CN114634789A - Light/moisture dual-curing polyurethane hot melt adhesive composition with high initial bonding strength and preparation method thereof - Google Patents
Light/moisture dual-curing polyurethane hot melt adhesive composition with high initial bonding strength and preparation method thereof Download PDFInfo
- Publication number
- CN114634789A CN114634789A CN202210397543.6A CN202210397543A CN114634789A CN 114634789 A CN114634789 A CN 114634789A CN 202210397543 A CN202210397543 A CN 202210397543A CN 114634789 A CN114634789 A CN 114634789A
- Authority
- CN
- China
- Prior art keywords
- prepolymer
- hot melt
- melt adhesive
- diisocyanate
- acrylate
- 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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- 239000004831 Hot glue Substances 0.000 title claims abstract description 65
- 239000004814 polyurethane Substances 0.000 title claims abstract description 56
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 56
- 239000000203 mixture Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title abstract description 8
- -1 dihydroxy (methyl) acrylate Chemical compound 0.000 claims abstract description 50
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 claims abstract description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229920005862 polyol Polymers 0.000 claims abstract description 25
- 150000003077 polyols Chemical class 0.000 claims abstract description 25
- 150000002009 diols Chemical class 0.000 claims abstract description 22
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 20
- 229920000642 polymer Polymers 0.000 claims abstract description 17
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000002318 adhesion promoter Substances 0.000 claims abstract description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 38
- 238000002156 mixing Methods 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 238000010438 heat treatment Methods 0.000 claims description 26
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 22
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 21
- RVIZJROSQMQZCG-UHFFFAOYSA-N adamantane-1,2-diol Chemical compound C1C(C2)CC3CC1C(O)C2(O)C3 RVIZJROSQMQZCG-UHFFFAOYSA-N 0.000 claims description 17
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 13
- MOLCWHCSXCKHAP-UHFFFAOYSA-N adamantane-1,3-diol Chemical compound C1C(C2)CC3CC1(O)CC2(O)C3 MOLCWHCSXCKHAP-UHFFFAOYSA-N 0.000 claims description 13
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 12
- 239000012948 isocyanate Substances 0.000 claims description 11
- 150000002513 isocyanates Chemical class 0.000 claims description 11
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 9
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- OWPUOLBODXJOKH-UHFFFAOYSA-N 2,3-dihydroxypropyl prop-2-enoate Chemical compound OCC(O)COC(=O)C=C OWPUOLBODXJOKH-UHFFFAOYSA-N 0.000 claims description 8
- AUKWRHADVIQZRJ-UHFFFAOYSA-N adamantane-1,4-diol Chemical compound C1C(C2)CC3C(O)C1CC2(O)C3 AUKWRHADVIQZRJ-UHFFFAOYSA-N 0.000 claims description 8
- 229920005906 polyester polyol Polymers 0.000 claims description 8
- 229960004063 propylene glycol Drugs 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 6
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- 239000003112 inhibitor Substances 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
- 229920000570 polyether Polymers 0.000 claims description 6
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- 239000002994 raw material Substances 0.000 claims description 5
- 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
- LUYHWJKHJNFYGV-UHFFFAOYSA-N 1,2-diisocyanato-3-phenylbenzene Chemical compound O=C=NC1=CC=CC(C=2C=CC=CC=2)=C1N=C=O LUYHWJKHJNFYGV-UHFFFAOYSA-N 0.000 claims description 3
- MTZUIIAIAKMWLI-UHFFFAOYSA-N 1,2-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC=C1N=C=O MTZUIIAIAKMWLI-UHFFFAOYSA-N 0.000 claims description 3
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 claims description 3
- DFPJRUKWEPYFJT-UHFFFAOYSA-N 1,5-diisocyanatopentane Chemical compound O=C=NCCCCCN=C=O DFPJRUKWEPYFJT-UHFFFAOYSA-N 0.000 claims description 3
- 229940043375 1,5-pentanediol Drugs 0.000 claims description 3
- QRIMLDXJAPZHJE-UHFFFAOYSA-N 2,3-dihydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)CO QRIMLDXJAPZHJE-UHFFFAOYSA-N 0.000 claims description 3
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 claims description 3
- MMEDJBFVJUFIDD-UHFFFAOYSA-N 2-[2-(carboxymethyl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=CC=C1CC(O)=O MMEDJBFVJUFIDD-UHFFFAOYSA-N 0.000 claims description 3
- QUVMSYUGOKEMPX-UHFFFAOYSA-N 2-methylpropan-1-olate;titanium(4+) Chemical compound [Ti+4].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] QUVMSYUGOKEMPX-UHFFFAOYSA-N 0.000 claims description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 3
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 3
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N alpha-Methyl-n-butyl acrylate Natural products CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- 235000019437 butane-1,3-diol Nutrition 0.000 claims description 3
- BVFSYZFXJYAPQJ-UHFFFAOYSA-N butyl(oxo)tin Chemical compound CCCC[Sn]=O BVFSYZFXJYAPQJ-UHFFFAOYSA-N 0.000 claims description 3
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 claims description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 3
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 claims description 3
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000013638 trimer Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 2
- 238000001723 curing Methods 0.000 abstract description 32
- 238000013008 moisture curing Methods 0.000 abstract description 7
- 239000002202 Polyethylene glycol Substances 0.000 description 23
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 22
- 229920001223 polyethylene glycol Polymers 0.000 description 18
