NO134469B - - Google Patents
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- NO134469B NO134469B NO2840/72A NO284072A NO134469B NO 134469 B NO134469 B NO 134469B NO 2840/72 A NO2840/72 A NO 2840/72A NO 284072 A NO284072 A NO 284072A NO 134469 B NO134469 B NO 134469B
- Authority
- NO
- Norway
- Prior art keywords
- weight
- parts
- tin
- compounds
- foam
- Prior art date
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- 239000006260 foam Substances 0.000 claims description 42
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 150000001875 compounds Chemical class 0.000 claims description 34
- 229910052718 tin Inorganic materials 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 229920001296 polysiloxane Polymers 0.000 claims description 16
- 150000003606 tin compounds Chemical class 0.000 claims description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 10
- 239000012948 isocyanate Substances 0.000 claims description 10
- 150000002513 isocyanates Chemical class 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 229920001228 polyisocyanate Polymers 0.000 claims description 9
- 239000005056 polyisocyanate Substances 0.000 claims description 9
- 150000001298 alcohols Chemical class 0.000 claims description 7
- 150000002989 phenols Chemical class 0.000 claims description 7
- XITYWQKWNJFZEG-UHFFFAOYSA-J tetraphenoxystannane Chemical class [Sn+4].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 XITYWQKWNJFZEG-UHFFFAOYSA-J 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 150000001735 carboxylic acids Chemical class 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 4
- 150000003512 tertiary amines Chemical class 0.000 claims description 3
- FJEKUEUBQQWPBY-UHFFFAOYSA-N 1$l^{2}-stanninane Chemical compound C1CC[Sn]CC1 FJEKUEUBQQWPBY-UHFFFAOYSA-N 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- -1 aromatic aminocarbonic acids Chemical class 0.000 description 27
- 229920001451 polypropylene glycol Polymers 0.000 description 24
- JXCHMDATRWUOAP-UHFFFAOYSA-N diisocyanatomethylbenzene Chemical compound O=C=NC(N=C=O)C1=CC=CC=C1 JXCHMDATRWUOAP-UHFFFAOYSA-N 0.000 description 22
- 238000005809 transesterification reaction Methods 0.000 description 21
- 239000002253 acid Substances 0.000 description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 18
- 239000000203 mixture Substances 0.000 description 15
- 239000006261 foam material Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000005187 foaming Methods 0.000 description 12
- 150000007513 acids Chemical class 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 150000001414 amino alcohols Chemical class 0.000 description 9
- 229920000728 polyester Polymers 0.000 description 9
- 230000000630 rising effect Effects 0.000 description 9
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 8
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 7
- ZXDVQYBUEVYUCG-UHFFFAOYSA-N dibutyltin(2+);methanolate Chemical compound CCCC[Sn](OC)(OC)CCCC ZXDVQYBUEVYUCG-UHFFFAOYSA-N 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- 229920002545 silicone oil Polymers 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 230000032050 esterification Effects 0.000 description 6
- 238000005886 esterification reaction Methods 0.000 description 6
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 150000005846 sugar alcohols Polymers 0.000 description 5
- ANWMNDOUSIJZBA-UHFFFAOYSA-N 2-[methyl(octadecyl)amino]ethanol Chemical compound CCCCCCCCCCCCCCCCCCN(C)CCO ANWMNDOUSIJZBA-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 4
- 239000004359 castor oil Substances 0.000 description 4
- 235000019438 castor oil Nutrition 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 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 4
- TZMQHOJDDMFGQX-UHFFFAOYSA-N hexane-1,1,1-triol Chemical class CCCCCC(O)(O)O TZMQHOJDDMFGQX-UHFFFAOYSA-N 0.000 description 4
- WDJHALXBUFZDSR-UHFFFAOYSA-N Acetoacetic acid Natural products CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical class C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 3
- MACVNMKPAKPZQG-UHFFFAOYSA-N dioctyltin(2+);methanolate Chemical compound CCCCCCCC[Sn](OC)(OC)CCCCCCCC MACVNMKPAKPZQG-UHFFFAOYSA-N 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 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 3
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 2
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 2
- XLAXYNXVOVMHMJ-UHFFFAOYSA-N 3-ethoxy-n,n-dimethylpropan-1-amine Chemical compound CCOCCCN(C)C XLAXYNXVOVMHMJ-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
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- 125000003118 aryl group Chemical group 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229960002887 deanol Drugs 0.000 description 2
- 230000006735 deficit Effects 0.000 description 2
- TUKJQFVDLYJABM-UHFFFAOYSA-N dibenzyl(dimethoxy)stannane Chemical compound C=1C=CC=CC=1C[Sn](OC)(OC)CC1=CC=CC=C1 TUKJQFVDLYJABM-UHFFFAOYSA-N 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical class OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
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- 230000002349 favourable effect Effects 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- AJVCYUNSYKAECT-UHFFFAOYSA-N methanolate;triethylstannanylium Chemical compound CC[Sn](CC)(CC)OC AJVCYUNSYKAECT-UHFFFAOYSA-N 0.000 description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
