CN112724324A - High-performance polyurethane-acrylate pressure-sensitive adhesive emulsion and preparation method thereof - Google Patents
High-performance polyurethane-acrylate pressure-sensitive adhesive emulsion and preparation method thereof Download PDFInfo
- Publication number
- CN112724324A CN112724324A CN202011522904.2A CN202011522904A CN112724324A CN 112724324 A CN112724324 A CN 112724324A CN 202011522904 A CN202011522904 A CN 202011522904A CN 112724324 A CN112724324 A CN 112724324A
- Authority
- CN
- China
- Prior art keywords
- acrylate
- emulsion
- sensitive adhesive
- methacrylate
- chain extender
- 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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- 239000000839 emulsion Substances 0.000 title claims abstract description 87
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000004945 emulsification Methods 0.000 title description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000004970 Chain extender Substances 0.000 claims abstract description 20
- 239000008367 deionised water Substances 0.000 claims abstract description 18
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 14
- -1 acrylic ester Chemical class 0.000 claims abstract description 12
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 10
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 9
- 239000007800 oxidant agent Substances 0.000 claims abstract description 9
- 230000001590 oxidative effect Effects 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 229920000642 polymer Polymers 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 7
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 7
- 239000003999 initiator Substances 0.000 claims abstract description 7
- 229920005862 polyol Polymers 0.000 claims abstract description 7
- 150000003077 polyols Chemical class 0.000 claims abstract description 7
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 6
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 6
- 239000004814 polyurethane Substances 0.000 claims description 31
- 238000001816 cooling Methods 0.000 claims description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 12
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical group CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 12
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 10
- 229920001451 polypropylene glycol Polymers 0.000 claims description 8
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 claims description 6
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 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 6
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical group [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 claims description 6
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 4
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 2
- 229940035437 1,3-propanediol Drugs 0.000 claims description 2
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 claims description 2
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims description 2
- VHNJXLWRTQNIPD-UHFFFAOYSA-N 3-hydroxybutyl 2-methylprop-2-enoate Chemical compound CC(O)CCOC(=O)C(C)=C VHNJXLWRTQNIPD-UHFFFAOYSA-N 0.000 claims description 2
- JRCGLALFKDKSAN-UHFFFAOYSA-N 3-hydroxybutyl prop-2-enoate Chemical compound CC(O)CCOC(=O)C=C JRCGLALFKDKSAN-UHFFFAOYSA-N 0.000 claims description 2
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 2
- CYUZOYPRAQASLN-UHFFFAOYSA-N 3-prop-2-enoyloxypropanoic acid Chemical compound OC(=O)CCOC(=O)C=C CYUZOYPRAQASLN-UHFFFAOYSA-N 0.000 claims description 2
- YKXAYLPDMSGWEV-UHFFFAOYSA-N 4-hydroxybutyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCO YKXAYLPDMSGWEV-UHFFFAOYSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 claims description 2
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 2
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 claims description 2
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 claims description 2
- WRAABIJFUKKEJQ-UHFFFAOYSA-N cyclopentyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCC1 WRAABIJFUKKEJQ-UHFFFAOYSA-N 0.000 claims description 2
- BTQLDZMOTPTCGG-UHFFFAOYSA-N cyclopentyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCC1 BTQLDZMOTPTCGG-UHFFFAOYSA-N 0.000 claims description 2
- 150000002009 diols Chemical class 0.000 claims description 2
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 claims description 2
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 claims description 2
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 2
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 2
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 claims description 2
- KCAMXZBMXVIIQN-UHFFFAOYSA-N octan-3-yl 2-methylprop-2-enoate Chemical compound CCCCCC(CC)OC(=O)C(C)=C KCAMXZBMXVIIQN-UHFFFAOYSA-N 0.000 claims description 2
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims 1
- 238000006073 displacement reaction Methods 0.000 description 9
- 229920002635 polyurethane Polymers 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 description 5
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
-
- 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
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- 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
