IE71041B1 - Coupling agent - Google Patents
Coupling agentInfo
- Publication number
- IE71041B1 IE71041B1 IE420091A IE420091A IE71041B1 IE 71041 B1 IE71041 B1 IE 71041B1 IE 420091 A IE420091 A IE 420091A IE 420091 A IE420091 A IE 420091A IE 71041 B1 IE71041 B1 IE 71041B1
- Authority
- IE
- Ireland
- Prior art keywords
- formula
- compound
- radical
- die
- equal
- Prior art date
Links
- 239000007822 coupling agent Substances 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims abstract description 55
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 24
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 24
- 150000003254 radicals Chemical class 0.000 claims abstract description 24
- 125000003118 aryl group Chemical class 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 125000000391 vinyl group Chemical class [H]C([*])=C([H])[H] 0.000 claims abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000001072 heteroaryl group Chemical class 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 3
- -1 cycloaliphatic Chemical group 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 22
- 125000001931 aliphatic group Chemical group 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 150000002148 esters Chemical class 0.000 claims description 8
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 6
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical group NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910052717 sulfur Chemical group 0.000 claims description 2
- 239000011593 sulfur Chemical group 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002318 adhesion promoter Substances 0.000 abstract description 14
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract description 4
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 abstract 4
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 abstract 1
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 abstract 1
- 239000005864 Sulphur Substances 0.000 abstract 1
- 150000007854 aminals Chemical class 0.000 description 33
- 239000004814 polyurethane Substances 0.000 description 18
- 239000000758 substrate Substances 0.000 description 18
- 239000012948 isocyanate Substances 0.000 description 17
- 229920002635 polyurethane Polymers 0.000 description 16
- 229920005862 polyol Polymers 0.000 description 15
- 150000003077 polyols Chemical class 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- 238000000921 elemental analysis Methods 0.000 description 13
- 125000005442 diisocyanate group Chemical group 0.000 description 12
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 12
- 150000002513 isocyanates Chemical class 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- 239000000853 adhesive Substances 0.000 description 10
- 230000001070 adhesive effect Effects 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 8
- 239000007858 starting material Substances 0.000 description 8
- 238000005481 NMR spectroscopy Methods 0.000 description 7
- 150000002466 imines Chemical class 0.000 description 7
- 229920000570 polyether Polymers 0.000 description 7
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 7
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 6
- 239000004721 Polyphenylene oxide Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- 229910000077 silane Inorganic materials 0.000 description 6
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 5
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 5
- 239000004417 polycarbonate Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000007259 addition reaction Methods 0.000 description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 4
- 238000013008 moisture curing Methods 0.000 description 4
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 229920005906 polyester polyol Polymers 0.000 description 4
- 239000004848 polyfunctional curative Substances 0.000 description 4
- 150000004756 silanes Chemical class 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000003677 Sheet moulding compound Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 238000006748 scratching Methods 0.000 description 3
- 230000002393 scratching effect Effects 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 229940117916 cinnamic aldehyde Drugs 0.000 description 2
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- JXCHMDATRWUOAP-UHFFFAOYSA-N diisocyanatomethylbenzene Chemical compound O=C=NC(N=C=O)C1=CC=CC=C1 JXCHMDATRWUOAP-UHFFFAOYSA-N 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000004872 foam stabilizing agent Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000011810 insulating material Substances 0.000 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 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- QHJABUZHRJTCAR-UHFFFAOYSA-N n'-methylpropane-1,3-diamine Chemical compound CNCCCN QHJABUZHRJTCAR-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003606 tin compounds Chemical class 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 2
- XMNDMAQKWSQVOV-UHFFFAOYSA-N (2-methylphenyl) diphenyl phosphate Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 XMNDMAQKWSQVOV-UHFFFAOYSA-N 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- DKYBVKMIZODYKL-UHFFFAOYSA-N 1,3-diazinane Chemical compound C1CNCNC1 DKYBVKMIZODYKL-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 description 1
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- BHCFVCRRNLIOGM-UHFFFAOYSA-J C(CO)(=O)[O-].[Mo+4].C(CO)(=O)[O-].C(CO)(=O)[O-].C(CO)(=O)[O-] Chemical compound C(CO)(=O)[O-].[Mo+4].C(CO)(=O)[O-].C(CO)(=O)[O-].C(CO)(=O)[O-] BHCFVCRRNLIOGM-UHFFFAOYSA-J 0.000 description 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 1
- 239000004965 Silica aerogel Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- PQYJRMFWJJONBO-UHFFFAOYSA-N Tris(2,3-dibromopropyl) phosphate Chemical compound BrCC(Br)COP(=O)(OCC(Br)CBr)OCC(Br)CBr PQYJRMFWJJONBO-UHFFFAOYSA-N 0.000 description 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000004705 aldimines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 229940053200 antiepileptics fatty acid derivative Drugs 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 235000012216 bentonite Nutrition 0.000 description 1
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000009954 braiding Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000004799 bromophenyl group Chemical group 0.000 description 1
- YFNONBGXNFCTMM-UHFFFAOYSA-N butoxybenzene Chemical group CCCCOC1=CC=CC=C1 YFNONBGXNFCTMM-UHFFFAOYSA-N 0.000 description 1
- SHZIWNPUGXLXDT-UHFFFAOYSA-N caproic acid ethyl ester Natural products CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000000068 chlorophenyl group Chemical group 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- JQZRVMZHTADUSY-UHFFFAOYSA-L di(octanoyloxy)tin Chemical compound [Sn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O JQZRVMZHTADUSY-UHFFFAOYSA-L 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 125000004188 dichlorophenyl group Chemical group 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 150000004662 dithiols Chemical class 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000001207 fluorophenyl group Chemical group 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- ZBKFYXZXZJPWNQ-UHFFFAOYSA-N isothiocyanate group Chemical group [N-]=C=S ZBKFYXZXZJPWNQ-UHFFFAOYSA-N 0.000 description 1
- 150000004658 ketimines Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000006233 lamp black Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000012764 mineral filler Chemical group 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- KFIGICHILYTCJF-UHFFFAOYSA-N n'-methylethane-1,2-diamine Chemical compound CNCCN KFIGICHILYTCJF-UHFFFAOYSA-N 0.000 description 1
- 125000004370 n-butenyl group Chemical group [H]\C([H])=C(/[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000006501 nitrophenyl group Chemical group 0.000 description 1
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical class OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- BGUWFUQJCDRPTL-UHFFFAOYSA-N pyridine-4-carbaldehyde Chemical compound O=CC1=CC=NC=C1 BGUWFUQJCDRPTL-UHFFFAOYSA-N 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 238000010107 reaction injection moulding Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical class [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- HQUQLFOMPYWACS-UHFFFAOYSA-N tris(2-chloroethyl) phosphate Chemical compound ClCCOP(=O)(OCCCl)OCCCl HQUQLFOMPYWACS-UHFFFAOYSA-N 0.000 description 1
- GTRSAMFYSUBAGN-UHFFFAOYSA-N tris(2-chloropropyl) phosphate Chemical compound CC(Cl)COP(=O)(OCC(C)Cl)OCC(C)Cl GTRSAMFYSUBAGN-UHFFFAOYSA-N 0.000 description 1
- 210000001745 uvea Anatomy 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- 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
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
- C08K5/5455—Silicon-containing compounds containing nitrogen containing at least one group
-
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/28—Non-macromolecular organic substances
- C08L2666/44—Silicon-containing compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Compounds of the general formula I in which R1 denotes C2-C3-alkylene and R2 denotes hydrogen, C1-C6-alkyl or C2-C6-alkenyl, each of which is unsubstituted or substituted by -OH, -CN or -Si(OR3)3-q(R4)q, where R3 is C1-C4-alkyl or two radicals R3 together represent C1-C4-alkylene, R4 is C1-C4-alkyl or phenyl and q can have values from 0 to 2, and E represents a radical of the formula in which R5 and R6 independently of one another are hydrogen, C1-C4-alkyl, aryl-substituted ethenyl, aryl, heteroaryl or radicals of the formulae IIa or IIb with the proviso that at least one of the radicals R5 or R6 denotes aryl-substituted ethenyl, aryl, heteroaryl or a radical of the formulae IIa or IIb, or E, together with R2, denotes a radical of the formula in which R7 is hydrogen, C1-C4-alkyl or -R9-Si(OR3)3-q(R4)q and R3, R4 and q have the above meaning and R9 denotes C1-C8-alkylene, and Y denotes oxygen or sulphur; and also T denotes a radical of the formula -R9-Si(OR3)3-q(R4)q or or, if R7 represents a radical of the formula -R9-Si(OR3)3-q(R4)q and m is greater than or equal to 2, denotes an m-valent radical Z, in which R3, R4, R9, Y and q have the above meanings, X is -S- or -NH- and Z is an organic radical which is derived from a polyisocyanate or a polyisothiocyanate having at least two NCO or NCS groups, and r is 1, 2 or 3 and p is 0 or 1 and m can have values greater than or equal to 1 and n can have values greater than or equal to 1, are suitable, for example, as adhesion promoters, in particular for one and two component polyurethane resin systems.
Description
The present invention relates to nitrogen-containing silane compounds and polyurethane resins containing these silane compounds as adhesion promoters.
The adhesion of cured polyurethanes to various substrates, such as glass, plastic or metal, is in many industrial applications unsatisfactory, which has led to die use of primers. This makes it possible to obtain a good bond between die polyurethane and the substrate. This bond is hardly impaired by high moisture, elevated temperatures and high mechanical stress. Examples of primers which have proven suitable are aminoalkylalkoxysilanes (cf. Plueddemann et al. Silane Coupling Agents, Plenum Press, NY [1982]). However, die most effective aminosilane adhesion promoters cannot be used as built-in adhesion promoters in moisture-curing polyurethanes in unmodified form, since die amino groups will react completely with isocyanate groups. Therefore, DE-A 3414 877 has described ketimines and aldimines of aminoalkylsilanes, which can be added to polyurethane adhesives without impairing their shelf life.
Furthermore, US-A 3,787,416 and 4,289,869 have described cyclic aminals as hardeners for polyurethane resins. Furthermore, reaction products of cyclic aminals with isocyanates to give adducts which are suitable as hardeners for polyurethane resins are disclosed in US-A 4,404,379. However, these aminals or aminal adducts do not contain silane-containing groups.
A group of compounds has now been found which can be added to 1- or 2-component polyurethane resin adhesives, sealing compositions, coating compositions and insulating materials, resulting in significantly improved adhesion to glass, metal, coated steel and plastics while at the same time not impairing or even increasing the curing rate.
The present invention relates to compounds of the general formula I ['
E-Rj-N— I(CH2)-0 * 1_ fO-lp-C-HN4—T . Jm (D
-271041 in which
Rj is C2-C3alkylenc and
R2 is hydrogen, Cj-Cgalkyl which is unsubstituted cor substituted by-OH,-CN or -Si(OR3)3^(R4)q or is C^-Cgalkenyl, in which
R3 is Cj-C4alkyl or two radicals R3 together are Cj-C4alkylene,
R4 is Cj-C4alkyl or phenyl and q can have values from 0 to 2, furthermore
E is a radical of the formula
in which
R5 and Rg, independently of one another, are hydrogen, Cj-C4alkyl, aryl-substituted ethenyl, aryl, heteroaryl or radicals of the formulae Da or Ob
O*C^HN-
(Ha) (Hb) with the proviso that ar least one of the radicals R5 or Rg is aryl-substituted ethenyl, aryl, heteroaryl or a radical of the formulae Da or Hb or
E together with R2 is a radical of die farmnla in which R7 is hydrogen, Cj-Cgalkyl or -R^iCORs^QQq and R3, Rg, Rs, Rg and q
-3are as defined above, and R$ is CpCgalkylene, and
Y is oxygen or sulfur; furthermore,
T is a radical of the formulae -Rg-SiCORs^CIQq or γ
II
ZH—NH-C — X
or, if R7 is a radical of the formula -R^SiCORj^CR^q and m is greater than or equal to 2, is an m-valent radical Z in which R3, Rq, Rg, Y and q are as defined above,
X is -S- or -NH- and
Z is an organic radical which is derived from a polyisocyanate or a polyisothiocyanate having at least 2 NCO or NCS groups, and r is 1,2 or 3 and p is 0 or 1 and m can have values of greater than or equal to 1 and n can have values oi greater than or equal to 1.
R3, R4, R5, R<5 and R7 as Cj-^alkyl or R2 as CrCgalkyl are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl and in the case of R2 additionally n-pentyl or n-hexyl.
The preferred meaning of R3 and R4 as alkyl is methyl and ethyl, in particular methyl.
Examples of R5 and Re as aryl are phenyl or naphthyl, which can be unsubstituted or substituted by Ci-C4alkyl, Cj-Qalkenyl, in particular -ΟΗ=€Η2, Cj-Qalkoxy, -NOj and halogen, in particular chlorine or bromine. Examples are methylphenyl, ethylphenyl, propylphenyl, isopropylphenyl, butylphenyl, isobutylphenyl and tert-butylphenyl; methoxyphenyl, ethoxyphenyl and butoxyphenyl; nitrophenyl, fluorophenyl, chlorophenyl, bromophenyl, dichlorophenyl and dibromophenyl and styryl.
Rs and R$ as heteroaryl are in particular heteroaromadcs having 5 or 6 ring members and one or two N, O or S atoms, which, if desired, can be benzo-fused, such as pyridyl, thienyl, benzothienyl, furyl, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl and
-4quinolyl.
Ri as CrQalkylene, two radicals R3 together as Ci-Qalkylene andRj as CpCgalkylene are straight-chain or branched alkylene, the straight-chain alkylene being preferred. Examples are methylene, ethylene, propylene, trimethylene, tetramethylene,
2-methyl-l,3-trimethylene for R3 and R9 and in the case of R$ additionally pentamethytene, 2-methyl- 1,4-tetramethytene, 3-propyl-l,3-triinethylene,
1,6-hexameihylene, 1,7-heptamethylene, l,8-octamethyleneor2-ethyl-l,2-hexamethylene, the meaning of Rj being limited to ethylene, propylene and trimethylene.
Preferably, R9 is CpCgalkylene, in particular trimethylene or ethylene.
R2 as Q-Cgalkenyl is straight-chain or branched alkenyl, preferably straight-chain alkenyl containing one or mate, but preferably one, double bond, such as ethenyl (vinyl), 2-propenyl (allyl), n-butenyl, 13-butadienyl, i-pentenyl, n-pentenyl or n-hexenyL
R2 as CpQalkyl substituted by OH, CN or -Si(OR3)3^(R4)q groups can be mono- or poly substituted, monosubstitution being preferred. The substitution can be present in any possible position, although the terminal position is preferred.
Preferably, R2 is CpQalkyl, in particular methyl.
Preferably, die parameter p in formula I has the value 0.
Also preferably, the parameter q has the value 0.
The radical Z is derived from a polyisocyanate or polyisothiocyanate having at least 2
NCO or NCS groups. This NCO or NSC functionality of greater than or equal to 2 of the polyisocyanate or polyisothiocyanate which is possible according to the invention is achieved by converting, for example, polyamines, such as amino-tenninal pdyetber polyols, to polyisocyanates or polyisothiocyanates having a functionality of greater than or equal to 2 by phosgenation or tiuophosgenation. The polyisocyanates or polyisothiocyanates thus obtainable can either be used directly or first convened with diols, polyols, dithiols, diamines or polyamines to NCO- or NCS-terminal prepolymers. The polyisocyanates obtainable in the manner described below can also be reacted in this way.
-5A further possibility to prepare polyisocyanates having an NCO functionality of greater than/equal to 2 consists in oligomerisation of diisocyanates. Thus, for example, diisocyanates, such as hexamethylene diisocyanate, can be converted by partial hydrolysis to products containing biuret groups (for example Desmodur® N100 from Bayer).
Furthermore, diisocyanates, such as hexamethylene diisocyanate, can be partially trimerised, leading to die formation of higher functional polyisocyanates containing isocyanurate rings (for example Desmodur® N3200 from Bayer).
Chain-lengthening by reaction of diisocyanates with polyfunctional compounds having acidic hydrogen and a functionality of greater than or equal to 2, such as triols, tetrols, pentols, triamines, pdyamines or polythiols, also leads to polyisocyanates having an NCO functionality of greater than/equal to 2. There, the NCO/OH ratio is greater than 1, but preferably greater than 3:1, in particular greater than 10:1.
Suitable diisocyanates are not only aromatic but also aliphatic, heterocyclic or monocyclic and polycyclic bifunctional isocyanate compounds. Examples of compounds of this type are toluylene diisocyanate, diphenylmethane diisocyanate, napthylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate or dicydohexylmethane diisocyanate.
The parameters m and n have, advantageously independently of one another, values from 1 to 49, preferably 1 to 9, particularly preferably 1 ro 5 and very particularly preferably 1,
2 and 3. The sum of n + m is advantageously 2 to 50, preferably 2 to 10, in particular 2 ro
6.
The radical Z has preferably an average molecular weight of less than 10 000, in particular an Mb of less than 4000.
Preference is given ro compounds of the formula I in which Y is oxygen.
Preferred compounds have the formula I in which Z is derived from an aliphatic, cycloaliphatic, aliphatic/aromatic, aromatic or heterocyclic polyisocyanate or polyisothiocyanate in which fee number of NCO ot NCS groups is greater than or equal 2, it being possible for this radical Z ro contain, if desired, one or more ester, ether, urethane,
-6thiourethane, isocyanurate, uvea ot biuret functions.
Particularly preferred compounds have the formula I in which Z is derived from an aliphatic or mixed aliphatic/aramatic polyisocyanate in which the number of NCO groups is 2 2, it being possible for this radical Z to contain, if desired, a total of one or two ester, ether, urethane, thiomethane, isocyanurate, urea or biuret functions.
In the compounds of foe formula I in which Z has ether oxygen atoms, Z can be a monoether or oligoether, for example a group of foe formula -(CHfCHJ-CHj-O)^ or -(CH2-CH2-CH2-CH2-O)y-, in which y is a number from 1 to 80, preferably from 1 to 20.
In foe compounds of foe formula I in which foe radical Z comprises urethane or thiourcthane groups, Z is a derivative which is obtainable by reaction of polyols with compounds containing isocyanate or isothiocyanate groups. This is also understood to include radicals which contain not only one or mote urethane groups but also one or more thiourethane groups, for example those containing a bridging member of foe formula o o o o
II II or H II or
-O-C-HN—D—NH-C-O- -S-C-HN—-D—NH-C — SO
II
S-C-HNO
II
-D—NH-C—O, in which D is the radical of foe polyol.
Examples of polyols which can also be used are OH-terminal polyethers or polyesters.
The radical Z in preferred compounds of foe formula I contains two ester, urethane, isocyanurate, urea or biuret functions, but in particularly preferred compounds only one. The ether functions represent a certain exception, since, as shown above, they are capable of forming oligoether bridging members. Compounds of this type can therefore contain up to 80, preferably up to 20, ether functions.
Preference is given to compounds of the formula I in which Rx is propylene.
Particular preference is given to compounds of die formula 1 in which at least one of the radicals R5 orR$ is a group of the formulae
-7A further preferred embodiment relates to compounds of the formula I in which T is a radical of the formulae ^-SifOR^^CR^q or
in particular those in which at least one radical X is -S-.
Special preference is given to compounds of the formula I in which p and q are 0, mis 1 and n is 2, Y is oxygen, X is-S-, R} and R$ are propylene, R2 and R3 are methyl, R5 is phenyl and R5 is hydrogen.
The compounds of the formula I are prepared by processes known per se, which can be most simply illustrated by means of the following reaction schemes.
I. Amine portion of die aminal or imine
HN—Rj— NH2
O
Ry-N
-RSh +
This preparation is carried out, for example, in the manner described in US-A4,404379. Starting materials (A) and (B) are known compounds, some of them being commercially available, or can be prepared in a simple, known manner. Suitable starting materials (A) are in particular 3-methylaminopropylamine and 3-(2-aminoethylamino)propyltiimethoxysilane. Examples of suitable starting materials (B) are the carbonyl compounds benzaldehyde, 4-pyridinecaiboxaldehyde, benzophenone, cinnamaldehyde, furfural, p-anisaldehyde or also terephthaldehyde.
Aminals of the formula (E)
(E) can be prepared by reaction of (C) with suitable compounds containing reactive double bonds, for example acrylonitrile, using die process described in EP-A 70 536.
Aminals (C) and (E) thus prepared can be reacted in a further step with a polyisocyanate Z-(NCO)n or a polyisothiocyanate Z-(NCS)„, in which n is greater than or equal to 2.
Π. Silane portion
The amino- or mercaptoalkoxysilanes used according to the invention are compounds which are known per se. Some are commercially available, or they can be prepared by methods known per se. Compounds of this type are described in detail, for example, in Silane Coupling Agents by EJ*. Plueddemann, Plenum Press, New York (1982).
HL Polyisocyanate Z-(NCO)& 2 or polyisothiocyanate Z-(NCS) 2
These isocyanates are prepared by methods known from the literature, such as are described in US-A 3,492,330, 3,394,164 and 3,567,763; in DE-A 19 29 034 and 20 04 048; in German patents 10 22 789; 12 22 067; 1101394; 10 27 394 and 12 31 688; in British patents 994,890,889,050,956,474 and 1,072,956 or in Belgian patent 723,640.
The polyisothiocyanates can be prepared analogously. Instead of the diisocyanates, die corresponding diisothiocyanates are used as starting materials. Aliphatic starting materials can be prepared by the methods described in US-A 3,787,472 and aromatic starting materials by die methods described in Org. Syntheses; Collective Volume 1, p. 447 John Wiley, New York (1948).
-9IV. Conversion of the pol yisoc yanates obtained bv the above process ΙΠ with the aminals (C) and/or (E) and with the silanes obtained by process Π to the compounds of thefonnula L
The reaction of the polyisocyanates or polyisothiocyanates with the other two components 5 can be carried out in succession or together. In the stepwise reaction, first the aminal compound can be reacted with die polyisocyanate or polyisothiocyanate and then the adduct can be reacted with the alkoxysilane or vice versa. In this reaction, it is also possible to ftxm polyisocyanate or -thiocyanate adducts with different aminal or «lme components, it being possible to react die various components alternately with one another, i.e., far example, first adduct formation with a silane, then adduct formation with the aminal and finally adduct formation with the second silane.
The reaction can be carried out in the absence of solvents, although, as a rule, one or all components are diluted with a suitable inert solvent, for example xylene, in order, fir example, to adjust the viscosity to the requirements.
The addition reaction itself is advantageously carried out at temperatures of between 15°C and 200°C, but preferably at temperatures of between 30°C and 140°G
The course of die reaction can be monitored by infrared spectroscopy or titration.
It is also possible to use catalysts of die type known per se in die addition reactions, fir example tertiary amines such as triethylamine, N-methylmorpholine, NJiJi* Ji’-tetra20 methylethylenediamine or l,4-diazabicyclo[2J.2]octane. Organometallic compounds, in particular organic tin compounds, can also be used as catalysts.
f
Examples of organic tin compounds are tin(II) salts of carboxylic acids, fir example tinQI) acetate, tin(II) octanoate and txn
The stoichiometric ratios during the addition reaction of the aminal and silane components with die polyisocyanates or -thiocyanates are maintained at such a value that die ratio of the NH groups of the aminals and die NH2 or SH groups of the silanes is approximately equimolar with respect to die NCO or NCS groups of the polyisocyanates or -thiocyanates. The adduct can still contain free NCO or NCS groups. Preferably, however, no free NCO
-10or NCS group is present
The ratio of aminal or urea imine radicals to silane radicals in die compounds according to the invention of the formula I can be controlled by the stoichiometric ratio of the starting materials during the addition reaction. For this purpose, the aminal or silane conpound is reacted with the polyisocyanate or -thiocyanate in separate steps. As anile, the first step takes place at a ratio of NH or SH groups to NCO or NCS groups of less than 1. The preferred aminal-NH/NCO or NCS ratio is between 1:2 and 1:6, in particular between 1:3 and 1:5. The preferred ratio of sUane-NH^/NCO or silane-SHZNCO or NCS groups is between 2:3 and 1:5, in particular between 2:3 and 1:2.
As a rule, the remaining free NCO or NCS groups are reacted completely in the second step with the aminal-NH or stiane-NH2 or -SH groups. To tins end, die stoichiometric ratio of die groups containing acidic hydrogen to die NCO or NCS groups is greater than or equal to 1, preferably 4:1 to 1:1, in particular 2:1 to 1:1.
However, it is also possible to react only a portion of the remaining free NCO or NCS groups in the second step. In this case, the same stoichiometric ratios as in the first addition step apply. Such a procedure is preferably used when two or more different aminal or silane compounds are added.
The compounds according to die invention can be used as adhesion promoters in substrates such as polyurethane resins. Their use is particularly effective in moisture-curing polyurethane resins which are used as adhesives, sealing compositions, coating compositions or insulating materials. If used in adhesives, die compounds according ro the invention have properties which enable diem to be used in two-component and very particularly in one-component systems. By using die compounds according to the invention as adhesion promoters in the substrates mentioned, a pretreatment of the surfaces to be braided with a primer is made superfluous. Suitable use examples are the braiding of windscreens and headlights in automobile construction. Compounds of the formula I in which m is greater dun or equal to 2 can furthermore be used as moisture-activated curing agents for the substrates mentioned. Moreover, compounds of the formula I can be used as primers for the pretreatment of the substrate.
A moisture-curing polyurethane as the substrate contains, as the main component, polyfunctional isocyanates andfar polyurethane prepolymers. Suitable compounds are both
-11aromatic as well as aliphatic, monocyclic as well as polycyclic, polyfunctional isocyanate compounds. Thus, according to a first embodiment, the aromatic isocyanate compound used is toluylene diisocyanate or diphenylmethanc diisocyanate. Technical grade diphenylmethane diisocyanate containing higher functional diisocyanates and having an isocyanate group functionality of greater than 2 is paiticulariy suitable. A further suitable aromatic diisocyanate is xylylene diisocyanate. In addition to these, a large number of aliphatic isocyanates having a functionality of 2 and higher can be used. Examples of these in die farm of cyclic aliphatic diisocyanates are isophorone diisocyanate and dicyclohexylmethane diisocyanate. Further examples are aliphatic, straight-chain diisocyanates, such as are obtained by phosgenation of diamines, for example tetramethylene diisocyanate or hexamethylene diisocyanate.
According to a preferred embodiment Oi the invention, polyurethane prepolymers are used instead of the polyfunctional isocyanate compounds. Prepolymers are understood in this context to mean adducts of an excess of palyfunctional isocyanates with polyfunctional alcohols, for example the reaction products of one of the abovementioned aromatic or aliphatic diisocyanates with ethylene glycol, propylene glycol, glycerol, trimethylolpropane or pentaerythritol. Reaction products of diisocyanates with polyether polyols, for example polyether polyols based on polyethylene oxide or based on polypropylene oxide, can also be used asprepolymers. Preference is given to polyurethane prepolymers based on polyether polyols having molecular weights of between 200 and 10000, in particular
500 and 3000. A person skilled in polyurethane chemistry is familiar with a large number of polyether polyols of this type; they are offered by many manufacturers and are characterised by their molecular weight (number-average), which can he calculated from end group determinations. Further suitable poiyether polyols are polyether polyols based (m polytetrahydrofuran.
Instead of polyeiher polyols, polyester polyols can also be used. Suitable polyester polyols are react»» products of polyfunctional acids with polyfunctional alcohols, for example polyesters based on aliphatic and/or aromatic dicarboxylic acids and polyfunctional alcohols having a functionality of 2-4. Thus, polymers obtained from adipic acid, sebacic acid, phthalic acid, hydrophthalic acid and/or trimellitic acid on the one hand and ethylene glycol, propylene glycol, neopentyl glycol, hexane glycol, glycerol and/or trimethylolpropane on the other hand can be used. In particular polyester polyols having a molecular weight (number-average) of between 500 and 5000, in particular between 600 and 2000, are suitable. Further suitable polyester polyols are die reaction products of caprolactone
-12with alcohols having a functionality of 2-4, for example fee adduct of
1-5 moles of caprolactone with 1 mole of ethylene glycol, propylene glycol, glycerol and/or frimefeylolpropane.
A further suitable group of polyfunctional alcohols are polybutadienols. These are oligomers based on butadiene and containing OH groups as end groups. Of these, suitable products are those in the molecular weight range 200-4000, in particular 500-3000. Furthermore, siloxane prepolymers, preferably in combination with other prepolymers, are suitable.
When the polyurethane prepolymers are prepared, the ratio of the OH groups of fee alcohol component to fee isocyanate groups is important. It is in general between 1:2 and 1:10. A high excess of isocyanate tends to give low-viscosity polyurethane prepolymers, while a small excess of isocyanate gives highly viscous preparations, which in most cases can only be applied by trowelling.
It is known to a person skilled in polyurethane chemistry that the crosslinking density and thus the hardness of the polyurethanes increases wife the functionality of fee isocyanate component or else of fee polyol. Reference may be made here to the general technical literature, for example to fee monograph by Saunders and Frisch Polyurethanes, Chemistry and Technology, Volume XVI of the series High Polymers Interscience Publishers, New York-London, Part I (1962) and Part Π (1964).
The polyurethane preparations according to fee invention can furthermore contain various auxiliaries. Examples of auxiliaries which can be used are fillers. Suitable fiflera are inorganic compounds which are unreactive towards isocyanates, for example chalk or ground chalk, precipitated and/or pyrogenic silicas, zeolites, bentonites, ground minerals and other inorganic fillers known to a person skilled in this technical field, in particular chopped fibres, and others. Far some applications, fillers are preferred which give fee preparations thixotropic properties, for example swellable plastics, in particular PVC.
Apart from fee compounds mentioned, fee polyurethane preparations according to fee invention can contain further auxiliaries, for example solvents. Suitable solvents are those which themselves do not react wife isocyanate groups, for example halogenated hydro30 carbons, esters, ketones and aromatic hydrocarbons. Plasticisers, retardants, dyes and anti-ageing agents, such as are known in polyurethane adhesives and sealing
-13compositions, can also be incorporated.
For some applications, it is desirable to add foam stabilisers to the polyurethane preparations according to the invention. So-called silicosurfactants can be used as foam stabilisers. These are understood to mean block copolymers which are composed of a polysiloxane block and one or mare polyoxyethylene and/or polyoxypropylene blocks.
The polyurethane preparations according to die invention can furthermore contain flameretardant and plasticising additives. Compounds containing phosphorus and/or halogen atoms, such as tricresyl phosphate, diphenyl cresyl phosphate, tris(2-chloroethyl) phosphate, tris(2-chloropropyl) phosphate and tris(2,3-dibromopropyl) phosphate are common. In addition, flame retardants can be used, for example chloroparaffins, phosphinic acid halides, ammonium phosphate and halogen- and phosphorus-containing resins. Far some applications, plasticisers are important as further additives.
Examples of these which axe suitable axe esters of phthalic acid or esters of long-chain dicarboxylic acids, for example sebacic or azelaic esters. So-called epoxide plasticisers, for example epoxidised fatty acid derivatives, can also be used.
Further possible additives arc basic accelerators. Examples of basic accelerators are tertiary bases, such as bis(N,N’-dimethylamino)diethyl ether, dimethylaminocyclohexane, NJQ-dimethylbenzylamine, N-methylmorpholine and die reaction products of dialkyl(B-hydroxyethyl)amines with monoisocyanates and esterification products of dialkyl20 (B-hydroxyethyl)amines with dicarboxylic acids. A further important accelerator is 1,4-diaminobicyclo[2.2J2]octane. Furthermore, non-basic substances can be used as accelerators. Of these, suitable substances are metal compounds, for example in» acetylacetonate and tm(H) 2-ethylhexanoate, dibutyltin dilaurate or molybdenum glycolate.
The compounds of the formula I axe added to the polyurethane resins in amounts of
0.1-20 % by weight, preferably 05-15 % by weight, in particular 2.5-10 % by weight, relative to the prepolymer.
Furthermore, the compounds of the formula I can also be used as hardeners. When used as hardeners, die molar ratio of released secondary NH groups to free isocyanate groups in the resin should be 0.5 to 1.5:1, preferably 0.9 to 1.1:1.
-14The examples below illustrate the invention.
I. Preparation of the starting materials
Example A: l,4-Bis(l-methylhexahydropyrimidin-2-yl)benzene ch3
1 mol of terephthalaldehyde in 500 ml of toluene is initially introduced into all sulfonating flask equipped with sriner, reflux condenser, thermometer and water separator. An equimolar amount of 3-methylaminopropylamine is then slowly added dropwise under nitrogen, followed by 0.1 % by weight of toluenesulfonic add as die catalyst The mixture is then refluxed for some time, during which die extent of the reaction can be monitored by the amount of water separated. The reaction mixture is then concentrated in a rotary evaporator, and the product is then worked up under a high vacuum.
Yield: 87%
Melting point: 135°C
Elemental analysis: calculated: C 70.03 %; H 9.55 %; N 20.42 % found: C 69.95 %; H 9.74 %; N 20.62 %
Example B: l-Methyl-2-phenylhexahydropyrimidine
The procedure of Example A is repeated, using 1 mol of benzaldehyde instead of the 20 terephthalaldehyde.
Yield :91%
Boiling point: 75°C/0.1 mbar
Elemental analysis: calculated: C 74.96 %; H 9.15 %; N 15.89 % found: C 74.94 %; H 9.10 %; N 15.99 %
-15Example C: l-Methyl-2£-diphenylhexahydropyrimidine
The procedure of Example A is repeated, using 1 mol of benzophenone instead of die terephthalaldehyde.
Yield: 39 %
Boiling point: 130°C/0.1 mbar
Elemental analysis: calculated: C 80.91 %; H 7.99 %; N 11.10 % found: C 81.76 %; H 7.68 %; N 8.85 %
Example D: l-Methyl-2-pyridin-4-ylhexahydropyrimidine
The procedure of Example A is repeated, using 1 mol of 4-pyridinecarboxaldehyde instead of the terephthalaldehyde.
Yield :46%
Boiling point: 70°CZ0.05 mbar
Elemental analysis: calculated: C 67.76 %; H 8 J3 %; N 23.71 % found: C 67.69 %; H 8.73 %; N 23.81 %
Example E: l-Methvl-2-(2-phenvlethenvl)hexahvdropvrimidine
The procedure of Example A is repeated, using 1 mol of cinnamaldehyde instead of the
-16terephthalaldehyde.
Yield: 28 %
Boiling point: 85°CA).17 mbar
Elemental analysis: calculated: C 77.18 %; H 8.97 %; N 13.85 % found: C 7327 %;H 9.80 %;N 17.00%
Example F: l-Methyl-2-furan-2-ylhexahydropyrimidine
h3c'
The procedure of Example A is repeated, using 1 mol of furfural instead of the terephthalaldehyde.
Yield :75%
Boiling point: 110°C/0.12 mbar
Elemental analysis: calculated: C 65.03 %; H 8.49 %; N 16.85 % found: C 64.88 %; H 831 %;N 16.84 %
Example G: l-Methyl-2-(4-methoxyphenyl)hexahydropyrimidine
h3c
The procedure of Example A is repeated, using 1 mol of p-anisaldehyde instead of the terephthalaldehyde.
Yield :78%
Boiling point: 97°C/0.04 mbar
Elemental analysis: calculated: C 69.87 %; H 8.80 %; N 13.58 % found: C 69.55 %; H 8.81 %; N 13.59 %
-17Π. Synthesis of the adhesion promoters
Example 1:
In a 100 ml sulfonating flask, 20 g (0.1032 mol of -NCO) of partially trimerised hexamethylene diisocyanate having an isocyanate content of 21.6 % (Desmodur® N 3200 from Bayer AG) are dissolved in 20 g of xylene, and the solution is heated to 80°C 13.51 g (0.0688 mol) of 3-mercaptqnppyltrimedxnysilane are then added dropwise under o nitrogen using a dropping funnel, and stirring of the mixture is then continued at 80°C fir
1.5 hours and then at 130°C fir 2.5 hours. After cooling to room temperature, 0.03441 mol of die aminal according to Example B is added dropwise at such a rate that die temperature always remains below 30°C. Stirring at roam temperature is then continued for another 4 hours, and the free NCO content is then checked by titration.
Viscosity (according to Epprecht): η = 76 800 mPa-s
Average molecular weight (GPC, polystyrene-calibrated):
1^=1680 g/mol Mw = 2640g/mol
Elemental analysis: found: C 56.40 %; H 8.34 %; N 10.26 %
2o Imine/aminal ratio (%, JH NMR analysis [N-CH-J): 61/39
Isocyanate group content: < 0.1 %
-18Example 2:
and
The procedure of Example 1 is repeated, using the aminal from Example A instead of the aminal from Example B.
Viscosity (according to Epprecht): η > 100 000 mPa-s Average molecular weight (GPC, polystyrene-calibrated):
-19M„= 1780 g/mol M, = 4 640 g/mol
Elemental analysis: found: C 53.33 %; H7.93%; N 7.42%
Imine/aminal ratio (%, τΗ NMR analysis [N-CHj]): 69/31
Isocyanate group content: < 0.1 %
The procedure of Example 1 is repeated, using the aminal from Example E instead of the aminal from Example B.
Viscosity (according to Epprecht): η = 12 000 mPa s Average molecular weight (GPC, polystyrene-calibrated):
M,,» 1480 g/mol 15 Mw = 2 320 g/mol
Elemental analysis: found: C 61.80 %; H8.44%; N 8.62%
Imine/aminal ratio (%, NMR analysis [N-CHJ): 61/39 Isocyanate group content: <0.1%
-20Example4:
The procedure of Example 1 is repeated, using the aminal from Example F instead of fee aminal from Example B.
Viscosity (according to Epprecht): η = 9 600 mPa s Average molecular weight (GPC, polystyrene-calibrated):
M„ = 1650 g/mol
Mw = 2 970 g/mol
Elemental analysts: found: C 59.25 %; H8.27%; N 850%
Imine/aminal ratio (%, Ή NMR analysis [N-CH3]): 68/32
Isocyanate group content: <0.1 %
The procedure of Example 1 is repeated, using the aminal from Example G instead of the aminal from Example B.
Viscosity (according to Epprecht): η = 4 800 mPa-s Average molecular weight (GPC, polystyrene-calibrated):
Mn = 2120gZmol
Mw = 4970g/inol
Elemental analysis: found: C 59.60 %; H7.92%; N 6.59%
Imine/aminal ratio (%, XH NMR analysis [N-CH3]): 68/32
Isocyanate group content: < 0.1 %
-22Example6:
The procedure of Example 1 is repeated, using the aminal from Example D instead of the aminal from Example B.
Viscosity (according to Epprecht): η = 38 400 mPa-s Average molecular weight (GPC, polystyrene-calibrated):
M„ = 1140 g/mol
Mw = 1 660 g/mol
Elemental analysis: found: C 55.92 %; H 8.43 %; N 10.97 % hnine/aminal ratio (%, JH NMR analysis (N-CHJ): 57/43
Isocyanate group content: <0.1%
and
The procedure of Example 1 is repeated, using the aminal from Example C instead of die aminal from Example B.
Viscosity (according to Epprecht): η = 1960 mPa-s Average molecular weight (GPC, polystyrene-calibrated):
Mn=l 080 g/mol 10 Mw = 2 460 g/mol
Elemental analysis: found: C 63.90 %; H8.21%; N7.47%
Imine/aminal ratio (%, Ή NMR analysis [N-CH3]): 61/39 Isocyanate group content: < 0.1 %
-24ΙΠ. Adhesive formulations
Example 8: One-component system (moisture-curing)
8A) Synthesis of the prepolymer
An isocyanate-tenninated prepolymer is prepared by adding a mixture of240 g of dry bishydroxy-terminated polypropylene glycol of molecular weight2000 (Desmophen® 1900 U from Bayer AG) and 0.3 ml of dibutyltin dilaurate at 80°C to 50 g of methylenediphenyl diisocyanate (Isonate® M125 from Upjohn) over a period of 1 hour. 1.0 g of trimethylolpropane is then added to the mixture obtained, which is stined at 80°C for another 2 hours until an isocyanate-tenninated prepolymer having an isocyanate content of 2.0 % has been formed.
8B) Formulation:
The adhesive formulation has the following composition:
55.1 % by weight of die prepolymer according to Example 8A 20 % by weight of ground lamp black
14.9 % by weight of dioctyl phthalate 5 % by weight of silica aerogel (thixotropic agent) % by weight of the adhesion promoter according to Example 1
8C) Adhesion to various substrates:
The adhesive formulation obtained in 8B) is poured onto a substrate (according to die table below) such that a 5 mm thick polyurethane layer is formed. After storage in air for 2 weeks, these samples are stored for 2 weeks in water at room temperature. The results are summarised in Table 1, in which (-) means that die layer can te peeled off with ease and die substrate surface remains dean; (-) means that the layer cante peeled off with difficulty and the substrate surface remains clean; (+/-) means that die majority of the layer cm the substrate surface can te removed by scratching using a knife; (+) means that die majority of the layer remains attached to die substrate surface despite scratching using a knife; (++) means drat the entire layer remains attached to die substrate surface despite scratching using a knife.
-25Table 1
Substrate without adhesion promoter with adhesion promoter according to Example 1 Glass - + + SMC - + PC + - RIM-PUR - + PA • · + -
SMC * Sheet Moulding Compound
PC = Polycmbonate
RIM-PUR = Reaction Injection Moulding - Polyurethane PA = Polyamide
Example 9: Two-component system (heat-curing)
9A) Formulation:
The adhesive formulation has die following composition:
100 parts by weight of polyol mainly comprising branched polyether polyols and mineral fillers parts by weight of isocyanate based on diphenylmethane diisocyanate 5 parts by weight of the adhesion promoter according to Example 1
9B) Mechanical properties
The tensile shear strengths of various samples were determined.
Test specimens: Substrate thickness 3.0 mm
Width 25.0mm
Overlapping 12.5 mm
Thickness of die adhesive joint 0.2 mm
The specimens were cured at 80°C over a period of 1 hour. The results are summarised in Table 2.
-26Table2
Substrate without adhesion promoter with adhesion promoter according to Example 1 PA 2.3 C(40%) 3.2 cno%) PC 3.5 Ad 5.0 C(50%) PP 1.6 Ad 45 MB
PA Polyamide
PC>* Polycarbonate
PP « Polypropylene (Qame-pKDeatod)
Ad» Adhesion break
C* Cohesion break MB=Material break, substrate break
The values obtained show that die use of die compounds according to die present invention as adhesion promoters substantially improves the tensile shear strength of these specimens.
Claims (21)
1. A compound of the general formula I ϊ ί τ_ E-Rj-N— I(CH 2 ^O- 1 —C-HN-J—T _Jm in which 5 Ri is CrQalkylene and R 2 is hydrogen, CpCgalkyl which is unsubstituted or substituted by -OH, -CN or -Si(OR 3 )3^(R4)q or is C
2. *C6aUcenyl, in which R 3 is Ci-Qalkyl or two radicals R 3 together are C r C4alkylene, R4 is CpQalkyl or phenyl and 10 q can have values from 0 to 2, furthermore E is a radical of the formula or E together with R 2 is a radical of the formula »5 A V in which R 5 and Re, independently of one another, are hydrogen, Ci-C 4 alkyl, aryl-substituted ethenyl, aryl, heteroaryl or radicals of the formulae Ha or lib (Ha) -28:=Ν Ζ 1 ’ k n z Sin > I r 2 (Hb) with tiie proviso that at least one of the radicals R5 or Re is aryl-substituted ethenyl, aryl, heteroaryl or a radical of the formulae Ila or Db and in which R 7 is hydrogen, CpC 4 alkyl or -R9-Si(OR 3 )3^(R4) q and R 3 , R4 andq are 5 as defined above, and R9 is CpCgalkylene, and Y is oxygen or sulfur; furthermore, T is a radical of the formulae -R 9 -Si(OR 3 ) 3q (R 4 ) q or or, if R 7 is a radical of the formula -Rp-SKORj^fRJq and m is greater than or equal to 2, is an m-valent radical Z in which R 3 , R4, R$, Y and q are as defined above, X is -S- or -NH- and Z is an organic radical which is derived from a polyisocyanate or a polyisothiocyanate 15 having at least 2 NCO or NCS groups, and r is 1,2 or 3 and p isOorland m can have values of greater than or equal to 1 and n can have values of greater than or equal to 1. 20 2. A compound of the formula I according to claim 1, in which Y is oxygen.
3. A compound of die formula I according to claim 1, in which Z is derived from an aliphatic, cycloaliphatic, aliphatic/aromatic, aromatic or heterocyclic polyisocyanate or polyisothiocyanate in which the number of NCO or NCS groups is greater than or equal to 2, it being possible for the radical Z to contain, if desired, one or mote ester, ether, -29urethane, thiourethane, isocyanurate, urea or biuret functions.
4. A compound of the formula I according to claim 3, in which Z is derived from an aliphatic or mixed aliphatic/aromatic polyisocyanate in which die number of NCO groups is greater than or equal to 2, it being possible for this radical Z to contain, if desired, a 5. Total of one or two ester, ether, urethane, thiourethane, isocyanurate, urea or biuret functions.
5. A compound of the formula I according to claim 1, in which the radical Z has an average molecular weight M„ of less than 10 000.
6. A compound of the formula I according to claim 1, in which m and n, independently of 10 one another, have values from 1 to 49.
7. A compound of the formula I according to claim 1, in which the sum of m + n is 2 to 50.
8. A compound of the formula I according to claim 1, in which n is 1,2 or 3 and mis 3,2 or 1.
9. A compound of the formula I according to claim 1, in which R } is propylene. 15
10. A compound of the formula I according to claim 1, in which p has the value 0.
11. A compound of the formula I according to claim 1, in which q has die value 0.
12. A compound of die formula I according to claim 1, in which at least one of the radicals R5 or Rg is a group of the formulae O - · · O'· 20
13. A compound of the formula I according to claim l,in which T is a radical of the formulae -R9-Si(OR 3 )3^(R4)q or -30in which X, Y, Z, R 3 , R4, Rg, q and n are as defined in claim 1. i
14. A compound of the formula I according to claim 13, in which at least one radical X is , -S-. *
15. A compound of the formula I according to claim 1, in which p and q are 0, m is 1 and 5 n is 2, Y is oxygen, X is -S-, R t and R9 are propylene, R 2 and R 3 are methyl, R 5 is phenyl and Rg is hydrogen.
16. A polyurethane resin containing at least one compound of the formula I according to claim 1.
17. A polyurethane resin according to claim 16, containing 0.1 to 20 % by weight of a 10 compound of the formula I.
18. A conpound aooording to claim 1, substantially as hereinbefore described and exenplified.
19. A process for preparing a compound according to claim 1, substantially as hereinbefore described and exenplified. 15
20. A compound according to claim 1, whenever prepared by a process claimed in claim 19.
21. A polyurethane resin according to claim 16, substantially as hereinbefore described and exenplified.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH381590 | 1990-12-04 |
Publications (2)
Publication Number | Publication Date |
---|---|
IE914200A1 IE914200A1 (en) | 1992-06-17 |
IE71041B1 true IE71041B1 (en) | 1997-01-15 |
Family
ID=4264064
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
IE420091A IE71041B1 (en) | 1990-12-04 | 1991-12-03 | Coupling agent |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0489688B1 (en) |
JP (1) | JP3230060B2 (en) |
CA (1) | CA2056751C (en) |
DE (1) | DE59107511D1 (en) |
IE (1) | IE71041B1 (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10103027A1 (en) | 2001-01-24 | 2002-07-25 | Bayer Ag | Adhesion promoter, e.g. for improving adhesion of silicon-based protective coatings to polymeric substrates, comprising two-component polyurethane binder based on alkoxysilane-modified polyisocyanate |
JP4298750B2 (en) | 2004-06-15 | 2009-07-22 | エルジー・ケム・リミテッド | Novel silane coupling agent and method for producing the same |
ES2632783T3 (en) * | 2014-12-19 | 2017-09-15 | Evonik Degussa Gmbh | Cover network systems for encapsulation sheets comprising bis- (alkenylamide) compounds |
PL3287477T3 (en) * | 2016-08-24 | 2020-01-31 | Henkel Ag & Co. Kgaa | Plastic adhesion promotion for 2k polyurethane adhesives |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6131461A (en) * | 1984-07-24 | 1986-02-13 | Shin Etsu Chem Co Ltd | Room temperature curing organosiloxane composition |
JPS62249992A (en) * | 1986-04-24 | 1987-10-30 | Nippon Kayaku Co Ltd | Novel silicon urethane (meth)acrylate, resin composition and coating agent using said compound |
ES2062485T3 (en) * | 1989-06-13 | 1994-12-16 | Ciba Geigy Ag | ADHERENTS. |
-
1991
- 1991-11-27 EP EP91810924A patent/EP0489688B1/en not_active Expired - Lifetime
- 1991-11-27 DE DE59107511T patent/DE59107511D1/en not_active Expired - Fee Related
- 1991-12-02 CA CA002056751A patent/CA2056751C/en not_active Expired - Fee Related
- 1991-12-03 JP JP34783991A patent/JP3230060B2/en not_active Expired - Fee Related
- 1991-12-03 IE IE420091A patent/IE71041B1/en not_active IP Right Cessation
Also Published As
Publication number | Publication date |
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JP3230060B2 (en) | 2001-11-19 |
EP0489688B1 (en) | 1996-03-06 |
CA2056751A1 (en) | 1992-06-05 |
CA2056751C (en) | 2002-06-04 |
IE914200A1 (en) | 1992-06-17 |
JPH04308596A (en) | 1992-10-30 |
DE59107511D1 (en) | 1996-04-11 |
EP0489688A1 (en) | 1992-06-10 |
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