US20190031812A1 - Silylated Polyurethanes, Their Preparation and Use - Google Patents
Silylated Polyurethanes, Their Preparation and Use Download PDFInfo
- Publication number
- US20190031812A1 US20190031812A1 US16/152,599 US201816152599A US2019031812A1 US 20190031812 A1 US20190031812 A1 US 20190031812A1 US 201816152599 A US201816152599 A US 201816152599A US 2019031812 A1 US2019031812 A1 US 2019031812A1
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- US
- United States
- Prior art keywords
- carbon atoms
- group
- hydroxyl
- acid
- polyol
- 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.)
- Abandoned
Links
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 42
- 239000004814 polyurethane Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 44
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 27
- 229920005862 polyol Polymers 0.000 claims abstract description 27
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 19
- BUZRAOJSFRKWPD-UHFFFAOYSA-N isocyanatosilane Chemical compound [SiH3]N=C=O BUZRAOJSFRKWPD-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000003077 polyols Chemical class 0.000 claims abstract description 19
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000000565 sealant Substances 0.000 claims abstract description 15
- 239000000853 adhesive Substances 0.000 claims abstract description 12
- 230000001070 adhesive effect Effects 0.000 claims abstract description 12
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 11
- 125000004423 acyloxy group Chemical group 0.000 claims abstract description 8
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 8
- 125000000962 organic group Chemical group 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims abstract description 5
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 4
- 239000000203 mixture Substances 0.000 claims description 59
- 229920000570 polyether Polymers 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 11
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 239000008199 coating composition Substances 0.000 claims description 6
- FMGBDYLOANULLW-UHFFFAOYSA-N 3-isocyanatopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCN=C=O FMGBDYLOANULLW-UHFFFAOYSA-N 0.000 claims description 5
- GLHFVDRCEKPJOJ-UHFFFAOYSA-N 2-isocyanatoethyl(dimethoxy)silane Chemical compound CO[SiH](CCN=C=O)OC GLHFVDRCEKPJOJ-UHFFFAOYSA-N 0.000 claims description 3
- NNTRMVRTACZZIO-UHFFFAOYSA-N 3-isocyanatopropyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)CCCN=C=O NNTRMVRTACZZIO-UHFFFAOYSA-N 0.000 claims description 3
- BIPHSHVAFQXNFR-UHFFFAOYSA-N diethoxy(2-isocyanatoethyl)silane Chemical compound CCO[SiH](CCN=C=O)OCC BIPHSHVAFQXNFR-UHFFFAOYSA-N 0.000 claims description 3
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 claims description 3
- BOTMPGMIDPRZGP-UHFFFAOYSA-N triethoxy(isocyanatomethyl)silane Chemical compound CCO[Si](OCC)(OCC)CN=C=O BOTMPGMIDPRZGP-UHFFFAOYSA-N 0.000 claims description 3
- MEQQJIDQTIXJIW-UHFFFAOYSA-N (1-isocyanato-2-methylpropan-2-yl)-trimethoxysilane Chemical compound CO[Si](OC)(OC)C(C)(C)CN=C=O MEQQJIDQTIXJIW-UHFFFAOYSA-N 0.000 claims description 2
- XLBNHVVSCQAMHG-UHFFFAOYSA-N 3-isocyanatopropyl-methoxy-dimethylsilane Chemical compound CO[Si](C)(C)CCCN=C=O XLBNHVVSCQAMHG-UHFFFAOYSA-N 0.000 claims description 2
- AONXMESMHBIONB-UHFFFAOYSA-N 4-isocyanatobutyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCN=C=O AONXMESMHBIONB-UHFFFAOYSA-N 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- XYMOLTLTUXWLLT-UHFFFAOYSA-N benzyl-(3-isocyanatopropyl)-methoxysilane Chemical compound O=C=NCCC[SiH](OC)CC1=CC=CC=C1 XYMOLTLTUXWLLT-UHFFFAOYSA-N 0.000 claims description 2
- PJIFJEUHCQYNHO-UHFFFAOYSA-N diethoxy-(3-isocyanatopropyl)-methylsilane Chemical compound CCO[Si](C)(OCC)CCCN=C=O PJIFJEUHCQYNHO-UHFFFAOYSA-N 0.000 claims description 2
- OOISEBIWKZXNII-UHFFFAOYSA-N diethoxy-ethyl-(3-isocyanatopropyl)silane Chemical compound CCO[Si](CC)(OCC)CCCN=C=O OOISEBIWKZXNII-UHFFFAOYSA-N 0.000 claims description 2
- QRFPECUQGPJPMV-UHFFFAOYSA-N isocyanatomethyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CN=C=O QRFPECUQGPJPMV-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- FUIRCICWWOAOLT-UHFFFAOYSA-N triethoxy(2-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CC(C)N=C=O FUIRCICWWOAOLT-UHFFFAOYSA-N 0.000 claims description 2
- ASUUSZXVXTVKDD-UHFFFAOYSA-N triethoxy(4-isocyanatobutyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCCN=C=O ASUUSZXVXTVKDD-UHFFFAOYSA-N 0.000 claims description 2
- LBZIZIVHMAFPRT-UHFFFAOYSA-N triethoxy-(1-isocyanato-2-methylpropan-2-yl)silane Chemical compound CCO[Si](OCC)(OCC)C(C)(C)CN=C=O LBZIZIVHMAFPRT-UHFFFAOYSA-N 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 abstract 1
- -1 polyethylene Polymers 0.000 description 35
- 229920000642 polymer Polymers 0.000 description 27
- 150000001875 compounds Chemical class 0.000 description 15
- 238000001723 curing Methods 0.000 description 13
- 239000004014 plasticizer Substances 0.000 description 13
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 239000000945 filler Substances 0.000 description 9
- 239000003085 diluting agent Substances 0.000 description 8
- 229920004482 WACKER® Polymers 0.000 description 7
- 125000005370 alkoxysilyl group Chemical group 0.000 description 7
- 125000005442 diisocyanate group Chemical group 0.000 description 7
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 6
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 6
- 239000002318 adhesion promoter Substances 0.000 description 6
- 239000013466 adhesive and sealant Substances 0.000 description 6
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 150000002430 hydrocarbons Chemical group 0.000 description 6
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 6
- 229920000768 polyamine Polymers 0.000 description 6
- 229920006254 polymer film Polymers 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 239000002671 adjuvant Substances 0.000 description 5
- 229910052797 bismuth Inorganic materials 0.000 description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 229910052738 indium Inorganic materials 0.000 description 5
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- 239000011591 potassium Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 150000004756 silanes Chemical class 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 4
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 4
- YZXBAPSDXZZRGB-DOFZRALJSA-N arachidonic acid Chemical compound CCCCC\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O YZXBAPSDXZZRGB-DOFZRALJSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 4
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 4
- KHAVLLBUVKBTBG-UHFFFAOYSA-N dec-9-enoic acid Chemical compound OC(=O)CCCCCCCC=C KHAVLLBUVKBTBG-UHFFFAOYSA-N 0.000 description 4
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 4
- 239000005011 phenolic resin Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 125000005369 trialkoxysilyl group Chemical group 0.000 description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 4
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000012963 UV stabilizer Substances 0.000 description 3
- 125000005595 acetylacetonate group Chemical group 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- IJTNSXPMYKJZPR-UHFFFAOYSA-N parinaric acid Chemical compound CCC=CC=CC=CC=CCCCCCCCC(O)=O IJTNSXPMYKJZPR-UHFFFAOYSA-N 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- 150000003021 phthalic acid derivatives Chemical class 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 230000001698 pyrogenic effect Effects 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- GWHCXVQVJPWHRF-KTKRTIGZSA-N (15Z)-tetracosenoic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCCCC(O)=O GWHCXVQVJPWHRF-KTKRTIGZSA-N 0.000 description 2
- CUXYLFPMQMFGPL-BGDVVUGTSA-N (9Z,11E,13Z)-octadecatrienoic acid Chemical compound CCCC\C=C/C=C/C=C\CCCCCCCC(O)=O CUXYLFPMQMFGPL-BGDVVUGTSA-N 0.000 description 2
- OZBHXFNXILWUHV-IJRZPAASSA-L (z)-2,3-bis(6-methylheptyl)but-2-enedioate;dioctyltin(2+) Chemical compound CCCCCCCC[Sn+2]CCCCCCCC.CC(C)CCCCC\C(C([O-])=O)=C(C([O-])=O)/CCCCCC(C)C OZBHXFNXILWUHV-IJRZPAASSA-L 0.000 description 2
- IJEJLDJAZOPKKI-SWJSCKDZSA-L (z)-2,3-dibenzylbut-2-enedioate;dibutyltin(2+) Chemical compound CCCC[Sn+2]CCCC.C=1C=CC=CC=1C/C(C([O-])=O)=C(C(=O)[O-])\CC1=CC=CC=C1 IJEJLDJAZOPKKI-SWJSCKDZSA-L 0.000 description 2
- BLJHJIWRKBGEDG-BZKIHGKGSA-L (z)-2,3-dibutylbut-2-enedioate;dibutyltin(2+) Chemical compound CCCC[Sn+2]CCCC.CCCC\C(C([O-])=O)=C(C([O-])=O)/CCCC BLJHJIWRKBGEDG-BZKIHGKGSA-L 0.000 description 2
- PJDIJZMPWJVMMM-WTUPQPTJSA-L (z)-2,3-diethylbut-2-enedioate;dioctyltin(2+) Chemical compound CC\C(C([O-])=O)=C(/CC)C([O-])=O.CCCCCCCC[Sn+2]CCCCCCCC PJDIJZMPWJVMMM-WTUPQPTJSA-L 0.000 description 2
- 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 2
- 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
- ZBBLRPRYYSJUCZ-GRHBHMESSA-L (z)-but-2-enedioate;dibutyltin(2+) Chemical compound [O-]C(=O)\C=C/C([O-])=O.CCCC[Sn+2]CCCC ZBBLRPRYYSJUCZ-GRHBHMESSA-L 0.000 description 2
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 2
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- ZKCRKOCVERWCLP-DJWHJZFYSA-N Hiragonic acid Chemical compound C\C=C\CC\C=C\CC\C=C\CCCCC(O)=O ZKCRKOCVERWCLP-DJWHJZFYSA-N 0.000 description 2
- GCORITRBZMICMI-HJWRWDBZSA-N Linderic acid Chemical compound CCCCCCC\C=C/CCC(O)=O GCORITRBZMICMI-HJWRWDBZSA-N 0.000 description 2
- GCORITRBZMICMI-UHFFFAOYSA-N Linderic acid Natural products CCCCCCCC=CCCC(O)=O GCORITRBZMICMI-UHFFFAOYSA-N 0.000 description 2
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 2
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- CUVLOCDGQCUQSI-KHPPLWFESA-N Tsuzuic acid Chemical compound CCCCCCCCC\C=C/CCC(O)=O CUVLOCDGQCUQSI-KHPPLWFESA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 description 2
- CQQXCSFSYHAZOO-UHFFFAOYSA-L [acetyloxy(dioctyl)stannyl] acetate Chemical compound CCCCCCCC[Sn](OC(C)=O)(OC(C)=O)CCCCCCCC CQQXCSFSYHAZOO-UHFFFAOYSA-L 0.000 description 2
- NBJODVYWAQLZOC-UHFFFAOYSA-L [dibutyl(octanoyloxy)stannyl] octanoate Chemical compound CCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCC NBJODVYWAQLZOC-UHFFFAOYSA-L 0.000 description 2
- UZFVQGTYOXJWTF-UHFFFAOYSA-L [octadecanoyloxy(dioctyl)stannyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCCCCCCCC UZFVQGTYOXJWTF-UHFFFAOYSA-L 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- IKHOZNOYZQPPCK-UHFFFAOYSA-K aluminum;4,4-diethyl-3-oxohexanoate Chemical class [Al+3].CCC(CC)(CC)C(=O)CC([O-])=O.CCC(CC)(CC)C(=O)CC([O-])=O.CCC(CC)(CC)C(=O)CC([O-])=O IKHOZNOYZQPPCK-UHFFFAOYSA-K 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 150000001565 benzotriazoles Chemical class 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
- 239000006229 carbon black Substances 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- KJDZDTDNIULJBE-QXMHVHEDSA-N cetoleic acid Chemical compound CCCCCCCCCC\C=C/CCCCCCCCCC(O)=O KJDZDTDNIULJBE-QXMHVHEDSA-N 0.000 description 2
- 239000013522 chelant Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
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- NZZIMKJIVMHWJC-UHFFFAOYSA-N dibenzoylmethane Chemical compound C=1C=CC=CC=1C(=O)CC(=O)C1=CC=CC=C1 NZZIMKJIVMHWJC-UHFFFAOYSA-N 0.000 description 1
- ORHSGYTWJUDWKU-UHFFFAOYSA-N dimethoxymethyl(ethenyl)silane Chemical compound COC(OC)[SiH2]C=C ORHSGYTWJUDWKU-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- AGDANEVFLMAYGL-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCCCCCC(O)=O AGDANEVFLMAYGL-UHFFFAOYSA-N 0.000 description 1
- WLGSIWNFEGRXDF-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O.CCCCCCCCCCCC(O)=O WLGSIWNFEGRXDF-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229910000267 dualite Inorganic materials 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002168 ethanoic acid esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- JLRBNGCMXSGALP-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O.CCCCCCC(O)=O JLRBNGCMXSGALP-UHFFFAOYSA-N 0.000 description 1
- TUFOVEWZORBKNG-UHFFFAOYSA-N hexacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O TUFOVEWZORBKNG-UHFFFAOYSA-N 0.000 description 1
- JYDNQSLNPKOEII-CFYXSCKTSA-N hexadec-9-enoic acid;(z)-hexadec-9-enoic acid Chemical compound CCCCCCC=CCCCCCCCC(O)=O.CCCCCC\C=C/CCCCCCCC(O)=O JYDNQSLNPKOEII-CFYXSCKTSA-N 0.000 description 1
