CN109957083A - A kind of manufacturing method of unsaturated polyol and photocurable polyurethane and they prepared therefrom - Google Patents
A kind of manufacturing method of unsaturated polyol and photocurable polyurethane and they prepared therefrom Download PDFInfo
- Publication number
- CN109957083A CN109957083A CN201810507846.2A CN201810507846A CN109957083A CN 109957083 A CN109957083 A CN 109957083A CN 201810507846 A CN201810507846 A CN 201810507846A CN 109957083 A CN109957083 A CN 109957083A
- Authority
- CN
- China
- Prior art keywords
- polyurethane
- polyol
- unsaturated
- photocurable
- group
- 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.)
- Granted
Links
- 239000004814 polyurethane Substances 0.000 title claims abstract description 115
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 115
- 229920005862 polyol Polymers 0.000 title claims abstract description 95
- 150000003077 polyols Chemical class 0.000 title claims abstract description 94
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 7
- 125000001302 tertiary amino group Chemical group 0.000 claims abstract 2
- -1 halogen acetyl halide Chemical class 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 25
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 16
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 16
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical group C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 229910052736 halogen Inorganic materials 0.000 claims description 10
- 239000012948 isocyanate Substances 0.000 claims description 10
- 150000002513 isocyanates Chemical class 0.000 claims description 10
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 9
- 239000013067 intermediate product Substances 0.000 claims description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 claims description 8
- LSTRKXWIZZZYAS-UHFFFAOYSA-N 2-bromoacetyl bromide Chemical compound BrCC(Br)=O LSTRKXWIZZZYAS-UHFFFAOYSA-N 0.000 claims description 8
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 7
- 125000005442 diisocyanate group Chemical group 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000005259 measurement Methods 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims description 3
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 claims description 3
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 claims description 3
- 229940043276 diisopropanolamine Drugs 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- UUORTJUPDJJXST-UHFFFAOYSA-N n-(2-hydroxyethyl)prop-2-enamide Chemical compound OCCNC(=O)C=C UUORTJUPDJJXST-UHFFFAOYSA-N 0.000 claims description 3
- ZEMHQYNMVKDBFJ-UHFFFAOYSA-N n-(3-hydroxypropyl)prop-2-enamide Chemical compound OCCCNC(=O)C=C ZEMHQYNMVKDBFJ-UHFFFAOYSA-N 0.000 claims description 3
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 abstract description 22
- 238000002360 preparation method Methods 0.000 abstract description 14
- 150000003512 tertiary amines Chemical class 0.000 abstract description 9
- 239000011527 polyurethane coating Substances 0.000 abstract description 7
- 239000000178 monomer Substances 0.000 abstract description 6
- 238000006116 polymerization reaction Methods 0.000 abstract description 5
- 238000013461 design Methods 0.000 abstract description 3
- 230000002269 spontaneous effect Effects 0.000 abstract description 2
- 238000001723 curing Methods 0.000 description 21
- 238000000576 coating method Methods 0.000 description 20
- 239000011248 coating agent Substances 0.000 description 17
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 16
- 150000002009 diols Chemical class 0.000 description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 9
- SEBSTKRLGYWNQR-UHFFFAOYSA-N [4-[3-[bis(2-hydroxyethyl)amino]propoxy]phenyl]-phenylmethanone Chemical compound C1=CC(OCCCN(CCO)CCO)=CC=C1C(=O)C1=CC=CC=C1 SEBSTKRLGYWNQR-UHFFFAOYSA-N 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical class CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 6
- 239000012965 benzophenone Substances 0.000 description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 description 6
- 229940043237 diethanolamine Drugs 0.000 description 6
- 229920001451 polypropylene glycol Polymers 0.000 description 6
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 5
- 239000004721 Polyphenylene oxide Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 229920000570 polyether Polymers 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000005855 radiation Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 4
- 229930182556 Polyacetal Natural products 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 230000000977 initiatory effect Effects 0.000 description 4
- 229920005906 polyester polyol Polymers 0.000 description 4
- 229920006324 polyoxymethylene Polymers 0.000 description 4
- 229920006295 polythiol Polymers 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 238000000016 photochemical curing Methods 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000005056 polyisocyanate Substances 0.000 description 3
- 229920001228 polyisocyanate Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- JIABEENURMZTTI-UHFFFAOYSA-N 1-isocyanato-2-[(2-isocyanatophenyl)methyl]benzene Chemical class O=C=NC1=CC=CC=C1CC1=CC=CC=C1N=C=O JIABEENURMZTTI-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229960003328 benzoyl peroxide Drugs 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 238000010345 tape casting Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical class O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 229940035437 1,3-propanediol Drugs 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 1
- 229940043375 1,5-pentanediol Drugs 0.000 description 1
- 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 description 1
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 description 1
- PVXVWWANJIWJOO-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-N-ethylpropan-2-amine Chemical compound CCNC(C)CC1=CC=C2OCOC2=C1 PVXVWWANJIWJOO-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- QMMZSJPSPRTHGB-UHFFFAOYSA-N MDEA Natural products CC(C)CCCCC=CCC=CC(O)=O QMMZSJPSPRTHGB-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- OMRDSWJXRLDPBB-UHFFFAOYSA-N N=C=O.N=C=O.C1CCCCC1 Chemical compound N=C=O.N=C=O.C1CCCCC1 OMRDSWJXRLDPBB-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- BSTIAEALIKFHRX-UHFFFAOYSA-N [4-[2-[bis(2-hydroxyethyl)amino]ethyl]phenyl]-phenylmethanone Chemical compound OCCN(CCO)CCC1=CC=C(C(=O)C2=CC=CC=C2)C=C1 BSTIAEALIKFHRX-UHFFFAOYSA-N 0.000 description 1
- LOIQXDAVWOXKMM-UHFFFAOYSA-N [4-[[bis(2-hydroxyethyl)amino]methyl]phenyl]-phenylmethanone Chemical compound C1=CC(CN(CCO)CCO)=CC=C1C(=O)C1=CC=CC=C1 LOIQXDAVWOXKMM-UHFFFAOYSA-N 0.000 description 1
- IOVBVLZPXJPVAA-UHFFFAOYSA-N [4-[bis(2-hydroxyethyl)amino]phenyl]-phenylmethanone Chemical compound C1=CC(N(CCO)CCO)=CC=C1C(=O)C1=CC=CC=C1 IOVBVLZPXJPVAA-UHFFFAOYSA-N 0.000 description 1
- SFLCYSCQVKQKMN-UHFFFAOYSA-N [4-[bis(2-hydroxypropyl)amino]phenyl]-phenylmethanone Chemical compound C1=CC(N(CC(C)O)CC(O)C)=CC=C1C(=O)C1=CC=CC=C1 SFLCYSCQVKQKMN-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 150000008365 aromatic ketones Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical compound C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 1
- 229920006378 biaxially oriented polypropylene Polymers 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 229930006711 bornane-2,3-dione Natural products 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000004917 polyol method Methods 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—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
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The present invention relates to the manufacturing methods of a kind of unsaturated polyol and photocurable polyurethane and they prepared therefrom.The unsaturated polyol includes the unit of unsaturated double-bond and coinitiator tertiary amine, photocurable polyurethane is obtained by the polyols preparation, contain tertiary amine group on its main chain, side chain has unsaturated double-bond group and photosensitive group unit, unsaturated double-bond group: the content ratio of photosensitive group is (4-10): (8-25), the polyurethane is not necessarily to additional photoinitiator under ultraviolet light, can spontaneous polymerization and crosslinking curing.Polyurethane structural design comparison of the invention is flexible, there are multiple crosslink sites for molecule, by adjusting the proportion of unsaturated polyol and the polyalcohol unsaturated double-bond group containing photosensitive group in polymerized monomer, the polyurethane coating big with light-initiated efficiency and crosslinking curing degree height, peel strength can be obtained.
