CN113512396A - Bi-component structural adhesive and preparation method and application thereof - Google Patents
Bi-component structural adhesive and preparation method and application thereof Download PDFInfo
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- CN113512396A CN113512396A CN202110541789.1A CN202110541789A CN113512396A CN 113512396 A CN113512396 A CN 113512396A CN 202110541789 A CN202110541789 A CN 202110541789A CN 113512396 A CN113512396 A CN 113512396A
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- 239000000853 adhesive Substances 0.000 title claims abstract description 70
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 60
- 239000000178 monomer Substances 0.000 claims abstract description 110
- 239000000203 mixture Substances 0.000 claims abstract description 48
- 239000003085 diluting agent Substances 0.000 claims abstract description 36
- 239000002994 raw material Substances 0.000 claims abstract description 29
- 229920005862 polyol Polymers 0.000 claims abstract description 27
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 26
- 150000003077 polyols Chemical class 0.000 claims abstract description 26
- 239000000843 powder Substances 0.000 claims abstract description 26
- 230000008719 thickening Effects 0.000 claims abstract description 26
- 229920000642 polymer Polymers 0.000 claims abstract description 24
- 239000012745 toughening agent Substances 0.000 claims abstract description 21
- 239000003999 initiator Substances 0.000 claims abstract description 19
- 150000002978 peroxides Chemical class 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 18
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 18
- 239000003381 stabilizer Substances 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims description 62
- 238000002156 mixing Methods 0.000 claims description 40
- 239000012948 isocyanate Substances 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 18
- 150000002513 isocyanates Chemical class 0.000 claims description 18
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 13
- 239000004593 Epoxy Substances 0.000 claims description 11
- 238000004132 cross linking Methods 0.000 claims description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 10
- -1 2- (phosphonooxy) ethyl Chemical group 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 7
- 230000002378 acidificating effect Effects 0.000 claims description 7
- 229920000570 polyether Polymers 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 5
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 5
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 claims description 5
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims description 5
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 claims description 5
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 5
- 239000004952 Polyamide Substances 0.000 claims description 5
- 239000000440 bentonite Substances 0.000 claims description 5
- 229910000278 bentonite Inorganic materials 0.000 claims description 5
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 5
- 239000001569 carbon dioxide Substances 0.000 claims description 5
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 5
- 230000002209 hydrophobic effect Effects 0.000 claims description 5
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 5
- 229920002647 polyamide Polymers 0.000 claims description 5
- 229920001451 polypropylene glycol Polymers 0.000 claims description 5
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 5
- 229910021485 fumed silica Inorganic materials 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical group OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 3
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical group C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 2
- YXRKNIZYMIXSAD-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical compound O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O YXRKNIZYMIXSAD-UHFFFAOYSA-N 0.000 claims description 2
- OGBWMWKMTUSNKE-UHFFFAOYSA-N 1-(2-methylprop-2-enoyloxy)hexyl 2-methylprop-2-enoate Chemical compound CCCCCC(OC(=O)C(C)=C)OC(=O)C(C)=C OGBWMWKMTUSNKE-UHFFFAOYSA-N 0.000 claims description 2
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 claims description 2
- VOBUAPTXJKMNCT-UHFFFAOYSA-N 1-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound CCCCCC(OC(=O)C=C)OC(=O)C=C VOBUAPTXJKMNCT-UHFFFAOYSA-N 0.000 claims description 2
- NXBXJOWBDCQIHF-UHFFFAOYSA-N 2-[hydroxy-[2-(2-methylprop-2-enoyloxy)ethoxy]phosphoryl]oxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOP(O)(=O)OCCOC(=O)C(C)=C NXBXJOWBDCQIHF-UHFFFAOYSA-N 0.000 claims description 2
- JJRDRFZYKKFYMO-UHFFFAOYSA-N 2-methyl-2-(2-methylbutan-2-ylperoxy)butane Chemical compound CCC(C)(C)OOC(C)(C)CC JJRDRFZYKKFYMO-UHFFFAOYSA-N 0.000 claims description 2
- XOJWAAUYNWGQAU-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCOC(=O)C(C)=C XOJWAAUYNWGQAU-UHFFFAOYSA-N 0.000 claims description 2
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 2
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 claims description 2
- NQSLZEHVGKWKAY-UHFFFAOYSA-N 6-methylheptyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C(C)=C NQSLZEHVGKWKAY-UHFFFAOYSA-N 0.000 claims description 2
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical group C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 2
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 2
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 2
- GYVGXEWAOAAJEU-UHFFFAOYSA-N n,n,4-trimethylaniline Chemical compound CN(C)C1=CC=C(C)C=C1 GYVGXEWAOAAJEU-UHFFFAOYSA-N 0.000 claims description 2
- MKQFOYWMVVVZHN-UHFFFAOYSA-N n,n-diethyl-4-methylcyclohexan-1-amine Chemical compound CCN(CC)C1CCC(C)CC1 MKQFOYWMVVVZHN-UHFFFAOYSA-N 0.000 claims description 2
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical group C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 2
- 229920005906 polyester polyol Polymers 0.000 claims description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 2
- RPJCYXCKWKJCCP-UHFFFAOYSA-N C(C=C)(=O)O.COCOC.CCC Chemical compound C(C=C)(=O)O.COCOC.CCC RPJCYXCKWKJCCP-UHFFFAOYSA-N 0.000 claims 1
- 150000002009 diols Chemical class 0.000 claims 1
- FNVQPLCHYJQMHP-UHFFFAOYSA-N methyl prop-2-enoate oxolane Chemical compound C(C=C)(=O)OC.O1CCCC1 FNVQPLCHYJQMHP-UHFFFAOYSA-N 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 17
- 230000007246 mechanism Effects 0.000 abstract description 13
- 230000008569 process Effects 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 59
- 229910052757 nitrogen Inorganic materials 0.000 description 30
- 239000003292 glue Substances 0.000 description 21
- 239000000047 product Substances 0.000 description 20
- 239000000126 substance Substances 0.000 description 13
- 238000007599 discharging Methods 0.000 description 8
- 229920003023 plastic Polymers 0.000 description 8
- 239000004033 plastic Substances 0.000 description 8
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000004417 polycarbonate Substances 0.000 description 7
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 6
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000010526 radical polymerization reaction Methods 0.000 description 6
- 150000005846 sugar alcohols Polymers 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 229910000838 Al alloy Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 238000007259 addition reaction Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000012994 photoredox catalyst Substances 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- MXHAQQVNGWIJRV-UHFFFAOYSA-N 2-methyloxolane prop-2-enoic acid Chemical compound OC(=O)C=C.CC1CCCO1 MXHAQQVNGWIJRV-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000003522 acrylic cement Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000009659 non-destructive testing Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004383 yellowing 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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- 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
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention provides a bi-component structural adhesive and a preparation method and application thereof. The two-component structural adhesive comprises: a component A and a component B; the preparation raw materials of the component A comprise: monomer diluent, macromolecular monomer mixture containing double bonds and isocyanate groups, pseudoplastic thickening powder, active tertiary amine accelerator and stabilizer; the preparation raw materials of the component B comprise: polyol polymer toughener and peroxide initiator. The invention is designed from the reaction mechanism according to the bonding process requirement in the assembly and manufacturing process of the electronic industry, develops a bi-component structural adhesive product, is particularly applied to bonding of structural members of electronic products, and has excellent bonding stability.