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- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 2
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- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
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- 125000001302 tertiary amino group Chemical group 0.000 description 2
- 230000007306 turnover Effects 0.000 description 2
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical group C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 description 1
- MTZUIIAIAKMWLI-UHFFFAOYSA-N 1,2-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC=C1N=C=O MTZUIIAIAKMWLI-UHFFFAOYSA-N 0.000 description 1
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- NDGWHQSOYIQHAS-UHFFFAOYSA-N 1-(furan-2-yl)-3-phenylpropane-1,3-dione Chemical compound C=1C=COC=1C(=O)CC(=O)C1=CC=CC=C1 NDGWHQSOYIQHAS-UHFFFAOYSA-N 0.000 description 1
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- IWSZDQRGNFLMJS-UHFFFAOYSA-N 2-(dibutylamino)ethanol Chemical compound CCCCN(CCO)CCCC IWSZDQRGNFLMJS-UHFFFAOYSA-N 0.000 description 1
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- WGLQHUKCXBXUDV-UHFFFAOYSA-N 3-aminophthalic acid Chemical class NC1=CC=CC(C(O)=O)=C1C(O)=O WGLQHUKCXBXUDV-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
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- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- WOWBFOBYOAGEEA-UHFFFAOYSA-N diafenthiuron Chemical compound 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
- SVSRQMUJHHQAAX-UHFFFAOYSA-N dibenzyltin Chemical compound C=1C=CC=CC=1C[Sn]CC1=CC=CC=C1 SVSRQMUJHHQAAX-UHFFFAOYSA-N 0.000 description 1
- MKANCOHERYHKAT-UHFFFAOYSA-L dibenzyltin(2+);dichloride Chemical compound C=1C=CC=CC=1C[Sn](Cl)(Cl)CC1=CC=CC=C1 MKANCOHERYHKAT-UHFFFAOYSA-L 0.000 description 1
- UROKUKHYYXBCQE-UHFFFAOYSA-L dibutyl(diphenoxy)stannane Chemical compound C=1C=CC=CC=1O[Sn](CCCC)(CCCC)OC1=CC=CC=C1 UROKUKHYYXBCQE-UHFFFAOYSA-L 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- HGQSXVKHVMGQRG-UHFFFAOYSA-N dioctyltin Chemical compound CCCCCCCC[Sn]CCCCCCCC HGQSXVKHVMGQRG-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 150000002168 ethanoic acid esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- JHZPNBKZPAWCJD-UHFFFAOYSA-N ethyl 2-oxocyclopentane-1-carboxylate Chemical compound CCOC(=O)C1CCCC1=O JHZPNBKZPAWCJD-UHFFFAOYSA-N 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000004872 foam stabilizing agent Substances 0.000 description 1
- 235000011087 fumaric acid Nutrition 0.000 description 1
- 150000002238 fumaric acids Chemical class 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical class CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 description 1
- 235000014304 histidine Nutrition 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- AGPKZVBTJJNPAG-UHFFFAOYSA-N isoleucine Natural products CCC(C)C(N)C(O)=O AGPKZVBTJJNPAG-UHFFFAOYSA-N 0.000 description 1
- 229960000310 isoleucine Drugs 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
- 238000010907 mechanical stirring Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229930182817 methionine Natural products 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- SBIDUCNDVPSWQT-UHFFFAOYSA-N n-ethyl-n-(oxiran-2-ylmethyl)ethanamine Chemical compound CCN(CC)CC1CO1 SBIDUCNDVPSWQT-UHFFFAOYSA-N 0.000 description 1
- QAZHYRJYZIMJJI-UHFFFAOYSA-N n-ethylpiperazin-1-amine Chemical class CCNN1CCNCC1 QAZHYRJYZIMJJI-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000004707 phenolate Chemical class 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 1
- 229940031826 phenolate Drugs 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003022 phthalic acids Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- LOAUVZALPPNFOQ-UHFFFAOYSA-N quinaldic acid Chemical class C1=CC=CC2=NC(C(=O)O)=CC=C21 LOAUVZALPPNFOQ-UHFFFAOYSA-N 0.000 description 1
- 150000003248 quinolines Chemical class 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical class CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 1
- 229950006389 thiodiglycol Drugs 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- JNLJTPIVUFSZCN-UHFFFAOYSA-M triethylstannanylium;phenoxide Chemical compound CC[Sn](CC)(CC)OC1=CC=CC=C1 JNLJTPIVUFSZCN-UHFFFAOYSA-M 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B21/00—Methods or apparatus for flushing boreholes, e.g. by use of exhaust air from motor
- E21B21/06—Arrangements for treating drilling fluids outside the borehole
- E21B21/063—Arrangements for treating drilling fluids outside the borehole by separating components
- E21B21/065—Separating solids from drilling fluids
- E21B21/066—Separating solids from drilling fluids with further treatment of the solids, e.g. for disposal
Landscapes
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Mining & Mineral Resources (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Environmental & Geological Engineering (AREA)
- Fluid Mechanics (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Separation Of Solids By Using Liquids Or Pneumatic Power (AREA)
- Polyurethanes Or Polyureas (AREA)
Description
Fremgangsmåte til fremstilling av skumstoffer på isocyanatbasis. Process for the production of isocyanate-based foams.
