CN117659930B - Double-component polyurethane structural adhesive and preparation method and application thereof - Google Patents
Double-component polyurethane structural adhesive and preparation method and application thereof Download PDFInfo
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- CN117659930B CN117659930B CN202311672265.1A CN202311672265A CN117659930B CN 117659930 B CN117659930 B CN 117659930B CN 202311672265 A CN202311672265 A CN 202311672265A CN 117659930 B CN117659930 B CN 117659930B
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- 230000001070 adhesive effect Effects 0.000 title claims abstract description 71
- 239000000853 adhesive Substances 0.000 title claims abstract description 69
- 239000004814 polyurethane Substances 0.000 title claims abstract description 69
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 25
- 229920000570 polyether Polymers 0.000 claims abstract description 25
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 23
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 claims abstract description 22
- 229920005862 polyol Polymers 0.000 claims abstract description 22
- 150000003077 polyols Chemical class 0.000 claims abstract description 22
- 239000002318 adhesion promoter Substances 0.000 claims abstract description 21
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 18
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 16
- 239000004593 Epoxy Substances 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000010276 construction Methods 0.000 claims description 22
- 239000000945 filler Substances 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 17
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 12
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 11
- 239000004014 plasticizer Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229910021485 fumed silica Inorganic materials 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000002516 radical scavenger Substances 0.000 claims description 10
- -1 small molecule diol Chemical class 0.000 claims description 9
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- 239000004927 clay Substances 0.000 claims description 6
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 5
- 229920002430 Fibre-reinforced plastic Polymers 0.000 claims description 5
- 239000011151 fibre-reinforced plastic Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 239000005995 Aluminium silicate Substances 0.000 claims description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 4
- 235000012211 aluminium silicate Nutrition 0.000 claims description 4
- PFXFKBDDQUKKTF-UHFFFAOYSA-N amino(phenyl)silicon Chemical compound N[Si]C1=CC=CC=C1 PFXFKBDDQUKKTF-UHFFFAOYSA-N 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 125000005442 diisocyanate group Chemical group 0.000 claims description 4
- 239000003292 glue Substances 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 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 4
- 239000003607 modifier Substances 0.000 claims description 4
- 239000002808 molecular sieve Substances 0.000 claims description 4
- 229910000077 silane Inorganic materials 0.000 claims description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 claims description 3
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 238000001816 cooling Methods 0.000 claims description 3
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 230000002209 hydrophobic effect Effects 0.000 claims description 3
- XFSXUCMYFWZRAF-NRFANRHFSA-N (2s)-2-(trityloxymethyl)oxirane Chemical compound C([C@H]1OC1)OC(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 XFSXUCMYFWZRAF-NRFANRHFSA-N 0.000 claims description 2
- KFUSXMDYOPXKKT-UHFFFAOYSA-N 2-[(2-methylphenoxy)methyl]oxirane Chemical compound CC1=CC=CC=C1OCC1OC1 KFUSXMDYOPXKKT-UHFFFAOYSA-N 0.000 claims description 2
- CUFXMPWHOWYNSO-UHFFFAOYSA-N 2-[(4-methylphenoxy)methyl]oxirane Chemical compound C1=CC(C)=CC=C1OCC1OC1 CUFXMPWHOWYNSO-UHFFFAOYSA-N 0.000 claims description 2
- UUODQIKUTGWMPT-UHFFFAOYSA-N 2-fluoro-5-(trifluoromethyl)pyridine Chemical compound FC1=CC=C(C(F)(F)F)C=N1 UUODQIKUTGWMPT-UHFFFAOYSA-N 0.000 claims description 2
- QBJMEQQDPPPRKV-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]oxypropan-1-amine Chemical compound NCCCO[Si](OC)(OC)C QBJMEQQDPPPRKV-UHFFFAOYSA-N 0.000 claims description 2
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 2
- VLJQDHDVZJXNQL-UHFFFAOYSA-N 4-methyl-n-(oxomethylidene)benzenesulfonamide Chemical compound CC1=CC=C(S(=O)(=O)N=C=O)C=C1 VLJQDHDVZJXNQL-UHFFFAOYSA-N 0.000 claims description 2
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 claims description 2
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 2
- MAVBUZJIOYZMRX-UHFFFAOYSA-N aniline;trimethoxy(propyl)silane Chemical compound NC1=CC=CC=C1.CCC[Si](OC)(OC)OC MAVBUZJIOYZMRX-UHFFFAOYSA-N 0.000 claims description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-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
- RJGHQTVXGKYATR-UHFFFAOYSA-L dibutyl(dichloro)stannane Chemical compound CCCC[Sn](Cl)(Cl)CCCC RJGHQTVXGKYATR-UHFFFAOYSA-L 0.000 claims description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 2
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 2