Description
Technical Field
The invention belongs to the technical field of adhesives for electronic products, and particularly relates to a bi-component structural adhesive and a preparation method and application thereof.
Background
The assembly and manufacturing process of electronic products such as mobile phones, notebook computers, tablet computers and the like comprises a large number of bonding processes, and bonded parts mainly comprise bonding of screen (including touch screens) ink glass and plastic frames, bonding of metal keyboard frames and plastic frameworks, bonding of metal shells and plastic frameworks and the like. The main materials of the bonded member include: glass, anode aluminum, ABS (acrylonitrile-butadiene-styrene terpolymer), PC (polycarbonate) plastic or alloy plastic, carbon fiber plate, and the like.
Different from the conventional structural adhesive, the parts of the electronic product are more precise, the bonding process usually mainly adopts a glue dispensing mode, the glue dispensing amount is small and precise, and the structural adhesive required by the bonding process has more special performance requirements. The aperture of the dispensing needle head used for electronic products is between 0.2 and 2mm, so that the glue used is required to have the characteristics of high solid content, low viscosity, high bonding strength (usually more than 10 MPa), appropriate thixotropy and the like, specifically, the phenomena of thread pulling, needle tip residue, needle head blockage and the like are not generated during dispensing, the dispensing needle head can be stably molded on a base material without glue overflow, and the bonding strength is not lower than the specified requirement.
At present, the commonly used dual-component structural adhesive in the market mainly comprises epoxy system structural adhesive, acrylic acid system structural adhesive and polyurethane system structural adhesive, and few precise adhesives specially used in the electronic industry have the problems of unclear reaction mechanism, unstable bonding performance, unclear definition of application, usage and application range and the like.
CN111394013A discloses a nondestructive testing bi-component structural adhesive, a preparation method, an application and an electronic product thereof, the purpose of curing is achieved by adopting a redox reaction mechanism to induce the free radical polymerization of acrylic ester in a system, but the defects are as follows: other raw materials used do not participate in the reaction to form bonds, and the strength of the raw materials is limited; the low boiling point monomer used is easy to be dissociated and volatilized during the manufacturing, storage and use processes; in particular, the component B uses monomers to formulate peroxide initiators, and there is a risk of polymerization under heated conditions.
CN110050048A discloses a reactive two-component adhesive system in the form of a film with improved heat and moisture resistance, which is also prepared by adopting a technology of mixing AB components and then carrying out free radical reaction curing.
Therefore, the development of a bonding adhesive more suitable for the structural members of electronic products is the focus of research in the field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a two-component structural adhesive and a preparation method and application thereof. The bi-component structural adhesive has stable bonding performance.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a two-component structural adhesive, comprising: a component A and a component B; the preparation raw materials of the component A comprise: monomer diluent, macromolecular monomer mixture containing double bonds and isocyanate groups, pseudoplastic thickening powder, active tertiary amine accelerator and stabilizer; the preparation raw materials of the component B comprise: polyol polymer toughener and peroxide initiator.
In the present invention, the reaction mechanism of the main functional groups after the mixing of the component a and the component B is as follows:
the above formula reaction is used to explain the addition reaction process of isocyanate and hydroxyl of polyol polymer toughening agent after AB material is mixed, and the structure containing curve and hydroxyl represents the polyol polymer toughening agent in B component, and does not represent that the invention must use or only use the substance in the formula.
The above formula is used to explain the mechanism of the AB component redox initiation system of the present invention to initiate the free radical polymerization reaction containing double bonds, and does not represent that the present invention must use or use only the substance represented by the formula.
Preferably, the volume ratio of the A component and the B component is (0.2-1):1, and may be, for example, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, etc.
Preferably, the molar ratio of isocyanate groups in the A component and hydroxyl groups in the B component is (0.9-1.1):1, and may be, for example, 0.9:1, 0.95:1, 1:1, 1.05:1, 1.1:1, and the like.
Preferably, the molar ratio of the active tertiary amine accelerator to the peroxide initiator is (0.5-2: 1, and may be, for example, 0.5:1, 0.6:1, 0.8:1, 1:1, 1.2:1, 1.4:1, 1.6:1, 1.8:1, 2:1, and the like.
Preferably, the monomer diluent is a double bond-containing monomer diluent having a flash point of 23 ℃ or higher (for example, 23 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃ or higher).
Preferably, the monomer diluent comprises any one or a combination of at least two of a soft monomer, an epoxy functional monomer, a macrocyclic viscosity-reducing hard monomer, a macrocyclic polar monomer, a crosslinking functional monomer or an acidic functional monomer, and preferably comprises a combination of a soft monomer, an epoxy functional monomer, a macrocyclic viscosity-reducing hard monomer, a macrocyclic polar monomer, a crosslinking functional monomer and an acidic functional monomer.