Fremstillingen av skumstoffer av polyhydroksy- og/eller polykarboksylforbindelser, polyisocyanater og eventuelt vann er kjent. Herved går man vanligvis ut fra polyhydroksyforbindelser med primære hydroksylgrupper som f. eks. fra polyestere, polyetere, polytioetere eller polyacetaler, idet den primære hydroksylgruppe på grunn av sin gode reaksjonsevne overfor isocyanatgruppen sikrer en hurtig oppbygging av bærestoffet, som må gå paral-lell med kulldioksydutviklingen. The production of foams from polyhydroxy and/or polycarboxylic compounds, polyisocyanates and possibly water is known. This is usually based on polyhydroxy compounds with primary hydroxyl groups such as e.g. from polyesters, polyethers, polythioethers or polyacetals, as the primary hydroxyl group, due to its good reactivity towards the isocyanate group, ensures a rapid build-up of the carrier, which must go parallel to the development of carbon dioxide.
Ved slike polyhydroksyforbindelser, som overveiende er i stand til å stille sekundære hydroksylgrupper til disposisjon for reaksjonen med isocyanatet og på grunn av en mindre polar oppbygging har en mindre utgangsviskositet, opptrer det imidlertid betraktelige vanskeligheter med forsøket å bringe den bærestoffoppbygde reaksjon i samklang med kulldioksydutviklingen. Av denne grunn foretrekker man å gjennomføre en forreaksjon, idet man først omsetter polyisocyanatet i overskudd i et spesielt reaksj onstrinn med polyhy-droksyforbindelsen og deretter overfører det isocyanatgruppeholdige fortilleirings-produkt under vann- og eventuelt ytterligere polyisocyanattilsetning i skumstoffet. En annen måte består i at man bringer reaksjonskomponentene til skumdannelse, riktignok i et fremgangsmåtetrinn, men ved hjelp av spesielle katalysatorer, som f. eks. endoetylenpiperazin, idet frem for alt innholdet av sterkt basiske påskynnings-midler bevirker en vesentlig økning av se-kundærreaksjoner, som f. eks. av polyme-risasjonsreaksjoner som videre kan influe-re på de fremstilte skumstoffers egenskaper på uønsket måte. In the case of such polyhydroxy compounds, which are predominantly capable of making secondary hydroxyl groups available for the reaction with the isocyanate and, due to a less polar structure, have a lower initial viscosity, there are, however, considerable difficulties with the attempt to bring the carrier-based reaction into harmony with the evolution of carbon dioxide. For this reason, it is preferred to carry out a pre-reaction, first reacting the polyisocyanate in excess in a special reaction step with the polyhydroxy compound and then transferring the isocyanate group-containing pre-coating product under addition of water and possibly further polyisocyanate into the foam material. Another way consists in bringing the reaction components to foam formation, admittedly in a process step, but with the help of special catalysts, such as e.g. endoethylene piperazine, since above all the content of strongly basic accelerators causes a significant increase in secondary reactions, such as e.g. of polymerization reactions which can further influence the properties of the manufactured foams in an undesirable way.
Det er nå fra det tyske patentskrift nr. 958 774 allerede kjent å avstemme på gunstig måte mot hverandre reaksjonene som forløper ved fremstillingen av skumstoffer på isocyanatbasis ved tilsetning av ikke-basiske, oppløselige tungmetallsalter eller organometallforbindelser sammen med de vanlige basiske påskyndingsmidler. Ifølge det tyske patentskrift nr. 964 988 anvendes flytende resp. ved lavere temperaturer smeltende metallalkoholater eller karbon-sure salter av ikkebasisk natur av flerverdige metaller som f. eks. av Ti, Sn, eller Zr ved skumdannelse av polyester/polyisocyanat/vannblandinger. It is now already known from the German patent document no. 958 774 to coordinate favorably with each other the reactions that take place in the production of isocyanate-based foams by adding non-basic, soluble heavy metal salts or organometallic compounds together with the usual basic accelerators. According to the German patent document no. 964 988, liquid resp. at lower temperatures melting metal alcoholates or carbonic acid salts of a non-basic nature of polyvalent metals such as e.g. of Ti, Sn, or Zr by foaming polyester/polyisocyanate/water mixtures.
