CN115491164B - Acrylic ester modified reactive polyurethane hot melt adhesive and preparation method and application and use method thereof - Google Patents
Acrylic ester modified reactive polyurethane hot melt adhesive and preparation method and application and use method thereof Download PDFInfo
- Publication number
- CN115491164B CN115491164B CN202211210102.7A CN202211210102A CN115491164B CN 115491164 B CN115491164 B CN 115491164B CN 202211210102 A CN202211210102 A CN 202211210102A CN 115491164 B CN115491164 B CN 115491164B
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- CN
- China
- Prior art keywords
- hot melt
- melt adhesive
- polyurethane hot
- acrylate
- reactive polyurethane
- 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.)
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- -1 Acrylic ester Chemical class 0.000 title claims abstract description 104
- 239000004831 Hot glue Substances 0.000 title claims abstract description 97
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 88
- 239000004814 polyurethane Substances 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 50
- 239000004417 polycarbonate Substances 0.000 claims abstract description 50
- 150000001875 compounds Chemical class 0.000 claims abstract description 46
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 43
- 229920001021 polysulfide Polymers 0.000 claims abstract description 42
- 239000005077 polysulfide Substances 0.000 claims abstract description 42
- 150000008117 polysulfides Polymers 0.000 claims abstract description 42
- 229920005989 resin Polymers 0.000 claims abstract description 42
- 239000011347 resin Substances 0.000 claims abstract description 42
- 238000003756 stirring Methods 0.000 claims abstract description 40
- 239000000853 adhesive Substances 0.000 claims abstract description 37
- 230000001070 adhesive effect Effects 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 33
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 33
- 229920005862 polyol Polymers 0.000 claims abstract description 33
- 150000003077 polyols Chemical class 0.000 claims abstract description 32
- 239000007788 liquid Substances 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 238000007789 sealing Methods 0.000 claims abstract description 15
- 239000012948 isocyanate Substances 0.000 claims abstract description 14
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 13
- 238000004321 preservation Methods 0.000 claims abstract description 3
- 150000002009 diols Chemical class 0.000 claims description 22
- 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 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 17
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 15
- VHJLVAABSRFDPM-QWWZWVQMSA-N dithiothreitol Chemical group SC[C@@H](O)[C@H](O)CS VHJLVAABSRFDPM-QWWZWVQMSA-N 0.000 claims description 14
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 13
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 11
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical class OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 125000005396 acrylic acid ester group Chemical group 0.000 claims description 9
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 8
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 7
- 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 6
- BSKLKCJVOHJWHU-UHFFFAOYSA-N 6-hydroxyhexyl hydrogen carbonate Chemical compound OCCCCCCOC(O)=O BSKLKCJVOHJWHU-UHFFFAOYSA-N 0.000 claims description 6
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 4
- 125000000732 arylene group Chemical group 0.000 claims description 4
- 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 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 claims description 3
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 claims description 3
- NLGDWWCZQDIASO-UHFFFAOYSA-N 2-hydroxy-1-(7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-yl)-2-phenylethanone Chemical compound OC(C(=O)c1cccc2Oc12)c1ccccc1 NLGDWWCZQDIASO-UHFFFAOYSA-N 0.000 claims description 3
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 3
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical class OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 3
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 claims description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- IIGAAOXXRKTFAM-UHFFFAOYSA-N N=C=O.N=C=O.CC1=C(C)C(C)=C(C)C(C)=C1C Chemical compound N=C=O.N=C=O.CC1=C(C)C(C)=C(C)C(C)=C1C IIGAAOXXRKTFAM-UHFFFAOYSA-N 0.000 claims description 3
- QORUGOXNWQUALA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 Chemical compound N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 QORUGOXNWQUALA-UHFFFAOYSA-N 0.000 claims description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- 239000012965 benzophenone Substances 0.000 claims description 3
- JGCWKVKYRNXTMD-UHFFFAOYSA-N bicyclo[2.2.1]heptane;isocyanic acid Chemical compound N=C=O.N=C=O.C1CC2CCC1C2 JGCWKVKYRNXTMD-UHFFFAOYSA-N 0.000 claims description 3
- KOMDZQSPRDYARS-UHFFFAOYSA-N cyclopenta-1,3-diene titanium Chemical compound [Ti].C1C=CC=C1.C1C=CC=C1 KOMDZQSPRDYARS-UHFFFAOYSA-N 0.000 claims description 3
- 125000005442 diisocyanate group Chemical group 0.000 claims description 3
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 229920000379 polypropylene carbonate Polymers 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 claims description 3
- AMJYHMCHKZQLAY-UHFFFAOYSA-N tris(2-isocyanatophenoxy)-sulfanylidene-$l^{5}-phosphane Chemical compound O=C=NC1=CC=CC=C1OP(=S)(OC=1C(=CC=CC=1)N=C=O)OC1=CC=CC=C1N=C=O AMJYHMCHKZQLAY-UHFFFAOYSA-N 0.000 claims description 3
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 2
- ANLVEXKNRYNLDH-UHFFFAOYSA-N 1,3-dioxonan-2-one Chemical compound O=C1OCCCCCCO1 ANLVEXKNRYNLDH-UHFFFAOYSA-N 0.000 claims description 2
- FEWFXBUNENSNBQ-UHFFFAOYSA-N 2-hydroxyacrylic acid Chemical class OC(=C)C(O)=O FEWFXBUNENSNBQ-UHFFFAOYSA-N 0.000 claims description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 16
- 239000000758 substrate Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- ZMSQJSMSLXVTKN-UHFFFAOYSA-N 4-[2-(2-morpholin-4-ylethoxy)ethyl]morpholine Chemical compound C1COCCN1CCOCCN1CCOCC1 ZMSQJSMSLXVTKN-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 238000001723 curing Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 238000006757 chemical reactions by type Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical group CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 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 description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 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 description 3
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 2
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 2
- 241000208140 Acer Species 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical class OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- VKSWWACDZPRJAP-UHFFFAOYSA-N 1,3-dioxepan-2-one Chemical compound O=C1OCCCCO1 VKSWWACDZPRJAP-UHFFFAOYSA-N 0.000 description 1
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- IYABWNGZIDDRAK-UHFFFAOYSA-N allene Chemical group C=C=C IYABWNGZIDDRAK-UHFFFAOYSA-N 0.000 description 1
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- XXKOQQBKBHUATC-UHFFFAOYSA-N cyclohexylmethylcyclohexane Chemical compound C1CCCCC1CC1CCCCC1 XXKOQQBKBHUATC-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000013008 moisture curing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 229920002578 polythiourethane polymer Polymers 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 125000006839 xylylene group Chemical group 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—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
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4081—Mixtures of compounds of group C08G18/64 with other macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- 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
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6453—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having sulfur
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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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
- C08G2170/20—Compositions for hot melt adhesives
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Abstract
The invention belongs to the field of adhesives, and relates to an acrylic ester modified reactive polyurethane hot melt adhesive, and a preparation method, application and a use method thereof. The preparation method of the acrylate modified reactive polyurethane hot melt adhesive comprises the following steps: s1, vacuum stirring and dehydrating polycarbonate polyol, liquid polysulfide resin and a catalyst at 110-120 ℃ for 1-5h, and cooling to 70-90 ℃ to obtain a pretreatment product; s2, carrying out vacuum stirring reaction on the pretreated product and the polyisocyanate compound for 1-5h at the temperature of 70-90 ℃ to obtain isocyanate double-ended prepolymer; s3, carrying out vacuum stirring reaction on the isocyanate double-end capped prepolymer, the hydroxy acrylic ester compound and the photoinitiator for 1-5h at the temperature of 70-90 ℃ to obtain the acrylic ester modified reactive polyurethane hot melt adhesive, and carrying out vacuum sealing and preservation in a dark place. The acrylate modified reactive polyurethane hot melt adhesive provided by the invention can be disassembled and disassembled, and has excellent flexibility, initial bonding strength, final bonding strength and heat resistance.