Wherein the soft monomer is used for plasticizing and toughening; the epoxy functional monomer has the function of increasing the adhesive force of the glue; the macrocyclic viscosity-reducing hard monomer mainly has the functions of dissolving, reducing viscosity, increasing hardness and enhancing plastic adhesion; the macrocyclic polar monomer mainly uses the adhesive force of the lifting glue to ABS, PC plastic or plastic alloy; (ii) a The crosslinking functional monomer mainly has the functions of improving the crosslinking degree of the glue after curing and increasing the cohesion after curing; the acid functional monomer mainly plays a role in improving the bonding force of the glue to the surfaces of metal and glass.
Preferably, the soft monomer is selected from isooctyl acrylate and/or isooctyl methacrylate.
Preferably, the epoxy functional monomer is selected from glycidyl acrylate and/or glycidyl methacrylate.
Preferably, the macrocyclic visbreaking hard monomer is selected from isobornyl acrylate and/or isobornyl methacrylate.
Preferably, the macrocyclic polar monomer is selected from N-vinyl pyrrolidone, methyl tetrahydrofuran acrylate or cyclomethylol propane formal acrylate.
Preferably, the crosslinking functional monomer is selected from any one of ethylene glycol dimethacrylate, butylene glycol diacrylate, butylene glycol dimethacrylate, hexanediol diacrylate, hexanediol dimethacrylate or tripropylene glycol diacrylate or a combination of at least two thereof.
Preferably, the acid functional monomer is selected from 2- (phosphonooxy) ethyl 2-methyl-2-propenoate and/or di (methacryloyloxyethyl) hydrogen phosphate.
Preferably, the monomer diluent comprises the following components in percentage by mass based on 100% of the total mass of the monomer diluent: 5-20% of soft monomer, 0-8% of epoxy functional monomer, 50-60% of macrocyclic viscosity-reducing hard monomer, 5-20% of macrocyclic polar monomer, 10-30% of crosslinking functional monomer and 0-3% of acidic functional monomer;
the soft monomer content is 5 to 20%, for example, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, etc., based on 100% by mass of the total monomer diluent.
The epoxy functional monomer content may be 0 to 8%, for example, 0%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, etc., based on 100% by mass of the total monomer diluent.
The content of the macrocyclic viscosity-reducing hard monomer is 50 to 60%, for example, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60% or the like, based on 100% by mass of the total monomer diluent.
The macrocyclic polar monomer content is 5 to 20%, for example, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, etc., based on 100% of the total mass of the monomer diluent.
The content of the crosslinking functional monomer is 10 to 30% based on 100% by mass of the total monomer diluent, and may be, for example, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 22%, 24%, 26%, 28%, 30%, or the like.
The content of the acidic functional monomer is 0 to 3% based on 100% by mass of the monomer diluent, and may be, for example, 0%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.8%, 1%, 1.2%, 1.4%, 1.6%, 1.8%, 2%, 2.2%, 2.4%, 2.6%, 2.8%, 3%, or the like.
Preferably, the content of the monomer diluent is 30 to 50% based on 100% by mass of the total preparation raw material of the a component, and may be, for example, 30%, 32%, 34%, 36%, 38%, 40%, 42%, 44%, 46%, 48%, 50%, etc.
Preferably, the raw materials for preparing the macromonomer mixture containing double bonds and isocyanate groups comprise isocyanate and acrylate monomers.
Wherein the isocyanate comprises HDI trimer and/or isophorone diisocyanate (IPDI): the acrylate monomer comprises any one or combination of at least two of hydroxyethyl methacrylate (HEMA), hydroxyethyl acrylate (HEA), 2-hydroxypropyl methacrylate (HPMA), 2-hydroxypropyl acrylate (HPA) or 4-hydroxybutyl acrylate (HBA);
preferably, the molar ratio of isocyanate to acrylate monomer is (0.55-0.95):1, and may be, for example, 0.55:1, 0.6:1, 0.65:1, 0.7:1, 0.75:1, 0.8:1, 0.85:1, 0.9:1, 0.95:1, and the like.
Preferably, the mixture of macromonomers containing double bonds and isocyanate groups is a combination of isocyanate bis-adducts and isocyanate based mono-adducts.
Wherein, the isocyanate double adduct refers to a reaction product of two isocyanate groups in an isocyanate compound and an acrylate monomer; the isocyanate monoadduct refers to a reaction product of one isocyanate group in an isocyanate compound and an acrylate monomer.
Preferably, the macromonomer mixture containing a double bond and an isocyanate group has a structural formula shown by a combination of the following formulas 2-1 or 2-2:
wherein the mixture 2-1 is named as HEMA-IPDI (including double addition HEMA-IPDI and single addition HEMA-IPDI) according to the rule; the mixture 2-2 can be named as HEMA-3HDI (including double addition HEMA-3HDI and single addition HEMA-3 HDI).
Wherein the dotted line in 2-1 and 2-2 can be replaced by non-hydroxyl part in hydroxyethyl acrylate (HEA), 2-hydroxypropyl methacrylate (HPMA), 2-hydroxypropyl acrylate (HPA), 4-hydroxybutyl acrylate (HBA) to obtain different mixed systems according to the formula requirements.
Preferably, the content of isocyanate group in the macromonomer mixture containing double bond and isocyanate group is 8-13%, for example, 8%, 9%, 10%, 11%, 12%, 13%, etc.
Preferably, the content of the mixture of macromonomers containing a double bond and an isocyanate group is 40 to 70%, for example, 40%, 45%, 50%, 55%, 60%, 65%, 70%, etc., based on 100% by mass of the total of the raw materials for preparation of the A-component.
Preferably, the pseudoplastic thickening powder is selected from any one or a combination of at least two of flame-process hydrophobic fumed silica, polyamide wax and attapulgite-morphology organic bentonite modified by oily or amphoteric groups.
Further optimization shows that the transparent type and colorless type products do not need to be added with organic bentonite, and polyamide wax is not added in the products which are required to be completely colorless and have any yellowing resistance requirement.