Description
Technical Field
The invention belongs to the technical field of photocuring, and particularly relates to unsaturated polyol and photocurable polyurethane prepared from the same.
Background
The ultraviolet light curing technology is a process technology which gives consideration to both environmental and economic benefits, has the characteristics of short curing time, simple and convenient equipment, excellent coating performance, environmental friendliness and the like compared with the traditional curing technology, and is widely applied to the fields of aerospace, electronics, medical health and the like. As a typical representative of the application of the technology, ultraviolet-curable coatings such as photocurable polyurethane have the characteristics of low energy consumption, high curing speed, excellent coating performance and the like, so that rapid development is achieved.
The formula of the ultraviolet curing coating is generally composed of an oligomer, a reactive diluent monomer, a photoinitiator and the like, and under the condition of illumination, the photoinitiator generates a reactive free radical to initiate the polymerization of the oligomer and the monomer, so that the aim of crosslinking and curing is fulfilled. However, lower molecular weight initiators and diluents remain in the polymer network after curing and are slowly migrated and diffused to the substrate surface over time into the surrounding environment. In addition, small molecular substances such as catalysts and auxiliary agents added in the curing process often have certain toxicity and irritation, and the use of these coatings in certain fields (such as the biomedical field) is limited due to safety considerations.
The appearance and the use of the macromolecular photoinitiator are expected to make up and solve the defects of the existing micromolecular photoinitiator, and when the macromolecular photoinitiator is used, the problems of residue, migration to the surface and volatilization can be reduced. This has been reported in a number of documents in recent years. For example, J.Wei et al have synthesized a series of benzophenone-based macrophotoinitiators (J.Polym.Sci., PartA: Polym.Chem.,2007(45), 576; Macromolecules,2007(40), 2344; Macromolecules,2009(42),5486) and used to initiate polymerization of acrylate monomers. Patent document 1 discloses a method for producing a polyurethane-based polymeric photoinitiator, which reduces or even eliminates migration and leaching of the photoinitiator and its by-products during use. Patent document 2 prepares a photosensitive polyurethane by reacting an isocyanate group and a hydroxyl group-substituted photosensitive small molecule compound. Patent document 3 discloses a photosensitive polyurethane containing sulfur and benzophenone in the side chain and co-initiator amine in the main chain, which can be used as a macro-molecular photoinitiator alone without adding a micro-molecular co-initiator.
Because the polyurethane has better elasticity and adhesiveness and strong coating recoating performance, researchers often use the polyurethane as a precoating material of the coating of the medical instrument and prepares various polyurethanes capable of being photocured by combining a photocuring technology with the characteristics of short curing time, simple and convenient equipment, environmental friendliness and the like. Most of the light-curable polyurethane structures described in the prior art only contain photosensitive groups or unsaturated double bond groups, the photosensitive groups or the unsaturated double bond groups cannot be organically combined, and active crosslinking monomers or micromolecular auxiliaries and the like still need to be added in the subsequent curing process. Patent document 4 discloses that a spontaneously curable polyurethane is prepared by introducing benzophenone into a side chain of polyurethane and capping with a hydroxy acrylate, but the photoinitiation efficiency and the crosslinking curing degree of the polyurethane structure are still limited because of a small number of double bond molecules contained per unit mass.
Patent document 1 WO2012/062333A
Patent document 2: US6031044A
Patent document 3: CN1884333A
Patent document 4: CN106366277A
Disclosure of Invention
Problems to be solved by the invention
In order to solve the above problems of the prior art, the present invention has devised a novel unsaturated polyol, and provides photocurable polyurethanes prepared therefrom and a method for producing the same. The main chain of the light-curable polyurethane contains tertiary amine groups, the side chain of the light-curable polyurethane contains unsaturated double bond groups and photosensitive group units, and the content ratio of the unsaturated double bond groups to the photosensitive groups is (4-10): (8-25) by1H NMR measurement; the light-curable polyurethane can be spontaneously polymerized and crosslinked for curing under the irradiation of ultraviolet light. The polyurethane of the invention has flexible structural design, a plurality of crosslinking sites exist in molecules, and the polyurethane coating with high photoinitiation efficiency, crosslinking curing degree and peeling strength can be obtained by adjusting the proportion of unsaturated polyol and photosensitive group-containing polyol in a polymerization monomer.
Means for solving the problems
The present invention provides, first, an unsaturated polyol having the following structural formula:
wherein:
x is- (CH)2)p-or-CH (CH)3)CH2-，p＝1～3；
Y is O or NH;
z is H or CH3；
A is- (CH)2)q-or-CH (CH)3)CH2-，q＝1～3。
The unsaturated polyol as set forth above wherein: y is O.
The unsaturated polyol as set forth above wherein: p is 2, and Z is H; further, wherein q is 2.
Further, the present invention provides a method for preparing the unsaturated polyol according to the above, comprising the steps of: reacting hydroxyalkyl (meth) acrylate or hydroxyalkyl (meth) acrylamide with halogen acetyl halide to synthesize an intermediate product containing halogen and unsaturated bonds; and then reacting the intermediate product with an amino compound to obtain the polyol.
The method for producing an unsaturated polyol as described above, wherein the hydroxyalkyl (meth) acrylate is any one selected from hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate; the hydroxyalkyl (meth) acrylamide is selected from any one of N-hydroxymethyl acrylamide, N-hydroxyethyl acrylamide and N-hydroxypropyl acrylamide; the amino compound is selected from any one of diethanolamine and diisopropanolamine; the halogen acetyl halide is selected from any one of bromoacetyl bromide and chloroacetyl chloride.
Further, the present invention provides a photocurable polyurethane obtained by reacting components including a polyol and an isocyanate, characterized in that: the polyol includes the unsaturated polyol described above in the present invention or the polyol prepared by the method for preparing the unsaturated polyol described above.
A photocurable polyurethane as described above wherein said polyol further comprises a photosensitive group-containing polyol.
The photocurable polyurethane as described above, wherein the photocurable polyurethane contains tertiary amine groups in the main chain and unsaturated side chains in the side chainDouble bond group and photosensitive group unit, the content ratio of unsaturated double bond group to photosensitive group is (4-10): (8-25) by1H NMR measurement.
