NO155339B - DEVICE FOR THE CONNECTION OF MISCELLANEOUS STACKED FORMING PLATES. - Google Patents
DEVICE FOR THE CONNECTION OF MISCELLANEOUS STACKED FORMING PLATES. Download PDFInfo
- Publication number
- NO155339B NO155339B NO803170A NO803170A NO155339B NO 155339 B NO155339 B NO 155339B NO 803170 A NO803170 A NO 803170A NO 803170 A NO803170 A NO 803170A NO 155339 B NO155339 B NO 155339B
- Authority
- NO
- Norway
- Prior art keywords
- parts
- compound
- tetra
- distannoxane
- mixture
- Prior art date
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- -1 isocyanate compound Chemical class 0.000 claims description 69
- 239000012948 isocyanate Substances 0.000 claims description 63
- 150000001875 compounds Chemical class 0.000 claims description 55
- 239000000203 mixture Substances 0.000 claims description 54
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 27
- 229920000642 polymer Polymers 0.000 claims description 17
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 14
- 150000002513 isocyanates Chemical class 0.000 claims description 14
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 27
- 239000000839 emulsion Substances 0.000 description 25
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 21
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 229920005906 polyester polyol Polymers 0.000 description 20
- 239000005056 polyisocyanate Substances 0.000 description 15
- 229920001228 polyisocyanate Polymers 0.000 description 15
- 229920005862 polyol Polymers 0.000 description 14
- 150000003077 polyols Chemical class 0.000 description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 12
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 229920000570 polyether Polymers 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 239000004721 Polyphenylene oxide Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 10
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- 229920001971 elastomer Polymers 0.000 description 9
- 239000005060 rubber Substances 0.000 description 9
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 9
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 8
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 8
- 239000002981 blocking agent Substances 0.000 description 8
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 8
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 7
- 239000004744 fabric Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000003973 paint Substances 0.000 description 7
- 229940113165 trimethylolpropane Drugs 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- TZMQHOJDDMFGQX-UHFFFAOYSA-N hexane-1,1,1-triol Chemical compound CCCCCC(O)(O)O TZMQHOJDDMFGQX-UHFFFAOYSA-N 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- 239000001361 adipic acid Substances 0.000 description 5
- 235000011037 adipic acid Nutrition 0.000 description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000004745 nonwoven fabric Substances 0.000 description 5
- 239000002985 plastic film Substances 0.000 description 5
- 230000008929 regeneration Effects 0.000 description 5
- 238000011069 regeneration method Methods 0.000 description 5
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 4
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 238000007259 addition reaction Methods 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000600 sorbitol Substances 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 238000012644 addition polymerization Methods 0.000 description 3
- 150000005215 alkyl ethers Chemical class 0.000 description 3
- 150000004982 aromatic amines Chemical class 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 150000002605 large molecules Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- JSCIARCQZHRULQ-UHFFFAOYSA-N 1,2-diphenylethane-1,1-diamine Chemical compound C=1C=CC=CC=1C(N)(N)CC1=CC=CC=C1 JSCIARCQZHRULQ-UHFFFAOYSA-N 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 2
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229930195725 Mannitol Natural products 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000004423 acyloxy group Chemical group 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000004359 castor oil Substances 0.000 description 2
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- 239000003795 chemical substances by application Substances 0.000 description 2
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 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 2
- 125000005843 halogen group Chemical group 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000000594 mannitol Substances 0.000 description 2
- 235000010355 mannitol Nutrition 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- JNYAEWCLZODPBN-KVTDHHQDSA-N (2r,3r,4r)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@@H](O)[C@H]1O JNYAEWCLZODPBN-KVTDHHQDSA-N 0.000 description 1
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- FJEKUEUBQQWPBY-UHFFFAOYSA-N 1$l^{2}-stanninane Chemical compound C1CC[Sn]CC1 FJEKUEUBQQWPBY-UHFFFAOYSA-N 0.000 description 1
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- 229940051269 1,3-dichloro-2-propanol Drugs 0.000 description 1
- DEWLEGDTCGBNGU-UHFFFAOYSA-N 1,3-dichloropropan-2-ol Chemical compound ClCC(O)CCl DEWLEGDTCGBNGU-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
- CMCBDXRRFKYBDG-UHFFFAOYSA-N 1-dodecoxydodecane Chemical compound CCCCCCCCCCCCOCCCCCCCCCCCC CMCBDXRRFKYBDG-UHFFFAOYSA-N 0.000 description 1
- ICLCCFKUSALICQ-UHFFFAOYSA-N 1-isocyanato-4-(4-isocyanato-3-methylphenyl)-2-methylbenzene Chemical compound C1=C(N=C=O)C(C)=CC(C=2C=C(C)C(N=C=O)=CC=2)=C1 ICLCCFKUSALICQ-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- CDULGHZNHURECF-UHFFFAOYSA-N 2,3-dimethylaniline 2,4-dimethylaniline 2,5-dimethylaniline 2,6-dimethylaniline 3,4-dimethylaniline 3,5-dimethylaniline Chemical group CC1=CC=C(N)C(C)=C1.CC1=CC=C(C)C(N)=C1.CC1=CC(C)=CC(N)=C1.CC1=CC=C(N)C=C1C.CC1=CC=CC(N)=C1C.CC1=CC=CC(C)=C1N CDULGHZNHURECF-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- ABROBCBIIWHVNS-UHFFFAOYSA-N 2-Ethylbenzenethiol Chemical compound CCC1=CC=CC=C1S ABROBCBIIWHVNS-UHFFFAOYSA-N 0.000 description 1
- LXUNZSDDXMPKLP-UHFFFAOYSA-N 2-Methylbenzenethiol Chemical compound CC1=CC=CC=C1S LXUNZSDDXMPKLP-UHFFFAOYSA-N 0.000 description 1
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- FRQQKWGDKVGLFI-UHFFFAOYSA-N 2-methylundecane-2-thiol Chemical compound CCCCCCCCCC(C)(C)S FRQQKWGDKVGLFI-UHFFFAOYSA-N 0.000 description 1
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
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- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 1
- ADYVCZCQSVYNPQ-UHFFFAOYSA-N N=C=O.N=C=O.C=1C=CC=CC=1C(C)C1=CC=CC=C1 Chemical compound N=C=O.N=C=O.C=1C=CC=CC=1C(C)C1=CC=CC=C1 ADYVCZCQSVYNPQ-UHFFFAOYSA-N 0.000 description 1
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- 239000004952 Polyamide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 241000158147 Sator Species 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical compound CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- XHDURIQJZSJICZ-UHFFFAOYSA-N alpha-Valerolactam Chemical compound CCCC1NC1=O XHDURIQJZSJICZ-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- 125000001231 benzoyloxy group Chemical group C(C1=CC=CC=C1)(=O)O* 0.000 description 1
- XTSFUENKKGFYNX-UHFFFAOYSA-N bis(aziridin-1-yl)methanone Chemical compound C1CN1C(=O)N1CC1 XTSFUENKKGFYNX-UHFFFAOYSA-N 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 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
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001716 carbazoles Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- WOWBFOBYOAGEEA-UHFFFAOYSA-N diafenthiuron Chemical class CC(C)C1=C(NC(=S)NC(C)(C)C)C(C(C)C)=CC(OC=2C=CC=CC=2)=C1 WOWBFOBYOAGEEA-UHFFFAOYSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- XMYQHJDBLRZMLW-UHFFFAOYSA-N methanolamine Chemical compound NCO XMYQHJDBLRZMLW-UHFFFAOYSA-N 0.000 description 1
- 229940087646 methanolamine Drugs 0.000 description 1
- SOOARYARZPXNAL-UHFFFAOYSA-N methyl-thiophenol Natural products CSC1=CC=CC=C1O SOOARYARZPXNAL-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- FGGAOQTXQHKQOW-UHFFFAOYSA-N n,n-diphenylnaphthalen-1-amine Chemical compound C1=CC=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=CC=C1 FGGAOQTXQHKQOW-UHFFFAOYSA-N 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
Classifications
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04G—SCAFFOLDING; FORMS; SHUTTERING; BUILDING IMPLEMENTS OR AIDS, OR THEIR USE; HANDLING BUILDING MATERIALS ON THE SITE; REPAIRING, BREAKING-UP OR OTHER WORK ON EXISTING BUILDINGS
- E04G19/00—Auxiliary treatment of forms, e.g. dismantling; Cleaning devices
- E04G19/003—Arrangements for stabilising the forms or for moving the forms from one place to another
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D67/00—Kinds or types of packaging elements not otherwise provided for
- B65D67/02—Clips or clamps for holding articles together for convenience of storage or transport
Description
Isocyanatblanding. Isocyanate mixture.
Foreliggende oppfinnelse angår en isocyanatblanding og mer spesielt en slik isocyanatblanding som består av en blokert isocyanatforbindelse og en ny katalysator for regenerering av en isocyanatgruppe fra den blokerte isocyanatforbindelse. The present invention relates to an isocyanate mixture and more particularly such an isocyanate mixture which consists of a blocked isocyanate compound and a new catalyst for the regeneration of an isocyanate group from the blocked isocyanate compound.
Ved fremstilling av en polymer forbindelse som kan anvendes f. eks. for film, malinger, belegningsmidler, impregnerings-midler, støpeforbindelser osv. ved reaksjon mellom en isocyanatforbindelse og en forbindelse som inneholder aktivt hydrogenatom har det vært kjent å anvende en blokert isocyanatforbindelse i stedet for den nevnte isocyanatforbindelse. When producing a polymer compound that can be used, e.g. for film, paints, coating agents, impregnating agents, molding compounds, etc., by reaction between an isocyanate compound and a compound containing an active hydrogen atom, it has been known to use a blocked isocyanate compound instead of the said isocyanate compound.
For fremstilling av den nevnte polymere forbindelse ved reaksjon mellom en blokert isocyanatforbindelse og en forbindelse som inneholder aktive hydrogenatomer er det imidlertid nødvendig å oppvarme reaksj onsdeltagerne til en slik høy temperatur som i området fra 170—ca. 230° C. Det er unødvendig å si at det ikke er øn-skelig ut fra et industrielt standpunkt å anvende en slik høy temperatur som nevnt ovenfor, og særlig gjør en slik behandling det umulig å anvende disse fremgangsmåter på fibre, plastark, gummi og emulsjonsmalinger som er følsomme for varme. However, for the production of the aforementioned polymeric compound by reaction between a blocked isocyanate compound and a compound containing active hydrogen atoms, it is necessary to heat the reaction participants to such a high temperature that in the range from 170 to approx. 230° C. It is needless to say that it is not desirable from an industrial point of view to use such a high temperature as mentioned above, and in particular such a treatment makes it impossible to apply these methods to fibres, plastic sheets, rubber and emulsion paints that are sensitive to heat.
Undersøkelsene er blitt fortsatt for å finne katalysatorer som akselererer regenereringen av en isocyanatgruppe fra en blokert isocyanatforbindelse og som et resultat er metylmorfolin blitt anvendt. Investigations have been continued to find catalysts which accelerate the regeneration of an isocyanate group from a blocked isocyanate compound and as a result methylmorpholine has been used.