- LIBWSLLLJZULCP-UHFFFAOYSA-N n-(3-triethoxysilylpropyl)aniline Chemical compound CCO[Si](OCC)(OCC)CCCNC1=CC=CC=C1 LIBWSLLLJZULCP-UHFFFAOYSA-N 0.000 claims description 2
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 claims description 2
- KOVKEDGZABFDPF-UHFFFAOYSA-N n-(triethoxysilylmethyl)aniline Chemical group CCO[Si](OCC)(OCC)CNC1=CC=CC=C1 KOVKEDGZABFDPF-UHFFFAOYSA-N 0.000 claims description 2
- VNBLTKHUCJLFSB-UHFFFAOYSA-N n-(trimethoxysilylmethyl)aniline Chemical compound CO[Si](OC)(OC)CNC1=CC=CC=C1 VNBLTKHUCJLFSB-UHFFFAOYSA-N 0.000 claims description 2
- 125000003884 phenylalkyl group Chemical group 0.000 claims description 2
- PZTAGFCBNDBBFZ-UHFFFAOYSA-N tert-butyl 2-(hydroxymethyl)piperidine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCCCC1CO PZTAGFCBNDBBFZ-UHFFFAOYSA-N 0.000 claims description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims 2
- 229910052623 talc Inorganic materials 0.000 claims 2
- 239000000463 material Substances 0.000 abstract description 9
- 238000012360 testing method Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 10
- 239000003677 Sheet moulding compound Substances 0.000 description 6
- 239000002390 adhesive tape Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000011152 fibreglass Substances 0.000 description 4
- 229920006805 PP-LGF Polymers 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 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 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- 238000003466 welding 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
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/69—Polymers of conjugated dienes
- C08G18/698—Mixtures with compounds of group C08G18/40
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention provides a double-component polyurethane structural adhesive and a preparation method and application thereof, wherein the double-component polyurethane structural adhesive comprises an A component and a B component, the A component comprises hydroxyl-terminated polybutadiene, micromolecular dihydric alcohol, liquid polyester polyol, epoxy modified polyether and an adhesion promoter, and the B component comprises polyisocyanate and polyurethane prepolymer; the specific component A and the specific component B are selected for matching, particularly hydroxyl-terminated polybutadiene and epoxy modified polyether polyol are selected for matching in the component A, and an adhesion promoter is added, so that the obtained double-component polyurethane structural adhesive has excellent adhesion performance with a base material after being cured, has high strength and high elasticity, and is suitable for adhesion of automobile parts.
Description
Technical Field
The invention belongs to the technical field of binders, and particularly relates to a bi-component polyurethane structural adhesive, a preparation method and application thereof.
Background
In recent years, the technology of automobile composite materials and plastics instead of steel plates has been developed rapidly, and particularly high-strength glass Fiber Reinforced Plastics (FRP), such as glass fiber reinforced polypropylene (PPGF), sheet Molding Composite (SMC), resin transfer molding composite (RTM), etc., are widely used in automobiles, however, SMC and RTM materials are inconvenient to assemble with a body frame using conventional welding technology, and these parts are required to be adhesively assembled with polyurethane adhesives.
At present, the adhesive for bonding automobile parts is generally a two-component PU adhesive, and can bear larger dynamic load and static load. CN103261252a discloses a two-component polyurethane adhesive, the two-component polyurethane adhesive system comprises a resin component a and a curing agent B, the resin component a comprises a monomeric polyisocyanate and a prepolymer. Curing agent B comprises a polyether polyol having a molecular weight of 3000 to 20000 and another polyol having 4 to 8 hydroxyl groups and a molecular weight of 200 to 1000, the system comprising a tin catalyst contained in the resin component and a blocked aza-type catalyst contained in the curing agent; the system has excellent storage stability, provides excellent open time at ambient temperature, and cures rapidly when heated to 65 ℃ or higher.
CN104371632a discloses a double-component polyurethane adhesive for bonding fiber reinforced plastics and a using method thereof, wherein the double-component polyurethane adhesive comprises a resin component A and a curing agent component B, and the composition and the mass percentage of the component A are as follows: 40-70% of polyisocyanate compound, 2-20% of polyurethane prepolymer, 0-10% of water scavenger, 0-30% of filler and 0-15% of plasticizer; the component B comprises the following components in percentage by mass: 5 to 40 percent of polyether polyol, 20 to 70 percent of hydrophobic polyol, 1 to 5 percent of silane coupling agent, 2 to 15 percent of resin, 0.05 to 0.5 percent of catalyst, 0 to 10 percent of molecular sieve and 0 to 20 percent of filler. The adhesive has good adhesion to glass fiber reinforced plastics, can achieve high fiber tearing damage to the adhesion of SMC base materials under the condition of no surface treatment (polishing, bottom coating, plasma, flame and the like), and has good adhesion effect to the glass fiber reinforced plastics.