- KYYWBEYKBLQSFW-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCC(O)=O KYYWBEYKBLQSFW-UHFFFAOYSA-N 0.000 description 1
- RSKGMYDENCAJEN-UHFFFAOYSA-N hexadecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OC)(OC)OC RSKGMYDENCAJEN-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229920006270 hydrocarbon resin Polymers 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- NHXTZGXYQYMODD-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCCCC(O)=O NHXTZGXYQYMODD-UHFFFAOYSA-N 0.000 description 1
- 238000013101 initial test Methods 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 239000004761 kevlar Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 235000020778 linoleic acid Nutrition 0.000 description 1
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 150000002690 malonic acid derivatives Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- SWDYEOBSKYXKLZ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O SWDYEOBSKYXKLZ-UHFFFAOYSA-N 0.000 description 1
- RQFLGKYCYMMRMC-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCC(O)=O RQFLGKYCYMMRMC-UHFFFAOYSA-N 0.000 description 1
- BARWIPMJPCRCTP-CLFAGFIQSA-N oleyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCCOC(=O)CCCCCCC\C=C/CCCCCCCC BARWIPMJPCRCTP-CLFAGFIQSA-N 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 230000036316 preload Effects 0.000 description 1
- 150000003151 propanoic acid esters Chemical class 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- JPPLPDOXWBVPCW-UHFFFAOYSA-N s-(3-triethoxysilylpropyl) octanethioate Chemical compound CCCCCCCC(=O)SCCC[Si](OCC)(OCC)OCC JPPLPDOXWBVPCW-UHFFFAOYSA-N 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000013467 silicone adhesive and sealant Substances 0.000 description 1
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 1
- 239000003707 silyl modified polymer Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- JIWBIWFOSCKQMA-UHFFFAOYSA-N stearidonic acid Natural products CCC=CCC=CCC=CCC=CCCCCC(O)=O JIWBIWFOSCKQMA-UHFFFAOYSA-N 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 150000003459 sulfonic acid esters Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- CBYCSRICVDBHMZ-UHFFFAOYSA-N tetracosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCCCCCCCC(O)=O CBYCSRICVDBHMZ-UHFFFAOYSA-N 0.000 description 1
- ZTUXEFFFLOVXQE-UHFFFAOYSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCC(O)=O ZTUXEFFFLOVXQE-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 231100000186 toxicological potential Toxicity 0.000 description 1
- AFGUVBVUFZMJMX-UHFFFAOYSA-N trans 5-tetradecenoic acid Natural products CCCCCCCCC=CCCCC(O)=O AFGUVBVUFZMJMX-UHFFFAOYSA-N 0.000 description 1
- XKZKQTCECFWKBN-UHFFFAOYSA-N trans-4-decenoic acid Natural products CCCCCC=CCCC(O)=O XKZKQTCECFWKBN-UHFFFAOYSA-N 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- CUXYLFPMQMFGPL-UYWAGRGNSA-N trichosanic acid Natural products CCCCC=C/C=C/C=CCCCCCCCC(=O)O CUXYLFPMQMFGPL-UYWAGRGNSA-N 0.000 description 1
- HXOGQBSDPSMHJK-UHFFFAOYSA-N triethoxy(6-methylheptyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCCCC(C)C HXOGQBSDPSMHJK-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- UWSYCPWEBZRZNJ-UHFFFAOYSA-N trimethoxy(2,4,4-trimethylpentyl)silane Chemical compound CO[Si](OC)(OC)CC(C)CC(C)(C)C UWSYCPWEBZRZNJ-UHFFFAOYSA-N 0.000 description 1
- NMEPHPOFYLLFTK-UHFFFAOYSA-N trimethoxy(octyl)silane Chemical compound CCCCCCCC[Si](OC)(OC)OC NMEPHPOFYLLFTK-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- 235000020234 walnut Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002025 wood fiber Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/227—Catalysts containing metal compounds of antimony, bismuth or arsenic
-
- 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
- C08G18/71—Monoisocyanates or monoisothiocyanates
- C08G18/718—Monoisocyanates or monoisothiocyanates containing silicon
-
- 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
- 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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
Definitions
- the present invention relates to silylated polyurethanes, their preparation and their use in adhesives, sealants, and in coating compositions.
- the polymers generally comprise an organic backbone that carries alkoxysilyl groups at the ends.
- the organic backbone can involve, for example, polyurethanes, polyesters, polyethers, etc.
- modified silane adhesives and sealants have the advantage, as compared with the polyurethane adhesives and sealants, of being free of isocyanate groups, in particular of monomeric diisocyanates; they are also notable for a broad adhesion spectrum to a plurality of substrates without surface pretreatment using primers.
- U.S. Pat. No. 4,222,925 A and U.S. Pat. No. 3,979,344 A describe siloxane-terminated organic sealant compositions, curable already at room temperature, based on reaction products of isocyanate-terminated polyurethane prepolymers with 3-aminopropyltrimethoxysilane or 2-aminoethyl- or 3-aminopropylmethoxysilane to yield isocyanate-free siloxane-terminated prepolymers.
- Adhesives and sealants based on these prepolymers have unsatisfactory mechanical properties, however, especially in terms of their elongation and breaking strength.
- EP 0931800 A1 describes the manufacture of silylated polyurethanes by reacting a polyol component having a terminal unsaturation of less than 0.02 meq/g with a diisocyanate to yield a hydroxyl-terminated prepolymer, and then reacting that with an isocyanatosilane of the formula OCN—R—Si—(X) m (—OR 1 ) 3-m , where m is 0, 1, or 2 and each R 1 residue is an alkyl group having 1 to 4 carbon atoms and R is a difunctional organic group.
- silylated polyurethanes exhibit a superior combination of mechanical properties, and cure in reasonable amounts of time to yield a low-tack sealant without exhibiting excessive viscosity.
- WO 2009/071542 A1 describes a method for preparing a silylated polyurethane, comprising reacting at least one polyol compound having a molecular weight of 4,000 to 30,000 g/mol and at least one monofunctional compound with regard to isocyanates with at least one diisocyanate, in a stoichiometric excess of the sum of the polyol compound(s) and monofunctional compound(s) relative to the diisocyanate compound(s), whereby a hydroxyl-terminated polyurethane prepolymer is formed which is subsequently reacted with isocyanatosilane.
- compositions based on silylated polyurethanes for use in adhesives and sealants that exhibit better performance, in particular, curing speed and mechanical strength after curing, and at the same time show acceptable viscosity, allowing the compositions to be easily applied.
- the object of the present invention is therefore to provide silylated polyurethanes and respective compositions having improved curing speed while having acceptable mechanical strength and viscosity.
- a hydroxyl-terminated polyurethane prepolymer is obtained by reacting at least one polyol with at least one triisocyanate.
- a “polyol” is understood for purpose of the present invention as a polymer having at least two hydroxyl groups.
- a large number of polymers carrying at least two hydroxyl groups such as polyester polyols, polycaprolactones, polybutadienes or polyisoprenes as well as hydrogenation products thereof, or also polyacrylates or polymethacrylates, can be used as polyol compounds. Mixtures of different polyol compounds can also be used.
- a polyether polyol is preferably used as the polyol.
- a “polyether” is understood for purpose of the present invention as a polymer whose repeating unit contains ether functionalities C—O—C in the main chain. Polymers having lateral ether groups, such as cellulose ethers, starch ethers, and vinyl ether polymers, as well as polyacetals, are therefore not covered by this definition.
- Polymers which contain polyethers as backbone have a flexible and elastic structure with which compositions that have outstanding elastic properties can be manufactured.
- Polyethers are not only flexible in their backbone, but also strong at the same time.
- polyethers in contrast to e.g., polyesters
- polyethers are not attacked or decomposed by water and bacteria.
- the polyol is a polyalkylene oxide, and more preferably polyethylene oxide and/or polypropylene oxide.
- polyethers having a narrow molecular weight distribution and thus a low polydispersity are used as polymer backbones.
- These can be prepared, for example, by so-called double metal cyanide (DMC) catalysis.
- DMC double metal cyanide
- Polyethers prepared in this way are notable for a particularly narrow molecular weight distribution, a high average molecular weight, and a very small number of double bonds at the ends of the polymer chains.
- the polyol is a polyether polyol having a polydispersity PD of less than 3, preferably less than 1.7, more preferably less than 1.5, and most preferably less than 1.3.
- the number average molecular weight M n of the polymer backbone of the polyol compounds is from 500 to 20,000 g/mol (daltons), preferably from 2,000 to 18,000 g/mol, and most preferably 2,000 to 12,000 g/mol, the terminal unsaturation being less than 0.05 meq/g, preferably less than 0.04 meq/g, and more preferably less than 0.02 meq/g.
- the number average molecular weight M n is determined by gel permeation chromatography (GPC, also known as SEC). This method is known to one skilled in the art.
- the ratio M w /M n also referred to as “polydispersity,” indicates the width of the molecular weight distribution and thus the differing degrees of polymerization of the individual chains in polydisperse polymers. For many polymers and polycondensates, the applicable polydispersity value is approximately 2. Strict monodispersity would exist for a value of 1. A low polydispersity (for example, less than 1.5) indicates a comparatively narrow molecular weight distribution and thus the specific expression of properties associated with molecular weight, for example viscosity.
- the triisocyanates suitable to convert the polyol compound into a hydroxyl-terminated polyurethane prepolymer can be derived from diisocyanates.
- the triisocyanates are derived from HDI, TDI, MDI, PDI or IPDI, or mixtures thereof. In particular, following triisocyanates are most preferred.
- a stoichiometric excess of the hydroxyl groups of the polyol compound(s) with respect to the NCO groups of the triisocyanate(s) or mixture of triisocyanates is used.
- the preferred molar ratio of the NCO groups to hydroxyl groups is from 0.05 to 0.45, preferably from 0.1 to 0.45, and more preferably from 0.2 to 0.45. This ensures that a polyurethane prepolymer having terminal hydroxyl groups is formed in step (a) according to the present invention.
- the polyurethane prepolymer having terminal hydroxyl groups that is thereby formed is then reacted with at least one isocyanatosilane of formula (1):
- m is 0, 1 or 2, preferably 0 or 1.
- Each R 1 is independently from each other a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, or —OCH(R 2 )COOR 3 , wherein R 2 is hydrogen or an alkyl group having 1 to 4 carbon atoms and R 3 is a straight-chain or branched alkyl group having 1 to 8 carbon atoms.
- each R 1 is independently of each other an alkoxy or acyloxy group having 1 to 4 carbon atoms. More preferably, each R 1 is independently of each other a methoxy or ethoxy group, particularly a methoxy group.
- Methoxy and ethoxy groups are very reactive and thus enable a rapid cure even with low use of catalyst. They are therefore of particular interest for systems in which a rapid cure is desired, such as e.g. in adhesives requiring high initial adhesion.
- methoxy group is used. The methoxy group displays the greatest reactivity among the alkoxy groups.
- Silyl groups of this type can therefore be used when a particularly rapid cure is desired.
- Higher aliphatic residues, such as ethoxy already bring about lower reactivity of the terminal alkoxysilyl group compared with methoxy groups and can advantageously be used to develop gradual crosslinking rates.
- R 1 is —OCH(R 2 )COOR 3 , wherein preferably R 2 is methyl group and R 3 is a straight-chain or branched alkyl group having 1 to 4 carbon atoms.