Med hruk av i og for seg kjent kataly- With a wrinkle of in and of itself well-known cataly-
sator slik som metylmorfolin er det imidlertid også nødvendig for fremstilling av en polymer forbindelse å oppvarme reaksj onsdeltagerne til høyere temperaturer enn ca. 160° C i en halv time eller lenger, sator such as methylmorpholine, however, it is also necessary for the production of a polymeric compound to heat the reaction participants to higher temperatures than approx. 160° C for half an hour or longer,
og de ovenfor nevnte ulemper ved kjente fremgangsmåter eksisterer derfor fremde- and the above-mentioned disadvantages of known methods therefore still exist
les. read.
Som et resultat av undersøkelser som As a result of surveys that
nu er utført ble det uventet funnet at forbindelsen som er vist i følgende generelle formel (1) muliggjør regenerering av en isocyanatgruppe fra en blokert isocyanatforbindelse ved en lavere temperatur enn når det anvendes i og for seg kjente katalysatorer, og den tillater en slik regenerert isocyanatgruppe å reagere lett med forbindelsen som inneholder aktive hydrogenatomer for å oppnå en polymer forbindelse. has now been carried out, it was unexpectedly found that the compound shown in the following general formula (1) enables the regeneration of an isocyanate group from a blocked isocyanate compound at a lower temperature than when used in per se known catalysts, and it allows such a regenerated isocyanate group to react readily with the compound containing active hydrogen atoms to obtain a polymeric compound.
Ved bruk av forbindelsen som er vist ved formel (1) blir det derfor mulig å anvende fremgangsmåten hvor det anvendes en blokert isocyanatforbindelse som iso-cyanatbestanddel for fibre, plastark, gummi, emulsjonsmalinger etc. som er følsom- When using the compound shown by formula (1), it is therefore possible to use the method where a blocked isocyanate compound is used as an isocyanate component for fibres, plastic sheets, rubber, emulsion paints etc. which are sensitive
me overfor varme. me to heat.
Oppfinnelsen vedrører isocyanatblanding for fremstilling av polymerisater som omfatter en blokert isocyanatforbindelse, eventuelt en forbindelse som inneholder aktive hydrogenatomer, og blandingen er karakterisert ved at den inneholder en forbindelse med den generelle formel hvori X, betyr halogen, hydroksyl, lavere alkoksy, karboksylacyloksy, NCO -eller NCS, X2 betyr hydroksyl, lavere alkoksy, karboksylacyloksy, NCO eller NCS og hver av Rj, R2, R:1 og R4 ibetyr lavere alkyl. The invention relates to isocyanate mixture for the production of polymers comprising a blocked isocyanate compound, possibly a compound containing active hydrogen atoms, and the mixture is characterized in that it contains a compound with the general formula in which X means halogen, hydroxyl, lower alkoxy, carboxyl acyloxy, NCO - or NCS, X 2 means hydroxyl, lower alkoxy, carboxylacyloxy, NCO or NCS and each of R 1 , R 2 , R 1 and R 4 means lower alkyl.
I foreliggende beskrivelse og påstan-der betyr en blokert isocyanatforbindelse en forbindelse som inneholder blokerte iso-cyanatgrupper erholdt ved en addisjonsreaksjon av polyisocyanatforbindelse med et isocyanatblokeringsmlddel. In the present description and claims, a blocked isocyanate compound means a compound containing blocked isocyanate groups obtained by an addition reaction of polyisocyanate compound with an isocyanate blocking agent.
Som polyisocyanatforbindelse kan nevnes (1) slike alifatiske polyisocyanater som tetrametylen-diisocyanat, heksametylen-diisocyanat, slike aromatiske polyisocyanater som fenylen-diisocyanat, tolylen-diisocyanat (TDI), dlfenylmetan-diisocyanat (MDI), difenyletan-diisocyanat (EDI), naf-tylen-diisocyanat, difenylmetan-triisocyanat, bitolylen-diisocyanat, dianisldin-diisocyanat, trifenylmetan-triisocyanat, dife-nyleter-itriisocyanat, w,w'-dlisocyanat-di-metylbenzen (MXDI), (2) slike addisjons-produkter som har to eller flere innestående NCO-grupper som fås ved reaksjon med et overskudd av ovennevnte polyisocyanater med lavmolekylære polyoler, slik som etylen-glykol, propylen-glykol, butylen-glykol, trimetylol-propan, heksan-triol, glycerol, sorbitol, pentaerytritol, cas-torolje, etylendiamin, heksametylendlamin, monoetanolamin, dietanolamin, trietanol-amin eller med slike polymere forbindelser som har aktive hydrogenatomer som polyeter-polyoler eller polyester-polyoler. As polyisocyanate compounds can be mentioned (1) such aliphatic polyisocyanates as tetramethylene diisocyanate, hexamethylene diisocyanate, such aromatic polyisocyanates as phenylene diisocyanate, tolylene diisocyanate (TDI), dlphenylmethane diisocyanate (MDI), diphenylethane diisocyanate (EDI), naf- tylene diisocyanate, diphenylmethane triisocyanate, bitolylene diisocyanate, dianisldine diisocyanate, triphenylmethane triisocyanate, diphenyl ether itriisocyanate, w,w'-disocyanate-dimethylbenzene (MXDI), (2) such addition products having two or several contained NCO groups obtained by reaction with an excess of the above-mentioned polyisocyanates with low molecular weight polyols, such as ethylene glycol, propylene glycol, butylene glycol, trimethylol propane, hexane triol, glycerol, sorbitol, pentaerythritol, cas- tallow oil, ethylenediamine, hexamethylenediamine, monoethanolamine, diethanolamine, triethanolamine or with such polymeric compounds which have active hydrogen atoms as polyether polyols or polyester polyols.
Av disse polyisocyanatforbindelser foretrekkes aromatiske polyisocyanater slik som TDI, MDI, MXDI eller EDI og tilset-ningsprodukter som har to eller flere innestående NCO-grupper erholdt ved tilset-ning av et overskudd av det nevnte aromatiske polylsocyanat med tidligere nevnte lav eller høy molekylar forbindelse som inneholder aktive hydrogenatomer. Of these polyisocyanate compounds, preferred are aromatic polyisocyanates such as TDI, MDI, MXDI or EDI and addition products which have two or more contained NCO groups obtained by adding an excess of the aforementioned aromatic polyisocyanate with the previously mentioned low or high molecular compound which contains active hydrogen atoms.
Som polyeter-polyoler som er nevnt i det foregående kan nevnes et slikt produkt som fås ved tilsetningpolymerisering av en eller flere alkylenoksyder, slike som etylen-oksyd, propylen-oksyd, butylen-oksyd eller styren-oksyd til en eller flere polyoler som initiatorer, slike som etylen-glykol, dietylen-glykol, propylen-glykol, glycerol, trimetylol-propan, heksantriol, pentaerytritol, sorbitol, sucrose, mannit, sorblt, man-nitan eller sorbitan og aminer slik som etylen-diamin, propylen-diamin, etanolamin under alkaliske eller sure betingelser. As polyether polyols mentioned above can be mentioned such a product which is obtained by addition polymerization of one or more alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide or styrene oxide to one or more polyols as initiators, such as ethylene glycol, diethylene glycol, propylene glycol, glycerol, trimethylol propane, hexanetriol, pentaerythritol, sorbitol, sucrose, mannitol, sorblt, mannitan or sorbitan and amines such as ethylene diamine, propylene diamine, ethanolamine under alkaline or acidic conditions.
Disse polyeter-polyoler kan fremstilles på i og for seg kjent måte som beskrevet i These polyether polyols can be produced in a manner known per se as described in
«High Polymer Vol. XIII. Polyethers Part 1» "High Polymer Vol. XIII. Polyethers Part 1»
(1963) av Norman G. Gaylord utgitt av In-terscience Publishers. Molekylvekten for polyeter-polyolene kan varieres alt etter formålet og velges generelt fra området på ca. 300 til ca. 3.000, fortrinnsvis ca. 400 til ca. 2.000. Som polyester-polyoler som er nevnt i det foregående kan anigis et slikt produkt som fås ved reaksjon mellom en eller flere polyoler, slik som etylen-glykol, propylen-glykol, dietylen-glykol, trietylen-glykol, butylen-glykol, trimetylol-propan, glycerol, heksan-triol eller pentaerytritol med en eller flere polykarbonsyrer, slik som oksalsyre, ravsyre, glutarsyre, adipinsyre, pimelinsyre, sutoerinsyre, azelainsyre, seba-cinsyre, maleinsyre, fumarsyre, itakonsyre, ftalsyre, isoftalsyre, tereftalsyre eller deres syreanhydrider. (1963) by Norman G. Gaylord published by Interscience Publishers. The molecular weight of the polyether polyols can be varied depending on the purpose and is generally chosen from the range of approx. 300 to approx. 3,000, preferably approx. 400 to approx. 2,000. As polyester polyols mentioned above can be classified as a product obtained by reaction between one or more polyols, such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, butylene glycol, trimethylol propane , glycerol, hexane-triol or pentaerythritol with one or more polycarboxylic acids, such as oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, sutoeric acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid or their acid anhydrides.
Disse polyeter-polyoler kan fremstilles på i og for seg kjent måte som beskrevet i «Polyesters and their Application», tredje utgave April 1959, utgitt av Bjorksten Re-search Lab. Inc., New York, USA. Molekylvekten for polyester-polyolene kan variere alt etter formålet og velges generelt fra området fra ca. 300 til ca. 3.000, fortrinnsvis fra ca. 400 til ca. 2.000. These polyether polyols can be prepared in a manner known per se as described in "Polyesters and their Application", third edition April 1959, published by Bjorksten Research Lab. Inc., New York, USA. The molecular weight of the polyester polyols can vary depending on the purpose and is generally chosen from the range of approx. 300 to approx. 3,000, preferably from approx. 400 to approx. 2,000.