Description
Technical Field
The invention belongs to the field of adhesives, and particularly relates to an acrylic ester modified reactive polyurethane hot melt adhesive, and a preparation method, application and a use method thereof.
Background
In electronic products such as smart phones, tablet computers, smart watches, TWS headphones and the like, parts of the electronic products are often fixed by reactive polyurethane hot melt adhesives. The electronic product parts of the reactive polyurethane hot melt adhesive are often high in value, and when the situations of poor assembly, after-sale repair of products, recovery of valuable electronic product parts and the like occur, the adhered parts are usually required to be disassembled, so that the adhesive is required to have the characteristics of reworkability and easy disassembly. However, most reactive polyurethane hot melt adhesives currently used are very difficult to disassemble once they are fully cured.
The existing detachable reactive polyurethane hot melt adhesive mainly comprises the steps of introducing a few raw materials with lower glass transition temperature or softening point into an adhesive component, and realizing the purpose of being detachable under a heating condition by utilizing the poor heat resistance and the reduced modulus of the material at a higher temperature. In addition, some thermally-expanded microspheres are introduced into the adhesive component, and the thermally-expanded microspheres can be thermally expanded in the cured resin phase, so that the cohesive strength of the resin phase can be reduced, and the purpose of detachability can be achieved. However, such adhesives that can be reworked by heating often have poor heat resistance, but although the adhesives have reworkable characteristics, generally the reworkable adhesives have low adhesive strength and poor heat resistance, and are not suitable for use in a scene where reliability requirements are high, particularly heat resistance is required to be higher than 100 ℃. In addition, the use of a heat-peelable adhesive is not suitable for a heat-peelable adherend. The problems of the existing reactive polyurethane hot melt adhesive mainly comprise: the disassembly temperature is too high, the flexibility is poor, the heat resistance is poor, and the like.
In addition, the traditional reactive polyurethane hot melt adhesive mainly relies on the reaction and solidification of isocyanate in the adhesive and moisture in the air, and the reaction speed of isocyanate and moisture is low, so that the curing usually needs a long time, the initial bonding strength is low, the pressure maintaining time is long, and the cost of the assembly process is increased.
Therefore, there is a strong need in the market for a reactive polyurethane hot melt adhesive that has excellent heat resistance, can be effectively disassembled under mild conditions without heating, and has excellent flexibility and both initial and final adhesive strength.
Disclosure of Invention
The first object of the present invention is to provide an acrylic acid ester modified reactive polyurethane hot melt adhesive which can be disassembled and disassembled by a specific reducing agent and has excellent flexibility, initial bonding strength, final bonding strength and heat resistance.
The second aim of the invention is to provide a preparation method of the acrylic ester modified reactive polyurethane hot melt adhesive.
The third object of the invention is to provide the application of the acrylic ester modified reactive polyurethane hot melt adhesive in the assembly of a smart phone shell, the assembly of a camera lens and the bonding of a loudspeaker.
The fourth object of the present invention is to provide a method for using the above-mentioned acrylate-modified reactive polyurethane hot melt adhesive, which comprises bonding the bonded parts with the acrylate-modified reactive polyurethane hot melt adhesive, and when the bonded parts are required to be disassembled, immersing the bonded parts in a debonder, wherein the debonder is a dithiothreitol solution.
Specifically, the invention provides an acrylic ester modified reactive polyurethane hot melt adhesive, wherein the acrylic ester modified reactive polyurethane hot melt adhesive comprises a polyurethane prepolymer and a photoinitiator, and the polyurethane prepolymer is prepared from polycarbonate polyol, liquid polysulfide resin, polyisocyanate compounds, hydroxyacrylate compounds and a catalyst; the molar ratio of hydroxyl groups in the polycarbonate polyol, mercapto groups in the liquid polysulfide resin, isocyanate groups in the polyisocyanate compound to hydroxyl groups in the hydroxyacrylate compound is 1 (1-3) (3-8) (0.375-2.5), and simultaneously (the molar amount of isocyanate groups in the polyisocyanate compound)/(the molar amount of hydroxyl groups in the polycarbonate polyol + the molar amount of mercapto groups in the liquid polysulfide resin) =1.5-2, and (the molar amount of isocyanate groups in the polyisocyanate compound-the molar amount of hydroxyl groups in the polycarbonate polyol-the molar amount of mercapto groups in the liquid polysulfide resin)/the molar amount of hydroxyacrylate compound=1.6-2.67; the liquid polysulfide resin has a structure shown in a formula (I), wherein n 1 An integer of 5 to 44;
in a preferred embodiment, the polyurethane prepolymer is present in an amount of 95 to 99.5% and the photoinitiator is present in an amount of 0.5 to 5% based on the total weight of the acrylate modified reactive polyurethane hot melt adhesive.
In a preferred embodiment, the polyisocyanate compound has a structure represented by formula (ii):
in the formula (II), R 1 Is substituted or unsubstituted C 1 -C 30 Alkylene, substituted or unsubstituted C 6 -C 30 Arylene, substituted or unsubstituted C 6 -C 30 Aralkylene, substituted or unsubstituted C 6 -C 30 Alkarylene groups, the substituents O, P, S, -CO-or-PS-.