- Each X is independently from each other an optionally substituted hydrocarbon group having 1 to 10 carbon atoms, more preferably having 1 to 4 carbon atoms, which can be interrupted by at least one heteroatom. “Interrupted by at least one heteroatom” means that the main chain of a residue comprises, as a chain member, at least one atom that differs from carbon atom.
- each X is independently from each other an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, particularly preferred methyl or ethyl.
- m in formula (1) has the value 0 or 1, so two or three hydroxyl- or hydrolysable groups, preferably alkoxy groups, are present.
- polymers that contain di- or trialkoxysilyl groups have highly reactive linking sites, which make rapid curing, high degrees of crosslinking and thus good final strengths possible.
- dialkoxysilyl groups are that the corresponding compositions are, after curing, softer and more elastic than systems containing trialkoxysilyl groups. They are therefore particularly suitable for utilization as sealants. In addition, they release less alcohol upon curing, and thus offer an application advantage from a physiological standpoint as well.
- trialkoxysilyl groups on the other hand, a higher degree of crosslinking can be achieved, which is particularly advantageous if a hard, solid substance is desired after curing.
- Trialkoxysilyl groups are moreover more reactive, i.e. crosslink more quickly, and thus decrease the quantity of catalyst required, and they have advantages in terms of “cold flow.”
- R is a difunctional organic group, which can be a hydrocarbon group having 1 to 12 carbon atoms, preferably an alkylene group having 1 to 6 carbon atoms, and particularly preferably an alkylene group having 1 to 3 carbon atoms. More preferably, R is a methylene, ethylene or n-propylene residue. Methylene and n-propylene residues are particularly preferably used. In particular, compounds where R is methylene exhibit high reactivity in the terminating silyl groups, which contributes to shorter curing and hardening times. If a propylene group is selected for R, these compounds then exhibit particularly high flexibility.
- the curing rate of formulations based on these polymers can also be influenced by means of the length of the hydrocarbon residues which form the link between the polymer backbone and silyl residue.
- the isocyanatosilanes listed below are particularly suitable: 3-isocyanatopropyltrimethoxysilane, 2-isocyanatoisopropyltrimethoxysilane, 4-isocyanato-n-butyltrimethoxysilane, 2-isocyanato-1,1-dimethylethyltrimethoxysilane, 1-isocyanatomethyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 2-isocyanato-2-methylethyltriethoxysilane, 4-isocyanatobutyltriethoxysilane, 2-isocyanato-1,1-dimethylethyltriethoxysilane, 1-isocyanatomethyltriethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, 3-isocyanatopropyldimethylmethoxysilane, 3-isocyanatopropylphen
- 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 1-isocyanatomethyltriethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, 1-isocyanatomethylmethyldimethoxysilane, 1-isocyanatomethylmethyldiethoxysilane, or mixtures thereof are more particularly preferred.
- aforementioned process for preparing a silylated polyurethane comprises further step of adding a catalyst.
- Suitable catalysts are well known. In principle, any compound that can catalyze reaction of a hydroxyl group and an isocyanato group to form a urethane bond can be used.
- Examples thereof include tin compounds, like tin carboxylates such as dibutyltin dilaurate (DBTL), dibutyltin diacetate, dibutyltin diethylhexanoate, dibutyltin dioctoate, dibutyltin dimethylmaleate, dibutyltin diethylmaleate, dibutyltin dibutylmaleate, dibutyltin diiosooctylmaleate, dibutyltin ditridecylmaleate, dibutyltin dibenzylmaleate, dibutyltin maleate, dibutyltin diacetate, tin octaoate, dioctyltin distearate, dioctyltin dilaurate (DOTL), dioctyltin diethylmaleate, dioctyltin diisooctylmaleate, diocty
- titanates such as tetrabutyl titanate and tetrapropyl titanate
- organoaluminum compounds such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, and diisopropoxyaluminum ethylacetoacetate
- chelate compounds such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate
- lead octanoate amine compounds or salts thereof with carboxylic acids, such as butylamine, octylamine, laurylamine, dibutylamines, monoethanolamines, diethanolamines, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamines, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris(
- the catalyst is selected from the group consisting of compounds of potassium, iron, indium, zinc, bismuth, and copper, preferably carboxylates (salts of aliphatic carboxylic acids) or acetylacetonates of potassium, iron, indium, zinc, bismuth, or copper.
- carboxylates salts of aliphatic carboxylic acids
- acetylacetonates of potassium, iron, indium, zinc, bismuth, or copper.
- C 4 to C 36 saturated, mono- or polyunsaturated monocarboxylic acids cab be used, in particular as aliphatic carboxylic acids.
- arachidic acid n-eicosanoic acid
- arachidonic acid all-cis-5,8,11,14-eicosatetraenoic acid
- behenic acid docosanoic acid
- butyric acid butanoic acid
- caproleic acid 9-decenoic acid
- capric acid n-decanoic acid
- caproic acid n-hexanoic acid
- caprylic acid n-octanoic acid
- cerotic acid hexacosanoic acid
- cetoleic acid cis-11-docosenoic acid
- clupanodonic acid all-cis-7,10,13,16,19-docosapentaenoic acid
- eleostearic acid trans-9-trans-11-cis-13-octadeca-9,11,13-trienoic acid
- enanthic acid (1-hexanecarboxylic acid
- erucic acid
- chelates of other ⁇ -dicarbonyl compounds of potassium, iron, indium, zinc, bismuth, or copper can also be used.
- Acetoacetic acid alkyl esters, dialkyl malonates, benzoylacetic esters, dibenzoylmethane, benzoylacetone, and dehydroacetoacetic acid may be recited concretely.
- the present invention also provides a process for preparing a silylated polyurethane comprising the following steps:
- the present invention also provides a curable composition, in particular an adhesive, sealant, or coating composition comprising at least one silylated polyurethane according to the invention or obtainable by the aforementioned process according to the present invention.
- the adhesive, sealant, coating composition according to the present invention can also contain, in addition to the aforementioned silylated polyurethane according to the present invention, further adjuvants and additives that impart to these adhesive, sealant, coating composition improved elastic properties, improved elastic recovery, a sufficiently long processing time, a fast curing time, and low residual tack.
- adjuvants and additives include, for example, catalysts, plasticizers, stabilizers, antioxidants, fillers, reactive diluents, drying agents, adhesion promoters and UV stabilizers, fungicides, flame retardants, rheological adjuvants, color pigments or color pastes, and/or optionally also, to a small extent, solvents.
- a “plasticizer” is understood as a substance that decreases the viscosity of the compositions and thus facilitates processability.
- the plasticizer is preferably selected from a fatty acid ester, a dicarboxylic acid ester, an ester of OH-group-carrying or epoxidized fatty acids, a fat, a glycolic acid ester, a benzoic acid ester, a phosphoric acid ester, a sulfonic acid ester, a trimellitic acid ester, an epoxidized plasticizer, a polyether plasticizer, a polystyrene, a hydrocarbon plasticizer, and a chlorinated paraffin, as well as mixtures of two or more thereof.
- Targeted selection of one of these plasticizers, or of a specific combination, can result not only in a decrease in viscosity and thus better processability, but also in further advantageous properties of the composition according to the present invention, e.g. the gelling capability of the polymers, low-temperature elasticity and/or low-temperature strength, or even antistatic properties.
- phthalic acid esters can be used as a plasticizer. However, these are not preferred due to their toxicological potential.
- polyether plasticizers it is preferred to use end-capped polyethylene glycols, for example polyethylene or polypropylene glycol di-C 1-4 alkyl ethers, in particular dimethyl or diethyl ethers of diethylene glycol or dipropylene glycol, as well as mixtures of two or more thereof.
- end-capped polyethylene glycols for example polyethylene or polypropylene glycol di-C 1-4 alkyl ethers, in particular dimethyl or diethyl ethers of diethylene glycol or dipropylene glycol, as well as mixtures of two or more thereof.
- plasticizers are, for example, esters of abietic acid, butyric acid esters, acetic acid esters, propionic acid esters, thiobutyric acid esters, citric acid esters, and esters based on nitrocellulose and polyvinyl acetate, as well as mixtures of two or more thereof.
- plasticizers are also suitable as plasticizers.
- plasticizers are diurethanes, which can be manufactured e.g.
- a further method for manufacturing diurethanes involves reacting monofunctional alcohols with diisocyanates, such that all the NCO groups react as completely as possible.
- Plasticizers can be additionally used in the composition at between 0 and 40, by preference between 0 and 20 wt %, based on the total weight of the composition.
- “Stabilizers” for purposes of this invention are to be understood as antioxidants, UV stabilizers, or hydrolysis stabilizers. Examples thereof are the commercially usual sterically hindered phenols and/or thioethers and/or substituted benzotriazoles and/or amines of the hindered amine light stabilizer (HALS) type. It is preferred in the context of the present invention if a UV stabilizer that carries a silyl group, and that is incorporated into the end product upon crosslinking or curing, is used. The products Lowilite 75, Lowilite 77 (Great Lakes, USA) are particularly suitable for this purpose. Benzotriazoles, benzophenones, benzoates, cyanoacrylates, acrylates, sterically hindered phenols, phosphorus, and/or sulfur can also be added.
- HALS hindered amine light stabilizer
- composition according to the present invention can contain up to approximately 2 wt %, by preference approximately 1 wt % stabilizers.
- composition according to the present invention can further contain up to approximately 7 wt %, in particular up to approximately 5 wt % antioxidants.
- the catalysts that can be used are all known compounds that can catalyze hydrolytic cleavage of the hydrolyzable groups of the silane groupings, as well as subsequent condensation of the Si—OH group to yield siloxane groupings (crosslinking reaction and adhesion promotion function).
- titanates such as tetrabutyl titanate and tetrapropyl titanate
- tin carboxylates such as dibutyltin dilaurate (DBTL), dibutyltin diacetate, dibutyltin diethylhexanoate, dibutyltin dioctoate, dibutyltin dimethylmaleate, dibutyltin diethylmaleate, dibutyltin dibutylmaleate, dibutyltin diiosooctylmaleate, dibutyltin ditridecylmaleate, dibutyltin dibenzylmaleate, dibutyltin maleate, dibutyltin diacetate, tin octaoate, dioctyltin distearate, dioctyltin dilaurate (DOTL), dioctyltin diethylmaleate, dioctyltin
- the catalyst preferably mixtures of several catalysts, can be used in a quantity from 0.01 to approximately 5 wt % based on the entire weight of the composition.
- composition according to the present invention can additionally contain fillers.
- fillers Suitable here are, for example, chalk, lime powder, precipitated and/or pyrogenic silicic acid, zeolites, bentonites, magnesium carbonate, diatomite, alumina, clay, talc, titanium oxide, iron oxide, zinc oxide, sand, quartz, flint, mica, glass powder, and other ground mineral substances.
- Organic fillers can also be used, in particular carbon black, graphite, wood fibers, wood flour, sawdust, cellulose, cotton, pulp, cotton, wood chips, chopped straw, chaff, ground walnut shells, and other chopped fibers. Short fibers such as glass fibers, glass filament, polyacrylonitrile, carbon fibers, Kevlar fibers, or polyethylene fibers can also be added.
- Aluminum powder is likewise suitable as a filler.
- the pyrogenic and/or precipitated silicic acids advantageously have a BET surface area from 10 to 90 m 2 /g. When they are used, they do not cause any additional increase in the viscosity of the composition according to the present invention, but do contribute to strengthening the cured composition.
- pyrogenic and/or precipitated silicic acids having a higher BET surface area, advantageously 100 to 250 m 2 /g, in particular 110 to 170 m 2 /g, as a filler. Because of the greater BET surface area, the same effect, e.g. strengthening the cured composition, is achieved with a smaller weight proportion of silicic acid. Further substances can thus be used to improve the composition according to the present invention in terms of different requirements.
- hollow spheres having a mineral shell or a plastic shell are also suitable as fillers.
- These can be, for example, hollow glass spheres that are obtainable commercially under the trade names Glass Bubbles®.
- Plastic-based hollow spheres e.g. Expancel® or Dualite®, are described e.g. in EP 0 520 426 B1. They are made up of inorganic or organic substances and each have a diameter of 1 mm or less, preferably 500 ⁇ m or less.
- Fillers that impart thixotropy to the composition are preferred for many applications.
- Such fillers are also described as rheological adjuvants, e.g. hydrogenated castor oil, fatty acid amides, or swellable plastics such as PVC.
- rheological adjuvants e.g. hydrogenated castor oil, fatty acid amides, or swellable plastics such as PVC.