Som isocyanatblokeringsmlddel ifølge foreliggende oppfinnelse kan anvendes slike som er tidligere 'kjent, f. eks. fenoliske forbindelser slik som fenol, tiofenol, klor-fenol, metyltiofenol, etyl-fenol, etyl-tiofenol, nitrofenol, kresol, xylenol eller resor-cinol, alkoholer slik som etanol, metanol, propanol, isopropanol, butanol, tertlær-butanol, tertiær-pentanol, tertiær-butan-tiol eller tertiær-heksanol eller deres deri-vater slik som etylen-klorhydrin, co-hydro-per-fluoralkoholer eller l,3-diklor-2-propanol, aromatiske aminer slik som difenyl-amin, difenylnaftylamin eller xylidin, imi-der slik som ravsyre-imid eller ftalsyre-imid, aktive metylenforbindelser slik som aceto-eddiksyreestere, acetyl-aceton eller malonsyre-diestere, merkaptaner slik som 2-imerkaptobonzo-tiazol eller tertiær-dodecyl merkaptan, laktamer slik som e-kapro-laktam, a-valerolaktam, Y"Dutyrolaktiam eller |3-propyllaktam, iminer slik som etylen-imin, urinstofforbindelser slik som urinstoff, tiourinstoff eller dietylen-urinstoff, oksimer slik som acetoksim, metyl-etylketonoksim eller cykloheksanonoksim, diarylforbindelser slik som karbazoler, fenylnaftyl-amin eller N-fenyl-xylidln, bi-sulfater og borater. Av disse blokerings-midler foretrekkes fenoliske forbindelser og etanol. En blokert isocyanatforbindelse ifølge foreliggende oppfinnelse kan lett fremstilles ved 1 og for seg kjente fremgangsmåter f. eks. ved reaksjon mellom en polyisocyanatforbindelse og ekvivalent eller et lite overskudd av et isocyanatbloker-ingsmiddel i nærvær eller fravær av et slikt oppløsningsmiddel som ikke har noe aktivt hydrogenatom, slik som ketoner, estere eller aromatiske hydrokarboner ved romtemperatur eller ca. 40 til ca. 120° C. The isocyanate blocking agent according to the present invention can be used which are previously known, e.g. phenolic compounds such as phenol, thiophenol, chlorophenol, methylthiophenol, ethylphenol, ethylthiophenol, nitrophenol, cresol, xylenol or resorcinol, alcohols such as ethanol, methanol, propanol, isopropanol, butanol, tert-butanol, tertiary -pentanol, tertiary-butane-thiol or tertiary-hexanol or their derivatives such as ethylene-chlorohydrin, co-hydro-per-fluoroalcohols or 1,3-dichloro-2-propanol, aromatic amines such as diphenylamine, diphenylnaphthylamine or xylidine, imides such as succinic imide or phthalic acid imide, active methylene compounds such as aceto-acetic acid esters, acetyl-acetone or malonic acid diesters, mercaptans such as 2-imercaptobonzo-thiazole or tertiary-dodecyl mercaptan, lactams such as e -caprolactam, α-valerolactam, Y"dutyrolactiam or |3-propyllactam, imines such as ethylene imine, urea compounds such as urea, thiourea or diethylene urea, oximes such as acetoxime, methyl ethyl ketone oxime or cyclohexanone oxime, diaryl compounds such as k as carbazoles, phenylnaphthyl-amine or N-phenyl-xylidln, bi-sulphates and borates. Of these blocking agents, phenolic compounds and ethanol are preferred. A blocked isocyanate compound according to the present invention can be easily prepared by methods known per se, e.g. by reaction between a polyisocyanate compound and equivalent or a small excess of an isocyanate blocking agent in the presence or absence of such a solvent which has no active hydrogen atom, such as ketones, esters or aromatic hydrocarbons at room temperature or approx. 40 to approx. 120°C.
I den generelle formel (I) er Xx og X2 de samme eller forskjellige og betyr halogenatomer (f. eks. klor, brom, jod etc), hydroksylgrupper, alkoksygrupper (f. eks. metoksy, etoksy, propoksy, butoksy etc.) karboksylacyloksygrupper (f. eks. formyl-oksy, acetoksy, propionoyloksy, butyroyl-oksy, heksanoyloksy, lauroyloksy, oleoyloksy, parmitoyloksy, stearoyloksy, allylkarbon-yloksy, cyanoacetoksy, fenyloyloksy, ben-zoyloksy, benzyloyloksy, alkyl-maleoyloksy etc.) unntatt i det tilfelle hvor både X, og X2 er halogenatomer fordi en slik forbindelse har lav aktivitet som katalysator. In the general formula (I), Xx and X2 are the same or different and mean halogen atoms (e.g. chlorine, bromine, iodine etc.), hydroxyl groups, alkoxy groups (e.g. methoxy, ethoxy, propoxy, butoxy etc.) carboxyl acyloxy groups (e.g. formyloxy, acetoxy, propionoyloxy, butyroyloxy, hexanoyloxy, lauroyloxy, oleoyloxy, paramitoyloxy, stearoyloxy, allylcarbonyloxy, cyanoacetoxy, phenyloyloxy, benzoyloxy, benzyloyloxy, alkylmaleoyloxy etc.) except in that case where both X and X2 are halogen atoms because such a compound has low activity as a catalyst.
Rt, R,, R3 og R4 er de samme eller forskjellige og betyr resp. en alkylgruppe slik som metyl, etyl, propyl, butyl, isopropyl, heptyl og heksyl, fortrinnsvis en alkylgruppe som har en til fire karbonatomer slik som metyl, etyl, propyl, butyl, isopropyl. Rt, R1, R3 and R4 are the same or different and mean resp. an alkyl group such as methyl, ethyl, propyl, butyl, isopropyl, heptyl and hexyl, preferably an alkyl group having one to four carbon atoms such as methyl, ethyl, propyl, butyl, isopropyl.
Disse forbindelser fremstilles f. eks. ved den fremgangsmåte som er beskrevet i «Journal of Organometallic Chemistry» Volume 1, nr. 1, side 81—88 (1963). Med hensyn til X, og X, foretrekkes det anvendt en slik forbindelse av den generelle formel (I) hvori X, er halogen og X2 er hydroksyl, både Xt og X2 er karboksylacyloksygrupper, Xx er karboksylacyloksy og X2 er hydroksyl, Xj er alkoksy og X2 er halogen, Xt er alkoksy og X2 er carboksylacyloksy eller bå-de Xt og X2 er NCO-grupper eller NCS-grupper. Med hensyn til karboksylacyloksygrupper er slike som har en til atten karbonatomer, som alkoksygrupper slike som har en til tre karbonatomer å foretrekke. These compounds are produced, e.g. by the method described in "Journal of Organometallic Chemistry" Volume 1, No. 1, pages 81-88 (1963). With regard to X, and X, it is preferred to use such a compound of the general formula (I) in which X, is halogen and X2 is hydroxyl, both Xt and X2 are carboxylacyloxy groups, Xx is carboxylacyloxy and X2 is hydroxyl, Xj is alkoxy and X2 is halogen, Xt is alkoxy and X2 is carboxylacyloxy or both Xt and X2 are NCO groups or NCS groups. With respect to carboxyl acyloxy groups, those having one to eighteen carbon atoms, such as alkoxy groups, those having one to three carbon atoms are preferred.
Av disse forbindelser som er beskrevet ovenfor er de mest ønskede forbindelser for praktisk anvendelse følgende eksempler: Tetra-butyl-l-klor-3-hydroksy-distannoksan Tetra-butyl-l,3-diacetoksy-distannoksan Tetra-butyl-1,3-distearoyloksy-distannoksan Of these compounds described above, the most desired compounds for practical use are the following examples: Tetra-butyl-1-chloro-3-hydroxy-distannoxane Tetra-butyl-1,3-diacetoxy-distannoxane Tetra-butyl-1,3- distearoyloxy-distannoxane
Tetra-butyl-l,3-diformyloksy-distannoksan Tetra-butyl-1,3-diformyloxy-distannoxane
TetraJbutyl-l,3-di-2-etyl-heksanoyloksy-distannoksan Tetrabutyl-1,3-di-2-ethyl-hexanoyloxy-distannoxane
Tetra-propyl-l-klor-3-hydroksy-distannoksan Tetra-butyl-1,3-dilauroyloksy-distannoksan Tetra-etyl-l-klor-3-hydroksy-distannoksan Tetra-propyl-1-chloro-3-hydroxy-distannoxane Tetra-butyl-1,3-dilauroyloxy-distannoxane Tetra-ethyl-1-chloro-3-hydroxy-distannoxane
Tetra-metyl-l-klor-3-hydroksy-distannoksan Tetra-propyl-l,3-diacetoksy-distannoksan Tetra-butyl-l,3-diakryloyloksy-distannoksan Tetra-methyl-1-chloro-3-hydroxy-distannoxane Tetra-propyl-1,3-diacetoxy-distannoxane Tetra-butyl-1,3-diacryloyloxy-distannoxane
Tetra-butyl-l,3-dicyanoacetoksy-distannoksan Tetra-butyl-1,3-dicyanoacetoxy-distannoxane
Tetra-butyl-l,3-dibenzyloyloksy-distannoksan Tetra-etyl-l,3-diacetoksy-distannoksan Tetra-metyl-l,3-distearoyloksy-distannoksan Tetra-metyl-l,3-diacetoksy-distannoksan Tetra-hutyl-1 -hydroksy-3-acetoksy-distannoksan Tetra-butyl-1,3-dibenzyloyloxy-distannoxane Tetra-ethyl-1,3-diacetoxy-distannoxane Tetra-methyl-1,3-distearoyloxy-distannoxane Tetra-methyl-1,3-diacetoxy-distannoxane Tetra-hutyl-1 - hydroxy-3-acetoxy-distannoxane
Tetra-butyl-l-hydroksy-3-formyloksy-distannoksan Tetra-butyl-1-hydroxy-3-formyloxy-distannoxane
Tetra-propyl-l-hydroksy-3-acetoksy-distannoksan Tetra-propyl-1-hydroxy-3-acetoxy-distannoxan
Tetra-butyl-l,3-bis-(mono-metyl-maleoyloksy-distannoksan Tetra-butyl-1,3-bis-(mono-methyl-maleoyloxy-distannoxane).
Tetra-butyl-l-hydroksy-3-lauroyloksy-distannoksan Tetra-butyl-1-hydroxy-3-lauroyloxy-distannoxane
Tetra-etyl-l-hydroksy-3-acetoksy-distannoksan Tetra-ethyl-1-hydroxy-3-acetoxy-distannoxan
Tetra-etyl-l-hydroksy-3-(2-etyl-heksyanoyloksy) -distannoksan Tetra-ethyl-1-hydroxy-3-(2-ethyl-hexyanoyloxy)-distannoxane
Tetra-butyl-1 -klor-3-metoksy-distannoksan Tetra-butyl-l-klor-3-etoksy-distannoksan Tetra-butyl-l-klor-3-propoksy-distannoksan Tetra-butyl-1-chloro-3-methoxy-distannoxane Tetra-butyl-1-chloro-3-ethoxy-distannoxane Tetra-butyl-1-chloro-3-propoxy-distannoxane
Tetra-propyl-l-klor-3-metoksy-distannoksan Tetra-propyl-1-chloro-3-methoxy-distannoxane
Tetra-etyl-l-klor-3-metoksy-distannoksan Tetra-butyl-l,3-diisocyanat-distannoksan Tetra-butyl-l,3-diisotiocyanat-dlstannoksan Tetra-ethyl-1-chloro-3-methoxy-distannoxane Tetra-butyl-1,3-diisocyanate-distannoxane Tetra-butyl-1,3-diisothiocyanate-dlstannoxane
Tetra-propyl-l,3-diisocyanat-distannoksan Tetra-etyl-l,3-diisocyanat-distannoksan Tetra-etyl-l,3-diisotiocyanat-distannoksan Tetra-propyl-1,3-diisocyanate-distannoxane Tetra-ethyl-1,3-diisocyanate-distannoxane Tetra-ethyl-1,3-diisothiocyanate-distannoxane
Tetra-propyl-l,3-diformyloksy-distanrioksan Tetra-etyl-l,3-diformyloksy-distannoksan Tetra-metyl-l,3-diformyloksy-distannoksan Tetra-propyl-1,3-diformyloxy-distannoxane Tetra-ethyl-1,3-diformyloxy-distannoxane Tetra-methyl-1,3-diformyloxy-distannoxane
Tetra-metyl-l-acetoksy-3-hydroifcsy-distannoksan Tetra-methyl-1-acetoxy-3-hydroifcsy-distannoxane
Tetra-etyl-l-formyloksy-3-hydroksy-distannoksan Tetra-ethyl-1-formyloxy-3-hydroxy-distannoxane
Tetra-propyl-l-formyloksy-3-hydroksy-distannoksan Tetra-propyl-1-formyloxy-3-hydroxy-distannoxane
Tetra-butyl-l-metoksy-3-acetoksy-distannoksan Tetra-butyl-1-methoxy-3-acetoxy-distannoxane
Tetra-butyl-l-metoksy-3-formyloksy-distannoksan Tetra-butyl-1-methoxy-3-formyloxy-distannoxane
Tetra-butyl-l-etoksy-3-acetoksy-distannoksan Tetra-butyl-1-ethoxy-3-acetoxy-distannoxane
Tetra-butyl-l,3-dioleoyloksy-distannoksan Tetra-butyl-1,3-dimaleoyloksy-distannoksan Tetra-butyl-1,3-dioleoyloxy-distannoxane Tetra-butyl-1,3-dimaleoyloxy-distannoxane
Tetra-butyl-l-hydroksy-3-mono-metyl-maleoyloksy-distannoksan Tetra-butyl-1-hydroxy-3-mono-methyl-maleoyloxy-distannoxane
Tetra-butyl-l-etoksy-3-stearoyloksy-distannoksan Tetra-butyl-1-ethoxy-3-stearoyloxy-distannoxane
Tetra-butyl-l-etoksy-3-formyloksy-distannoksan Tetra-butyl-1-ethoxy-3-formyloxy-distannoxane
Tetra-propyl-l-metoksy-3-acetoksy-distannoksan Tetra-propyl-1-methoxy-3-acetoxy-distannoxan
Tetra-ibutyl-l-propoksy-3-acetoksy-distannoksan Tetra-butyl-1-propoxy-3-acetoxy-distannoxane
Tetra-propyl-l-metoksy-3-lauroyloksy-distannoksan Tetra-propyl-1-methoxy-3-lauroyloxy-distannoxane
Andre forbindelser, såfremt disse faller inn under den generelle formel, 'har også høyere aktivitet som katalysator for regenerering av NCO-gruppen fra en blokert isocyanatforbindelse enn kjente katalysatorer. Other compounds, provided they fall under the general formula, also have higher activity as a catalyst for the regeneration of the NCO group from a blocked isocyanate compound than known catalysts.
Foreliggende oppfinnelse omfatter blandingen (A) som består av blokert isocyanatforbindelse som nevnt ovenfor og forbindelsen som er vist ved den generelle formel (I) og blandingen (B) som består av en slik blokert isocyanatforbindelse som nevnt ovenfor, forbindelsen vist med den generelle formel (I) og en «tilsetningsforbindelse» inneholdende aktive hydrogenatomer. The present invention comprises the mixture (A) which consists of a blocked isocyanate compound as mentioned above and the compound shown by the general formula (I) and the mixture (B) which consists of such a blocked isocyanate compound as mentioned above, the compound shown with the general formula ( I) and an "addition compound" containing active hydrogen atoms.
For fremstilling av blandingen (A) ifølge foreliggende oppfinnelse foretrekkes det å anvende som blokert isocyanatforbindelse reaksjonsproduktet mellom et blokeringsmiddel og en høymolekylar forbindelse som inneholder innestående NCO-grupper erholdt ved å omsette et overskudd av polyisocyanatforbindelse med en slik høymo-lekylar forbindelse som inneholder aktive hydrogenatomer som den tidligere nevnte polyeter-glykol eller polyester-glykol, mer hensiktsmessig polyester-polyol. Molekylvekten for polyester-polyolen eller polyeter-polyolen er hensiktsmessig fra ca. 1.500 til ca. 2.000, og funksjonaliteten er hensiktsmessig fra 3 til 5. For the preparation of the mixture (A) according to the present invention, it is preferred to use as blocked isocyanate compound the reaction product between a blocking agent and a high-molecular compound containing contained NCO groups obtained by reacting an excess of polyisocyanate compound with such a high-molecular compound containing active hydrogen atoms such as the previously mentioned polyether glycol or polyester glycol, more appropriately polyester polyol. The molecular weight of the polyester polyol or polyether polyol is suitable from approx. 1,500 to approx. 2,000, and the functionality is appropriate from 3 to 5.
Ved oppvarming av blandingen (A) regenereres NCO-grupper, og således regenererte NCO-grupper reagerer med fuktigheten i luften og resulterer i polymere forbindelser. When the mixture (A) is heated, NCO groups are regenerated, and thus regenerated NCO groups react with the moisture in the air and result in polymeric compounds.
Som «tilsetningsforbindelse» som inneholder aktive hydrogenatomer i blandingen As "addition compound" that contains active hydrogen atoms in the mixture
(B) ifølge foreliggende oppfinnelse kan an- (B) according to the present invention can an-
gis f. eks. en slik høy molekylar forbindelse given, e.g. such a high molecular compound
som polyeter-polyol eller polyester-polyol, som er nevnt i det foregående, cellulose, polyamider, polyvinyl-alkohol, polyvinyl-acetater og lave molekylare forbindelser slik som polyoler (f. eks. etylen-glykol, propylen-glykol, dietylen-glykol, butylen-glykol, trietylen-glykol, trimetylolpropan, glycerol, heksan-triol, pentaerytritol, manni-tol, sorbitol eller sukrose), amino-alkoholer (f. eks. etanolamin eller metanolamin), alifatiske aminer (f. eks. etylendiamin, hydrazin, trietylen-diamin, heksametylen-diamin eller propylen-diamin) og aromatiske aminer (f. eks. fenylendiamin, dife-nylmetan-diamin, difenyletan-diamin, 4,4'-metylen-bis-(2-kloranilin) eller co,co'-dia-mino-dimetylbenzen). such as polyether polyol or polyester polyol, as mentioned above, cellulose, polyamides, polyvinyl alcohol, polyvinyl acetates and low molecular weight compounds such as polyols (e.g. ethylene glycol, propylene glycol, diethylene glycol , butylene glycol, triethylene glycol, trimethylolpropane, glycerol, hexane triol, pentaerythritol, mannitol, sorbitol or sucrose), amino alcohols (e.g. ethanolamine or methanolamine), aliphatic amines (e.g. ethylenediamine, hydrazine, triethylenediamine, hexamethylenediamine or propylenediamine) and aromatic amines (e.g. phenylenediamine, diphenylmethanediamine, diphenylethanediamine, 4,4'-methylene-bis-(2-chloroaniline) or co ,co'-diamino-dimethylbenzene).
For blandingen (B) i det tilfelle at den blokerte isocyanatforbindelse er lavmolekylær, dvs. reaksjonsproduktet mellom et For the mixture (B) in the case that the blocked isocyanate compound is low molecular weight, i.e. the reaction product between a
blokeringsmiddel av ovennevnte alifatiske blocking agent of the above aliphatic
eller aromatiske polyisocyanatforbindelse eller med et lavmolekylært tilsetningspro-dukt inneholdende innestående NCO-grupper som fås ved addisjonsreaksjon av et overskudd av den alifatiske eller aromatiske polyisocyanatforbindelse med en tidligere nevnt lavmolekylær forbindelse som inneholder aktive hydrogenatomer foretrekkes det å anvende som tilsetningsforbindelse som inneholder aktive hydrogenatomer en høymolekylær av slike som er angitt i det foregående, mer generelt polyeter-polyol eller polyester-polyol. or aromatic polyisocyanate compound or with a low molecular weight additive product containing contained NCO groups obtained by addition reaction of an excess of the aliphatic or aromatic polyisocyanate compound with a previously mentioned low molecular weight compound containing active hydrogen atoms, it is preferred to use as additive compound containing active hydrogen atoms a high molecular of those indicated above, more generally polyether polyol or polyester polyol.
Molekylvekten for tilsetningshøymole-kylærforbindelsen som inneholder aktive hydrogenatomer skal ikke være lavere enn The molecular weight of the additive high molecular weight compound containing active hydrogen atoms shall not be lower than
ca. 150 og mer hensiktsmessig fra ca. 300 about. 150 and more appropriate from approx. 300
til ca. 2.000. Hvis den anvendte blokerte isocyanatforbindelse imidlertid er høymoleky-lær, dvs. reaksjonsproduktet mellom et blokeringsmiddel og et høymolekylært tilset-ningsprodukt inneholdende innestående NCO-grupper som fås ved addisjonsreak-sjonen av den alifatiske eller aromatiske polyisocyanatforbindelse i overskudd med en tidligere nevnt høymolekylær forbindelse som inneholder aktive hydrogenatomer anvendes fortrinnsvis både en tilsetnings-høymolekylærforbindelse som inneholder aktive hydrogenatomer og en tilsetnings-lavmolekylærforbindelse som angitt som eksempel i det foregående for blanding to approx. 2,000. If the blocked isocyanate compound used is, however, high molecular weight, i.e. the reaction product between a blocking agent and a high molecular weight addition product containing contained NCO groups which is obtained by the addition reaction of the aliphatic or aromatic polyisocyanate compound in excess with a previously mentioned high molecular weight compound containing active hydrogen atoms are preferably used both an additive high molecular weight compound containing active hydrogen atoms and an additive low molecular weight compound as indicated as an example above for mixing
(B). (B).
I det siste tilfelle er som tilsetnlngs-lavmolekylærforbindelse som inneholder aktive hydrogenatomer slike aromatiske aminer som fenylen-dlamin, difenylmetan-diamin, difenyletan-diamin, 4,4<*->metylen-bis-(2-kloranilin) eller o3,co'-diamino-dime-tylbenzen å foretrekke og som tilsetnings-høymolekylærforbindelse polyeter-polyol og polyester-polyol nevnt i det foregående, hvis molekylvekter ikke bør være mindre enn ca. 150, mer hensiktsmessig Æra ca. 300 til ca. 2.000. In the latter case, as additional low-molecular compounds containing active hydrogen atoms are such aromatic amines as phenylenediamine, diphenylmethanediamine, diphenylethanediamine, 4,4<*->methylene-bis-(2-chloroaniline) or o3,co' -diamino-dimethylbenzene preferably and as additive high-molecular compound polyether-polyol and polyester-polyol mentioned above, whose molecular weights should not be less than approx. 150, more appropriate Era ca. 300 to approx. 2,000.
Ved opphetning av blandingen (B) regenereres NCO-grupper og således regenererte NCO-grupper reagerer med en «tilsetningsforbindelse» som inneholder aktive hydrogenatomer og som eksisterer i blandingen (B) slik at de gir en polymer forbindelse. When the mixture (B) is heated, NCO groups are regenerated and thus regenerated NCO groups react with an "addition compound" containing active hydrogen atoms and which exists in the mixture (B) so that they give a polymeric compound.
Egenskapene for en. polymer forbindelse som fremstilles ved opphetning av blandingen (A) eller (B) varierer sterkt med typen, molekylvekten og funksjonaliteten for den blokerte isocyanatforbindelse som anvendes og/eller av «tilsetningsforbindelse» som inneholder aktive hydrogenatomer, og av-hengig av formålet med foreliggende oppfinnelse velges en blokert isocyanatforbindelse og/eller «tilsetningsforbindelse» som inneholder aktive hydrogenatomer. The properties for a. polymeric compound produced by heating the mixture (A) or (B) varies greatly with the type, molecular weight and functionality of the blocked isocyanate compound used and/or of "addition compound" containing active hydrogen atoms, and depending on the purpose of the present invention a blocked isocyanate compound and/or "addition compound" containing active hydrogen atoms is chosen.
Generelt talt jo lavere molekylvekten for en blokert isocyanatforbindelse som anvendes og/eller av den «tilsetningsforbindelse» som inneholder aktive hydrogenatomer er, og jo høyere deres funksjonalitet blir, jo mer fast blir en polymer forbindelse som fremstilles ved oppvarming av blandingen ifølge foreliggende oppfinnelse. Jo høyere deres molekylvekt og lavere deres funksjonalitet blir, jo mer elastisk blir den polymere forbindelse. Generally speaking, the lower the molecular weight of a blocked isocyanate compound used and/or of the "addition compound" containing active hydrogen atoms, and the higher their functionality, the more solid a polymer compound produced by heating the mixture according to the present invention becomes. The higher their molecular weight and the lower their functionality, the more elastic the polymeric compound becomes.
Blandingen ifølge foreliggende oppfinnelse fremstilles ved å blande en blokert isocyanatforbindelse, den forbindelse som er vist ved formel (1) og, om ønskes en «tilsetningsforbindelse» som inneholder aktive hydrogenatomer. The mixture according to the present invention is prepared by mixing a blocked isocyanate compound, the compound shown by formula (1) and, if desired, an "addition compound" containing active hydrogen atoms.
Blandingsmåten kan være en hvilken som helst i og for seg kjent, og f. eks. kan blandingen ifølge foreliggende oppfinnelse fremstilles ved å sette forbindelsen med formel (I) slik som den er eller som en opp-løsning eller emulsjon til en blokert iso-cyanatfonbindelse eller til en blanding som består av blokert Isocyanatforbindelse og «tilsetningsforbindelse» som inneholder aktive hydrogenatomer. The mixing method can be any known in and of itself, and e.g. the mixture according to the present invention can be prepared by adding the compound of formula (I) as it is or as a solution or emulsion to a blocked isocyanate bond or to a mixture consisting of blocked isocyanate compound and "addition compound" containing active hydrogen atoms .
Da forbindelsen som er vist med den generelle formel (I) også påskynder reaksjonen av en NCO-gruppe med et aktivt hydrogenatom kan blokert isocyanatforbindelse lett fremstilles ved å omsette polyisocyanater med et blokeringsmiddel 1 nærvær av forbindelsen som er vist med den generelle formel (I), og et således erholdt reaksjonsprodukt består av en blokert isocyanatforbindelse og forbindelsen vist med formel (I). Since the compound shown with the general formula (I) also accelerates the reaction of an NCO group with an active hydrogen atom, blocked isocyanate compound can be easily prepared by reacting polyisocyanates with a blocking agent 1 in the presence of the compound shown with the general formula (I) , and a reaction product thus obtained consists of a blocked isocyanate compound and the compound shown by formula (I).
Ved hjelp av ovennevnte fremgangsmåte kan således blandingen (A) ifølge foreliggende oppfinnelse fremstilles i ett trinn. By means of the above-mentioned method, the mixture (A) according to the present invention can thus be prepared in one step.
Jo større mengde av forbindelsen med formel (I) som anvendes, jo lavere er dén temperatur hvilken NCO-gruppen regenereres fra det blokerte isocyanat, og således regenerert NCO-gruppe reagerer med aktive hydrogenatomer for å gi en polymer forbindelse. Og mengden av forbindelsen med formel (I) kan generelt være fra ca. 0,01 til ca. 5 vektsdeler pr. 100 vektsdeler blokert isocyanatforbindelse, fortrinsvis fra ca. 0,1 til ca. 1 del. The greater the amount of the compound of formula (I) used, the lower the temperature at which the NCO group is regenerated from the blocked isocyanate, and thus regenerated NCO group reacts with active hydrogen atoms to give a polymeric compound. And the amount of the compound of formula (I) can generally be from approx. 0.01 to approx. 5 parts by weight per 100 parts by weight blocked isocyanate compound, preferably from approx. 0.1 to approx. 1 part.
Mengden av en «tilsetningsforbindelse» som inneholder aktive hydrogenatomer kan variere innenfor de områder som utgjør formålet med blandingen ifølge foreliggende oppfinnelse og kan generelt være slik at antall mol blokerte NCO-grupper er halv-parten eller mer av antall mol av aktive hydrogenatomer. The amount of an "addition compound" containing active hydrogen atoms can vary within the ranges that constitute the purpose of the mixture according to the present invention and can generally be such that the number of moles of blocked NCO groups is half or more of the number of moles of active hydrogen atoms.
Da forbindelsen ifølge den generelle formel (I) akselererer regenereringen av NCO-grupper fra en blokert isocyanatforbindelse, er oppvarmningstemperaturen for å fremstille polymer forbindelse fra blandingen ifølge foreliggende oppfinnelse langt lavere enn de kjente tilfelle for en blokert isocyanatforbindelse. As the compound according to the general formula (I) accelerates the regeneration of NCO groups from a blocked isocyanate compound, the heating temperature to produce polymer compound from the mixture according to the present invention is far lower than the known case for a blocked isocyanate compound.
Blandingen ifølge foreliggende oppfinnelse kan derfor anvendes effektivt over store industriområder, mer spesielt på slike områder som tekstiler, plast-ark, gummi og emulsjonsmalinger, hvortil en blokert isocyanatblanding er blitt betraktet som nes-ten umulig på grunn av dens følsomhet overfor varme. The mixture according to the present invention can therefore be used effectively over large industrial areas, more particularly in such areas as textiles, plastic sheets, rubber and emulsion paints, for which a blocked isocyanate mixture has been considered almost impossible due to its sensitivity to heat.
F. eks. kan emulsjonsmalinger fremstilles ved å oppløse eller emulgere blandingen ifølge foreliggende oppfinnelse i slike oppløsningsmidler som estere (f. eks. butyl-acetat, etyl-acetat, metyl-acetat, cellosolve-acetat eller metylcellosolve-acetat) og ketoner (f. eks. aceton eller metyliso-butyl-keton) og om ønskes blandes med fortynningsmidler slik som benzen, toluen eller xylen. For example emulsion paints can be prepared by dissolving or emulsifying the mixture according to the present invention in such solvents as esters (e.g. butyl acetate, ethyl acetate, methyl acetate, cellosolve acetate or methylcellosolve acetate) and ketones (e.g. acetone or methyl isobutyl ketone) and if desired mixed with diluents such as benzene, toluene or xylene.
Således tilberedte emulsjonsmalinger kan anvendes på et hvilket som helst ma-teriale, f. eks. metaller, tre, plast, lær, gummi osv. Emulsion paints prepared in this way can be used on any material, e.g. metals, wood, plastic, leather, rubber, etc.
Ved å oppvarme materialene som er be-handlet med malingen ved lavere temperatur en kort periode kan det dannes fil-mer med gode egenskaper -på overflaten uten at det har noen uheldig innvirkning på selve materialene. By heating the materials which have been treated with the paint at a lower temperature for a short period, films with good properties can be formed on the surface without this having any adverse effect on the materials themselves.
Emulsjonen som fremstilles ved å emulgere blandingen ifølge foreliggende oppfinnelse er nyttig som impregneiings-mlddel og adhesiv. The emulsion produced by emulsifying the composition of the present invention is useful as an impregnating agent and adhesive.
F. eks. dyppes tekstiler, ikke-vevede stoffer, klær, papir og plast-ark i emulsjonen, tørkes og oppvarmes til lav temperatur i et kort tidsrom for å fremstille en polymer forbindelse på overflaten. Således forbedres egenskapene for de nevnte materialer. Ved hjelp av en slik fremgangsmåte at et hvilket som helst av de materialer som 'f. eks. er nevnt slik som gummi, tre, metaller, stoff, tekstiler, klær, plast-ark osv., påføres emulsjonen, tørkes, legges sammen med de andre materialer som er valgt fra de ovenfor nevnte og oppvarmes til lav temperatur et kort tidsrom fås en kraftig adhesjon mellom de to materialer. For example textiles, non-woven fabrics, clothing, paper and plastic sheets are dipped in the emulsion, dried and heated to a low temperature for a short period of time to produce a polymeric compound on the surface. Thus, the properties of the aforementioned materials are improved. By means of such a method that any of the materials such as 'f. e.g. are mentioned such as rubber, wood, metals, fabric, textiles, clothing, plastic sheets, etc., the emulsion is applied, dried, combined with the other materials selected from those mentioned above and heated to a low temperature for a short period of time, a strong adhesion between the two materials.
Det er klart fra det foregående at foreliggende oppfinnelse og anvendelsen av en forbindelse med formel (I) som katalysator ifølge foreliggende oppfinnelse har store verdi ut fra et industrielt synspunkt. It is clear from the foregoing that the present invention and the use of a compound of formula (I) as a catalyst according to the present invention has great value from an industrial point of view.
For bedre å forstå foreliggende oppfinnelse angis følgende eksempler på fore-trukne utførelser. In order to better understand the present invention, the following examples of preferred embodiments are given.
I disse eksempler er mengdene uttrykt som vektsdeler hvis intet annet er angitt. In these examples, the amounts are expressed as parts by weight unless otherwise stated.
Resultatene er som følger: The results are as follows:
Vektsdeler har det samme forhold til vo-lumdeler som gram til milliliter. Parts by weight have the same relationship to parts by volume as grams to milliliters.
Eksempel 1. Example 1.
En blokert isocyanatforbindelse (100 deler) som er fremstilt ved å omsette MDI (250 deler) med fenol (190 deler) blandes med tetra-n-butyl-l,3-diacetoksy-distannoksan (0,1 deler) og deretter blandes denne igjen med polyester-polyol (100 deler) med hydroksyl tall 253 oppløst i toluen (200 deler) som erholdes ved kondensasjon av adipinsyre (438 deler), 1,4-ibu tylen-gly kol (180 deler) og heksan-triol (268 deler). A blocked isocyanate compound (100 parts) prepared by reacting MDI (250 parts) with phenol (190 parts) is mixed with tetra-n-butyl-1,3-diacetoxy-distannoxane (0.1 part) and then mixed again with polyester polyol (100 parts) with hydroxyl number 253 dissolved in toluene (200 parts) obtained by condensation of adipic acid (438 parts), 1,4-ibutylene glycol (180 parts) and hexane-triol (268 parts) ).
Den således erholdte 'blanding påføres en metallplate og oppvarmes i en elektrisk ovn for å herde polyester-polyolen med NCO-grupper som genereres ved oppvarming. The mixture thus obtained is applied to a metal plate and heated in an electric furnace to cure the polyester polyol with NCO groups generated by heating.
Som kontroll fremstilles en blanding bestående av de samme bestanddeler som ovenfor med unntagelse av N-metyl-mor-folin (0,1 deler i og for seg kjent katalysator) anvendes istedet for tetra-n-foutyl-1,3-diacetoksy-distannoksan eller med den unntagelse at det ikke anvendes noen katalysator og de underkastes lignende behandling som ovenfor for å herde polyester-polyolen. As a control, a mixture consisting of the same ingredients as above is prepared with the exception of N-methyl-morpholine (0.1 parts in and of itself known catalyst) is used instead of tetra-n-foutyl-1,3-diacetoxy-distannoxane or with the exception that no catalyst is used and they are subjected to similar treatment as above to cure the polyester polyol.
Eksempel 2. Example 2.
En 'biokert polyisocyanat (50 deler) som er fremstilt ved addisjonsreaksjon av fenol (3 mol) med reaksjonsprodukt av TDI (3 mol) og trimetylol-propan (1 mol) oppløses i etyl-acetat (100 deler). A biocured polyisocyanate (50 parts) which is prepared by the addition reaction of phenol (3 mol) with the reaction product of TDI (3 mol) and trimethylol-propane (1 mol) is dissolved in ethyl acetate (100 parts).
Denne oppløsning (300 deler) blandes med tetra-n-propyl-l-klor-3-hydroksy-distannoksan (varierer) og deretter blandes dette igjen med samme polyester-polyol (100 deler) som i eksempel 1 oppløst i toluen (200 deler). This solution (300 parts) is mixed with tetra-n-propyl-1-chloro-3-hydroxy-distannoxane (varies) and then this is mixed again with the same polyester polyol (100 parts) as in example 1 dissolved in toluene (200 parts ).
Den således erholdte blanding påføres en metallplate og oppvarmes i en elektrisk ovn for å herde polyester-polyolen med NCO-grupper regenerert ved oppvarming. The mixture thus obtained is applied to a metal plate and heated in an electric oven to cure the polyester polyol with NCO groups regenerated by heating.
Resultatene er som følger: The results are as follows:
Eksempel 3. Example 3.
Polyeter-triol (60,4 deler) med hydroksyltall 160 som fås ved addisjonspolymerisasjon av propylen-oksyd til glycerol som initiator, trimetylol-propan (16 deler) og TDI (38 deler) tillates å reagere med hver-andre ved 60° C for å gi en prepolymer hvis NCO innhold er 4,8 pst. Polyether triol (60.4 parts) with hydroxyl number 160 obtained by addition polymerization of propylene oxide to glycerol as initiator, trimethylol propane (16 parts) and TDI (38 parts) are allowed to react with each other at 60°C for to give a prepolymer whose NCO content is 4.8 percent.
Den prepolymere (880 deler) tillates å reagere med m-kresol (108 deler) ved 140° C i to timer og gir en blokert isocyanatforbindelse. The prepolymer (880 parts) is allowed to react with m-cresol (108 parts) at 140°C for two hours to give a blocked isocyanate compound.
Den blokerte isocyanatforbindelse (50 deler) oppløses i 100 deler etylacetat. The blocked isocyanate compound (50 parts) is dissolved in 100 parts of ethyl acetate.
Oppløsningen (100 deler) blandes med 0,5 deler tetra-n-butyl-l,3-diacetoksy-distannoksan etterfulgt av emulgering av blandingen i en vanndig oppløsning (67 deler) inneholdende dialkylsulfosuccinat (3 deler) som emulgeringsmiddel. The solution (100 parts) is mixed with 0.5 parts of tetra-n-butyl-1,3-diacetoxy-distannoxane followed by emulsification of the mixture in an aqueous solution (67 parts) containing dialkyl sulfosuccinate (3 parts) as an emulsifier.
Den således erholdte emulsjon påføres en glassplate og oppvarmes i en elektrisk ovn. The emulsion thus obtained is applied to a glass plate and heated in an electric oven.
Med reaksjonen av regenererte NCO-grupper og fuktighet i luften er herdingen fullstendig ved oppvarming til 90° C i 20 minutter. With the reaction of regenerated NCO groups and moisture in the air, curing is complete by heating to 90°C for 20 minutes.
Men uten tetra-n-butyl-l,3-diacetoksy-distannoksan oppnås ikke herding ved oppvarming til 180° C i 20 minutter eller lenger. But without tetra-n-butyl-1,3-diacetoxy-distannoxane, curing is not achieved by heating to 180° C. for 20 minutes or longer.
Eksempel 4. Example 4.
TDI (520 deler) tillates å reagere med kastorolje (1000 deler) ved 60° C for å gi en prepolymer, som deretter tillates å reagere med fenol (324 deler) ved 140° C for å gi en blokert isocyanatforbindelse. TDI (520 parts) is allowed to react with castor oil (1000 parts) at 60°C to give a prepolymer, which is then allowed to react with phenol (324 parts) at 140°C to give a blocked isocyanate compound.
Den blokerte isocyanatforbindelse (50 deler) oppløses i etylacetat (100 deler). The blocked isocyanate compound (50 parts) is dissolved in ethyl acetate (100 parts).
Oppløsningen (100 deler) tilsettes tetra-n-butyl-l,3-diacetoksy-distannoksan (0,2 deler) og deretter blandes dette igjen med 4,4'-metylen-bis-(2-kloranllin) (15 deler) etterfulgt av at blandingen helles i en vandig oppløsning (67 deler) inneholdende natrium-alkyl-naftalin-sulfonat (2 deler) og den kopolymere (3 deler) av etylen-oksyd og propylen-oksyd for å gl en emulsjon. To the solution (100 parts) is added tetra-n-butyl-1,3-diacetoxy-distannoxane (0.2 parts) and this is then mixed again with 4,4'-methylene-bis-(2-chloroanllin) (15 parts) followed by of the mixture being poured into an aqueous solution (67 parts) containing sodium alkyl naphthalene sulphonate (2 parts) and the copolymer (3 parts) of ethylene oxide and propylene oxide to form an emulsion.
Den således erholdte emulsjon påføres en glassplate og oppvarmes til 120° C i en elektrisk ovn og gir innen 20 minutter herdet fast film som har en hårdhet som re-fererer til Sward rocker-verdi på 57. The emulsion thus obtained is applied to a glass plate and heated to 120° C in an electric oven and within 20 minutes gives a hardened solid film which has a hardness that refers to a Sward rocker value of 57.
Eksempel 5. Example 5.
Den samme blokerte isocyanatforbindelse (65 deler) som i eksempel 3, oppløses i etyl-acetat (100 deler). Oppløsningen tilsettes tetra-metyl-1,3-diacetoksy-dlstan-noksan (0,4 deler) og deretter blandes denne blanding igjen med polyester-polyol (80 deler) som fås ved kondensasjon av etylen-glykol (71 deler) og adipinsyre (146 deler) etterfulgt av at blandingen helles i en vandig oppløsning (67 deler) inneholdende natrium-alkylbenzensulfonat (2 deler) og polyetylen-oksyd-dodecyl-eter (3 deler) for å gi en emulsjon. The same blocked isocyanate compound (65 parts) as in example 3 is dissolved in ethyl acetate (100 parts). Tetra-methyl-1,3-diacetoxy-dlstannoxane (0.4 parts) is added to the solution and then this mixture is mixed again with polyester polyol (80 parts) which is obtained by condensation of ethylene glycol (71 parts) and adipic acid ( 146 parts) followed by pouring the mixture into an aqueous solution (67 parts) containing sodium alkylbenzene sulphonate (2 parts) and polyethylene oxide dodecyl ether (3 parts) to give an emulsion.
Den således erholdte emulsjon påføres en glassplate og oppvarmes til 120° C i en elektrisk ovn for, innen 20 minutter, å gl en seig og elastisk film. The emulsion thus obtained is applied to a glass plate and heated to 120° C in an electric oven to melt a tough and elastic film within 20 minutes.
Eksempel 6. Example 6.
TDI (522) tillates å reagere med trimetylolpropan (134 deler) ved 80° C i to timer for å gi en prepolymer med isocyanatinn-hold på 21,8 pst. TDI (522) is allowed to react with trimethylolpropane (134 parts) at 80° C. for two hours to give a prepolymer with an isocyanate content of 21.8%.
Den prepolymere (8656 deler) omsettes med m-kresol (324 deler) ved ca. 130° C til ca. 150° C i en time og gir en gulaktig blokert isocyanatforbindelse. The prepolymer (8656 parts) is reacted with m-cresol (324 parts) at approx. 130° C to approx. 150° C for one hour and gives a yellowish blocked isocyanate compound.
Den blokerte isocyanatforbindelse (20 deler) oppløses i en oppløsning som inneholder polyester-polyol (14 deler) med et hydroksyltall på 253 som fås ved kondensasjon av adipinsyre (438 deler), 1,4-butylen-glykol (180 deler) og heksan-triol (268 deler), etyl-acetat (22 deler), toluen (22 deler) og cellosolve-acetat (22 deler). Den således erholdte oppløsning (100 deler) tilsettes tetra-n-propyl-l-klor-3-hydroksy-distannoksan (0,1 deler). The blocked isocyanate compound (20 parts) is dissolved in a solution containing polyester polyol (14 parts) with a hydroxyl number of 253 obtained by condensation of adipic acid (438 parts), 1,4-butylene glycol (180 parts) and hexane- triol (268 parts), ethyl acetate (22 parts), toluene (22 parts) and cellosolve acetate (22 parts). Tetra-n-propyl-1-chloro-3-hydroxy-distannoxane (0.1 parts) is added to the solution thus obtained (100 parts).
Blandingen sprøytes på en metallplate og oppvarmes i en elektrisk ovn for å danne en herdet film. The mixture is sprayed onto a metal plate and heated in an electric oven to form a cured film.
Som kontroll underkastes slike blan-dinger av de samme bestanddeler som ovenfor, med unntagelse av at det anvendes N-metylmorfolin (0,1 deler) i stedet for det nevnte stannoksan eller at det ikke anvendes noen katalysator, en lignende fremgangsmåte som ovenfor for å fremkalle den ønskede herding. As a control, such mixtures of the same components as above, with the exception that N-methylmorpholine (0.1 parts) is used instead of the aforementioned stannoxane or that no catalyst is used, are subjected to a similar procedure as above in order to induce the desired hardening.
Resultatene er som følger: The results are as follows:
Eksempel 7. Example 7.
Samme oppløsning (100 deler) inneholdende blokert isocyanatforbindelse opp-løst i en blanding av polyester-rpolyol, etyl-acetat, toluen og cellosolve-acetat som den som fås i eksempel 6, blandes med tetra-n-butyl-l,3-dlacetoksy-distannoksan (variabel). The same solution (100 parts) containing blocked isocyanate compound dissolved in a mixture of polyester polyol, ethyl acetate, toluene and cellosolve acetate as obtained in Example 6 is mixed with tetra-n-butyl-1,3-dacetoxy -distannoxan (variable).
Den således erholdte blanding sprøytes på en j ernplate og oppvarmes i en elektrisk ovn for å danne en herdet film. The mixture thus obtained is sprayed onto an iron plate and heated in an electric furnace to form a hardened film.
Ved dypping av jernplaten, som er be-lagt med herdet film, i butyl-acetat og iakttar den således behandlede film etter noen tid, måles motstandsevnen mot kjemikalier. By dipping the iron plate, which is coated with hardened film, in butyl acetate and observing the thus treated film after some time, the resistance to chemicals is measured.
Eksempel S. Example S.
Samme oppløsning (100 deler) inneholdende blokert isocyanatforbindelse opp-løst i en blanding av polyester-polyol, etyl-acetat, toluen og cellosolve-acetat som den som fås i eksempel 6, blandes med 0,1 deler distannoksaner (variable). The same solution (100 parts) containing blocked isocyanate compound dissolved in a mixture of polyester polyol, ethyl acetate, toluene and cellosolve acetate as that obtained in example 6, is mixed with 0.1 parts of distannoxanes (variable).
Med bruk av de således erholdte blan-dinger utføres en lignende fremgangsmåte som angitt i eksempel 7. Using the mixtures thus obtained, a similar procedure is carried out as indicated in example 7.
Resultatene er som følger: The results are as follows:
NB. NB.
A, B, C har samme betydning som i eksempel 7. A, B, C have the same meaning as in example 7.
Pr., Bu., Ph. betyr respektivt propyl, butyl og fenyl. Pr., Bu., Ph. means propyl, butyl and phenyl respectively.
Eksempel 9. Example 9.
Samme oppløsning (100 deler) inneholdende blokert isocyanatforbindelse opp-løst i en blanding av polyesterpolyol, etyl-acetat, toluen og cellosolve-acetat som den som fås i eksempel 6, blandes med 0,1 deler tetra-n-ibutyl-l,3-diacetoksy-distannoksan. The same solution (100 parts) containing blocked isocyanate compound dissolved in a mixture of polyester polyol, ethyl acetate, toluene and cellosolve acetate as that obtained in Example 6, is mixed with 0.1 part of tetra-n-butyl-1,3 -diacetoxy-distannoxan.
Den således erholdte blanding sprøytes på en jernplate og oppvarmes til 120° C i 30 minutter for å danne en herdet film. The mixture thus obtained is sprayed onto an iron plate and heated to 120°C for 30 minutes to form a hardened film.
Egenskapene for den herdede film som er dannet på overflaten av en jernplate un-dersøkes. The properties of the cured film formed on the surface of an iron plate are investigated.
Resultatene er som følger: The results are as follows:
Eksempel 10. Example 10.
Den samme prepolymere (880 deler) hvis NCO-innhold er 4,8 pst. som i eksempel 3, blandes med fenol (94 deler), xylen (47 deler) og cellosolve-acetat (47 deler). Blandingen opphetes til 140° C i to timer for å gi blokert isocyanatforbindelse. The same prepolymer (880 parts) whose NCO content is 4.8% as in Example 3 is mixed with phenol (94 parts), xylene (47 parts) and cellosolve acetate (47 parts). The mixture is heated to 140° C. for two hours to give blocked isocyanate compound.
Det blokerte isocyanat blandes med tetra-n-butyl-l,3-diformyloksy-distannoksan (0,5 deler) etterfulgt ved å helle den således erholdte blanding i en vandig oppløsning (67 deler) som inneholder dial-kyl-sulfosuccinat (3 deler) og polyoksyetylen-alkyl-eter (2 deler) for å gi en emulsjon. The blocked isocyanate is mixed with tetra-n-butyl-1,3-diformyloxy-distannoxane (0.5 parts) followed by pouring the mixture thus obtained into an aqueous solution (67 parts) containing dialkyl sulfosuccinate (3 parts ) and polyoxyethylene alkyl ether (2 parts) to give an emulsion.
Vulkanisert naturlig gummiark dyppes i emulsjonen som fås som ovenfor og tør-kes ved 40° C i 5 minutter, deretter behandles gummiarket ved 100° C i 20 minutter for å danne herdet film på overflaten av gummiarket ved reaksjon mellom regenererte NCO-grupper og fuktigheten i luften. Vulcanized natural rubber sheet is dipped in the emulsion obtained as above and dried at 40°C for 5 minutes, then the rubber sheet is treated at 100°C for 20 minutes to form hardened film on the surface of the rubber sheet by reaction between regenerated NCO groups and the moisture in the air.
Uten distannoksan dannes imidlertid However, without distannoxane, it is formed
ikke filmen ved oppvarming til 170° C i 20 minutter eller lenger. not the film when heated to 170°C for 20 minutes or longer.
Egenskapene for den således dannede film er som følger: The properties of the film thus formed are as follows:
Eksempel 11. Example 11.
Emulsjonen (50 deler) som erholdes ifølge eksempel 10 blandes med polyester-polyol (1,7 deler) med et hydroksyltall på 460 som fås ved addisjonspolymerisasjon av propylen-oksyd og glycerol som initiator. The emulsion (50 parts) obtained according to example 10 is mixed with polyester polyol (1.7 parts) with a hydroxyl number of 460 which is obtained by addition polymerization of propylene oxide and glycerol as initiator.
Vulkanisert naturlig gummiark dyppes i blandingen som fås ovenfor og tørkes ved 40° C i 5 minutter, og deretter oppvarmes den behandlede gummi til 100° C i 20 minutter for å danne en herdet film på overflaten av gummien. Vulcanized natural rubber sheet is dipped in the mixture obtained above and dried at 40°C for 5 minutes, and then the treated rubber is heated to 100°C for 20 minutes to form a hardened film on the surface of the rubber.
Uten distannoksan dannes imidlertid However, without distannoxane, it is formed
ikke noen herdet film. not any hardened film.
Egenskapene for den således dannede film er som følger: The properties of the film thus formed are as follows:
Eksempel 12. Example 12.
Kastorolje (27,6 deler) og 1,2,6-heksan-triol oppløses i et oppløsningsmiddel som består av xylen (20 deler) og cellosolve-acetat (20 deler) etterfulgt av at blandingen omsettes med tolylen-diisocyanat (27,6 deler) ved 60° C i 3 timer for å gi en prepolymer som inneholder 5,4 pst. isocyanat. Castor oil (27.6 parts) and 1,2,6-hexane-triol are dissolved in a solvent consisting of xylene (20 parts) and cellosolve acetate (20 parts) followed by reaction of the mixture with tolylene diisocyanate (27.6 parts) at 60° C. for 3 hours to give a prepolymer containing 5.4% isocyanate.
Den prepolymere (780 deler) tillates å reagere med m-kresol (108 deler) ved oppvarming til 140° C i to timer i nærvær av et oppløsningsmiddel som består av xylen (36 deler) og cellosolve-acetat (36 deler) for å gl en gulaktig blokert isocyanatforbindelse. The prepolymer (780 parts) is allowed to react with m-cresol (108 parts) by heating to 140° C. for two hours in the presence of a solvent consisting of xylene (36 parts) and cellosolve acetate (36 parts) to gl a yellowish blocked isocyanate compound.
Den prepolymere (100 deler) blandes med tetra-n-butyl-l,3-diacetoksy-distannoksan (0,2 deler) og 4,4'-metylen-bis-(2-kloranllin) (15 deler) etterfulgt ved at blandingen helles i en vandig oppløsning (135 deler) inneholdende natrium-alkyl-naftalin-sulfonat (2 deler) og blokk-kopolymer (2 deler) av etylen-oksyd og propylen-oksyd for å gi en emulsjon. The prepolymer (100 parts) is mixed with tetra-n-butyl-1,3-diacetoxy-distannoxane (0.2 parts) and 4,4'-methylene-bis-(2-chloroaniline) (15 parts) followed by the mixture is poured into an aqueous solution (135 parts) containing sodium alkyl naphthalene sulfonate (2 parts) and block copolymer (2 parts) of ethylene oxide and propylene oxide to give an emulsion.
Ifølge en lignende fremgangsmåte som i eksempel 9 med bruk av den således erholdte emulsjon dannes herdet film, og dennes egenskaper ble undersøkt. According to a similar method as in example 9 using the emulsion thus obtained, a cured film is formed, and its properties were examined.
Resultatene er som følger: The results are as follows:
Eksempel 13. Example 13.
Polypropylen-glykol (259 deler) med en molekylvekt på 1000 tillates å reagere med 87 deler TDi for å gi en viskøs prepolymer som inneholder 5,8 pst. NCO. Polypropylene glycol (259 parts) having a molecular weight of 1000 is allowed to react with 87 parts of TDi to give a viscous prepolymer containing 5.8% NCO.
Den prepolymere (576 deler) tillates å reagere med m-kresol (8,6 deler) ved 70° C i 6 timer i nærvær av tetra-n-butyl-1,4-diacetoksy-distannoksan (0,3 deler) for å gi en flytende blanding som består av blokert isocyanatforbindelse og den nevnte distannoksan. The prepolymer (576 parts) is allowed to react with m-cresol (8.6 parts) at 70°C for 6 hours in the presence of tetra-n-butyl-1,4-diacetoxy-distannoxane (0.3 parts) to give a liquid mixture consisting of blocked isocyanate compound and the said distanoxane.
Blandingen (662 deler) iblandes med 4,4'-metylen-bis-(2-kloraniMn) (96,2 deler) etterfulgt av oppvarming av den således erholdte blanding først til 105° C og deretter til 120° C i 2 timer for å gi polyuretan-elastomer. The mixture (662 parts) is mixed with 4,4'-methylene-bis-(2-chloroaniMn) (96.2 parts) followed by heating the mixture thus obtained first to 105° C. and then to 120° C. for 2 hours for to give polyurethane elastomers.
Eksempel 14. Example 14.
Den samme prepolymer (880 deler) som i eksempel 3, inneholdende 4,8 pst. NCO tillates å reagere med fenol (98 deler) ved 60° C 1 2 timer for å gi blokert isocyanatforbindelse. The same prepolymer (880 parts) as in Example 3, containing 4.8% NCO is allowed to react with phenol (98 parts) at 60° C. for 12 hours to give the blocked isocyanate compound.
Den blokerte isocyanatforbindelse (101 deler), tetra-n-butyl-l,3-diakryloksy-distannoksan (0,2 deler) og polyeter-polyol (6 deler) med en molekylarvekt på 600 og hydroksyltall på 460 som fås ved addisjons-polymer isas jon av propylen-oksyd til sorbitol og glycerol som initiator helles i en vandig oppløsning (109 deler) inneholdende blokk-kopolymer (1,8 deler) av etylen-oksyd og propylen-oksyd og polyoksyetylen-alkyl-eter (1,2 deler) for å gi en emulsjon. The blocked isocyanate compound (101 parts), tetra-n-butyl-1,3-diacryloxy-distannoxane (0.2 parts) and polyether polyol (6 parts) having a molecular weight of 600 and a hydroxyl number of 460 obtained by addition polymer isation of propylene oxide to sorbitol and glycerol as initiator is poured into an aqueous solution (109 parts) containing block copolymer (1.8 parts) of ethylene oxide and propylene oxide and polyoxyethylene alkyl ether (1.2 parts ) to give an emulsion.
Ikke-vevet tekstil dyppes i den erholdte emulsjon og etter at overskuddet av emulsjon er presset ut fra det således behandlede ikke-vevede stoff oppvarmes det til 110° C i 30 minutter for å fremstille ikke-vevet stoff med forbedrede egenskaper, f. eks. god fleksibilitet. Non-woven fabric is dipped in the obtained emulsion and after the excess of emulsion has been squeezed out from the non-woven fabric thus treated, it is heated to 110°C for 30 minutes to produce non-woven fabric with improved properties, e.g. good flexibility.
Strekkstyrke for det således erholdte Tensile strength for the thus obtained
ikke-vevede stoff er 3,2 kg pr. mm<2>. non-woven fabric is 3.2 kg per mm<2>.
Hvis de erholdte stoffer behandles med trikloretylen, frigjøres 4 deler av den totale harpiks fra dem. If the substances obtained are treated with trichlorethylene, 4 parts of the total resin are released from them.
Eksempel 15. Example 15.
Heksametylen-diisocyanat (168 deler) oppløst i butyl-acetat (441 deler) tillates å reagere med laurylalkohol (186 deler) ved 80° C i en halv time, og reaksjonsproduktet omsettes deretter med metyl-etyl-ke-ton-oksim (87 deler) ved 80° C i 2 timer. Hexamethylene diisocyanate (168 parts) dissolved in butyl acetate (441 parts) is allowed to react with lauryl alcohol (186 parts) at 80° C. for half an hour, and the reaction product is then reacted with methyl ethyl ketone oxime (87 parts) at 80° C for 2 hours.
Således erholdt reaksjonsprodukt blandes med tetra-n-butyl-l,3-diacetoksy-distannoksan (1,7deler) etterfulgt av at blandingen helles i en vandig oppløsning (1324 deler) inneholdende blokk-kopolymer (14 deler) av etylen-oksyd med propylen-oksyd og polyoksyetylen-alkyl-eter (8 deler) for å gi en emulsjon. The reaction product thus obtained is mixed with tetra-n-butyl-1,3-diacetoxy-distannoxane (1.7 parts) followed by the mixture being poured into an aqueous solution (1324 parts) containing block copolymer (14 parts) of ethylene oxide with propylene -oxide and polyoxyethylene alkyl ether (8 parts) to give an emulsion.
Bomullstøy dyppes i den ovenstående erholdte emulsjon, og overskuddet av emulsjonen presses ut av tøyet. Cotton fabric is dipped in the emulsion obtained above, and the excess of the emulsion is squeezed out of the fabric.
Ved opphetning av tøyet som er be-handlet som ovenfor til 130° C i en halv time fremstilles et porøst og vannfast bom-ullstøy som resultat av reaksjonen mellom hydroksyl-grupper i tøyet med regenererte NCO-grupper. By heating the cloth which has been treated as above to 130° C for half an hour, a porous and waterproof cotton wool fabric is produced as a result of the reaction between hydroxyl groups in the cloth with regenerated NCO groups.
Den vannfaste egenskap for det således fremstilte bomullstøy går ikke tapt endog ved vasking. The water-resistant property of the cotton fabric produced in this way is not lost even when washed.
Eksempel 16. Example 16.
co,co'-diisocyanat-l,3-diimetylbenzen (188 deler) omsettes med hydroperfluoro-alkohol ((CHj-CFo-CF^-CHoOH) (292 deler) slik at det gir en voksaktig blokert isocyanatforbindelse. co,co'-diisocyanate-1,3-dimethylbenzene (188 parts) is reacted with hydroperfluoroalcohol ((CHj-CFo-CF^-CHoOH) (292 parts) to give a waxy blocked isocyanate compound.
Den blokerte isocyanatforbindelse (48 deler) og polyester-polyol med hydroksyltall 253 som fås ved kondensasjon av adipinsyre (438 deler), 1,4-butylen-glykol (180 deler) oppløses i cellosolve-acetat (140 deler) og blandes med tetra-n-butyl-1,3-diacetoksy-distannoksan (0,3 deler). rer NCO-grupper med krystallvann i The blocked isocyanate compound (48 parts) and polyester polyol with hydroxyl number 253 obtained by condensation of adipic acid (438 parts), 1,4-butylene glycol (180 parts) are dissolved in cellosolve acetate (140 parts) and mixed with tetra- n-butyl-1,3-diacetoxy-distannoxane (0.3 parts). rer NCO groups with crystal water i
En jernplate påføres den således er- MgS047H20, slik at det utvikles kanbondi-holdte blanding og oppvarmes til 120° C i oksydgass. 30 minutter og gir en herdet film med god Blandingen oppvarmes trinnvis i strøm motstandsevne mot kjemikalier på jern- av nitrogengass, og gassen som utvikles ved platens overflate. oppvarming innføres kontinuerlig i bari- um-hydroksyd-oppløsning, og den temperatur ved hvilken barium-hydroksyd-opp-Eksempel 17. løsningen blir 'hvit noteres som regenerer- ingstemperaturen for den blokerte isocya-Blokert isocyanatforbindelse (100 de- natgruppe. An iron plate is thus applied to it is MgS047H20, so that a canbondi-held mixture is developed and heated to 120° C in oxide gas. 30 minutes and gives a hardened film with good The mixture is heated step by step in current resistance to chemicals on iron of nitrogen gas, and the gas that is developed at the plate's surface. heating is introduced continuously in bari- um-hydroxide solution, and the temperature at which barium-hydroxide-up-Example 17. the solution turns 'white is noted as regenerating- ing temperature for the blocked isocya- Blocked isocyanate compound (100 de- nate group.
ler) (variabel) blandes med magnesium- Med blandingen som ikke inneholder sulfat (MgS047H20) og 1 del tetra-n-1,3- noe distannoksan utføres lignende frem-diacetoksy-distannoksan. gangsmåter. ler) (variable) is mixed with magnesium- With the mixture that does not contain sulfate (MgS047H20) and 1 part tetra-n-1,3- some distannoxane, a similar pre-diacetoxy distannoxane is carried out. ways of walking.
Ved oppvarming av blandingen reage- Resultatene er som følger: When the mixture is heated, the results are as follows:
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2943274A DE2943274C2 (en) | 1979-10-26 | 1979-10-26 | Stacking protection, consisting of at least one angle rail resting against a vertical stacking edge |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| NO803170L NO803170L (en) | 1981-04-27 |
| NO155339B true NO155339B (en) | 1986-12-08 |
| NO155339C NO155339C (en) | 1987-03-18 |
Family
ID=6084426
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO803170A NO155339C (en) | 1979-10-26 | 1980-10-24 | DEVICE FOR THE CONNECTION OF MISCELLANEOUS STACKED FORMING PLATES. |
Country Status (13)
| Country | Link |
|---|---|
| AT (1) | AT376948B (en) |
| BE (1) | BE885748A (en) |
| CH (1) | CH648813A5 (en) |
| DE (1) | DE2943274C2 (en) |
| DK (1) | DK147658C (en) |
| ES (1) | ES494541A0 (en) |
| FI (1) | FI69285C (en) |
| FR (1) | FR2468518A1 (en) |
| IT (1) | IT1134019B (en) |
| NL (1) | NL189456C (en) |
| NO (1) | NO155339C (en) |
| PT (1) | PT71866B (en) |
| SE (1) | SE429745B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4427073B4 (en) * | 1993-01-30 | 2005-10-06 | Walter Siegler | Stack of frame formwork elements |
| DE4302604B4 (en) * | 1993-01-30 | 2004-12-30 | Walter Siegler | Stack of frame formwork elements |
| DE9419472U1 (en) * | 1994-12-05 | 1995-02-16 | Effkemann Manfred | Stacking device for formwork panels |
| SG116455A1 (en) * | 2002-06-04 | 2005-11-28 | Wang Ching Wong | Packing frame structure. |
| DE102012217827A1 (en) * | 2012-09-28 | 2014-04-03 | Harsco Infrastructure Services Gmbh | Chalkboard with corner recess and component |
| DE102015117905A1 (en) * | 2015-10-21 | 2017-04-27 | Bundesdruckerei Gmbh | Transport device for securing stacked goods and method for securing stacked goods |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1137244A (en) * | 1967-09-11 | 1968-12-18 | Erik Nobel | A framework for use with a load-bearing plate |
| DE2137505C3 (en) * | 1971-07-27 | 1980-11-20 | Josef 7611 Steinach Maier | Device for connecting adjacent formwork panels |
| FR2190091A5 (en) * | 1972-06-16 | 1974-01-25 | Technifil | |
| FR2268712A1 (en) * | 1974-04-29 | 1975-11-21 | Lebre Charles | Device to retain assembly of boxes on pallet - consists of corner pieces joined by strips of elastic material |
| US4107958A (en) * | 1976-07-30 | 1978-08-22 | Manley Jr Paul P | Lock for stacked materials |
| DE7908756U1 (en) * | 1979-03-28 | 1979-07-26 | Huedig Kg, 3100 Celle | COMPOSITE DEVICE FOR STACKING PIPES AND EQUIPMENT IN HORIZONTAL AND OVERLAYING LAYERS |
-
1979
- 1979-10-26 DE DE2943274A patent/DE2943274C2/en not_active Expired
-
1980
- 1980-07-29 AT AT0392880A patent/AT376948B/en not_active IP Right Cessation
- 1980-08-27 ES ES494541A patent/ES494541A0/en active Granted
- 1980-08-28 NL NLAANVRAGE8004881,A patent/NL189456C/en not_active IP Right Cessation
- 1980-09-30 FI FI803090A patent/FI69285C/en not_active IP Right Cessation
- 1980-10-02 CH CH7385/80A patent/CH648813A5/en not_active IP Right Cessation
- 1980-10-02 FR FR8021383A patent/FR2468518A1/en active Granted
- 1980-10-02 PT PT71866A patent/PT71866B/en not_active IP Right Cessation
- 1980-10-16 BE BE0/202490A patent/BE885748A/en not_active IP Right Cessation
- 1980-10-23 SE SE8007456A patent/SE429745B/en not_active IP Right Cessation
- 1980-10-24 NO NO803170A patent/NO155339C/en unknown
- 1980-10-24 DK DK452580A patent/DK147658C/en not_active IP Right Cessation
- 1980-10-24 IT IT25553/80A patent/IT1134019B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| NO155339C (en) | 1987-03-18 |
| DE2943274C2 (en) | 1982-03-25 |
| DK147658B (en) | 1984-11-05 |
| FI69285B (en) | 1985-09-30 |
| SE8007456L (en) | 1981-04-27 |
| SE429745B (en) | 1983-09-26 |
| NO803170L (en) | 1981-04-27 |
| IT1134019B (en) | 1986-07-24 |
| FI803090A (en) | 1981-04-27 |
| ATA392880A (en) | 1984-06-15 |
| AT376948B (en) | 1985-01-25 |
| ES8104119A1 (en) | 1981-04-01 |
| ES494541A0 (en) | 1981-04-01 |
| NL8004881A (en) | 1981-04-28 |
| PT71866A (en) | 1980-11-01 |
| DK452580A (en) | 1981-04-27 |
| FR2468518A1 (en) | 1981-05-08 |
| NL189456C (en) | 1993-04-16 |
| DE2943274A1 (en) | 1981-05-14 |
| BE885748A (en) | 1981-02-16 |
| IT8025553A0 (en) | 1980-10-24 |
| FI69285C (en) | 1986-01-10 |
| PT71866B (en) | 1981-08-04 |
| FR2468518B1 (en) | 1984-12-21 |
| DK147658C (en) | 1985-04-29 |
| CH648813A5 (en) | 1985-04-15 |
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