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 16
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 14
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 12
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 11
- 238000004132 cross linking Methods 0.000 description 9
- 238000000016 photochemical curing Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 244000028419 Styrax benzoin Species 0.000 description 8
- 235000000126 Styrax benzoin Nutrition 0.000 description 8
- 235000008411 Sumatra benzointree Nutrition 0.000 description 8
- 229960002130 benzoin Drugs 0.000 description 8
- 235000019382 gum benzoic Nutrition 0.000 description 8
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 239000004970 Chain extender Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- DZZAHLOABNWIFA-UHFFFAOYSA-N 2-butoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCCCC)C(=O)C1=CC=CC=C1 DZZAHLOABNWIFA-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 229920000463 Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) Polymers 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 230000014759 maintenance of location Effects 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
- JXDUSMKXFUVGQT-UHFFFAOYSA-N propyl 2,3-dihydroxyprop-2-enoate Chemical compound CCCOC(=O)C(O)=CO JXDUSMKXFUVGQT-UHFFFAOYSA-N 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
-
- 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
-
- 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
-
- 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
- C08G18/675—Low-molecular-weight compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2170/00—Compositions for adhesives
- C08G2170/20—Compositions for hot melt adhesives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyurethanes Or Polyureas (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention provides a light/moisture dual-curing polyurethane hot melt adhesive composition with high initial bonding strength and a preparation method thereof, and relates to the technical field of hot melt adhesives. The dual-curing polyurethane hot melt adhesive composition comprises, by weight, 70-100 parts of polymer polyol, 1-5 parts of low molecular weight saturated dihydric alcohol, 0.3-1 part of dihydroxy (methyl) acrylate, 15-30 parts of adamantane dihydric alcohol, 25-50 parts of diisocyanate, 1-5 parts of photoinitiator, 1-3 parts of hydroxyalkyl acrylate, 0.1-1 part of catalyst and 1-3 parts of adhesion promoter; the average molecular weight of the polymer polyol is not less than 500, and the molecular weight of the low molecular weight saturated diol is not more than 200. The dual-curing polyurethane hot melt adhesive composition has the characteristics of high initial bonding strength, high moisture curing speed and high final bonding strength.
Description
Technical Field
The invention belongs to the technical field of hot melt adhesives, and relates to a light/moisture dual-curing polyurethane hot melt adhesive composition with high initial bonding strength and a preparation method thereof.
Background
When the light/moisture dual-curing polyurethane hot melt adhesive is constructed on the surface of a base material, the initial bonding strength can be obtained through ultraviolet fast curing, and then the bonding layer with higher bonding strength is finally formed through slow penetration and curing of moisture and curing for several days to more than ten days. The light/moisture dual-curing polyurethane hot melt adhesive can provide certain initial bonding strength and is widely applied to electronic products.
However, the initial bonding strength of the bonding layer formed by ultraviolet light curing of the light/moisture dual-curing polyurethane hot melt adhesive in the prior art is not high enough, and the application has certain limitations.
Disclosure of Invention
Through a large number of experiments, the inventor of the present application finds that one important reason that the initial bonding strength of the light/moisture dual-curing polyurethane hot melt adhesive after being subjected to ultraviolet light curing is not high is that the hot melt adhesive has a certain volume shrinkage during light curing, so that the adhesion to a substrate is not high enough. The main reason for this volume shrinkage is not caused by cooling after uv curing, but by crosslinking reaction of unsaturated carbon-carbon double bonds during uv curing. In view of the above, the present invention aims to overcome the defects of the prior art and provide a light/moisture dual-curing polyurethane hot melt adhesive composition with high initial bonding strength.
The invention also provides a preparation method of the light/moisture dual-curing polyurethane hot melt adhesive composition with high initial bonding strength.
The technical scheme of the invention is as follows:
a high initial bonding strength light and moisture dual-curing polyurethane hot melt adhesive composition comprises, by weight, 70-100 parts of polymer polyol, 1-5 parts of low molecular weight saturated dihydric alcohol, 0.3-1 part of dihydroxy (methyl) acrylate, 15-30 parts of adamantane dihydric alcohol, 25-50 parts of diisocyanate, 1-5 parts of photoinitiator, 1-3 parts of hydroxyalkyl acrylate, 0.1-1 part of catalyst and 1-3 parts of adhesion promoter;
the average molecular weight of the polymer polyol is not less than 500;
the low molecular weight saturated diol has a molecular weight of no more than 200.
Preferably, the polymer polyol is selected from one or a combination of polyester polyol and polyether polyol.
Preferably, the saturated diol with low molecular weight is one or a combination of more of ethylene glycol, 1, 3-propylene glycol, 1, 2-propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, 1, 4-cyclohexanediol, 1, 4-butanediol, 1, 2-pentanediol, 1, 5-pentanediol, 1, 6-hexanediol and 1, 3-butanediol.