- a suitable dispensing apparatus e.g. a tube
- such compositions possess a viscosity from 3000 to 150,000, preferably 40,000 to 80,000 mPas, or even 50,000 to 60,000 mPas.
- the fillers can be used by preference in a quantity from 1 to 80 wt %, by preference from 5 to 60 wt %, based on the total weight of the composition.
- Suitable pigments are titanium dioxide, iron oxides, or carbon black.
- composition according to the present invention In order to enhance shelf life even further, it is often advisable to further stabilize the composition according to the present invention with respect to moisture penetration using drying agents. A need occasionally also exists to lower the viscosity of the adhesive or sealant according to the present invention for specific applications, by using a reactive diluent. All compounds that are miscible with the adhesive or sealant with a reduction in viscosity, and that possess at least one group that is reactive with the binder, can be used as reactive diluents.
- polyalkylene glycols reacted with isocyanatosilanes e.g. Synalox 100-50B, Dow
- isocyanatosilanes e.g. Synalox 100-50B, Dow
- vinyltriethoxysilane phenyltrimethoxysilane, phenyltriethoxysilane, octyltrimethoxysilane, tetraethoxysilane, vinyldimethoxymethylsilane (XL12, Wacker), vinyltriethoxysilane (GF56, Wacker), vinyltriacetoxysilane (GF62, Wacker), isooctyltrimethoxysilane (10 Trim
- reactive diluents are the following polymers of Kaneka Corp.: MS S203H, MS S303H, MS SAT 010, and MS SAX 350.
- Silane-modified polymers that are derived, for example, from the reaction of isocyanatosilane with Synalox grades can likewise be used.
- silylated polyurethanes according to the present invention can be used in a mixture with usual polymers or prepolymers known per se, optionally with concurrent use of the aforementioned reactive diluents, fillers, and further adjuvants and additives.
- “Usual polymers or prepolymers” can be selected in this context from polyesters, polyoxyalkylenes, polyacrylates, polymethacrylates, or mixtures thereof; these can be free of groups reactive with siloxane groups, but optionally can also comprise alkoxysilyl groups or hydroxyl groups.
- a plurality of the aforementioned silane-functional reactive diluents have at the same time a drying and/or adhesion-promoting effect in the composition.
- These reactive diluents may be used in quantities between 0.1 and 15 wt %, by preference between 1 and 5 wt %, based on the total weight of the composition.
- adhesion promoters are so-called tackifying agents, such as hydrocarbon resins, phenol resins, terpene-phenolic resins, resorcinol resins or derivatives thereof, modified or unmodified resin acids or resin esters (abietic acid derivatives), polyamines, polyaminoamides, anhydrides, and anhydride-containing copolymers.
- tackifying agents such as hydrocarbon resins, phenol resins, terpene-phenolic resins, resorcinol resins or derivatives thereof, modified or unmodified resin acids or resin esters (abietic acid derivatives), polyamines, polyaminoamides, anhydrides, and anhydride-containing copolymers.
- tackifying agents such as hydrocarbon resins, phenol resins, terpene-phenolic resins, resorcinol resins or derivatives thereof, modified or unmodified resin acids or resin esters (abietic acid derivatives), polyamines, polyaminoamides, anhydr
- tackifying agents are used as adhesion promoters, their nature and quantity depend on the adhesive/sealant composition and on the substrate onto which it is applied.
- Typical tackifying resins such as, for example, terpene-phenolic resins or resin acid derivatives, may be used in concentrations between 5 and 20 wt %;
- typical adhesion promoters such as polyamines, polyaminoamides, or phenolic resins or resorcinol derivatives may be used in the range between 0.1 and 10 wt %, based on the total weight of the composition.
- the present invention also provides the use of the silylated polyurethane according to the present invention as an adhesive, sealant, coating composition, or for the production thereof.
- Example 1 A similar procedure to Example 1 was carried out except that HDI was used instead of triisocyanate.
- the viscosity was 28,200 mPas. Details are summarized in Table 1.
- the viscosity was 78,600 mPas. Details are summarized in Table 1.
- Example 2 A similar procedure to Example 2 was carried out except that HDI was used instead of triisocyanate.
- the viscosity was 10,600 mPas. Details are summarized in Table 1.
- the viscosity values were determined using Brookfield viscometer (DV-II+Pro), spindle 7, 20 rpm, at 23° C.
- Each prepared silylated polyurethane according to above examples was heated for 24 hours at 23° C. and then 0.35 g of N-(2-Aminoethyl)-3-aminopropyltrimethoxysilane (Geniosil GF 91) and 0.14 g of DOTL or DBU were added to 34.51 g of each of the prepared polymer. This mixture was homogenized twice for 60 seconds at 2700 rpm in a SpeedMixer (DAC 150 FC).
- DAC 150 FC SpeedMixer
- the aforementioned mixtures were homogenized and applied in a frame (50 ⁇ 130 ⁇ 2 mm). Each mixture was evenly distributed so that the frame can be completely filled. A thin polymer film was thereby obtained.
- the time to form a skin was determined for these compositions using a tool which has a rounded spatula at the tip (150 ⁇ 5 mm). The tip of the spatula was gently contacted with the surface of the polymer film every 1 to 5 minutes and removed carefully. The SOT was measured once no more residue of the formulation remains on the spatula when removing it from the surface of the polymer film. Then, the resulting string must be removed from the spatula without residue. The polymer film returned to its original shape. In examining the SOT a different part of the surface of the polymer film must be used every time. The test was performed at 23° C. and 50% relative humidity.
- Examples 1 to 2 show that the mixtures A, C, and E containing a silylated polyurethane according the present invention (Examples 1 to 2), show reasonable viscosity, exhibit significantly shorter SOT than mixtures comprising a silylated polyurethane according to the Comparative Examples 1 to 2, while having good mechanical strength (tensil strength and elongation).
- comparison of Examples E and F shows that even in case of using non-tin catalyst the mixture containing a silylated polyurethane according the present invention also exhibits short SOT and good mechanical properties.
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Abstract
A silylated polyurethane obtainable by a process comprising the following steps: (a) reacting at least one polyol with at least one triisocyanate to form a hydroxyl-terminated polyurethane prepolymer, and (b) reacting said polyurethane prepolymer with at least one isocyanatosilane of the formula (1): OCN—R—Si—(X)m(R1)3-m, wherein m is 0, 1 or 2, each R1 is independently from each other a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, or —OCH(R2)COOR3, wherein R2 is hydrogen or an alkyl group having 1 to 4 carbon atoms and R3 is a straight-chain or branched alkyl group having 1 to 8 carbon atoms, each X is independently from each other and optionally substituted hydrocarbon group having 1 to 10 carbon atoms, which can be interrupted by at least one heteroatom, and R is a difunctional organic group, to endcap the hydroxyl groups on said prepolymer with said isocyanatosilane. The silylated polyurethanes are suitable for use in a preparation as an adhesive, sealant, or coating agent.
Description
- The present invention relates to silylated polyurethanes, their preparation and their use in adhesives, sealants, and in coating compositions.
- Polymer systems that possess reactive alkoxysilyl groups are known. In the presence of atmospheric moisture these alkoxysilane-terminated polymers are capable, already at room temperature, of condensing with one another with release of the alkoxy groups. What forms in this context, depending on the concentration of alkoxysilyl groups and their configuration, are principally long-chain polymers (thermoplastics), relatively wide-mesh three-dimensional networks (elastomers), or highly crosslinked systems (thermosetting plastics).
- The polymers generally comprise an organic backbone that carries alkoxysilyl groups at the ends. The organic backbone can involve, for example, polyurethanes, polyesters, polyethers, etc.
- One-component, moisture-curing adhesives and sealants have played for years a significant role in numerous technical applications. In addition to the polyurethane adhesives and sealants having free isocyanate groups, and the traditional silicone adhesives and sealants based on dimethylpolysiloxanes, the so-called modified silane adhesives and sealants have also been increasingly used recently. In this latter group, the main constituent of the polymer backbone is a polyether, and the reactive and crosslinkable terminal groups are alkoxysilyl groups. The modified silane adhesives and sealants have the advantage, as compared with the polyurethane adhesives and sealants, of being free of isocyanate groups, in particular of monomeric diisocyanates; they are also notable for a broad adhesion spectrum to a plurality of substrates without surface pretreatment using primers.
- U.S. Pat. No. 4,222,925 A and U.S. Pat. No. 3,979,344 A describe siloxane-terminated organic sealant compositions, curable already at room temperature, based on reaction products of isocyanate-terminated polyurethane prepolymers with 3-aminopropyltrimethoxysilane or 2-aminoethyl- or 3-aminopropylmethoxysilane to yield isocyanate-free siloxane-terminated prepolymers. Adhesives and sealants based on these prepolymers have unsatisfactory mechanical properties, however, especially in terms of their elongation and breaking strength.
- The methods set forth below for the manufacture of silane-terminated prepolymers based on polyethers have already been described:
-
- Copolymerization of unsaturated monomers with ones that comprise alkoxysilyl groups, for example vinyltrimethoxysilane.
- Grafting unsaturated monomers, such as vinyltrimethoxysilane, onto thermoplastics such as polyethylene.
- Hydroxyfunctional polyethers are converted in an ether synthesis, using unsaturated chlorine compounds, e.g. allyl chloride, into polyethers having terminal olefinic double bounds, which in turn are reacted with hydrosilane compounds that have hydrolyzable groups, for example HSi(OCH3)3, in a hydrosilylation reaction under the catalytic influence of, for example, transition metal compounds of the eighth group, to yield silane-terminated polyethers.
- In another method, the polyethers containing olefinically unsaturated groups are reacted with a mercaptosilane such as, for example, 3-mercaptopropyltrialkoxysilane.
- In a further method, firstly hydroxyl-group-containing polyethers are reacted with di- or polyisocyanates, which are then in turn reacted with aminofunctional silanes or mercaptofunctional silanes to yield silane-terminated prepolymers.
- A further possibility provides for the reaction of hydroxyfunctional polyethers with isocyanatofunctional silanes such as, for example, 3-isocyanatopropyltrimethoxysilane.
- These manufacturing methods, and the use of the aforementioned silane-terminated prepolymers in adhesive/sealant applications, are recited e.g. in the following patent documents: U.S. Pat. No. 3,971,751 A, EP-A-70475, DE-A-19849817, U.S. Pat. No. 6,124,387 A, U.S. Pat. No. 5,990,257 A, U.S. Pat. No. 4,960,844 A, U.S. Pat. No. 3,979,344 A, U.S. Pat. No. 3,632,557 A, DE-A-4029504, EP-A-601021, or EP-A-370464.
- EP 0931800 A1 describes the manufacture of silylated polyurethanes by reacting a polyol component having a terminal unsaturation of less than 0.02 meq/g with a diisocyanate to yield a hydroxyl-terminated prepolymer, and then reacting that with an isocyanatosilane of the formula OCN—R—Si—(X)m(—OR1)3-m, where m is 0, 1, or 2 and each R1 residue is an alkyl group having 1 to 4 carbon atoms and R is a difunctional organic group. According to the teaching of this document, such silylated polyurethanes exhibit a superior combination of mechanical properties, and cure in reasonable amounts of time to yield a low-tack sealant without exhibiting excessive viscosity.
- WO 2009/071542 A1 describes a method for preparing a silylated polyurethane, comprising reacting at least one polyol compound having a molecular weight of 4,000 to 30,000 g/mol and at least one monofunctional compound with regard to isocyanates with at least one diisocyanate, in a stoichiometric excess of the sum of the polyol compound(s) and monofunctional compound(s) relative to the diisocyanate compound(s), whereby a hydroxyl-terminated polyurethane prepolymer is formed which is subsequently reacted with isocyanatosilane.
- A need still exists for compositions based on silylated polyurethanes for use in adhesives and sealants that exhibit better performance, in particular, curing speed and mechanical strength after curing, and at the same time show acceptable viscosity, allowing the compositions to be easily applied. The object of the present invention is therefore to provide silylated polyurethanes and respective compositions having improved curing speed while having acceptable mechanical strength and viscosity.
- The manner in which the object is achieved by the invention may be gathered from the Claims. It contains essentially of a silylated polyurethane obtainable by a process comprising the following steps:
-
- (a) reacting at least one polyol with at least one triisocyanate to form a hydroxyl-terminated polyurethane prepolymer; and
- (b) reacting said polyurethane prepolymer with at least one isocyanatosilane of the formula (1)
-
OCN—R—Si—(X)m(R1)3-m (1) -
- wherein
- m is 0, 1 or 2,
- each R1 is independently from each other a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, or —OCH(R2)COOR3, wherein R2 is hydrogen or an alkyl group having 1 to 4 carbon atoms and R3 is a straight-chain or branched alkyl group having 1 to 8 carbon atoms,
- each X is independently from each other and optionally substituted hydrocarbon group having 1 to 10 carbon atoms, which can be interrupted by at least one heteroatom, and
- R is a difunctional organic group,
- to endcap the hydroxyl groups on said prepolymer with said isocyanatosilane.