In a preferred embodiment, the polyisocyanate compound is selected from at least one of isophorone diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4, 4' -diisocyanate, hydrogenated diphenylmethane-4, 4' -diisocyanate, polydiphenylmethane-4, 4' -diisocyanate, 1, 5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanatophenyl) thiophosphate, tetramethylxylene diisocyanate, and 1,6, 10-undecane triisocyanate.
In a preferred embodiment, the polycarbonate polyol has a structure represented by formula (III):
in the formula (IV), R 2 Is C 2 -C 6 Alkylene group, R 3 Is C 2 -C 6 Alkylene group, n 2 Is an integer of 5 to 27.
In a preferred embodiment, the polycarbonate polyol is selected from at least one of poly (1, 6-hexanediol carbonate) polyol, poly (1, 4-butanediol-1, 6-hexanediol carbonate) diol, poly (1, 5-pentanediol-1, 6-hexanediol carbonate) diol, poly (caprolactone) methylene glycol, poly (1, 4-cyclohexanedimethanol-1, 6-hexanediol carbonate) diol, poly (ethylene carbonate) diol, poly (propylene carbonate) diol, poly (butylene carbonate) diol, poly (hexamethylene carbonate) diol.
In a preferred embodiment, the hydroxyacrylate compound has a structure represented by formula (iv):
in the formula (V), R 4 is-H or methyl, R 5 Is C 2 -C 4 Alkylene groups of (a).
In a preferred embodiment, the hydroxyacrylate compound is selected from at least one of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, caprolactone-modified hydroxyethyl acrylate and caprolactone-modified hydroxypropyl acrylate.
In a preferred embodiment, the catalyst is an organotin-based catalyst and/or an amine-based catalyst.
In a preferred embodiment, the photoinitiator is selected from at least one of benzophenone-based compounds, acetophenone-based compounds, acylphosphine oxide-based compounds, titanocene-based compounds, oxime ester-based compounds, benzoin ether-based compounds, and thioxanthones.
The preparation method of the acrylate modified reactive polyurethane hot melt adhesive provided by the invention comprises the following steps:
s1, vacuum stirring and dehydrating polycarbonate polyol, liquid polysulfide resin and a catalyst at 110-120 ℃ for 1-5h, and then cooling to 70-90 ℃ to obtain a pretreatment product;
s2, carrying out vacuum stirring reaction on the pretreated product and the polyisocyanate compound for 1-5h at the temperature of 70-90 ℃ to obtain isocyanate double-ended prepolymer;
s3, carrying out vacuum stirring reaction on the isocyanate double-end capped prepolymer, the hydroxy acrylic ester compound and the photoinitiator for 1-5h at the temperature of 70-90 ℃ to obtain the acrylic ester modified reactive polyurethane hot melt adhesive, and carrying out vacuum sealing and preservation in a dark place.
In a preferred embodiment, the catalyst is used in an amount of 0.1 to 0.5% by weight based on the total weight of the polycarbonate polyol, the liquid polysulfide resin, the polyisocyanate-based compound, the hydroxyacrylate-based compound, the catalyst and the photoinitiator.
The invention also provides application of the acrylic ester modified reactive polyurethane hot melt adhesive in smart phone shell assembly, camera lens assembly and loudspeaker adhesion.
In addition, the invention also provides a use method of the adhesive, which comprises the step of bonding the bonded parts by the acrylic ester modified reactive polyurethane hot melt adhesive, and when the bonded parts are required to be disassembled, soaking the bonded parts in a debonder, wherein the debonder is dithiothreitol solution.
The invention firstly uses polycarbonate polyol, specific liquid polysulfide resin and polyisocyanate compound to react to prepare the polysulfide isocyanate, and then the polysulfide isocyanate is further reacted with hydroxy acrylic ester to prepare the acrylic ester modified reactive polyurethane hot melt adhesive, which not only has excellent flexibility, but also has higher bonding strength compared with the adhesive prepared by the traditional polyether type PUA resin. In addition, the acrylate modified reactive polyurethane hot melt adhesive contains a large number of disulfide bonds, and can break bonds under the action of a dithiothreitol reducing agent to realize a detachable function under mild conditions, and the dithiothreitol is mainly applied to the field of biological medicines and is commonly used for opening disulfide bonds in protein or polypeptide chains. In the application method, dithiothreitol is creatively used for disassembling the acrylic ester modified reactive polyurethane hot melt adhesive containing aliphatic disulfide bonds, so that the acrylic ester modified reactive polyurethane hot melt adhesive can be disassembled under mild conditions.
The invention utilizes polycarbonate polyol, specific liquid polysulfide resin, polyisocyanate and hydroxy acrylic ester to prepare polyurethane prepolymer, wherein part or all of the polyurethane prepolymer is polyurethane acrylic ester with one end modified by acrylic ester. The urethane acrylate modified at one end with acrylate has three characteristics: (1) One end of the molecular chain is an acrylate group capable of being cured by UV light and the other end is an isocyanato capable of being cured by moisture; (2) an aliphatic disulfide bond is contained in the molecular chain; (3) The molecular chain contains an aminosulfate bond (-NHCOS-). The invention innovatively combines the sulfhydryl-terminated polysulfide resin with polycarbonate polyol, polyisocyanate and hydroxy acrylic ester to prepare polyurethane prepolymer; the sulfamate bond (-NHCOS-) formed by the reaction of mercapto and isocyanate is different from the urethane bond (-NHCOO-) formed by the reaction of hydroxy and isocyanate, and the structure containing the sulfamate bond has better flexibility because the radius of sulfur atom is larger than that of oxygen atom and the bond energy of carbon-sulfur bond is lower than that of carbon-oxygen bond; according to the invention, the acrylate functional group is introduced to prepare the acrylate modified reactive polyurethane hot melt adhesive containing the aliphatic disulfide bond, and the acrylate modified reactive polyurethane hot melt adhesive can form higher crosslinking density after being cured, has better thermal stability, reduces the influence of disulfide bond fracture on the reduction of the bonding strength of the integral adhesive at high temperature, so that the reduction of the bonding strength of the adhesive at 100 ℃ is less, and the heat resistance and the stability are improved. In addition, the invention introduces the acrylate component capable of being cured by UV light on the basis of the traditional acrylate modified reactive polyurethane hot melt adhesive, and the acrylate component can be cured and crosslinked rapidly after UV light irradiation to form higher bonding strength. The introduction of the acrylic ester component increases the curing speed and the bonding strength of the acrylic ester modified reactive polyurethane hot melt adhesive and the heat resistance of the final cured product. In addition, the introduction of the polycarbonate diol as a polyol compound into the adhesive can effectively improve the heat resistance of the final cured product.