Further, the photocurable polyurethane has the following structural formula:
wherein,
x is- (CH)2)p-or-CH (CH)3)CH2-，p＝1～3；
Y is O or NH;
z is H or CH3；
A is- (CH)2)q-or-CH (CH)3)CH2-，q＝1～3；
R is a polymeric polyol;
R1is the residue of a diisocyanate;
R2is- (CH)2)k-，k＝1-4；
m, n, e and f are the number of repeating units and are integers not equal to 0; preferably, m and n are integers from 1 to 200, and e and f are integers from 1 to 100.
In addition, the invention also provides a preparation method of the light-curable polyurethane, which comprises the following steps:
(1) under the protection of inert gas, dissolving polyalcohol and isocyanate in an organic solvent to react to obtain a polyurethane prepolymer-1;
(2) dissolving the unsaturated polyol, the polyol containing a benzophenone group and the catalyst in a solvent, adding the mixture into a polyurethane prepolymer-1, and heating to react to obtain a polyurethane prepolymer-2 with a side chain containing a photosensitive group and an unsaturated double bond group;
(3) and adding the micromolecular dihydric alcohol into the polyurethane prepolymer-2 to carry out chain extension and end capping to obtain the light-curable polyurethane.
The preparation method of the photocurable polyurethane comprises the steps of (1) preparing a polyol, wherein the polyol is one or a mixture of polyether diol, polyester diol, polyacetal diol and polythioether diol; the isocyanate is diisocyanate or polyisocyanate, preferably one or two of aliphatic diisocyanate or aromatic diisocyanate; the molar ratio of the unsaturated polyol to the benzophenone group-containing polyol is 2:1 to 1: 5.
ADVANTAGEOUS EFFECTS OF INVENTION
The invention designs and synthesizes novel unsaturated polyol and ultraviolet light-curable polyurethane, and simultaneously introduces unsaturated double bonds, photosensitive groups and co-initiation groups into a polyurethane chain segment, thereby avoiding the use of micromolecular photoinitiator and auxiliary agents with pungent odor and solving the problems of migration and leaching caused by the use of micromolecular substances. According to the invention, the content of double bonds and photosensitive groups in the polyurethane can be controlled by adjusting the ratio of unsaturated polyol and benzophenone group-containing polyol, so that the polyurethane with different structures, performances and molecular weights can be synthesized, and the controllability of the whole structure is enhanced. In addition, the unsaturated polyol structure contains a coinitiator tertiary amine structure, and the introduction of the tertiary amine group enhances the energy transfer in the polyurethane chain segment molecule, enhances the initiation efficiency of the photosensitive group, and improves the curing rate and the bonding strength of the polyurethane.
Drawings
FIG. 1: 2- (N, N-dihydroxyethyl) -2-acetoxyEthyl acrylate nuclear magnetic hydrogen spectrum (1H NMR) spectrum.
FIG. 2: example 1 ultraviolet-curable polyurethane Nuclear magnetic Hydrogen Spectrum prepared (1H NMR) spectrum.
Detailed Description
The technical solution of the present invention will be described in detail with reference to the following examples.
The term "unit" in the present invention means not only a functional group (e.g., photosensitive group) but also an additional chemical group having a small influence on the functional group, such as an alkyl group, an alkylene group, etc.
In the present invention, the term "(meth) acrylamide" is understood to encompass both acryloyl and methacryloyl compounds or derivatives and mixtures thereof, as well as the term "(meth) acrylate".
The photocuring process in the present invention takes place by methods known per se, via irradiation with light or UV radiation in the wavelength range from 100 to 600 nm. Illumination sources that may be used are sunlight or artificial lamps or lasers. For example, high, medium or low pressure mercury lamps and xenon and tungsten lamps are advantageous. Also excimer, solid state and diode based lasers are advantageous. Diode-based light sources are generally advantageous for initiating chemical reactions.
< unsaturated polyol >
The unsaturated polyol of the present invention has the following structural formula:
wherein:
x is- (CH)2)p-or-CH (CH)3)CH2-，p＝1～3；
Y is O or NH;
z is H or CH3；
A is- (CH)2)q-or-CH (CH)3)CH2-，q＝1～3。
Compared with the conventional dihydric alcohol (such as MDEA) containing amino, the unsaturated polyhydric alcohol designed by the invention can introduce a longer side chain containing unsaturated double bonds into the polyurethane, greatly increases the content of C-C double bonds of the polyurethane, improves the ultraviolet curing crosslinking density, and in addition, polar groups in the unsaturated polyhydric alcohol, such as ester groups and amide groups, can improve the coating force of the polyurethane on polar materials and the coating hydrophilicity.
In the unsaturated polyol of the present invention, preferably Y is O; more preferably, p ═ 2, q ═ 2, and Z is H, i.e., the unsaturated polyols described in the present invention are preferably of the formula:
the polyurethane obtained from the unsaturated polyol of this structure has better curing crosslinking performance and can greatly enhance the initiation efficiency of the photosensitive group.
Further, the present invention provides a method for preparing the unsaturated polyol according to the above, comprising the steps of: 1) reacting hydroxyalkyl (meth) acrylate or hydroxyalkyl (meth) acrylamide with halogen acetyl halide to synthesize an intermediate product containing halogen and unsaturated bonds; 2) and then reacting the intermediate product with an amino compound to obtain the unsaturated polyol.
Preferably, the step 1) is to dissolve the hydroxyalkyl (meth) acrylate or hydroxyalkyl (meth) acrylamide in a solvent, dropwise add halogen acetyl halide at low temperature, and react under the action of a catalyst to obtain an intermediate product. The hydroxyalkyl (meth) acrylate is selected from one or more of hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate; the hydroxyalkyl (meth) acrylamide is selected from one or more of N-methylolacrylamide, N-hydroxyethyl acrylamide and N-hydroxypropyl acrylamide; the halogen acetyl halide is selected from any one of bromoacetyl bromide and chloroacetyl chloride; the molar ratio of the haloacetyl halide to the hydroxyalkyl (meth) acrylate or hydroxyalkyl (meth) acrylamide is 1.5:1 to 1.1:1, more preferably 1.1: 1. The solvent is selected from the group consisting of ethyl acetate, dichloromethane, chloroform and tetrahydrofuran, more preferably the solvent is dichloromethane. The catalyst is a basic catalyst, such as inorganic bases such as sodium hydroxide, potassium hydroxide and sodium carbonate, and organic bases such as triethylamine and pyridine.
The reaction temperature of the step 1) is 20-40 ℃, the reaction can be directly carried out at room temperature, and the preferable temperature is 25-30 ℃; the reaction time is 10 to 20 hours, and more preferably 15 to 18 hours.
Step 2) preferably, mixing and dissolving the intermediate product obtained in the step 1) and the amino compound in a molar ratio of 1: 1-1:2 (more preferably, the molar ratio of the intermediate product to the amino compound is 1: 1.2-1: 1.5) in a solvent, and heating and reacting under a catalyst to obtain the unsaturated polyol. More preferably, the amino compound is selected from any one or more of diethanolamine and diisopropanolamine; the solvent used in the step is dioxane, and the catalyst is triethylamine; the reaction temperature is 40-80 ℃, preferably 50-70 ℃, and the reaction time is 3-8 hours, preferably 5-6 hours.