- According to the present invention, a hydroxyl-terminated polyurethane prepolymer is obtained by reacting at least one polyol with at least one triisocyanate.
- A “polyol” is understood for purpose of the present invention as a polymer having at least two hydroxyl groups. In principle, a large number of polymers carrying at least two hydroxyl groups, such as polyester polyols, polycaprolactones, polybutadienes or polyisoprenes as well as hydrogenation products thereof, or also polyacrylates or polymethacrylates, can be used as polyol compounds. Mixtures of different polyol compounds can also be used.
- According to the present invention, a polyether polyol is preferably used as the polyol. A “polyether” is understood for purpose of the present invention as a polymer whose repeating unit contains ether functionalities C—O—C in the main chain. Polymers having lateral ether groups, such as cellulose ethers, starch ethers, and vinyl ether polymers, as well as polyacetals, are therefore not covered by this definition.
- Polymers which contain polyethers as backbone have a flexible and elastic structure with which compositions that have outstanding elastic properties can be manufactured. Polyethers are not only flexible in their backbone, but also strong at the same time. Thus, for example, polyethers (in contrast to e.g., polyesters) are not attacked or decomposed by water and bacteria.
- In a preferred embodiment of the present invention, the polyol is a polyalkylene oxide, and more preferably polyethylene oxide and/or polypropylene oxide.
- Particularly advantageous viscoelastic properties can be achieved if polyethers having a narrow molecular weight distribution, and thus a low polydispersity are used as polymer backbones. These can be prepared, for example, by so-called double metal cyanide (DMC) catalysis. Polyethers prepared in this way are notable for a particularly narrow molecular weight distribution, a high average molecular weight, and a very small number of double bonds at the ends of the polymer chains.
- In a specific embodiment of the present invention, the polyol is a polyether polyol having a polydispersity PD of less than 3, preferably less than 1.7, more preferably less than 1.5, and most preferably less than 1.3.
- According to the present invention, the number average molecular weight Mn of the polymer backbone of the polyol compounds is from 500 to 20,000 g/mol (daltons), preferably from 2,000 to 18,000 g/mol, and most preferably 2,000 to 12,000 g/mol, the terminal unsaturation being less than 0.05 meq/g, preferably less than 0.04 meq/g, and more preferably less than 0.02 meq/g.
- These molecular weights are particularly advantageous because these polyols are readily available commercially and the resulting polyurethanes or the compositions based thereon have a good balance of viscosity (ease of processing) prior to curing and strength and elasticity after curing.
- The number average molecular weight Mn, as well as the weight average molecular weight Mw, is determined by gel permeation chromatography (GPC, also known as SEC). This method is known to one skilled in the art. The polydispersity is derived from the average molecular weights Mw and Mn. It is calculated as PD=Mw/Mn.
- The ratio Mw/Mn, also referred to as “polydispersity,” indicates the width of the molecular weight distribution and thus the differing degrees of polymerization of the individual chains in polydisperse polymers. For many polymers and polycondensates, the applicable polydispersity value is approximately 2. Strict monodispersity would exist for a value of 1. A low polydispersity (for example, less than 1.5) indicates a comparatively narrow molecular weight distribution and thus the specific expression of properties associated with molecular weight, for example viscosity.
- The triisocyanates suitable to convert the polyol compound into a hydroxyl-terminated polyurethane prepolymer can be derived from diisocyanates. Preferably, the triisocyanates are derived from HDI, TDI, MDI, PDI or IPDI, or mixtures thereof. In particular, following triisocyanates are most preferred.
- According to the present invention, a stoichiometric excess of the hydroxyl groups of the polyol compound(s) with respect to the NCO groups of the triisocyanate(s) or mixture of triisocyanates is used. The preferred molar ratio of the NCO groups to hydroxyl groups is from 0.05 to 0.45, preferably from 0.1 to 0.45, and more preferably from 0.2 to 0.45. This ensures that a polyurethane prepolymer having terminal hydroxyl groups is formed in step (a) according to the present invention.
- The polyurethane prepolymer having terminal hydroxyl groups that is thereby formed is then reacted with at least one isocyanatosilane of formula (1):
-
OCN—R—Si—(X)m(R1)3-m, - to endcap the hydroxyl groups on said prepolymer with said isocyanatosilane.
In formula (1) m is 0, 1 or 2, preferably 0 or 1. - Each R1 is independently from each other a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, or —OCH(R2)COOR3, wherein R2 is hydrogen or an alkyl group having 1 to 4 carbon atoms and R3 is a straight-chain or branched alkyl group having 1 to 8 carbon atoms.
- In a preferred embodiment of the present invention, each R1 is independently of each other an alkoxy or acyloxy group having 1 to 4 carbon atoms. More preferably, each R1 is independently of each other a methoxy or ethoxy group, particularly a methoxy group. Methoxy and ethoxy groups, as comparatively small hydrolyzable groups with low steric bulk, are very reactive and thus enable a rapid cure even with low use of catalyst. They are therefore of particular interest for systems in which a rapid cure is desired, such as e.g. in adhesives requiring high initial adhesion. Particularly preferably, methoxy group is used. The methoxy group displays the greatest reactivity among the alkoxy groups. Silyl groups of this type can therefore be used when a particularly rapid cure is desired. Higher aliphatic residues, such as ethoxy, already bring about lower reactivity of the terminal alkoxysilyl group compared with methoxy groups and can advantageously be used to develop gradual crosslinking rates.
- In another preferred embodiment of the present invention, R1 is —OCH(R2)COOR3, wherein preferably R2 is methyl group and R3 is a straight-chain or branched alkyl group having 1 to 4 carbon atoms.
- Each X is independently from each other an optionally substituted hydrocarbon group having 1 to 10 carbon atoms, more preferably having 1 to 4 carbon atoms, which can be interrupted by at least one heteroatom. “Interrupted by at least one heteroatom” means that the main chain of a residue comprises, as a chain member, at least one atom that differs from carbon atom. Preferably, each X is independently from each other an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, particularly preferred methyl or ethyl.
- In a preferred embodiment of the present invention, m in formula (1) has the value 0 or 1, so two or three hydroxyl- or hydrolysable groups, preferably alkoxy groups, are present. Generally, polymers that contain di- or trialkoxysilyl groups have highly reactive linking sites, which make rapid curing, high degrees of crosslinking and thus good final strengths possible. The particular advantage of dialkoxysilyl groups is that the corresponding compositions are, after curing, softer and more elastic than systems containing trialkoxysilyl groups. They are therefore particularly suitable for utilization as sealants. In addition, they release less alcohol upon curing, and thus offer an application advantage from a physiological standpoint as well. With trialkoxysilyl groups, on the other hand, a higher degree of crosslinking can be achieved, which is particularly advantageous if a hard, solid substance is desired after curing. Trialkoxysilyl groups are moreover more reactive, i.e. crosslink more quickly, and thus decrease the quantity of catalyst required, and they have advantages in terms of “cold flow.”
- R is a difunctional organic group, which can be a hydrocarbon group having 1 to 12 carbon atoms, preferably an alkylene group having 1 to 6 carbon atoms, and particularly preferably an alkylene group having 1 to 3 carbon atoms. More preferably, R is a methylene, ethylene or n-propylene residue. Methylene and n-propylene residues are particularly preferably used. In particular, compounds where R is methylene exhibit high reactivity in the terminating silyl groups, which contributes to shorter curing and hardening times. If a propylene group is selected for R, these compounds then exhibit particularly high flexibility. The curing rate of formulations based on these polymers can also be influenced by means of the length of the hydrocarbon residues which form the link between the polymer backbone and silyl residue.
- The isocyanatosilanes listed below are particularly suitable: 3-isocyanatopropyltrimethoxysilane, 2-isocyanatoisopropyltrimethoxysilane, 4-isocyanato-n-butyltrimethoxysilane, 2-isocyanato-1,1-dimethylethyltrimethoxysilane, 1-isocyanatomethyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 2-isocyanato-2-methylethyltriethoxysilane, 4-isocyanatobutyltriethoxysilane, 2-isocyanato-1,1-dimethylethyltriethoxysilane, 1-isocyanatomethyltriethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, 3-isocyanatopropyldimethylmethoxysilane, 3-isocyanatopropylphenylmethylmethoxysilane, 1-isocyanatomethylmethyldimethoxysilane, 3-isocyanatopropylethyldiethoxysilane, 3-isocyanatopropylmethyldiethoxysilane, 1-isocyanatomethylmethyldiethoxysilane, and mixtures thereof.
- 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 1-isocyanatomethyltriethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, 1-isocyanatomethylmethyldimethoxysilane, 1-isocyanatomethylmethyldiethoxysilane, or mixtures thereof are more particularly preferred.
- In a specific embodiment, according to the present invention, aforementioned process for preparing a silylated polyurethane comprises further step of adding a catalyst. Suitable catalysts are well known. In principle, any compound that can catalyze reaction of a hydroxyl group and an isocyanato group to form a urethane bond can be used. Examples thereof include tin compounds, like tin carboxylates such as dibutyltin dilaurate (DBTL), dibutyltin diacetate, dibutyltin diethylhexanoate, dibutyltin dioctoate, dibutyltin dimethylmaleate, dibutyltin diethylmaleate, dibutyltin dibutylmaleate, dibutyltin diiosooctylmaleate, dibutyltin ditridecylmaleate, dibutyltin dibenzylmaleate, dibutyltin maleate, dibutyltin diacetate, tin octaoate, dioctyltin distearate, dioctyltin dilaurate (DOTL), dioctyltin diethylmaleate, dioctyltin diisooctylmaleate, dioctyltin diacetate, and tin naphthenoate; tin alkoxides such as dibutyltin dimethoxide, dibutyltin diphenoxide, and dibutyltin diisoproxide; tin oxides such as dibutyltin oxide and dioctyltin oxide; reaction products between dibutyltin oxides and phthalic acid esters, dibutyltin bisacetylacetonate; as well as non-tin compounds. The latter include titanates such as tetrabutyl titanate and tetrapropyl titanate; organoaluminum compounds such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, and diisopropoxyaluminum ethylacetoacetate; chelate compounds such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate; lead octanoate; amine compounds or salts thereof with carboxylic acids, such as butylamine, octylamine, laurylamine, dibutylamines, monoethanolamines, diethanolamines, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamines, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris(dimethylaminomethyl)phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, and 1,8-diazabicyclo-(5,4,0)-undecene-7 (DBU), a low-molecular-weight polyamide resin obtained from an excess of a polyamine and a polybasic acid, adducts of a polyamine in excess with an epoxy, silane adhesion promoters having amino groups, such as 3-aminopropyltrimethoxysilane and aminoethyl)aminopropylmethyldimethoxysilane, as well as compounds of potassium, iron, indium, zinc, bismuth, and copper, preferably carboxylates (salts of aliphatic carboxylic acids) or acetylacetonates of potassium, iron, indium, zinc, bismuth, or copper. Preferably, the catalyst is selected from the group consisting of compounds of potassium, iron, indium, zinc, bismuth, and copper, preferably carboxylates (salts of aliphatic carboxylic acids) or acetylacetonates of potassium, iron, indium, zinc, bismuth, or copper. C4 to C36 saturated, mono- or polyunsaturated monocarboxylic acids cab be used, in particular as aliphatic carboxylic acids. Examples thereof are: arachidic acid (n-eicosanoic acid), arachidonic acid (all-cis-5,8,11,14-eicosatetraenoic acid), behenic acid (docosanoic acid), butyric acid (butanoic acid), caproleic acid (9-decenoic acid), capric acid (n-decanoic acid), caproic acid (n-hexanoic acid), caprylic acid (n-octanoic acid), cerotic acid (hexacosanoic acid), cetoleic acid (cis-11-docosenoic acid), clupanodonic acid (all-cis-7,10,13,16,19-docosapentaenoic acid), eleostearic acid (trans-9-trans-11-cis-13-octadeca-9,11,13-trienoic acid), enanthic acid (1-hexanecarboxylic acid), erucic acid (cis-13-docosenoic acid), gadoleic acid (9-eicosenoic acid), gondoic acid (cis-11-eicosenoic acid), hiragonic acid (6,10,14-hexadecatrienoic acid), lauric acid (dodecanoic acid), lignoceric acid (tetracosanoic acid), linderic acid (cis-4-dodecenoic acid), linoleic acid ((cis,cis)-octadeca-9,12-dienoic acid), linolenic acid ((all-cis)-octadeca-9,12,15-trienoic acid), melissic acid (triacontanoic acid), montanic acid (octacosanoic acid), stearidonic acid (cis-6-cis-9-cis-12-cis-15-octadecatetraenoic acid), myristic acid (tetradecanoic acid), myristoleic acid (cis-9-tetradecenoic acid), naphthenic acid, neodecanoic acid, obtusilic acid (cis-4-decenoic acid), caprylic acid (n-octanoic acid), neooctanoic acid, oleic acid (cis-9-octadecenoic acid), palmitic acid (n-hexadecanoic acid), palmitoleic acid (cis-9-hexadecenoic acid), parinaric acid (9,11,13,15-octadecatetraenoic acid), petroselinic acid (cis-6-octadecenoic acid), physeteric acid (5-tetradecenoic acid), punicic acid (cis-9-trans-11-cis-13-octadeca-9,11,13-trienoic acid), scoliodonic acid (cis-5-cis-11-cis-14-eicosatrienoic acid), selacholeic acid (15-tetracosenoic acid), stearic acid (n-octadecanoic acid), tricosanoic acid, tsuzuic acid (cis-4-tetradecenoic acid), trans-vaccenic acid (trans-11-octadecenoic acid), palmitoleic acid (9-hexadecenoic acid). In addition to the acetylacetonates, chelates of other β-dicarbonyl compounds of potassium, iron, indium, zinc, bismuth, or copper can also be used. Acetoacetic acid alkyl esters, dialkyl malonates, benzoylacetic esters, dibenzoylmethane, benzoylacetone, and dehydroacetoacetic acid may be recited concretely.