Preferably, the content of the pseudoplastic thickening powder is 0.5 to 3%, for example, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, etc., based on 100% by mass of the total raw materials for preparation of the a component.
Preferably, the active tertiary amine promoter comprises any one of or a combination of at least two of N, N-dimethyl (p-methyl) aniline, N-diethyl (p-methyl) aniline, N-dimethyl (p-methyl) cyclohexylamine, or N, N-diethyl (p-methyl) cyclohexylamine.
Further optimization shows that: the cyclohexane amine does not change color or changes little color during reaction, and is more suitable for products which are colorless or have higher requirements on color.
Preferably, the content of the active tertiary amine accelerator is 1 to 2%, for example, 1%, 1.2%, 1.4%, 1.6%, 1.8%, 2%, etc., based on 100% by mass of the total preparation raw materials of the a component.
Preferably, the stabilizer is selected from p-hydroxyphenol and/or p-hydroxyanisole.
Further explanation is as follows: the stabilizer is selected from any one or two of p-hydroxyphenol and p-hydroxyanisole, and has the function of preventing polymerization of the component A during storage.
Preferably, the content of the stabilizer is 0.02 to 0.1%, for example, 0.02%, 0.03%, 0.04%, 0.05%, 0.08%, 0.09%, 0.1%, etc., based on 100% by mass of the total preparation raw materials of the A component.
Preferably, the polyol polymer toughening agent is a low molecular weight polyester polyol and/or a polyether polyol.
Preferably, the polyol polymer toughening agent is selected from any one of polytetrahydrofuran glycol, carbon dioxide based polyether polyol (carbon dioxide-ethylene oxide copolymer, also known as PCE polyol) or polypropylene glycol ether or a combination of at least two thereof.
Preferably, the content of the polyol polymer toughening agent is 90-95% based on 100% of the total mass of the preparation raw materials of the B component, and can be, for example, 90%, 91%, 92%, 93%, 94%, 95% and the like.
Preferably, the weight average molecular weight of the polytetrahydrofuran glycol is 500-3000, and may be, for example, 500, 600, 800, 1000, 1200, 1400, 1600, 1800, 2000, 2200, 2400, 2600, 3000, and the like.
Preferably, the weight average molecular weight of the carbon dioxide based polyether polyol is 650-1500, and may be 650, 700, 800, 1000, 1100, 1200, 1400, 1500, etc.
Preferably, the weight average molecular weight of the polypropylene glycol ether is 1000-8000, and may be, for example, 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000, and the like.
Preferably, the polyol polymer has a content of a hydroxy ester group of 2 to 20%, for example, 2%, 4%, 6%, 8%, 10%, 12%, 14%, 16%, 18%, 20%, etc.
Preferably, the peroxide initiator is selected from any one of or a combination of at least two of benzoyl peroxide, tert-butyl peroxide, tert-amyl peroxide or tert-butyl peroxybenzoate.
Preferably, the peroxide initiator is present in an amount of 4 to 10%, for example, 4%, 5%, 6%, 7%, 8%, 9%, 10%, etc., based on 100% by mass of the total raw materials for the preparation of the B component.
Preferably, the preparation raw materials of the component B also comprise pseudoplastic thickening powder.
Preferably, the pseudoplastic thickening powder is selected from any one or a combination of at least two of flame-process hydrophobic fumed silica, polyamide wax and attapulgite-morphology organic bentonite modified by oily or amphoteric groups.
Preferably, the specific surface area of the flame method hydrophobic type fumed silica is 100-200m2G, may be, for example, 100m2/g、120m2/g、140m2/g、160m2/g、180m2/g、200m2And/g, etc.
Preferably, the content of the pseudoplastic thickening powder is 0.5 to 3%, for example, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, etc., based on 100% by mass of the total raw materials for the preparation of the B component.
In a second aspect, the present invention provides a method for preparing a two-component structural adhesive according to the first aspect, the method for preparing the two-component structural adhesive comprises the following steps:
preparation of component A: heating a monomer diluent, mixing (completely dissolving) the monomer diluent with an active tertiary amine accelerator, and then sequentially mixing and stirring the monomer diluent, a pseudoplastic thickening powder, a macromonomer mixture containing double bonds and isocyanate groups and a stabilizer to obtain a component A; preparation of the component B: and mixing the polyol polymer toughening agent and the peroxide initiator to obtain the component B.
Preferably, the preparation of the A component specifically comprises the following steps:
(1) heating the monomer diluent, adding an active tertiary amine accelerator, and mixing and stirring;
(2) adding the pseudoplastic thickening powder into the mixture obtained in the step (1), and mixing and stirring;
(3) and (3) adding a macromonomer mixture of isocyanate groups and a stabilizer into the mixture obtained in the step (2), mixing, stirring and exhausting to obtain the component A.
Preferably, in the step (1), the temperature is raised to 30 to 60 ℃ and may be, for example, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃ or the like.
Preferably, in the step (1) and the step (2), the mixing and stirring temperature is 30 to 60 ℃ independently of each other, and may be, for example, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃ or the like. The mixing and stirring time is 5-20min, such as 5min, 6min, 8min, 10min, 12min, 14min, 16min, 18min, 20min, etc.
Preferably, in the step (3), the temperature of the mixing and stirring is 30-60 ℃, for example, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃ and the like, and the time of the mixing and stirring is 20-40min, for example, 20min, 22min, 24min, 26min, 28min, 30min, 32min, 34min, 36min, 38min, 40min and the like.
Preferably, in the step (3), the viscosity of the A component is 4000-16000cps, for example, 4000cps, 5000cps, 6000cps, 7000cps, 8000cps, 9000cps, 10000cps, 11000cps, 12000cps, 13000cps, 14000cps, 15000cps, 16000cps and the like may be mentioned.
Preferably, the preparation of the B component specifically comprises the following steps:
(1') heating the polyol polymer toughening agent, adding a peroxide initiator, and mixing and stirring;
(2') adding an optional pseudoplastic thickening powder into the mixture obtained in the step (1'), and mixing and stirring to obtain a component B.
Preferably, in step (1'), the temperature is raised to 30 to 50 ℃ and may be, for example, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃ or the like.