However, the two-component polyurethane structural adhesive provided by the prior art including the invention can not meet the requirements of high strength and high elasticity at the same time, and the application of the fiber reinforced plastic in automobile parts is limited.
Therefore, there is an urgent need for a two-component polyurethane structural adhesive with high strength and high elasticity to solve the above technical problems.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a double-component polyurethane structural adhesive, a preparation method and application thereof, wherein the double-component polyurethane structural adhesive comprises an A component and a B component, and the A component comprises hydroxyl-terminated polybutadiene, micromolecular dihydric alcohol, liquid polyester polyol, epoxy modified polyether polyol and an adhesion promoter, and is matched with the specific B component, so that the obtained double-component polyurethane structural adhesive has higher strength and higher elasticity after being solidified, and is suitable for being applied to the adhesion of automobile parts made of glass fiber reinforced plastics.
To achieve the purpose, the invention adopts the following technical scheme:
In a first aspect, the present invention provides a two-component polyurethane structural adhesive comprising an a-component and a B-component;
The component A comprises hydroxyl-terminated polybutadiene, small molecular dihydric alcohol, liquid polyester polyol, epoxy modified polyether polyol and an adhesion promoter;
the component B comprises polyisocyanate and polyurethane prepolymer.
The double-component polyurethane structural adhesive provided by the invention comprises an A component and a B component, wherein the A component comprises hydroxyl-terminated polybutadiene, micromolecular dihydric alcohol, liquid polyester polyol, epoxy modified polyether polyol and an adhesion promoter, and the B component comprises polyisocyanate and polyurethane prepolymer, and the hydroxyl-terminated polybutadiene and the epoxy modified polyether are added into the A component for matching, and the adhesion promoter is added, so that the obtained double-component polyurethane structural adhesive can have high strength and high elasticity after being cured, and is suitable for bonding automobile parts (SMC and other base materials).
Preferably, the component A comprises the following components in parts by weight:
As the preferable technical scheme of the invention, the component A is further limited to comprise the specific parts of the raw materials, so that the obtained double-component polyurethane structural adhesive has higher strength and higher elasticity after being cured; wherein the hydroxyl-terminated polybutadiene may be 17 parts by weight, 19 parts by weight, 21 parts by weight, 23 parts by weight, 25 parts by weight, 27 parts by weight, 29 parts by weight, or the like; the small molecule diol may be 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, or 4.5 parts by weight; the liquid polyester polyol may be 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, or the like; the epoxy-modified polyether polyol may be 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, or the like; the adhesion promoter may be 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, or the like.
Preferably, the hydroxyl-terminated polybutadiene has a hydroxyl number of 0.5 to 1.8meq/g, such as 0.7meq/g, 0.9meq/g, 1.1meq/g, 1.3meq/g, 1.5meq/g, or 1.7meq/g, etc., for example, specifically selected from Yingchangzhucai Poly bdR-20LM, or Poly bdR-45M, poly bdR-45HTLO, polyvestHT, any one or a combination of at least two of the types HTPB-I, HTPB-II, HTPB-IV, HFHTPB-I.
Preferably, the small molecular dihydric alcohol is any one or a combination of at least two of ethylene glycol, butanediol, propylene glycol, glycerol, dipropylene glycol, 1, 4-butanediol, 1, 6-hexanediol or 2-ethyl-1, 3-hexanediol.
Preferably, the liquid polyester polyol may specifically be any one or a combination of at least two of Priplast-3190, priplast-3186, priplast-3192, TPEEGA-1301 or ULTRAOLSTM-P1000.
Preferably, the epoxy-modified polyether may specifically be any one or a combination of at least two of HP2210, HP2240, HP2000L, HP, 2280, HM6210 or HM 6140.
Preferably, the raw materials for preparing the adhesion promoter comprise aminophenylsilane and a silane modifier.
Preferably, the aminophenylsilane comprises any one or a combination of at least two of N-phenyl-gamma-aminopropyl trimethoxysilane, N-phenyl-gamma-aminopropyl triethoxysilane, N-phenylaminomethyl trimethoxysilane and N-phenylaminomethyl triethoxy or gamma-aminopropyl triethoxysilane.