- The present invention also provides a process for preparing a silylated polyurethane comprising the following steps:
-
- (a) reacting at least one polyol with at least one triisocyanate to form a hydroxyl-terminated polyurethane prepolymer; and
- (b) reacting said polyurethane prepolymer with at least one isocyanatosilane of the formula (1)
-
OCN—R—Si—(X)m(R1)3-m (1) -
- wherein
- m is 0, 1 or 2,
- each R1 is independently from each other a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, or —OCH(R2)COOR3, wherein R2 is hydrogen or an alkyl group having 1 to 4 carbon atoms and R3 is a straight-chain or branched alkyl group having 1 to 8 carbon atoms,
- each X is independently from each other an optionally substituted hydrocarbon group having 1 to 10 carbon atoms, which can be interrupted by at least one heteroatom, and
- R is a difunctional organic group,
- to endcap the hydroxyl groups on said prepolymer with said isocyanatosilane.
- The general, preferred, and particularly preferred embodiments described for the silylated polyurethane according to the present invention thus also apply to the process for preparing the silylated polyurethane according to the present invention.
- The present invention also provides a curable composition, in particular an adhesive, sealant, or coating composition comprising at least one silylated polyurethane according to the invention or obtainable by the aforementioned process according to the present invention.
- The adhesive, sealant, coating composition according to the present invention can also contain, in addition to the aforementioned silylated polyurethane according to the present invention, further adjuvants and additives that impart to these adhesive, sealant, coating composition improved elastic properties, improved elastic recovery, a sufficiently long processing time, a fast curing time, and low residual tack. Included among these adjuvants and additives are, for example, catalysts, plasticizers, stabilizers, antioxidants, fillers, reactive diluents, drying agents, adhesion promoters and UV stabilizers, fungicides, flame retardants, rheological adjuvants, color pigments or color pastes, and/or optionally also, to a small extent, solvents.
- A “plasticizer” is understood as a substance that decreases the viscosity of the compositions and thus facilitates processability. The plasticizer is preferably selected from a fatty acid ester, a dicarboxylic acid ester, an ester of OH-group-carrying or epoxidized fatty acids, a fat, a glycolic acid ester, a benzoic acid ester, a phosphoric acid ester, a sulfonic acid ester, a trimellitic acid ester, an epoxidized plasticizer, a polyether plasticizer, a polystyrene, a hydrocarbon plasticizer, and a chlorinated paraffin, as well as mixtures of two or more thereof. Targeted selection of one of these plasticizers, or of a specific combination, can result not only in a decrease in viscosity and thus better processability, but also in further advantageous properties of the composition according to the present invention, e.g. the gelling capability of the polymers, low-temperature elasticity and/or low-temperature strength, or even antistatic properties.
- In principle, phthalic acid esters can be used as a plasticizer. However, these are not preferred due to their toxicological potential.
- Of the polyether plasticizers, it is preferred to use end-capped polyethylene glycols, for example polyethylene or polypropylene glycol di-C1-4 alkyl ethers, in particular dimethyl or diethyl ethers of diethylene glycol or dipropylene glycol, as well as mixtures of two or more thereof. Also suitable as plasticizers are, for example, esters of abietic acid, butyric acid esters, acetic acid esters, propionic acid esters, thiobutyric acid esters, citric acid esters, and esters based on nitrocellulose and polyvinyl acetate, as well as mixtures of two or more thereof. Also suitable are, for example, the asymmetrical esters of adipic acid monooctyl ester with 2-ethylhexanol (Edenol DOA, Cognis Deutschland GmbH, Düsseldorf). The pure or mixed ethers of monofunctional, linear or branched C4-16 alcohols, or mixtures of two or more different ethers of such alcohols, for example dioctyl ethers (obtainable as Cetiol OE, Cognis Deutschland GmbH, Düsseldorf), are also suitable as plasticizers. Likewise, suitable in the context of the present invention as plasticizers are diurethanes, which can be manufactured e.g. by reacting diols having OH terminal groups with monofunctional isocyanates, by selecting the stoichiometry so that substantially all the free OH groups react completely. A further method for manufacturing diurethanes involves reacting monofunctional alcohols with diisocyanates, such that all the NCO groups react as completely as possible.
- Plasticizers can be additionally used in the composition at between 0 and 40, by preference between 0 and 20 wt %, based on the total weight of the composition.
- “Stabilizers” for purposes of this invention are to be understood as antioxidants, UV stabilizers, or hydrolysis stabilizers. Examples thereof are the commercially usual sterically hindered phenols and/or thioethers and/or substituted benzotriazoles and/or amines of the hindered amine light stabilizer (HALS) type. It is preferred in the context of the present invention if a UV stabilizer that carries a silyl group, and that is incorporated into the end product upon crosslinking or curing, is used. The products Lowilite 75, Lowilite 77 (Great Lakes, USA) are particularly suitable for this purpose. Benzotriazoles, benzophenones, benzoates, cyanoacrylates, acrylates, sterically hindered phenols, phosphorus, and/or sulfur can also be added.
- The composition according to the present invention can contain up to approximately 2 wt %, by preference approximately 1 wt % stabilizers. In addition, the composition according to the present invention can further contain up to approximately 7 wt %, in particular up to approximately 5 wt % antioxidants.
- The catalysts that can be used are all known compounds that can catalyze hydrolytic cleavage of the hydrolyzable groups of the silane groupings, as well as subsequent condensation of the Si—OH group to yield siloxane groupings (crosslinking reaction and adhesion promotion function). Examples thereof are titanates such as tetrabutyl titanate and tetrapropyl titanate, tin carboxylates such as dibutyltin dilaurate (DBTL), dibutyltin diacetate, dibutyltin diethylhexanoate, dibutyltin dioctoate, dibutyltin dimethylmaleate, dibutyltin diethylmaleate, dibutyltin dibutylmaleate, dibutyltin diiosooctylmaleate, dibutyltin ditridecylmaleate, dibutyltin dibenzylmaleate, dibutyltin maleate, dibutyltin diacetate, tin octaoate, dioctyltin distearate, dioctyltin dilaurate (DOTL), dioctyltin diethylmaleate, dioctyltin diisooctylmaleate, dioctyltin diacetate, and tin naphthenoate; tin alkoxides such as dibutyltin dimethoxide, dibutyltin diphenoxide, and dibutyltin diisoproxide; tin oxides such as dibutyltin oxide and dioctyltin oxide; reaction products between dibutyltin oxides and phthalic acid esters, dibutyltin bisacetylacetonate; organoaluminum compounds such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, and diisopropoxyaluminum ethylacetoacetate; chelate compounds such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate; lead octanoate; amine compounds or salts thereof with carboxylic acids, such as butylamine, octylamine, laurylamine, dibutylamines, monoethanolamines, diethanolamines, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamines, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris(dimethylaminomethyl)phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, und 1,8-diazabicyclo-(5,4,0)-undecene-7 (DBU), a low-molecular-weight polyamide resin obtained from an excess of a polyamine and a polybasic acid, adducts of a polyamine in excess with an epoxy, silane adhesion promoters having amino groups, such as 3-aminopropyltrimethoxysilane and N-(β-aminoethyl)aminopropylmethyldimethoxysilane.
- The catalyst, preferably mixtures of several catalysts, can be used in a quantity from 0.01 to approximately 5 wt % based on the entire weight of the composition.
- The composition according to the present invention can additionally contain fillers. Suitable here are, for example, chalk, lime powder, precipitated and/or pyrogenic silicic acid, zeolites, bentonites, magnesium carbonate, diatomite, alumina, clay, talc, titanium oxide, iron oxide, zinc oxide, sand, quartz, flint, mica, glass powder, and other ground mineral substances. Organic fillers can also be used, in particular carbon black, graphite, wood fibers, wood flour, sawdust, cellulose, cotton, pulp, cotton, wood chips, chopped straw, chaff, ground walnut shells, and other chopped fibers. Short fibers such as glass fibers, glass filament, polyacrylonitrile, carbon fibers, Kevlar fibers, or polyethylene fibers can also be added. Aluminum powder is likewise suitable as a filler.
- The pyrogenic and/or precipitated silicic acids advantageously have a BET surface area from 10 to 90 m2/g. When they are used, they do not cause any additional increase in the viscosity of the composition according to the present invention, but do contribute to strengthening the cured composition.
- It is likewise conceivable to use pyrogenic and/or precipitated silicic acids having a higher BET surface area, advantageously 100 to 250 m2/g, in particular 110 to 170 m2/g, as a filler. Because of the greater BET surface area, the same effect, e.g. strengthening the cured composition, is achieved with a smaller weight proportion of silicic acid. Further substances can thus be used to improve the composition according to the present invention in terms of different requirements.
- Also suitable as fillers are hollow spheres having a mineral shell or a plastic shell. These can be, for example, hollow glass spheres that are obtainable commercially under the trade names Glass Bubbles®. Plastic-based hollow spheres, e.g. Expancel® or Dualite®, are described e.g. in EP 0 520 426 B1. They are made up of inorganic or organic substances and each have a diameter of 1 mm or less, preferably 500 μm or less.
- Fillers that impart thixotropy to the composition are preferred for many applications. Such fillers are also described as rheological adjuvants, e.g. hydrogenated castor oil, fatty acid amides, or swellable plastics such as PVC. In order to be readily squeezable out of a suitable dispensing apparatus (e.g. a tube), such compositions possess a viscosity from 3000 to 150,000, preferably 40,000 to 80,000 mPas, or even 50,000 to 60,000 mPas.
- The fillers can be used by preference in a quantity from 1 to 80 wt %, by preference from 5 to 60 wt %, based on the total weight of the composition.
- Examples of suitable pigments are titanium dioxide, iron oxides, or carbon black.
- In order to enhance shelf life even further, it is often advisable to further stabilize the composition according to the present invention with respect to moisture penetration using drying agents. A need occasionally also exists to lower the viscosity of the adhesive or sealant according to the present invention for specific applications, by using a reactive diluent. All compounds that are miscible with the adhesive or sealant with a reduction in viscosity, and that possess at least one group that is reactive with the binder, can be used as reactive diluents.
- The following substances can be used, for example, as reactive diluents: polyalkylene glycols reacted with isocyanatosilanes (e.g. Synalox 100-50B, Dow), carbamatopropyltrimethoxysilane, alkyltrimethoxysilane, alkyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, and vinyltrimethoxysilane (VTMO Geniosil XL 10, Wacker), vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, octyltrimethoxysilane, tetraethoxysilane, vinyldimethoxymethylsilane (XL12, Wacker), vinyltriethoxysilane (GF56, Wacker), vinyltriacetoxysilane (GF62, Wacker), isooctyltrimethoxysilane (10 Trimethoxy), isooctyltriethoxysilane (10 Triethoxy, Wacker), N-trimethoxysilylmethyl-O-methyl carbamate (XL63, Wacker), N-dimethoxy(methyl)silylmethyl-O-methyl carbamate (XL65, Wacker), hexadecyltrimethoxysilane, 3-octanoylthio-1-propyltriethoxysilane, and partial hydrolysates of the aforementioned compounds.
