by selecting appropriate additives, the properties of the adhesive can be changed to have outstanding properties, and as can be seen from the results of examples 17-24, the addition of fillers and coupling agents can increase the tensile properties of the adhesive, particularly aluminum hydroxide and aluminum oxide fillers, can reduce the curing temperature, and can improve the stability of the adhesive by adding defoamers.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (4)
1. The single-component epoxy resin adhesive is characterized by comprising, by weight, 80-100 parts of epoxy resin, 5-15 parts of a latent curing agent and 1-10 parts of a microcapsule accelerator, wherein the microcapsule accelerator comprises a wall material with a melting point of 50-70 ℃ and an accelerator core material, the latent curing agent is dicyandiamide, the average granularity of dicyandiamide is 1-2 mu m, the accelerator core material is a mixture of ketimine, polythiol and stannous octoate, and the mass ratio of the wall material to the accelerator core material is 1:1-3, wherein the wall material is polyethylene glycol with molecular weight of 4000, 6000 or 8000, and the mass ratio of ketimine, polythiol and stannous octoate in the mixture is (3-5): 10.
2. The method for preparing a one-component epoxy resin adhesive easy to store according to claim 1, comprising the steps of:
S1, dissolving a dispersing agent and an emulsifying agent in deionized water, and stirring to obtain a water phase solution;
s2, mixing, heating and melting the accelerator core material and the wall material according to a proportion, then dissolving the mixture in dichloromethane, and obtaining an oil phase mixed solution after ultrasonic treatment;
s3, mixing the oil phase mixed solution and the aqueous phase solution in proportion, and emulsifying in a high-speed homogenizer to obtain an oil-in-water emulsion;
S4, adding the oil-in-water emulsion into 0.01g/mL PVA solution, stirring and heating to volatilize the organic solvent, and forming microcapsule solution;
s5, placing the microcapsule solution into a centrifuge, adopting 8500 r/min for separation and extraction, and drying to obtain the microcapsule accelerator;
and S6, mixing the microcapsule accelerator, the epoxy resin and the latent curing agent according to different proportions, stirring and dispersing, and removing bubbles in vacuum to obtain the epoxy resin adhesive.
3. The method for preparing a one-component epoxy resin adhesive easy to store according to claim 2, wherein in the step S1, the dispersing agent is polyvinylpyrrolidone, the emulsifying agent is a mixed emulsifying agent of sodium dodecyl sulfate and gum arabic, and the mass ratio of polyvinylpyrrolidone, sodium dodecyl sulfate and gum arabic is 1 (0.1-0.5): 0.5-0.9.
4. The method for preparing a one-component epoxy resin adhesive easy to store according to claim 3, wherein in the step S3, the mixing volume ratio of the oil phase mixed solution to the aqueous phase solution is 1 (1.5-3).
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| CN110894412A (en) * | 2019-12-19 | 2020-03-20 | 长安大学 | Accelerator microcapsule and preparation method thereof, single-component epoxy resin grouting material and preparation method thereof |
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