Detailed Description
The acrylate modified reactive polyurethane hot melt adhesive provided by the invention comprises polyurethane prepolymer and photoinitiator. Wherein the content of the polyurethane prepolymer is preferably 95-99.5%, such as 95%, 96%, 97%, 98%, 99%, 99.5%, etc., and the content of the photoinitiator is preferably 0.5-5%, such as 0.5%, 1%, 2%, 3%, 4%, 5%, etc.
The polyurethane prepolymer is prepared from polycarbonate polyol, liquid polysulfide resin, polyisocyanate compounds, hydroxy acrylic ester compounds and a catalyst. In one specific embodiment, the preparation method of the acrylate modified reactive polyurethane hot melt adhesive comprises the following steps and the specific reaction process is as follows: s1, vacuum stirring and dehydrating polycarbonate polyol, liquid polysulfide resin and a catalyst at 110-120 ℃ for 1-5h, and then cooling to 70-90 ℃ to obtain a pretreatment product; s2, carrying out vacuum stirring reaction on the pretreated product and the polyisocyanate compound for 1-5h at the temperature of 70-90 ℃ to obtain isocyanate double-ended prepolymer; s3, carrying out vacuum stirring reaction on the isocyanate double-ended prepolymer, the hydroxy acrylic ester compound and the photoinitiator for 1-5h at the temperature of 70-90 ℃ to obtain the acrylic ester modified reactive polyurethane hot melt adhesive. The purpose of the vacuum stirring and dehydration in the step S1 is to avoid the reaction of residual water in the raw materials with the polyisocyanate groups to interfere with the smooth progress of the reaction. In addition, the rotational speeds of stirring in steps S1, S2 and S3 may each independently be 100-200r/min.
In the preparation process of the acrylic ester modified reactive polyurethane hot melt adhesive, the molar ratio of hydroxyl groups in the polycarbonate polyol, mercapto groups in the liquid polysulfide resin, isocyanate groups in the polyisocyanate compounds to hydroxyl groups in the hydroxy acrylic ester compounds is preferably 1 (1-3): 3-8): 0.375-2.5. The amount of mercapto groups in the liquid polysulfide resin is 1 to 3 moles, such as 1 mole, 1.2 mole, 1.5 mole, 1.8 mole, 2 mole, 2.2 mole, 2.5 mole, 2.8 mole, 3 mole, etc., based on 1 mole of hydroxyl groups in the polycarbonate polyol; the amount of isocyanate groups in the polyisocyanate compound is 3 to 8mol, such as 3mol, 3.5mol, 4mol, 4.5mol, 5mol, 5.5mol, 6mol, 6.5mol, 7mol, 7.5mol, 8mol, etc.; the hydroxyl group content in the hydroxy acrylic compound is 0.375-2.5mol, such as 0.375mol, 0.4mol, 0.5mol, 0.8mol, 1mol, 1.2mol, 1.5mol, 1.8mol, 2mol, 2.2mol, 2.5mol, etc. In addition, (the molar amount of isocyanate groups in the polyisocyanate compound)/(the molar amount of hydroxyl groups in the polycarbonate polyol+the molar amount of mercapto groups in the liquid polysulfide resin) =1.5 to 2 (e.g., 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, etc.), and (the molar amount of isocyanate groups in the polyisocyanate compound-the molar amount of hydroxyl groups in the polycarbonate polyol-the molar amount of mercapto groups in the liquid polysulfide resin)/the molar amount of hydroxyacrylate compound=1.6 to 2.67 (e.g., 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.67, etc.), the resulting polyurethane prepolymer contains at least one end of the urethane acrylate modified with the acrylic ester, and the corresponding polyurethane hot melt adhesive has good flexibility, initial adhesive strength, final adhesive strength, and heat resistance. In a preferred embodiment, (molar amount of isocyanate groups in the polyisocyanate compound)/(molar amount of hydroxyl groups in the polycarbonate polyol + molar amount of mercapto groups in the liquid polysulfide resin) =1.5-2, and (molar amount of isocyanate groups in the polyisocyanate compound-molar amount of hydroxyl groups in the liquid polysulfide resin)/molar amount of hydroxyacrylate compound=2, at which time the respective raw materials are substantially completely reacted to form a long-chain urethane acrylate having a UV-light-curable acrylate group at one end and a moisture-curable isocyanate group at the other end, that is, a long-chain urethane acrylate having a UV-light-curable acrylate group at one end and a moisture-curable isocyanate group at the other end in the reaction product, not only has the dual advantages of UV-light curing and moisture curing but also can avoid the adverse effects brought by the small-molecular side reaction products, corresponding to flexibility, initial strength, final strength and adhesion of the corresponding urethane hot-melt adhesive, and can all achieve an optimal state.
The catalyst is used in an amount of 0.1-0.5%, such as 0.1%, 0.2%, 0.3%, 0.4%, 0.5% of the total weight of the polycarbonate polyol, the liquid polysulfide resin, the polyisocyanate compound, the hydroxyacrylate compound, the catalyst and the photoinitiator. The amount of the photoinitiator is 0.5-5%, such as 0.5%, 1%, 2%, 3%, 4%, 5% of the total weight of the polycarbonate polyol, the liquid polysulfide resin, the polyisocyanate compound, the hydroxy acrylate compound, the catalyst and the photoinitiator.
The polysulfide resin is liquid at room temperature and has a structure shown as the following formula (I), wherein n 1 An integer of 5 to 44, such as 5, 8, 10, 15, 20, 25, 30, 35, 40, 44, etc.:
the polysulfide resin may be prepared by various methods available in the art, and may be commercially available, for example, from LP-3, LP-33, LP-23, LP-980, LP-2, LP-32, LP-12, LP-31, LP-55, LP-56, etc. of east Asia.
The polyisocyanate is a compound with two or more isocyanate groups at the molecular chain terminal, and the specific structure is shown as a formula (II), wherein R 1 Is substituted or unsubstituted C 1 -C 30 Alkylene, substituted or unsubstituted C 6 -C 30 Arylene, substituted or unsubstituted C 6 -C 30 Aralkylene, substituted or unsubstituted C 6 -C 30 Alkarylene radicals, substituted radicals O, P, S, -CO-or-PS- & lt- & gt>Wherein C is 1 -C 30 The alkylene group may be methylene, ethylene, n-propylene, isopropylene, n-butylene, sec-butylene, isobutylene, tert-butylene, n-pentylene, isopentylene, tert-pentylene, neopentylene, n-hexylene, n-pentyleneHeptyl, n-octyl, n-nonyl, n-sunflower, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, and the like. C (C) 6 -C 30 Arylene groups may be phenylene, biphenylene, naphthylene, and the like. C (C) 6 -C 30 The aralkylene group may be xylylene, benzylene, etc. C (C) 6 -C 30 The alkarylene group may be a toluene group. Specific examples of the polyisocyanate include, but are not limited to, from the viewpoint of raw material availability: at least one of isophorone diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4, 4' -diisocyanate (MDI), hydrogenated diphenylmethane-4, 4' -diisocyanate (hydrogenated MDI), polydiphenylmethane-4, 4' -diisocyanate (polymeric MDI), 1, 5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanatophenyl) thiophosphate, tetramethylxylene diisocyanate, and 1,6, 10-undecane triisocyanate.
The specific structure of the polycarbonate polyol is shown as a formula (III), wherein R 2 Is C 2 -C 6 Alkylene group, R 3 Is C 2 -C 6 Alkylene group, n 2 Is an integer of 5 to 27. C (C) 2 -C 6 The alkylene group of (a) may be ethylene, n-propylene, isopropylene, n-butylene, sec-butylene, isobutylene, tert-butylene, n-pentylene, isopentylene, tert-pentylene or neopentylene. n is n 2 Is an integer of 5 to 27, such as 5, 8, 10, 12, 15, 17, 20, 22, 25, 27, etc. Specific examples of the polycarbonate polyol include, but are not limited to, from the viewpoint of raw material availability: poly (1, 6-hexanediol carbonate) polyol and poly (1, 4-butylene carbonate)At least one of diol-1, 6-hexanediol diol, poly-1, 5-pentanediol-1, 6-hexanediol diol, poly-caprolactone-methylene glycol, poly-1, 4-cyclohexanedimethanol-1, 6-hexanediol diol, poly-ethylene carbonate diol, poly-propylene carbonate diol, poly-butylene carbonate diol, and poly-butylene carbonate diol. In addition, the number average molecular weight of the polycarbonate polyol is preferably 1000 to 4000.
The specific structure of the hydroxy acrylic ester is shown as a formula (IV), wherein R is 4 is-H or methyl, R 5 Is C 2 -C 4 Alkylene groups of (a). C (C) 2 -C 4 The alkylene group of (a) may be ethylene, n-propylene, isopropylene, n-butylene, sec-butylene, isobutylene or tert-butylene. Specific examples of the hydroxyacrylates include, but are not limited to, from the standpoint of raw material availability: at least one of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, caprolactone-modified hydroxyethyl acrylate and caprolactone-modified hydroxypropyl acrylate.
The catalyst may be an organotin-based catalyst and/or an amine-based catalyst. Examples of the organotin-based catalyst include dibutyltin dilaurate and stannous octoate. Examples of the amine catalyst include triethylamine, diethylenetriamine, triethylenediamine, N-ethylmorpholine, and 2, 2-dimorpholinodiethyl ether.
The photoinitiator may be any of various conventional compounds capable of generating radicals by absorbing ultraviolet light energy to initiate polymerization of unsaturated monomers, and is preferably a radical photoinitiator, and specifically includes at least one of benzophenone-based compounds, acetophenone-based compounds, acylphosphine oxide-based compounds, titanocene-based compounds, oxime ester-based compounds, benzoin ether-based compounds, and thioxanthones.
The invention also provides application of the acrylic ester modified reactive polyurethane hot melt adhesive in smart phone shell assembly, camera lens assembly and loudspeaker adhesion.
The application method of the adhesive comprises the steps of bonding the bonded parts by the acrylate modified reactive polyurethane hot melt adhesive, and soaking the bonded parts in a debonder when the bonded parts are required to be disassembled, wherein the debonder is a dithiothreitol solution. Wherein the dithiothreitol solution is a compound solution of dithiothreitol and an organic solvent. Wherein, the weight ratio of dithiothreitol to organic solvent can be (0.2-0.6): 1, such as 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, etc. The organic solvent is preferably a low-toxicity solvent such as ethanol, isopropanol, dimethyl sulfoxide (DMSO), dimethyl carbonate, diethyl carbonate, or the like. Disulfide bonds in polythiourethane acrylate oligomers contained in the acrylate modified reactive polyurethane hot melt adhesive can be broken under the action of dithiothreitol, and the cured acrylate modified reactive polyurethane hot melt adhesive is soaked in the dithiothreitol solution, so that the detachable function under mild conditions can be realized.
The present invention will be described in detail by examples.
Example 1
25.3g (0.025 mol) of a polysulfide resin LP3 of number average molecular weight 1000, 50.5g (0.025 mol) of a poly (1, 6-hexanediol) diol of number average molecular weight 2000, 0.3g of 2, 2-dimorpholinodiethyl ether were added by weight to a reaction flask, heated to 110℃and dehydrated under stirring at 150r/min for 2 hours; cooling to 80 ℃, adding 19.0g (0.075 mol) of 4,4' -diphenylmethane diisocyanate (MDI), and reacting for 2 hours under vacuum at a stirring speed of 150 r/min; then 2.9g (0.025 mol) of 2-hydroxyethyl acrylate and 2g of TPO photoinitiator are taken and added into a reaction kettle, and the mixture is discharged after being reacted for 2 hours at a stirring speed of 150r/min under a vacuum condition, so as to obtain the acrylic ester modified reactive polyurethane hot melt adhesive, and the acrylic ester modified polyurethane hot melt adhesive is preserved in a vacuum sealing way in a dark place.
Example 2
62.0g (0.025 mol) of polysulfide resin LP23 with a number average molecular weight of 2500, 12.4g (0.012 mol) of poly-1, 4-butanediol-1, 6-hexanediol ester diol with a number average molecular weight of 1000, 0.2g of dibutyltin dilaurate were added to a reaction flask, heated to 110℃and dehydrated in vacuo with stirring at 150r/min for 2h; cooling to 80 ℃, adding 19.5g (0.074 mol) of 4, 4-diisocyanate dicyclohexylmethane (HMDI), and reacting for 2 hours under vacuum at a stirring speed of 150 r/min; then 4.8g (0.037 mol) of 2-hydroxypropyl acrylate and 1g of photoinitiator 819 are taken and added into a reaction kettle, and the materials are discharged after reacting for 2 hours at a stirring speed of 150r/min under a vacuum condition, so as to obtain the acrylic ester modified reactive polyurethane hot melt adhesive, and the polyurethane hot melt adhesive is preserved in a vacuum sealing way in a dark place.