- Also, usable as reactive diluents are the following polymers of Kaneka Corp.: MS S203H, MS S303H, MS SAT 010, and MS SAX 350.
- Silane-modified polymers that are derived, for example, from the reaction of isocyanatosilane with Synalox grades can likewise be used.
- In the same manner, the silylated polyurethanes according to the present invention can be used in a mixture with usual polymers or prepolymers known per se, optionally with concurrent use of the aforementioned reactive diluents, fillers, and further adjuvants and additives. “Usual polymers or prepolymers” can be selected in this context from polyesters, polyoxyalkylenes, polyacrylates, polymethacrylates, or mixtures thereof; these can be free of groups reactive with siloxane groups, but optionally can also comprise alkoxysilyl groups or hydroxyl groups.
- A plurality of the aforementioned silane-functional reactive diluents have at the same time a drying and/or adhesion-promoting effect in the composition. These reactive diluents may be used in quantities between 0.1 and 15 wt %, by preference between 1 and 5 wt %, based on the total weight of the composition.
- Also suitable as adhesion promoters, however, are so-called tackifying agents, such as hydrocarbon resins, phenol resins, terpene-phenolic resins, resorcinol resins or derivatives thereof, modified or unmodified resin acids or resin esters (abietic acid derivatives), polyamines, polyaminoamides, anhydrides, and anhydride-containing copolymers. The addition of polyepoxide resins in small quantities can also improve adhesion on many substrates. The solid epoxy resins having a molecular weight of over 700, in finely ground form, are then preferably used for this. If tackifying agents are used as adhesion promoters, their nature and quantity depend on the adhesive/sealant composition and on the substrate onto which it is applied. Typical tackifying resins (tackifiers) such as, for example, terpene-phenolic resins or resin acid derivatives, may be used in concentrations between 5 and 20 wt %; typical adhesion promoters such as polyamines, polyaminoamides, or phenolic resins or resorcinol derivatives may be used in the range between 0.1 and 10 wt %, based on the total weight of the composition.
- The present invention also provides the use of the silylated polyurethane according to the present invention as an adhesive, sealant, coating composition, or for the production thereof.
- In principle in the present invention, all features listed within the context of the present text, particularly the embodiments, proportional ranges, components and other features of the composition according to the invention, of the method according to the invention and of the use according to the invention identified as preferred and/or special, can be implemented in all possible and not mutually exclusive combinations, with combinations of features identified as preferred and/or special also being regarded as preferred and/or special.
- Manufacture of a Silylated Polyurethane (Use of Triisocyanate):
- 384.02 g (33.88 mmol) of polypropylene ether polyol (Acclaim 12200, hydroxyl value=9.90) were dried in a 500 ml three-necked flask at 80-90° C. under vacuum. Under a nitrogen atmosphere, 0.28 g of bismuth neodecanoate (Borchi Kat 315) were added with stirring. Then, 2.52 g (4.52 mmol) of triisocyanate (Tolonate HDT-LV) were added (NCO/OH ratio=0.2) with stirring. The mixture was left for one hour at 80-95° C. The conversion was accomplished with NCO monitoring, and as soon as the theoretical NCO value of the prepolymer had been reached titrimetrically (% NCO=0), 13.18 g (62.69 mmol) of 3-isocyanatopropyltrimethoxysilane (Geniosil GF 40) were added with stirring and the mixture was left for a further hour at 80-95° C. (% NCO=0.00 to 0.09). A star-shaped polymer was obtained. The resulting polymer was stored in a moisture-proof glass vessel under a nitrogen atmosphere before being processed further into a curable composition. The viscosity was 41,200 mPas.
- Manufacture of a Silylated Polyurethane (Use of Diisocyanate):
- A similar procedure to Example 1 was carried out except that HDI was used instead of triisocyanate. The viscosity was 28,200 mPas. Details are summarized in Table 1.
- Manufacture of a Silylated Polyurethane (Use of Triisocyanate):
- A similar procedure to Example 1 was carried out except that NCO/OH ratio=0.4 and Acclaim 4200 (hydroxyl value=29.50) was used instead of Acclaim 12200.
- The viscosity was 78,600 mPas. Details are summarized in Table 1.
- Manufacture of a Silylated Polyurethane (Use of Diisocyanate):
- A similar procedure to Example 2 was carried out except that HDI was used instead of triisocyanate. The viscosity was 10,600 mPas. Details are summarized in Table 1.
-
TABLE 1 Ex 1 Comp 1 Ex 2 Comp 2 Acclaim 384.02 g 385.33 g 12200 (33.88 mmol) (34.00 mmol) Acclaim 4200 357.13 g 364.02 g (93.90 mmol) (95.71 mmol) Borchi Kat 0.28 g 0.28 g 0.28 g 0.28 g 315 Tolonate 2.52 g 13.95 g HDT-LV (4.52 mmol) (25.04 mmol) HDI 1.16 g 6.52 g (6.80 mmol) (38.28 mmol) NCO/OH ratio 0.2 0.2 0.4 0.4 Geniosil GF 13.18 g 13.23 g 28.64 g 29.18 g 40 (62.69 mmol) (62.90 mmol) (136.15 mmol) (138.78 mmol) % NCO 0.00-0.09 0.00-0.09 0.00-0.25 0.00-0.25 after adding Geniosil GF 40 Viscosity 41,200 mPas 28,200 mPas 78,600 mPas 10,600 mPas - The viscosity values were determined using Brookfield viscometer (DV-II+Pro), spindle 7, 20 rpm, at 23° C.
- Manufacture of Compositions Comprising a Silylated Polyurethane:
- Each prepared silylated polyurethane according to above examples was heated for 24 hours at 23° C. and then 0.35 g of N-(2-Aminoethyl)-3-aminopropyltrimethoxysilane (Geniosil GF 91) and 0.14 g of DOTL or DBU were added to 34.51 g of each of the prepared polymer. This mixture was homogenized twice for 60 seconds at 2700 rpm in a SpeedMixer (DAC 150 FC).
- The time to form a skin (skin over time/SOT) and mechanical strength (tensil strength and elongation) were determined for the abovementioned mixtures. The results are summarized in Table 2 below. DOTL was used in preparing Examples A to D and DBU was used as a tin-free catalyst in preparing Examples E to F.
-
TABLE 2 A B C D E F Silylated Ex 1 Comp 1 Ex 2 Comp 2 Ex 1 Comp 1 Polyurethane SOT 14 min 16 min 22 min 1 h 21 min 33 min 44 min Tensil 0.88 0.85 1.10 0.89 0.80 0.76 Strength (N/mm2) Elongation 57.98 61.75 43.28 39.38 55.53 53.88 (%) - The aforementioned mixtures were homogenized and applied in a frame (50×130×2 mm). Each mixture was evenly distributed so that the frame can be completely filled. A thin polymer film was thereby obtained. The time to form a skin (skin-over time/SOT) was determined for these compositions using a tool which has a rounded spatula at the tip (150×5 mm). The tip of the spatula was gently contacted with the surface of the polymer film every 1 to 5 minutes and removed carefully. The SOT was measured once no more residue of the formulation remains on the spatula when removing it from the surface of the polymer film. Then, the resulting string must be removed from the spatula without residue. The polymer film returned to its original shape. In examining the SOT a different part of the surface of the polymer film must be used every time. The test was performed at 23° C. and 50% relative humidity.
- After being stored for 7 days (23° C., 50% relative humidity), four specimens were prepared from the polymer film and punched using a Mäder press (APK T3-5-40) and a punching tool unit according to DIN 53504-S3A. The mechanical data were determined by reference to DIN 53504:2009-10. Each specimen was set to the initial test position using a pre-load of 0.05 MPa and a speed rate of 40 mm/min. Actual measurement was done using a speed rate of 50 mm/min.
- The examples show that the mixtures A, C, and E containing a silylated polyurethane according the present invention (Examples 1 to 2), show reasonable viscosity, exhibit significantly shorter SOT than mixtures comprising a silylated polyurethane according to the Comparative Examples 1 to 2, while having good mechanical strength (tensil strength and elongation). In addition, comparison of Examples E and F shows that even in case of using non-tin catalyst the mixture containing a silylated polyurethane according the present invention also exhibits short SOT and good mechanical properties.
Claims (10)
1. A silylated polyurethane obtained by a process comprising the following steps:
(a) reacting at least one polyol with at least one triisocyanate to form a hydroxyl-terminated polyurethane prepolymer; and
(b) reacting the hydroxyl-terminated polyurethane prepolymer with at least one isocyanatosilane of formula (1) to endcap the hydroxyl groups on the hydroxyl-terminated polyurethane prepolymer with the isocyanatosilane,
OCN—R—Si—(X)m(R1)3-m (1)
OCN—R—Si—(X)m(R1)3-m (1)
wherein
m is 0, 1 or 2,
each R1 is independently from each other a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, or —OCH(R2)COOR3, wherein R2 is hydrogen or an alkyl group having 1 to 4 carbon atoms and R3 is a straight-chain or branched alkyl group having 1 to 8 carbon atoms,
each X is independently from each other an optionally substituted hydrocarbon group having 1 to 10 carbon atoms, which can be interrupted by at least one heteroatom, and
R is a difunctional organic group.
2. The silylated polyurethane according to claim 1 , wherein a molar ratio of the NCO groups of the triisocyanate to hydroxyl groups of the polyol is from 0.05 to 0.45.
3. The silylated polyurethane according to claim 1 , wherein said polyol is a polyether polyol.
4. The silylated polyurethane according to claim 1 , wherein said polyol has a number average molecular weight of from 500 to 20,000 g/mol.
5. The silylated polyurethane according to claim 1 , wherein said triisocyanate is derived from HDI, TDI, MDI, PDI, IPDI, or mixtures thereof.
6. The silylated polyurethane according to claim 1 , wherein said isocyanatosilane is selected from the group consisting of 3-isocyanatopropyltrimethoxysilane, 2-isocyanatoisopropyltrimethoxysilane, 4-isocyanato-n-butyltrimethoxysilane, 2-isocyanato-1,1-dimethylethyltrimethoxysilane, 1-isocyanatomethyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 2-isocyanato-2-methylethyltriethoxysilane, 4-isocyanatobutyltriethoxysilane, 2-isocyanato-1,1-dimethylethyltriethoxysilane, 1-isocyanatomethyltriethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, 3-isocyanatopropyldimethylmethoxysilane, 3-isocyanatopropylphenylmethylmethoxysilane, 1-isocyanatomethylmethyldimethoxysilane, 3-isocyanatopropylethyldiethoxysilane, 3-isocyanatopropylmethyldiethoxysilane, 1-isocyanatomethylmethyldiethoxysilane, and mixtures thereof.
7. The silylated polyurethane according to claim 1 , wherein said process comprises further step of adding a catalyst.
8. A process for preparing a silylated polyurethane comprising the following steps:
(a) reacting at least one polyol with at least one triisocyanate to form a hydroxyl-terminated polyurethane prepolymer; and
(b) reacting the hydroxyl-terminated polyurethane prepolymer with at least one isocyanatosilane of formula (1) to endcap the hydroxyl groups on the hydroxyl-terminated polyurethane prepolymer with the isocyanatosilane,
OCN—R—Si—(X)m(R1)3-m (1)
OCN—R—Si—(X)m(R1)3-m (1)
wherein
m is 0, 1 or 2,
each R1 is independently from each other a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, or —OCH(R2)COOR3, wherein R2 is hydrogen or an alkyl group having 1 to 4 carbon atoms and R3 is a straight-chain or branched alkyl group having 1 to 8 carbon atoms,
each X is independently from each other an optionally substituted hydrocarbon group having 1 to 10 carbon atoms, which can be interrupted by at least one heteroatom, and
R is a difunctional organic group.
9. An adhesive, sealant, or coating composition comprising the silylated polyurethane according to claim 1 .
10. A silylated polyurethane that is the reaction product of a mixture comprising:
(a) the hydroxyl terminated polyurethane prepolymer reaction product of a mixture comprising at least one polyol and at least one triisocyanate; and
(b) at least one isocyanatosilane of formula (1)
OCN—R—Si—(X)m(R1)3-m (1)
OCN—R—Si—(X)m(R1)3-m (1)
wherein
m is 0, 1 or 2,
each R1 is independently from each other a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, or —OCH(R2)COOR3, wherein R2 is hydrogen or an alkyl group having 1 to 4 carbon atoms and R3 is a straight-chain or branched alkyl group having 1 to 8 carbon atoms,
each X is independently from each other an optionally substituted hydrocarbon group having 1 to 10 carbon atoms, which can be interrupted by at least one heteroatom, and
R is a difunctional organic group.