Without limitation, in one embodiment of the present invention, the unsaturated polyol is prepared by the following method: reacting hydroxyethyl acrylate with bromoacetyl bromide to synthesize 2- (2-bromoacetoxyl) ethyl acrylate; then reacting with diethanol amine to obtain 2- (N, N-dihydroxyethyl) -2-acetoxyl ethyl acrylate.
Specifically, the preparation method of the 2- (N, N-dihydroxyethyl) -2-acetoxyl ethyl acrylate comprises the following steps:
(1) synthesis of 2- (2-bromoacetoxy) ethyl acrylate:
dissolving hydroxyethyl acrylate in a solvent, dropwise adding bromoacetyl bromide into the solution at a low temperature, reacting for 0.2-1 h under the action of a catalyst, heating to 25-30 ℃, continuing to react for 15-18 h, and purifying and drying to obtain 2- (2-bromoacetoxyl) ethyl acrylate; the molar ratio of bromoacetyl bromide to hydroxyethyl acrylate is 1.1: 1;
(2) synthesis of 2- (N, N-dihydroxyethyl) -2-acetoxyethyl acrylate:
and (3) dissolving the product obtained in the first step and diethanol amine in dioxane, reacting for 5-6 h at 50-70 ℃ under the action of triethylamine, and separating, purifying and drying to obtain the product. The molar ratio of the 2- (2-bromoacetoxyl) ethyl acrylate to the diethanolamine is preferably 1:1.2 to 1: 1.5.
< light-curable polyurethane >
Polyurethanes are typically prepared by the reaction of a polyol with an isocyanate. The unsaturated polyol of the present invention described above can be used to prepare the photocurable polyurethane of the present invention.
In order to make the polyurethane itself photosensitive, it is preferred that the polyol from which the polyurethane is made further comprises a polyol containing a photosensitive group derived from benzophenone, phenylaminoalkyl ketone, thioxanthone, benzil ketal, phenylhydroxyalkyl ketone, α -dialkoxy-acetophenone, α -hydroxy-alkyl-benzophenone, α -amino-alkyl-benzophenone, acyl-phosphine oxide, phenylcoumarin ketone, silane, camphorquinone, maleimide and derivatives thereof, and further preferably the polyol containing a photosensitive group is a polyol containing a benzophenone group, such as 4- {3- [ bis (2-hydroxyethyl) amino ] propoxy } benzophenone, 4- { [ bis (2-hydroxyethyl) amino ] methyl } benzophenone, 4- { [ bis (2-hydroxyethyl) amino ] ethyl } benzophenone, 4- [ bis (2-hydroxyethyl) amino ] benzophenone, 4- [ bis (2-hydroxypropyl) amino ] benzophenone and the like, more preferably 4- {3- [ bis (2-hydroxyethyl) amino ] propoxy } benzophenone, see preparation example WO 0621/333A.
Other conventional polyols may also be added to the present invention. For example, the polyurethane prepolymer-1 can be synthesized by using a polymeric polyol. The molecular weight of the polymeric polyol is not particularly limited, and the number average molecular weight is preferably not more than 5000, preferably not more than 2000, more preferably not more than 1000. Examples of the polyhydric polyol include polyester polyol, polyether polyol, polyacetal diol, polythioether diol, polybutadiene polyol, silicon polyol, and polyacrylate polyol, and combinations thereof, and preferably one or a mixture of several of polyether diol, polyester diol, polyacetal diol, and polythioether diol. Suitable polyether polyols include polyethylene glycol, polypropylene glycol and polytetramethylene glycol or block copolymers thereof. Suitable polyester polyols are preferably the hydroxylation reaction products of dihydric alcohols with polycarboxylic acids, preferably dicarboxylic acids, or their corresponding anhydrides, and also the products obtained by ring-opening polymerization of lactones. The polycarboxylic acids which can be used to form these polyester polyols can be aliphatic, cycloaliphatic, aromatic and/or heterocyclic and they can be substituted, saturated or unsaturated. Examples of dicarboxylic acids are succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, isophthalic acid, terephthalic acid, phthalic acid, and the like; dihydric alcohols include ethylene glycol, propylene glycol, 1, 3-propanediol, 1, 3-butanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, neopentyl glycol, 1, 4-cyclohexanedimethanol, bisphenol A and the like. The polyester polyol may also use polyhydric alcohols such as glycerin, trimethylolethane, trimethylolpropane and pentaerythritol. In addition, small-molecule polyols such as ethylene glycol, diethylene glycol, propylene glycol, 1, 4-butanediol or 1, 6-hexanediol, etc. can also be used as blocking agents for polyurethanes.
The use of aliphatic and aromatic diisocyanates and polyisocyanates in the present invention to prepare polyurethane prepolymer-1 and photocurable polyurethanes is preferred to be diisocyanates, but it is within the scope of the present invention to include small amounts, i.e., no more than about 20 mole percent, of trifunctional isocyanates or higher functionality, preferred isocyanates include, but are not limited to, aliphatic linear isocyanates, e.g., α, omega alkylene diisocyanates, preferably tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, etc., having 5 to 20 carbon atoms, cycloaliphatic diisocyanates, e.g., isophorone diisocyanate, cyclohexane diisocyanate, preferably 1, 4-cyclohexane diisocyanate, fully hydrogenated aromatic diisocyanates, e.g., hydrogenated tetramethylxylylene diisocyanate, hydrogenated toluene diisocyanate, hydrogenated methylenediphenylene diisocyanate, aromatic diisocyanates, e.g., toluene diisocyanate, particularly the 2, 4-isomer thereof, methylenediphenylene diisocyanate, tetramethylxylene diisocyanate, etc., the aromatic diisocyanates may also include polymethylene polyphenylene polyisocyanates having a functionality greater than 2.
Without limitation, in one embodiment of the present invention, the main chain of the photocurable polyurethane of the present invention contains tertiary amine groups, the side chain has unsaturated double bond groups and photosensitive group units, and the introduction of unsaturated double bonds and photosensitive group units into the side chain can realize effective control of crosslinking curing and photoinitiation efficiency. Preferably, the content ratio of the unsaturated double bond group to the photosensitive group is (4-10): (8-25) by1H NMR determination, and calculating the respective mol percent (mol%) of the unsaturated double bond group and the photosensitive group by utilizing a nuclear magnetic spectrum to obtain the content ratio. To obtain optimum crosslinking performance and peel strengthFurther preferably, the content ratio of the unsaturated double bond group to the photosensitive group is (5-7): (10-23), further in an embodiment of the present invention, the photocurable polyurethane preferably has a double bond molar percentage of 5-6.5% and a photosensitive group molar percentage of 10-23%.
Further, the photocurable polyurethane of the present invention is preferably of the formula:
wherein X, Y, Z, A is as defined above for the unsaturated polyol of the present invention;
r is a polymeric polyol;
R1is the residue of a diisocyanate;
R2is- (CH)2)k-，k＝1-4；
m, n, e and f are the number of repeating units and are integers not equal to 0; preferably, m and n are integers from 1 to 200, and e and f are integers from 1 to 100.