Preferably, the silane modifier comprises any one or a combination of at least two of o-tolylglycidyl ether, p-tolylglycidyl ether, phenyl glycidylether, trityl- (S) -glycidylether and resorcinol diglycidyl ether or gamma-glycidylether oxypropyl trimethoxysilane.
Preferably, the a component further comprises 0.1 to 0.5 parts by weight (e.g., 0.15 parts by weight, 0.2 parts by weight, 0.25 parts by weight, 0.3 parts by weight, 0.35 parts by weight, 0.4 parts by weight, or 0.45 parts by weight, etc.) of a catalyst.
Preferably, the catalyst comprises any one or a combination of at least two of dibutyltin dichloride, dibutyltin dilaurate or stannous octoate and dibutyltin diacetate.
Preferably, the a component further comprises 2 to 10 parts by weight (e.g., 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, etc.) of a silane coupling agent.
Preferably, the silane coupling agent comprises any one or a combination of at least two of gamma-glycidoxypropyl methyl trimethoxysilane, gamma-mercaptopropyl triethoxysilane, gamma-aminopropyl trimethoxysilane, gamma-aminopropyl triethoxysilane, aminoethyl methyl trimethoxysilane, aniline propyl trimethoxysilane or methacryloxypropyl trimethoxysilane.
Preferably, the a component further comprises 35 to 55 parts by weight (e.g., 37 parts by weight, 39 parts by weight, 41 parts by weight, 43 parts by weight, 45 parts by weight, 47 parts by weight, 49 parts by weight, 51 parts by weight, 53 parts by weight, etc.) of filler.
Preferably, the filler comprises any one or a combination of at least two of kaolin, clay, nano calcium carbonate, light calcium carbonate or talcum powder.
Preferably, the component B comprises the following components in parts by weight:
2-10 parts by weight of polyisocyanate;
20-40 parts of polyurethane prepolymer.
As the preferable technical scheme of the invention, the component B is limited to comprise the polyisocyanate and the polyurethane prepolymer in specific parts, so that the obtained double-component polyurethane structural adhesive has higher strength and higher elasticity after being cured; wherein the polyisocyanate may be 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, or the like; the polyurethane prepolymer may be 22 parts by weight, 24 parts by weight, 26 parts by weight, 28 parts by weight, 30 parts by weight, 32 parts by weight, 34 parts by weight, 36 parts by weight, 38 parts by weight, or the like.
Preferably, the polyisocyanate may specifically be any one or a combination of at least two of the smoke-stage Van-type MDI100L, MDI-50, the modified MDI 8239 or the PM 200.
Preferably, the mass percentage of isocyanate groups in the polyurethane prepolymer is 5 to 10%, for example 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9% or 9.5%, etc.
Preferably, the polyurethane prepolymer is obtained by reacting a diisocyanate and a hydroxyl compound.
Preferably, the hydroxyl compound comprises a polyether polyol and a hydroxyl-terminated polybutadiene.
Preferably, the B component further comprises no more than 8 parts by weight (e.g., 7 parts by weight, 6 parts by weight, 5 parts by weight, 4 parts by weight, 3 parts by weight, 2 parts by weight, 1 part by weight, etc.) of a water scavenger.
Preferably, the water scavenger comprises any one or a combination of at least two of calcium oxide, molecular sieve or p-toluenesulfonic acid isocyanate.
Preferably, the B component further comprises 5 to 20 parts by weight (e.g., 7 parts by weight, 9 parts by weight, 11 parts by weight, 13 parts by weight, 15 parts by weight, 17 parts by weight, 19 parts by weight, etc.) of a plasticizer.
Preferably, the plasticizer comprises any one or a combination of at least two of dipropylene glycol dibenzoate, phenyl alkyl sulfonate or diisononyl phthalate.
Preferably, the component B further comprises 1 to 5 parts by weight (e.g., 2 parts by weight, 3 parts by weight, 4 parts by weight, etc.) of fumed silica.
Preferably, the fumed silica is hydrophobic fumed silica, for example, any one or a combination of at least two of wack H18, wack H20, win-wound R974, win-wound R202, or cabot TS720 may be specifically selected.
Preferably, the B component further comprises 20 to 45 parts by weight (e.g., 22 parts by weight, 24 parts by weight, 26 parts by weight, 28 parts by weight, 30 parts by weight, 32 parts by weight, 34 parts by weight, 36 parts by weight, 38 parts by weight, 40 parts by weight, 42 parts by weight, 44 parts by weight, etc.) of filler.
Preferably, the filler comprises any one or a combination of at least two of kaolin, clay, nano calcium carbonate, light calcium carbonate or talcum powder.
