CN116640288A - Aqueous polyurethane emulsion, preparation method thereof and two-component polyurethane adhesive - Google Patents
Aqueous polyurethane emulsion, preparation method thereof and two-component polyurethane adhesive Download PDFInfo
- Publication number
- CN116640288A CN116640288A CN202310762601.5A CN202310762601A CN116640288A CN 116640288 A CN116640288 A CN 116640288A CN 202310762601 A CN202310762601 A CN 202310762601A CN 116640288 A CN116640288 A CN 116640288A
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- Prior art keywords
- optionally
- chain extender
- monomer
- component
- isocyanate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 96
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 96
- 239000000839 emulsion Substances 0.000 title claims abstract description 61
- 239000000853 adhesive Substances 0.000 title claims abstract description 42
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 239000004970 Chain extender Substances 0.000 claims abstract description 55
- 239000012948 isocyanate Substances 0.000 claims abstract description 42
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 42
- 229920005862 polyol Polymers 0.000 claims abstract description 35
- 150000003077 polyols Chemical class 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000002156 mixing Methods 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 32
- 150000007942 carboxylates Chemical class 0.000 claims abstract description 27
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 24
- -1 acrylic ester Chemical class 0.000 claims abstract description 17
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 239000000178 monomer Substances 0.000 claims description 48
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 28
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 18
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 14
- 229920005906 polyester polyol Polymers 0.000 claims description 14
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 13
- 229920000570 polyether Polymers 0.000 claims description 13
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 13
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 11
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 11
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 9
- 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 9
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 claims description 8
- 229940047670 sodium acrylate Drugs 0.000 claims description 8
- 239000002562 thickening agent Substances 0.000 claims description 8
- 125000003368 amide group Chemical group 0.000 claims description 7
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 7
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 claims description 7
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 6
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 6
- 239000013530 defoamer Substances 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 150000004985 diamines Chemical class 0.000 claims description 4
- 150000002009 diols Chemical class 0.000 claims description 4
- 239000004973 liquid crystal related substance Substances 0.000 claims description 4
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 4
- 229920001610 polycaprolactone Polymers 0.000 claims description 4
- 238000010526 radical polymerization reaction Methods 0.000 claims description 4
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 claims description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- IEVADDDOVGMCSI-UHFFFAOYSA-N 2-hydroxybutyl 2-methylprop-2-enoate Chemical compound CCC(O)COC(=O)C(C)=C IEVADDDOVGMCSI-UHFFFAOYSA-N 0.000 claims description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 3
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 3
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 3
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 claims description 3
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 3
- 239000004632 polycaprolactone Substances 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 239000005056 polyisocyanate Substances 0.000 claims description 3
- 229920001228 polyisocyanate Polymers 0.000 claims description 3
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 24
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 238000006386 neutralization reaction Methods 0.000 abstract description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 18
- 238000012360 testing method Methods 0.000 description 11
- 238000009775 high-speed stirring Methods 0.000 description 10
- 239000007787 solid Substances 0.000 description 9
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000004945 emulsification Methods 0.000 description 6
- 239000010985 leather Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000004448 titration Methods 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 2
- 238000004026 adhesive bonding Methods 0.000 description 2
- 239000002313 adhesive film Substances 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- MGSRCZKZVOBKFT-UHFFFAOYSA-N thymol Chemical compound CC(C)C1=CC=C(C)C=C1O MGSRCZKZVOBKFT-UHFFFAOYSA-N 0.000 description 2
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- QAKHVURZPCJUQA-UHFFFAOYSA-N 2-cyanopropane-1-sulfonic acid Chemical compound N#CC(C)CS(O)(=O)=O QAKHVURZPCJUQA-UHFFFAOYSA-N 0.000 description 1
- XRUKRHLZDVJJSX-UHFFFAOYSA-N 4-cyanopentanoic acid Chemical compound N#CC(C)CCC(O)=O XRUKRHLZDVJJSX-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005844 Thymol Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- BLAKAEFIFWAFGH-UHFFFAOYSA-N acetyl acetate;pyridine Chemical compound C1=CC=NC=C1.CC(=O)OC(C)=O BLAKAEFIFWAFGH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229940048053 acrylate Drugs 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 231100000206 health hazard Toxicity 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- VCZJXEMVLNYRAS-UHFFFAOYSA-M sodium 1,4-diaminobutane-1-sulfonate Chemical compound [Na+].NCCCC(S(=O)(=O)[O-])N VCZJXEMVLNYRAS-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 229960000790 thymol Drugs 0.000 description 1
Classifications
-
- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6655—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4063—Mixtures of compounds of group C08G18/62 with other macromolecular compounds
-
- 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
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- 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
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
-
- 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
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
- C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
- C08G18/722—Combination of two or more aliphatic and/or cycloaliphatic polyisocyanates
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- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- 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
- C09J175/06—Polyurethanes from polyesters
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to the technical field of adhesives, and provides a waterborne polyurethane emulsion, a preparation method thereof and a double-component polyurethane adhesive. The method for preparing the aqueous polyurethane emulsion comprises the following steps: mixing an oligomer polyol, a first isocyanate, a first chain extender, a second chain extender and water to obtain an aqueous polyurethane emulsion; wherein the first chain extender comprises at least one of polyacrylate carboxylate, polyacrylate sulfonate, and polyacrylate carboxylate/sulfonate. The method can realize hydrophilic chain extension and acrylic ester modification of polyurethane, has mild hydrophilic chain extension reaction, can reduce the solvent consumption, does not need neutralization, and has stable properties of the obtained aqueous polyurethane emulsion.