The main chain of the polyurethane with the structure is provided with a plurality of tertiary amine groups, and the tertiary amine auxiliary agent with low molecular weight can be partially or completely replaced; the polyurethane has a photosensitive group on its side chain, and the aromatic ketone moiety can abstract the tertiary amine proton from the carbon atom adjacent to the amino nitrogen, and can generate a reactive group for initiating polymerization or crosslinking; in addition, the unsaturated double bonds in the side chains can lead to a good spontaneous crosslinking function of the polyurethane.
Preferably, the photocurable polyurethane of the present invention is prepared by the following method:
(1) under the protection of inert gas, dissolving polyalcohol and isocyanate in an organic solvent to react to obtain a polyurethane prepolymer-1;
(2) dissolving the unsaturated polyol, the polyol containing the photosensitive group and the catalyst in a solvent, adding the solution into a polyurethane prepolymer-1, and heating to react to obtain a polyurethane prepolymer-2 with a side chain containing the photosensitive group and an unsaturated double bond group;
(3) and adding the micromolecular dihydric alcohol into the polyurethane prepolymer-2 to carry out chain extension and end capping to obtain the light-curable polyurethane.
Further preferably, the reaction in step (1) is always carried out under the protection of nitrogen, and the polymeric polyol is preferably one or a mixture of several of polyether diol, polyester diol, polyacetal diol and polythioether diol; the organic solvent is one or two of acetone, butanone, 1, 4-dioxane, cyclohexanone, 4-methyl-2-pentanone, N, N-dimethylformamide and N-methylpyrrolidone, and the reaction in the step (1) is preferably carried out at 60-90 ℃ for 1-4 hours. In the step (2), dibutyltin dilaurate is used as a catalyst, the polyol containing a photosensitive group is preferably a polyol containing a benzophenone group, the molar ratio of the unsaturated polyol to the polyol containing the benzophenone group is 2:1-1:5, and is further preferably 2:1-1:2, and a polyurethane coating film with good crosslinking degree and peeling strength can be obtained by adopting the proportion range; the reaction in the step (2) is carried out for 2 to 5 hours at the temperature of between 70 and 90 ℃. The reaction of step (3) is preferably carried out at 50 to 70 ℃ for 1 to 3 hours; the small molecular diol in the step (3) is preferably ethylene glycol or 1, 4-butanediol.
The photocurable polyurethane of the present invention can be cured by exposure to UV radiation using a radiation source having a wavelength of at least 300nm, preferably 320-500 nm. Curing may be carried out in solution. The photocurable polyurethane according to the invention can be dissolved in a suitable solvent and sprayed, for example, onto a tube and subsequently exposed to UV radiation. The solvent may then be evaporated or remain in the coating and act as a swelling medium providing the desired gel.
The photocurable polyurethanes of the present invention are preferably used for the preparation of coatings, adhesives, sealants and the like. The photocurable polyurethane of the present invention may also be used in combination with additives commonly used in the art, depending on the particular application, including but not limited to: dispersing agents, flow aids, thickeners, defoamers, deaerators, pigments, fillers, matting agents and wetting agents. Preferably, the photocurable polyurethane of the present invention can be directly used as a photocurable coating. The photocurable polyurethanes of the present invention can be applied to a variety of substrates by any method known to those skilled in the art, including but not limited to spraying, roll coating, knife coating, casting, brushing, dipping, putty knife coating, or doctor blade coating, and the time for which the coated substrate is irradiated depends on the spectral overlap of the lamp emission spectrum and the absorption spectrum of the photoinitiator, the distance from the radiation source, and the lamp intensity, solvent content of the formulation, temperature and humidity of the curing environment, but is typically as little as 10 minutes and as little as 0.1 second.
The invention is further illustrated, but not limited, by the following examples.
Examples
The present invention is described below by way of examples, which are not exhaustive, as those skilled in the art will appreciate that the examples are illustrative only. The preparation examples are compound synthesis examples, and the related chemical raw materials and reagents are all sold in the market or synthesized according to the published documents.
The content of double bonds and the content of photosensitive groups are determined by1H NMR spectroscopy.
The degree (%) of crosslinking of the coating was determined by soxhlet extraction: weighing a certain mass of cured coating sample, cutting the coating sample, extracting the cut coating sample for 12 hours at 120 ℃ by using a Soxhlet extractor, performing vacuum drying after extraction, weighing, and calculating the crosslinking degree of the coating.
The peel strength (N/mm) of the polyurethane coating was tested according to GB/T8808-1988.
Preparation example 1: synthesis of unsaturated polyols
Dissolving hydroxyethyl acrylate (11.5mL, 0.1mol) in dichloromethane, dropwise adding bromoacetyl bromide (9.6mL, 0.11mol) into the solution at low temperature, wherein the molar ratio of the bromoacetyl bromide to the hydroxyethyl acrylate is 1.1:1, reacting for 0.5h under the action of sodium hydroxide (4g, 0.1mol), heating to 30 ℃, continuing to react for 16h, and obtaining 2- (2-bromoacetoxy) ethyl acrylate (16.5g, the yield is 70%) after purification and drying; then, 2- (2-bromoacetoxy) ethyl acrylate (11.8g, 0.05mol) and diethanolamine (6.3g, 0.06mol) were dissolved in dioxane, reacted at 60 ℃ for 5h under the catalysis of triethylamine (6.1g, 0.06mol), separated, purified, and dried to obtain 2- (N, N-dihydroxyethyl) -2-acetoxy ethyl acrylate (10.2g, yield 78%). The nuclear magnetic spectrum of the product is shown in figure 1,1H NMR(δ/ppm):2.51(m,4H,CH2),3.35(s,2H,CH2),3.52(m,4H,CH2),4.28(m,2H,CH2),4.38(m,2H,CH2),5.83(m，H,CH＝CH2),6.12(m,H,CH＝CH2),6.45(m,H,CH＝CH2). The attribution and integral area of each characteristic peak are consistent with the structure of a target product.
Example 1: synthesis of light-curable polyurethane
(1) Under the protection of nitrogen, 3.5g of toluene diisocyanate was added into a round-bottomed flask equipped with a thermometer, a condenser and a stirrer, the flask was put in an oil bath at 75 ℃, 10g of polypropylene glycol was dropped into a four-necked reaction flask by using a constant-pressure funnel, and the mixture was allowed to react for 2.5 hours while maintaining the temperature, and the viscosity of the reaction solution was adjusted with acetone to obtain polyurethane prepolymer-1.
(2) 2.6g of the unsaturated polyol obtained in preparation example 1 and 1.7g of 4- {3- [ bis (2-hydroxyethyl) amino ] propoxy } benzophenone (molar ratio of these two is 2/1) were dissolved in DMF, and added to prepolymer-1, and 0.1g of dibutyltin dilaurate as a catalyst was added thereto, and the mixture was reacted at 65 ℃ for 3 hours to obtain polyurethane prepolymer-2 having a side chain containing a photosensitive group and an unsaturated double bond group.
