WO2022263306A1 - Aldehyde-blocked organic polyisocyanates - Google Patents
Aldehyde-blocked organic polyisocyanates Download PDFInfo
- Publication number
- WO2022263306A1 WO2022263306A1 PCT/EP2022/065796 EP2022065796W WO2022263306A1 WO 2022263306 A1 WO2022263306 A1 WO 2022263306A1 EP 2022065796 W EP2022065796 W EP 2022065796W WO 2022263306 A1 WO2022263306 A1 WO 2022263306A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polyisocyanates
- carbon atoms
- organic polyisocyanates
- isocyanate groups
- blocked
- Prior art date
Links
- 239000005056 polyisocyanate Substances 0.000 title claims abstract description 70
- 229920001228 polyisocyanate Polymers 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000000576 coating method Methods 0.000 claims abstract description 20
- 239000013466 adhesive and sealant Substances 0.000 claims abstract description 8
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 27
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 125000005442 diisocyanate group Chemical group 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 239000000853 adhesive Substances 0.000 claims description 7
- 230000001070 adhesive effect Effects 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 7
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 claims description 7
- PCHXZXKMYCGVFA-UHFFFAOYSA-N 1,3-diazetidine-2,4-dione Chemical compound O=C1NC(=O)N1 PCHXZXKMYCGVFA-UHFFFAOYSA-N 0.000 claims description 6
- PJMDLNIAGSYXLA-UHFFFAOYSA-N 6-iminooxadiazine-4,5-dione Chemical compound N=C1ON=NC(=O)C1=O PJMDLNIAGSYXLA-UHFFFAOYSA-N 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- HXSACZWWBYWLIS-UHFFFAOYSA-N oxadiazine-4,5,6-trione Chemical group O=C1ON=NC(=O)C1=O HXSACZWWBYWLIS-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 125000005842 heteroatom Chemical group 0.000 claims description 4
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 239000011593 sulfur Chemical group 0.000 claims description 4
- 238000004132 cross linking Methods 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 3
- 230000004048 modification Effects 0.000 claims 2
- 238000012986 modification Methods 0.000 claims 2
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 4
- 239000004971 Cross linker Substances 0.000 abstract description 3
- -1 and the coatings Substances 0.000 description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 239000002904 solvent Substances 0.000 description 12
- 150000001299 aldehydes Chemical class 0.000 description 11
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 150000003254 radicals Chemical class 0.000 description 8
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 8
- 150000001298 alcohols Chemical class 0.000 description 7
- 239000012948 isocyanate Substances 0.000 description 7
- 150000002513 isocyanates Chemical class 0.000 description 7
- 229920000570 polyether Polymers 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000004721 Polyphenylene oxide Substances 0.000 description 5
- 239000002981 blocking agent Substances 0.000 description 5
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid group Chemical group C(CCCCC)(=O)O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 5
- HYNDYAQJODYUGF-UHFFFAOYSA-N 1,2,3,4,5,7,8,9-octahydropyrido[1,2-a][1,4]diazepine Chemical compound C1NCCCN2CCCC=C21 HYNDYAQJODYUGF-UHFFFAOYSA-N 0.000 description 4
- SGUVLZREKBPKCE-UHFFFAOYSA-N 1,5-diazabicyclo[4.3.0]-non-5-ene Chemical compound C1CCN=C2CCCN21 SGUVLZREKBPKCE-UHFFFAOYSA-N 0.000 description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N anhydrous diethylene glycol Natural products OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- WCRDXYSYPCEIAK-UHFFFAOYSA-N dibutylstannane Chemical compound CCCC[SnH2]CCCC WCRDXYSYPCEIAK-UHFFFAOYSA-N 0.000 description 4
- SHZIWNPUGXLXDT-UHFFFAOYSA-N ethyl hexanoate Chemical compound CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 4
- 229920005862 polyol Polymers 0.000 description 4
- 150000003077 polyols Chemical class 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 4
- 235000012141 vanillin Nutrition 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- IFNXAMCERSVZCV-UHFFFAOYSA-L zinc;2-ethylhexanoate Chemical compound [Zn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O IFNXAMCERSVZCV-UHFFFAOYSA-L 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-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
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 239000000463 material Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- TYKCBTYOMAUNLH-MTOQALJVSA-J (z)-4-oxopent-2-en-2-olate;titanium(4+) Chemical compound [Ti+4].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O TYKCBTYOMAUNLH-MTOQALJVSA-J 0.000 description 2
- DFPJRUKWEPYFJT-UHFFFAOYSA-N 1,5-diisocyanatopentane Chemical compound O=C=NCCCCCN=C=O DFPJRUKWEPYFJT-UHFFFAOYSA-N 0.000 description 2
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 2
- IVGRSQBDVIJNDA-UHFFFAOYSA-N 2-(2-aminoethylamino)ethanesulfonic acid Chemical compound NCCNCCS(O)(=O)=O IVGRSQBDVIJNDA-UHFFFAOYSA-N 0.000 description 2
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 2
- NNLRDVBAHRQMHK-UHFFFAOYSA-N 3-(2-aminoethylamino)propanoic acid Chemical compound NCCNCCC(O)=O NNLRDVBAHRQMHK-UHFFFAOYSA-N 0.000 description 2
- XBIUWALDKXACEA-UHFFFAOYSA-N 3-[bis(2,4-dioxopentan-3-yl)alumanyl]pentane-2,4-dione Chemical compound CC(=O)C(C(C)=O)[Al](C(C(C)=O)C(C)=O)C(C(C)=O)C(C)=O XBIUWALDKXACEA-UHFFFAOYSA-N 0.000 description 2
- HNVRRHSXBLFLIG-UHFFFAOYSA-N 3-hydroxy-3-methylbut-1-ene Chemical compound CC(C)(O)C=C HNVRRHSXBLFLIG-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- BHCFVCRRNLIOGM-UHFFFAOYSA-J C(CO)(=O)[O-].[Mo+4].C(CO)(=O)[O-].C(CO)(=O)[O-].C(CO)(=O)[O-] Chemical compound C(CO)(=O)[O-].[Mo+4].C(CO)(=O)[O-].C(CO)(=O)[O-].C(CO)(=O)[O-] BHCFVCRRNLIOGM-UHFFFAOYSA-J 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- JYFHYPJRHGVZDY-UHFFFAOYSA-N Dibutyl phosphate Chemical compound CCCCOP(O)(=O)OCCCC JYFHYPJRHGVZDY-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- JJLKTTCRRLHVGL-UHFFFAOYSA-L [acetyloxy(dibutyl)stannyl] acetate Chemical compound CC([O-])=O.CC([O-])=O.CCCC[Sn+2]CCCC JJLKTTCRRLHVGL-UHFFFAOYSA-L 0.000 description 2
- 125000003172 aldehyde group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- MQPPCKJJFDNPHJ-UHFFFAOYSA-K aluminum;3-oxohexanoate Chemical compound [Al+3].CCCC(=O)CC([O-])=O.CCCC(=O)CC([O-])=O.CCCC(=O)CC([O-])=O MQPPCKJJFDNPHJ-UHFFFAOYSA-K 0.000 description 2
- 150000001409 amidines Chemical class 0.000 description 2
- FKOASGGZYSYPBI-UHFFFAOYSA-K bis(trifluoromethylsulfonyloxy)alumanyl trifluoromethanesulfonate Chemical compound [Al+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F FKOASGGZYSYPBI-UHFFFAOYSA-K 0.000 description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- SMUSIFOACPPWGZ-UHFFFAOYSA-L di(hexadecanoyloxy)tin Chemical compound [Sn+2].CCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCC([O-])=O SMUSIFOACPPWGZ-UHFFFAOYSA-L 0.000 description 2
- JQZRVMZHTADUSY-UHFFFAOYSA-L di(octanoyloxy)tin Chemical compound [Sn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O JQZRVMZHTADUSY-UHFFFAOYSA-L 0.000 description 2
- RJGHQTVXGKYATR-UHFFFAOYSA-L dibutyl(dichloro)stannane Chemical compound CCCC[Sn](Cl)(Cl)CCCC RJGHQTVXGKYATR-UHFFFAOYSA-L 0.000 description 2
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 2
- HGQSXVKHVMGQRG-UHFFFAOYSA-N dioctyltin Chemical compound CCCCCCCC[Sn]CCCCCCCC HGQSXVKHVMGQRG-UHFFFAOYSA-N 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- PYBNTRWJKQJDRE-UHFFFAOYSA-L dodecanoate;tin(2+) Chemical compound [Sn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O PYBNTRWJKQJDRE-UHFFFAOYSA-L 0.000 description 2
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- CJMZLCRLBNZJQR-UHFFFAOYSA-N ethyl 2-amino-4-(4-fluorophenyl)thiophene-3-carboxylate Chemical compound CCOC(=O)C1=C(N)SC=C1C1=CC=C(F)C=C1 CJMZLCRLBNZJQR-UHFFFAOYSA-N 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- PRCNQQRRDGMPKS-UHFFFAOYSA-N pentane-2,4-dione;zinc Chemical compound [Zn].CC(=O)CC(C)=O.CC(=O)CC(C)=O PRCNQQRRDGMPKS-UHFFFAOYSA-N 0.000 description 2
- 150000003009 phosphonic acids Chemical class 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical class OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N tetraisopropyl titanate Substances CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical compound [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 description 2
- HIAIVILTZQDDNY-UHFFFAOYSA-J tin(4+);trifluoromethanesulfonate Chemical compound [Sn+4].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F HIAIVILTZQDDNY-UHFFFAOYSA-J 0.000 description 2
- 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 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- DKZBBWMURDFHNE-UHFFFAOYSA-N trans-coniferylaldehyde Natural products COC1=CC(C=CC=O)=CC=C1O DKZBBWMURDFHNE-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- WOZZOSDBXABUFO-UHFFFAOYSA-N tri(butan-2-yloxy)alumane Chemical compound [Al+3].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] WOZZOSDBXABUFO-UHFFFAOYSA-N 0.000 description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 2
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 2
- UNMJLQGKEDTEKJ-UHFFFAOYSA-N (3-ethyloxetan-3-yl)methanol Chemical compound CCC1(CO)COC1 UNMJLQGKEDTEKJ-UHFFFAOYSA-N 0.000 description 1
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- OOCCDEMITAIZTP-QPJJXVBHSA-N (E)-cinnamyl alcohol Chemical compound OC\C=C\C1=CC=CC=C1 OOCCDEMITAIZTP-QPJJXVBHSA-N 0.000 description 1
- YOUHVVBPILYPKM-NSCUHMNNSA-N (e)-but-2-ene-1,1-diol Chemical compound C\C=C\C(O)O YOUHVVBPILYPKM-NSCUHMNNSA-N 0.000 description 1
- VNMOIBZLSJDQEO-UHFFFAOYSA-N 1,10-diisocyanatodecane Chemical compound O=C=NCCCCCCCCCCN=C=O VNMOIBZLSJDQEO-UHFFFAOYSA-N 0.000 description 1
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- AZYRZNIYJDKRHO-UHFFFAOYSA-N 1,3-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC(C(C)(C)N=C=O)=C1 AZYRZNIYJDKRHO-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- AGJCSCSSMFRMFQ-UHFFFAOYSA-N 1,4-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=C(C(C)(C)N=C=O)C=C1 AGJCSCSSMFRMFQ-UHFFFAOYSA-N 0.000 description 1
- OHLKMGYGBHFODF-UHFFFAOYSA-N 1,4-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=C(CN=C=O)C=C1 OHLKMGYGBHFODF-UHFFFAOYSA-N 0.000 description 1
- ROHUXHMNZLHBSF-UHFFFAOYSA-N 1,4-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CCC(CN=C=O)CC1 ROHUXHMNZLHBSF-UHFFFAOYSA-N 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
- 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 description 1
- OUJCKESIGPLCRN-UHFFFAOYSA-N 1,5-diisocyanato-2,2-dimethylpentane Chemical compound O=C=NCC(C)(C)CCCN=C=O OUJCKESIGPLCRN-UHFFFAOYSA-N 0.000 description 1
- AHBNSOZREBSAMG-UHFFFAOYSA-N 1,5-diisocyanato-2-methylpentane Chemical compound O=C=NCC(C)CCCN=C=O AHBNSOZREBSAMG-UHFFFAOYSA-N 0.000 description 1
- QGLRLXLDMZCFBP-UHFFFAOYSA-N 1,6-diisocyanato-2,4,4-trimethylhexane Chemical compound O=C=NCC(C)CC(C)(C)CCN=C=O QGLRLXLDMZCFBP-UHFFFAOYSA-N 0.000 description 1
- VTBOTOBFGSVRMA-UHFFFAOYSA-N 1-Methylcyclohexanol Chemical class CC1(O)CCCCC1 VTBOTOBFGSVRMA-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical group COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 1
- UENRXLSRMCSUSN-UHFFFAOYSA-N 3,5-diaminobenzoic acid Chemical compound NC1=CC(N)=CC(C(O)=O)=C1 UENRXLSRMCSUSN-UHFFFAOYSA-N 0.000 description 1
- RDFQSFOGKVZWKF-UHFFFAOYSA-N 3-hydroxy-2,2-dimethylpropanoic acid Chemical compound OCC(C)(C)C(O)=O RDFQSFOGKVZWKF-UHFFFAOYSA-N 0.000 description 1
- QMYGFTJCQFEDST-UHFFFAOYSA-N 3-methoxybutyl acetate Chemical compound COC(C)CCOC(C)=O QMYGFTJCQFEDST-UHFFFAOYSA-N 0.000 description 1
- VATRWWPJWVCZTA-UHFFFAOYSA-N 3-oxo-n-[2-(trifluoromethyl)phenyl]butanamide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1C(F)(F)F VATRWWPJWVCZTA-UHFFFAOYSA-N 0.000 description 1
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
- MGYGFNQQGAQEON-UHFFFAOYSA-N 4-tolyl isocyanate Chemical compound CC1=CC=C(N=C=O)C=C1 MGYGFNQQGAQEON-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- SAIKULLUBZKPDA-UHFFFAOYSA-N Bis(2-ethylhexyl) amine Chemical compound CCCCC(CC)CNCC(CC)CCCC SAIKULLUBZKPDA-UHFFFAOYSA-N 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- PJWWRFATQTVXHA-UHFFFAOYSA-N Cyclohexylaminopropanesulfonic acid Chemical compound OS(=O)(=O)CCCNC1CCCCC1 PJWWRFATQTVXHA-UHFFFAOYSA-N 0.000 description 1
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-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
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- ZWXPDGCFMMFNRW-UHFFFAOYSA-N N-methylcaprolactam Chemical compound CN1CCCCCC1=O ZWXPDGCFMMFNRW-UHFFFAOYSA-N 0.000 description 1
- XTUVJUMINZSXGF-UHFFFAOYSA-N N-methylcyclohexylamine Chemical compound CNC1CCCCC1 XTUVJUMINZSXGF-UHFFFAOYSA-N 0.000 description 1
- PAMIQIKDUOTOBW-UHFFFAOYSA-N N-methylcyclohexylamine Natural products CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 235000012550 Pimpinella anisum Nutrition 0.000 description 1
- 240000004760 Pimpinella anisum Species 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 description 1
- KVXNKFYSHAUJIA-UHFFFAOYSA-N acetic acid;ethoxyethane Chemical compound CC(O)=O.CCOCC KVXNKFYSHAUJIA-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- OOCCDEMITAIZTP-UHFFFAOYSA-N allylic benzylic alcohol Natural products OCC=CC1=CC=CC=C1 OOCCDEMITAIZTP-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- VEZXCJBBBCKRPI-UHFFFAOYSA-N beta-propiolactone Chemical compound O=C1CCO1 VEZXCJBBBCKRPI-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- QDHFHIQKOVNCNC-UHFFFAOYSA-N butane-1-sulfonic acid Chemical compound CCCCS(O)(=O)=O QDHFHIQKOVNCNC-UHFFFAOYSA-N 0.000 description 1
- 150000004651 carbonic acid esters Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- ALSTYHKOOCGGFT-UHFFFAOYSA-N cis-oleyl alcohol Natural products CCCCCCCCC=CCCCCCCCCO ALSTYHKOOCGGFT-UHFFFAOYSA-N 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- VSSAZBXXNIABDN-UHFFFAOYSA-N cyclohexylmethanol Chemical compound OCC1CCCCC1 VSSAZBXXNIABDN-UHFFFAOYSA-N 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- UYAAVKFHBMJOJZ-UHFFFAOYSA-N diimidazo[1,3-b:1',3'-e]pyrazine-5,10-dione Chemical compound O=C1C2=CN=CN2C(=O)C2=CN=CN12 UYAAVKFHBMJOJZ-UHFFFAOYSA-N 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical class COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- DUDXQIXWPJMPRQ-UHFFFAOYSA-N isocyanatomethylcyclohexane Chemical compound O=C=NCC1CCCCC1 DUDXQIXWPJMPRQ-UHFFFAOYSA-N 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- AGVKXDPPPSLISR-UHFFFAOYSA-N n-ethylcyclohexanamine Chemical compound CCNC1CCCCC1 AGVKXDPPPSLISR-UHFFFAOYSA-N 0.000 description 1
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical class CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N pentanoic acid group Chemical group C(CCCC)(=O)O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229960000380 propiolactone Drugs 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 229940116423 propylene glycol diacetate Drugs 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-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
- C08G18/70—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
-
- 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
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/24—Catalysts containing metal compounds of tin
- C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
- C08G18/246—Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
-
- 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
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/8064—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with monohydroxy compounds
- C08G18/8067—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with monohydroxy compounds phenolic compounds
-
- 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
-
- 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
Definitions
- the present invention relates to new blocked polyisocyanates, a process for their preparation and their use as crosslinkers in coating materials, adhesives and sealants, and the coatings, adhesives and seals themselves that can be obtained from them.
- Blocking agents known from the literature such as, for example, alcohols, imidazole derivatives or, more specifically, ⁇ -caprolactam, often have high deblocking temperatures of over 180°C.
- High deblocking temperatures are not only disadvantageous from an energy-efficient point of view, but also from a performance point of view.
- Systems with low deblocking temperatures are to be preferred, particularly with regard to applications as coating materials for plastics and with regard to thermal stability.
- the object of the present invention was therefore to provide new blocking agents for polyisocyanates with a low deblocking temperature.
- the present invention relates to organic polyisocyanates having at least two isocyanate groups, with at least some of these isocyanate groups having aldehydes of the general formula I in which RI for the rest stands, where
- R 2 and R 3 independently represent a linear or branched aliphatic radical having up to 6 carbon atoms, preferably a methylene or ethylene radical,
- X and Y independently represent 0 or 1 and preferably both represent 0, and one or two of the radicals R 4 to R 7 , in the latter case independently of one another, represent an alkoxy group having up to 2 carbon atoms and the remaining of these four radicals represent hydrogen stand, and
- Z is O, S or N(H), preferably O, are blocked.
- At least some of the isocyanate groups means at least one of the at least two isocyanate groups.
- the present invention also relates to the blocked organic polyisocyanates mentioned above, comprising at least one structural element of the general formula II (II) where Z and RI are as defined above.
- A3) optionally at least one hydrophilizing agent.
- Another subject are blocked organic polyisocyanates obtainable by the process described above.
- a further object are blocked organic polyisocyanates, obtainable by the process described above, comprising at least one structural element of the general formula II where Z and RI have the meaning given above.
- aldehyde A1 of the general formula I which is to be used with preference in the preparation of the blocked organic polyisocyanates according to the invention is vaniline (4-hydroxy-3-methoxybenzaldehyde).
- the polyisocyanate component A2 comprises isocyanates with a functionality >2.
- diisocyanate refers to an organic compound which contains two isocyanate groups.
- Polyisocyanate refers to an organic compound containing two or more isocyanate groups. Diisocyanates are therefore a subgroup of polyisocyanates.
- suitable polyisocyanates for preparing the blocked organic polyisocyanates according to the invention are monomeric polyisocyanates. These include any monomeric diisocyanates which are accessible via phosgenation in the liquid or gas phase or via a phosgene-free route. Preferred diisocyanates are those in the molecular weight range from 140 to 400 g/mol with aliphatically, cycloaliphatically, araliphatically and/or aromatically bound isocyanate groups, such as e.g. B.
- 1,4-diisocyanatobutane 1,5-diisocyanatopentane (pentamethylene diisocyanate, PDI), 1,6-diisocyanatohexane (hexamethylene diisocyanate, HDI), 2-methyl-1,5-diisocyanatopentane, 1,5-diisocyanato-2,2- dimethylpentane, 2,2,4- or 2,4,4-trimethyl 1,6-diisocyanatohexane, 1,10-diisocyanatodecane, 1,3- and 1,4-diisocyanatocyclohexane, 1,3- and 1,4-bis(isocyanatomethyl)cyclohexane, l-isocyanato-3,3,5- trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 4,4'-diisocyanatodicyclohexylmethane,
- Suitable isocyanates for preparing the blocked organic polyisocyanates according to the invention are aliphatic, cycloaliphatic, araliphatic and aromatic di- and polyisocyanates with uretdione, isocyanurate, allophanate, urea, biuret, iminooxadiazinedione and/or oxadiazinetrione structures. These can be obtained from monomeric di- and polyisocyanates of the type described above. Their synthesis is, for example, in J. Prakt. Chem.
- di- and polyisocyanates with uretdione, isocyanurate, allophanate, urea, biuret, iminooxadiazinedione and/or oxadiazinetrione structures of the type mentioned, which have a content of monomeric diisocyanates of less than 1% by weight, preferably less than 0.5% by weight, particularly preferably less than 0.3% by weight.
- the residual monomer content is measured according to DIN EN ISO 10283:2007-11 by gas chromatography using an internal standard.
- Di- and polyisocyanates with uretdione, isocyanurate, allophanate, urea, biuret, iminooxadiazinedione and/or oxadiazinetrione structures of the type mentioned with exclusively aliphatically and/or cycloaliphatically bonded isocyanate groups are particularly preferred as polyisocyanate component A2 for the process according to the invention.
- Di- and polyisocyanates with an isocyanurate and/or allophanate structure which have exclusively aliphatically and/or cycloaliphatically bonded isocyanate groups are very particularly preferred as polyisocyanate component A2, most preferably those based on PDI, HDI, IPDI and/or 4,4'- diisocyanatodicyclohexylmethane.
- the blocked organic polyisocyanates according to the invention can be rendered hydrophilic using component A3.
- the hydrophilization can take place by means of nonionic or potentially ionic and/or ionic groups.
- compounds are used which, in addition to the groups mentioned having a hydrophilic effect, have isocyanate-reactive groups, preferably hydroxyl and amino groups, via which these compounds are incorporated into the polyisocyanates to be rendered hydrophilic.
- the hydrophilization can be carried out by first hydrophilizing some of the isocyanate groups of at least one isocyanate of the polyisocyanate component A2 by reaction with the hydrophilizing agent(s) A3 and then reacting the aldehyde component A1 with the hydrophilized isocyanate(s).
- component A3 can also be reacted with unreacted isocyanate groups of a reaction product of Al and A2.
- Nonionic hydrophilizing compounds are, for example, monohydric polyalkylene oxide polyether alcohols having a statistical average of 5 to 70, preferably 5 to 55 ethylene oxide units per molecule, such as are accessible in a manner known per se by alkoxylating suitable starter molecules (e.g. in Ullmann's Encyclopedia of Industrial Chemistry, 4th edition , Volume 19, Verlag Chemie, Weinheim, p. 31-38).
- Suitable starter molecules are, for example, saturated monoalcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, the isomers pentanoic, hexanoic, octanols and nonanols, n-decanol, n-dodecanol, n-tetradecanol, n -hexadecanol, n-octadecanol, cyclohexanol, the isomeric methylcyclohexanols or hydroxymethylcyclohexane, 3-ethyl-3-hydroxymethyloxetane, or tetrahydrofurfuryl alcohol; Diethylene glycol monoalkyl ethers such as diethylene glycol monobutyl ether; unsaturated alcohols such as allyl alcohol, 1,1-dimethylallyl alcohol or
- Alkylene oxides suitable for the alkoxylation reaction are, in particular, ethylene oxide and propylene oxide, which can be used in any order or as a mixture in the alkoxylation reaction.
- the polyalkylene oxide polyether alcohols are preferably pure polyethylene oxide polyethers or mixed polyalkylene oxide polyethers, the alkylene oxide units of which consist of at least 30 mol %, preferably at least 40 mol %, of ethylene oxide units.
- Particularly preferred polyalkylene oxide polyether alcohols are those which have been prepared using the abovementioned monoalcohols with a molecular weight in the range from 32 to 150 as starter molecules.
- Very particularly preferred polyether alcohols are pure polyethylene glycol monomethyl ether alcohols which have a statistical average of 5 to 50, very particularly preferably 5 to 25, ethylene oxide units.
- nonionic hydrophilizing compounds are known in principle and is described, for example, in EP-B 0206 059 and EP-B 0 540 985.
- These compounds are preferably mono- or dihydroxy-functional carboxylic, sulfonic or phosphonic acids, mono- or diamino-functional carboxylic, sulfonic or phosphonic acids, which can be present in the form of internal salts (zwitterions, betaines, ylides) or as metal or ammonium salts.
- Examples of the ionically or potentially ionically hydrophilizing compounds mentioned are dimethylolpropionic acid, hydroxypivalic acid, N-(2-aminoethyl)- ⁇ -alanine, 2-(2-aminoethylamino)ethanesulfonic acid, ethylenediaminepropyl or butylsulfonic acid, 1,2 - or 1,3-propylenediamine- ⁇ -ethylsulfonic acid, lysine, 3,5-diaminobenzoic acid, the hydrophilizing agent according to Example 1 from EP-A 0 916 647 and their alkali metal and/or ammonium salts; the adduct of sodium bisulfite with butene-2-diol-1,4, polyethersulfonate, the propoxylated adduct of 2- Butenediol and NaHSC (for example in DE-A 2446 440, page 5-9, formula I-III) and compounds which contain, for example amine
- Particularly preferred ionically or potentially ionically hydrophilizing compounds are N-(2-aminoethyl)- ⁇ -alanine, 2-(2-aminoethylamino)ethanesulfonic acid, dimethylolpropionic acid, the hydrophilizing agent according to Example 1 of EP-A 0 916 647, and their metal or ammonium salts.
- the blocked organic polyisocyanates according to the invention are prepared in a molar ratio of the NCO groups of component A2 to the NCO-reactive groups of component Al and optionally A3 (Al and A3 in total) of 0.6 to 1.4, preferably 0 .8 to 1.2, more preferably 0.9 to 1.1, most preferably from 1: 1.
- the NCO groups and NCO-reactive groups are each reacted at temperatures of 20 to 120.degree. C., preferably at 30 to 100.degree. C., particularly preferably at 50 to 80.degree. This applies to the reaction of Al with A2, for the optionally subsequent reaction with A3 and also for the reaction of Al with a reaction product from A2 with A3.
- the reaction takes place up to an NCO content of the blocked organic polyisocyanates of ⁇ 0.1% by weight.
- the NCO content is determined by means of FT-IR spectroscopy on a Lumos FTIR microscope from Bruker.
- the isocyanate valence vibration between 2300 and 2250 cm 1 is used to determine the excess NCO content.
- the blocked organic polyisocyanates according to the invention can be prepared without solvents, but also in the presence of solvents.
- Suitable solvents are those which are inert towards the reactive groups of the starting components.
- Suitable solvents are, for example, the conventional solvents known per se, such as. B.
- the blocked organic polyisocyanates according to the invention can be prepared using catalysts.
- Suitable catalysts are metal salts and chelates, salts of transition metals or semimetals, acids or bases.
- Acids which can preferably be used are aromatic sulfonic acids, such as dodecylbenzenesulfonic acid, para-toluenesulfonic acid, trifluoromethanesulfonic acid and dinonylnaphthalenesulfonic acid, or sulfuric acid, acetic acid, trifluoroacetic acid or dibutyl phosphate.
- N-substituted amidines such as 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) and 1,5-diazabicyclo[5.4.0]undec-7-ene (DBU) can preferably be used as bases.
- a further object of the present invention is the use of the blocked organic polyisocyanates according to the invention as described above as crosslinkers in coating materials, adhesives and sealants, these preferably being 1-component systems.
- the present invention also relates to coatings, adhesives and sealants, which are preferably 1-component systems containing blocked organic polyisocyanates as described above, and the coatings, adhesives and sealants obtainable from these coatings, adhesives and sealants.
- Another subject is a process for the production of coatings, bonds and seals, whereby
- R 1 is a saturated or unsaturated, linear or branched aliphatic, an optionally substituted aromatic, heterocyclic, cycloaliphatic or araliphatic radical with up to 18 carbon atoms, which can contain up to three heteroatoms from the group consisting of oxygen, sulfur or nitrogen, and
- Z represents O, S or N(H), preferably represents O, is blocked, - is crosslinked (cured) with deblocking with at least one isocyanate-reactive compound.
- Deblocking is to be understood as meaning the splitting back into aldehyde groups and isocyanate groups.
- Another subject is the above process for the production of coatings, adhesive bonds and seals, wherein the at least one organic polyisocyanate contains at least one structural element of the general formula II includes, where Z and RI have the meaning given above.
- a further object is the above process for producing coatings, adhesive bonds and seals, the at least one organic polyisocyanate being obtainable from the reaction
- Al at least one aldehyde of the general formula I where Z and RI have the meaning given above,
- A3) optionally at least one hydrophilizing agent.
- Another subject is the above method for producing coatings, adhesive bonds and seals, wherein the at least one organic polyisocyanate contains at least one structural element of the general formula II includes, and is obtainable from the implementation
- A3) optionally at least one hydrophilizing agent, where Z and RI are as defined above.
- RI in formula I or II is the radical in which
- R 2 and R 3 independently represent a linear or branched aliphatic radical having up to 6 carbon atoms, preferably a methylene or ethylene radical,
- X and Y independently represent 0 or 1 and preferably both represent 0, and R 4 to R 7 independently represent hydrogen or a linear or branched aliphatic radical with up to 6 carbon atoms, preferably a linear aliphatic radical with up to 2 carbon atoms ,
- the heteroatoms such as oxygen, sulfur or nitrogen, preferably oxygen, may contain.
- Up to 2 of the radicals R 4 to R 7 are preferably an alkoxy group having up to 2 carbon atoms and the remaining four radicals are hydrogen.
- One or two of the radicals R 4 to R 7 in the latter case independently of one another, particularly preferably represent an alkoxy group having up to 2 carbon atoms and the remaining of these four radicals represent hydrogen
- aldehyde A1 of the general formula I which is to be used with particular preference is vaniline (4-hydroxy-3-methoxybenzaldehyde).
- Suitable isocyanate-reactive compounds for the production of coatings, adhesive bonds and seals are di- and polyhydroxy compounds or di- and polyamines.
- Suitable polyols are, for example, polyether polyols, polyester polyols, polycarbonate polyols or polyacrylate polyols.
- the crosslinking temperatures are from 100 to 170.degree. C., preferably from 110 to 150.degree. C., particularly preferably from 100 to 140.degree.
- a catalyst is preferably added to accelerate curing.
- Suitable catalysts are metal salts and chelates, salts of transition metals or semimetals, acids or bases.
- Acids which can preferably be used are aromatic sulfonic acids, such as dodecylbenzenesulfonic acid, para-toluenesulfonic acid, trifluoromethanesulfonic acid and dinonylnaphthalenesulfonic acid, or sulfuric acid, acetic acid, trifluoroacetic acid or dibutyl phosphate.
- N-substituted amidines such as 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) and 1,5-diazabicyclo[5.4.0]undec-7-ene (DBU) can preferably be used as bases.
- iron(III) chloride aluminum tri(ethylacetoacetate), zinc chloride, zinc(II) n-octanoate, zinc(II) 2-ethyl-1-hexanoate, zinc(II )-2-ethylcaproate, zinc(II) stearate, zinc(II) naphthenate, zinc(II) acetylacetonate, tin(II) n-octanoate, tin(II) 2-ethyl-l-hexanoate, tin (II) ethyl caproate, tin(II) laurate, tin(II) palmitate, dibutyltin(IV) oxide, dibutyltin(IV) dichloride, dibutyltin(IV) diacetate, dibutyltin(IV) dimaleate, Dibutyltin(IV)
- the present invention also relates to coatings, adhesive bonds and seals obtainable by the process described above.
- the NCO contents were determined and the deblocking temperature was investigated using the Lumos FTIR microscope from Bruker.
- Desmodur ultra N 3600 was purchased from Covestro Deutschland AG.
- Vanillin was purchased from Merck (Sigma Aldrich).
- Solvents such as dimethyl sulfoxide (anhydrous) were purchased from Merck (Sigma Aldrich).
- Dibutyltin dilaurate (0.01% in butyl acetate) was purchased from Merck (Sigma Aldrich).
- Acetic acid was purchased from Merck (Sigma Aldrich).
- the blocked polyisocyanates produced in this way were examined with regard to their deblocking by means of IR spectroscopy in the temperature range from 100 to 170° C. and the deblocking temperature was determined from the spectra recorded.
- the deblocking temperature was determined via the elimination of the blocking agent and the resulting isocyanate band, which was determined as an NCO valence vibration between 2300 and 2250 cm 1 .
- the influence of 0.5% by weight acetic acid as a deblocking catalyst was also examined.
- Table 1 shows the determined deblocking temperatures T debi. various blocking agents with/without 0.5% by weight acetic acid as a catalyst.
- Table 1 Detected deblocking temperatures T debi .
Abstract
The present invention relates to new polyisocyanates, a process of producing same and their use as crosslinkers in coating agents, adhesives and sealants, and to the coatings, bonds and seals obtained using them.
Description
Organische Polyisocyanate mit Aldehydblockierung Organic polyisocyanates with aldehyde blocking
Die vorliegende Erfindung betrifft neue blockierte Polyisocyanate, ein Verfahren zu deren Herstellung und deren Verwendung als Vernetzer in Beschichtungsmitteln, Klebstoffen und Dichtstoffen, sowie die daraus erhältlichen Beschichtungen, Klebungen und Dichtungen selbst. The present invention relates to new blocked polyisocyanates, a process for their preparation and their use as crosslinkers in coating materials, adhesives and sealants, and the coatings, adhesives and seals themselves that can be obtained from them.
Die Herstellung und Verwendung blockierter Polyisocyanate ist seit langem bekannt. Hierbei werden die freien NCO-Gruppen von Polyisocyanaten (vorübergehend) desaktiviert, um zu Produkten zu gelangen, die vorzugsweise in einkomponentig zu verarbeitenden Formulierungen eingesetzt werden können (vgl. D. A. Wieks und Z. W. Wieks Jr., Progr. Org. Coatings, vol 36, 1999, S. 148 ff und darin zitierte Literatur). The production and use of blocked polyisocyanates has been known for a long time. Here, the free NCO groups of polyisocyanates are (temporarily) deactivated in order to obtain products which can preferably be used in formulations to be processed as one component (cf. DA Wieks and ZW Wieks Jr., Progr. Org. Coatings, vol. 36, 1999, p. 148 ff and literature cited therein).
Literaturbekannte Blockierungsmittel, wie beispielsweise Alkohole, Imidazol-Derivate oder spezieller e-Caprolactam, weisen oft hohe Deblockierungstemperatur von über 180°C auf. Hohe Deblockierungstemperaturen sind nicht nur aus Energie-effizienter Sicht sondern auch aus anwendungstechnischer Sicht von Nachteil. Besonders in Hinblick auf Anwendungen als Beschichtungsmittel von Kunststoffen und in Hinblick auf die Thermostabilität sind Systeme mit niedrigen Deblockierungstemperaturen zu bevorzugen. Aufgabe der vorliegenden Erfindung war es daher neue Blockierungsmittel für Polyisocyanate mit niedriger Deblockierungstemperatur bereitzustellen. Blocking agents known from the literature, such as, for example, alcohols, imidazole derivatives or, more specifically, ε-caprolactam, often have high deblocking temperatures of over 180°C. High deblocking temperatures are not only disadvantageous from an energy-efficient point of view, but also from a performance point of view. Systems with low deblocking temperatures are to be preferred, particularly with regard to applications as coating materials for plastics and with regard to thermal stability. The object of the present invention was therefore to provide new blocking agents for polyisocyanates with a low deblocking temperature.
In der JP S50 139721 A, der WO 2020/079073 Al, sowie im Artikel „One-pot synthesis of dibenzaldehyde-terminated poly(ethylene glycol) for preparation of dynamic chitosan-based amphiphilic hydrogels“ (Sohrab Rahmani et al, Polymer Bulletin, Springer, Heidelberg (2021) 78:2887-2909, https://doi.org/10.1007/s00289-020-03244-x) werden Produkte auf Basis von Polyisocyanaten und 4-Hydroxybenzaldehyd beschrieben. Keines der Dokument jedoch beschreibt Polyisocyanate, die mit Hydroxybenzaldehyden, die wenigstens eine Alkoxygruppe am aromatischen Ring aufweisen, blockiert sind. Auch beschreibt keines der Dokumente die unter Deblockierung einhergehende Vernetzung von mit Hydroxybenzaldehyden blockierten Polyisocyanaten mit isocyanatreaktiven Verbindungen. In JP S50 139721 A, WO 2020/079073 A1, and in the article "One-pot synthesis of dibenzaldehyde-terminated poly(ethylene glycol) for preparation of dynamic chitosan-based amphiphilic hydrogels" (Sohrab Rahmani et al, Polymer Bulletin, Springer, Heidelberg (2021) 78:2887-2909, https://doi.org/10.1007/s00289-020-03244-x) describes products based on polyisocyanates and 4-hydroxybenzaldehyde. However, none of the documents describe polyisocyanates blocked with hydroxybenzaldehydes having at least one alkoxy group on the aromatic ring. Neither of the documents describes the crosslinking of polyisocyanates blocked with hydroxybenzaldehydes with isocyanate-reactive compounds, which goes along with deblocking.
Gegenstand der vorliegenden Erfindung sind organische Polyisocyanate mit mindestens zwei Isocyanatgruppen, wobei mindestens ein Teil dieser Isocyanatgruppen mit Aldehyden der allgemeinen Formel I
in welcher RI für den Rest
steht, wobei The present invention relates to organic polyisocyanates having at least two isocyanate groups, with at least some of these isocyanate groups having aldehydes of the general formula I in which RI for the rest stands, where
R2 und R3 unabhängig voneinander für einen linearen oder verzweigten aliphatischen Rest mit bis zu 6 Kohlenstoffatomen, bevorzugt einen Methylen- oder Ethylenrest stehen, R 2 and R 3 independently represent a linear or branched aliphatic radical having up to 6 carbon atoms, preferably a methylene or ethylene radical,
X und Y unabhängig voneinander für 0 oder 1 und bevorzugt beide für 0 stehen, und einer oder zwei der Reste R4bis R7, im letztgenannten Fall unabhängig voneinander, für eine Alkoxygruppe mit bis zu 2 Kohlenstoffatomen und die übrigen dieser vier Reste für Wasserstoff stehen, und X and Y independently represent 0 or 1 and preferably both represent 0, and one or two of the radicals R 4 to R 7 , in the latter case independently of one another, represent an alkoxy group having up to 2 carbon atoms and the remaining of these four radicals represent hydrogen stand, and
Z für O, S oder N(H) steht, bevorzugt für O steht, blockiert sind. Z is O, S or N(H), preferably O, are blocked.
Der Ausdruck, dass „mindestens ein Teil der Isocyanatgruppen mit Aldehyden der allgemeinen Formel I blockiert ist“ ist so zu verstehen, dass mindestens ein Teil der mindestens 2 Isocyanatgruppen mit den Aldehydgruppen der Aldehyde der Formel I umgesetzt ist. The expression that “at least some of the isocyanate groups are blocked with aldehydes of the general formula I” is to be understood as meaning that at least some of the at least 2 isocyanate groups have reacted with the aldehyde groups of the aldehydes of the formula I.
„Mindestens ein Teil der Isocyanatgruppen“ bedeutet wenigstens eine der wenigstens zwei Isocyanatgruppen. "At least some of the isocyanate groups" means at least one of the at least two isocyanate groups.
Gegenstand der vorliegenden Erfindung sind auch die oben genannten blockierten organische Polyisocyanate, umfassend mindestens ein Strukturelement der allgemeinen Formel II
(II), wobei Z und RI die oben genannte Bedeutung haben. The present invention also relates to the blocked organic polyisocyanates mentioned above, comprising at least one structural element of the general formula II (II) where Z and RI are as defined above.
Gegenstand ist auch ein Verfahren zur Herstellung der oben genannten blockierten organischen Polyisocyanate, umfassend die oder bestehend aus der Umsetzung Al) mindestens eines Aldehyds der allgemeinen Formel I
wobei Z und RI die oben genannte Bedeutung haben, Also provided is a process for preparing the abovementioned blocked organic polyisocyanates, comprising or consisting of the reaction A1) of at least one aldehyde of the general formula I where Z and RI have the meaning given above,
A2) mindestens eines Polyisocyanats mit mindestens zwei Isocyanatgruppen und A2) at least one polyisocyanate having at least two isocyanate groups and
A3) gegebenenfalls mindestens eines Hydrophilierungsmittels. A3) optionally at least one hydrophilizing agent.
Ein weiterer Gegenstand sind blockierte organische Polyisocyanate, erhältlich nach dem zuvor beschriebenen Verfahren. Another subject are blocked organic polyisocyanates obtainable by the process described above.
Ein weiterer Gegenstand sind blockierte organische Polyisocyanate, erhältlich nach dem zuvor beschriebenen Verfahren, umfassend mindestens ein Strukturelement der allgemeinen Formel II
wobei Z und RI die oben genannte Bedeutung haben. A further object are blocked organic polyisocyanates, obtainable by the process described above, comprising at least one structural element of the general formula II where Z and RI have the meaning given above.
Ein bei der Herstellung der erfindungsgemäßen blockierten organischen Polyisocyanate bevorzugt einzusetzendes Aldehyd Al der allgemeinen Formel I ist beispielsweise Vanilin (4-Hydroxy-3- methoxybenzaldehyd) . An example of an aldehyde A1 of the general formula I which is to be used with preference in the preparation of the blocked organic polyisocyanates according to the invention is vaniline (4-hydroxy-3-methoxybenzaldehyde).
Die Polyisocyanatkomponente A2 umfasst Isocyanate mit einer Funktionalität > 2. Als "Diisocyanat" wird im Rahmen der vorliegenden Erfindung eine organische Verbindung bezeichnet, die zwei Isocyanatgruppen enthält. Als "Polyisocyanat" wird eine organische Verbindung bezeichnet, die zwei oder mehr Isocyanatgruppen enthält. Diisocyanate sind daher eine Untergruppe von Polyisocyanaten. The polyisocyanate component A2 comprises isocyanates with a functionality >2. In the context of the present invention, “diisocyanate” refers to an organic compound which contains two isocyanate groups. "Polyisocyanate" refers to an organic compound containing two or more isocyanate groups. Diisocyanates are therefore a subgroup of polyisocyanates.
Geeignet Polyisocyanate zur Herstellung der erfindungsgemäßen blockierten organischen Polyisocyanate sind beispielsweise monomere Polyisocyanate. Dazu gehören beliebige monomere Diisocyanate, welche über Phosgenierung in der Flüssig- oder Gasphase oder auf phosgenfreiem Wege zugänglich sind. Bevorzugte Diisocyanate sind solche des Molekulargewichtsbereichs 140 bis 400 g/mol mit aliphatisch, cycloaliphatisch, araliphatisch und/oder aromatisch gebundenen Isocyanatgruppen, wie z. B. 1,4-Diisocyanatobutan, 1,5-Diisocyanatopentan (Pentamethylendiisocyanat, PDI), 1,6-Diisocyanatohexan (Hexamethylendiisocyanat, HDI), 2- Methyl-l,5-diisocyanatopentan, l,5-Diisocyanato-2,2-dimethylpentan, 2,2,4- bzw. 2,4,4-Trimethyl-
1,6-diisocyanatohexan, 1,10-Diisocyanatodecan, 1,3- und 1,4-Diisocyanatocy clohexan, 1,3- und 1,4- Bis-(isocyanatomethyl)cyclohexan, l-Isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexan (Isophorondiisocyanat, IPDI), 4,4'-Diisocyanatodicyclohexylmethan, 1-Isocyanato-l-methyl- 4(3)isocyanato-methylcyclohexan, Bis-(isocyanatomethyl)-norboman, 1,3- und 1,4- Bis(isocyanatomethyl)benzol (Xylylendiisocyanat, XDI), 1,3- und l,4-Bis-(2-isocyanato-prop-2-yl)- benzol (Tetramethylxylylendiisocyanat , TMXDI), 2,4- und 2,6-Diisocyanatotoluol (Toluylendiisocyanat, TDI), 2,4'- und 4,4'-Diisocyanatodiphenylmethan (MDI), 1,5- Diisocyanatonaphthalin oder Mischungen aus mindestens zwei solcher Diisocyanate. Examples of suitable polyisocyanates for preparing the blocked organic polyisocyanates according to the invention are monomeric polyisocyanates. These include any monomeric diisocyanates which are accessible via phosgenation in the liquid or gas phase or via a phosgene-free route. Preferred diisocyanates are those in the molecular weight range from 140 to 400 g/mol with aliphatically, cycloaliphatically, araliphatically and/or aromatically bound isocyanate groups, such as e.g. B. 1,4-diisocyanatobutane, 1,5-diisocyanatopentane (pentamethylene diisocyanate, PDI), 1,6-diisocyanatohexane (hexamethylene diisocyanate, HDI), 2-methyl-1,5-diisocyanatopentane, 1,5-diisocyanato-2,2- dimethylpentane, 2,2,4- or 2,4,4-trimethyl 1,6-diisocyanatohexane, 1,10-diisocyanatodecane, 1,3- and 1,4-diisocyanatocyclohexane, 1,3- and 1,4-bis(isocyanatomethyl)cyclohexane, l-isocyanato-3,3,5- trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 4,4'-diisocyanatodicyclohexylmethane, 1-isocyanato-1-methyl-4(3)isocyanatomethylcyclohexane, bis(isocyanatomethyl)norbomane, 1,3- and 1,4 - bis(isocyanatomethyl)benzene (xylylene diisocyanate, XDI), 1,3- and 1,4-bis(2-isocyanato-prop-2-yl)-benzene (tetramethylxylylene diisocyanate, TMXDI), 2,4- and 2,6 -Diisocyanatotoluene (tolylene diisocyanate, TDI), 2,4'- and 4,4'-diisocyanatodiphenylmethane (MDI), 1,5-diisocyanatonaphthalene or mixtures of at least two such diisocyanates.
Weitere geeignete Isocyanate zur Herstellung der erfmdungsgemäßen blockierten organischen Polyisocyanate sind aliphatische, cycloaliphatische, araliphatische und aromatische Di- und Polyisocyanate mit Uretdion-, Isocyanurat-, Allophanat-, Harnstoff-, Biuret-, Iminooxadiazindion- und/oder Oxadiazintrionstrukturen. Diese können aus monomeren Di- und Polyisocyanaten der oben beschriebenen Art erhalten werden. Ihre Synthese ist beispielsweise in J. Prakt. Chem. 336 (1994) 185 - 200, in DE-A 1 670 666, DE-A 1 954 093, DE-A 2 414 413, DE-A 2 452 532, DE-A 2 641 380, DE-A 3 700 209, DE-A 3 900 053 und DE-A 3 928 503 oder in EP-A 0 336205, EP-A 0 339 396 und EP-A 0 798 299 sowie in DE-A 870 400, DE-A 953 012, DE-A 1 090 196, EP-A 0 546 399, CN 105218780, CN 103881050, CN 101717571, US 3 183 112, EP-A 0 416 338, EP-A 0 751 163, EP-A 1 378 529, EP-A 1 378 530, EP-A 2 174 967, JP 63260915 und JP 56059828 beispielhaft beschrieben sind. Other suitable isocyanates for preparing the blocked organic polyisocyanates according to the invention are aliphatic, cycloaliphatic, araliphatic and aromatic di- and polyisocyanates with uretdione, isocyanurate, allophanate, urea, biuret, iminooxadiazinedione and/or oxadiazinetrione structures. These can be obtained from monomeric di- and polyisocyanates of the type described above. Their synthesis is, for example, in J. Prakt. Chem. 336 (1994) 185-200, in DE-A 1 670 666, DE-A 1 954 093, DE-A 2 414 413, DE-A 2 452 532, DE-A 2 641 380, DE-A 3 700 209, DE-A 3 900 053 and DE-A 3 928 503 or in EP-A 0 336205, EP-A 0 339 396 and EP-A 0 798 299 as well as in DE-A 870 400, DE-A 953 012 , DE-A 1 090 196, EP-A 0 546 399, CN 105218780, CN 103881050, CN 101717571, US 3 183 112, EP-A 0 416 338, EP-A 0 751 163, EP-A 1 378 529, EP-A 1 378 530, EP-A 2 174 967, JP 63260915 and JP 56059828 are described by way of example.
Bei der Herstellung dieser Di- und Polyisocyanate schließt sich an die eigentliche Modifizierungsreaktion mit Uretdion-, Isocyanurat-, Allophanat-, Harnstoff-, Biuret-, Iminooxadiazindion- und/oder Oxadiazintrionstrukturen in der Regel ein weiterer Verfahrenschritt zur Abtrennung der nicht umgesetzten überschüssigen monomeren Isocyanate an. Diese Monomerenabtrennung erfolgt nach an sich bekannten Verfahren vorzugsweise durch Dünnschichtdestillation im Hochvakuum oder durch Extraktion mit geeigneten gegenüber Isocyanatgruppen inerten Lösemitteln, beispielsweise aliphatischen oder cycloaliphatischen Kohlenwasserstoffen wie Pentan, Hexan, Heptan, Cyclopentan oder Cyclohexan. In the preparation of these di- and polyisocyanates, the actual modification reaction with uretdione, isocyanurate, allophanate, urea, biuret, iminooxadiazinedione and/or oxadiazinetrione structures is usually followed by a further process step for separating off the unreacted excess monomeric isocyanates on. This removal of monomers is carried out according to methods known per se, preferably by thin-layer distillation under high vacuum or by extraction with suitable solvents which are inert towards isocyanate groups, for example aliphatic or cycloaliphatic hydrocarbons such as pentane, hexane, heptane, cyclopentane or cyclohexane.
Bevorzugt kommen bei der Herstellung der erfmdungsgemäßen blockierten organischen Polyisocyanate Di- und Polyisocyanate mit Uretdion-, Isocyanurat-, Allophanat-, Harnstoff-, Biuret-, Iminooxadiazindion- und/oder Oxadiazintrionstrukturen der genannten Art zum Einsatz, die einen Gehalt an monomeren Diisocyanaten von weniger als 1 Gew.-%, vorzugsweise weniger als 0,5 Gew.-%, besonders bevorzugt von weniger als 0,3 Gew.-% aufweisen. Die Rest-Monomeren Gehalte werden nach DIN EN ISO 10283:2007-11 gaschromatographisch mit internem Standard gemessen.
Besonders bevorzugt als Polyisocyanatkomponente A2 für das erfindungsgemäße Verfahren sind Di- und Polyisocyanate mit Uretdion-, Isocyanurat-, Allophanat-, Harnstoff-, Biuret-, Iminooxadiazindion- und/oder Oxadiazintrionstrukturen der genannten Art mit ausschließlich aliphatisch und/oder cycloaliphatisch gebundenen Isocyanatgruppen. In the production of the blocked organic polyisocyanates according to the invention, preference is given to using di- and polyisocyanates with uretdione, isocyanurate, allophanate, urea, biuret, iminooxadiazinedione and/or oxadiazinetrione structures of the type mentioned, which have a content of monomeric diisocyanates of less than 1% by weight, preferably less than 0.5% by weight, particularly preferably less than 0.3% by weight. The residual monomer content is measured according to DIN EN ISO 10283:2007-11 by gas chromatography using an internal standard. Di- and polyisocyanates with uretdione, isocyanurate, allophanate, urea, biuret, iminooxadiazinedione and/or oxadiazinetrione structures of the type mentioned with exclusively aliphatically and/or cycloaliphatically bonded isocyanate groups are particularly preferred as polyisocyanate component A2 for the process according to the invention.
Ganz besonders bevorzugt als Polyisocyanatkomponente A2 sind Di- und Polyisocyanate mit Isocyanurat- und/oder Allophanatstruktur, die ausschließlich aliphatisch und/oder cycloaliphatisch gebundene Isocyanatgruppen aufweisen, am meisten bevorzugt solche auf Basis von PDI, HDI, IPDI und/oder 4,4'-Diisocyanatodicyclohexylmethan. Di- and polyisocyanates with an isocyanurate and/or allophanate structure which have exclusively aliphatically and/or cycloaliphatically bonded isocyanate groups are very particularly preferred as polyisocyanate component A2, most preferably those based on PDI, HDI, IPDI and/or 4,4'- diisocyanatodicyclohexylmethane.
Die erfindungsgemäßen blockierten organischen Polyisocyanate können mittels Komponente A3 hydrophiliert werden. Die Hydrophilierung kann mittels nichtionischer bzw. potentiell ionischer und/oder ionischer Gruppen erfolgen. Zur Hydrophilierung werden Verbindungen eingesetzt, die neben den genannten hydrophilierend wirkenden Gruppen isocyanatreaktive Gruppen aufweisen, bevorzugt Hydroxyl- und Aminogruppen, über die diese Verbindungen in die zu hydrophilierenden Polyisocyanate eingebaut werden. Die Hydrophilierung kann erfolgen, indem zunächst ein Teil der Isocyanatgruppen wenigstens eines Isocyanats der Polyisocyanatkomponente A2 durch Umsetzung mit dem/den Hydrophilierungsmittel/n A3 hydrophiliert wird und dann die Aldehydkomponente Al mit dem/den hydrophiliertem/en Isocyanat/en umgesetzt wird. Alternativ kann auch Komponente A3 mit nicht umgesetzten Isocyanatgruppen eines Reaktionsproduktes aus Al und A2 umgesetzt werden. The blocked organic polyisocyanates according to the invention can be rendered hydrophilic using component A3. The hydrophilization can take place by means of nonionic or potentially ionic and/or ionic groups. For the hydrophilization, compounds are used which, in addition to the groups mentioned having a hydrophilic effect, have isocyanate-reactive groups, preferably hydroxyl and amino groups, via which these compounds are incorporated into the polyisocyanates to be rendered hydrophilic. The hydrophilization can be carried out by first hydrophilizing some of the isocyanate groups of at least one isocyanate of the polyisocyanate component A2 by reaction with the hydrophilizing agent(s) A3 and then reacting the aldehyde component A1 with the hydrophilized isocyanate(s). Alternatively, component A3 can also be reacted with unreacted isocyanate groups of a reaction product of Al and A2.
Nichtionisch hydrophilierende Verbindungen sind beispielsweise einwertige, im statistischen Mittel 5 bis 70, bevorzugt 5 bis 55 Ethylenoxideinheiten pro Molekül aufweisende Polyalkylen oxidpolyetheralkohole, wie sie in an sich bekannter Weise durch Alkoxylierung geeigneter Startermoleküle zugänglich sind (z.B. in Ullmanns Encyclopädie der technischen Chemie, 4.Auflage, Band 19, Verlag Chemie, Weinheim S. 31-38). Nonionic hydrophilizing compounds are, for example, monohydric polyalkylene oxide polyether alcohols having a statistical average of 5 to 70, preferably 5 to 55 ethylene oxide units per molecule, such as are accessible in a manner known per se by alkoxylating suitable starter molecules (e.g. in Ullmann's Encyclopedia of Industrial Chemistry, 4th edition , Volume 19, Verlag Chemie, Weinheim, p. 31-38).
Geeignete Startermoleküle sind beispielsweise gesättigte Monoalkohole wie Methanol, Ethanol, n- Propanol, Isopropanol, n-Butanol, Isobutanol, sec-Butanol, die Isomeren Pentanoie, Hexanoie, Octanole und Nonanole, n-Decanol, n-Dodecanol, n-Tetradecanol, n-Hexadecanol, n-Octadecanol, Cyclohexanol, die isomeren Methylcyclohexanole oder Hydroxymethylcy clohexan, 3-Ethyl-3- hydroxymethyloxetan, oder Tetrahydrofürfürylalkohol; Diethylenglykol-monoalkylether wie bei spielsweise Diethylenglykolmonobutylether; ungesättigte Alkohole wie Allylalkohol, 1,1- Dimethylallylalkohol oder Oleinalkohol, aromatische Alkohole wie Phenol, die isomeren Kresole oder Methoxyphenole, araliphatische Alkohole wie Benzylalkohol, Anisalkohol oder Zimtalkohol; sekundäre Monoamine wie Dimethylamin, Diethylamin, Dipropylamin, Diisopropylamin,
Dibutylamin, Bis-(2-ethylhexyl)-amin, N-Methyl- und N-Ethylcyclohexylamin oder Dicyclohexylamin sowie heterocyclische sekundäre Amine wie Morpholin, Pyrrolidin, Piperidin oder lH-Pyrazol. Bevorzugte Startermoleküle sind gesättigte Monoalkohole, sowie Diethylenglykol- monoalkylether. Suitable starter molecules are, for example, saturated monoalcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, the isomers pentanoic, hexanoic, octanols and nonanols, n-decanol, n-dodecanol, n-tetradecanol, n -hexadecanol, n-octadecanol, cyclohexanol, the isomeric methylcyclohexanols or hydroxymethylcyclohexane, 3-ethyl-3-hydroxymethyloxetane, or tetrahydrofurfuryl alcohol; Diethylene glycol monoalkyl ethers such as diethylene glycol monobutyl ether; unsaturated alcohols such as allyl alcohol, 1,1-dimethylallyl alcohol or oleic alcohol, aromatic alcohols such as phenol, the isomeric cresols or methoxyphenols, araliphatic alcohols such as benzyl alcohol, aniseed alcohol or cinnamic alcohol; secondary monoamines such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, Dibutylamine, bis(2-ethylhexyl)amine, N-methylcyclohexylamine and N-ethylcyclohexylamine or dicyclohexylamine and heterocyclic secondary amines such as morpholine, pyrrolidine, piperidine or 1H-pyrazole. Preferred starter molecules are saturated monoalcohols and diethylene glycol monoalkyl ethers.
Für die Alkoxylierungsreaktion geeignete Alkylenoxide sind insbesondere Ethylenoxid und Propylenoxid, die in beliebiger Reihenfolge oder auch im Gemisch bei der Alkoxylierungsreaktion eingesetzt werden können. Alkylene oxides suitable for the alkoxylation reaction are, in particular, ethylene oxide and propylene oxide, which can be used in any order or as a mixture in the alkoxylation reaction.
Bevorzugt handelt es sich bei den Polyalkylenoxidpolyetheralkoholen um reine Poly ethylenoxidpolyether oder gemischte Polyalkylenoxidpolyether, deren Alkylenoxideinheiten zu mindestens 30 mol-%, bevorzugt zu mindestens 40 mol-% aus Ethylenoxideinheiten bestehen. The polyalkylene oxide polyether alcohols are preferably pure polyethylene oxide polyethers or mixed polyalkylene oxide polyethers, the alkylene oxide units of which consist of at least 30 mol %, preferably at least 40 mol %, of ethylene oxide units.
Besonders bevorzugte Polyalkylenoxidpolyetheralkohole sind solche, die unter Verwendung der oben genannten Monoalkohole des Molekulargewichtsbereiches 32 bis 150 als Startermoleküle hergestellt wurden. Ganz besonders bevorzugte Polyetheralkohole sind reine Polyethylenglycol- monomethyletheralkohole, die im statistischen Mittel 5 bis 50, ganz besonders bevorzugt 5 bis 25 Ethylenoxideinheiten aufweisen. Particularly preferred polyalkylene oxide polyether alcohols are those which have been prepared using the abovementioned monoalcohols with a molecular weight in the range from 32 to 150 as starter molecules. Very particularly preferred polyether alcohols are pure polyethylene glycol monomethyl ether alcohols which have a statistical average of 5 to 50, very particularly preferably 5 to 25, ethylene oxide units.
Die Herstellung solcher nichtionischer hydrophilierender Verbindungen ist prinzipiell bekannt und beispielsweise in EP-B 0206 059 und EP-B 0 540 985 beschrieben. The preparation of such nonionic hydrophilizing compounds is known in principle and is described, for example, in EP-B 0206 059 and EP-B 0 540 985.
Unter ionisch bzw. potentiell ionisch hydrophilierenden Verbindungen werden Verbindungen verstanden, die mindestens eine isocyanatreaktive Gruppe sowie mindestens eine Funktionalität, wie z.B. -COOY, -S03Y, -PO(OY)2 (Y = H, NH4 +, Metallkation), -NR2, -NR3 + (R = H, Alkyl, Aryl), aufweisen, die bei Wechselwirkung mit wässrigen Medien ein ggf. pH-Wert-abhängiges Dissoziationsgleichgewicht eingeht und auf diese Weise negativ, positiv oder neutral geladen sein kann. Ionically or potentially ionically hydrophilizing compounds are understood to mean compounds which have at least one isocyanate-reactive group and at least one functionality, such as -COOY, -S0 3 Y, -PO(OY) 2 (Y=H, NH 4 + , metal cation), -NR 2 , -NR 3 + (R=H, alkyl, aryl), which, when interacting with aqueous media, enters into an optionally pH-dependent dissociation equilibrium and can thus be negatively, positively or neutrally charged.
Bevorzugt sind diese Verbindungen mono- oder dihydroxyfunktionelle Carbon-, Sulfon- oder Phosphonsäuren, mono- oder diaminofunktionelle Carbon-, Sulfon- oder Phosphonsäuren, die in Form innerer Salze (Zwitterionen, Betaine, Ylide) oder als Metall- oder Ammoniumsalze vorliegen können. Beispiele für die genannten ionisch bzw. potentiell ionisch hydrophilierenden Verbindungen sind Dimethylolpropionsäure, Hydroxypivalinsäure, N-(2-Aminoethyl)-ß-alanin, 2-(2-Amino- ethylamino)-ethansulfonsäure, Ethylendiamin-propyl- oder butylsulfonsäure, 1,2- oder 1,3- Propylendiamin- ß-ethylsulfonsäure, Lysin, 3,5-Diaminobenzoesäure, das Hydrophilierungsmittel gemäß Beispiel 1 aus der EP-A 0 916 647 und deren Alkali- und/oder Ammoniumsalze; das Addukt von Natriumbisulfit an Buten-2-diol-l,4, Polyethersulfonat, das propoxylierte Addukt aus 2-
Butendiol und NaHSC (z.B. in der DE-A 2446 440, Seite 5-9, Formel I-III) sowie Verbindungen, die in kationische Gruppen überführbare, z.B. amin-basierende, Bausteine wie N-Methyl-diethanol- amin als hydrophile Aufbaukomponenten enthalten. Weiterhin kann auch CAPS (Cyclohexylaminopropansulfonsäure) wie z.B. in der WO 01/88006 verwendet werden. These compounds are preferably mono- or dihydroxy-functional carboxylic, sulfonic or phosphonic acids, mono- or diamino-functional carboxylic, sulfonic or phosphonic acids, which can be present in the form of internal salts (zwitterions, betaines, ylides) or as metal or ammonium salts. Examples of the ionically or potentially ionically hydrophilizing compounds mentioned are dimethylolpropionic acid, hydroxypivalic acid, N-(2-aminoethyl)-β-alanine, 2-(2-aminoethylamino)ethanesulfonic acid, ethylenediaminepropyl or butylsulfonic acid, 1,2 - or 1,3-propylenediamine-β-ethylsulfonic acid, lysine, 3,5-diaminobenzoic acid, the hydrophilizing agent according to Example 1 from EP-A 0 916 647 and their alkali metal and/or ammonium salts; the adduct of sodium bisulfite with butene-2-diol-1,4, polyethersulfonate, the propoxylated adduct of 2- Butenediol and NaHSC (for example in DE-A 2446 440, page 5-9, formula I-III) and compounds which contain, for example amine-based, building blocks which can be converted into cationic groups, such as N-methyldiethanolamine, as hydrophilic structural components . Furthermore, CAPS (cyclohexylaminopropanesulfonic acid) can also be used, for example in WO 01/88006.
Besonders bevorzugte ionisch bzw. potentiell ionisch hydrophilerende Verbindungen sind N-(2- Aminoethyl)-ß-alanin, 2-(2-Amino-ethylamino)-ethansulfonsäure, Dimethylolpropionsäure, des Hydrophilierungsmittels gemäß Beispiel 1 der EP-A 0 916 647, sowie deren Metall- oder Ammoniumsalze . Particularly preferred ionically or potentially ionically hydrophilizing compounds are N-(2-aminoethyl)-β-alanine, 2-(2-aminoethylamino)ethanesulfonic acid, dimethylolpropionic acid, the hydrophilizing agent according to Example 1 of EP-A 0 916 647, and their metal or ammonium salts.
Die Herstellung der erfindungsgemäßen blockierten organischen Polyisocyanate erfolgt in einem Stoffmengen-Verhältnis der NCO-Gruppen der Komponente A2 zu den NCO-reaktiven Gruppen der Komponente Al und gegebenenfalls A3 (Al und A3 in Summe) von 0,6 bis 1,4, bevorzugt 0,8 bis 1,2, besonders bevorzugt 0,9 bis 1,1, am meisten bevorzugt von 1: 1. The blocked organic polyisocyanates according to the invention are prepared in a molar ratio of the NCO groups of component A2 to the NCO-reactive groups of component Al and optionally A3 (Al and A3 in total) of 0.6 to 1.4, preferably 0 .8 to 1.2, more preferably 0.9 to 1.1, most preferably from 1: 1.
Die Umsetzung der NCO-Gruppen und NCO-reaktiven Gruppen erfolgt jeweils bei Temperaturen von 20 bis 120 °C, vorzugsweise bei 30 bis 100 °C, besonders bevorzugt bei 50 bis 80 °C. Dies gilt für die Reaktion von Al mit A2, für die sich gegebenenfalls anschließende Reaktion mit A3 und ebenso für die Reaktion von Al mit einem Reaktionsprodukt aus A2 mit A3. The NCO groups and NCO-reactive groups are each reacted at temperatures of 20 to 120.degree. C., preferably at 30 to 100.degree. C., particularly preferably at 50 to 80.degree. This applies to the reaction of Al with A2, for the optionally subsequent reaction with A3 and also for the reaction of Al with a reaction product from A2 with A3.
Die Umsetzung erfolgt bis zu einem NCO-Gehalt der blockierten organischen Polyisocyanate von < 0,1 Gew.-%. The reaction takes place up to an NCO content of the blocked organic polyisocyanates of <0.1% by weight.
Die Bestimmung des NCO-Gehaltes wird mittels FT-IR Spektroskopie an einem Lumos FTIR Mikroskop der Firma Bruker. Zur Bestimmung des überschüssigen NCO-Gehaltes wird die Isocyanat- Valenzschwingung zwischen 2300 und 2250 cm 1 herangezogen. The NCO content is determined by means of FT-IR spectroscopy on a Lumos FTIR microscope from Bruker. The isocyanate valence vibration between 2300 and 2250 cm 1 is used to determine the excess NCO content.
Die erfindungsgemäßen blockierten organischen Polyisocyanate können lösemittelfrei, aber auch in Gegenwart von Fösemitteln hergestellt werden. Geeignete Fösemittel sind solche, die sich gegenüber den reaktiven Gruppen der Ausgangskomponenten inert zeigen. Geeignete Fösemittel sind beispielsweise die an sich bekannten üblichen Facklösemittel, wie z. B. Ethylacetat, Butylacetat, Ethylenglykolmonomethyl- oder -ethyletheracetat, l-Methoxypropyl-2-acetat, 3-Methoxy-n- butylacetat, Aceton, 2-Butanon, 4-Methyl-2-pentanon, Cyclohexanon, Toluol, Xylol, Chlorbenzol, Testbenzin, höher substituierte Aromaten, wie sie beispielsweise unter den Bezeichnungen Solventnaphtha, Solvesso®, Isopar®, Nappar® (Deutsche EXXON CHEMICAL GmbH, Köln, DE) und Shellsol® (Deutsche Shell Chemie GmbH, Eschborn, DE) im Handel sind, Dimethylsulfoxid, Kohlensäureester, wie Dimethylcarbonat, Diethylcarbonat, 1,2-Ethylencarbonat und 1,2- Propylencarbonat, Lactone, wie ß-Propiolacton, g-Butyrolacton, e-Caprolacton und e-
Methylcaprolacton, aber auch Lösemittel wie Propylenglykoldiacetat, Diethylenglykoldimethylether, Dipropylenglykoldimethylether, Butylglykolacetat, Butyldiglykolacetat, 1,3-Dioxolan, N-Methylpyrrolidon und N-Methylcaprolactam, oder beliebige Gemische solcher Lösemittel. Das Lösemittel kann dabei einem oder mehreren der Reaktionspartner zugegeben werden. The blocked organic polyisocyanates according to the invention can be prepared without solvents, but also in the presence of solvents. Suitable solvents are those which are inert towards the reactive groups of the starting components. Suitable solvents are, for example, the conventional solvents known per se, such as. B. ethyl acetate, butyl acetate, ethylene glycol monomethyl or ethyl ether acetate, l-methoxypropyl-2-acetate, 3-methoxy-n-butyl acetate, acetone, 2-butanone, 4-methyl-2-pentanone, cyclohexanone, toluene, xylene, chlorobenzene, White spirit, more highly substituted aromatics, such as those commercially available under the names Solventnaphtha, Solvesso®, Isopar®, Nappar® (Deutsche EXXON CHEMICAL GmbH, Cologne, DE) and Shellsol® (Deutsche Shell Chemie GmbH, Eschborn, DE), dimethyl sulfoxide , Carbonic acid esters such as dimethyl carbonate, diethyl carbonate, 1,2-ethylene carbonate and 1,2-propylene carbonate, lactones such as ß-propiolactone, g-butyrolactone, e-caprolactone and e- Methylcaprolactone, but also solvents such as propylene glycol diacetate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, butyl glycol acetate, butyl diglycol acetate, 1,3-dioxolane, N-methylpyrrolidone and N-methylcaprolactam, or any mixtures of such solvents. The solvent can be added to one or more of the reactants.
Die Herstellung der erfindungsgemäßen blockierten organischen Polyisocyanate kann unter Einsatz von Katalysatoren stattfinden. Geeignete Katalysatoren sind Metallsalze und -chelate, Salze von Übergangsmetallen oder Halbmetallen, Säuren oder Basen. Als Säuren können vorzugsweise aromatische Sulfonsäuren, wie Dodecylbenzolsulfonsäure, para-Toluolsulfonsäure, Trifluormethan- Sulfonsäure und Dinonylnaphthalinsulfonsäure sein, oder Schwefelsäure, Essigsäure, Trifluoressigsäure, oder Dibutylphosphat eingesetzt werden. Als Basen können vorzugsweise N- substituierte Amidine, wie l,5-Diazabicyclo[4.3.0]non-5-en (DBN) und 1,5- Diazabicyclo[5.4.0]undec-7-en (DBU) eingesetzt werden. Als katalytisch wirkende Metallsalze und -chelate können vorzugsweise Eisen(III)-chlorid, Aluminium-tri(ethylacetoacetat), Zinkchlorid, Zink(II)-n-octanoat, Zink(II)-2-ethyl-l-hexanoat, Zink(II)-2-ethylcaproat, Zink(II)-stearat, Zink(II)- naphthenat, Zink(II)-acetylacetonat, Zinn(II)-n-octanoat, Zinn(II)-2-ethyl-l-hexanoat, Zinn(II)- ethylcaproat, Zinn(II)-laurat, Zinn(II)-palmitat, Dibutyl-zinn(IV)-oxid, Dibutylzinn(IV)-dichlorid, Dibutylzinn(IV)-diacetat, Dibutylzinn(IV)-dimaleat, Dibutylzinn(IV)-dilaurat, Dioctylzinn(IV)- diacetat, Molybdänglykolat sowie Tetraisopropyltitanat, Tetrabutyltitanat, Titan(IV)acetylacetonat, Aluminium-tri-sec-butylat, Aluminiumacetylacetonat, Aluminiumtriflat oder Zinntriflat oder beliebige Gemische solcher Katalysatoren verwendet werden. The blocked organic polyisocyanates according to the invention can be prepared using catalysts. Suitable catalysts are metal salts and chelates, salts of transition metals or semimetals, acids or bases. Acids which can preferably be used are aromatic sulfonic acids, such as dodecylbenzenesulfonic acid, para-toluenesulfonic acid, trifluoromethanesulfonic acid and dinonylnaphthalenesulfonic acid, or sulfuric acid, acetic acid, trifluoroacetic acid or dibutyl phosphate. N-substituted amidines such as 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) and 1,5-diazabicyclo[5.4.0]undec-7-ene (DBU) can preferably be used as bases. Iron(III) chloride, aluminum tri(ethylacetoacetate), zinc chloride, zinc(II) n-octanoate, zinc(II) 2-ethyl-1-hexanoate, zinc(II )-2-ethylcaproate, zinc(II) stearate, zinc(II) naphthenate, zinc(II) acetylacetonate, tin(II) n-octanoate, tin(II) 2-ethyl-l-hexanoate, tin (II) ethyl caproate, tin(II) laurate, tin(II) palmitate, dibutyltin(IV) oxide, dibutyltin(IV) dichloride, dibutyltin(IV) diacetate, dibutyltin(IV) dimaleate, Dibutyltin(IV) dilaurate, dioctyltin(IV) diacetate, molybdenum glycolate and tetraisopropyl titanate, tetrabutyl titanate, titanium(IV) acetylacetonate, aluminum tri-sec-butylate, aluminum acetylacetonate, aluminum triflate or tin triflate or any mixtures of such catalysts can be used.
Die folgenden Abbildungen zeigen beispielhaft erfindungsgemäße blockierte organischen Polyisocyanate:
Ein weiterer Gegenstand der vorliegenden Erfindung ist die Verwendung der oben beschriebenen erfindungsgemäßen blockierten organischen Polyisocyanate als Vernetzer in Beschichtungsmitteln, Klebstoffen und Dichtstoffen, wobei es sich bevorzugt um 1-K-Systeme handelt. Ebenso sind Gegenstand der vorliegenden Erfindung Beschichtungsmittel, Klebstoffe und Dichtstoffe, wobei es sich bevorzugt um 1-K-Systeme handelt, enthaltend blockierte organische Polyisocyanate gemäß vorstehender Beschreibung, sowie die aus diesen Beschichtungsmitteln, Klebstoffen und Dichtstoffen erhältlichen Beschichtungen, Klebungen und Dichtungen. The following figures show examples of blocked organic polyisocyanates according to the invention: A further object of the present invention is the use of the blocked organic polyisocyanates according to the invention as described above as crosslinkers in coating materials, adhesives and sealants, these preferably being 1-component systems. The present invention also relates to coatings, adhesives and sealants, which are preferably 1-component systems containing blocked organic polyisocyanates as described above, and the coatings, adhesives and sealants obtainable from these coatings, adhesives and sealants.
Weiterer Gegenstand ist ein Verfahren zur Herstellung von Beschichtungen, Klebungen und Dichtungen, wobei Another subject is a process for the production of coatings, bonds and seals, whereby
- mindestens ein organisches Polyisocyanat mit mindestens zwei Isocyanatgruppen, wobei mindestens ein Teil dieser Isocyanatgruppen mit Aldehyden der allgemeinen Formel I
in welcher - at least one organic polyisocyanate having at least two isocyanate groups, at least some of these isocyanate groups being bonded with aldehydes of the general formula I in which
R1 ein gesättigter oder ungesättigter, linearer oder verzweigter aliphatischer, ein gegebenenfalls substituierter aromatischer, heterocyclischer, cycloaliphatischer oder araliphatischer Rest mit bis zu 18 Kohlenstoffatomen ist, der bis zu drei Heteroatome aus der Reihe Sauerstoff, Schwefel oder Stickstoff enthalten kann, und R 1 is a saturated or unsaturated, linear or branched aliphatic, an optionally substituted aromatic, heterocyclic, cycloaliphatic or araliphatic radical with up to 18 carbon atoms, which can contain up to three heteroatoms from the group consisting of oxygen, sulfur or nitrogen, and
Z für O, S oder N(H) steht, bevorzugt für O steht, blockiert ist,
- unter Deblockierung mit mindestens einer Isocyanat-reaktiven Verbindung vernetzt (ausgehärtet) wird. Z represents O, S or N(H), preferably represents O, is blocked, - is crosslinked (cured) with deblocking with at least one isocyanate-reactive compound.
Unter Deblockierung ist die Rückspaltung zu Aldehydgruppen und Isocyanatgruppen zu verstehen. Deblocking is to be understood as meaning the splitting back into aldehyde groups and isocyanate groups.
Weiterer Gegenstand ist das obige Verfahren zur Herstellung von Beschichtungen, Klebungen und Dichtungen, wobei das mindestens eine organische Polyisocyanat mindestens ein Strukturelement der allgemeinen Formel II
umfasst, wobei Z und RI die oben genannte Bedeutung haben. Another subject is the above process for the production of coatings, adhesive bonds and seals, wherein the at least one organic polyisocyanate contains at least one structural element of the general formula II includes, where Z and RI have the meaning given above.
Ein weiterer Gegenstand ist das obige Verfahren zur Herstellung von Beschichtungen, Klebungen und Dichtungen, wobei das mindestens eine organische Polyisocyanat erhältlich ist aus der Umsetzung A further object is the above process for producing coatings, adhesive bonds and seals, the at least one organic polyisocyanate being obtainable from the reaction
Al) mindestens eines Aldehyds der allgemeinen Formel I
wobei Z und RI die oben genannte Bedeutung haben, Al) at least one aldehyde of the general formula I where Z and RI have the meaning given above,
A2) mindestens eines Polyisocyanats mit mindestens zwei Isocyanatgruppen und A2) at least one polyisocyanate having at least two isocyanate groups and
A3) gegebenenfalls mindestens eines Hydrophilierungsmittels. A3) optionally at least one hydrophilizing agent.
Ein weiterer Gegenstand ist das obige Verfahren zur Herstellung von Beschichtungen, Klebungen und Dichtungen, wobei das mindestens eine organische Polyisocyanat mindestens ein Strukturelement der allgemeinen Formel II
umfasst, und erhältlich ist aus der Umsetzung Another subject is the above method for producing coatings, adhesive bonds and seals, wherein the at least one organic polyisocyanate contains at least one structural element of the general formula II includes, and is obtainable from the implementation
Al) mindestens eines Aldehyds der allgemeinen Formel I
A2) mindestens eines Polyisocyanats mit mindestens zwei Isocyanatgruppen und Al) at least one aldehyde of the general formula I A2) at least one polyisocyanate having at least two isocyanate groups and
A3) gegebenenfalls mindestens eines Hydrophilierungsmittels, wobei Z und RI die oben genannte Bedeutung haben. A3) optionally at least one hydrophilizing agent, where Z and RI are as defined above.
In einer bevorzugten Ausführungsform steht RI in Formel I bzw. II für den Rest
wobei In a preferred embodiment, RI in formula I or II is the radical in which
R2 und R3 unabhängig voneinander für einen linearen oder verzweigten aliphatischen Rest mit bis zu 6 Kohlenstoffatomen, bevorzugt einen Methylen- oder Ethylenrest stehen, R 2 and R 3 independently represent a linear or branched aliphatic radical having up to 6 carbon atoms, preferably a methylene or ethylene radical,
X und Y unabhängig voneinander für 0 oder 1 und bevorzugt beide für 0 stehen, und R4 bis R7 unabhängig voneinander für Wasserstoff oder einen linearen oder verzweigten aliphatischen Rest mit bis zu 6 Kohlenstoffatomen, bevorzugt einen linearen aliphatischen Rest mit bis zu 2 Kohlenstoffatomen stehen, der Heteroatome, wie Sauerstoff, Schwefel oder Stickstoff, bevorzugt Sauerstoff, enthalten kann. Bevorzugt stehen bis zu 2 der Reste R4 bis R7 für eine Alkoxygruppe mit bis zu 2 Kohlenstoffatomen und die übrigen dieser vier Reste für Wasserstoff. Besonders bevorzugt stehen einer oder zwei der Reste R4bis R7, im letztgenannten Fall unabhängig voneinander, für eine Alkoxygruppe mit bis zu 2 Kohlenstoffatomen und die übrigen dieser vier Reste für Wasserstoff stehen X and Y independently represent 0 or 1 and preferably both represent 0, and R 4 to R 7 independently represent hydrogen or a linear or branched aliphatic radical with up to 6 carbon atoms, preferably a linear aliphatic radical with up to 2 carbon atoms , The heteroatoms such as oxygen, sulfur or nitrogen, preferably oxygen, may contain. Up to 2 of the radicals R 4 to R 7 are preferably an alkoxy group having up to 2 carbon atoms and the remaining four radicals are hydrogen. One or two of the radicals R 4 to R 7 , in the latter case independently of one another, particularly preferably represent an alkoxy group having up to 2 carbon atoms and the remaining of these four radicals represent hydrogen
Ein ganz besonders bevorzugt einzusetzendes Aldehyd Al der allgemeinen Formel I ist beispielsweise Vanilin (4-Hydroxy-3-methoxybenzaldehyd). An example of an aldehyde A1 of the general formula I which is to be used with particular preference is vaniline (4-hydroxy-3-methoxybenzaldehyde).
Bezüglich der Komponenten A2 und A3, weiterer Komponenten und Parameter zur Herstellung der organischen Polyisocyanate wird an dieser Stelle auf die vorangegangenen Ausführungen verwiesen. With regard to components A2 and A3, further components and parameters for the preparation of the organic polyisocyanates, reference is made at this point to the statements made above.
Als Isocyanat-reaktive Verbindungen zur Herstellung von Beschichtungen, Klebungen und Dichtungen kommen beispielsweise Di- und Polyhydroxyverbindungen oder Di- und Polyamine in Betracht. Geeignete Polyole sind, beispielsweise, Polyether Polyole, Polyester Polyole, Polycarbonate Polyol oder Polyacrylat Polyole.
Die Vemetzungstemperaturen liegen bei 100 bis 170 °C, bevorzugt bei 110 bis 150°C, besonders bevorzugt bei 100 bis 140 °C. Examples of suitable isocyanate-reactive compounds for the production of coatings, adhesive bonds and seals are di- and polyhydroxy compounds or di- and polyamines. Suitable polyols are, for example, polyether polyols, polyester polyols, polycarbonate polyols or polyacrylate polyols. The crosslinking temperatures are from 100 to 170.degree. C., preferably from 110 to 150.degree. C., particularly preferably from 100 to 140.degree.
Bevorzugt wird zur Beschleunigung der Aushärtung ein Katalysator zugegeben. Geeignete Katalysatoren sind Metallsalze und -chelate, Salze von Übergangsmetallen oder Halbmetallen, Säuren oder Basen. Als Säuren können vorzugsweise aromatische Sulfonsäuren, wie Dodecylbenzolsulfonsäure, para-Toluolsulfonsäure, Trifluormethan-sulfonsäure und Dinonylnaphthalinsulfonsäure sein, oder Schwefelsäure, Essigsäure, Trifluoressigsäure, oder Dibutylphosphat eingesetzt werden. Als Basen können vorzugsweise N-substituierte Amidine, wie l,5-Diazabicyclo[4.3.0]non-5-en (DBN) und l,5-Diazabicyclo[5.4.0]undec-7-en (DBU) eingesetzt werden. Als katalytisch wirkende Metallsalze und -chelate können vorzugsweise Eisen(III)-chlorid, Aluminium -tri (ethylacetoacetat), Zinkchlorid, Zink(II)-n-octanoat, Zink(II)-2-ethyl-l-hexanoat, Zink(II)-2-ethylcaproat, Zink(II)-stearat, Zink(II)-naphthenat, Zink(II)-acetylacetonat, Zinn(II)-n- octanoat, Zinn(II)-2-ethyl-l-hexanoat, Zinn(II)-ethylcaproat, Zinn(II)-laurat, Zinn(II)-palmitat, Dibutyl-zinn(IV)-oxid, Dibutylzinn(IV)-dichlorid, Dibutylzinn(IV)-diacetat, Dibutylzinn(IV)- dimaleat, Dibutylzinn(IV)-dilaurat, Dioctylzinn(IV)-diacetat, Molybdänglykolat sowie Tetraisopropyltitanat, Tetrabutyltitanat, Titan(IV)acetylacetonat, Aluminium-tri-sec-butylat, Aluminiumacetylacetonat, Aluminiumtriflat oder Zinntriflat oder beliebige Gemische solcher Katalysatoren verwendet werden. A catalyst is preferably added to accelerate curing. Suitable catalysts are metal salts and chelates, salts of transition metals or semimetals, acids or bases. Acids which can preferably be used are aromatic sulfonic acids, such as dodecylbenzenesulfonic acid, para-toluenesulfonic acid, trifluoromethanesulfonic acid and dinonylnaphthalenesulfonic acid, or sulfuric acid, acetic acid, trifluoroacetic acid or dibutyl phosphate. N-substituted amidines such as 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) and 1,5-diazabicyclo[5.4.0]undec-7-ene (DBU) can preferably be used as bases. As catalytically active metal salts and chelates, iron(III) chloride, aluminum tri(ethylacetoacetate), zinc chloride, zinc(II) n-octanoate, zinc(II) 2-ethyl-1-hexanoate, zinc(II )-2-ethylcaproate, zinc(II) stearate, zinc(II) naphthenate, zinc(II) acetylacetonate, tin(II) n-octanoate, tin(II) 2-ethyl-l-hexanoate, tin (II) ethyl caproate, tin(II) laurate, tin(II) palmitate, dibutyltin(IV) oxide, dibutyltin(IV) dichloride, dibutyltin(IV) diacetate, dibutyltin(IV) dimaleate, Dibutyltin(IV) dilaurate, dioctyltin(IV) diacetate, molybdenum glycolate and tetraisopropyl titanate, tetrabutyl titanate, titanium(IV) acetylacetonate, aluminum tri-sec-butoxide, aluminum acetylacetonate, aluminum triflate or tin triflate or any mixtures of such catalysts can be used.
Ein Gegenstand der vorliegenden Erfindung sind auch Beschichtungen, Klebungen und Dichtungen, erhältlich nach dem zuvor beschriebenen Verfahren.
The present invention also relates to coatings, adhesive bonds and seals obtainable by the process described above.
Experimenteller Teil - Beispiele Experimental part - examples
Alle Prozentangaben beziehen sich, soweit nichts Anderslautendes vermerkt, auf das Gewicht.All percentages are by weight unless otherwise noted.
Die Bestimmung der NCO-Gehalte sowie die Untersuchung der Deblockierungstemperatur erfolgte mittels des Lumos FTIR Mikroskops der Firma Bruker. The NCO contents were determined and the deblocking temperature was investigated using the Lumos FTIR microscope from Bruker.
Liste der Handelsnamen und Abkürzungen List of trade names and abbreviations
Desmodur ultra N 3600 wurde von der Firma Covestro Deutschland AG bezogen. Desmodur ultra N 3600 was purchased from Covestro Deutschland AG.
4-Hydroxybenzaldehyd wurde von der Firma Merck (Sigma Aldrich) bezogen. 4-Hydroxybenzaldehyde was purchased from Merck (Sigma Aldrich).
Vanillin wurde von der Firma Merck (Sigma Aldrich) bezogen. Vanillin was purchased from Merck (Sigma Aldrich).
Lösemittel wie Dimethylsulfoxid (wasserfrei) wurde von der Firma Merck (Sigma Aldrich) bezogen. Dibutylzinndilaurat (0.01%ig in Butylacetat) wurde von der Firma Merck (Sigma Aldrich) bezogen. Essigsäure wurde von der Firma Merck (Sigma Aldrich) bezogen. Solvents such as dimethyl sulfoxide (anhydrous) were purchased from Merck (Sigma Aldrich). Dibutyltin dilaurate (0.01% in butyl acetate) was purchased from Merck (Sigma Aldrich). Acetic acid was purchased from Merck (Sigma Aldrich).
Beispiel 1: Example 1:
9,97 g 4-Hydroxybenzaldehyd und die entsprechende Menge des Lösemittel zur Herstellung eines 50 Gew.-%igen Produktes wurden bei Raumtemperatur vorgelegt und das 4-Hydroxybenzaldehyd unter Rühren gelöst. Anschließend wurden 14,91 g Desmodur ultra N 3600 hinzugegeben und die Mischung unter Rühren homogenisiert. Es wurden 0,25 g Dibutylzinndilaurat-Lösung (0,01%ig in Butylacetat) zugeben und die Mischung unter stetigem Rühren auf 70°C erwärmt. Das Reaktionsgemisch wurde bei 70 °C gerührt bis der theoretische NCO Gehalt von 0,0 Gew.-% erreicht war. 9.97 g of 4-hydroxybenzaldehyde and the appropriate amount of solvent for the production of a 50% strength by weight product were introduced at room temperature and the 4-hydroxybenzaldehyde was dissolved with stirring. Then 14.91 g of Desmodur ultra N 3600 were added and the mixture was homogenized with stirring. 0.25 g of dibutyltin dilaurate solution (0.01% in butyl acetate) was added and the mixture heated to 70°C with constant stirring. The reaction mixture was stirred at 70° C. until the theoretical NCO content of 0.0% by weight was reached.
Beispiel 2 example 2
11,31 g Vanillin und die entsprechende Menge des Lösemittel zur Herstellung eines 50 Gew.-%igen Produktes wurden bei Raumtemperatur vorgelegt und das Vanillin unter Rühren gelöst. Anschließend wurden 13,57 g Desmodur ultra N 3600 hinzugegeben und die Mischung unter Rühren homogenisiert. Es wurden 0,25 g Dibutylzinndilaurat-Lösung (0,01%ig in Butylacetat) zugeben und die Mischung unter stetigem Rühren auf 70°C erwärmt. Das Reaktionsgemisch wurde bei 70 °C gerührt bis der theoretische NCO Gehalt von 0,0 Gew.-% erreicht war. 11.31 g of vanillin and the corresponding amount of solvent for the production of a 50% strength by weight product were introduced at room temperature and the vanillin was dissolved with stirring. Then 13.57 g of Desmodur ultra N 3600 were added and the mixture was homogenized with stirring. 0.25 g of dibutyltin dilaurate solution (0.01% in butyl acetate) was added and the mixture heated to 70°C with constant stirring. The reaction mixture was stirred at 70° C. until the theoretical NCO content of 0.0% by weight was reached.
Untersuchung der Deblockierungstemperaturen Study of deblocking temperatures
Die so hergestellten blockierten Polyisocyanate wurden hinsichtlich ihrer Deblockierung mittels IR Spektroskopie im Temperaturbereich von 100 bis 170 °C untersucht und aus den aufgenommen Spektren die Deblockierungstemperatur ermittelt. Die Deblockierungstemperatur wurde über die Abspaltung des Blockierungsmittels und der damit entstehenden Isocyanat-Bande, welche als NCO- Valenzschwingung zwischen 2300 und 2250 cm 1 ermittelt. Es wurde dabei auch der Einfluss von 0,5 Gew.-% Essigsäure als Deblockierungskatalysator untersucht. Tabelle 1 zeigt die ermittelten Deblockierungstemperaturen Tdebi. verschiedener Blockierungsmittel mit/ ohne 0,5 Gew.-% Essigsäure als Katalysator.
T abeile 1: Ermittelte Deblockierungstemperaturen Tdebi.
The blocked polyisocyanates produced in this way were examined with regard to their deblocking by means of IR spectroscopy in the temperature range from 100 to 170° C. and the deblocking temperature was determined from the spectra recorded. The deblocking temperature was determined via the elimination of the blocking agent and the resulting isocyanate band, which was determined as an NCO valence vibration between 2300 and 2250 cm 1 . The influence of 0.5% by weight acetic acid as a deblocking catalyst was also examined. Table 1 shows the determined deblocking temperatures T debi. various blocking agents with/without 0.5% by weight acetic acid as a catalyst. Table 1: Detected deblocking temperatures T debi .
Es wurde festgestellt, dass unter Verwendung von Vanillin als Blockierungsmittel eine Deblockierung bereits ab 100 °C, bei Verwendung von 4-Hydroxybenzaldehyd ab 140°C stattfindet.
It was found that when vanillin is used as a blocking agent, deblocking takes place from as little as 100°C, and when using 4-hydroxybenzaldehyde from 140°C.
Claims
1. Organische Polyisocyanate mit mindestens zwei Isocyanatgruppen, wobei mindestens ein Teil dieser Isocyanatgruppen mit Aldehyden der allgemeinen Formel I
in welcher RI für den Rest
steht, wobei R2 und R3 unabhängig voneinander für einen linearen oder verzweigten aliphatischen Rest mit bis zu 6 Kohlenstoffatomen, bevorzugt einen Methylen- oder Ethylenrest stehen, 1. Organic polyisocyanates having at least two isocyanate groups, at least some of these isocyanate groups having aldehydes of the general formula I in which RI for the rest where R 2 and R 3 are independently a linear or branched aliphatic radical having up to 6 carbon atoms, preferably a methylene or ethylene radical,
X und Y unabhängig voneinander für 0 oder 1 und bevorzugt beide für 0 stehen, und einer oder zwei der Reste R4 bis R7, im letztgenannten Fall unabhängig voneinander, für eine Alkoxygruppe mit bis zu 2 Kohlenstoffatomen und die übrigen dieser vier Reste für Wasserstoff stehen, und X and Y independently represent 0 or 1 and preferably both represent 0, and one or two of the radicals R 4 to R 7 , in the latter case independently of one another, represent an alkoxy group having up to 2 carbon atoms and the remaining of these four radicals represent hydrogen stand, and
Z für O, S oder N(H) steht, bevorzugt für O steht, blockiert ist. Z is O, S or N(H), preferably O, is blocked.
2 Organische Polyisocyanate gemäß Anspruch 1, umfassend mindestens ein Strukturelement der allgemeinen Formel II
wobei Z und RI die in Anspruch 1 genannte Bedeutung haben. 2 Organic polyisocyanates according to claim 1, comprising at least one structural element of the general formula II where Z and RI are as defined in claim 1.
3. Organische Polyisocyanate gemäß Anspruch 1 oder 2, wobei die organischen Polyisocyanate eine nichtionische, potentiell ionische und/oder ionische Hydrophilierung aufweisen.
3. Organic polyisocyanates according to claim 1 or 2, wherein the organic polyisocyanates have nonionic, potentially ionic and/or ionic hydrophilicity.
4. Verfahren zur Herstellung von blockierten organischen Polyisocyanaten, umfassend die oder bestehend aus der Umsetzung 4. A process for preparing blocked organic polyisocyanates, comprising or consisting of the reaction
Al) mindestens eines Aldehyds der allgemeinen Formel I
wobei Z und RI die in Anspruch 1 genannte Bedeutung haben, Al) at least one aldehyde of the general formula I where Z and RI are as defined in claim 1,
A2) mindestens eines Polyisocyanats mit mindestens zwei Isocyanatgruppen und A2) at least one polyisocyanate having at least two isocyanate groups and
A3) gegebenenfalls mindestens eines Hydrophilierungsmittels. A3) optionally at least one hydrophilizing agent.
5. Organische Polyisocyanate gemäß einem der Ansprüche 1 bis 3, bzw. Verfahren zur Herstellung von blockierten organischen Polyisocyanaten gemäß Anspruch 4, wobei die organischen Polyisocyanate auf Di- und Polyisocyanaten basieren, ausgewählt ist aus der Gruppe bestehend aus monomeren Diisocyanaten mit aliphatisch, cycloaliphatisch, araliphatisch und/oder aromatisch gebundenen Isocyanatgruppen und durch Modifizierung von monomeren aliphatischen, cycloaliphatischen, araliphatischen und/oder aromatischen Diisocyanaten erhältlichen oligomeren Di- oder Polyisocyanaten mit Uretdion-, Isocyanurat-, Allophanat-, Harnstoff-, Biuret-, Iminooxadiazindion- und/oder Oxadiazintrionstruktur. 5. Organic polyisocyanates according to any one of claims 1 to 3, or a process for the preparation of blocked organic polyisocyanates according to claim 4, wherein the organic polyisocyanates are based on di- and polyisocyanates selected from the group consisting of monomeric diisocyanates with aliphatic, cycloaliphatic, araliphatically and/or aromatically bound isocyanate groups and oligomeric di- or polyisocyanates with uretdione, isocyanurate, allophanate, urea, biuret, iminooxadiazinedione and/or oxadiazinetrione structure obtainable by modification of monomeric aliphatic, cycloaliphatic, araliphatic and/or aromatic diisocyanates .
6. Verfahren zur Herstellung von blockierten organischen Polyisocyanaten gemäß einem der Ansprüche 4 oder 5, wobei die Herstellung in einem Verhältnis der NCO-Gruppen der Komponente A2 zu den NCO-reaktiven Gruppen der Komponente Al und gegebenenfalls A3 von 0,6 bis 1,4, bevorzugt 0,8 bis 1,2, besonders bevorzugt 0,9 bis 1,1, am meisten bevorzugt 1 : 1 erfolgt. 6. Process for the preparation of blocked organic polyisocyanates according to one of claims 4 or 5, wherein the preparation in a ratio of the NCO groups of component A2 to the NCO-reactive groups of component A1 and optionally A3 of 0.6 to 1.4 , preferably 0.8 to 1.2, more preferably 0.9 to 1.1, most preferably 1:1.
7. Beschichtungsmittel, Klebstoffe und Dichtstoffe, wobei es sich bevorzugt um 1-K-Systeme handelt, enthaltend organische Polyisocyanate gemäß einem der Ansprüche 1 bis 3 oder 5, sowie die aus diesen Beschichtungsmitteln, Klebstoffen und Dichtstoffen erhältlichen Beschichtungen, Klebungen und Dichtungen. 7. Coatings, adhesives and sealants, which are preferably 1-component systems, containing organic polyisocyanates as claimed in any of claims 1 to 3 or 5, and the coatings, adhesives and sealants obtainable from these coatings, adhesives and seals.
8. Verfahren zur Herstellung von Beschichtungen, Klebungen und Dichtungen, wobei 8. Process for the production of coatings, bonds and seals, wherein
- mindestens ein organisches Polyisocyanat mit mindestens zwei Isocyanatgruppen, wobei mindestens ein Teil dieser Isocyanatgruppen mit Aldehyden der allgemeinen Formel I
in welcher - at least one organic polyisocyanate having at least two isocyanate groups, at least some of these isocyanate groups being bonded with aldehydes of the general formula I in which
R1 ein gesättigter oder ungesättigter, linearer oder verzweigter aliphatischer, ein gegebenenfalls substituierter aromatischer, heterocyclischer, cycloaliphatischer oder araliphatischer Rest mit bis zu 18 Kohlenstoffatomen ist, der bis zu drei Heteroatome aus der Reihe Sauerstoff, Schwefel oder Stickstoff enthalten kann, und R 1 is a saturated or unsaturated, linear or branched aliphatic, an optionally substituted aromatic, heterocyclic, cycloaliphatic or araliphatic radical with up to 18 carbon atoms, which can contain up to three heteroatoms from the group consisting of oxygen, sulfur or nitrogen, and
Z für O, S oder N(H) steht, bevorzugt für O steht, blockiert ist, Z represents O, S or N(H), preferably represents O, is blocked,
- unter Deblockierung mit mindestens einer Isocyanat-reaktiven Verbindung vernetzt wird. - Is crosslinked with deblocking with at least one isocyanate-reactive compound.
9. Verfahren gemäß Anspruch 8, wobei das mindestens eine organische Polyisocyanat mindestens ein Strukturelement der allgemeinen Formel II
umfasst, wobei Z und RI die in Anspruch 8 genannte Bedeutung haben. 9. The method according to claim 8, wherein the at least one organic polyisocyanate has at least one structural element of the general formula II comprises, where Z and RI have the meaning given in claim 8.
10. Verfahren gemäß Anspruch 8 oder 9, wobei das mindestens eine organische Polyisocyanat eine nichtionische, potentiell ionische und/oder ionische Hydrophilierung aufweist. 10. The method according to claim 8 or 9, wherein the at least one organic polyisocyanate has a nonionic, potentially ionic and / or ionic hydrophilicity.
11. Verfahren gemäß einem der Ansprüche 8 bis 10, wobei RI für den Rest
steht, wobei 11. The method according to any one of claims 8 to 10, wherein RI for the rest stands, where
R2 und R3 unabhängig voneinander für einen linearen oder verzweigten aliphatischen Rest mit bis zu 6 Kohlenstoffatomen, bevorzugt einen Methylen- oder Ethylenrest stehen, R 2 and R 3 independently represent a linear or branched aliphatic radical having up to 6 carbon atoms, preferably a methylene or ethylene radical,
X und Y unabhängig voneinander für 0 oder 1 und bevorzugt beide für 0 stehen, und R4 bis R7 unabhängig voneinander für Wasserstoff oder einen linearen oder verzweigten aliphatischen Rest mit bis zu 6 Kohlenstoffatomen, bevorzugt einen linearen aliphatischen Rest mit bis zu 2 Kohlenstoffatomen stehen, der Heteroatome, wie Sauerstoff, Schwefel oder Stickstoff, bevorzugt Sauerstoff, enthalten kann.
X and Y independently represent 0 or 1 and preferably both represent 0, and R 4 to R 7 independently represent hydrogen or a linear or branched aliphatic radical with up to 6 carbon atoms, preferably a linear aliphatic radical with up to 2 carbon atoms , The heteroatoms such as oxygen, sulfur or nitrogen, preferably oxygen, may contain.
12. Verfahren gemäß Anspruch 11, wobei bis zu 2 der Reste R4 bis R7 unabhängig voneinander für eine Alkoxygruppe mit bis zu 2 Kohlenstoffatomen und die übrigen dieser vier Reste für Wasserstoff stehen, und bevorzugt einer oder zwei der Reste R4 bis R7, im letztgenannten Fall unabhängig voneinander, für eine Alkoxygruppe mit bis zu 2 Kohlenstoffatomen und die übrigen dieser vier Reste für Wasserstoff stehen. 12. The method according to claim 11, wherein up to 2 of the radicals R 4 to R 7 independently represent an alkoxy group having up to 2 carbon atoms and the remaining of these four radicals represent hydrogen, and preferably one or two of the radicals R 4 to R 7 , in the latter case independently, represent an alkoxy group having up to 2 carbon atoms and the remaining of these four radicals are hydrogen.
13. Verfahren gemäß einem der Ansprüche 8 bis 12, wobei das mindestens eine organische Polyisocyanat auf Di- und Polyisocyanaten basiert, ausgewählt aus der Gruppe bestehend aus monomeren Diisocyanaten mit aliphatisch, cycloaliphatisch, araliphatisch und/oder aromatisch gebundenen Isocyanatgruppen und durch Modifizierung von monomeren aliphatischen, cycloaliphatischen, araliphatischen und/oder aromatischen Diisocyanaten erhältlichen oligomeren Di- oder Polyisocyanaten mit Uretdion-, Isocyanurat-, Allophanat-, Harnstoff-, Biuret-, Iminooxadiazindion- und/oder Oxadiazintrionstruktur. 13. The method according to any one of claims 8 to 12, wherein the at least one organic polyisocyanate is based on di- and polyisocyanates selected from the group consisting of monomeric diisocyanates with aliphatic, cycloaliphatic, araliphatic and / or aromatic bonded isocyanate groups and by modification of monomeric aliphatic Oligomeric di- or polyisocyanates with uretdione, isocyanurate, allophanate, urea, biuret, iminooxadiazinedione and/or oxadiazinetrione structure obtainable from cycloaliphatic, araliphatic and/or aromatic diisocyanates.
14. Verfahren gemäß einem der Ansprüche 8 bis 13, wobei die Vemetzungstemperaturen bei 100 bis 170 °C, bevorzugt bei 110 bis 150°C, besonders bevorzugt bei 100 bis 140 °C liegen. 14. The process as claimed in any of claims 8 to 13, where the crosslinking temperatures are from 100 to 170.degree. C., preferably from 110 to 150.degree. C., particularly preferably from 100 to 140.degree.
15. Verfahren gemäß einem der Ansprüche 8 bis 14, wobei in dem Verfahren ein oder mehrere Katalysatoren eingesetzt werden. 15. The method according to any one of claims 8 to 14, wherein one or more catalysts are used in the process.
16. Beschichtungen, Klebungen und Dichtungen, erhältlich nach einem Verfahren gemäß einem der Ansprüche 8 bis 15.
16. Coatings, bonds and seals obtainable by a method according to any one of claims 8 to 15.
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