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
-
- 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
- C08G18/4825—Polyethers containing two hydroxy groups
-
- 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
- C08G18/4829—Polyethers containing at least three hydroxy groups
-
- 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
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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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
- C08G18/28—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
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
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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
- C08G18/28—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
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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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
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/08—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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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
- C08G2170/00—Compositions for adhesives
- C08G2170/40—Compositions for pressure-sensitive adhesives
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
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- Polymers & Plastics (AREA)
- Polyurethanes Or Polyureas (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to a high-performance polyurethane-acrylate pressure-sensitive adhesive emulsion and a preparation method thereof, wherein the pressure-sensitive adhesive emulsion comprises a PU seed emulsion component and an acrylate pre-emulsion component, and the PU seed emulsion component comprises: 10-30 wt% of diisocyanate, 10-40 wt% of polymer polyol, 0.01-0.05 wt% of organic metal catalyst, 1-5 wt% of first chain extender, 0-5 wt% of second chain extender, 2-6 wt% of hydroxyl acrylate monomer, 0.8-7 wt% of neutralizing agent, 10-20 wt% of organic solvent and 30-70 wt% of deionized water; the acrylate pre-emulsion component comprises: 35-60 wt% of vinyl monomer, 0-5 wt% of cross-linking agent, 0.5-3 wt% of reactive emulsifier, 0.2-1 wt% of water-soluble initiator and 35-60 wt% of deionized water; the acrylic ester pre-emulsion accounts for 100-500 wt% of the PU seed emulsion; the high-performance polyurethane-acrylate pressure-sensitive adhesive emulsion also comprises 0.03-0.08 wt% of oxidant, 0.03-0.08 wt% of reducing agent and 0.1-1 wt% of pH regulator, wherein the oxidant, the reducing agent and the pH regulator are respectively contained in the components of the acrylate pre-emulsion; the first chain extender is a hydrophilic chain extender.
Description
Technical Field
The invention relates to the field of emulsion pressure-sensitive adhesives, in particular to a high-performance polyurethane-acrylate pressure-sensitive adhesive emulsion and a preparation method thereof.
Background
The acrylate emulsion is used as an important branch in the field of pressure-sensitive adhesive materials, has the characteristics of low viscosity, convenience in coating, no organic solvent, friendliness to human bodies and environment and the like, and has wide application in the fields of protective films, functional adhesive tapes, labels and the like for a long time.
The polyurethane is a high molecular compound with a main chain containing repeated carbamate structural units, and the aqueous polyurethane emulsion has the advantages of good physical and mechanical properties, excellent cold resistance, alkali resistance, elasticity, small change of hardness and softness along with temperature and the like, but the application range is limited by poor high temperature resistance and initial viscosity.
Therefore, the advantages of the two polymers are complemented, and the aqueous pressure-sensitive adhesive emulsion with excellent performance can be prepared.
Disclosure of Invention
The invention aims to provide a high-performance polyurethane-acrylate pressure-sensitive adhesive emulsion and a preparation method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that: comprises PU seed emulsion and acrylic ester pre-emulsion; the PU seed emulsion comprises: 10-30 wt% of diisocyanate, 10-40 wt% of polymer polyol, 0.01-0.05 wt% of organic metal catalyst, 1-5 wt% of first chain extender, 0-5 wt% of second chain extender, 2-6 wt% of hydroxyl acrylate monomer, 0.8-7 wt% of neutralizing agent, 10-20 wt% of organic solvent and 30-60 wt% of deionized water; the acrylate pre-emulsion comprises: 35-60 wt% of vinyl monomer, 0-5 wt% of cross-linking agent, 0.5-3 wt% of reactive emulsifier, 0.2-1 wt% of water-soluble initiator and 35-60 wt% of deionized water; the acrylic ester pre-emulsion accounts for 100-500 wt% of the PU seed emulsion; the high-performance polyurethane-acrylate pressure-sensitive adhesive emulsion also comprises 0.03-0.08 wt% of oxidant, 0.03-0.08 wt% of reducing agent and 0.1-1 wt% of pH regulator, wherein the oxidant, the reducing agent and the pH regulator are respectively contained in the components of the acrylate pre-emulsion; the first chain extender is a hydrophilic chain extender.
Further, the diisocyanate is selected from one or a combination of at least two of isophorone diisocyanate, hexamethylene diisocyanate and dicyclohexyl methane diisocyanate;
the polymer polyol is selected from one or a combination of two of polyoxypropylene diol and polyoxypropylene triol with the number average molecular weight of 400-8000 g/mol;
the first chain extender is one or the combination of at least two of dimethylolpropionic acid, dimethylolbutyric acid, 1, 2-propanediol-3-sodium sulfonate, 1, 4-butanediol-2-sodium sulfonate and trimethylolpropane polyethylene glycol monomethyl ether;
the second chain extender is one of 1, 4-butanediol, 1, 3-propanediol and ethylene glycol;
the hydroxy acrylate monomer is selected from one or the combination of at least two of 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate and 4-hydroxybutyl methacrylate;
the vinyl monomer is at least one or a combination of at least two of acrylic acid, methacrylic acid, beta-acryloxypropionic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, n-butyl acrylate, octadecyl methacrylate, dodecyl acrylate, isobornyl methacrylate, dodecyl methacrylate, hexyl acrylate, hexyl methacrylate, ethylhexyl acrylate, ethylhexyl methacrylate, cyclopentyl acrylate, cyclopentyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, styrene and vinyl acetate;
the cross-linking agent is one of N-hydroxymethyl acrylamide, glycidyl acrylate and glycidyl methacrylate;
the water-soluble initiator is one of potassium persulfate, ammonium persulfate and sodium persulfate;
the organic solvent is acetone or butanone;
the oxidant is tert-butyl hydroperoxide;
the reducing agent is sodium formaldehyde sulfoxylate;
the pH regulator is ammonia water;
the neutralizer is triethylamine;
the organometallic catalyst was dibutyltin dilaurate.
On the basis, the invention also provides a preparation method of the high-performance polyurethane-acrylate pressure-sensitive adhesive emulsion, which comprises the following specific steps:
step A: removing water from polymer polyol at 110-120 ℃ for 1-2 h, cooling to 60-70 ℃, adding diisocyanate and an organic metal catalyst, reacting at 70-90 ℃ for 2-3 h, adding an organic solvent to adjust the viscosity to 500-800 mPa & s, sequentially adding a first chain extender, a second chain extender and a hydroxy acrylate monomer, and reacting for 2-3 h;
and B: after the reaction is finished, cooling to 40-50 ℃, adding a neutralizing agent, and reacting for 20-30 min; adding deionized water at the temperature of 30-40 ℃ for mixing, and evaporating the uniformly mixed product under the conditions that the temperature is 35-45 ℃ and the vacuum degree is-0.09 Mpa to obtain the PU seed emulsion of the waterborne polyurethane containing vinyl;
and C: mixing ethylene monomer, cross-linking agent, reactive emulsifier, water-soluble initiator and deionized water to obtain pre-emulsion; and C, heating the PU seed emulsion prepared in the step B to 82-85 ℃, dropwise adding the pre-emulsion into the PU seed emulsion for 2-3 h, preserving heat for 1-2 h, then cooling to 70-72 ℃, sequentially adding an oxidant and a reducing agent, preserving heat for 30-40 min, cooling to below 50 ℃, adding a pH regulator until the pH value is 7-8, filtering and discharging to obtain the high-performance waterborne polyurethane-acrylate pressure-sensitive adhesive emulsion.
Further, in step B, evaporation was performed using a rotary evaporator.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
according to the pressure-sensitive adhesive emulsion disclosed by the invention, a polyurethane structure is introduced, so that the pressure-sensitive adhesive emulsion can keep better flexibility at a low temperature, the problem of poor bonding property of the traditional acrylate pressure-sensitive adhesive at a low temperature is effectively solved, and the prepared pressure-sensitive adhesive emulsion also has better bonding property at a normal temperature.
Detailed Description
The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The technical features mentioned in the different embodiments of the invention described below can be combined with each other as long as they do not conflict with each other.
Example 1
Step A: removing water from 30g of polyoxypropylene glycol with the molecular weight of 4000 at the temperature of 110-120 ℃ for 1-2 h, cooling to 60-70 ℃, adding 11g of isophorone diisocyanate and 0.02g of dibutyltin dilaurate, reacting at the temperature of 70-90 ℃ for 2-3 h, adding acetone to adjust the viscosity to 500-800 mPa & s, sequentially adding 2g of dimethylolbutyric acid, 0.2g of 1, 3-propylene glycol and 4g of hydroxybutyl acrylate, and reacting for 2-3 h;
and B: after the reaction is finished, cooling to 40-50 ℃, adding 1.2g of triethylamine, and reacting for 20-30 min; adding 40g of deionized water at the temperature of 30-40 ℃ for mixing, and performing rotary evaporation on the uniformly mixed product under the conditions that the temperature is 35-45 ℃ and the vacuum degree is-0.09 Mpa to obtain PU seed emulsion;
and C: mixing 30g of isooctyl acrylate, 55g of butyl acrylate, 10g of methyl acrylate, 2g N-hydroxymethyl acrylamide, 1.2g of reactive emulsifier SR-10, 1g of ER-10, 0.42g of ammonium persulfate and 100g of deionized water to obtain a pre-emulsion; and C, heating the PU seed emulsion prepared in the step B to 82-85 ℃, dropwise adding the pre-emulsion into the PU seed emulsion for 2-3 h, preserving heat for 1-2 h, then cooling to 70-72 ℃, sequentially adding 0.08g of tert-butyl hydroperoxide and 0.06g of sodium formaldehyde sulfoxylate, preserving heat for 30-40 min, cooling to below 50 ℃, adding ammonia water to adjust the pH value to 7-8, filtering and discharging.
Example 2
Step A: removing water from 20g of polyoxypropylene triol with the molecular weight of 4000 at the temperature of 110-120 ℃ for 1-2 h, cooling to 60-70 ℃, adding 11g of isophorone diisocyanate and 0.02g of dibutyltin dilaurate, reacting at the temperature of 70-90 ℃ for 2-3 h, adding acetone to adjust the viscosity to 500-800 mPa & s, sequentially adding 2g of dimethylolbutyric acid, 0.2g of 1, 3-propylene glycol and 4g of hydroxybutyl acrylate, and reacting for 2-3 h;
and B: after the reaction is finished, cooling to 40-50 ℃, adding 1.2g of triethylamine, and reacting for 20-30 min; adding 40g of deionized water at the temperature of 30-40 ℃ for mixing, and performing rotary evaporation on the uniformly mixed product under the conditions that the temperature is 35-45 ℃ and the vacuum degree is-0.09 Mpa to obtain PU seed emulsion;
and C: mixing 30g of isooctyl acrylate, 55g of butyl acrylate, 10g of methyl acrylate, 2g N-hydroxymethyl acrylamide, 1.2g of reactive emulsifier SR-10, 1g of ER-10, 0.42g of ammonium persulfate and 100g of deionized water to obtain a pre-emulsion; and C, heating the PU seed emulsion prepared in the step B to 82-85 ℃, dropwise adding the pre-emulsion into the PU seed emulsion for 2-3 h, preserving heat for 1-2 h, then cooling to 70-72 ℃, sequentially adding 0.08g of tert-butyl hydroperoxide and 0.06g of sodium formaldehyde sulfoxylate, preserving heat for 30-40 min, cooling to below 50 ℃, adding ammonia water to adjust the pH value to 7-8, filtering and discharging.
Example 3
Step A: removing water from 20g of polyoxypropylene triol with the molecular weight of 4000 at the temperature of 110-120 ℃ for 1-2 h, cooling to 60-70 ℃, adding 11g of isophorone diisocyanate and 0.02g of dibutyltin dilaurate, reacting at the temperature of 70-90 ℃ for 2-3 h, adding acetone to adjust the viscosity to 500-800 mPa & s, sequentially adding 2g of dimethylolbutyric acid, 0.2g of 1, 3-propylene glycol and 4g of hydroxybutyl acrylate, and reacting for 2-3 h;
and B: after the reaction is finished, cooling to 40-50 ℃, adding 1.2g of triethylamine, and reacting for 20-30 min; adding 40g of deionized water at the temperature of 30-40 ℃ for mixing, and performing rotary evaporation on the uniformly mixed product under the conditions that the temperature is 35-45 ℃ and the vacuum degree is-0.09 Mpa to obtain PU seed emulsion;
and C: mixing 35g of isooctyl acrylate, 55g of butyl acrylate, 10g of methyl acrylate, 2g N-hydroxymethyl acrylamide, 1.2g of reactive emulsifier SR-10, 1g of ER-10, 0.42g of ammonium persulfate and 100g of deionized water to obtain a pre-emulsion; and C, heating the PU seed emulsion prepared in the step B to 82-85 ℃, dropwise adding the pre-emulsion into the PU seed emulsion for 2-3 h, preserving heat for 1-2 h, then cooling to 70-72 ℃, sequentially adding 0.08g of tert-butyl hydroperoxide and 0.06g of sodium formaldehyde sulfoxylate, preserving heat for 30-40 min, cooling to below 50 ℃, adding ammonia water to adjust the pH value to 7-8, filtering and discharging.
Example 4
Step A: removing water from 30g of polyoxypropylene triol with the molecular weight of 4000 at the temperature of 110-120 ℃ for 1-2 h, cooling to 60-70 ℃, adding 11g of isophorone diisocyanate and 0.02g of dibutyltin dilaurate, reacting at the temperature of 70-90 ℃ for 2-3 h, adding acetone to adjust the viscosity to 500-800 mPa & s, sequentially adding 2g of dimethylolbutyric acid, 0.2g of 1, 3-propylene glycol and 4g of hydroxybutyl acrylate, and reacting for 2-3 h;
and B: after the reaction is finished, cooling to 40-50 ℃, adding 1.2g of triethylamine, and reacting for 20-30 min; adding 40g of deionized water at the temperature of 30-40 ℃ for mixing, and performing rotary evaporation on the uniformly mixed product under the conditions that the temperature is 35-45 ℃ and the vacuum degree is-0.09 Mpa to obtain PU seed emulsion;
and C: mixing 35g of isooctyl acrylate, 55g of butyl acrylate, 10g of methyl acrylate, 2g N-hydroxymethyl acrylamide, 1.2g of reactive emulsifier SR-10, 1g of ER-10, 0.2g of ammonium persulfate and 100g of deionized water to obtain a pre-emulsion; and C, heating the PU seed emulsion prepared in the step B to 82-85 ℃, dropwise adding the pre-emulsion into the PU seed emulsion for 2-3 h, preserving heat for 1-2 h, then cooling to 70-72 ℃, sequentially adding 0.08g of tert-butyl hydroperoxide and 0.06g of sodium formaldehyde sulfoxylate, preserving heat for 30-40 min, cooling to below 50 ℃, adding ammonia water to adjust the pH value to 7-8, filtering and discharging.
The reactive emulsifier in the above examples 1 to 4 is one or a combination of at least two of SR-10 and ER-10 of fine chemical Co., Ltd, COPS-1 of Rodia, France, and E9001 of St.japonicus.
Respectively weighing a part of the glue solution prepared in the embodiments 1-4, adding 0.8% of aqueous aziridine curing agent, fully stirring, coating the glue solution on PET, controlling the thickness of the PET to be 20 microns, curing at 80 ℃ for 3-5 min, taking out, using a film laminating machine to adhere a release film with the thickness of 15 microns on the glue layer, and performing sample preparation test; and the same type of commercially available glue solution without introduced polyurethane structure is sampled by the same method and tested as comparative example 1.
The test method comprises the following steps: the permanent adhesion test is carried out according to the method for the permanent adhesion test of the pressure-sensitive adhesive tape in GB/T4851-2014; the peel force test is carried out according to the 180-degree peel strength test method of the GB/T2792-2014 pressure-sensitive adhesive tape.
The test results obtained are given in table 1 below:
| normal temperature 180 degree peel force (N/25 mm) | Normal temperature holding adhesive (h) | Low temperature-20 ℃ Peel force (N/25 mm) | Low temperature-20 ℃ hold adhesion (h) | |
| Example 1 | 10.5 | >72h without displacement | 8.9 | >72h without displacement |
| Example 2 | 9.3 | >72h without displacement | 7.3 | >72h without displacement |
| Example 3 | 9.6 | >72h without displacement | 7.5 | >72h without displacement |
| Example 4 | 10.2 | >72h without displacement | 8.7 | >72h without displacement |
| Comparative example 1 | 9.1 | >72h with displacement | 4.6 | <48h |
TABLE 1
The test results of comparative examples 1,2 show that: within the scope of the formula of the invention, the weight of the key components is changed, the weight of other components is not changed, and the change of the adhesive property along with the reduction of time and temperature is not large;
the test results of comparative examples 3, 4 show that: within the scope of the formula, the weight of key components is partially changed, and the weight of other components is only changed, so that the adhesive property of the adhesive is not greatly changed along with the reduction of time and temperature;
the test results of comparative examples 1-4 and comparative example 1 show that: in the formula range of the invention, the adhesive property and low temperature resistance of the pressure-sensitive adhesive emulsion modified by the waterborne polyurethane seed emulsion are superior to those of the unmodified traditional acrylate pressure-sensitive adhesive emulsion, and especially under the low temperature condition, the adhesive property of the traditional acrylate pressure-sensitive adhesive emulsion is obviously reduced.
The high-performance polyurethane-acrylate pressure-sensitive adhesive emulsion in the embodiment introduces a polyurethane structure, so that the pressure-sensitive adhesive emulsion can keep better flexibility at a low temperature, the problem that the bonding performance of the traditional acrylate pressure-sensitive adhesive is poor at the low temperature is effectively solved, and the prepared pressure-sensitive adhesive emulsion also has better bonding performance at the normal temperature.
The above embodiments are merely illustrative of the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the invention, and not to limit the scope of the invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered by the scope of the present invention.
Claims (8)
1. A high-performance polyurethane-acrylate pressure-sensitive adhesive emulsion comprises a PU seed emulsion and an acrylate pre-emulsion, and is characterized in that: the PU seed emulsion comprises: 10-30 wt% of diisocyanate, 10-40 wt% of polymer polyol, 0.01-0.05 wt% of organic metal catalyst, 1-5 wt% of first chain extender, 0-5 wt% of second chain extender, 2-6 wt% of hydroxyl acrylate monomer, 0.8-7 wt% of neutralizing agent, 10-20 wt% of organic solvent and 30-60 wt% of deionized water; the acrylate pre-emulsion comprises: 35-60 wt% of vinyl monomer, 0-5 wt% of cross-linking agent, 0.5-3 wt% of reactive emulsifier, 0.2-1 wt% of water-soluble initiator and 35-60 wt% of deionized water; the acrylic ester pre-emulsion accounts for 100-500 wt% of the PU seed emulsion; the high-performance polyurethane-acrylate pressure-sensitive adhesive emulsion also comprises an oxidant accounting for 0.03-0.08 wt% of the acrylate pre-emulsion, a reducing agent accounting for 0.03-0.08 wt% of the acrylate pre-emulsion, and a pH regulator accounting for 0.1-1 wt% of the acrylate pre-emulsion; the first chain extender is a hydrophilic chain extender.
2. The high performance polyurethane-acrylate pressure sensitive adhesive emulsion of claim 1, wherein: the diisocyanate is selected from one or the combination of at least two of isophorone diisocyanate, hexamethylene diisocyanate and dicyclohexyl methane diisocyanate; the polymer polyol is one or two of polyoxypropylene diol and polyoxypropylene triol with the number average molecular weight of 400-8000 g/mol.
3. The high performance polyurethane-acrylate pressure sensitive adhesive emulsion of claim 1, wherein: the first chain extender is one or the combination of at least two of dimethylolpropionic acid, dimethylolbutyric acid, 1, 2-propanediol-3-sodium sulfonate, 1, 4-butanediol-2-sodium sulfonate and trimethylolpropane polyethylene glycol monomethyl ether; the second chain extender is one of 1, 4-butanediol, 1, 3-propanediol and ethylene glycol.
4. The high performance polyurethane-acrylate pressure sensitive adhesive emulsion of claim 1, wherein: the hydroxyl acrylate monomer is selected from one or the combination of at least two of 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate and 4-hydroxybutyl methacrylate.
5. The high performance polyurethane-acrylate pressure sensitive adhesive emulsion of claim 1, wherein: the vinyl monomer is at least one or a combination of at least two of acrylic acid, methacrylic acid, beta-acryloxypropionic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, n-butyl acrylate, octadecyl methacrylate, dodecyl acrylate, isobornyl methacrylate, dodecyl methacrylate, hexyl acrylate, hexyl methacrylate, ethylhexyl acrylate, ethylhexyl methacrylate, cyclopentyl acrylate, cyclopentyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, styrene and vinyl acetate.
6. The high performance polyurethane-acrylate pressure sensitive adhesive emulsion of claim 1, wherein: the cross-linking agent is one of N-methylol acrylamide, glycidyl acrylate and glycidyl methacrylate; the water-soluble initiator is one of potassium persulfate, ammonium persulfate and sodium persulfate; the organic solvent is acetone or butanone; the oxidant is tert-butyl hydroperoxide; the reducing agent is a rongalite; the pH regulator is ammonia water; the neutralizing agent is triethylamine; the organic metal catalyst is dibutyltin dilaurate.
7. The preparation method of the high-performance polyurethane-acrylate pressure-sensitive adhesive emulsion based on the claims 1-6 is characterized by comprising the following specific steps:
step A: removing water from polymer polyol at 110-120 ℃ for 1-2 h, cooling to 60-70 ℃, adding diisocyanate and an organic metal catalyst, reacting at 70-90 ℃ for 2-3 h, adding an organic solvent to adjust the viscosity to 500-800 mPa & s, sequentially adding a first chain extender, a second chain extender and a hydroxy acrylate monomer, and reacting for 2-3 h;
and B: after the reaction is finished, cooling to 40-50 ℃, adding a neutralizing agent, and reacting for 20-30 min; adding deionized water with the temperature of 30-40 ℃ for mixing, and evaporating the uniformly mixed product under the conditions that the temperature is 35-45 ℃ and the vacuum degree is-0.09 Mpa to obtain the PU seed emulsion;
and C: mixing ethylene monomer, cross-linking agent, reactive emulsifier, water-soluble initiator and deionized water to obtain pre-emulsion; heating the PU seed emulsion prepared in the step B to 82-85 ℃, dropwise adding the pre-emulsion into the PU seed emulsion for 2-3 h, preserving heat for 1-2 h, then cooling to 70-72 ℃, sequentially adding an oxidant and a reducing agent, preserving heat for 30-40 min, cooling to below 50 ℃, adding a pH regulator until the pH value is 7-8, filtering and discharging to obtain the high-performance waterborne polyurethane-acrylate pressure-sensitive adhesive emulsion.
8. A preparation method of the high-performance polyurethane-acrylate pressure-sensitive adhesive emulsion based on claim 7 is characterized in that: and in the step B, evaporating by adopting a rotary evaporator.
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Application publication date: 20210430 |