Preferably, in step (1'), the temperature of the mixing and stirring is 30 to 50 ℃, for example, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃ and the like, and the time of the mixing and stirring is 5 to 10min, for example, 5min, 6min, 7min, 8min, 9min, 10min and the like.
Preferably, in step (2'), the temperature of the mixing and stirring is 30-50 ℃, for example, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃ and the like, and the time of the mixing and stirring is 20-30minn, for example, 20min, 22min, 24min, 26min, 28min, 30min and the like.
Preferably, in step (2'), the viscosity of the B component is 2000-8000cps, and may be, for example, 2000cps, 3000cps, 4000cps, 5000cps, 6000cps, 7000cps, 8000cps, etc.
In a third aspect, the present invention provides a use of the two-component structural adhesive according to the first aspect in assembling and manufacturing electronic products.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the macromolecular chain tail crisscross network structure formed after the bi-component structural adhesive is cured, the saturated C-C bond formed by free radical polymerization has stable performance (reaction mechanism formula II) and provides cohesion and strength, the long-chain polymer connected with ester amino provides flexibility and elasticity (reaction mechanism formula I), and the adhesive can be applied to structural member bonding, can not provide excellent bonding strength, and can also counteract expansion and contraction with heat, creep force, bending force and impact force, and prevent the phenomena of brittle fracture, degumming and the like;
(2) in the bi-component structural adhesive, the used toughening or plasticizing components are cured in an addition reaction mode (a reaction mechanism formula I), so that the phenomenon of phase separation in the curing process of the adhesive or the dissociation of the solidified plasticizer is avoided, and the cured adhesive has more stable performance;
(3) the invention has the advantages of clear design target, obvious functional group characteristics, clear reaction mechanism and clear application material, and effectively solves the problem that the definition of the application, usage and application range of the existing glue in the market is not clear;
(4) the shear strength of the prepared bi-component structural adhesive can reach 14-25 MPa when the PC and the PC are bonded, the shear strength can reach 17-29 MPa when the aluminum alloy and the aluminum alloy are bonded, and the shear strength can reach 17-22 MPa when the ABS and the ABS are bonded.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The sources of the components in the following examples are as follows:
example 1
The embodiment provides a two-component structural adhesive, which specifically comprises the following components:
wherein the volume ratio of the component A to the component B is 0.5: 1;
the specific preparation method of the two-component structural adhesive comprises the following steps:
preparation of component A:
(1) adding a monomer diluent into a kettle which can replace nitrogen, is heated by a jacket and is stirred by two stars, and slowly heating to 40 ℃; keeping the temperature at 40 ℃, adding an active tertiary amine accelerator, stirring for 10min, and fully dissolving;
(2) adding pseudoplastic thickening powder into the mixture obtained in the step (1), replacing dry nitrogen, and stirring for 10min under the condition of continuous nitrogen protection to fully dissolve;
(3) adding a macromonomer mixture containing double bonds and isocyanate groups and a stabilizer into the mixture obtained in the step (2) under the condition of continuous drying nitrogen protection, fully stirring for 30min to obtain a glue-like substance with the viscosity of 14000cps in a stirring state, and pumping negative pressure to discharge bubbles to obtain a finished product A component;
preparation of the component B:
adding polyalcohol polymer toughening agent into a kettle capable of replacing nitrogen, heating with a jacket and stirring with two stars, replacing nitrogen, heating to 40 deg.C, adding peroxide initiator, mixing and stirring for 5min to obtain glue-like substance with viscosity of 6000cps, i.e. finished product B component.
Example 2
The embodiment provides a two-component structural adhesive, which specifically comprises the following components:
wherein the volume ratio of the component A to the component B is 0.6: 1;
the specific preparation method of the two-component structural adhesive comprises the following steps:
preparation of component A:
(1) adding a monomer diluent into a kettle which can replace nitrogen, is heated by a jacket and is stirred by two stars, and slowly heating to 45 ℃; keeping the temperature at 45 ℃, adding an active tertiary amine accelerator, stirring for 10min, and fully dissolving;
(2) adding pseudoplastic thickening powder into the mixture obtained in the step (1), replacing dry nitrogen, and stirring for 10min under the condition of continuous nitrogen protection to fully dissolve;
(3) adding a macromonomer mixture containing double bonds and isocyanate groups and a stabilizer into the mixture obtained in the step (2) under the condition of continuous drying nitrogen protection, fully stirring for 30min, vacuumizing and discharging bubbles under the stirring state to obtain a glue-like substance with the viscosity of 13000cps, and vacuumizing and discharging bubbles to obtain a finished product A component;
preparation of the component B:
adding polyalcohol polymer toughening agent into a kettle capable of replacing nitrogen, heating with a jacket and stirring with two stars, replacing nitrogen, heating to 50 deg.C, adding peroxide initiator, mixing and stirring for 10min to obtain glue-like substance with viscosity of 3000cps, i.e. component B.
Example 3
The embodiment provides a two-component structural adhesive, which specifically comprises the following components:
wherein the volume ratio of the component A to the component B is 0.4: 1;
the specific preparation method of the two-component structural adhesive comprises the following steps:
preparation of component A:
(1) adding a monomer diluent into a double-star stirring kettle which can replace nitrogen and is heated by a jacket, and slowly heating to 40 ℃; keeping the temperature at 40 ℃, adding an active tertiary amine accelerator, stirring for 10min, and fully dissolving;
(2) adding pseudoplastic thickening powder into the mixture obtained in the step (1), replacing dry nitrogen, and stirring for 10min under the condition of continuous nitrogen protection to fully dissolve;
(3) adding a macromonomer mixture containing double bonds and isocyanate groups and a stabilizer into the mixture obtained in the step (2) under the condition of continuous drying nitrogen protection, fully stirring for 30min, vacuumizing and discharging bubbles under the stirring state to obtain a glue-like substance with the viscosity of 10000cps, and vacuumizing and discharging bubbles to obtain a finished product A component;
preparation of the component B:
adding polyalcohol polymer toughening agent into a double-star stirring kettle which has replaceable nitrogen and is heated with a jacket, replacing nitrogen, heating to 40 ℃, adding peroxide initiator, mixing and stirring for 5min to obtain a glue-like substance with the viscosity of 5000cps, namely the finished product component B.