Description
Technical Field
The invention relates to the technical field of adhesives, in particular to a waterborne polyurethane emulsion, a preparation method thereof and a double-component polyurethane adhesive.
Background
The aqueous polyurethane adhesive has the characteristics of excellent wear resistance, chemical corrosion resistance, excellent flexibility, good adhesive force and high glossiness, is widely used in industries of shoemaking, clothing, building, automobile and food packaging, kitchen supplies, composite films and the like, has low content of volatile organic solvents, has the characteristics of no toxicity, flame retardance, no peculiar smell, environmental friendliness, no health hazard to operators and the like, and becomes a key development direction of the polyurethane adhesive. However, the current aqueous polyurethane adhesive shows poor adhesion when bonding low surface tension substrates, and the adhesive bonding piece has poor high temperature resistance, and the adhesive bonding strength of the adhesive in a high temperature environment reduces the hydrolysis resistance and is not enough. In addition, the aqueous polyurethane has a lower solids content, which in turn increases both transportation and drying costs.
Therefore, studies on aqueous polyurethane adhesives are in progress.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the related art to some extent.
In one aspect of the invention, the invention provides a method of preparing an aqueous polyurethane emulsion, the method comprising: mixing an oligomer polyol, a first isocyanate, a first chain extender, a second chain extender and water to obtain an aqueous polyurethane emulsion; wherein the first chain extender comprises at least one of polyacrylate carboxylate, polyacrylate sulfonate, and polyacrylate carboxylate/sulfonate. The method can realize hydrophilic chain extension and acrylic ester modification of polyurethane, has mild hydrophilic chain extension reaction, can reduce the solvent consumption, and does not need neutralization, so that the obtained aqueous polyurethane emulsion has stable property.
According to an embodiment of the invention, the mixing is performed according to the following steps:
(1) First mixing an oligomeric polyol with a first isocyanate to obtain a prepolymer;
(2) Second mixing the prepolymer with a first chain extender;
(3) Thirdly mixing the product obtained in the step (2) with a second chain extender;
(4) And (3) fourth mixing the product obtained in the step (3) with water so as to obtain the aqueous polyurethane emulsion. Thus, the sufficient reaction of the raw materials can be promoted, and stable aqueous polyurethane emulsion can be formed.
According to an embodiment of the present invention, the molar ratio of the oligomer polyol to the first isocyanate is (0.2-2) to 1 such that a prepolymer having reactive end groups (isocyanate groups) is formed, which facilitates the subsequent chain extension reaction.
According to an embodiment of the invention, the oligomer polyol comprises a polyester polyol and optionally a polyether polyol.
According to an embodiment of the present invention, the weight average molecular weight of the polyester polyol is 500 to 10000.
According to an embodiment of the present invention, the polyester polyol includes at least one of polybutylene adipate glycol, polycaprolactone diol, and polycarbonate diol.
According to an embodiment of the invention, the polyether polyol has a weight average molecular weight of 90-2000.
According to an embodiment of the present invention, the polyether polyol includes at least one of polytetrahydrofuran ether glycol, polypropylene glycol and polyethylene glycol.
According to an embodiment of the present invention, the first isocyanate monomer includes at least one of hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate, dicyclohexylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, and xylylene diisocyanate.
According to an embodiment of the present invention, the weight average molecular weight of the first chain extender is 500 to 5000.
According to an embodiment of the invention, the hydroxyl value of the first chain extender is from 15mgKOH/g to 77mgKOH/g.
According to an embodiment of the invention, the content of carboxylate groups or/and sulfonate groups of the first chain extender is 0.1mmol/g-2mmol/g.
According to an embodiment of the present invention, the content of amide groups of the first chain extender is 0.1mmol/g-1mmol/g.
According to an embodiment of the present invention, a method of preparing the first chain extender includes: in the presence of an initiator and a solvent, carrying out free radical polymerization reaction on an acrylic monomer, a first monomer and a second monomer; wherein the first monomer is selected from an acrylic hydroxy ester monomer and/or an acrylamide monomer; the second monomer is selected from at least one of sodium acrylate and sodium acrylate.
According to the embodiment of the invention, the weight parts ratio of the acrylic monomer to the first monomer to the second monomer is (0.3-20) to (0.1-21) to (0.5-13) to 1.
According to an embodiment of the present invention, the acrylic monomer includes at least one of acrylic acid and methacrylic acid from the viewpoint of easy availability of raw materials.
According to an embodiment of the present invention, the acrylic monomer includes at least one of methyl methacrylate, butyl methacrylate, ethyl acrylate, ethyl methacrylate, and isooctyl acrylate.
According to an embodiment of the present invention, the hydroxy acrylate monomer includes at least one of hydroxy ethyl acrylate, hydroxy ethyl methacrylate, hydroxy propyl acrylate, hydroxy propyl methacrylate, hydroxy butyl acrylate, and hydroxy butyl methacrylate.
According to the embodiment of the invention, from the standpoint of easy availability of raw materials, the acrylamide monomer includes at least one of acrylamide and methacrylamide.
According to the embodiment of the invention, the mass ratio of the first chain extender to the prepolymer is 1:7-40.
According to an embodiment of the invention, the second chain extender comprises a diamine and/or an alcohol amine.
According to an embodiment of the present invention, the mass content of the second chain extender is 0.5% -5% with respect to the total mass of the reactants.
In another aspect of the invention, an aqueous polyurethane emulsion is provided, which is prepared by the aforementioned method. The aqueous polyurethane emulsion has higher stability and adhesive force.
In yet another aspect of the present invention, a two-component polyurethane adhesive is provided comprising an A component and a B component, wherein the A component comprises the aqueous polyurethane emulsion described above and the B component comprises a second isocyanate. Therefore, the obtained double-component polyurethane adhesive has stronger cohesive force, better high-temperature and high-humidity resistance, stronger mechanical property and better hydrophilicity, and the double-component polyurethane adhesive has large molecular weight, high solid content and high crosslinking degree.
According to the embodiment of the invention, the mass content of the isocyanate groups in the second isocyanate is 13-25%.
According to the embodiment of the invention, the mass ratio of the aqueous polyurethane emulsion to the second isocyanate is (12-25) to 1. Therefore, after the two components are mixed, a cross-linked product with high cross-linking degree is formed, and the binding force is further improved.
According to an embodiment of the present invention, the a-component further comprises an additive comprising at least one of a thickener, an antifoaming agent, and a leveling agent. Therefore, the uniformity of the adhesive after film formation can be improved, and the use effect of the adhesive is ensured.
According to the embodiment of the invention, the mass content of the aqueous polyurethane emulsion is 70-90 parts based on 100 parts of the total weight of the component A.
Drawings
The foregoing and/or additional aspects and advantages of the invention will become apparent and may be better understood from the following description of embodiments taken in conjunction with the accompanying drawings in which:
FIG. 1 is a flow chart of a process for preparing an aqueous polyurethane emulsion according to some embodiments of the present invention;
FIG. 2 is a flow chart of a method for preparing a two-component polyurethane adhesive according to some embodiments of the present invention.
Detailed Description
Embodiments of the present invention are described in detail below, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to like or similar elements or elements having like or similar functions throughout. The embodiments described below by referring to the drawings are illustrative and intended to explain the present invention and should not be construed as limiting the invention.
According to a first aspect of the present invention, there is provided a method of preparing an aqueous polyurethane emulsion comprising:
mixing an oligomer polyol, a first isocyanate, a first chain extender, a second chain extender and water to obtain an aqueous polyurethane emulsion;
wherein the first chain extender comprises at least one of polyacrylate carboxylate, polyacrylate sulfonate, and polyacrylate carboxylate/sulfonate.
In some embodiments, as shown in fig. 1, the method includes the steps of:
s100: the oligomer polyol and the first isocyanate are first mixed to obtain a prepolymer.
In this step, the oligomer polyol and the first isocyanate are subjected to an addition reaction by the first mixing to obtain a prepolymer.
In some embodiments, the temperature of the first mixing is from 40 ℃ to 80 ℃ and the first mixing is performed under stirring conditions. Specifically, after the oligomer polyol and the first isocyanate are uniformly mixed, the mixture is reacted at the temperature, in the reaction process, the isocyanate content in a reaction system is tracked and measured by a chemical titration method, after the isocyanate content reaches a theoretical value, the temperature of the reaction system is reduced to 20-60 ℃, and acetone is added to adjust the viscosity of the system, so that the prepolymer is obtained.
In some embodiments, prior to performing the first mixing, the method further comprises: the oligomer polyol is pretreated to remove small molecules such as water possibly existing in the oligomer polyol, so that the water and polyurethane raw materials are prevented from undergoing curing reaction, and the emulsion stability is prevented from being influenced. The method of preprocessing may include: distilling under reduced pressure at 100-130deg.C for 1-3 h, controlling the reduced pressure not greater than-0.08 MPa, and controlling the water mass content in the system below 0.1%, such as 0.05% -0.1%.
In some embodiments, the oligomer polyol is a polyester polyol. In other embodiments, the oligomer polyols are polyester polyols and polyether polyols.
In some embodiments, the mass ratio of the polyester polyol to the polyether polyol is 1: (0-0.4). Preferably, the mass ratio of the polyester polyol to the polyether polyol is 1:0.01-0.4, and the solid content of the aqueous polyurethane emulsion can be improved by introducing a small amount of polyether polyol, so that the storage space and the transportation cost of the emulsion are reduced, and the polyurethane adhesive layer has higher elongation at break and tensile strength.
In some embodiments, the polyester polyol has a weight average molecular weight (Mw) of 500 to 10000, such as 500, 650, 850, 1000, 2000, 3000, 5000, 8000, 10000, and the like. Thereby controlling the molecular weight of polyurethane and improving the emulsification effect of polyurethane. The polyester polyols may be obtained by methods well known in the art and also commercially available, for example, from Huada chemical company.
In some embodiments, the polyether polyol has a weight average molecular weight of 90-2000, such as 90, 100, 250, 650, 1000, 2000, etc. Therefore, the solubility of the prepolymer in the solvent can be improved, the subsequent chain extension reaction can be promoted, the emulsifying effect can be improved, and the ether bond can be controlled in a proper range, so that the adhesive force can be improved. The polyester polyols may be obtained by methods well known in the art and also commercially available, for example, from basf, various polyether polyols such as PTMG650 and the like.
In some embodiments, the molar ratio of the oligomeric polyol to the first isocyanate is (0.2-2) to 1. While the oligomer polyol and the first isocyanate are in the foregoing ranges, the resulting polyurethane prepolymer has a higher bond line strength and a higher elongation at break of the bond line.
Optionally, the polyester polyol comprises at least one of polybutylene adipate glycol (PBA), polyhexamethylene adipate glycol (PHA), polycaprolactone glycol (PCL), and polycarbonate glycol (PCD).
Alternatively, the polyether polyol comprises at least one of polytetrahydrofuran ether glycol, polypropylene glycol and polyethylene glycol.
Alternatively, the first isocyanate includes at least one of hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate, dicyclohexylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, and xylylene diisocyanate.
In some preferred embodiments, the first isocyanate is a combination of hexamethylene diisocyanate and isophorone diisocyanate, and the molar ratio of hexamethylene diisocyanate to isophorone diisocyanate is from 90:10 to 70:30. Because the hexamethylene diisocyanate has a symmetrical and regular structure, if the hexamethylene diisocyanate occupies a relatively large area, the hexamethylene diisocyanate is favorable for the rapid crystallization of the aqueous polyurethane, so that the obtained adhesive layer has high strength; the isophorone diisocyanate has small crystallization contribution degree to the waterborne polyurethane, but because the reactivity difference of two isocyanate groups is large, only one isocyanate group usually participates in the reaction and can be used as a blocking agent, and the reserved isocyanate group reacts with the amino group with extremely high activity in the post-emulsification stage to further chain extend, so that the molecular weight of the waterborne polyurethane is further increased. Thus, a polyurethane prepolymer having a relatively high molecular weight can be obtained.
S200: the prepolymer is second mixed with the first chain extender. Reacting the prepolymer with the first chain extender by the second mixing to further increase the molecular weight of the polyurethane.
According to an embodiment of the invention, the second mixing comprises: and (3) dropwise adding the first chain extender into the prepolymer obtained in the step (S100) under high-speed stirring, for example, dropwise adding for 10-30 min, and continuing the high-speed stirring reaction for 20-60 min after the completion of the dropwise adding. The high-speed stirring speed is, for example, 1500rpm to 5000rpm.
In some embodiments, the mass ratio of the first chain extender to the prepolymer amount is 1: (7-40). Wherein the mass of the prepolymer is determined by the total amount of reactants (isocyanate and polyol).
In the present invention, the first chain extender includes at least one of polyacrylate carboxylate, polyacrylate sulfonate, and polyacrylate carboxylate/sulfonate. Wherein polyacrylate carboxylate/sulfonate refers to polyacrylate having both carboxylate and sulfonate groups on the molecular chain.
In some embodiments, the first chain extender further has hydroxyl and/or amide groups thereon.
In some embodiments, the first chain extender has a weight average molecular weight of 500 to 5000, such as 500, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, 5000, and the like; hydroxyl values of 15mgKOH/g to 77mgKOH/g, such as 15mgKOH/g, 30mgKOH/g, 45mgKOH/g, 60mgKOH/g, 77mgKOH/g, etc.; the content of carboxylate groups or/and sulfonate groups is 0.1mmol/g-2mmol/g, such as 0.1mmol/g, 0.5mmol/g, 1mmol/g, 1.5mmol/g, 2mmol/g, etc.); the content of the amide group is 0.1mmol/g to 1mmol/g, such as 0.1mmol/g, 0.2mmol/g, 0.4mmol/g, 0.6mmol/g, 0.8mmol/g, 1mmol/g, etc. Under the above parameter conditions, the first chain extender and the prepolymer obtained in step S100 can be uniformly and effectively mixed to perform chain extension, so as to obtain the acrylate modified polyurethane, and the molecular weight of the finally obtained waterborne polyurethane is increased.
In the present invention, "content of carboxylate groups or/and sulfonate groups" refers to the total content of carboxylate groups and sulfonate groups on the first chain extender, and is selected according to the specific type of first chain extender. For example, when the first chain extender is a polyacrylate carboxylate, "the content of carboxylate groups or/and sulfonate groups" refers to the content of carboxylate groups; when the first chain extender is polyacrylate sulfonate, "carboxylate group or/and sulfonate group content" refers to sulfonate group content; when the first chain extender is a polyacrylate carboxylate and polyacrylate sulfonate combination or is a polyacrylate carboxylate/sulfonate, "the content of carboxylate groups or/and sulfonate groups" refers to the total content of carboxylate groups and sulfonate groups.
In some embodiments, the method of preparing the first chain extender described above comprises: mixing an initiator, an acrylic monomer, a first monomer (an acrylic hydroxy ester monomer and/or an acrylamide monomer) and a second monomer (at least one of sodium acrylate and sodium acrylate) with a solvent, performing free radical polymerization, and removing the solvent under reduced pressure after the polymerization is finished. Wherein the weight ratio of the acrylic monomer to the first monomer to the second monomer is (0.3-20) to (0.1-21) to (0.5-13) to 1.
The temperature of the free radical polymerization reaction can be 60-80 ℃ and the reaction time can be 2-4 h.
As an example, the acrylic monomer may be selected from one or more of monomers having 3 to 8 carbon atoms. Optionally, the acrylic monomer comprises an acrylic monomer comprising acrylic acid and/or methacrylic acid.
As an example, the acrylic monomer may be selected from one or more monomers having 4 to 12 carbon atoms. Optionally, the acrylic monomer includes at least one of methyl methacrylate, butyl methacrylate, ethyl acrylate, ethyl methacrylate, and isooctyl acrylate.
As an example, the hydroxy acrylate monomer may be selected from one or more of monomers having 5 to 12 carbon atoms. Optionally, the hydroxy acrylate monomer includes at least one of hydroxy ethyl acrylate, hydroxy ethyl methacrylate, hydroxy propyl acrylate, hydroxy propyl methacrylate, hydroxy butyl acrylate, and hydroxy butyl methacrylate.
As an example, the acrylamide-based monomer may be selected from one or more of monomers having 3 to 6 carbon atoms. Optionally, the acrylamide-based monomer comprises acrylamide and/or methacryloyl.
In the present invention, the initiator may be various radical initiators for initiating polymerization of the above monomers. In some embodiments, the initiator comprises dibenzoyl peroxide, t-butyl peroxybenzoate, azobisisobutyronitrile, azobisisoheptonitrile, cyclohexanone peroxide, t-butyl hydroperoxide, cumene peroxide, hydrogen peroxide, persulfate, dimethyl azobisisobutyrate, azobisisobutylamidine hydrochloride, 2 ， -azobis (2-methyl-4-carboxybutyronitrile) and 2,2 ， -at least one of azobis (2-cyanopropane-1-sulfonate); the solvent may include at least one of ethyl acetate and toluene.
S300: and thirdly mixing the product obtained in the step S200 with a second chain extender. Thereby, the second chain extender further extends the chain, so that the molecular weight of the aqueous polyurethane is further increased.
In this step, the second chain extender may be added to the product obtained in step S200 with stirring to perform post-chain extension. In some embodiments, the second chain extender comprises at least one of a diamine and an alcohol amine. The diamine is, for example, ethylenediamine and the alcohol amine is, for example, ethanolamine. The mass amount of the second chain extender may be 0.5% -5% with respect to the total amount of reactants. Wherein the total amount of reactants is determined by the total amount of reactants (oligomer polyol, first isocyanate, first chain extender, second chain extender and water).
In this step, the temperature of the third mixture (i.e., the chain extension reaction) may be 20℃to 40℃and the time may be 10min to 50min.
S400: and fourth mixing the product obtained in the step S300 with water. The emulsion is achieved by adding water (e.g., dropwise) as an emulsifier to disperse the polyurethane at high speed. The aqueous polyurethane emulsion with the solid content reaching 40-75% can be obtained through the emulsification.
In some embodiments, the method may further comprise: acetone was removed under reduced pressure. The acetone distilled off under reduced pressure can be recycled.
According to a second aspect of the present invention there is provided an aqueous polyurethane emulsion prepared by the process.
In some embodiments, the aqueous polyurethane emulsion has a solids content of 50% to 75% and an average particle size of 100nm to 150nm.
The aqueous polyurethane emulsion also has higher stability, and does not have layering phenomenon after being placed for a long time (more than or equal to 180 days) at room temperature.
According to a third aspect of the present invention, there is provided a two-component polyurethane adhesive comprising an a-component and a B-component, wherein the a-component comprises the aqueous polyurethane emulsion provided in the second aspect of the present invention and the B-component comprises a second isocyanate.
According to the invention, the A-component may also comprise additives, which additives may be selected with reference to existing two-component polyurethane adhesives. In some embodiments, the additive includes at least one of a thickener, an antifoaming agent, and a leveling agent. The additive is typically an aqueous material.
Further, in the component A, the mass content of the aqueous polyurethane emulsion is 70-90 parts based on 100 parts of the total weight of the component A.
As an example, in the a component, 85 to 99 parts by mass of the aqueous polyurethane emulsion, 0.05 to 5 parts by mass of the aqueous thickener, 0.03 to 6 parts by mass of the aqueous defoamer, 0.02 to 4 parts by mass of the aqueous leveling agent, and 100 parts by mass of the total amount of the a component.
According to the invention, the B component may also comprise an aqueous color paste and water. The aqueous color paste can be window pigment, and in the glue mixing stage, whether the two components are uniformly mixed is judged A, B for the convenience and clarity of operators.
In some embodiments, in the component B, the second isocyanate is 80 to 90 parts by mass, the aqueous color paste is 0 to 1 part by mass, the water is 10 to 19 parts by mass, and the total amount of the component B is 100 parts by mass.
In some embodiments, the two-part polyurethane adhesive is prepared according to the following method: and respectively preparing an A component containing the aqueous polyurethane emulsion and a B component containing the second isocyanate to obtain the double-component polyurethane adhesive.
In other embodiments, the two-part polyurethane adhesive is prepared according to the following method: respectively preparing an A component containing aqueous polyurethane emulsion and a B component containing second isocyanate; then, as shown in fig. 2, S500: the component a comprising the aqueous polyurethane emulsion is mixed with the component B comprising the second isocyanate in order to obtain a two-component polyurethane adhesive. The mixing may be performed at room temperature.
In some embodiments, the mass ratio of the amount of the A component to the amount of the B component is (10-20) to 1. Thus, the double-component polyurethane adhesive can be prepared by mixing the component A and the component B. Wherein the mass ratio of the aqueous polyurethane emulsion to the second isocyanate is (12-25): 1.
further, the second isocyanate is an isocyanate curing agent, for example, an isocyanate polymer. The isocyanate cured product is commercially available, for example, including at least one of basf DesmodurDN, desmodurN3600, bayhydur3100, bayhydur xp2547, bayhydur xp2451, and AQ-140 of NPU. In addition, the isocyanate group (NCO) content of the isocyanate curing agent may be 13 to 25% by mass.
It will be understood by those skilled in the art that the adhesive of the present invention is a two-component reaction curable adhesive, that is, when the adhesive is applied to the surface of an object to be bonded, the polyurethane in the a component and the second isocyanate in the B component may undergo a curing reaction, and a cured film may be formed on the surface of the object to be bonded. Wherein the curing conditions may include: the temperature is 20-50 ℃ and the time is 24-168 h.