Example 3
54.9g (0.014 mol) of polysulfide resin LP32 having a number average molecular weight of 4000, 27.4g (0.009 mol) of poly-1, 5-pentanediol-1, 6-hexanediol ester diol having a number average molecular weight of 3000, 0.1g of stannous octoate were added by weight to a reaction flask, heated to 110℃and dehydrated in vacuo under 150r/min stirring for 2 hours; cooling to 80 ℃, adding 7.7g (0.046 mol) of Hexamethylene Diisocyanate (HDI), and reacting for 2 hours under vacuum at a stirring speed of 150 r/min; then 7.9g (0.023 mol) of caprolactone modified acrylic ester PLACCEL FA D and 2g of photoinitiator 184 are taken and added into a reaction kettle, and the materials are discharged after reacting for 2 hours at a stirring speed of 150r/min under a vacuum condition, so as to obtain the acrylic ester modified reactive polyurethane hot melt adhesive, and the polyurethane hot melt adhesive is preserved in a vacuum sealing way in a dark place.
Example 4
46.0g (0.011 mol) of a polysulfide resin LP55 having a number average molecular weight of 4000, 34.5g (0.011 mol) of a polypropylene carbonate diol having a number average molecular weight of 3000, 0.4g of 2, 2-dimorpholinodiethyl ether were added to a reaction flask, heated to 110℃and dehydrated in vacuo under 150r/min stirring for 2 hours; cooling to 80 ℃, adding 10.20g (0.045 mol) of isophorone diisocyanate (IPDI), and reacting for 2 hours under vacuum at a stirring speed of 150 r/min; then 7.9g (0.023 mol) of caprolactone modified acrylic ester PLACCEL FA D and 2g of photoinitiator 184 are taken and added into a reaction kettle, and the materials are discharged after reacting for 2 hours at a stirring speed of 150r/min under a vacuum condition, so as to obtain the acrylic ester modified reactive polyurethane hot melt adhesive, and the polyurethane hot melt adhesive is preserved in a vacuum sealing way in a dark place.
Example 5
45.4g (0.045 mol) of polysulfide resin LP3 with a number average molecular weight of 1000, 15.1g (0.015 mol) of poly-1, 4-cyclohexanedimethanol-1, 6-hexanediol ester diol with a number average molecular weight of 1000, 0.2g of dibutyltin dilaurate were added to a reaction flask, heated to 110℃and dehydrated in vacuo with stirring at 150r/min for 2h; cooling to 80 ℃, adding 30.3g (0.121 mol) of 4,4' -diphenylmethane diisocyanate (MDI), and reacting for 2 hours under vacuum at a stirring speed of 150 r/min; and then 7.0g (0.061 mol) of 2-hydroxyethyl acrylate and 2g of photo initiator TPO are taken and added into a reaction kettle to react for 2 hours at a stirring speed of 150r/min under a vacuum condition, and then the materials are discharged, so that the acrylic ester modified reactive polyurethane hot melt adhesive is obtained and is preserved in a vacuum sealing way in a dark place.
Example 6
57.6g (0.023 mol) of polysulfide LP23 of number average molecular weight 2500, 23.1g (0.012 mol) of poly-1, 4-butanediol-1, 6-hexanediol ester diol of number average molecular weight 2000, 0.2g of stannous octoate are added to a reaction flask, heated to 110℃and dehydrated in vacuo under 150r/min stirring for 2h; cooling to 80 ℃, adding 11.6g (0.068 mol) of Hexamethylene Diisocyanate (HDI), and reacting for 2 hours under vacuum at a stirring speed of 150 r/min; then 4.5g (0.035 mol) of 2-hydroxypropyl acrylate and 3g of photoinitiator ITX are taken and added into a reaction kettle, and the mixture is discharged after being reacted for 2 hours at a stirring speed of 150r/min under a vacuum condition, thus obtaining the acrylic ester modified reactive polyurethane hot melt adhesive which is preserved in a vacuum sealing way in a dark place.
Example 7
An acrylic acid ester modified reactive polyurethane hot melt adhesive was prepared as in example 1, except that the amount of 2-hydroxyethyl acrylate was adjusted to 3.6g (0.031 mol), and the other conditions were the same as in example 1, to obtain an acrylic acid ester modified reactive polyurethane hot melt adhesive, which was stored under vacuum sealing in a dark place.
Example 8
An acrylic acid ester modified reactive polyurethane hot melt adhesive was prepared in the same manner as in example 1 except that the amount of 2-hydroxyethyl acrylate was adjusted to 2.2g (0.019 mol) and the other conditions were the same as in example 1 to obtain an acrylic acid ester modified reactive polyurethane hot melt adhesive which was stored under vacuum sealing against light.
Comparative example 1
A reactive polyurethane hot melt adhesive was prepared as in example 1, except that the polysulfide resin LP3 was replaced with the same molar amount of polytetrahydrofuran ether glycol, specifically:
25.3g (0.025 mol) of polytetrahydrofuran ether glycol having a number average molecular weight of 1000, 50.5g (0.025 mol) of poly (1, 6-hexanediol) carbonate having a number average molecular weight of 2000, 0.3g of 2, 2-dimorpholinodiethyl ether are added by weight to a reaction flask, heated to 110℃and dehydrated in vacuo with stirring at 150r/min for 2h; cooling to 80 ℃, adding 19.0g (0.075 mol) of 4,4' -diphenylmethane diisocyanate (MDI), and reacting for 2 hours under vacuum at a stirring speed of 150 r/min; then 2.9g (0.025 mol) of 2-hydroxyethyl acrylate and 2g of TPO photoinitiator are taken and added into a reaction kettle, and the reaction is carried out for 2 hours at a stirring speed of 150r/min under a vacuum condition, and then the discharge is carried out, thus obtaining the comparative reference acrylate modified reaction type polyurethane hot melt adhesive without disulfide bonds, and the comparative reference acrylate modified reaction type polyurethane hot melt adhesive is preserved in a vacuum sealing way in a dark place.
Comparative example 2
A reactive polyurethane hot melt adhesive was prepared as in example 1, except that the poly (1, 6 hexanediol carbonate) diol was replaced with the same molar amount of polyoxypropylene ether diol, specifically:
25.3g (0.025 mol) of a polysulfide resin LP3 of number average molecular weight 1000, 50.5g (0.025 mol) of a polyoxypropylene ether glycol of number average molecular weight 2000, 0.3g of 2, 2-dimorpholinodiethyl ether were added by weight to a reaction flask, heated to 110℃and dehydrated under stirring at 150r/min for 2 hours; cooling to 80 ℃, adding 19.00g (0.075 mol) of 4,4' -diphenylmethane diisocyanate (MDI), and reacting for 2 hours under vacuum at a stirring speed of 150 r/min; then 2.9g (0.025 mol) of 2-hydroxyethyl acrylate and 2g of TPO photoinitiator are taken and added into a reaction kettle, and the reaction is carried out for 2 hours at a stirring speed of 150r/min under a vacuum condition, and then the discharge is carried out, thus obtaining the comparative reference type acrylic ester modified reaction type polyurethane hot melt adhesive without polycarbonate diol, and the comparative reference type acrylic ester modified reaction type polyurethane hot melt adhesive is preserved in a vacuum sealing way in a dark place.
Comparative example 3
26.6g (0.027 mol) of polysulfide resin LP3 of number average molecular weight 1000, 53.2g (0.027 mol) of poly (1, 6-hexanediol carbonate) diol of number average molecular weight 2000, 0.3g of 2, 2-dimorpholinodiethyl ether are added by weight to a reaction flask, heated to 110℃and dehydrated in vacuo with stirring at 150r/min for 2h; then cooling to 80 ℃, adding 19.9g (0.080 mol) of 4,4' -diphenylmethane diisocyanate (MDI), reacting for 2 hours at a stirring speed of 150r/min under vacuum condition, discharging to obtain the acrylic ester modified reactive polyurethane hot melt adhesive which is not modified by acrylic ester, and preserving in a vacuum sealing way in a dark place.
Comparative example 4
An acrylic acid ester modified reactive polyurethane hot melt adhesive was prepared in the same manner as in example 1 except that the amount of 2-hydroxyethyl acrylate was adjusted to 1.7g (0.015 mol) and the remaining conditions were the same as in example 1, to obtain an acrylic acid ester modified reactive polyurethane hot melt adhesive, which was stored under vacuum sealing against light.
Preparation example 1
30 parts by weight of dithiothreitol is dissolved in 100 parts by weight of dimethyl maple solvent, and uniformly mixed to obtain a uniform and transparent solution, which is designated as a dispergator 1.
Preparation example 2
50 parts by weight of dithiothreitol is dissolved in 100 parts by weight of dimethyl maple solvent, and the solution is uniformly mixed to obtain a uniform and transparent solution which is marked as a dispergator 2.
Test case
The produced samples of examples 1 to 8 and the produced samples of comparative examples 1 to 4 were tested for melt viscosity, modulus, elongation at break, adhesive strength and removability in the following manner, and the obtained results are shown in Table 2.
(1) Melt viscosity:
and (3) placing the polyurethane hot melt adhesive which is sealed well in a cylinder heater at 110 ℃ for 10min, at this time, pouring the hot melt adhesive into a sleeve in a Brookfield-DV2T viscometer rapidly, setting the temperature of the heater at 110 ℃ and keeping for 10min, so that the internal temperature of the hot melt adhesive is uniform and defoamed. The constant temperature melt viscosity of the hot melt adhesive was measured at 110 ℃.
(2) Modulus, elongation at break:
a0.2 mm thick film was prepared according to standard ASTM D-0638, cut into a dumbbell shape, and the prepared dumbbell-shaped specimen was stretched at a speed of 100mm/min using a tensile tester, and modulus and elongation at break of the specimen were measured.
(3) Adhesive strength:
a. adhesive strength for 15min and 24 h: the hot melt adhesives obtained in examples and comparative examples were dispensed at 110℃using a dispenser to coat a 25mm by 25mm rectangular frame of adhesive on a polycarbonate substrate with a width of about 1 mm. Then, another polycarbonate substrate was bonded to the polycarbonate substrate, and after the dispensing and lamination, 2000MJ/cm of the polycarbonate substrate was irradiated with 365nmUV light 2 And then curing the sample in an environment of 25 ℃ and 50% RH for 15min and 24h, using a universal material tester to run the manufactured bonding sample along the drawing direction at a speed of 10mm/min until the bonding of the sample fails, recording the maximum force value displayed by the instrument, and calculating the bonding strength of the hot melt adhesive to the polycarbonate substrate by combining the bonding area.
b. Adhesive strength at 80 ℃): the hot melt adhesives obtained in examples and comparative examples were dispensed at 110℃using a dispenser to coat a 25mm by 25mm rectangular frame of adhesive on a polycarbonate substrate with a width of about 1 mm. Then, another polycarbonate substrate was bonded to the polycarbonate substrate, and after the dispensing and lamination, 2000MJ/cm of the polycarbonate substrate was irradiated with 365nmUV light 2 And then curing the sample in a temperature and humidity environment of 25 ℃ and 50%RH for 3 days, using a universal material tester with a heating oven, setting the temperature of the oven to 80 ℃, keeping the temperature of the bonded sample in the oven for 10 minutes, starting testing, running the manufactured sample for evaluating the bonding strength along the drawing direction at a speed of 10mm/min until the bonding of the sample fails, recording the maximum force value displayed by the instrument, and calculating the bonding strength of the hot melt adhesive to the polycarbonate substrate by combining the bonding area.
c. Adhesive strength after debonding agent immersion:the hot melt adhesives obtained in examples and comparative examples were dispensed at 110℃using a dispenser to coat a 25mm by 25mm rectangular frame of adhesive on a polycarbonate substrate with a width of about 1 mm. Then, another polycarbonate substrate was bonded to the polycarbonate substrate, and after the dispensing and lamination, 2000MJ/cm of the polycarbonate substrate was irradiated with 365nmUV light 2 And then curing the sample in a temperature and humidity environment of 25 ℃ and 50%RH for 3 days, soaking the bonded substrate in a debonding agent for 12 hours, using a universal material tester to run the soaked bonding sample along the drawing direction at a speed of 10mm/min until the bonding of the sample fails, recording the maximum force value displayed by the instrument, and calculating the bonding strength of the hot melt adhesive to the polycarbonate substrate by combining the bonding area.
From the results of the table, the melt viscosity of the acrylate modified polyurethane hot melt adhesive provided by the invention is in a proper range, which indicates that the acrylate modified polyurethane hot melt adhesive can be conveniently used for melt sizing, and can meet the sizing process of general adhesive dispensing. As can be seen from the comparison of the modulus and elongation at break of examples 1-8 with comparative example 1, examples 1-8 have lower modulus and higher elongation at break, demonstrating the superior flexibility of the acrylate modified polyurethane hot melt adhesives prepared based on mercapto-terminated polysulfide resins of the present invention. The comparison of the adhesive strength of examples 1-8 and comparative example 1 after the debonding agent soaking treatment shows that the disulfide bond-containing adhesive of the present invention directly falls off after the debonding agent soaking treatment, indicating that the adhesive of the present invention has a function of being detachable under mild conditions. The better heat resistance of the polycarbonate diol-containing adhesives of the invention can be demonstrated by comparing the adhesive strength variation at 80℃for examples 1-8 with comparative example 2. As can be seen from the comparison of the adhesive strengths of examples 1 to 8 with comparative example 3 for 15min and 24h, the acrylate-modified polyurethane hot melt adhesives of the present invention have a faster curing speed and a higher adhesive strength than the polyurethane hot melt adhesives without acrylate modification. In conclusion, the acrylate modified polyurethane hot melt adhesive provided by the invention has high bonding strength, good flexibility and heat resistance, and a function of being detachable under mild conditions.
Although embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives, and variations may be made in the above embodiments by those skilled in the art without departing from the spirit and principles of the invention.
Claims (12)
1. The acrylate modified reactive polyurethane hot melt adhesive is characterized by comprising a polyurethane prepolymer and a photoinitiator, wherein the polyurethane prepolymer is prepared from polycarbonate polyol, liquid polysulfide resin, polyisocyanate compounds, hydroxyacrylate compounds and a catalyst; the molar ratio of hydroxyl groups in the polycarbonate polyol, mercapto groups in the liquid polysulfide resin, isocyanate groups in the polyisocyanate compound to hydroxyl groups in the hydroxyacrylate compound is 1 (1-3) (3-8) (0.375-2.5), and simultaneously (the molar amount of isocyanate groups in the polyisocyanate compound)/(the molar amount of hydroxyl groups in the polycarbonate polyol + the molar amount of mercapto groups in the liquid polysulfide resin) =1.5-2, and (the molar amount of isocyanate groups in the polyisocyanate compound-the molar amount of hydroxyl groups in the polycarbonate polyol-the molar amount of mercapto groups in the liquid polysulfide resin)/the molar amount of hydroxyacrylate compound=1.6-2.67; the liquid polysulfide resin has a structure shown in a formula (I), wherein n 1 An integer of 5 to 44;
（Ⅰ）；
the polycarbonate polyol has a structure represented by formula (III):
（Ⅲ）
in the formula (IV), R 2 Is C 2 -C 6 Alkylene group, R 3 Is C 2 -C 6 Alkylene group, n 2 An integer of 5 to 27;
the hydroxy acrylic ester compound has a structure shown in a formula (IV):
（Ⅳ）
in the formula (IV), R 4 is-H or methyl, R 5 Is C 2 -C 4 Alkylene groups of (a).
2. The acrylic acid ester modified reactive polyurethane hot melt adhesive according to claim 1, wherein the content of the polyurethane prepolymer is 95-99.5% and the content of the photoinitiator is 0.5-5% based on the total weight of the acrylic acid ester modified reactive polyurethane hot melt adhesive.
3. The acrylate-modified reactive polyurethane hot melt adhesive according to claim 1, wherein the polyisocyanate compound has a structure represented by formula (ii):
（Ⅱ）
in the formula (II), R 1 Is substituted or unsubstituted C 1 -C 30 Alkylene, substituted or unsubstituted C 6 -C 30 Arylene, substituted or unsubstituted C 6 -C 30 Aralkylene, substituted or unsubstituted C 6 -C 30 Alkarylene groups, the substituents O, P, S, -CO-or-PS-.
4. The acrylate-modified reactive polyurethane hot melt adhesive according to claim 1, wherein the polyisocyanate compound is at least one selected from isophorone diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4, 4' -diisocyanate, hydrogenated diphenylmethane-4, 4' -diisocyanate, polydidiphenylmethane-4, 4' -diisocyanate, 1, 5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanatophenyl) thiophosphate, tetramethylxylene diisocyanate, and 1,6, 10-undecane triisocyanate.
5. The acrylate-modified reactive polyurethane hot melt adhesive of claim 1, wherein the polycarbonate polyol is selected from at least one of poly (1, 6-hexanediol carbonate) polyol, poly (1, 4-butanediol-1, 6-hexanediol carbonate) diol, poly (1, 5-pentanediol-1, 6-hexanediol carbonate) diol, poly (caprolactone-methylene carbonate) diol, poly (1, 4-cyclohexanedimethanol-1, 6-hexanediol carbonate) diol, poly (ethylene carbonate) diol, poly (propylene carbonate) diol, poly (butylene carbonate) diol, poly (hexamethylene carbonate) diol.
6. The acrylate-modified reactive polyurethane hot melt adhesive according to claim 1, wherein the hydroxyacrylate compound is at least one selected from the group consisting of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, caprolactone-modified hydroxyethyl acrylate and caprolactone-modified hydroxypropyl acrylate.
7. The acrylate-modified reactive polyurethane hot melt adhesive according to claim 1, wherein the catalyst is an organotin-based catalyst and/or an amine-based catalyst.
8. The acrylate-modified reactive polyurethane hot melt adhesive according to claim 1, wherein the photoinitiator is at least one selected from the group consisting of benzophenone-based compounds, acetophenone-based compounds, acylphosphine oxide-based compounds, titanocene-based compounds, oxime ester-based compounds, benzoin ether-based compounds, and thioxanthones.
9. The method for preparing the acrylate modified reactive polyurethane hot melt adhesive according to any one of claims 1 to 8, which is characterized by comprising the following steps:
s1, vacuum stirring and dehydrating polycarbonate polyol, liquid polysulfide resin and a catalyst at 110-120 ℃ for 1-5h, and then cooling to 70-90 ℃ to obtain a pretreatment product;
s2, carrying out vacuum stirring reaction on the pretreated product and the polyisocyanate compound for 1-5h at the temperature of 70-90 ℃ to obtain isocyanate double-ended prepolymer;
s3, carrying out vacuum stirring reaction on the isocyanate double-end capped prepolymer, the hydroxy acrylic ester compound and the photoinitiator for 1-5h at the temperature of 70-90 ℃ to obtain the acrylic ester modified reactive polyurethane hot melt adhesive, and carrying out vacuum sealing and preservation in a dark place.
10. The method for preparing an acrylic ester modified reactive polyurethane hot melt adhesive according to claim 9, wherein the catalyst is used in an amount of 0.1 to 0.5% based on the total weight of the polycarbonate polyol, the liquid polysulfide resin, the polyisocyanate compound, the hydroxyacrylate compound, the catalyst and the photoinitiator.
11. Use of the acrylate-modified reactive polyurethane hot melt adhesive of any one of claims 1-8 in smartphone housing assembly, camera lens assembly, and speaker bonding.
12. The method for using the adhesive is characterized by comprising the steps of bonding the bonded parts by the acrylate modified reactive polyurethane hot melt adhesive according to any one of claims 1-8, and soaking the bonded parts in a debonder when the bonded parts are required to be disassembled, wherein the debonder is a dithiothreitol solution.
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