Example 4
The embodiment provides a two-component structural adhesive, which specifically comprises the following components:
wherein the volume ratio of the component A to the component B is 0.5: 1;
the specific preparation method of the two-component structural adhesive comprises the following steps:
preparation of component A:
(1) adding a monomer diluent into a double-star stirring kettle which can replace nitrogen and is heated by a jacket, and slowly heating to 40 ℃; keeping the temperature at 40 ℃, adding an active tertiary amine accelerator, stirring for 10min, and fully dissolving;
(2) adding pseudoplastic thickening powder into the mixture obtained in the step (1), replacing dry nitrogen, and stirring for 10min under the condition of continuous nitrogen protection to fully dissolve;
(3) adding the mixture obtained in the step (2) into a macromonomer mixture containing double bonds and isocyanate groups and a stabilizer under the condition of continuous dry nitrogen protection, fully stirring for 30min, vacuumizing and discharging bubbles under the stirring state to obtain a glue-like substance with the viscosity of 8000cps, and vacuumizing and discharging bubbles to obtain a finished product A component;
preparation of the component B:
adding a polyalcohol polymer toughening agent into a double-star stirring kettle which has replaceable nitrogen and is heated by a jacket, replacing the nitrogen, heating to 40 ℃, adding a peroxide initiator, mixing and stirring for 5min to obtain a glue-like substance with viscosity of 5500cps, namely the finished product component B.
Example 5
The embodiment provides a two-component structural adhesive, which specifically comprises the following components:
wherein the volume ratio of the component A to the component B is 0.5: 1;
the specific preparation method of the two-component structural adhesive comprises the following steps:
preparation of component A:
(1) adding a monomer diluent into a double-star stirring kettle which can replace nitrogen and is heated by a jacket, and slowly heating to 40 ℃; keeping the temperature at 40 ℃, adding an active tertiary amine accelerator, stirring for 10min, and fully dissolving;
(2) adding pseudoplastic thickening powder into the mixture obtained in the step (1), replacing dry nitrogen, and stirring for 10min under the condition of continuous nitrogen protection to fully dissolve;
(3) adding a macromonomer mixture containing double bonds and isocyanate groups and a stabilizer into the mixture obtained in the step (2) under the condition of continuous drying nitrogen protection, fully stirring for 30min, vacuumizing and discharging bubbles under the stirring state to obtain a glue-like substance with the viscosity of 11000cps, and vacuumizing and discharging bubbles to obtain a finished product A component;
preparation of the component B:
(1') in a double-star stirring kettle which has replaceable nitrogen and is heated by a jacket, adding a polyol polymer toughening agent to replace the nitrogen, heating to 40 ℃, adding a peroxide initiator, and mixing and stirring for 5 min;
(2') adding the pseudoplastic thickening powder into the mixture obtained in the step (1'), mixing and stirring for 25min to obtain a glue-like substance with the viscosity of 7000cps, namely a finished product component B.
Example 6
This example provides a two-component structural adhesive, which differs from example 1 only in that mixture 2-1(HEMA-IPDI) is replaced by mixture 2-2(HEMA-3HDI) with equal isocyanate content, and the other component contents and preparation method are the same as example 1.
Example 7
This example provides a two-component structural adhesive, which differs from example 1 only in that mixture 2-1(HEMA-IPDI) is replaced by a mixture with an equal isocyanate value content (HEMA-3HDI), and the contents of the other components and the preparation method are the same as in example 1.
Example 8
This example provides a two-component structural adhesive, which differs from example 1 only in that the mixture 2-1(HEMA-IPDI) is replaced by a mixture with an equal isocyanate content (HPA-IPDI), and the contents of the other components and the preparation method are the same as in example 1.
Examples 9 to 14
Examples 9 to 14 provide different two-component structural adhesives, which are different from example 1 only in that the contents of other components and the preparation method are completely the same as those of example 1 except that the following monomer diluent components are different;
comparative example 1
This comparative example provides a two-component construction adhesive, which differs from example 1 only in that mixture 2-1(HEMA-IPDI) is replaced by IPDI with an equal isocyanate content, and the other component contents and preparation method are the same as example 1.
IPDI has no double bond, and does not participate in redox-promoted free radical polymerization reaction in the second reaction, wherein the polyol in the component B can be crosslinked with IPDI to generate an elastomer, each monomer in the component A is subjected to free radical polymerization to generate hard polyacrylate, a uniform crosslinked net cannot be formed, and the two parts are equivalent to be formed by mutual interpenetration, so that the strength is not as high as that provided by a single crosslinked net structure.
Comparative example 2
This comparative example provides a two-component construction adhesive, which differs from example 1 only in that mixture 2-1(HEMA-IPDI) is replaced by HEMA of equal mass, and the contents of the other components and the preparation method are the same as in example 1.
HEMA does not contain-NCO group which can react with the toughening agent in the component B, after AB is mixed, functional group reaction in the first reaction can not occur, the polyhydric alcohol in the component B can not participate in curing in a chemical bonding mode, the glue can have solid-liquid separation or free seepage risk of the polyhydric alcohol after curing, and the strength is extremely low;
comparative example 3
The comparative example provides a two-component structural adhesive, which is different from the example 1 only in that the pseudoplastic thickening powder is not added into the component A, the insufficient part of the component A is supplemented to 100 percent by the monomer diluent, and the contents of other components and the preparation method are the same as the example 1.
According to the scheme, the viscosity of the obtained glue is far lower than that of normal glue, and when the structure is bonded, the glue flows or is rapidly spread at the glue dispensing position during glue dispensing, so that the glue dispensing exceeds a set range or the glue layer is too thin to achieve the bonding purpose.
Performance testing
Various performance tests were performed on the two-component structural adhesives provided in examples 1-14 and comparative examples 1-3 above; the specific test method comprises the following steps: testing the shear strength of the glue after the glue is bonded to the target rigid material according to GB/T7124-2008; the specific test results are shown in table 1 below, where "-" represents no compliance or no need for testing:
TABLE 1
The test data in Table 1 show that the shear strength of the prepared bi-component structural adhesive can reach 14-25 MPa when the bi-component structural adhesive is used for bonding PC and PC, 17-29 MPa when the bi-component structural adhesive is used for bonding aluminum alloy and aluminum alloy, and 17-22 MPa when the bi-component structural adhesive is used for bonding ABS and ABS. Therefore, the macromolecular chain tail crisscross network structure formed after the bi-component structural adhesive is cured has stable saturated C-C bond performance (reaction mechanism formula II) formed by free radical polymerization and provides cohesion and strength, the long-chain polymer connected with ester amino provides flexibility and elasticity (reaction mechanism formula I), and the adhesive can not provide excellent adhesive strength when being applied to structural member adhesion, and can also counteract the phenomena of expansion caused by heat and contraction caused by cold, creep force, bending force and impact force, and prevent the phenomena of glue embrittlement, degumming and the like.
In the bi-component structural adhesive, the used toughening or plasticizing components are cured in an addition reaction mode (a reaction mechanism formula I), so that the phenomenon of phase separation in the curing process of the adhesive or the dissociation of the solidified plasticizer is avoided, and the cured adhesive has more stable performance; the invention has the advantages of clear design target, obvious functional group characteristics, clear reaction mechanism and clear application material, and effectively solves the problem that the definition of the application, usage and application range of the existing glue in the market is not clear.
The applicant states that the present invention is illustrated by the above examples of the two-component structural adhesive and the preparation method and application thereof, but the present invention is not limited to the above examples, i.e. it does not mean that the present invention must be implemented by the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A two-component structural adhesive, comprising: a component A and a component B; the preparation raw materials of the component A comprise: monomer diluent, macromolecular monomer mixture containing double bonds and isocyanate groups, pseudoplastic thickening powder, active tertiary amine accelerator and stabilizer; the preparation raw materials of the component B comprise: polyol polymer toughener and peroxide initiator.
2. The two-component structural adhesive of claim 1, wherein the volume ratio of the A component to the B component is (0.2-1): 1;
preferably, the molar ratio of isocyanate groups in the A component to hydroxyl groups in the B component is (0.9-1.1): 1;
preferably, the molar ratio of the active tertiary amine accelerator to the peroxide initiator is (0.5-2): 1.
3. The two-component structural adhesive of claim 1 or 2, wherein the monomer diluent is a double bond-containing monomer diluent having a flash point above 23 ℃;
preferably, the monomer diluent comprises any one or a combination of at least two of a soft monomer, an epoxy functional monomer, a macrocyclic viscosity-reducing hard monomer, a macrocyclic polar monomer, a crosslinking functional monomer or an acidic functional monomer, and preferably comprises a combination of a soft monomer, an epoxy functional monomer, a macrocyclic viscosity-reducing hard monomer, a macrocyclic polar monomer, a crosslinking functional monomer and an acidic functional monomer;
preferably, the soft monomer is selected from isooctyl acrylate and/or isooctyl methacrylate;
preferably, the epoxy functional monomer is selected from glycidyl acrylate and/or glycidyl methacrylate;
preferably, the macrocyclic visbreaking hard monomer is selected from isobornyl acrylate and/or isobornyl methacrylate;
preferably, the macrocyclic polar monomer is selected from N-vinyl pyrrolidone, tetrahydrofuran methyl acrylate or cyclomethylol propane methylal acrylate;
preferably, the crosslinking functional monomer is selected from any one of ethylene glycol dimethacrylate, butylene glycol diacrylate, butylene glycol dimethacrylate, hexanediol diacrylate, hexanediol dimethacrylate or tripropylene glycol diacrylate or a combination of at least two of the two;
preferably, the acid functional monomer is selected from 2- (phosphonooxy) ethyl 2-methyl-2-acrylate and/or di (methacryloyloxyethyl) hydrogen phosphate;
preferably, the monomer diluent comprises the following components in percentage by mass based on 100% of the total mass of the monomer diluent: 5-20% of soft monomer, 0-8% of epoxy functional monomer, 50-60% of macrocyclic viscosity-reducing hard monomer, 5-20% of macrocyclic polar monomer, 10-30% of crosslinking functional monomer and 0-3% of acidic functional monomer;
preferably, the content of the monomer diluent is 30-50% based on 100% of the total mass of the preparation raw materials of the A component.
4. The two-component structural adhesive according to any one of claims 1 to 3, wherein the raw material for preparing the macromonomer mixture comprising a double bond and an isocyanate group comprises an isocyanate and an acrylate monomer; wherein the isocyanate comprises HDI trimer and/or isophorone diisocyanate: the acrylic ester monomer comprises any one or the combination of at least two of hydroxyethyl methacrylate, hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate or 4-hydroxybutyl acrylate;
preferably, the molar ratio of the isocyanate to the acrylate monomer is (0.55-0.95) to 1;
preferably, the mixture of macromonomers containing double bonds and isocyanate groups is a combination of isocyanate bis-adducts and isocyanate mono-adducts;
preferably, in the macromonomer mixture containing double bonds and isocyanate groups, the mass percentage of isocyanate is 8-13%;
preferably, the content of the macromonomer mixture containing a double bond and an isocyanate group is 40 to 70% based on 100% by mass of the total preparation raw materials of the A component.
5. The two-component structural adhesive according to any one of claims 1 to 4, wherein the pseudoplastic thickening powder is selected from any one or a combination of at least two of flame-process hydrophobic fumed silica, polyamide wax, oily or amphoteric group-modified attapulgite-morphology organic bentonite;
preferably, the content of the pseudoplastic thickening powder is 0.5-3% by taking the total mass of the preparation raw materials of the component A as 100%;
preferably, the active tertiary amine promoter comprises any one or a combination of at least two of N, N-dimethyl (p-methyl) aniline, N-diethyl (p-methyl) aniline, N-dimethyl (p-methyl) cyclohexylamine, or N, N-diethyl (p-methyl) cyclohexylamine;
preferably, the content of the active tertiary amine accelerator is 1-2% based on 100% of the total mass of the preparation raw materials of the component A;
preferably, the stabilizer is selected from the group consisting of p-hydroxyphenol and/or p-hydroxyanisole;
preferably, the content of the stabilizer is 0.02-0.1% of the total mass of the preparation raw materials of the component A.
6. The two-component structural adhesive of any one of claims 1-5, wherein the polyol-based polymer toughening agent is a low molecular weight polyester polyol and/or a polyether polyol;
preferably, the polyol polymer toughening agent is selected from any one of polytetrahydrofuran glycol, carbon dioxide-based polyether polyol or polypropylene glycol ether or a combination of at least two of the polytetrahydrofuran glycol, the carbon dioxide-based polyether polyol and the polypropylene glycol ether;
preferably, the content of the polyol polymer toughening agent is 90-95% by taking the total mass of the preparation raw materials of the component B as 100%;
preferably, the weight average molecular weight of the polytetrahydrofuran diol is 500-3000;
preferably, the weight average molecular weight of the carbon dioxide-based polyether polyol is 650-1500;
preferably, the weight average molecular weight of the polypropylene glycol ether is 1000-8000;
preferably, in the polyol polymer, the mass percentage of the hydroxy ester is 0.5-7%.
7. The two-component structural adhesive according to any one of claims 1 to 6, wherein the peroxide initiator is selected from any one of or a combination of at least two of benzoyl peroxide, tert-butyl peroxide, tert-amyl peroxide or tert-butyl peroxybenzoate;
preferably, the content of the peroxide initiator is 4-10% based on 100% of the total mass of the raw materials for preparing the component B;
preferably, the preparation raw materials of the component B also comprise pseudoplastic thickening powder;
preferably, the pseudoplastic thickening powder is selected from any one or a combination of at least two of flame-process hydrophobic gas-phase silicon dioxide, polyamide wax and attapulgite-morphology organic bentonite modified by oily or amphoteric groups;
preferably, the content of the pseudoplastic thickening powder is 0.5-3% by taking the total mass of the preparation raw materials of the component B as 100%.
8. The method for preparing the two-component structural adhesive according to any one of claims 1 to 7, wherein the method for preparing the two-component structural adhesive comprises the following steps:
preparation of component A: heating a monomer diluent, mixing the monomer diluent with an active tertiary amine accelerator, and then sequentially mixing and stirring the monomer diluent, the pseudoplastic thickening powder, the macromonomer mixture containing double bonds and isocyanate groups and the stabilizer to obtain a component A;
preparation of the component B: and mixing the polyol polymer toughening agent and the peroxide initiator to obtain the component B.
9. The method for preparing the two-component structural adhesive according to claim 8, wherein the preparation of the component A specifically comprises the following steps:
(1) heating the monomer diluent, adding an active tertiary amine accelerator, and mixing and stirring;
(2) adding the pseudoplastic thickening powder into the mixture obtained in the step (1), and mixing and stirring;
(3) adding a macromonomer mixture of isocyanate groups and a stabilizer into the mixture obtained in the step (2), mixing, stirring and exhausting to obtain the component A;
preferably, in the step (1), the temperature is increased to 30-60 ℃;
preferably, in the step (1) and the step (2), the temperature of the mixing and stirring is respectively and independently 30-60 ℃, and the time of the mixing and stirring is respectively and independently 5-20 min;
preferably, in the step (3), the temperature of the mixing and stirring is 30-60 ℃, and the time of the mixing and stirring is 20-40 min;
preferably, in step (3), the viscosity of the A component is 4000-16000 cps;
preferably, the preparation of the B component specifically comprises the following steps:
(1') heating the polyol polymer toughening agent, adding a peroxide initiator, and mixing and stirring;
(2') adding optional pseudoplastic thickening powder into the mixture obtained in the step (1'), and mixing and stirring to obtain a component B;
preferably, in step (1'), the temperature is raised to 30-50 ℃;
preferably, in the step (1'), the temperature of the mixing and stirring is 30-50 ℃, and the time of the mixing and stirring is 5-10 min;
preferably, in the step (2'), the temperature of the mixing and stirring is 30-50 ℃, and the time of the mixing and stirring is 20-30 min;
preferably, in step (2'), the viscosity of the B component is 2000-8000 cps.
10. Use of the two-component structural adhesive according to any one of claims 1 to 7 in the assembly of manufactured electronic products.
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Citations (4)
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|---|---|---|---|---|
| EP0603046A1 (en) * | 1992-12-16 | 1994-06-22 | Ceca S.A. | Polyurethane acrylate polymers precurable by heat and postcurable by humidity and one-can adhesive compositions containing them |
| US20020049349A1 (en) * | 2000-08-08 | 2002-04-25 | Degussa Ag | Low monomer 1:1-monoadducts from hydroxy (meth) acrylates and diisocyanates and a process for their manufacture |
| US20150099818A1 (en) * | 2013-10-08 | 2015-04-09 | Dymax Corporation | Tri-curable adhesive composition and method |
| CN110128994A (en) * | 2019-04-09 | 2019-08-16 | 中海油常州涂料化工研究院有限公司 | A kind of anaerobic adhesive of moisture-curable and preparation method thereof |
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2021
- 2021-05-18 CN CN202110541789.1A patent/CN113512396A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0603046A1 (en) * | 1992-12-16 | 1994-06-22 | Ceca S.A. | Polyurethane acrylate polymers precurable by heat and postcurable by humidity and one-can adhesive compositions containing them |
| US20020049349A1 (en) * | 2000-08-08 | 2002-04-25 | Degussa Ag | Low monomer 1:1-monoadducts from hydroxy (meth) acrylates and diisocyanates and a process for their manufacture |
| US20150099818A1 (en) * | 2013-10-08 | 2015-04-09 | Dymax Corporation | Tri-curable adhesive composition and method |
| CN110128994A (en) * | 2019-04-09 | 2019-08-16 | 中海油常州涂料化工研究院有限公司 | A kind of anaerobic adhesive of moisture-curable and preparation method thereof |
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Application publication date: 20211019 |