(3) And cooling to 50 ℃, adding 1.6g of 1, 4-butanediol into the prepolymer-2 by using a dropping funnel, reacting for 2 hours at 60 ℃, and carrying out chain extension and end capping to obtain the light-curable polyurethane. The nuclear magnetic spectrum of the resulting photocurable polyurethane is shown in FIG. 2. As can be seen from FIG. 2, the characteristic peak corresponding to the main chain structure of polyurethane at 1.2-4.6ppm, the characteristic peak at the position of 7.43-7.85ppm proves that benzene rings exist in the polyurethane, the peak at the position of 5.72-5.79ppm proves that double bonds exist in the polyurethane, and the molar percentage of unsaturated double bonds is 8.4% and the molar percentage of benzophenone groups is 10.0% through measurement.
Example 2:
(1) under the protection of nitrogen, 3.5g of toluene diisocyanate was added into a round-bottomed flask equipped with a thermometer, a condenser and a stirrer, the flask was put in an oil bath at 80 ℃, 10g of polypropylene glycol was dropped into a four-necked reaction flask by using a constant-pressure funnel, and the mixture was allowed to react for 2.5 hours while maintaining the temperature, and the viscosity of the reaction solution was adjusted with acetone to obtain polyurethane prepolymer-1.
(2) 1.95g of the unsaturated polyol obtained in preparation example 1 and 1.7g of 4- {3- [ bis (2-hydroxyethyl) amino ] propoxy } benzophenone (molar ratio of 1.5/1) were dissolved in DMF, and added to prepolymer-1, 0.15g of dibutyltin dilaurate as a catalyst was added thereto, and the mixture was reacted at 70 ℃ for 3 hours to obtain polyurethane prepolymer-2 having a photosensitive group and an unsaturated double bond group in a side chain.
(3) Cooling to 50 ℃, adding 2.0g of 1, 4-butanediol into the prepolymer-2 by using a dropping funnel, reacting for 2 hours at 65 ℃, chain extending and end capping to obtain the light-curable polyurethane, wherein the molar percentage of unsaturated double bonds is 6.5 percent and the molar percentage of benzophenone groups is 10.0 percent.
Example 3:
(1) under the protection of nitrogen, 3.5g of toluene diisocyanate was added into a round-bottomed flask equipped with a thermometer, a condenser and a stirrer, the flask was put in an oil bath at 70 ℃, 10g of polypropylene glycol was dropped into a four-necked reaction flask by using a constant-pressure funnel, and the mixture was allowed to react for 2.5 hours while maintaining the temperature, and the viscosity of the reaction solution was adjusted with acetone to obtain polyurethane prepolymer-1.
(2) 1.3g of the unsaturated polyol obtained in preparation example 1 and 1.7g of 4- {3- [ bis (2-hydroxyethyl) amino ] propoxy } benzophenone (molar ratio of these two is 1/1) were dissolved in DMF, and added to prepolymer-1, to which 0.1g of dibutyltin dilaurate as a catalyst was added, followed by reaction at 70 ℃ for 3 hours to obtain polyurethane prepolymer-2 having a side chain containing a photosensitive group and an unsaturated double bond group.
(3) Cooling to 50 ℃, adding 1.8g of 1, 4-butanediol into the prepolymer-2 by using a dropping funnel, reacting for 2 hours at 50 ℃, carrying out chain extension and end capping to obtain the light-curable polyurethane, wherein the molar percentage of unsaturated double bonds is 5.0 percent and the molar percentage of benzophenone groups is 10.0 percent.
Example 4:
(1) under the protection of nitrogen, 3.5g of toluene diisocyanate was added into a round-bottomed flask equipped with a thermometer, a condenser and a stirrer, the flask was put in an oil bath at 70 ℃, 10g of polypropylene glycol was dropped into a four-necked reaction flask by using a constant-pressure funnel, the reaction was maintained for 2 hours, and the viscosity of the reaction solution was adjusted with acetone to obtain polyurethane prepolymer-1.
(2) 1.3g of the unsaturated polyol obtained in preparation example 1 and 3.4g of 4- {3- [ bis (2-hydroxyethyl) amino ] propoxy } benzophenone (molar ratio of these two is 1/2) were dissolved in DMF, and added to prepolymer-1, to which 0.15g of dibutyltin dilaurate as a catalyst was added, followed by reaction at 80 ℃ for 3 hours to obtain polyurethane prepolymer-2 having a side chain containing a photosensitive group and an unsaturated double bond group.
(3) Cooling to 60 ℃, adding 1.5g of 1, 4-butanediol into the prepolymer-2 by using a dropping funnel, reacting for 2 hours at 60 ℃, carrying out chain extension and end capping to obtain the light-curable polyurethane, wherein the molar percentage of unsaturated double bonds is 5.0 percent and the molar percentage of benzophenone groups is 17.2 percent.
Example 5:
(1) under the protection of nitrogen, 3.5g of toluene diisocyanate was added into a round-bottomed flask equipped with a thermometer, a condenser and a stirrer, the flask was put in an oil bath at 85 ℃, 10g of polypropylene glycol was dropped into a four-necked reaction flask by using a constant-pressure funnel, the reaction was maintained for 2 hours, and the viscosity of the reaction solution was adjusted with acetone to obtain polyurethane prepolymer-1.
(2) The temperature was reduced to 60 ℃, 1.3g of the unsaturated polyol obtained in preparation example 1, 8.5g of 4- {3- [ bis (2-hydroxyethyl) amino ] propoxy } benzophenone (the molar ratio of the two was 1/5) was dissolved in acetone, and added to prepolymer-1, 0.18g of dibutyltin dilaurate (mass fraction was 0.5% of the total amount of the reaction solution) as a catalyst was added thereto, and the temperature was raised to 80 ℃ and reacted for 2.5 hours to obtain polyurethane prepolymer-2 having a side chain containing a photosensitive group and an unsaturated double bond group.
(3) Cooling to 60 ℃, adding 1.4g of 1, 4-butanediol into the prepolymer-2 by using a dropping funnel, reacting for 2 hours at 60 ℃, carrying out chain extension and end capping to obtain the light-curable polyurethane, wherein the molar percentage of unsaturated double bonds is 5.0 percent and the molar percentage of benzophenone groups is 22.3 percent.
Application example
The light-curable polyurethane prepared in the embodiment 1-5 is compounded with a BOPP film-aluminum foil, or the polyurethane is coated on a tinplate and is cured for 2-3 min by ultraviolet light, wherein the curing distance is 20cm, and the light intensity is 20-30 mw/cm2The peel strength and the degree of crosslinking of the cured film were measured.
TABLE 1 Photocurable polyurethane compositions and coating Properties thereof
It can be seen from the above examples that in the case where the content of the photosensitive group in the polyurethane composition is constant (examples 1 to 3), the density of the crosslinking points increases with the increase of the double bond content, and thus the degree of crosslinking of the polyurethane coating layer increases. In the case of a certain double bond content in the polyurethane composition (examples 3 to 5), the degree of crosslinking of the polyurethane coating increases to a certain extent with increasing content of photosensitive groups, since free-radical coupling crosslinking can likewise take place between the photosensitive groups in the polyurethane structure of the invention. Furthermore, as the double bond and photosensitive group content increases, the peel strength of the coating decreases, which may be related to polyurethane shrinkage during curing. Therefore, the relative amounts of the unsaturated polyol and the polyol containing a photosensitive group in the invention need to be reasonably regulated and controlled so that the contents of the photosensitive group and the double bond in the prepared photocurable polyurethane structure are equivalent, and then the polyurethane coating with optimal crosslinking performance and peel strength can be obtained.
However, the above description is only a preferred embodiment of the present invention, and it is natural that those skilled in the art can change the present invention based on the actual requirement after understanding the technical means of the present invention. Therefore, all equivalent changes and modifications made in accordance with the claims of the present invention should still fall within the scope of the present invention.
Claims (10)
1. An unsaturated polyol characterized in that:
has the following structural formula:
wherein:
x is- (CH)2)p-or-CH (CH)3)CH2-，p＝1～3；
Y is O or NH;
z is H or CH3；
A is- (CH)2)q-or-CH (CH)3)CH2-，q＝1～3。
2. The unsaturated polyol of claim 1, wherein: y is O.
3. The unsaturated polyol of claim 1 or 2, wherein: p is 2, q is 2 and Z is H.
4. The method for producing an unsaturated polyol according to any one of claims 1 to 3, wherein a hydroxyalkyl (meth) acrylate or hydroxyalkyl (meth) acrylamide and a halogen acetyl halide are reacted to synthesize an intermediate product containing a halogen and an unsaturated bond; and then reacting the intermediate product with an amino compound to obtain the unsaturated polyol.
5. The method for producing an unsaturated polyol according to claim 4, wherein said hydroxyalkyl (meth) acrylate is any one selected from the group consisting of hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate; the hydroxyalkyl (meth) acrylamide is selected from any one of N-hydroxymethyl acrylamide, N-hydroxyethyl acrylamide and N-hydroxypropyl acrylamide; the amino compound is selected from any one of diethanolamine and diisopropanolamine; the halogen acetyl halide is selected from any one of bromoacetyl bromide and chloroacetyl chloride.
6. A photocurable polyurethane obtained by the reaction of components comprising a polyol and an isocyanate, characterized in that: the polyol includes the unsaturated polyol described in any one of claims 1 to 3 or the unsaturated polyol produced by the production method described in any one of claims 4 or 5.
7. A photocurable polyurethane as recited in claim 6, wherein: the polyols also include polyols containing photosensitive groups.
8. A photocurable polyurethane as claimed in claim 6 or 7, characterized in that: the main chain of the light-curable polyurethane contains tertiary amine groups, the side chain of the light-curable polyurethane contains unsaturated double-bond groups and photosensitive group units, and the content ratio of the unsaturated double-bond groups to the photosensitive groups is (4-10): (8-25) by1H NMR measurement.
9. A photocurable polyurethane according to any one of claims 6-8 characterised in that the photocurable polyurethane has the following structural formula:
wherein X, Y, Z, A is as defined in claim 1;
r is a polymeric polyol;
R1is the residue of a diisocyanate;
R2is- (CH)2)k-，k＝1-4；
m, n, e and f are the number of repeating units and are integers not equal to 0.
10. The process for producing photocurable polyurethane according to any one of claims 6-9, characterized in that:
(1) under the protection of inert gas, dissolving polyalcohol and isocyanate in an organic solvent to react to obtain a polyurethane prepolymer-1;
(2) dissolving unsaturated polyol, polyol containing benzophenone groups and a catalyst in a solvent, adding the solution into a polyurethane prepolymer-1, and heating the solution to react to obtain a polyurethane prepolymer-2 with a side chain containing photosensitive groups and unsaturated double bond groups; the unsaturated polyol is the polyol according to any one of claims 1 to 3 or the polyol produced by the production method according to any one of claims 4 or 5;
(3) and adding the micromolecular dihydric alcohol into the polyurethane prepolymer-2 to carry out chain extension and end capping to obtain the light-curable polyurethane.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711416167 | 2017-12-25 | ||
| CN2017114161676 | 2017-12-25 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109957083A true CN109957083A (en) | 2019-07-02 |
| CN109957083B CN109957083B (en) | 2021-06-29 |
Family
ID=67023111
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810507846.2A Active CN109957083B (en) | 2017-12-25 | 2018-05-24 | Unsaturated polyol, photocurable polyurethane prepared from unsaturated polyol and preparation methods of unsaturated polyol and photocurable polyurethane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109957083B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110819224A (en) * | 2018-08-09 | 2020-02-21 | 江苏百赛飞生物科技有限公司 | Coating composition, protective coating based on coating composition and coated product |
| CN113278125A (en) * | 2021-05-28 | 2021-08-20 | 南京玖泰新材料科技有限公司 | Photo-curing polyurethane and application thereof |
| CN113861350A (en) * | 2021-10-14 | 2021-12-31 | 王俊生 | Preparation method of polymerizable resin, ink and coating |
| CN115490811A (en) * | 2022-10-11 | 2022-12-20 | 上海东升新材料有限公司 | Low-foaming high-water-resistance aqueous adhesive for lawn back adhesive and preparation method thereof |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1248586A (en) * | 1999-08-06 | 2000-03-29 | 中国科学技术大学 | Radiation-curable amino superbranching polyester and preparation process thereof |
| CN1350021A (en) * | 2000-10-20 | 2002-05-22 | 中国科学技术大学 | Semi-crystalline dendritic polyether amide oligomer capable of being radiation cured and its prepn |
| US6559261B1 (en) * | 1998-07-25 | 2003-05-06 | Qinetiq Limited | Polymer production |
| JP2006290790A (en) * | 2005-04-11 | 2006-10-26 | Nippon Shokubai Co Ltd | Method for producing curable compound and curable compound obtained therefrom |
| US20080183000A1 (en) * | 2007-01-30 | 2008-07-31 | Thames Shelby F | Glycerol ester-free functionalized vegetable oil derivatives and their latex compositions |
| CN101255229A (en) * | 2008-03-27 | 2008-09-03 | 广州市博兴化工科技有限公司 | Self-sensitive polymeric hyper branched polyestermethylmethacrylate oligomer and preparation thereof |
| CN102838713A (en) * | 2012-09-28 | 2012-12-26 | 广东多正化工科技有限公司 | Water-based polyurethane composite emulsion and preparation method thereof |
| CN103201295A (en) * | 2010-11-12 | 2013-07-10 | 科洛普拉斯特公司 | Novel polymeric photoinitiators |
| US20140316060A1 (en) * | 2011-08-24 | 2014-10-23 | Lambson Limited | Polymers Comprising Photoinitiator Moieties and Dye Moieties |
| CN104151483A (en) * | 2014-06-04 | 2014-11-19 | 常州大学 | Preparation method of hydroxyl-terminated hyperbranched polyacrylate |
| CN104231228A (en) * | 2014-08-14 | 2014-12-24 | 广东工业大学 | Waterborne fluorine-containing polyurethane resin capable of being cured by UV (Ultraviolet) and preparation method of waterborne fluorine-containing polyurethane resin |
| CN104987435A (en) * | 2015-06-23 | 2015-10-21 | 天津久日化学股份有限公司 | Benzophenone macromolecular photoinitiator and preparation method thereof |
| CN106220522A (en) * | 2016-08-09 | 2016-12-14 | 陕西科技大学 | A kind of Mannich base quarternary ammonium salt compound and preparation method thereof |
| CN106366277A (en) * | 2016-08-29 | 2017-02-01 | 中山大学 | Preparing method of ultraviolet light cross-linking and solidifying waterborne polyurethane and application |
-
2018
- 2018-05-24 CN CN201810507846.2A patent/CN109957083B/en active Active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6559261B1 (en) * | 1998-07-25 | 2003-05-06 | Qinetiq Limited | Polymer production |
| CN1248586A (en) * | 1999-08-06 | 2000-03-29 | 中国科学技术大学 | Radiation-curable amino superbranching polyester and preparation process thereof |
| CN1350021A (en) * | 2000-10-20 | 2002-05-22 | 中国科学技术大学 | Semi-crystalline dendritic polyether amide oligomer capable of being radiation cured and its prepn |
| JP2006290790A (en) * | 2005-04-11 | 2006-10-26 | Nippon Shokubai Co Ltd | Method for producing curable compound and curable compound obtained therefrom |
| US20080183000A1 (en) * | 2007-01-30 | 2008-07-31 | Thames Shelby F | Glycerol ester-free functionalized vegetable oil derivatives and their latex compositions |
| CN101255229A (en) * | 2008-03-27 | 2008-09-03 | 广州市博兴化工科技有限公司 | Self-sensitive polymeric hyper branched polyestermethylmethacrylate oligomer and preparation thereof |
| CN103201295A (en) * | 2010-11-12 | 2013-07-10 | 科洛普拉斯特公司 | Novel polymeric photoinitiators |
| US20140316060A1 (en) * | 2011-08-24 | 2014-10-23 | Lambson Limited | Polymers Comprising Photoinitiator Moieties and Dye Moieties |
| CN102838713A (en) * | 2012-09-28 | 2012-12-26 | 广东多正化工科技有限公司 | Water-based polyurethane composite emulsion and preparation method thereof |
| CN104151483A (en) * | 2014-06-04 | 2014-11-19 | 常州大学 | Preparation method of hydroxyl-terminated hyperbranched polyacrylate |
| CN104231228A (en) * | 2014-08-14 | 2014-12-24 | 广东工业大学 | Waterborne fluorine-containing polyurethane resin capable of being cured by UV (Ultraviolet) and preparation method of waterborne fluorine-containing polyurethane resin |
| CN104987435A (en) * | 2015-06-23 | 2015-10-21 | 天津久日化学股份有限公司 | Benzophenone macromolecular photoinitiator and preparation method thereof |
| CN106220522A (en) * | 2016-08-09 | 2016-12-14 | 陕西科技大学 | A kind of Mannich base quarternary ammonium salt compound and preparation method thereof |
| CN106366277A (en) * | 2016-08-29 | 2017-02-01 | 中山大学 | Preparing method of ultraviolet light cross-linking and solidifying waterborne polyurethane and application |
Non-Patent Citations (4)
| Title |
|---|
| FENFEN BAO等: "Synthesis and properties of hyperbranched polyurethane acrylate used for UV curing coatings", 《PROGRESS IN ORGANIC COATINGS》 * |
| SHUILAI QIU等: "Preparation of UV-curable functionalized phosphazene-containing nanotube/polyurethane acrylate nanocomposite coatings with enhanced thermal and mechanical properties", 《RSC ADVANCES》 * |
| 王可答等: "超支化聚合物的合成及光固化涂层性能", 《涂料工业》 * |
| 陈炜等: "超支化聚合物的合成及光固化涂层性能", 《应用化学》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110819224A (en) * | 2018-08-09 | 2020-02-21 | 江苏百赛飞生物科技有限公司 | Coating composition, protective coating based on coating composition and coated product |
| CN110819224B (en) * | 2018-08-09 | 2021-06-25 | 江苏百赛飞生物科技有限公司 | Coating composition, protective coating based on coating composition and coated product |
| CN113278125A (en) * | 2021-05-28 | 2021-08-20 | 南京玖泰新材料科技有限公司 | Photo-curing polyurethane and application thereof |
| CN113861350A (en) * | 2021-10-14 | 2021-12-31 | 王俊生 | Preparation method of polymerizable resin, ink and coating |
| CN115490811A (en) * | 2022-10-11 | 2022-12-20 | 上海东升新材料有限公司 | Low-foaming high-water-resistance aqueous adhesive for lawn back adhesive and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109957083B (en) | 2021-06-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2638077B1 (en) | Novel polymeric photoinitiators | |
| CN109957083B (en) | Unsaturated polyol, photocurable polyurethane prepared from unsaturated polyol and preparation methods of unsaturated polyol and photocurable polyurethane | |
| CA1200647A (en) | Actinic radiation cured polyurethane acrylic copolymer | |
| JP5623802B2 (en) | Michael acceptor containing multiple hydroxyl groups and Michael addition products derived therefrom | |
| US9708425B2 (en) | Routes to polyacrylates | |
| CN110835397B (en) | Self-crosslinking water-based photocuring polyurethane and preparation method and application thereof | |
| CN1205716A (en) | Compounds with isocyanate groups and masked groups reactive in relation to isocyanates | |
| Meng et al. | Design and Preparation of Tertiary Amine Modified Polyurethane Acrylate Oligomer with Co‐Initiation/Polymerization Bifunctions for Photo‐Curable Inkjet Printing of Textiles | |
| CN111514380B (en) | Ureteral stent and preparation method thereof | |
| CN100386346C (en) | Cleavage-type photoinitiator containing macromolecular segment and its preparation method and application | |
| CN107325288B (en) | Organic silicon modified photoinitiator for improving surface curing effect and preparation method thereof | |
| CN106366277A (en) | Preparing method of ultraviolet light cross-linking and solidifying waterborne polyurethane and application | |
| CN111944112B (en) | Polymerizable polyurethane associative thickener with side group at end and preparation method and application thereof | |
| İnan et al. | Preparation and Characterization of Novel UV‐Curable Urethane Methacrylate Difunctional Monomers and Their Structure‐Property Relationships, 1 | |
| CN1884333A (en) | Photo-sensitive polyurethane with thio- and benzophenone structural side chain and its preparation method | |
| Yang et al. | Synthesis of vinyl functionalized polyurethane acrylate oligomers and their photopolymerization via thiol-ene click reaction | |
| JP3338331B2 (en) | Two-component acrylic urethane sealant composition | |
| JPH0940741A (en) | Photocurable urethane acrylate oligomer and photocurable composition | |
| KR100903209B1 (en) | Michael addition intermediates and interior photocurable urethane (meth) acrylate resin composition comprising the same | |
| JPS62241925A (en) | Curable polyene-polythiol resin composition | |
| JPH0747726B2 (en) | Adhesive composition | |
| JPS62197411A (en) | Radiation/ultraviolet-curable damping material composition | |
| Ahn | Benzoin Ether Photoinitiators Bound to Acrylated Prepolymers | |
| JPH0552327B2 (en) | ||
| JPS61103917A (en) | Novel urethane prepolymer, its manufacturing method, and photocurable resin composition using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |