CN112646523A - High-performance medium-temperature curing single-component epoxy structural adhesive and preparation method thereof - Google Patents
High-performance medium-temperature curing single-component epoxy structural adhesive and preparation method thereof Download PDFInfo
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- CN112646523A CN112646523A CN202011536561.5A CN202011536561A CN112646523A CN 112646523 A CN112646523 A CN 112646523A CN 202011536561 A CN202011536561 A CN 202011536561A CN 112646523 A CN112646523 A CN 112646523A
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- epoxy resin
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- 239000000853 adhesive Substances 0.000 title claims abstract description 75
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 75
- 239000004593 Epoxy Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000003822 epoxy resin Substances 0.000 claims abstract description 27
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 27
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 17
- 230000009974 thixotropic effect Effects 0.000 claims abstract description 17
- 239000000945 filler Substances 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 239000003085 diluting agent Substances 0.000 claims abstract description 14
- 239000012745 toughening agent Substances 0.000 claims abstract description 14
- 239000007822 coupling agent Substances 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- 150000003672 ureas Chemical class 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 239000011258 core-shell material Substances 0.000 claims description 4
- 229920001971 elastomer Polymers 0.000 claims description 4
- 150000002460 imidazoles Chemical class 0.000 claims description 4
- 229920002635 polyurethane Polymers 0.000 claims description 4
- 239000004814 polyurethane Substances 0.000 claims description 4
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 claims description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical group NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 3
- 229910021485 fumed silica Inorganic materials 0.000 claims description 3
- 230000002209 hydrophobic effect Effects 0.000 claims description 3
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 3
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 2
- NKVCYHYQKKNFJI-UHFFFAOYSA-N 2-(hexacosan-13-yloxymethyl)oxirane Chemical compound CCCCCCCCCCCCCC(CCCCCCCCCCCC)OCC1CO1 NKVCYHYQKKNFJI-UHFFFAOYSA-N 0.000 claims description 2
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 claims description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 claims description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- XUCHXOAWJMEFLF-UHFFFAOYSA-N bisphenol F diglycidyl ether Chemical compound C1OC1COC(C=C1)=CC=C1CC(C=C1)=CC=C1OCC1CO1 XUCHXOAWJMEFLF-UHFFFAOYSA-N 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 239000004359 castor oil Substances 0.000 claims description 2
- 235000019438 castor oil Nutrition 0.000 claims description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims 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 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 1
- 229920001296 polysiloxane Polymers 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 12
- 238000001723 curing Methods 0.000 description 24
- 239000000463 material Substances 0.000 description 4
- 238000005476 soldering Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 229920004482 WACKER® Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000013008 moisture curing Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
- C08G59/4021—Ureas; Thioureas; Guanidines; Dicyandiamides
-
- 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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
A high-performance medium-temperature curing single-component epoxy structural adhesive comprises the following components in parts by weight: 100 parts of epoxy resin; 0-30 parts of a diluent; 10-15 parts of a latent curing agent; 30-40 parts of a toughening agent; 3-7 parts of an accelerator; 3-7 parts of thixotropic reinforcing agent; 3-5 parts of a coupling agent; 20-30 parts of a filler. The invention also provides a preparation method of the structural adhesive, which comprises the following steps: 1) taking the epoxy resin, the diluent, the toughening agent, the filler and the thixotropic reinforcing agent according to the proportion, and uniformly stirring; 2) vacuum dewatering at 100 deg.c, cooling to room temperature, mixing the latent curing agent, promoter and coupling agent in certain proportion, stirring at 40 deg.c, and vacuum defoaming to obtain the structural adhesive. The structural adhesive has high toughness, high bonding strength and long storage period, can resist high temperature (up to 280 ℃) for a short time, and can effectively meet the use requirement of the market on the single-component epoxy structural adhesive.
Description
Technical Field
The invention relates to the field of adhesives, in particular to a high-performance medium-temperature curing single-component epoxy structural adhesive and a preparation method thereof.
Background
The single-component epoxy structural adhesive has the advantages of only one component without metering and mixing, convenient operation, no solvent, environmental protection, good adhesion to various base materials, low curing shrinkage, environmental resistance and the like, and is widely applied to the industries of automobile industry, building manufacture, electronic communication and the like.
The one-component epoxy structural adhesive is classified into a moisture curing type and a heat curing type. The curing temperature can be roughly divided into low-temperature (less than or equal to 80 ℃) curing type single-component epoxy, medium-temperature (80-150 ℃) curing type single-component epoxy and high-temperature (more than or equal to 150 ℃) curing type single-component epoxy.
The existing medium-temperature curing epoxy structural adhesive is mainly used for packaging sealing and structural bonding in industries such as electronic printed circuits, medical appliances and the like, however, the existing medium-temperature curing single-component epoxy structural adhesive often has the problems of low toughness and short storage time, and the problems need to be solved urgently along with the continuous increase of market demands on the single-component epoxy adhesive.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the high-performance medium-temperature curing single-component epoxy structural adhesive which has the advantages of high toughness, high bonding strength, long storage period, short-time high temperature resistance (up to 280 ℃), and capability of effectively meeting the use requirements of the market on the single-component epoxy structural adhesive.
The technical scheme of the invention is as follows: a high-performance medium-temperature curing single-component epoxy structural adhesive comprises the following components in parts by weight:
100 parts of epoxy resin;
0-30 parts of a diluent;
10-15 parts of a latent curing agent;
30-40 parts of a toughening agent;
3-7 parts of an accelerator;
3-7 parts of thixotropic reinforcing agent;
3-5 parts of a coupling agent;
20-30 parts of a filler.
Preferably, the structural adhesive comprises the following components in parts by weight: 100 parts of epoxy resin, 0-25 parts of diluent, 10-12 parts of latent curing agent, 30-35 parts of toughening agent, 4-6 parts of accelerator, 5-7 parts of thixotropic reinforcing agent, 3-5 parts of coupling agent and 20-25 parts of filler.
Further, the epoxy resin is any one or a mixture of bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, castor oil modified epoxy resin, polyurethane modified epoxy resin, organosilicon modified epoxy resin and acrylate modified epoxy resin.
Furthermore, the diluent is one or a mixture of more of propylene oxide butyl ether, dodecyl-tetradecyl glycidyl ether, 1, 4-butanediol diglycidyl ether and 1, 6-hexanediol diglycidyl ether, and the coupling agent is one or a mixture of more of gamma- (2, 3-glycidoxy) propyl trimethoxy silane, gamma-methacryloxypropyl trimethoxy silane and N- (beta-aminoethyl) -gamma-aminopropyl trimethoxy silane.
Further, the latent curing agent is dicyandiamide or hydrazide.
Further, the toughening agent is core-shell polymer and liquid rubber.
Furthermore, the accelerant is any one or a mixture of imidazole, imidazole derivatives and substituted urea.
Further, the thixotropic reinforcing agent is hydrophobic fumed silica.
Further, the filler is any one or a mixture of several of nano calcium carbonate, silica micropowder, calcium oxide, mica powder, talcum powder and kaolin.
The preparation method of the structural adhesive comprises the following steps:
1) taking the epoxy resin, the diluent, the toughening agent, the filler and the thixotropic reinforcing agent according to the proportion, and uniformly stirring;
2) vacuum dewatering at 100 deg.c, cooling to room temperature, mixing the latent curing agent, promoter and coupling agent in certain proportion, stirring at 40 deg.c, and vacuum defoaming to obtain the structural adhesive.
Adopt above-mentioned technical scheme to have following beneficial effect:
1. according to the single-component epoxy structural adhesive provided by the invention, the epoxy resin is used as the main resin, and the filler and the thixotropic reinforcing agent are cooperatively used as the reinforcing agent, so that the structural adhesive has good temperature resistance and extremely high bonding strength after being cured; meanwhile, the core-shell polymer and the liquid rubber are used for synergistic toughening, so that the toughness of a glue layer after the structural glue is cured is excellent, the problem of degumming or cracking can not occur even after reflow soldering or wave soldering at the temperature of 280 ℃ for a short time, and the application range of the structural glue can be greatly improved; in addition, imidazole derivatives and substituted urea are used as a synergistic accelerator, the disadvantage that the substituted urea accelerator needs to be cured at high temperature is made up, the structural adhesive can be cured at the temperature as low as 100 ℃, the advantage of excellent stability of the substituted urea accelerator is kept, and the storage period of the structural adhesive is 2 months at normal temperature and 12 months at low temperature (-20 ℃).
2. According to the single-component epoxy structural adhesive provided by the invention, the added diluent dilutes solid epoxy at high temperature, so that the components are conveniently added, the operability of the finished adhesive is excellent, and if the content is higher than 30 parts, the thixotropic property of the finished adhesive is reduced; the added latent curing agent is used as a hardening agent of the adhesive, the adhesive can be quickly cured and crosslinked to generate bonding force when reaching a certain temperature, if the content is lower than 10 parts, the adhesive is not completely cured and the bonding performance is reduced, and if the content is higher than 15 parts, the adhesive is excessively crosslinked and the bonding performance is reduced, and meanwhile, the storage stability is reduced; the added toughening agent endows the adhesive with excellent impact resistance, and if the addition amount is insufficient, the phenomenon of insufficient impact resistance can occur; the curing temperature of the adhesive can be greatly reduced by the added accelerant, if the content is lower than 3 parts, incomplete curing of the adhesive and reduction of the bonding performance can occur, and if the content is higher than 7 parts, the storage stability can be reduced; the added thixotropic reinforcing agent endows the adhesive with excellent operability and a certain reinforcing effect, if the content is less than 3 parts, the operability of the adhesive is poor, the strength is reduced, and if the thixotropic reinforcing agent is added too much, the viscosity of the adhesive is increased, and the operability is reduced; the adhesive force of the adhesive can be enhanced by the added coupling agent, if the content is lower than 3 parts, the adhesive force is reduced, and if the content is higher than 5 parts, the viscosity of the adhesive is reduced, so that the operability is poor; the added filler enables the adhesive to have excellent operability, and can reduce the curing shrinkage of the adhesive, if the content is lower than 20 parts, the viscosity of the adhesive is too low, the operability is reduced, and if the content is higher than 30 parts, the viscosity of the adhesive is too high, the operability is reduced, and the bonding force is reduced.
3. According to the preparation method of the structural adhesive, the epoxy resin, the diluent, the toughening agent, the filler and the thixotropic reinforcing agent are uniformly mixed and then are dehydrated in vacuum at the temperature of more than 100 ℃, and the storage stability of the adhesive can be greatly improved and the defects of the cured adhesive layer can be reduced through high-temperature dehydration; after cooling, adding a latent curing agent, an accelerant and a coupling agent, uniformly stirring at the temperature of less than 40 ℃, vacuumizing and defoaming, and controlling the mixing temperature to be less than 40 ℃ so as to avoid high-temperature curing and crosslinking of the adhesive and influence on the later-period storage stability; the vacuum defoaming can reduce the air hole defect of the solidified adhesive layer.
The test of the applicant proves that the single-component epoxy structural adhesive provided by the invention has high toughness after being cured, the impact peeling can reach 58N/mm, the curing temperature can be as low as 100 ℃, the normal-temperature storage can reach 2 months, and the low-temperature (-20 ℃) storage can reach 12 months.
In the present invention, the parts by weight are usually g and kg.
The following is a further description with reference to specific examples.
Detailed Description
In the invention, NPEL-128 is 128 epoxy resin of south Asia new material, 901 solid epoxy resin of NPES-901 south Asia new material, E44 is E44 epoxy resin of Zhuhai Hongchang electronic company, 622 is 1, 4-butanediol diglycidyl ether of Anhui New and remote chemical engineering company, NPER-133L is 133L polyurethane epoxy resin of south Asia, 102C-5 is polyurethane epoxy resin of Tazhou Hengchuang insulation new material, MX-153 is core shell toughening resin of Nippon Chiense company, XA-290 and XA-297 are liquid rubber of Shenzhejiadida company, CTBN is liquid terminal carboxyl nitrile rubber of Lanzhou petrochemical company, DDA5 is superfine dicyandiamide of CVC company, U52M is substituted urea accelerator of CVC company, PN-23 is imidazole derivative accelerator of Nippon gou company, nano calcium carbonate is superfine nano calcium carbonate of Guangxi Huana calcium Limited company, NPES, H18 is hydrophobic fumed silica from Wacker, Germany, and KH-560 is gamma- (2, 3-glycidoxy) propyl trimethoxysilane from Newcastle of Hubei.
Example 1
The components and the weight of the components of the structural adhesive are shown in the following table:
| component name | Mass portion/Kg |
| NPEL-128 | 80 |
| NPER-133L | 25 |
| 102C-5 | 20 |
| MX-153 | 33 |
| XA-297 | 2 |
| DDA5 | 12 |
| U52M | 4 |
| PN-23 | 1.5 |
| Nano calcium carbonate | 20 |
| H18 | 7 |
| KH-560 | 4 |
Example 2
The components and the weight of the components of the structural adhesive are shown in the following table:
| component name | Mass portion/Kg |
| NPES-901 | 55 |
| 622 | 25 |
| NPER-133L | 25 |
| 102C-5 | 20 |
| MX-153 | 33 |
| XA-290 | 2 |
| DDA5 | 12 |
| U52M | 4 |
| PN-23 | 1.5 |
| Nano calcium carbonate | 20 |
| H18 | 7 |
| KH-560 | 4 |
Example 3
The components and the weight of the components of the structural adhesive are shown in the following table:
| component name | Mass portion/Kg |
| E44 | 80 |
| NPER-133L | 25 |
| 102C-5 | 20 |
| MX-153 | 33 |
| CTBN | 1.5 |
| DDA5 | 12 |
| U52M | 4 |
| PN-23 | 1.5 |
| Nano calcium carbonate | 20 |
| H18 | 7 |
| KH-560 | 4 |
Each of the structural adhesives of examples 1-3 was prepared as follows:
1) taking epoxy resin, a diluent, a toughening agent, a filler and a thixotropic reinforcing agent according to a proportion, adding into a planetary stirrer, and highly stirring until the epoxy resin, the diluent, the toughening agent, the filler and the thixotropic reinforcing agent are completely and uniformly dispersed;
2) vacuum dehydrating at 110 deg.C for 10min, cooling to room temperature, proportionally mixing latent curing agent, promoter and coupling agent, stirring at 30 deg.C until they are completely dispersed, and vacuum degassing for 30min to obtain the structural adhesive.
Taking the structural adhesive prepared in the embodiments 1-3 as a test example, taking a product sold in H351 of Shenzhen Shangcheng science and technology Limited as a comparison example, curing at 120 ℃/30min, and testing the adhesive pair according to GB/T7124 to 45≠The normal temperature and 80 ℃ lap shear strength of carbon steel are tested, the normal temperature T peel strength of the adhesive to DC04 steel is tested according to GB/T2791, the normal temperature impact peel strength of the adhesive to DC01 steel is tested according to GB/T36877, and the storage life of the adhesive is tested according to GB/T7123.2. The test results were as follows:
as shown in the above table, compared with the existing commercial products, the single-component epoxy structural adhesive prepared by the invention has the advantages that the bonding strength can reach 31.2MPa, the impact peel strength can reach 58N/mm, the bonding strength is strong and high, and the impact resistance is excellent; meanwhile, the structural adhesive can be cured at the temperature of as low as 100 ℃, so that energy is greatly saved; in addition, the structural adhesive has excellent storage period, can be stored for 2 months at normal temperature and can be stored for one year at low temperature (-20 ℃); finally, the lap joint shear strength of the structural adhesive at 80 ℃ can reach 16.7Mpa, and the structural adhesive does not come unstuck and crack after wave soldering and reflow soldering. Is a structural adhesive with excellent performance.
Claims (10)
1. The high-performance medium-temperature curing single-component epoxy structural adhesive is characterized by comprising the following components in parts by weight:
100 parts of epoxy resin;
0-30 parts of a diluent;
10-15 parts of a latent curing agent;
30-40 parts of a toughening agent;
3-7 parts of an accelerator;
3-7 parts of thixotropic reinforcing agent;
3-5 parts of a coupling agent;
20-30 parts of a filler.
2. The structural adhesive of claim 1, which comprises the following components in parts by weight: 100 parts of epoxy resin, 0-25 parts of diluent, 10-12 parts of latent curing agent, 30-35 parts of toughening agent, 4-6 parts of accelerator, 5-7 parts of thixotropic reinforcing agent, 3-5 parts of coupling agent and 20-25 parts of filler.
3. The structural adhesive according to claim 1 or 2, wherein the epoxy resin is any one or a mixture of bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, castor oil modified epoxy resin, polyurethane modified epoxy resin, silicone modified epoxy resin and acrylate modified epoxy resin.
4. The structural adhesive according to claim 1 or 2, wherein the diluent is one or more of propylene oxide butyl ether, dodecyl-tetradecyl glycidyl ether, 1, 4-butanediol diglycidyl ether and 1, 6-hexanediol diglycidyl ether, and the coupling agent is one or more of gamma- (2, 3-glycidoxy) propyl trimethoxy silane, gamma-methacryloxypropyl trimethoxy silane and N- (beta-aminoethyl) -gamma-aminopropyl trimethoxy silane.
5. The structural adhesive of claim 1 or 2, wherein the latent curing agent is dicyandiamide or hydrazide.
6. The structural adhesive of claim 1 or 2, wherein the toughening agent is a core-shell polymer and a liquid rubber.
7. The structural adhesive of claim 1 or 2, wherein the accelerator is any one or a mixture of imidazole, imidazole derivatives, and substituted urea.
8. The structural adhesive of claim 1 or 2, wherein the thixotropic reinforcing agent is hydrophobic fumed silica.
9. The structural adhesive of claim 1 or 2, wherein the filler is one or more of nano calcium carbonate, silica powder, calcium oxide, mica powder, talc powder and kaolin.
10. A process for the preparation of a structural adhesive according to any of claims 1 to 9, characterized in that it comprises the following steps:
1) taking the epoxy resin, the diluent, the toughening agent, the filler and the thixotropic reinforcing agent according to the proportion, and uniformly stirring;
2) vacuum dewatering at 100 deg.c, cooling to room temperature, mixing the latent curing agent, promoter and coupling agent in certain proportion, stirring at 40 deg.c, and vacuum defoaming to obtain the structural adhesive.
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| CN116535654A (en) * | 2023-05-08 | 2023-08-04 | 哈尔滨工业大学 | Preparation method of low-cost high-toughness epoxy resin |
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| CN114032056A (en) * | 2021-11-15 | 2022-02-11 | 烟台海利泰粘合材料有限公司 | Single-component epoxy resin magnetic steel bonding structural adhesive |
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