In a second aspect, the present invention provides a method for preparing the two-component polyurethane structural adhesive according to the first aspect, wherein the preparation method comprises the preparation of a component A and the preparation of a component B;
The preparation of the component A comprises the following steps: mixing hydroxyl-terminated polybutadiene, small molecular dihydric alcohol, liquid polyester polyol, epoxy modified polyether polyol, an adhesion promoter, optionally a catalyst, optionally a silane coupling agent and optionally a filler to obtain a component A;
the preparation of the component B comprises the following steps: mixing polyisocyanate, polyurethane prepolymer, optional water scavenger, optional plasticizer, optional fumed silica and optional filler to obtain component B.
Preferably, the preparation of the component A specifically comprises: mixing hydroxyl-terminated polybutadiene, small molecular dihydric alcohol, liquid polyester polyol and epoxy modified polyether polyol, adding optional filler, heating to 100-120 ℃ (e.g. 102 ℃, 104 ℃, 106 ℃, 108 ℃, 110 ℃,112 ℃,114 ℃,116 ℃ or 118 ℃, etc.), mixing for 2-3 hours (e.g. 2.1h, 2.2h, 2.3h, 2.4h, 2.5h, 2.6h, 2.7h, 2.8h or 2.9h, etc.), cooling to normal temperature, adding an adhesion promoter, optional silane coupling agent and optional catalyst, mixing for 0.5-1.5 hours (e.g. 0.6h, 0.7h, 0.9h, 1.1h or 1.3h, etc.), and obtaining the component A.
Preferably, the preparation of the component B specifically comprises: mixing polyisocyanate, polyurethane prepolymer, optional water scavenger and optional plasticizer, adding optional gas phase white carbon black and optional filler, and mixing for 0.5-1.5 h (e.g. 0.6h, 0.7h, 0.9h, 1.1h or 1.3h, etc.), to obtain the component B.
In a third aspect, the present invention provides a method for using the two-component polyurethane structural adhesive according to the first aspect, the method comprising: and mixing the component A and the component B, coating the mixture on the surface of a substrate to be bonded, and curing to finish the use of the double-component polyurethane structural adhesive.
Preferably, the substrate to be bonded comprises a plastic substrate.
In a fourth aspect, the present invention provides a use of the two-component polyurethane construction adhesive according to the first aspect for bonding automotive parts.
Preferably, the material of the automobile part is fiber reinforced plastic.
Compared with the prior art, the invention has the following beneficial effects:
The double-component polyurethane structural adhesive provided by the invention comprises an A component and a B component, wherein the A component comprises hydroxyl-terminated polybutadiene, micromolecular dihydric alcohol, liquid polyester polyol, epoxy modified polyether and an adhesion promoter, and the B component comprises polyisocyanate and polyurethane prepolymer; the specific component A and the specific component B are selected for matching, particularly hydroxyl-terminated polybutadiene and epoxy modified polyether are selected for matching in the component A, and an adhesion promoter is added, so that the obtained double-component polyurethane structural adhesive has high strength and high elasticity after being cured, and is suitable for adhesion of automobile parts (SMC and other base materials).
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The information of part of raw materials involved in the specific embodiment of the invention is as follows:
and (3) a component A:
(1) Hydroxyl-terminated polybutadiene: winning polyvestHT, hydroxyl number 0.85meq/g, average functionality 2.5;
(2) 1, 4-butanediol: a national drug group;
(3) 2-ethyl-1, 3-hexanediol: jiangsu Runfeng synthetic technology Co., ltd;
(4) Dipropylene glycol: a national drug group;
(5) Liquid polyester polyol: graminea chemical (Shanghai) limited, priplast TM 3192;
(6) Epoxy modified polyether polyol: nantong Ogyu chemical Co., ltd., HP2240;
(7) Methacryloxypropyl trimethoxysilane: win the traumata and solidity;
(8) Clay: shanxi Jin Yuke, inc., B-95;
(9) Catalyst: shanghai Jide chemical Co., ltd., organic bismuth Bi. -Octoat 8.2.
And the component B comprises the following components:
(1) Polyisocyanates: a smoke table Wanhua chemical group, PM-200;
(2) Water scavenger: 4A molecular sieve activated powder, suzhou little you new materials Co., ltd;
(3) And (3) a plasticizer: langmuir Cheng Huaxue (China) Inc., MESAMOLLs;
(4) Fumed silica: h18, wake chemistry (China) Inc.;
(5) Clay: shanxi Jin Yuke, inc., B-95.
Preparation example 1
An adhesion promoter, the method of preparation comprising: 884g of gamma-aminopropyl triethoxysilane is added into a three-neck flask, the mixture is vacuumized and stirred, the temperature is raised to 55 ℃, the vacuum is removed by nitrogen, 944g of gamma-glycidol ether oxypropyl trimethoxysilane is slowly added into the three-neck flask, the mixture is vacuumized and stirred at 55 ℃ for 4 hours, and then the mixture is cooled and discharged, so that the adhesion promoter is obtained.
Preparation example 2
A polyurethane prepolymer, the method of preparation comprising: 700g of hydroxyl-terminated polybutadiene (polyvestHT) was added to a three-necked flask, heated to 60℃and 300g of diisocyanate (MDI-100) was added thereto, and the temperature was raised to 80℃for reaction for 5 hours to prepare a polyurethane prepolymer having an NCO content of 7.5%.
Preparation example 3
A polyurethane prepolymer, the method of preparation comprising: 700g of polyether polyol F3135 was charged into a three-necked flask, and heated to 60℃to add 270g of diisocyanate (MDI-100), and the reaction was carried out at 80℃for 5 hours to obtain a polyurethane prepolymer having an NCO content of 7.5%.
Examples 1 to 9
The double-component polyurethane structural adhesive comprises an A component and a B component, the specific compositions are shown in a table 1, and the dosage of each component in the table 1 is weight part;
TABLE 1
The preparation method of the two-component polyurethane structural adhesive provided in examples 1 to 9 comprises the preparation of the component A and the preparation of the component B;
The preparation method of the component A comprises the following steps: adding hydroxyl-terminated polybutadiene, micromolecular dihydric alcohol and liquid polyester polyol into a 5L planetary stirrer, vacuumizing and stirring at medium speed for 10min, adding a filler, heating to 115 ℃, stirring and dehydrating for 2.5h under a vacuum state, cooling to normal temperature, adding an adhesion promoter, a silane coupling agent and a catalyst, stirring uniformly for 1h under a vacuum condition, discharging glue into a rubber tube, and sealing and preserving to obtain a component A;
the preparation method of the component B comprises the following steps: adding polyisocyanate, polyurethane prepolymer, a water removing agent and a plasticizer into a 5L planetary stirrer, vacuumizing and stirring for 10min at medium speed, adding gas-phase white carbon black and a filler, uniformly stirring for 1h under a vacuum condition, discharging glue into a rubber tube, and sealing and preserving to obtain a component B.
Comparative example 1
A two-component polyurethane construction adhesive was distinguished from example 1 in that no adhesion promoter was added, the filler was added in an amount of 54 parts by weight, and the other components, amounts and preparation methods were the same as in example 1.
Comparative example 2
A two-component polyurethane construction adhesive was distinguished from example 1 in that no liquid polyester polyol was added, the filler was added in an amount of 54 parts by weight, and the other components, amounts and preparation methods were the same as in example 1.
Comparative example 3
A two-component polyurethane construction adhesive is distinguished from example 1 in that no epoxy-modified polyether polyol is added, the hydroxyl-terminated polybutadiene is added in an amount of 33 parts by weight, and the other components, amounts and preparation methods are the same as in example 1.
Performance test:
(1) Shear strength: preparing a sample according to the specification of GB/T7124-2008, wherein a glass fiber reinforced polypropylene (PP-LGF) with the thickness of 4.0mm is selected as a test base material, the width of a shearing sample piece is 10mm, the A component and the B component of the double-component polyurethane structural adhesive are mixed according to the mass ratio of 1:0.9, the thickness of an adhesive layer is 2mm, the prepared sample is placed at normal temperature for 168 hours, then the test is carried out, and the test speed is 20mm/min;
(2) Tensile strength and elongation at break: performing test according to the specification of GB/T528-2009, wherein a dumbbell-shaped test piece of type 2 is adopted, the prepared test piece is placed under standard test conditions for 168 hours, and then the test is performed at the test speed of 500mm/min;
(3) Interfacial adhesion: mixing the component A and the component B in the bi-component polyurethane structural adhesive according to the mass ratio of 1:0.9, wherein the base material is glass fiber reinforced polypropylene (PP-LGF) with the size of 150 multiplied by 100 multiplied by 4mm; the test steps are as follows: a) Cleaning the PP-LGF board with a cleaning agent, and airing for 5min; b) Coating the glass cement on the sample plate by a cement extruding gun to form a semicircular adhesive tape with phi of 10 multiplied by 150 mm; c) Placing the test piece at normal temperature for 168 hours to fully solidify the test piece; d) The test piece is taken out, one end of the solidified adhesive tape is clamped by a pair of locking pliers, the adhesive tape is pulled, the adhesive tape is cut by a blade along the horizontal direction with the axis of the adhesive tape, and the damage condition (CF is the damage of the adhesive tape and cohesive damage) is observed.
The two-component polyurethane structural adhesives provided in examples 1 to 9 and comparative examples 1 to 3 were subjected to the following test according to the above-described test method, and the test results are shown in table 2;
TABLE 2
As can be seen from the data in table 2: the double-component polyurethane structural adhesive provided by the invention has excellent adhesive property with a base material after being cured, and simultaneously has high strength and high elasticity;
Specifically, the shear strength of the two-component polyurethane structural adhesive provided in examples 1-4 is 6.61-7.62 MPa, the tensile strength is 8.86-9.34 MPa, the elongation at break is 204-312%, and the interfacial adhesion is 100% CF failure;
Comparing example 1 with comparative example 1, it was found that the two-component polyurethane structural adhesive without liquid polyester polyol provided in comparative example 1 was lower in both shear strength and tensile strength, and the interfacial adhesion showed only 30% cf failure, indicating poor cohesion;
Comparing example 1 with comparative example 2, it can be seen that the two-component polyurethane structural adhesive without the epoxy-modified polyether polyol provided in comparative example 2 has a similarly lower shear strength and exhibits only 50% cf failure, indicating that the cohesion is also poor;
Comparing example 1 with comparative example 3, it can be seen that the two-component polyurethane structural adhesive without the epoxy-modified polyether polyol provided in comparative example 3 has a higher interfacial adhesion but a lower shear strength and tensile strength;
Further comparing examples 1 and 5 to 9, it is also found that the addition or non-addition of the silane coupling agent, the addition or non-addition of the adhesion promoter, and the addition or non-addition of the epoxy-modified polyether polyol adversely affect the properties of the finally prepared two-component polyurethane structural adhesive, which cannot combine excellent adhesive properties, high strength and high elasticity after curing.
The applicant states that the present invention is illustrated by the above examples as a two-component polyurethane construction adhesive and a method of preparing and using the same, but the present invention is not limited to, i.e., does not mean that the present invention must be practiced in dependence upon the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (28)
1. The two-component polyurethane structural adhesive is characterized by comprising an A component and a B component;
The component A comprises the following components in parts by weight:
15-30 parts by weight of hydroxyl-terminated polybutadiene;
1-5 parts by weight of small molecular dihydric alcohol;
4-10 parts by weight of liquid polyester polyol;
4-10 parts by weight of epoxy modified polyether polyol;
1-6 parts by weight of an adhesion promoter;
2-10 parts by weight of a silane coupling agent;
the component B comprises polyisocyanate and polyurethane prepolymer;
The raw materials for preparing the adhesion promoter comprise aminophenylsilane and a silane modifier.
2. The two-component polyurethane structural adhesive of claim 1, wherein the hydroxyl-terminated polybutadiene has a hydroxyl number of 0.5 to 1.8 meq/g.
3. The two-component polyurethane construction adhesive according to claim 1, wherein the small molecule diol is any one or a combination of at least two of ethylene glycol, butanediol, propylene glycol, glycerol, dipropylene glycol, 1, 4-butanediol, 1, 6-hexanediol or 2-ethyl-1, 3-hexanediol.
4. The two-part polyurethane construction adhesive of claim 1, wherein the aminophenylsilane comprises any one or a combination of at least two of N-phenyl- γ -aminopropyl trimethoxysilane, N-phenyl- γ -aminopropyl triethoxysilane, N-phenylaminomethyl trimethoxysilane, and N-phenylaminomethyl triethoxy or γ -aminopropyl triethoxy silane.
5. The two-part polyurethane structural adhesive of claim 1, wherein the silane modifier comprises any one or a combination of at least two of o-tolylglycidyl ether, p-tolylglycidyl ether, phenyl glycidyl ether, trityl- (S) -glycidyl ether, and resorcinol diglycidyl ether or gamma-glycidyl ether oxypropyl trimethoxysilane.
6. The two-component polyurethane construction adhesive according to claim 1, wherein the a component further comprises 0.1 to 0.5 parts by weight of a catalyst.
7. The two-component polyurethane construction adhesive of claim 6, wherein the catalyst comprises any one or a combination of at least two of dibutyltin dichloride, dibutyltin dilaurate or stannous octoate, dibutyltin diacetate.
8. The two-component polyurethane construction adhesive according to claim 1, wherein the silane coupling agent comprises any one or a combination of at least two of gamma-glycidoxypropyl methyl trimethoxysilane, gamma-mercaptopropyl triethoxysilane, gamma-aminopropyl trimethoxysilane, gamma-aminopropyl triethoxysilane, aminoethyl methyl trimethoxysilane, aniline propyl trimethoxysilane, or methacryloxypropyl trimethoxysilane.
9. The two-component polyurethane construction adhesive according to claim 1, wherein the a component further comprises 35 to 55 parts by weight of a filler.
10. The two-component polyurethane construction glue of claim 9, wherein the filler comprises any one or a combination of at least two of kaolin, clay, nano calcium carbonate, light calcium carbonate, or talc.
11. The two-component polyurethane construction adhesive according to claim 1, wherein the B component comprises the following components in parts by weight:
2-10 parts by weight of polyisocyanate;
20-40 parts of polyurethane prepolymer.
12. The two-component polyurethane structural adhesive according to claim 1, wherein the mass percentage of isocyanate groups in the polyurethane prepolymer is 5-10%.
13. The two-component polyurethane construction adhesive according to claim 1, wherein the polyurethane prepolymer is obtained by reacting a diisocyanate and a hydroxyl compound.
14. The two-part polyurethane construction adhesive of claim 13 wherein the hydroxyl compound comprises a polyether polyol and a hydroxyl-terminated polybutadiene.
15. The two-part polyurethane construction adhesive of claim 1 wherein the B-part further comprises no more than 8 parts by weight of a water scavenger.
16. The two-component polyurethane construction adhesive of claim 15, wherein the water scavenger comprises any one or a combination of at least two of calcium oxide, molecular sieve, or p-toluenesulfonic acid isocyanate.
17. The two-component polyurethane construction adhesive according to claim 1, wherein the B component further comprises 5 to 20 parts by weight of a plasticizer.
18. The two-part polyurethane construction adhesive of claim 17, wherein the plasticizer comprises any one or a combination of at least two of dipropylene glycol dibenzoate, phenyl alkyl sulfonate, or diisononyl phthalate.
19. The two-component polyurethane structural adhesive according to claim 1, wherein the component B further comprises 1-5 parts by weight of fumed silica.
20. The two-component polyurethane construction adhesive of claim 19, wherein the fumed silica is a hydrophobic fumed silica.
21. The two-component polyurethane construction adhesive according to claim 1, wherein the B component further comprises 20 to 45 parts by weight of a filler.
22. The two-component polyurethane construction glue of claim 21, wherein the filler comprises any one or a combination of at least two of kaolin clay, nano calcium carbonate, light calcium carbonate, or talc.
23. A method for preparing the two-component polyurethane structural adhesive according to any one of claims 1 to 22, wherein the preparation method comprises the preparation of a component a and the preparation of a component B;
The preparation of the component A comprises the following steps: mixing hydroxyl-terminated polybutadiene, small molecular dihydric alcohol, liquid polyester polyol, epoxy modified polyether polyol, an adhesion promoter, optionally a catalyst, optionally a silane coupling agent and optionally a filler to obtain a component A;
the preparation of the component B comprises the following steps: mixing polyisocyanate, polyurethane prepolymer, optional water scavenger, optional plasticizer, optional fumed silica and optional filler to obtain component B.
24. The preparation method according to claim 23, wherein the preparation of the a component specifically comprises: mixing hydroxyl-terminated polybutadiene, micromolecular dihydric alcohol, liquid polyester polyol and epoxy modified polyether polyol, adding optional filler, heating to 100-120 ℃, mixing for 2-3 h, cooling to normal temperature, adding an adhesion promoter, optional silane coupling agent and optional catalyst, and mixing for 0.5-1.5 h to obtain the component A.
25. The preparation method according to claim 23, wherein the preparation of the B component specifically comprises: mixing polyisocyanate, polyurethane prepolymer, optional water scavenger and optional plasticizer, adding optional fumed silica and optional filler, and mixing for 0.5-1.5 h to obtain the component B.
26. A method of using the two-component polyurethane structural adhesive of any one of claims 1-22, comprising: and mixing the component A and the component B, coating the mixture on the surface of a substrate to be bonded, and curing to finish the use of the double-component polyurethane structural adhesive.
27. Use of the two-component polyurethane structural adhesive according to any one of claims 1 to 22 for bonding automotive parts.
28. The use according to claim 27, wherein the automotive component is made of fiber reinforced plastic.
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| CN115975586A (en) * | 2022-12-08 | 2023-04-18 | 湖北回天新材料股份有限公司 | Double-component polyurethane structural adhesive and application thereof |
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| CN115975586A (en) * | 2022-12-08 | 2023-04-18 | 湖北回天新材料股份有限公司 | Double-component polyurethane structural adhesive and application thereof |
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| 木质素基聚酯型聚氨酯胶黏剂的制备及表征;来雅赟 等;化学与黏合;20180630;第40卷(第6期);397-400 * |
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