Preferably, the dihydroxy (meth) acrylate is selected from one or more of 2, 3-dihydroxy propyl acrylate, 2, 3-dihydroxy propyl methacrylate, 2, 4-dihydroxy butyl acrylate and 2, 4-dihydroxy butyl methacrylate.
Preferably, the weight ratio of the bishydroxy (meth) acrylate to the hydroxyalkyl acrylate is 0.2 to 0.7: 1.
Preferably, the adamantane diol is selected from one or two of 1, 3-adamantane diol and 1, 4-adamantane diol;
preferably, the weight ratio of the dihydroxy (meth) acrylate to the adamantanediol is 1: 20-50.
Preferably, the diisocyanate is selected from one or more of toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, phenylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, biphenyl diisocyanate, xylylene diisocyanate and toluene diisocyanate trimer.
Preferably, the structure of the hydroxyalkyl acrylateHas a general formula of CH2＝CR1COOR2OH, wherein R1Selected from methyl or hydrogen, R2Selected from C2-C8 alkylene.
Preferably, the catalyst is selected from one or more of stannous octoate, dibutyltin dilaurate, monobutyltin oxide, organic potassium carboxylate, organic bismuth carboxylate, cobalt octoate, zinc naphthenate and tetraisobutyl titanate.
A method for preparing the polyurethane hot melt adhesive composition according to any one of the above embodiments comprises the following steps,
s1, drying the raw material components to be dried;
s2, adding the low-molecular-weight saturated dihydric alcohol and the adamantane dihydric alcohol into a container, heating to 70-90 ℃, uniformly mixing, adding the diisocyanate, stirring for reacting for 2-5 hours, adding the polymer polyol and the catalyst, and continuously reacting for 2-5 hours to obtain a prepolymer A;
s3, dividing prepolymer A obtained in the step S1 into a first part of prepolymer and a second part of prepolymer, wherein the mole number of isocyanate in the first part of prepolymer is the same as that of the hydroxyalkyl acrylate;
s4, mixing the first part of prepolymer, the hydroxyalkyl acrylate and 0.001-0.01 part of polymerization inhibitor, and heating to 70-85 ℃ for end-capping reaction for 2-5 hours to obtain prepolymer B;
s5, mixing the second part of prepolymer, the dihydroxy (methyl) acrylate and 0.001-0.01 part of polymerization inhibitor, and heating to 70-90 ℃ to perform chain extension reaction for 2-5 hours to obtain prepolymer C;
s6, uniformly mixing the prepolymer B obtained in the step S4, the prepolymer C obtained in the step S5, the photoinitiator and the adhesion promoter to obtain the polyurethane hot melt adhesive composition.
The invention has the beneficial effects that:
(1) aiming at the problem of volume shrinkage caused by crosslinking and curing of carbon-carbon double bonds, adamantane diol with a three-dimensional structure and a larger volume is added in the preparation of the polyurethane prepolymer, and the adamantane diol with the large three-dimensional structure is bonded into the main chain of the polyurethane prepolymer, so that the volume shrinkage of hot melt adhesive during ultraviolet curing is reduced, and the initial bonding strength is improved.
(2) The inventor of the present application finds that the introduction of an adamantane structure into the main chain structure of the polyurethane prepolymer can enhance the cohesive strength of the hot melt adhesive and improve the adhesion effect.
(3) In addition, the inventor of the present application has also found that the introduction of adamantane structure into the main chain structure of the polyurethane prepolymer results in less dense internal structure of the molecules of the hot melt adhesive after ultraviolet curing due to the larger volume structure of adamantane, and larger gaps exist between the molecular chain segments, which is more favorable for moisture penetration, thus accelerating the moisture curing rate and shortening the curing time.
(4) The inventor of the present application has also found that the use of dihydroxy (meth) acrylate as a chain extender in an isocyanate-terminated prepolymer not only can introduce carbon-carbon double bonds into side chains to participate in ultraviolet curing, increase the crosslinking density during photocuring, and further improve the initial bonding strength, but also can form a more dense final crosslinking structure after moisture curing, resulting in a better final viscosity strength.
(5) The prepolymer B terminated by carbon-carbon double bonds and the chain-extended prepolymer C terminated by isocyanate are separately prepared and then are combined together to prepare the hot melt adhesive, so that the polyurethane hot melt adhesive with better bonding property can be obtained.
Detailed Description
The technical solution of the present invention is further illustrated and described by the following detailed description.
The invention provides a high initial bonding strength light and moisture dual-curing polyurethane hot melt adhesive composition which comprises, by weight, 70-100 parts of polymer polyol, 1-5 parts of low molecular weight saturated dihydric alcohol, 0.3-1 part of dihydroxy (methyl) acrylate, 15-30 parts of adamantane dihydric alcohol, 25-50 parts of diisocyanate, 1-5 parts of photoinitiator, 1-3 parts of hydroxyalkyl acrylate, 0.1-1 part of catalyst and 1-3 parts of adhesion promoter; the average molecular weight of the polymer polyol is not less than 500; the low molecular weight saturated diol has a molecular weight of no more than 200. In the present invention, the low molecular weight saturated diol refers to a low molecular weight saturated diol having no repeating unit or having a repeating unit number of 2 or 3 in a molecular structure, for example, ethylene glycol and diethylene glycol are low molecular weight saturated diols, and polyethylene glycol having an average molecular weight of 150 is not a low molecular weight saturated diol having a definite structure.
In a preferred embodiment of the present invention, the polymeric polyol is selected from a combination of one or more of polyester polyols and polyether polyols. In the present invention, both the polyester polyol and the polyether polyol are polyols commonly used in polyurethane for reacting with an isocyanate group to form a polyurethane structure. The polyester polyol can be aromatic polyester polyol and is prepared by reacting aromatic phthalic anhydride and dihydric alcohol; the mixed acid type polyester polyol is prepared by reacting different types of fatty acid, anhydride and dihydric alcohol; aliphatic polyester polyol is prepared by reacting saturated aliphatic dibasic acid or anhydride with dihydric alcohol. The polyether polyol is usually a homopolymer of polyethylene glycol (PEO), polypropylene glycol (PPO), polytetramethylene glycol (PTMG), or the like, or a copolymer of two or more components thereof, such as a PEO-PPO copolymer, a PEO-PPO-PEO copolymer, a PEO-PTMG-PEO copolymer, a PPO-PTMG-PPO copolymer, or the like. The polymer polyol is more preferably a polyester polyol in view of the heat resistance of the hot melt adhesive. The polymer polyol is more preferably a polyether polyol from the viewpoint of hydrolysis resistance of the hot melt adhesive.
In a preferred embodiment of the present invention, the saturated diol with low molecular weight is selected from one or more of ethylene glycol, 1, 3-propylene glycol, 1, 2-propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, 1, 4-cyclohexanediol, 1, 4-butanediol, 1, 2-pentanediol, 1, 5-pentanediol, 1, 6-hexanediol and 1, 3-butanediol. The present inventors found that, in order to achieve a better reduction in volume shrinkage during uv curing of hot melt adhesives, relatively more adamantane diol needs to be added, and the adamantane diol has a larger molecular volume, so that the reaction with diisocyanate cannot be completed due to a larger steric hindrance, and the function of the adamantane diol is deteriorated. Therefore, the low molecular weight saturated dihydric alcohol and the adamantane dihydric alcohol react with the diisocyanate simultaneously, the low steric hindrance effect of the low molecular weight saturated dihydric alcohol is used as a spacer for the reaction of the adamantane dihydric alcohol and the diisocyanate, the steric hindrance effect of the adamantane dihydric alcohol in the direct reaction of the diisocyanate and the adamantane dihydric alcohol is reduced, and the adamantane dihydric alcohol can fully and completely react with the diisocyanate, thereby playing a role.
In a preferred embodiment of the present invention, the dihydroxy (meth) acrylate is selected from one or more of 2, 3-dihydroxy propyl acrylate, 2, 3-dihydroxy propyl methacrylate, 2, 4-dihydroxy butyl acrylate and 2, 4-dihydroxy butyl methacrylate. In the invention, the dihydroxy (methyl) acrylate is used as a chain extender of the isocyanate prepolymer, and carbon-carbon double bonds can be introduced into a side chain to participate in the photocuring reaction. Compared with the prior art that the isocyanate prepolymer does not have carbon-carbon double bonds and can not generate photocuring reaction, the light/moisture dual-cured hot melt adhesive forms a semi-interpenetrating polymer network after photocuring, and the hot melt adhesive forms an interpenetrating polymer network after photocuring, so that the cross-linking density is higher, and the initial bonding strength is also better. Meanwhile, the steric hindrance of the carbon-carbon double bond at the side chain is lower than that of the carbon-carbon double bond at the main chain, and the carbon-carbon double bond can better participate in the crosslinking reaction under the irradiation of ultraviolet light.
In a preferred embodiment of the invention, the weight ratio of the bishydroxy (meth) acrylate to the hydroxyalkyl acrylate is 0.2 to 0.7: 1. The proportion of isocyanate-terminated polyurethane and carbon-carbon double bond-terminated polyurethane in the polyurethane hot melt adhesive can be controlled by controlling the weight ratio of the dihydroxy (methyl) acrylate to the hydroxyalkyl acrylate, so that the polyurethane hot melt adhesive has good initial bonding strength after photocuring and good final bonding strength after moisture curing. Further preferably, the weight ratio of the bishydroxy (meth) acrylate to the hydroxyalkyl acrylate is 0.25 to 0.6: 1. Still more preferably, the weight ratio of the bishydroxy (meth) acrylate to the hydroxyalkyl acrylate is 0.3 to 0.5: 1.
In a preferred embodiment of the invention, the adamantane diol is selected from one or a combination of 1, 3-adamantane diol and 1, 4-adamantane diol. In a preferred embodiment of the invention, the weight ratio of the bishydroxy (meth) acrylate to the adamantanediol is 1:20 to 50. As the dihydroxyl (methyl) acrylate is adopted as the chain extender to introduce carbon-carbon double bonds into the side chain to participate in the photocuring reaction, in order to control the volume shrinkage rate of the hot melt adhesive during photocuring within a very small range, the weight ratio of the hydroxyl (methyl) acrylate to the adamantane diol needs to be controlled within a proper range. If the content of the hydroxyl (methyl) acrylate is higher, the crosslinking density after ultraviolet curing is larger, and the volume shrinkage rate is larger; if the content of the hydroxy (meth) acrylate is relatively low, the crosslinking density after the uv curing may be relatively low, affecting the initial bond strength. More preferably, the weight ratio of the dihydroxy (meth) acrylate to the adamantane diol is 1:27 to 45. Still more preferably, the weight ratio of the bishydroxy (meth) acrylate to the adamantane diol is 1:30 to 42.
In a preferred embodiment of the present invention, the diisocyanate is selected from one or more of toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, phenylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, biphenyl diisocyanate, xylylene diisocyanate, and toluene diisocyanate trimer.
In the present invention, the photoinitiator is a photoinitiator commonly used for UV curing, and is not particularly limited, but may be selected from benzoin photoinitiators, such as benzoin dimethyl ether, benzoin butyl ether, benzoin ethyl ether, and the like, and may be selected from benzophenone photoinitiators, such as photoinitiator-1173, photoinitiator-184, and the like, and may be selected from other photoinitiators, such as photoinitiator-907, photoinitiator-1110, photoinitiator-1105, photoinitiator-1101, photoinitiator-1220, photoinitiator-1156, photoinitiator-810, photoinitiator-EHA, photoinitiator-MBZ, and the like.
In a preferred embodiment of the present invention, the hydroxyalkyl acrylate has the general structural formula CH2＝CR1COOR2OH, wherein R1Selected from methyl or hydrogen, R2Is selected from C2-C8 alkylene. More preferably, the hydroxyalkyl acrylate is selected from one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate. In the invention, the hydroxyalkyl acrylate is used for blocking the isocyanate-terminated prepolymer, so that the terminal group is converted into a carbon-carbon double bond structure from an isocyanate structure, thereby being capable of carrying out ultraviolet crosslinking reaction.
In a preferred embodiment of the present invention, the catalyst is selected from one or more of stannous octoate, dibutyltin dilaurate, monobutyltin oxide, organic potassium carboxylate, organic bismuth carboxylate, cobalt octoate, zinc naphthenate and tetraisobutyl titanate.
The adhesion promoter in the invention is an adhesion promoter commonly used in the field of polyurethane hot melt adhesives, is not particularly limited, and can be selected from silane coupling agents, such as epoxy silane coupling agents, specifically KH-560, or amino silane coupling agents, specifically KH-550, KH-792 and the like, or alkenyl silane coupling agents, specifically KH-171, KH-172, KH-570 and the like.
The invention also provides a preparation method of the polyurethane hot melt adhesive composition, which comprises the following steps,
s1, drying the raw material components to be dried; in the present invention, the raw materials to be dried include a polymeric polyol and an adamantane diol;
s2, adding the low-molecular-weight saturated dihydric alcohol and the adamantane dihydric alcohol into a container, heating to 70-90 ℃, uniformly mixing, adding the diisocyanate, stirring for reacting for 2-5 hours, adding the polymer polyol and the catalyst, and continuously reacting for 2-5 hours to obtain a prepolymer A;
s3, dividing prepolymer A obtained in the step S1 into a first part of prepolymer and a second part of prepolymer, wherein the mole number of isocyanate in the first part of prepolymer is the same as that of the hydroxyalkyl acrylate;
s4, mixing the first part of prepolymer, the hydroxyalkyl acrylate and 0.001-0.01 part of polymerization inhibitor, and heating to 70-85 ℃ to carry out end capping reaction for 2-5 hours to obtain prepolymer B;
s5, mixing the second part of prepolymer, the dihydroxy (methyl) acrylate and 0.001-0.01 part of polymerization inhibitor, and heating to 70-90 ℃ to perform chain extension reaction for 2-5 hours to obtain prepolymer C;
s6, uniformly mixing the prepolymer B obtained in the step S4, the prepolymer C obtained in the step S5, the photoinitiator and the adhesion promoter to obtain the polyurethane hot melt adhesive composition.
In the preparation method, the prepolymer A is divided into the first prepolymer and the second prepolymer and then respectively reacted to obtain the prepolymer B and the prepolymer C, and the prepolymer B and the prepolymer C are mixed, so that the reaction of light curing and moisture curing is better controlled, the initial bonding strength of the obtained polyurethane hot melt adhesive after photocuring is better, and the final bonding strength of the polyurethane hot melt adhesive after moisture curing is also better.
The technical solution of the present invention will be further described and illustrated below with reference to various embodiments. Unless otherwise specified, the parts described in the following examples are parts by weight.
Example 1
According to the formula: 95 parts of PEO (10) -PPO (5) diol (10 and 5 of which represent the average degree of polymerization of PEO and PPO, respectively, and the like hereinafter), 4 parts of ethylene glycol, 0.5 part of 2, 3-dihydroxypropyl acrylate, 15 parts of 1, 3-adamantanediol, 35 parts of hexamethylene diisocyanate, 3 parts of benzoin dimethyl ether, 2 parts of hydroxypropyl acrylate, 0.5 part of stannous octoate, and 1.5 parts of KH-560.
Drying PEO (10) -PPO (5) diol and adamantane diol at 60 deg.C under vacuum;
adding ethylene glycol and 1, 3-adamantane diol into a container, heating to 70-75 ℃, uniformly mixing, adding hexamethylene diisocyanate, stirring for reacting for 3 hours, adding PEO (10) -PPO (5) diol and stannous octoate, and continuously reacting for 3 hours to obtain prepolymer A;
dividing prepolymer A into a first part of prepolymer and a second part of prepolymer, wherein the mole number of isocyanate in the first part of prepolymer is the same as that of hydroxypropyl acrylate;
mixing the first part of prepolymer, hydroxypropyl acrylate and 0.005 part of hydroquinone, heating to 75-80 ℃ for end capping reaction for 4 hours to obtain prepolymer B;
mixing the second part of prepolymer, 2, 3-dihydroxy propyl acrylate and 0.003 part of hydroquinone, and heating to 80-85 ℃ for chain extension reaction for 3 hours to obtain prepolymer C;
and uniformly mixing the prepolymer B, the prepolymer C, benzoin dimethyl ether and KH-560 to obtain the polyurethane hot melt adhesive composition.
Example 2
The hydroxypropyl acrylate in example 1 was adjusted to 1.5 parts, and the remaining steps were kept unchanged to obtain a polyurethane hot melt adhesive.
Example 3
The hydroxypropyl acrylate in example 1 was adjusted to 1 part, and the remaining steps were kept unchanged to obtain a polyurethane hot melt adhesive.
Example 4
The 1, 3-adamantanediol in example 1 was adjusted to 20 parts, and the remaining steps were kept unchanged to obtain a polyurethane hot melt adhesive.
Example 5
The 1, 3-adamantanediol in example 1 was adjusted to 25 parts, and the remaining steps were kept unchanged to obtain a polyurethane hot melt adhesive.
Example 6
According to the formula: 75 parts of PEO (10) -PPO (5) -PEO (10) glycol, 4 parts of propylene glycol, 0.8 part of 2, 4-dihydroxy butyl acrylate, 20 parts of 1, 4-adamantanediol, 45 parts of isophorone diisocyanate, 3.5 parts of a photoinitiator-1173, 1.6 parts of hydroxyethyl acrylate, 0.3 part of stannous octoate and 1 part of KH-560.
Drying PEO (10) -PPO (5) -PEO (10) glycol and adamantane glycol at 60 deg.C under vacuum;
adding propylene glycol and 1, 4-adamantane diol into a container, heating to 80-85 ℃, uniformly mixing, adding isophorone diisocyanate, stirring for reacting for 2.5 hours, adding PEO (10) -PPO (5) -PEO (10) diol and stannous octoate, and continuously reacting for 4 hours to obtain prepolymer A;
dividing the prepolymer A into a first part of prepolymer and a second part of prepolymer, wherein the mole number of isocyanate in the first part of prepolymer is the same as that of hydroxyethyl acrylate;
mixing the first part of prepolymer, hydroxyethyl acrylate and 0.002 part of hydroquinone, heating to 77-82 ℃ for end capping reaction for 4 hours to obtain prepolymer B;
mixing the second part of prepolymer, 2, 4-dihydroxy butyl acrylate and 0.002 part of hydroquinone, heating to 75-80 ℃ for chain extension reaction for 5 hours to obtain prepolymer C;
and uniformly mixing the prepolymer B, the prepolymer C, the photoinitiator-1173 and the KH-560 to obtain the polyurethane hot melt adhesive composition.
Example 7
The 1, 4-adamantanediol in example 6 was adjusted to 24 parts, and the remaining steps were kept unchanged to obtain a polyurethane hot melt adhesive.
Example 8
The 1, 4-adamantanediol in example 6 was adjusted to 28 parts, and the remaining steps were kept unchanged to obtain a polyurethane hot melt adhesive.
Example 9
The hydroxyethyl acrylate in example 6 was adjusted to 2 parts, and the remaining steps were kept unchanged to obtain a polyurethane hot melt adhesive.
Comparative example 1
According to the formula: 95 parts of PEO (10) -PPO (5) diol, 4 parts of ethylene glycol, 0.5 part of 2, 3-dihydroxypropyl acrylate, 35 parts of hexamethylene diisocyanate, 3 parts of benzoin dimethyl ether, 2 parts of hydroxypropyl acrylate, 0.5 part of stannous octoate and 1.5 parts of KH-560.
Drying PEO (10) -PPO (5) diol at 60 deg.C under vacuum;
adding ethylene glycol into a container, heating to 70-75 ℃, adding hexamethylene diisocyanate, stirring for reaction for 3 hours, adding PEO (10) -PPO (5) diol and stannous octoate, and continuing to react for 3 hours to obtain prepolymer A;
dividing prepolymer A into a first part of prepolymer and a second part of prepolymer, wherein the mole number of isocyanate in the first part of prepolymer is the same as that of hydroxypropyl acrylate;
mixing the first part of prepolymer, hydroxypropyl acrylate and 0.005 part of hydroquinone, heating to 75-80 ℃ for end capping reaction for 4 hours to obtain prepolymer B;
mixing the second part of prepolymer, 2, 3-dihydroxy propyl acrylate and 0.003 part of hydroquinone, and heating to 80-85 ℃ for chain extension reaction for 3 hours to obtain prepolymer C;
and uniformly mixing the prepolymer B, the prepolymer C, benzoin dimethyl ether and KH-560 to obtain the polyurethane hot melt adhesive composition.
Comparative example 2
The formulation in example 6 was followed.
Adding 1, 4-adamantane diol into a container, heating to 80-85 ℃, adding isophorone diisocyanate, stirring for reacting for 2.5 hours, adding propylene glycol, PEO (10) -PPO (5) -PEO (10) diol and stannous octoate, and continuing to react for 4 hours to obtain prepolymer A;
dividing the prepolymer A into a first part of prepolymer and a second part of prepolymer, wherein the mole number of isocyanate in the first part of prepolymer is the same as that of hydroxyethyl acrylate;
mixing the first part of prepolymer, hydroxyethyl acrylate and 0.002 part of hydroquinone, heating to 77-82 ℃ for end capping reaction for 4 hours to obtain prepolymer B;
mixing the second part of prepolymer, 2, 4-dihydroxy butyl acrylate and 0.002 part of hydroquinone, heating to 75-80 ℃ for chain extension reaction for 5 hours to obtain prepolymer C;
and uniformly mixing the prepolymer B, the prepolymer C, the photoinitiator-1173 and the KH-560 to obtain the polyurethane hot melt adhesive composition.
Comparative example 3
The weight of 1, 3-adamantanediol in example 1 was changed to 8 parts, and the remaining steps were kept unchanged to obtain a polyurethane hot melt adhesive composition.
Comparative example 4
The weight of 1, 3-adamantanediol in example 1 was changed to 31 parts, and the remaining steps were kept unchanged to obtain a polyurethane hot melt adhesive composition.
Comparative example 5
The formulation of example 2 was followed except that the same parts by weight of propylene glycol were used in place of the propyl 2, 3-dihydroxyacrylate.
Drying PEO (10) -PPO (5) diol and 1, 3-adamantane diol at 60 deg.C under vacuum;
adding ethylene glycol and 1, 3-adamantane diol into a container, heating to 70-75 ℃, uniformly mixing, adding hexamethylene diisocyanate, stirring for reacting for 3 hours, adding PEO (10) -PPO (5) diol and stannous octoate, and continuously reacting for 3 hours to obtain prepolymer A;
dividing prepolymer A into a first part of prepolymer and a second part of prepolymer, wherein the mole number of isocyanate in the first part of prepolymer is the same as that of hydroxypropyl acrylate;
mixing the first part of prepolymer, hydroxypropyl acrylate and 0.005 part of hydroquinone, heating to 75-80 ℃ for end capping reaction for 4 hours to obtain prepolymer B;
mixing the second part of prepolymer, propylene glycol and 0.003 part of hydroquinone, heating to 80-85 ℃ for chain extension reaction for 3 hours to obtain prepolymer C;
and uniformly mixing the prepolymer B, the prepolymer C, benzoin dimethyl ether and KH-560 to obtain the polyurethane hot melt adhesive composition.
Comparative example 6
The formulation of example 2 was followed.
PEO (10) -PPO (5) diol and 1, 3-adamantane diol are subjected to vacuum drying treatment at 60 ℃;
adding ethylene glycol and 1, 3-adamantane diol into a container, heating to 70-75 ℃, uniformly mixing, adding hexamethylene diisocyanate, stirring for reacting for 3 hours, adding PEO (10) -PPO (5) diol and stannous octoate, and continuously reacting for 3 hours to obtain prepolymer A;
adding 2, 3-dihydroxy propyl acrylate and 0.003 part of hydroquinone into the prepolymer A, heating to 80-85 ℃ for chain extension reaction for 3 hours, then adding hydroxypropyl acrylate, carrying out end-capping reaction for 4 hours at 75-80 ℃, cooling, and adding benzoin dimethyl ether and KH-560 to obtain the polyurethane hot melt adhesive composition.
Test example
The polyurethane hot melt adhesives of examples 1 to 9 and comparative examples 1 to 6 were coated on a PET film to a thickness of about 0.2mm, cured by ultraviolet irradiation, left at room temperature for 5min to test the initial 180 ° peel strength, the samples were placed in a room-temperature constant-humidity environment with a humidity of 65%, sampled every 24 hours to test the 180 ° peel strength to examine the degree of curing, and the final 180 ° peel strength and shear strength were tested after the samples were completely cured. Each sample was taken and 3 slices were tested, and the average of 3 slices was taken.
And testing the completely cured sample for 72 hours at 85 ℃ and 95% humidity for high temperature and high humidity, and then placing the sample at room temperature for 24 hours to test the peel strength, namely the 180-degree peel strength after the high temperature and high humidity test.
Retention of 180 DEG peel strength after high temperature and high humidity test (Q)1/Q0X 100%, wherein Q1Is 180 DEG peel strength, Q, after high temperature and high humidity testing0Final 180 ° peel strength.
The complete cure time was judged to be 95% or more of the final 180 ° peel strength.
The results are shown in Table 1.
TABLE 1
From the results in table 1, it can be seen that the light/moisture dual-curing polyurethane hot melt adhesive of the present invention has high initial adhesive strength after being irradiated by ultraviolet light, faster moisture curing speed, and high final adhesive strength, and simultaneously has high shear strength after being completely cured by adding a sufficient amount of adamantane diol, and also has good results in wet heat resistance tests.
The foregoing has shown and described the principles, major features, and advantages of the invention. It should be understood by those skilled in the art that the present invention is not limited by the foregoing embodiments, which are merely preferred embodiments of the present invention, and the scope of the present invention should not be limited thereby, and that equivalent changes and modifications made within the scope of the present invention and the specification should be covered thereby. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. A light/moisture dual-curing polyurethane hot melt adhesive composition with high initial bonding strength is characterized in that: the adhesive comprises the following raw material components, by weight, 70-100 parts of polymer polyol, 1-5 parts of low molecular weight saturated dihydric alcohol, 0.3-1 part of dihydroxy (methyl) acrylate, 15-30 parts of adamantane dihydric alcohol, 25-50 parts of diisocyanate, 1-5 parts of photoinitiator, 1-3 parts of hydroxyalkyl acrylate, 0.1-1 part of catalyst and 1-3 parts of adhesion promoter;
the average molecular weight of the polymer polyol is not less than 500;
the low molecular weight saturated diol has a molecular weight of no more than 200.
2. The polyurethane hot melt adhesive composition according to claim 1, wherein: the polymer type polyol is selected from one or a combination of polyester polyol and polyether polyol.
3. The polyurethane hot melt adhesive composition according to claim 1, wherein: the saturated dihydric alcohol with low molecular weight is one or a combination of a plurality of ethylene glycol, 1, 3-propylene glycol, 1, 2-propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, 1, 4-cyclohexanediol, 1, 4-butanediol, 1, 2-pentanediol, 1, 5-pentanediol, 1, 6-hexanediol and 1, 3-butanediol.
4. The polyurethane hot melt adhesive composition according to claim 1, wherein: the dihydroxy (methyl) acrylate is selected from one or more of 2, 3-dihydroxy propyl acrylate, 2, 3-dihydroxy propyl methacrylate, 2, 4-dihydroxy butyl acrylate and 2, 4-dihydroxy butyl methacrylate.
5. The polyurethane hot melt adhesive composition of claim 1, wherein: the weight ratio of the bishydroxy (meth) acrylate to the hydroxyalkyl acrylate is 0.2 to 0.7: 1.
6. The polyurethane hot melt adhesive composition according to claim 1, wherein: the adamantane diol is one or two of 1, 3-adamantane diol and 1, 4-adamantane diol;
the weight ratio of the dihydroxy (methyl) acrylate to the adamantanediol is 1: 20-50.
7. The polyurethane hot melt adhesive composition according to claim 1, wherein: the diisocyanate is selected from one or a combination of toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, phenylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, biphenyl diisocyanate, xylylene diisocyanate and toluene diisocyanate trimer.
8. The polyurethane hot melt adhesive composition according to claim 1, wherein: the structural general formula of the hydroxyalkyl acrylate is CH2＝CR1COOR2OH, wherein R1Selected from methyl or hydrogen, R2Is selected from C2-C8 alkylene.
9. The polyurethane hot melt adhesive composition according to claim 1, wherein: the catalyst is selected from one or a combination of stannous octoate, dibutyltin dilaurate, monobutyltin oxide, organic potassium carboxylate, organic bismuth carboxylate, cobalt octoate, zinc naphthenate and tetraisobutyl titanate.
10. A method for preparing the polyurethane hot melt adhesive composition of any one of claims 1 to 9, which is characterized in that: comprises the following steps of (a) carrying out,
s1, drying the raw material components to be dried;
s2, adding the low-molecular-weight saturated dihydric alcohol and the adamantane dihydric alcohol into a container, heating to 70-90 ℃, uniformly mixing, adding the diisocyanate, stirring for reacting for 2-5 hours, adding the polymer polyol and the catalyst, and continuously reacting for 2-5 hours to obtain a prepolymer A;
s3, dividing prepolymer A obtained in the step S1 into a first part of prepolymer and a second part of prepolymer, wherein the mole number of isocyanate in the first part of prepolymer is the same as that of the hydroxyalkyl acrylate;
s4, mixing the first part of prepolymer, the hydroxyalkyl acrylate and 0.001-0.01 part of polymerization inhibitor, and heating to 70-85 ℃ for end-capping reaction for 2-5 hours to obtain prepolymer B;
s5, mixing the second part of prepolymer, the dihydroxy (methyl) acrylate and 0.001-0.01 part of polymerization inhibitor, and heating to 70-90 ℃ to perform chain extension reaction for 2-5 hours to obtain prepolymer C;
s6, uniformly mixing the prepolymer B obtained in the step S4, the prepolymer C obtained in the step S5, the photoinitiator and the adhesion promoter to obtain the polyurethane hot melt adhesive composition.
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| WO2024130663A1 (en) * | 2022-12-22 | 2024-06-27 | Henkel Ag & Co. Kgaa | Dually curable adhesive composition |
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