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CA3059467A1 (en) * | 2017-04-26 | 2018-11-01 | Henkel IP & Holding GmbH | Silane modified polymers with improved properties |
EP3696205B1 (en) * | 2017-11-27 | 2021-10-06 | Yantai Darbond Technology Co., Ltd. | Method for preparing high temperature-resistant polyurethane hot melt adhesive |
EP3501642A1 (en) * | 2017-12-22 | 2019-06-26 | Covestro Deutschland AG | Method for the preparation of mixed silane terminated polymers |
CN112004862A (en) * | 2018-04-25 | 2020-11-27 | 汉高股份有限及两合公司 | Process for preparing hydroxy-functionalized polyether-polysiloxane block copolymers |
US11326017B2 (en) * | 2018-09-10 | 2022-05-10 | Evonik Operations Gmbh | Tin-free catalysis of silane-functional polyurethane crosslinkers |
CN112142945B (en) * | 2019-06-27 | 2022-07-12 | 万华化学集团股份有限公司 | High-stability silyl-terminated polymer resin and preparation method thereof |
CN111978850A (en) * | 2020-07-22 | 2020-11-24 | 上海三棵树防水技术有限公司 | Silane modified waterproof coating and preparation method thereof |
Citations (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4345053A (en) * | 1981-07-17 | 1982-08-17 | Essex Chemical Corp. | Silicon-terminated polyurethane polymer |
US4625012A (en) * | 1985-08-26 | 1986-11-25 | Essex Specialty Products, Inc. | Moisture curable polyurethane polymers |
US6060560A (en) * | 1997-05-23 | 2000-05-09 | Shell Oil Company | Polyurethane compositions made from hydroxy-terminated polydiene polymers |
US20030105263A1 (en) * | 2000-08-16 | 2003-06-05 | Fan Wayne W. | Urethane-based stain-release coatings |
US20070100108A1 (en) * | 2005-10-27 | 2007-05-03 | Misty Huang | Process for making moisture-curable silylated resin composition, the resulting composition and moisture-curable products containing the composition |
US7435787B2 (en) * | 2005-09-14 | 2008-10-14 | Momentive Performance Materials Inc. | Process for the continuous production of silylated resin |
US20100317796A1 (en) * | 2009-05-01 | 2010-12-16 | Misty Huang | Moisture Curable Silylated Polymer Compositions Containing Reactive Modifiers |
US20110155320A1 (en) * | 2008-08-27 | 2011-06-30 | Sika Technology Ag | Silane/urea compound as a heat-activatable curing agent for epoxide resin compositions |
US8138297B2 (en) * | 2009-02-09 | 2012-03-20 | Momentive Performance Materials Inc. | Moisture-curable silylated polymer possessing improved storage stability |
US20130303804A1 (en) * | 2010-06-29 | 2013-11-14 | Construction Research & Technology Gmbh | Process For Preparing A Thixotroping Agent And Use Thereof |
US8834670B2 (en) * | 2010-12-29 | 2014-09-16 | Cheil Industries, Inc. | Optical adhesive composition and display panel including the same |
CN104327245A (en) * | 2014-11-05 | 2015-02-04 | 山东禹王实业有限公司化工分公司 | Silane end-capped polyurethane plasticizer and preparation method thereof |
US20150274918A1 (en) * | 2012-10-24 | 2015-10-01 | Bayer Materialscience Ag | Multicomponent system for production of alkoxysilane-based spray foams |
US20150284499A1 (en) * | 2012-10-24 | 2015-10-08 | Bayer Materialscience Ag | Alkoxysilane-terminated prepolymer based on polyether carbonate polyols, for spray foams |
US20150284610A1 (en) * | 2012-12-17 | 2015-10-08 | Henkel Ag & Co. Kgaa | Low-modulus silylated polyurethanes |
US20170183534A1 (en) * | 2014-10-22 | 2017-06-29 | The Government Of The United States Of America, As Represented By The Secretary Of The Navy | Siloxane-based coatings containing polymers with urea linkages and terminal alkoxysilanes |
US10118984B2 (en) * | 2015-03-11 | 2018-11-06 | Henkel Ag & Co. Kgaa | Silylated polyurethanes, their preparation and use |
Family Cites Families (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1207594A (en) | 1967-03-16 | 1970-10-07 | Union Carbide Corp | One component room temperature vulcanizable silicon terminated polymers |
US3979344A (en) | 1974-11-19 | 1976-09-07 | Inmont Corporation | Vulcanizable silicon terminated polyurethane polymer composition having improved cure speed |
US3971751A (en) | 1975-06-09 | 1976-07-27 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Vulcanizable silylether terminated polymer |
US4222925A (en) | 1978-08-02 | 1980-09-16 | Inmont Corporation | Vulcanizable silicon terminated polyurethane polymer compositions having improved cure speed |
JPS63110272A (en) * | 1986-10-27 | 1988-05-14 | Sumitomo Deyurezu Kk | Adhesive composition for composite laminate |
US4960844A (en) | 1988-08-03 | 1990-10-02 | Products Research & Chemical Corporation | Silane terminated liquid polymers |
JPH02140220A (en) | 1988-11-21 | 1990-05-29 | Kanegafuchi Chem Ind Co Ltd | Curable resin composition |
DE4029504A1 (en) | 1990-09-18 | 1992-03-19 | Henkel Kgaa | SEALING AND ADHESIVE MATERIALS WITH SPECIAL SOFTENERS |
JPH051225A (en) | 1991-06-25 | 1993-01-08 | Kanegafuchi Chem Ind Co Ltd | Curable composition |
US5225512A (en) | 1991-08-29 | 1993-07-06 | Basf Corporation | Polymer and adhesive composition |
US5990257A (en) * | 1998-01-22 | 1999-11-23 | Witco Corporation | Process for producing prepolymers which cure to improved sealants, and products formed thereby |
DE19908562A1 (en) * | 1998-03-25 | 1999-10-07 | Henkel Kgaa | Polyurethane, used in e.g. adhesives |
US6008305A (en) * | 1998-06-30 | 1999-12-28 | Adco Products, Inc. | Primer for improving the bonding of adhesives to nonporous substrates |
US6299980B1 (en) * | 1998-09-29 | 2001-10-09 | Medtronic Ave, Inc. | One step lubricious coating |
DE19849817A1 (en) | 1998-10-29 | 2000-05-04 | Bayer Ag | Polyurethane prepolymers containing alkoxysilane end groups, a process for their preparation and their use for the production of sealants |
US6124387A (en) | 1998-12-22 | 2000-09-26 | Adco Products, Inc. | Fast-cure silylated polymer adhesive |
US6833423B2 (en) * | 2002-06-18 | 2004-12-21 | Bayer Polymers Llc | Moisture-curable, polyether urethanes with reactive silane groups and their use as sealants, adhesives and coatings |
DE102006021917A1 (en) * | 2006-05-11 | 2007-11-15 | Basf Coatings Ag | Branched polyols having on average two or more hydroxyl groups in the molecule, processes for their preparation and their use |
DE102007058483A1 (en) | 2007-12-04 | 2009-06-10 | Henkel Ag & Co. Kgaa | Curable compositions containing silylated polyurethanes |
DE102008020980A1 (en) * | 2008-04-25 | 2009-10-29 | Henkel Ag & Co. Kgaa | Curable compositions containing silylated polyurethanes based on polyether block polymers |
WO2010110166A1 (en) * | 2009-03-25 | 2010-09-30 | ダイキン工業株式会社 | Non-fouling ordinary-temperature-curable coating composition |
DE102009028640A1 (en) | 2009-08-19 | 2011-02-24 | Evonik Goldschmidt Gmbh | Curable composition containing urethane-containing silylated polymers and their use in sealants and adhesives, binders and / or surface modifiers |
US9572868B2 (en) | 2011-09-29 | 2017-02-21 | Covestro Deutschland Ag | Fast-setting alkoxysilane spray foams |
US9156981B2 (en) * | 2013-07-24 | 2015-10-13 | Momentive Performance Materials Inc. | Moisture curable compositions with enhanced elongation and tear strength properties |
-
2015
- 2015-03-11 PL PL15158615T patent/PL3067375T3/en unknown
- 2015-03-11 ES ES15158615.3T patent/ES2645863T3/en active Active
- 2015-03-11 EP EP15158615.3A patent/EP3067375B1/en active Active
-
2016
- 2016-03-09 CA CA2978978A patent/CA2978978C/en active Active
- 2016-03-09 CN CN201680014607.2A patent/CN107406570B/en not_active Expired - Fee Related
- 2016-03-09 WO PCT/EP2016/055005 patent/WO2016142416A1/en active Application Filing
- 2016-03-09 KR KR1020177028252A patent/KR20170128418A/en not_active Application Discontinuation
- 2016-03-09 JP JP2017547447A patent/JP6867294B2/en active Active
- 2016-03-09 MX MX2017011530A patent/MX2017011530A/en unknown
- 2016-03-09 BR BR112017017856A patent/BR112017017856A2/en not_active Application Discontinuation
- 2016-03-09 RU RU2017134961A patent/RU2690688C2/en active
-
2017
- 2017-09-07 CL CL2017002261A patent/CL2017002261A1/en unknown
- 2017-09-07 US US15/697,499 patent/US10118984B2/en active Active
-
2018
- 2018-10-05 US US16/152,599 patent/US20190031812A1/en not_active Abandoned
Patent Citations (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4345053A (en) * | 1981-07-17 | 1982-08-17 | Essex Chemical Corp. | Silicon-terminated polyurethane polymer |
US4625012A (en) * | 1985-08-26 | 1986-11-25 | Essex Specialty Products, Inc. | Moisture curable polyurethane polymers |
US6060560A (en) * | 1997-05-23 | 2000-05-09 | Shell Oil Company | Polyurethane compositions made from hydroxy-terminated polydiene polymers |
US20030105263A1 (en) * | 2000-08-16 | 2003-06-05 | Fan Wayne W. | Urethane-based stain-release coatings |
US7435787B2 (en) * | 2005-09-14 | 2008-10-14 | Momentive Performance Materials Inc. | Process for the continuous production of silylated resin |
US20070100108A1 (en) * | 2005-10-27 | 2007-05-03 | Misty Huang | Process for making moisture-curable silylated resin composition, the resulting composition and moisture-curable products containing the composition |
US20110155320A1 (en) * | 2008-08-27 | 2011-06-30 | Sika Technology Ag | Silane/urea compound as a heat-activatable curing agent for epoxide resin compositions |
US8138297B2 (en) * | 2009-02-09 | 2012-03-20 | Momentive Performance Materials Inc. | Moisture-curable silylated polymer possessing improved storage stability |
US20100317796A1 (en) * | 2009-05-01 | 2010-12-16 | Misty Huang | Moisture Curable Silylated Polymer Compositions Containing Reactive Modifiers |
US20130303804A1 (en) * | 2010-06-29 | 2013-11-14 | Construction Research & Technology Gmbh | Process For Preparing A Thixotroping Agent And Use Thereof |
US8834670B2 (en) * | 2010-12-29 | 2014-09-16 | Cheil Industries, Inc. | Optical adhesive composition and display panel including the same |
US20150274918A1 (en) * | 2012-10-24 | 2015-10-01 | Bayer Materialscience Ag | Multicomponent system for production of alkoxysilane-based spray foams |
US20150284499A1 (en) * | 2012-10-24 | 2015-10-08 | Bayer Materialscience Ag | Alkoxysilane-terminated prepolymer based on polyether carbonate polyols, for spray foams |
US20150284610A1 (en) * | 2012-12-17 | 2015-10-08 | Henkel Ag & Co. Kgaa | Low-modulus silylated polyurethanes |
US20170183534A1 (en) * | 2014-10-22 | 2017-06-29 | The Government Of The United States Of America, As Represented By The Secretary Of The Navy | Siloxane-based coatings containing polymers with urea linkages and terminal alkoxysilanes |
CN104327245A (en) * | 2014-11-05 | 2015-02-04 | 山东禹王实业有限公司化工分公司 | Silane end-capped polyurethane plasticizer and preparation method thereof |
US10118984B2 (en) * | 2015-03-11 | 2018-11-06 | Henkel Ag & Co. Kgaa | Silylated polyurethanes, their preparation and use |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2022162106A1 (en) | 2021-01-30 | 2022-08-04 | Merz + Benteli Ag | Silane-terminated polymers |
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KR20170128418A (en) | 2017-11-22 |
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STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |