US20010025096A1 - Polyisocyanates - Google Patents
Polyisocyanates Download PDFInfo
- Publication number
- US20010025096A1 US20010025096A1 US09/811,201 US81120101A US2001025096A1 US 20010025096 A1 US20010025096 A1 US 20010025096A1 US 81120101 A US81120101 A US 81120101A US 2001025096 A1 US2001025096 A1 US 2001025096A1
- Authority
- US
- United States
- Prior art keywords
- diisocyanate
- isocyanate
- groups
- polyisocyanate
- product
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000005056 polyisocyanate Substances 0.000 title claims abstract description 73
- 229920001228 polyisocyanate Polymers 0.000 title claims abstract description 73
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 64
- 239000012948 isocyanate Substances 0.000 claims abstract description 39
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000009257 reactivity Effects 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000007259 addition reaction Methods 0.000 claims abstract description 9
- 125000000524 functional group Chemical group 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims description 24
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 20
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 18
- -1 2,4,4-trimethylhexamethylene Chemical group 0.000 claims description 16
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 16
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 14
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 14
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 12
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 11
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 11
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 5
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 5
- PCHXZXKMYCGVFA-UHFFFAOYSA-N 1,3-diazetidine-2,4-dione Chemical compound O=C1NC(=O)N1 PCHXZXKMYCGVFA-UHFFFAOYSA-N 0.000 claims description 4
- 150000001718 carbodiimides Chemical class 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 4
- 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 claims description 3
- LUYHWJKHJNFYGV-UHFFFAOYSA-N 1,2-diisocyanato-3-phenylbenzene Chemical compound O=C=NC1=CC=CC(C=2C=CC=CC=2)=C1N=C=O LUYHWJKHJNFYGV-UHFFFAOYSA-N 0.000 claims description 3
- ROHUXHMNZLHBSF-UHFFFAOYSA-N 1,4-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CCC(CN=C=O)CC1 ROHUXHMNZLHBSF-UHFFFAOYSA-N 0.000 claims description 3
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 claims description 3
- DWIHAOZQQZSSBB-UHFFFAOYSA-N 1-isocyanato-1-(2-isocyanatopropyl)cyclohexane Chemical compound O=C=NC(C)CC1(N=C=O)CCCCC1 DWIHAOZQQZSSBB-UHFFFAOYSA-N 0.000 claims description 3
- LFSYUSUFCBOHGU-UHFFFAOYSA-N 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=CC=C1N=C=O LFSYUSUFCBOHGU-UHFFFAOYSA-N 0.000 claims description 3
- HTGCVLNFLVVCST-UHFFFAOYSA-N 1-piperazin-1-ylethanol Chemical compound CC(O)N1CCNCC1 HTGCVLNFLVVCST-UHFFFAOYSA-N 0.000 claims description 3
- QNIXMCINXVRKGG-UHFFFAOYSA-N 4-ethyl-1-isocyanato-4-(isocyanatomethyl)octane Chemical compound CCCCC(CC)(CN=C=O)CCCN=C=O QNIXMCINXVRKGG-UHFFFAOYSA-N 0.000 claims description 3
- PJMDLNIAGSYXLA-UHFFFAOYSA-N 6-iminooxadiazine-4,5-dione Chemical group N=C1ON=NC(=O)C1=O PJMDLNIAGSYXLA-UHFFFAOYSA-N 0.000 claims description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 3
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 claims description 3
- XXKOQQBKBHUATC-UHFFFAOYSA-N cyclohexylmethylcyclohexane Chemical compound C1CCCCC1CC1CCCCC1 XXKOQQBKBHUATC-UHFFFAOYSA-N 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 claims description 3
- 239000000806 elastomer Substances 0.000 claims description 3
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 3
- 239000006260 foam Substances 0.000 claims description 3
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 3
- 125000004957 naphthylene group Chemical group 0.000 claims description 3
- 239000003973 paint Substances 0.000 claims description 3
- HDOWRFHMPULYOA-UHFFFAOYSA-N piperidin-4-ol Chemical compound OC1CCNCC1 HDOWRFHMPULYOA-UHFFFAOYSA-N 0.000 claims description 3
- 239000000565 sealant Substances 0.000 claims description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 3
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 claims description 3
- 239000002966 varnish Substances 0.000 claims description 3
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims description 2
- PFJZOBRGDTYDQC-UHFFFAOYSA-N 1,4-diisocyanato-4-methylpentane Chemical compound O=C=NC(C)(C)CCCN=C=O PFJZOBRGDTYDQC-UHFFFAOYSA-N 0.000 claims description 2
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 claims description 2
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004472 Lysine Substances 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 230000008878 coupling Effects 0.000 claims description 2
- 238000010168 coupling process Methods 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 2
- HXSACZWWBYWLIS-UHFFFAOYSA-N oxadiazine-4,5,6-trione Chemical compound O=C1ON=NC(=O)C1=O HXSACZWWBYWLIS-UHFFFAOYSA-N 0.000 claims description 2
- 235000013772 propylene glycol Nutrition 0.000 claims description 2
- AHBNSOZREBSAMG-UHFFFAOYSA-N 1,5-diisocyanato-2-methylpentane Chemical compound O=C=NCC(C)CCCN=C=O AHBNSOZREBSAMG-UHFFFAOYSA-N 0.000 claims 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims 1
- 239000004202 carbamide Substances 0.000 claims 1
- 239000000047 product Substances 0.000 description 65
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 description 6
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 5
- 229940043232 butyl acetate Drugs 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 5
- 230000008092 positive effect Effects 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- KCZQSKKNAGZQSZ-UHFFFAOYSA-N 1,3,5-tris(6-isocyanatohexyl)-1,3,5-triazin-2,4,6-trione Chemical compound O=C=NCCCCCCN1C(=O)N(CCCCCCN=C=O)C(=O)N(CCCCCCN=C=O)C1=O KCZQSKKNAGZQSZ-UHFFFAOYSA-N 0.000 description 2
- NFDXQGNDWIPXQL-UHFFFAOYSA-N 1-cyclooctyldiazocane Chemical compound C1CCCCCCC1N1NCCCCCC1 NFDXQGNDWIPXQL-UHFFFAOYSA-N 0.000 description 2
- QDFXRVAOBHEBGJ-UHFFFAOYSA-N 3-(cyclononen-1-yl)-4,5,6,7,8,9-hexahydro-1h-diazonine Chemical compound C1CCCCCCC=C1C1=NNCCCCCC1 QDFXRVAOBHEBGJ-UHFFFAOYSA-N 0.000 description 2
- WADSJYLPJPTMLN-UHFFFAOYSA-N 3-(cycloundecen-1-yl)-1,2-diazacycloundec-2-ene Chemical compound C1CCCCCCCCC=C1C1=NNCCCCCCCC1 WADSJYLPJPTMLN-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000012973 diazabicyclooctane Substances 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].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 YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 description 1
- LFTMJBWNOFFSRW-UHFFFAOYSA-N 1,2-Butanedithiol Chemical compound CCC(S)CS LFTMJBWNOFFSRW-UHFFFAOYSA-N 0.000 description 1
- XBYRMPXUBGMOJC-UHFFFAOYSA-N 1,2-dihydropyrazol-3-one Chemical class OC=1C=CNN=1 XBYRMPXUBGMOJC-UHFFFAOYSA-N 0.000 description 1
- YGKHJWTVMIMEPQ-UHFFFAOYSA-N 1,2-propanedithiol Chemical compound CC(S)CS YGKHJWTVMIMEPQ-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- IXRAZHMEXBNECJ-UHFFFAOYSA-N 1-aminopropane-1-thiol Chemical compound CCC(N)S IXRAZHMEXBNECJ-UHFFFAOYSA-N 0.000 description 1
- HKNNAYPWWDWHFR-UHFFFAOYSA-N 1-sulfanylbutan-1-ol Chemical compound CCCC(O)S HKNNAYPWWDWHFR-UHFFFAOYSA-N 0.000 description 1
- AEUVIXACNOXTBX-UHFFFAOYSA-N 1-sulfanylpropan-1-ol Chemical compound CCC(O)S AEUVIXACNOXTBX-UHFFFAOYSA-N 0.000 description 1
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 description 1
- LJDSTRZHPWMDPG-UHFFFAOYSA-N 2-(butylamino)ethanol Chemical compound CCCCNCCO LJDSTRZHPWMDPG-UHFFFAOYSA-N 0.000 description 1
- MGUMZJAQENFQKN-UHFFFAOYSA-N 2-(cyclohexylamino)ethanol Chemical compound OCCNC1CCCCC1 MGUMZJAQENFQKN-UHFFFAOYSA-N 0.000 description 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 1
- JCBPETKZIGVZRE-UHFFFAOYSA-N 2-aminobutan-1-ol Chemical compound CCC(N)CO JCBPETKZIGVZRE-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- CCTFMNIEFHGTDU-UHFFFAOYSA-N 3-methoxypropyl acetate Chemical compound COCCCOC(C)=O CCTFMNIEFHGTDU-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-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
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 150000001622 bismuth compounds Chemical class 0.000 description 1
- 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 1
- 235000013877 carbamide Nutrition 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- UFULAYFCSOUIOV-UHFFFAOYSA-O cysteaminium Chemical compound [NH3+]CCS UFULAYFCSOUIOV-UHFFFAOYSA-O 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229940102253 isopropanolamine Drugs 0.000 description 1
- 229960003151 mercaptamine Drugs 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N tolylenediamine group Chemical group CC1=C(C=C(C=C1)N)N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003755 zirconium compounds Chemical class 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
- C08G18/80—Masked polyisocyanates
- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
- C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
- C08G18/8012—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with diols
- C08G18/8016—Masked aliphatic or cycloaliphatic polyisocyanates
-
- 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
- C08G18/02—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only
-
- 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
-
- 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
- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
- C08G18/8041—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3271
Definitions
- the present invention relates to polyisocyanates based on two different diisocyanates or polyisocyanates and to a process for preparing them.
- polyisocyanates can generally be advantageously used, inter alia, as building blocks for polyurethane production, e.g. for producing paints and varnishes, coatings, adhesives, sealants, pourable elastomers or foams.
- Polyisocyanates based on different diisocyanates or diisocyanates and polyisocyanates can be used particularly advantageously for the abovementioned purposes, but their commercial availability is limited.
- EP-A-755 954 describes the cotrimerization of tolylene diisocyanate (TDI) and hexamethylene diisocyanate (HDI) so as to obtain a polyisocyanate mixture containing isocyanurate groups for the production of polyurethane coating compositions.
- This product is meant to combine the positive properties of the two isocyanates in PU coating systems, high reactivity and hardness of the aromatic isocyanate and the light stability and resistance to chemicals of the aliphatic isocyanate.
- this reaction gives a very nonuniform product mixture which comprises mainly the homotrimers of tolylene diisocyanate and of hexamethylene diisocyanate and only small proportions of the cotrimers.
- the reaction is continued to only a partial conversion and unreacted diisocyanates are subsequently removed from the reaction mixture by distillation under reduced pressure.
- EP-A-47452 describes the cotrimerization of hexamethylene diisocyanate and isophorone diisocyanate (IPDI). Since the reactivities of the NCO groups of HDI and IPDI are not very different, the cotrimerization is successful here but gives an oligomer mixture having a random HDI/IPDI product distribution. Hereto, unreacted diisocyanate is removed from the reaction mixture by vacuum distillation after the reaction.
- a further object is to provide a process for preparing these polyisocyanates.
- the invention accordingly provides a process for preparing polyisocyanates, which comprises
- the invention further provides the polyisocyanates prepared by this process.
- the invention also provides for the use of the polyisocyanates of the present invention as building blocks for producing paints and varnishes, coatings, adhesives, sealants, pourable elastomers or foams and provides polyaddition products obtainable using the polyisocyanates of the present invention.
- Possible diisocyanates I are the aliphatic, cycloaliphatic and aromatic isocyanates known from the prior art.
- Preferred diisocyanates I are diphenylmethane 4,4′-diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane 4,4′-diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, dodecyl diisocyanate, 1,3- and 1,4-bis(isocyanatomethyl)cyclohexane, lysine alkyl ester diisocyanate, where alkyl is C 1 -C 10 -alkyl, 2,2,4- or 2,4,4-trimethylhexamethylene 1,6-diisocyanate and 1,4-diisocyanatocyclohexane.
- diisocyanates having NCO groups of differing reactivity for example tolylene 2,4-diisocyanate (2,4-TDI), diphenylmethane 2,4′-diisocyanate (2,4′-MDI), isophorone diisocyanate (IPDI), 2-butyl-2-ethylpentamethylene diisocyanate, 2-isocyanatopropylcyclohexyl isocyanate, 3(4)-isocyanatomethyl-1-methylcyclohexyl isocyanate, 1,4-diisocyanato-4-methylpentane, dicyclohexylmethane 2,4′-diisocyanate and 4-methylcyclohexane 1,3-diisocyanate (H-TDI).
- tolylene 2,4-diisocyanate (2,4-TDI)
- diphenylmethane 2,4′-diisocyanate (2,4′-MDI
- IPDI iso
- diisocyanates whose NCO groups initially have the same reactivity but in which addition of an alcohol or amine to a first NCO group induces a decrease in the reactivity of the second NCO group.
- isocyanates whose NCO groups are coupled via a delocalized electron system e.g. phenylene 1,3- and 1,4-diisocyanate, naphthylene 1,5-diisocyanate, biphenyl diisocyanate, tolidine diisocyanate or tolylene 2,6-diisocyanate.
- Possible diisocyanates and polyisocyanates II are all aliphatic, cycloaliphatic and aromatic isocyanates known from the prior art. Apart from the abovementioned diisocyanates and polyisocyanates, it is also possible to use, for example, oligoisocyanates or polyisocyanates which can be prepared from the abovementioned diisocyanates or mixtures thereof by coupling by means of urethane, allophanate, ureas, biuret, uretdione, amide, isocyanurate, carbodiimide, uretonimine, oxadiazinetrione or iminooxadiazinedione structures.
- diisocyanates and polyisocyanates II particular preference is given to using diphenylmethane 4,4′-diisocyanate, mixtures of diphenylmethane diisocyanates and oligomeric diphenylmethane diisocyanates (polymeric MDI), phenylene 1,3- and 1,4-diisocyanate, isophorone diisocyanate, oligomers of isophorone diisocyanate containing isocyanurate, uretdione, urethane or allophanate groups, hexamethylene diisocyanate, oligomers of hexamethylene diisocyanate containing isocyanurate, uretdione, urethane, allophanate, iminooxadiazinedione or biuret groups, 4-isocyanatomethyloctamethylene 1,8-diisocyanate, oligomers of MDI containing urethane, allo
- the diisocyanates and polyisocyanates II used have a mean functionality of at least 2, in particular from 2 to 8.
- the diisocyanates or polyisocyanates II used are isocyanates having a mean functionality of more than 2, preferably from 2.1 to 5.
- the compounds (b) having two isocyanate-reactive groups which are used in the preparation of the addition product (A) are selected from among compounds containing hydroxyl groups, mercapto groups or amino groups. Preference is given to hydroxyl groups and amino groups.
- isocyanate-reactive compounds whose functional groups which are reactive toward isocyanate initially have the same reactivity but in which addition of at least one isocyanate can induce a reactivity decrease in the second isocyanate-reactive group as a result of steric or electronic effects.
- Examples of compounds (b) having two groups which are reactive toward isocyanate are ethylene glycol, diethylene glycol, triethylene glycol, 1,2- and 1,3-propanediol, neopentyl glycol, 1,2-, 1,3- and 1,4-butanediol, 1,2-, 1,3- and 1,5-pentanediol, hexanediol, propane-1,2-dithiol, butane-1,2-dithiol, mercaptoethanol, mercaptopropanol, mercaptobutanol, ethylenediamine, tolylenediamine, isophoronediamine, cysteamine, ethanolamine, N-methylethanolamine, propanolamine, isopropanolamine, 2-(butylamino)ethanol, 2-(cyclohexylamino)ethanol, 2-amino-1-butanol, 2-(2′-aminoethoxy)ethanol or higher alkoxylation products
- the reaction to form the addition product (A) usually takes place at from ⁇ 20 to 120° C., preferably from ⁇ 15 to 100° C.
- the diisocyanate I is placed in the reaction vessel first and the compound (b) is added.
- the addition products (A) are usually not stable over a prolonged period and are therefore preferably reacted immediately after their preparation with the diisocyanate or polyisocyanate II.
- the addition product (A) can be converted by means of an intermolecular addition reaction of the addition product (A) into a polyaddition product (P).
- the isocyanate-reactive group of the addition product (A) adds onto the isocyanate group of a further molecule of the addition product (A).
- the number of molecules of the addition product (A) which are added to form a polyaddition product (P) is generally not restricted. From a practical point of view, the addition reaction is usually stopped before the polyaddition product (P) has, for example due to an excessively high molecular weight or for steric reasons, acquired disadvantageous properties such as an excessively high viscosity or an excessively poor solubility.
- the resultant polyaddition products (P) have one group which is reactive toward isocyanate and one isocyanate group.
- the intermolecular polyaddition reaction of an addition product (A) to form a polyaddition product (P) can usually be carried out in situ after the reaction to form the addition product (A) is complete by increasing the temperature.
- Suitable catalysts are generally compounds which catalyze the urethane reaction, for example amines, ammonium compounds, organic aluminum compounds, organic tin compounds, organic titanium compounds, organic zirconium compounds or organic bismuth compounds.
- DABCO diazabicyclooctane
- DBN diazabicyclononene
- DBU diazabicycloundecene
- titanium tetrabutoxide titanium tetrabutoxide
- dibutyltin dilaurate zirconium acetylacetonate and mixtures thereof.
- the catalyst is generally added in an amount of from 50 to 10,000 ppm by weight, preferably from 100 to 5000 ppm by weight, based on the amount of isocyanate used.
- the intermolecular polyaddition reaction can be controlled both by addition of a suitable catalyst and by selection of a suitable temperature.
- the temperature can be reduced to a level at which the addition reaction ceases and the addition product (A) or the polyaddition product (P) is storage-stable.
- a diisocyanate or polyisocyanate II is added to stop the polyaddition reaction (P) as soon as the intermolecular addition reaction of the addition product (A) has produced a polyaddition product (P) having the desired degree of polyaddition.
- the diisocyanate or polyisocyanate II can be added to an addition product (A) which has not yet been reacted in an intermolecular addition reaction to give a polyaddition product (P).
- the reaction of the diisocyanate I with compounds (b) containing two groups which are reactive toward isocyanate is generally carried out in an equimolar ratio. It is also possible to use the isocyanate-reactive component (b) in a small molar excess so as to bring about essentially complete reaction of the diisocyanate I. In both procedures, an advantage is that a possibly complicated removal of an unreacted diisocyanate I is dispensed with.
- the reaction of the addition product (A) and/or the polyaddition product (P) with the diisocyanate or polyisocyanate II it is usual to react at least one isocyanate group of the diisocyanate or polyisocyanate II with the isocyanate-reactive group of the addition product (A) and/or the polyaddition product (P).
- at least 10%, in particular at least 40% and particularly preferably 50-100%, of the free isocyanate groups of the diisocyanate or polyisocyanate II are reacted with a corresponding number of equivalents of an addition product (A) and/or polyaddition product (P) to form the polyisocyanate of the present invention.
- one isocyanate group of a diisocyanate or polyisocyanate II is firstly reacted with an addition product (A1) or a polyaddition product (P1), followed by reaction of at least one further isocyanate group of the diisocyanate or polyisocyanate II with an addition product (A2) or a polyaddition product (P2), with the addition products (A1) and (A2) or the polyaddition products (P1) and (P2) not being identical.
- the preparation of the polyisocyanates of the present invention is usually carried out in solvents.
- solvents it is generally possible to use all solvents which are inert toward the respective starting materials.
- organic solvents such as diethyl ether, tetrahydrofuran, acetone, 2-butanone, methyl isobutyl ketone, ethyl acetate, butyl acetate, benzene, toluene, chlorobenzene, xylene, methoxyethyl acetate, methoxypropyl acetate, dimethylformamide, dimethylacetamide or solvent naphtha.
- organic solvents such as diethyl ether, tetrahydrofuran, acetone, 2-butanone, methyl isobutyl ketone, ethyl acetate, butyl acetate, benzene, toluene, chlorobenzene, xylene, methoxyethyl a
- the preparation of the polyisocyanates of the present invention is usually carried out in a pressure range from 2 mbar to 20 bar, preferably at atmospheric pressure, in reactors or reactor cascades which can be operated batchwise, semicontinuously or continuously.
- the polyisocyanates obtained by the process of the present invention can, if required, also be made hydrophobic, made hydrophilic or their functional groups can be modified.
- the NCO-terminated products are reacted or partially reacted with, for example, fatty alcohols, fatty amines, hydroxycarboxylic acids, hydroxysulfonic acids, amino acids or monoalcohols containing acrylate groups, e.g. hydroxyethyl acrylate or hydroxyethyl methacrylate.
- the isocyanate groups of the polyisocyanates of the present invention can also be present in capped form.
- Suitable capping agents for NCO groups are, for example, oximes, phenols, imidazoles, triazoles, pyrazoles, pyrazolinones, diketopiperazines, caprolactam, malonic esters or compounds as are mentioned in the publications by Z. W. Wicks, Prog. Org. Coat. 3 (1975), 73-99 and Prog. Org. Coat. 9 (1981), 3-28 and also in Houben-Weyl, Methoden der Organischen Chemie, Volume XIV/2, 61 ff., Georg Thieme Verlag, Stuttgart 1963.
- the present invention makes it possible to obtain the desired properties of the polyisocyanates of the present invention by specific choice of the appropriate starting materials, in particular the diisocyanates I or diisocyanates or polyisocyanates II.
- the polyisocyanates of the present invention make it possible, for example, to combine positive properties of customary aromatic isocyanates with positive properties of customary aliphatic isocyanates or to combine the positive properties of customary aliphatic isocyanates with the positive properties of customary cycloaliphatic isocyanates.
- a polyisocyanate according to the present invention is prepared from HDI isocyanurate oligomer as diisocyanate or polyisocyanate II and TDI as diisocyanate I, this polyisocyanate molecule can, depending the choice of the amount of the isocyanate II, contain both aromatic and aliphatic NCO groups which have significantly different reactivities. These different NCO reactivities within a polyisocyanate molecule can then be utilized advantageously in industry.
- a polyisocyanate according to the present invention is prepared from HDI isocyanurate oligomer as diisocyanate or polyisocyanate II and IPDI as diisocyanate I, then a PU coating composition produced using this polyisocyanate can have both properties such as elasticity and flexibility and properties such as hardness, scratch resistance and resistance to chemicals.
- a further advantage of the process of the present invention is that it can be carried out economically.
- Both the reaction of diisocyanate I to form an addition product (A) and/or polyaddition product (P) and the reaction of (A) or (P) with a diisocyanate or polyisocyanate II to give the polyisocyanate of the present invention can be carried out in one reaction apparatus and without a distillation step, which is technically and economically advantageous.
Abstract
Polyisocyanates are prepared by a process which comprises
(i) preparation of an addition product (A) which contains one group which is reactive toward isocyanate and one isocyanate group by reacting
(a) a diisocyanate I with
(b) compounds containing two groups which are reactive toward isocyanate, where at least one of the components (a) or (b) has functional groups having differing reactivities toward the functional groups of the other component,
(ii) if desired, intermolecular addition reaction of the addition product (A) to form a polyaddition product (P) which contains one group which is reactive toward isocyanate and one isocyanate group and
(iii) reaction of the addition product (A) and/or the polyaddition product (P) with a diisocyanate or polyisocyanate II which is different from diisocyanate I.
Description
- The present invention relates to polyisocyanates based on two different diisocyanates or polyisocyanates and to a process for preparing them.
- In industry, polyisocyanates can generally be advantageously used, inter alia, as building blocks for polyurethane production, e.g. for producing paints and varnishes, coatings, adhesives, sealants, pourable elastomers or foams.
- Polyisocyanates based on different diisocyanates or diisocyanates and polyisocyanates can be used particularly advantageously for the abovementioned purposes, but their commercial availability is limited.
- Thus, EP-A-755 954 describes the cotrimerization of tolylene diisocyanate (TDI) and hexamethylene diisocyanate (HDI) so as to obtain a polyisocyanate mixture containing isocyanurate groups for the production of polyurethane coating compositions. This product is meant to combine the positive properties of the two isocyanates in PU coating systems, high reactivity and hardness of the aromatic isocyanate and the light stability and resistance to chemicals of the aliphatic isocyanate. However, owing to the large reactivity differences between the aromatically bound and aliphatically bound NCO groups of the starting materials, this reaction gives a very nonuniform product mixture which comprises mainly the homotrimers of tolylene diisocyanate and of hexamethylene diisocyanate and only small proportions of the cotrimers. The reaction is continued to only a partial conversion and unreacted diisocyanates are subsequently removed from the reaction mixture by distillation under reduced pressure.
- EP-A-47452 describes the cotrimerization of hexamethylene diisocyanate and isophorone diisocyanate (IPDI). Since the reactivities of the NCO groups of HDI and IPDI are not very different, the cotrimerization is successful here but gives an oligomer mixture having a random HDI/IPDI product distribution. Hereto, unreacted diisocyanate is removed from the reaction mixture by vacuum distillation after the reaction.
- It is an object of the present invention to provide polyisocyanates which, owing to their defined structure, combine advantageous properties such as high reactivity, low viscosity and good solubility and can be prepared by simple means, i.e. if possible without work-up by distillation. A further object is to provide a process for preparing these polyisocyanates.
- We have found that these objects are achieved by reacting an addition product (A) and/or a polyaddition product (P) which is obtainable by reacting a diisocyanate I with a compound which is reactive toward isocyanate and has one group which is reactive toward isocyanate and one isocyanate group with a diisocyanate or polyisocyanate II which is different from diisocyanate I.
- The invention accordingly provides a process for preparing polyisocyanates, which comprises
- (i) preparation of an addition product (A) which contains one group which is reactive toward isocyanate and one isocyanate group by reacting
- (a) a diisocyanate I with
- (b) compounds containing two groups which are reactive toward isocyanate, where at least one of the components (a) or (b) has functional groups having differing reactivities toward the functional groups of the other component,
- (ii) if desired, intermolecular addition reaction of the addition product (A) to form a polyaddition product (P) which contains one group which is reactive toward isocyanate and one isocyanate group and
- (iii) reaction of the addition product (A) and/or the polyaddition product (P) with a diisocyanate or polyisocyanate II which is different from diisocyanate I.
- The invention further provides the polyisocyanates prepared by this process.
- The invention also provides for the use of the polyisocyanates of the present invention as building blocks for producing paints and varnishes, coatings, adhesives, sealants, pourable elastomers or foams and provides polyaddition products obtainable using the polyisocyanates of the present invention.
- Possible diisocyanates I are the aliphatic, cycloaliphatic and aromatic isocyanates known from the prior art. Preferred diisocyanates I are diphenylmethane 4,4′-diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane 4,4′-diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, dodecyl diisocyanate, 1,3- and 1,4-bis(isocyanatomethyl)cyclohexane, lysine alkyl ester diisocyanate, where alkyl is C1-C10-alkyl, 2,2,4- or 2,4,4-trimethylhexamethylene 1,6-diisocyanate and 1,4-diisocyanatocyclohexane.
- Particular preference is given to diisocyanates having NCO groups of differing reactivity, for example tolylene 2,4-diisocyanate (2,4-TDI), diphenylmethane 2,4′-diisocyanate (2,4′-MDI), isophorone diisocyanate (IPDI), 2-butyl-2-ethylpentamethylene diisocyanate, 2-isocyanatopropylcyclohexyl isocyanate, 3(4)-isocyanatomethyl-1-methylcyclohexyl isocyanate, 1,4-diisocyanato-4-methylpentane, dicyclohexylmethane 2,4′-diisocyanate and 4-methylcyclohexane 1,3-diisocyanate (H-TDI).
- Particular preference is also given to diisocyanates whose NCO groups initially have the same reactivity but in which addition of an alcohol or amine to a first NCO group induces a decrease in the reactivity of the second NCO group. Examples are isocyanates whose NCO groups are coupled via a delocalized electron system, e.g. phenylene 1,3- and 1,4-diisocyanate, naphthylene 1,5-diisocyanate, biphenyl diisocyanate, tolidine diisocyanate or tolylene 2,6-diisocyanate.
- Possible diisocyanates and polyisocyanates II are all aliphatic, cycloaliphatic and aromatic isocyanates known from the prior art. Apart from the abovementioned diisocyanates and polyisocyanates, it is also possible to use, for example, oligoisocyanates or polyisocyanates which can be prepared from the abovementioned diisocyanates or mixtures thereof by coupling by means of urethane, allophanate, ureas, biuret, uretdione, amide, isocyanurate, carbodiimide, uretonimine, oxadiazinetrione or iminooxadiazinedione structures.
- As diisocyanates and polyisocyanates II, particular preference is given to using diphenylmethane 4,4′-diisocyanate, mixtures of diphenylmethane diisocyanates and oligomeric diphenylmethane diisocyanates (polymeric MDI), phenylene 1,3- and 1,4-diisocyanate, isophorone diisocyanate, oligomers of isophorone diisocyanate containing isocyanurate, uretdione, urethane or allophanate groups, hexamethylene diisocyanate, oligomers of hexamethylene diisocyanate containing isocyanurate, uretdione, urethane, allophanate, iminooxadiazinedione or biuret groups, 4-isocyanatomethyloctamethylene 1,8-diisocyanate, oligomers of MDI containing urethane, allophanate, carbodiimide or uretonimine groups or oligomers of TDI containing urethane, allophanate, carbodiimide or uretonimine groups.
- In general, the diisocyanates and polyisocyanates II used have a mean functionality of at least 2, in particular from 2 to 8. In a preferred embodiment, the diisocyanates or polyisocyanates II used are isocyanates having a mean functionality of more than 2, preferably from 2.1 to 5.
- Both for the diisocyanates I and for the diisocyanates and polyisocyanates II, it is also possible to use mixtures of the isocyanates mentioned.
- The compounds (b) having two isocyanate-reactive groups which are used in the preparation of the addition product (A) are selected from among compounds containing hydroxyl groups, mercapto groups or amino groups. Preference is given to hydroxyl groups and amino groups.
- In the preparation of the addition product (A), it is likewise possible to use compounds (b) having two isocyanate-reactive groups selected from among the abovementioned functional groups or mixtures thereof and having differing reactivities toward NCO groups. Preference is here given to compounds having one primary and one secondary or tertiary hydroxyl group, one hydroxyl group and one mercapto group or one hydroxyl group and one amino group in the molecule, since the reactivity of the amino group in the reaction with isocyanate is significantly higher than that of the hydroxyl group.
- Preference is also given to isocyanate-reactive compounds whose functional groups which are reactive toward isocyanate initially have the same reactivity but in which addition of at least one isocyanate can induce a reactivity decrease in the second isocyanate-reactive group as a result of steric or electronic effects.
- Examples of compounds (b) having two groups which are reactive toward isocyanate are ethylene glycol, diethylene glycol, triethylene glycol, 1,2- and 1,3-propanediol, neopentyl glycol, 1,2-, 1,3- and 1,4-butanediol, 1,2-, 1,3- and 1,5-pentanediol, hexanediol, propane-1,2-dithiol, butane-1,2-dithiol, mercaptoethanol, mercaptopropanol, mercaptobutanol, ethylenediamine, tolylenediamine, isophoronediamine, cysteamine, ethanolamine, N-methylethanolamine, propanolamine, isopropanolamine, 2-(butylamino)ethanol, 2-(cyclohexylamino)ethanol, 2-amino-1-butanol, 2-(2′-aminoethoxy)ethanol or higher alkoxylation products of ammonia, 4-hydroxypiperidine, 1-hydroxyethylpiperazine, aminopropanethiol or bifunctional polyetherols or polyesterols. Particular preference is given to 1,2-propanediol, 1,2- and 1,3-butanediol, ethanolamine, propanolamine, mercaptoethanol, 4-hydroxypiperidine and 1-hydroxyethylpiperazine.
- It is also possible to use mixtures of the compounds mentioned.
- In the preparation of the addition product (A), it is necessary for the ratio of diisocyanate I to compounds (b) containing two groups which are reactive toward isocyanate to be equimolar, so that the resulting addition product (A) contains one group which is reactive toward isocyanate and one free NCO group.
- The reaction to form the addition product (A) usually takes place at from −20 to 120° C., preferably from −15 to 100° C. In a preferred embodiment, the diisocyanate I is placed in the reaction vessel first and the compound (b) is added. The addition products (A) are usually not stable over a prolonged period and are therefore preferably reacted immediately after their preparation with the diisocyanate or polyisocyanate II.
- In a preferred embodiment, the addition product (A) can be converted by means of an intermolecular addition reaction of the addition product (A) into a polyaddition product (P). Here, the isocyanate-reactive group of the addition product (A) adds onto the isocyanate group of a further molecule of the addition product (A). The number of molecules of the addition product (A) which are added to form a polyaddition product (P) is generally not restricted. From a practical point of view, the addition reaction is usually stopped before the polyaddition product (P) has, for example due to an excessively high molecular weight or for steric reasons, acquired disadvantageous properties such as an excessively high viscosity or an excessively poor solubility.
- The resultant polyaddition products (P) have one group which is reactive toward isocyanate and one isocyanate group.
- The intermolecular polyaddition reaction of an addition product (A) to form a polyaddition product (P) can usually be carried out in situ after the reaction to form the addition product (A) is complete by increasing the temperature.
- Furthermore, it is also possible to add a suitable catalyst or a suitable catalyst mixture. Suitable catalysts are generally compounds which catalyze the urethane reaction, for example amines, ammonium compounds, organic aluminum compounds, organic tin compounds, organic titanium compounds, organic zirconium compounds or organic bismuth compounds.
- Examples which may be mentioned are diazabicyclooctane (DABCO), diazabicyclononene (DBN) and diazabicycloundecene (DBU), titanium tetrabutoxide, dibutyltin dilaurate, zirconium acetylacetonate and mixtures thereof.
- The catalyst is generally added in an amount of from 50 to 10,000 ppm by weight, preferably from 100 to 5000 ppm by weight, based on the amount of isocyanate used.
- Furthermore, the intermolecular polyaddition reaction can be controlled both by addition of a suitable catalyst and by selection of a suitable temperature.
- There are various possible ways of stopping the intermolecular polyaddition reaction. For example, the temperature can be reduced to a level at which the addition reaction ceases and the addition product (A) or the polyaddition product (P) is storage-stable.
- In a preferred embodiment, a diisocyanate or polyisocyanate II is added to stop the polyaddition reaction (P) as soon as the intermolecular addition reaction of the addition product (A) has produced a polyaddition product (P) having the desired degree of polyaddition.
- Reaction of the polyaddition product (P) with the diisocyanate or polyisocyanate II gives the polyisocyanates of the present invention.
- As an alternative, the diisocyanate or polyisocyanate II can be added to an addition product (A) which has not yet been reacted in an intermolecular addition reaction to give a polyaddition product (P).
- However, it is usually advantageous in industry to carry out the intermolecular addition reaction to at least a small extent, since small amounts of unreacted diisocyanate I may still be present as impurity in the addition product (A) and these impurities can then be incorporated into the polyaddition product (P) by means of the intermolecular polyaddition reaction.
- The reaction of the diisocyanate I with compounds (b) containing two groups which are reactive toward isocyanate is generally carried out in an equimolar ratio. It is also possible to use the isocyanate-reactive component (b) in a small molar excess so as to bring about essentially complete reaction of the diisocyanate I. In both procedures, an advantage is that a possibly complicated removal of an unreacted diisocyanate I is dispensed with.
- In the reaction of the addition product (A) and/or the polyaddition product (P) with the diisocyanate or polyisocyanate II, it is usual to react at least one isocyanate group of the diisocyanate or polyisocyanate II with the isocyanate-reactive group of the addition product (A) and/or the polyaddition product (P). In a preferred embodiment, at least 10%, in particular at least 40% and particularly preferably 50-100%, of the free isocyanate groups of the diisocyanate or polyisocyanate II are reacted with a corresponding number of equivalents of an addition product (A) and/or polyaddition product (P) to form the polyisocyanate of the present invention.
- In a further embodiment, one isocyanate group of a diisocyanate or polyisocyanate II is firstly reacted with an addition product (A1) or a polyaddition product (P1), followed by reaction of at least one further isocyanate group of the diisocyanate or polyisocyanate II with an addition product (A2) or a polyaddition product (P2), with the addition products (A1) and (A2) or the polyaddition products (P1) and (P2) not being identical. In this embodiment, preference is given to using a diisocyanate or polyisocyanate II which has isocyanate groups of differing reactivity toward the isocyanate-reactive groups of the components (A) and/or (P).
- The preparation of the polyisocyanates of the present invention is usually carried out in solvents. Here, it is generally possible to use all solvents which are inert toward the respective starting materials. Preference is given to using organic solvents such as diethyl ether, tetrahydrofuran, acetone, 2-butanone, methyl isobutyl ketone, ethyl acetate, butyl acetate, benzene, toluene, chlorobenzene, xylene, methoxyethyl acetate, methoxypropyl acetate, dimethylformamide, dimethylacetamide or solvent naphtha.
- The preparation of the polyisocyanates of the present invention is usually carried out in a pressure range from 2 mbar to 20 bar, preferably at atmospheric pressure, in reactors or reactor cascades which can be operated batchwise, semicontinuously or continuously.
- The abovementioned setting of the reaction conditions and possibly the choice of a suitable solvent enables the products according to the present invention to be processed further without further purification after their preparation.
- The polyisocyanates obtained by the process of the present invention can, if required, also be made hydrophobic, made hydrophilic or their functional groups can be modified. For this purpose, the NCO-terminated products are reacted or partially reacted with, for example, fatty alcohols, fatty amines, hydroxycarboxylic acids, hydroxysulfonic acids, amino acids or monoalcohols containing acrylate groups, e.g. hydroxyethyl acrylate or hydroxyethyl methacrylate.
- The isocyanate groups of the polyisocyanates of the present invention can also be present in capped form. Suitable capping agents for NCO groups are, for example, oximes, phenols, imidazoles, triazoles, pyrazoles, pyrazolinones, diketopiperazines, caprolactam, malonic esters or compounds as are mentioned in the publications by Z. W. Wicks, Prog. Org. Coat. 3 (1975), 73-99 and Prog. Org. Coat. 9 (1981), 3-28 and also in Houben-Weyl, Methoden der Organischen Chemie, Volume XIV/2, 61 ff., Georg Thieme Verlag, Stuttgart 1963.
- The present invention makes it possible to obtain the desired properties of the polyisocyanates of the present invention by specific choice of the appropriate starting materials, in particular the diisocyanates I or diisocyanates or polyisocyanates II. Thus, the polyisocyanates of the present invention make it possible, for example, to combine positive properties of customary aromatic isocyanates with positive properties of customary aliphatic isocyanates or to combine the positive properties of customary aliphatic isocyanates with the positive properties of customary cycloaliphatic isocyanates.
- If, for example, a polyisocyanate according to the present invention is prepared from HDI isocyanurate oligomer as diisocyanate or polyisocyanate II and TDI as diisocyanate I, this polyisocyanate molecule can, depending the choice of the amount of the isocyanate II, contain both aromatic and aliphatic NCO groups which have significantly different reactivities. These different NCO reactivities within a polyisocyanate molecule can then be utilized advantageously in industry.
- If, for example, a polyisocyanate according to the present invention is prepared from HDI isocyanurate oligomer as diisocyanate or polyisocyanate II and IPDI as diisocyanate I, then a PU coating composition produced using this polyisocyanate can have both properties such as elasticity and flexibility and properties such as hardness, scratch resistance and resistance to chemicals.
- A further advantage of the process of the present invention is that it can be carried out economically. Both the reaction of diisocyanate I to form an addition product (A) and/or polyaddition product (P) and the reaction of (A) or (P) with a diisocyanate or polyisocyanate II to give the polyisocyanate of the present invention can be carried out in one reaction apparatus and without a distillation step, which is technically and economically advantageous.
- The present invention is illustrated by the following examples.
- Preparation of an addition product (A) having a mean OH and NCO functionality of 1 from IPDI and ethanolamine
- 1000 g of IPDI were dissolved in 270 g of dimethylacetamide (DMAc) and cooled to 0° C. under a blanket of nitrogen. At this temperature, 270 g of ethanolamine dissolved in 1000 g of DMAc were added with good stirring over a period of 10 minutes and the reaction mixture was stirred at 0° C. for another 30 minutes. After this time, the reaction product had an NCO content of 7.4% by weight and a mean NCO functionality of 1 and a mean OH functionality of 1.
- Preparation of a polyaddition product (P) having a degree of polymerization of 3 and a mean OH and NCO functionality of 1 from IPDI and ethanolamine
- 1000 g of IPDI were dissolved in 270 g of dimethylacetamide (DMAc) and cooled to 0° C. under a blanket of nitrogen. At this temperature, 270 g of ethanolamine dissolved in 1000 g of DMAc were added with good stirring over a period of 10 minutes and the reaction mixture was stirred at 0° C. for another 30 minutes. The product mixture was subsequently heated to 60° C. and 200 mg of dibutyltin dilaurate (DBTL) were added. The NCO content of the mixture decreased continuously as the molar mass increased. At an NCO content of 2.4% by weight, the product had a mean degree of polymerization of 3 and a mean NCO functionality of 1 and a mean OH functionality of 1.
- Preparation of an addition product (A) having a mean OH and NCO functionality of 1 from IPDI and 1,3-butanediol
- 1000 g of IPDI were dissolved in 1000 g of butyl acetate at room temperature (23° C.) under a blanket of nitrogen. 200 mg of dibutyltin dilaurate were added, after which a mixture of 405 g of 1,3-butanediol and 405 g of butylacetate was added over a period of 20 minutes while stirring vigorously. The reaction mixture was stirred at room temperature and the decrease in the NCO content was followed titrimetrically. At an NCO content of 6.7% by weight, the reaction product had a mean NCO functionality of 1 and a mean OH functionality of 1.
- Preparation of a polyaddition product (P) having a degree of polymerization of 7 and a mean OH and NCO functionality of 1 from TDI and ethanolamine
- 174 g (1 mol) of TDI were dissolved in 522 g of dried dimethylacetamide (DMAc) and cooled to −15° C. At this temperature, 61 g (1 mol) of ethanolamine dissolved in 183 g of dried DMAc were added dropwise with good stirring over a period of 1 hour. The product mixture was slowly warmed to room temperature (23° C.) while stirring, during which time the NCO content of the mixture decreased continuously as the molar mass increased. At an NCO content of 0.64%, the reaction product had a mean degree of polymerization of 7 and a mean OH and NCO functionality of 1.
- Preparation of a polyisocyanate having a mean NCO functionality of 3.7 from IPDI, ethanolamine and HDI polyisocyanate
- Immediately after the addition product (A) from Example 1 had been prepared, 1700 g of BASONAT HI 100, dissolved in 1700 g of DMAc, and 400 mg of dibutyltin dilaurate were added to it, the mixture was heated to 40° C. and stirred at this temperature for 3 hours. The end product had an NCO content of 6.0% by weight and a viscosity of 170 mPas measured at 25° C. The mean molar mass of the polyisocyanate was 1457 g/mol and the mean functionality was 3.7.
- BASONAT® HI 100, BASF: HDI polyisocyanate, viscosity about 3200 mPas, solids content=100%, NCO content=22% by weight.
- Preparation of a polyisocyanate having a mean NCO functionality of 3.7 from IPDI, 1,3-butanediol and HDI polyisocyanate
- Immediately after the addition product (A) from Example 3 had been prepared, 1720 g of BASONAT HI 100 dissolved in 1720 g of butyl acetate were added to it, the mixture was heated to 60° C. and stirred at this temperature for 3 hours. The end product had an NCO content of 6.0% by weight and a viscosity of 63 mPas measured at 25° C. The mean molar mass of the polyisocyanate was 1544 g/mol and the mean functionality was 3.7.
- Preparation of a polyisocyanate having a mean NCO functionality of 2.5 from IPDI, 1,3-butanediol and polymeric MDI
- Immediately after the addition product (A) from Example 3 had been prepared, 1240 g of LUPRANAT M 20 W, dissolved in 1240 g of butyl acetate, and 0.2 g of dibutyltin dilaurate were added to it, the mixture was heated to 60° C. and stirred at this temperature for 3 hours. The end product had an NCO content of 7.0% by weight and a viscosity of 45 mPas measured at 25° C. The mean molar mass of the polyisocyanate was 905 g/mol and the mean functionality was 2.5.
- LUPRANAT® M 20 W, BASF: Polymeric MDI, viscosity about 200 mPas (25° C.), solids content=100%, NCO content=31% by weight.
Claims (12)
1. A process for preparing polyisocyanates, which comprises
(i) preparation of an addition product (A) which contains one group which is reactive toward isocyanate and one isocyanate group by reacting
(a) a diisocyanate I with
(b) compounds containing two groups which are reactive toward isocyanate,
where at least one of the components (a) or (b) has functional groups having differing reactivities toward the functional groups of the other component,
(ii) if desired, intermolecular addition reaction of the addition product (A) to form a polyaddition product (P) which contains one group which is reactive toward isocyanate and one isocyanate group and
(iii) reaction of the addition product (A) and/or the polyaddition product (P) with a diisocyanate or polyisocyanate II which is different from diisocyanate I.
2. A process as claimed in , wherein the diisocyanate I used is tetramethylene diisocyanate, hexamethylene diisocyanate, dodecyl diisocyanate, 1,3- or 1,4-bis(isocyanatomethyl)cyclohexane, xyxylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane 4,4′-diisocyanate or a mixture thereof.
claim 1
3. A process as claimed in , wherein the diisocyanate I is an isocyanate having two isocyanate groups of differing reactivity in first and second addition and is selected from among tolylene 2,4-diisocyanate, tolylene 2,6-diisocyanate, diphenylmethane 2,4′-diisocyanate, phenylene 1,3- and 1,4-diisocyanate, naphthylene 1,5-diisocyanate, tolidine diisocyanate, biphenyl diisocyanate, isophorone diisocyanate, 2-butyl-2-ethylpentamethylene diisocyanate, 2-isocyanatopropylcyclohexyl isocyanate, 3(4)-isocyanatomethyl-1-methylcyclohexyl isocyanate, 1,4-diisocyanato-4-methylpentane, 4-methylcyclohexane 1,3-diisocyanate, dicyclohexylmethane 2,4′-diisocyanate and mixtures thereof.
claim 1
4. A process as claimed in , wherein the diisocyanate or polyisocyanate II is selected from among tolylene 2,4-diisocyanate, tolylene 2,6-diisocyanate, diphenylmethane 4,4′-diisocyanate, diphenylmethane 2,4′-diisocyanate, mixtures of diphenylmethane diisocyanate and higher homologues of diphenylmethane diisocyanate (polymeric MDI), naphthylene 1,5-diisocyanate, tolidine diisocyanate, phenylene 1,3- and 1,4-diisocyanate, biphenyl diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecyl diisocyanate, lysine alkyl ester diisocyanate, where alkyl is C1-C10alkyl, isophorone diisocyanate, 2-methylpentamethylene diisocyanate, 2,2,4- and 2,4,4-trimethylhexamethylene 1,6-diisocyanate, 1,3- and 1,4-diisocyanatocyclohexane, 3(4)-isocyanatomethyl-1-methyl-1-isocyanatocyclohexane, 2-butyl-2-ethylpentamethylene diisocyanate, 2-isocyanatopropylcyclohexyl isocyanate, 2- and 4-methylcyclohexane 1,3-diisocyanate, dicyclohexylmethane 4,4′- and 2,4′-diisocyanate, 1,3- and 1,4-bis(isocyanatomethyl)cyclohexane, xylylene diisocyanate, tetramethylxylylene diisocyanate, 4-isocyanatomethyloctamethylene 1,8-diisocyanate, triisocyanatotoluene and oligoisocyanates or polyisocyanates prepared from the isocyanates listed by coupling by means of urethane, allophanate, urea, biuret, uretdione, amide, isocyanurate, carbodiimide, uretonimine, oxadiazinetrione or iminooxadiazinedione structures or from among mixtures of the isocyanates mentioned.
claim 1
5. A process as claimed in , wherein the diisocyanate or polyisocyanate II has a mean functionality of more than 2, preferably in the range from 2.1 to 5.
claim 1
6. A process as claimed in , wherein, in the reaction of the addition product (A) and/or the polyaddition product (P) with the diisocyanate or polyisocyanate II, the ratio of isocyanate groups of the diisocyanate or polyisocyanate II to the isocyanate-reactive groups of the addition product (A) or the polyaddition product (P) is selected so that at least 10%, preferably at least 40%, of the NCO groups of the diisocyanate or polyisocyanate II are reacted.
claim 1
7. A process as claimed in , wherein the isocyanate-reactive groups of the component (b) are selected from among hydroxyl groups, mercapto groups, amino groups and mixtures thereof.
claim 1
8. A process as claimed in , wherein the compounds (b) having two groups which are reactive toward isocyanate are 1,2-propanediol, 1,2- and 1,3-butanediol, ethanolamine, propanolamine, mercaptoethanol, 4-hydroxypiperidine and 1-hydroxyethylpiperazine.
claim 1
9. A polyisocyanate which can be prepared as claimed in .
claim 1
10. A polyisocyanate which can be prepared as claimed in and has both aliphatically and aromatically bound isocyanate groups.
claim 1
11. The use of a polyisocyanate as claimed in for producing paints and varnishes, coatings, adhesives, sealants, pourable elastomers and/or foams.
claim 9
12. A polyaddition product obtainable using a polyisocyanate as claimed in .
claim 9
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DE10013186.7 | 2000-03-17 | ||
DE10013186A DE10013186A1 (en) | 2000-03-17 | 2000-03-17 | Polyisocyanates |
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EP (1) | EP1134246B1 (en) |
JP (1) | JP2001261770A (en) |
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US4332742A (en) * | 1981-06-22 | 1982-06-01 | Mobay Chemical Corporation | Low temperature storage stable liquid diphenylmethane diisocyanates |
US4463143A (en) * | 1981-12-28 | 1984-07-31 | Ford Motor Company | Diblocked diisocyanate urea urethane oligomers and coating compositions comprising same |
DE3401129A1 (en) | 1984-01-14 | 1985-07-18 | Henkel KGaA, 4000 Düsseldorf | METHOD FOR PRODUCING MIXED POLYURETHANE PREPOLYMERS |
EP0752433B1 (en) * | 1995-07-01 | 2001-05-30 | BASF Aktiengesellschaft | One-component or two-component polyurethane coating masses |
DE19526079A1 (en) * | 1995-07-18 | 1997-01-23 | Basf Ag | Water emulsifiable polyisocyanates |
US5679756A (en) * | 1995-12-22 | 1997-10-21 | Optima Inc. | Optical thermoplastic thiourethane-urethane copolymers |
DE19649290A1 (en) * | 1996-11-28 | 1998-06-04 | Bayer Ag | Thermoplastic processable polyurethanes containing special wax mixtures |
DE19921412A1 (en) * | 1999-05-08 | 2000-11-09 | Basf Ag | Linear oligo- and polyurethanes with a defined structure, their manufacture and their use |
DE19924090C1 (en) * | 1999-05-26 | 2001-01-25 | Bayer Ag | Process for the continuous production of thermoplastically processable polyurethanes with improved softening behavior |
DE19924089C1 (en) * | 1999-05-26 | 2001-01-25 | Bayer Ag | Process for the continuous production of thermoplastically processable polyurethanes with improved softening behavior |
-
2000
- 2000-03-17 DE DE10013186A patent/DE10013186A1/en not_active Withdrawn
-
2001
- 2001-03-06 EP EP01105546A patent/EP1134246B1/en not_active Expired - Lifetime
- 2001-03-12 JP JP2001068523A patent/JP2001261770A/en not_active Withdrawn
- 2001-03-15 CA CA002341004A patent/CA2341004A1/en not_active Abandoned
- 2001-03-16 US US09/811,201 patent/US6416686B2/en not_active Expired - Lifetime
- 2001-03-16 KR KR1020010013662A patent/KR100697747B1/en active IP Right Grant
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102013222915A1 (en) | 2012-11-12 | 2014-05-15 | Renesas Mobile Corporation | Device and method |
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CA2341004A1 (en) | 2001-09-17 |
KR20010089999A (en) | 2001-10-17 |
EP1134246A3 (en) | 2002-03-13 |
EP1134246A2 (en) | 2001-09-19 |
KR100697747B1 (en) | 2007-03-22 |
EP1134246B1 (en) | 2012-09-26 |
DE10013186A1 (en) | 2001-09-20 |
US6416686B2 (en) | 2002-07-09 |
JP2001261770A (en) | 2001-09-26 |
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