The double-component polyurethane adhesive has the advantages of strong adhesive force, high temperature and high humidity resistance, strong mechanical property, high hydrophilicity, large molecular weight, high solid content, high crosslinking degree and the like.
The following detailed description of embodiments of the invention is provided for the purpose of illustration only and is not to be construed as limiting the invention. In addition, all reagents employed in the examples below are commercially available or may be synthesized according to methods herein or known, and are readily available to those skilled in the art for reaction conditions not listed, if not explicitly stated.
In the following examples and comparative examples,
the leveling agent is BYK-301 of Pick, the thickener is TEGO ViscoPlus3030 of Di high, the defoamer is BYK-028 of Pick, and the aqueous color paste is B6153-SA of Kedi.
The preparation examples are given to illustrate the first chain extender and the method of preparing it.
Preparation example 1
A monomer mixture containing 2.3g of methacrylic acid, 1g of methyl methacrylate, 3g of ethyl acrylate, 0.53g of hydroxyethyl methacrylate, 1.42g of acrylamide, 1.44g of sodium acrylate and 0.9g of sodium acrylate was added dropwise to a solution of 20g of ethyl acetate in which azobisisobutyronitrile (0.08 g) was dissolved under stirring, and after the completion of the dropwise addition, the polymerization was carried out at 70℃for 3 hours, and after the completion of the reaction, the solvent was removed under reduced pressure to give a polyacrylate sulfonate, which was designated as A1. The characterization results are shown in Table 1.
Preparation examples 2 to 7
A first chain extender was prepared as in preparation example 1, except that the amounts of the reaction materials, the amounts of the raw materials and the characterization results of the prepared products are shown in Table 1, and the prepared products were A2 to A7, respectively.
TABLE 1
In table 1, the hydroxyl number test method: acetic anhydride-pyridine process.
Sulfonate group content, carboxylate group test method: the content of sulfonate groups and carboxylate groups in the system is determined by thymol blue-methylene blue acid split-phase titration.
The method for testing the content of the amide group comprises the following steps: and dissolving the first chain extender by using a dimethyl sulfoxide (DMSO) solvent, testing a nuclear magnetic hydrogen spectrum (frequency 600 MHz), and calculating the content of the amide group according to the characteristic peak area of the amide group.
Example 1
1) Preparation of aqueous polyurethane emulsion
(1) 80g of polybutylene adipate glycol (Mw=2000) is decompressed and dehydrated for 3 hours at the temperature of 120 ℃, the decompression pressure is controlled to be minus 0.06MPa, then the temperature is reduced to 50 ℃, 4.46g of isophorone diisocyanate and 10.12g of hexamethylene diisocyanate are added into the system and stirred, after the isocyanate content in the reaction system reaches the theoretical value (-NCO content is 2.9%) by a chemical titration method tracking measurement, the temperature is reduced to 40 ℃, and 80g of acetone is added to regulate the viscosity of the system, thus obtaining the prepolymer.
(2) Under high-speed stirring, the dropping speed was controlled to be over 30min, 10g of polyacrylate sulfonate obtained in preparation example 1 was added dropwise to the prepolymer, and after the completion of the dropping, the stirring reaction was continued for 50min.
(3) And (3) adding 1.20g of ethylenediamine and 1.28g of ethanolamine into the product obtained in the step (2) for post chain extension, and stirring and reacting at 30 ℃ for 25min.
(4) And (3) dropwise adding 60g of deionized water into the product obtained in the step (3) for emulsification to form emulsion, and removing acetone under reduced pressure to obtain the aqueous polyurethane emulsion with the solid content of 57%.
2) Preparation of two-component polyurethane adhesive
Preparing a component A: 90 parts of aqueous polyurethane emulsion, 3 parts of thickener, 5 parts of defoamer and 2 parts of flatting agent;
and (3) preparing a component B: according to the mass parts, the basf Desmodur DN85 parts, the water-based color paste accounts for 1 part and the water accounts for 14 parts.
And uniformly mixing the component A and the component B at room temperature according to the mass ratio of 20:1.
Examples 2 to 7
Aqueous polyurethane emulsion and two-component polyurethane adhesive were prepared as in example 1, except that the amount of the oligomer polyol, the type of the first chain extender and the amount of the first chain extender were adjusted in preparing the aqueous polyurethane emulsion, as shown in Table 2.
Comparative example 1
1) Preparation of aqueous polyurethane emulsion
(1) Mixing 80g of polybutylene adipate glycol with a weight average molecular weight of 650 and 1.5g of polytetrahydrofuran ether glycol with a weight average molecular weight of 650 at a temperature of 120 ℃, decompressing and dehydrating, controlling the decompressing pressure to be-0.06 MPa, controlling the water content in a system to be 0.08%, cooling to 50 ℃ after dehydrating, adding 2.25g of isophorone diisocyanate and 13.46g of hexamethylene diisocyanate into the system to uniformly mix, and cooling to 40 ℃ and adding 160g of acetone to adjust the viscosity of the system after the isocyanate content in the reaction system reaches a theoretical value (-NCO content is 3.7%) by a chemical titration method, so as to obtain the prepolymer.
(2) Under high-speed stirring, the dripping speed is controlled to be over 30min, 4.75g of 2- (2-aminoethyl) aminoethanesulfonic acid sodium salt is dripped into the prepolymer to be mixed, and after the dripping is over, the reaction is continued under high-speed stirring for 50min.
(3) And (3) adding 0.24g of ethylenediamine and 1.58g of ethanolamine into the product obtained in the step (2) under high-speed stirring for post chain extension, wherein the reaction temperature is 30 ℃, the reaction time is 25min, dropwise adding 260g of deionized water for emulsification, uniformly mixing to form emulsion, and removing acetone under reduced pressure after forming the emulsion to obtain the aqueous polyurethane emulsion with the solid content of 37%.
2) Preparation of two-component polyurethane adhesive
Preparing a component A: 90 parts of water-based polyurethane, 3 parts of water-based thickener, 5 parts of water-based defoamer and 2 parts of water-based flatting agent;
and (3) preparing a component B: according to the mass parts, the Pasteur Desmodur DN accounts for 85 parts, the water-based color paste accounts for 1 part, and the water accounts for 14 parts.
And uniformly mixing the component A and the component B at room temperature according to the mass ratio of 20:1.
Comparative example 2
1) Preparation of aqueous polyurethane emulsion
(1) Mixing 80g of polybutylene adipate glycol with a weight-average molecular weight of 2000 and 32g of polytetrahydrofuran ether glycol with a weight-average molecular weight of 250 at a temperature of 120 ℃, decompressing and dehydrating, controlling the decompressing pressure to be minus 0.06MPa, controlling the water content in the system to be 0.08%, cooling to 50 ℃ after dehydrating, adding 3.03g of isophorone diisocyanate and 16.84g of hexamethylene diisocyanate into the system to uniformly mix, tracking and measuring the isocyanate content in the reaction system to reach a theoretical value (-NCO content is 2.3%) by a chemical titration method, cooling to 40 ℃, and adding 200g of acetone to adjust the viscosity of the system so as to obtain the prepolymer.
(2) Under high-speed stirring, the dropping speed is controlled to be over within 30min, 3.36g of dimethyl propionic acid is added into 85 mass parts of prepolymer in a dropwise manner to be mixed, and after the dropping is over, the reaction is continued to be carried out for 50min under high-speed stirring.
(3) And (3) adding 0.24g of ethylenediamine and 1.58g of ethanolamine into the product obtained in the step (2) under high-speed stirring for chain extension, dripping 100g of deionized water for emulsification, uniformly mixing to form emulsion, and removing acetone under reduced pressure after forming the emulsion to obtain the aqueous polyurethane emulsion with the solid content of 59%.
2) Preparation of two-component polyurethane adhesive
Preparing a component A: 90 parts of aqueous polyurethane; 3 parts of water-based thickener; the water-based defoamer accounts for 5 parts; the water-based leveling agent accounts for 2 parts;
and (3) preparing a component B: basf Desmodur DN at 85 parts; 1 part of water-based color paste and 14 parts of water.
And uniformly mixing the component A and the component B at room temperature according to the mass ratio of 20:1.
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In table 2, the average particle diameter of the aqueous polyurethane emulsion was measured by: after a small amount of aqueous polyurethane emulsion A is added into deionized water for dilution, the particle size of the emulsion is tested by a laser particle sizer, the testing temperature is (23+/-2) DEG C, and the relative humidity is (50+/-5)%.
The test method of emulsion stability comprises the following steps: the storage stability was simulated by the centrifugal acceleration sedimentation test, and after centrifugal sedimentation at 3000r/min for 15min in the centrifuge, it was considered that the storage stability period was 6 months or more if there was no sedimentation.
Test case
1. Test of peel Strength
The two-component adhesive is coated on one surface of an ABS plate and soft leather, and the coating weight is 120g/m 2 ) After that, soft leather is adhered on an ABS plate, and the soft leather is kept for 3min under the condition of room temperature (25 ℃ and 50% humidity) after the pressure is applied at 90 ℃, the peeling force is tested according to the 180-degree peeling strength test method of GB/T2790 adhesive, and the peeling speed is 300mm/min. Wherein, the liquid crystal display device comprises a liquid crystal display device,
namely peel force: the peel force was tested within 0.5h after coating;
peel force: after being placed at room temperature for 72 hours, the peeling force is tested;
heat aging peel force at 100 ℃): after the soft leather adhered to the ABS plate is completely solidified, cutting the leather into strips with the width of 25+/-0.5 mm and the degree of more than 200mm by using a cutting knife, placing the strips in a blast oven at the temperature of 100 ℃, taking out the strips after aging for 168 hours, cooling for 0.5 hour, and testing the stripping force.
2. Creep deformation resistance test
The soft leather (25 plus or minus 0.5mm wide) which is bonded on the ABS plate and is completely solidified is manually peeled for 10mm from a section of bonding interface of the sample, a line is made at the peeling end point, then the sample is placed into an environment box at 90 ℃ to be heated for 30min, and then a 100g weight is loaded on the surface of the peeling end, and the sample is kept for 24h. And taking out the sample strip after the test is finished, and measuring the distance from the scribing line to the stripping end point by using a ruler.
3. Tensile Strength and elongation at break according to GB/T1040.3 2006 test
Preparation of the samples: pouring the component A into a polytetrahydrofuran mould of a water platform, casting to form a film, standing for 3 hours at room temperature, and standing for foam removal. And then heating and drying in a blast drying oven at 60+/-2 ℃ for 6 hours, and preparing the adhesive film in a natural cooling area at room temperature. The adhesive film prepared was cut into strips of width 25.+ -. 0.5mm, thickness 4.+ -. 0.5mm and length 200mm according to GB/T1040.3.
Test conditions: the sample to be tested was left for more than 24 hours under the standard conditions (23.+ -. 2) and (50.+ -. 5) percent relative humidity specified in GB/T2918, and tested in this environment, with a draw speed of 100mm/min.
The results are shown in Table 3:
TABLE 3 Table 3
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As is clear from Table 3, the tensile strength, elongation at break and the peel strength, heat aging peel strength at 100℃and creep resistance of the two-component polyurethane adhesives of the polyurethane emulsion-containing A component prepared in examples 1 to 7 were higher than those of the adhesives prepared in comparative examples 1 and 2.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the description of the present invention, the meaning of "a plurality" is two or more, unless explicitly defined otherwise.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
Claims (10)
1. A method of preparing an aqueous polyurethane emulsion comprising:
mixing an oligomer polyol, a first isocyanate, a first chain extender, a second chain extender and water to obtain an aqueous polyurethane emulsion;
wherein the first chain extender comprises at least one of polyacrylate carboxylate, polyacrylate sulfonate, and polyacrylate carboxylate/sulfonate.
2. The method according to claim 1, wherein the mixing is performed according to the following steps:
(1) First mixing an oligomeric polyol with a first isocyanate to obtain a prepolymer;
(2) Second mixing the prepolymer with a first chain extender;
(3) Thirdly mixing the product obtained in the step (2) with a second chain extender;
(4) And (3) fourth mixing the product obtained in the step (3) with water so as to obtain the aqueous polyurethane emulsion.
3. The process according to claim 1 or 2, wherein the molar ratio of the oligomeric polyol to the first isocyanate is (0.2-2) to 1;
optionally, the oligomer polyol comprises a polyester polyol and optionally a polyether polyol;
optionally, the polyester polyol has a weight average molecular weight of 500 to 10000;
optionally, the polyester polyol comprises at least one of a polybutylene adipate glycol, a polycaprolactone diol, and a polycarbonate diol;
optionally, the polyether polyol has a weight average molecular weight of 90 to 2000;
optionally, the polyether polyol comprises at least one of polytetrahydrofuran ether glycol, polypropylene glycol, and polyethylene glycol;
optionally, the first isocyanate comprises at least one of hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate, dicyclohexylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, and xylylene diisocyanate.
4. The method of claim 1 or 2, wherein the first chain extender meets at least one of the following conditions:
the weight average molecular weight is 500-5000;
hydroxyl value is 15mgKOH/g-77mgKOH/g;
the content of carboxylate groups or/and sulfonate groups is 0.1mmol/g-2mmol/g;
the content of the amide groups is 0.1mmol/g-1mmol/g.
5. The method of claim 4, wherein the method of preparing the first chain extender comprises:
in the presence of an initiator and a solvent, carrying out free radical polymerization reaction on an acrylic monomer, a first monomer and a second monomer; wherein, the liquid crystal display device comprises a liquid crystal display device,
the first monomer is selected from an acrylic hydroxy ester monomer and/or an acrylamide monomer;
the second monomer is selected from at least one of sodium acrylate sulfonate and sodium acrylate;
optionally, the weight ratio of the acrylic monomer to the weight ratio of the first monomer to the second monomer is (0.3-20) to (0.1-21) to (0.5-13) to 1;
optionally, the acrylic monomer comprises at least one of acrylic acid and methacrylic acid;
optionally, the acrylic monomer comprises at least one of methyl methacrylate, butyl methacrylate, ethyl acrylate, ethyl methacrylate, and isooctyl acrylate;
optionally, the hydroxy acrylate monomer comprises at least one of hydroxy ethyl acrylate, hydroxy ethyl methacrylate, hydroxy propyl acrylate, hydroxy propyl methacrylate, hydroxy butyl acrylate, and hydroxy butyl methacrylate;
optionally, the acrylamide-based monomer comprises at least one of acrylamide and methacrylamide.
6. The method according to claim 1 or 2, wherein the mass ratio of the first chain extender to the prepolymer is 1: (7-40).
7. The method according to claim 1 or 2, wherein the second chain extender comprises a diamine and/or an alcohol amine;
optionally, the mass content of the second chain extender is 0.5% -5% relative to the total mass of reactants.
8. An aqueous polyurethane emulsion prepared by the method of any one of claims 1-7.
9. A two-component polyurethane adhesive comprising an a-component and a B-component, wherein the a-component comprises the aqueous polyurethane emulsion of claim 8 and the B-component comprises a second isocyanate.
10. The two-component polyurethane adhesive according to claim 9, wherein the mass content of isocyanate groups in the second isocyanate is 13% -25%;
optionally, the mass ratio of the aqueous polyurethane emulsion to the second isocyanate is (12-25) to 1;
optionally, the a-component further comprises an additive comprising at least one of a thickener, defoamer and leveling agent;
optionally, the mass content of the aqueous polyurethane emulsion is 70-90 parts based on 100 parts of the total weight of the component A.
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| CN117551415A (en) * | 2024-01-09 | 2024-02-13 | 黎明化工研究设计院有限责任公司 | Polyurethane adhesive and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117551415A (en) * | 2024-01-09 | 2024-02-13 | 黎明化工研究设计院有限责任公司 | Polyurethane adhesive and preparation method thereof |
| CN117551415B (en) * | 2024-01-09 | 2024-03-12 | 黎明化工研究设计院有限责任公司 | Polyurethane adhesive and preparation method thereof |
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