Det er nå blitt funnet at de reaksjoner som forløper ved fremstillingen av skumstoffer på isocyanatbasis på særlig gunstig måte kan katalyseres og avstemmes på hverandre ved hjelp av tinnsalter, -alkoholater resp. -fenolater med fireverdig tinn av karbonsyrer, alkoholer resp. fenoler, som minst inneholder et tertiært nitrogenatom, eller ved organiske kompleks-forbindelser av det fireverdige tinn, som minst inneholder et tertiært nitrogenatom, og idet hvert tinnatom er forbundet med en organisk rest over minst en C-Sn-binding. It has now been found that the reactions that take place in the production of isocyanate-based foams can be catalyzed and coordinated in a particularly favorable way by means of tin salts, -alcoholates or -phenolates with tetravalent tin of carboxylic acids, alcohols or phenols, which contain at least one tertiary nitrogen atom, or in the case of organic complex compounds of tetravalent tin, which contain at least one tertiary nitrogen atom, and each tin atom is connected to an organic residue via at least one C-Sn bond.
De spesielle tinnforbindelser, som iføl-ge oppfinnelsen, skal anvendes som katalysatorer viser selv en overfor de kjente metallkatalysatorer vesentlig øket stabilitet overfor innvirkningen av vann, luft eller oksygen, særlig i nærvær av ytterligere tilsetningsstoffer, som ofte medanvendes ved skumstoffremstillingen. De etterlater på grunn av deres lukt- og fargeløshet ingen påfallende spor i det ferdige skumstoff. På grunn av deres basiske karakter er det ikke nødvendig med noen ekstra anvendelse av de vanlig kjente basiske påskyndere. På grunn av deres forsterkede virkning, som spesielt bevirker en påskyndelse av omsetningen av reaksjonstrege, sekundære hydroksylgrupper kan disse anvendes i mindre mengder enn de hittil vanlige katalysatorer. Anvender man tinnforbindelser av flerverdige karbonsyrer, alkoholer resp. fenoler og går man ut, istedenfor forbindelser med et enkelt fireverdig tinnatom, fra slike med stannoksangruppering i molekylet, så utmerker disse høyere mo-lekylære tinnforbindelser seg ved en ennå ytterligere forbedret stabilitet. Hertil kommer at i mange tinnforbindelser kan det mellom tinnatomet og et tertiært nitrogenatom dannes bivalenser, som likeledes influerer gunstig på metallkatalysatorens stabilitet. The special tin compounds which, according to the invention, are to be used as catalysts even show a significantly increased stability compared to the known metal catalysts to the influence of water, air or oxygen, especially in the presence of further additives, which are often used in the foam preparation. Due to their odorlessness and colourlessness, they leave no noticeable traces in the finished foam material. Because of their basic nature, no additional application of the commonly known basic accelerators is necessary. Due to their enhanced effect, which in particular causes an acceleration of the turnover of reaction-slow, secondary hydroxyl groups, these can be used in smaller quantities than the previously common catalysts. Tin compounds of polyhydric carboxylic acids, alcohols or phenols and, instead of compounds with a single tetravalent tin atom, one starts from those with stannoxane grouping in the molecule, these higher molecular tin compounds are characterized by an even further improved stability. In addition, in many tin compounds, bivalences can form between the tin atom and a tertiary nitrogen atom, which also have a favorable influence on the stability of the metal catalyst.
Til gjennomførelse av fremgangsmå-ten ifølge oppfinnelsen egner seg særlig polyhydroksyforbindelser, som helt eller for den største del inneholder sekundære hydroksylgrupper. Som eksempler kan det anføres rene polymerisater av alkylenoksyder som propylenoksyd, butylenoksydene, styroloksyd, epiklorhydrin eller også addi-sjonsproduktene av disse oksyder til to- eller flerverdige alkoholer og fenoler som til etylenglykol, polyetylenglykoler, alkandioler og alkantrioler, alkendioler, alkindioler, pentaerytrit, trimetylolpropan, hydrokinon, 4, 4'-dioksy-diefenylmetan, 4, 4'-dioksydi-fenyldimetylmetan, deres hydreringspro-dukter, dioksynaftaliner, til mono- eller polyaminet av alifatisk eller aromatisk natur, som minst har to aktive hydrogenatomer som alkylendiaminer, dietylentria-min, anilin, piperazin, til aminoalkoholer med minst to aktive hydrogenatomer som etanolamin, N-alkyletanolaminer, dietano-laminer, N-alkyldietanolaminer, trietanolamin, til polyestere som minst har to OH-grupper som rizinusolje, men også til øv-rige forbindelser med flere aktive hydrogenatomer som f. eks. til sukker. Ved ok-sydenes polykondensasjon kan også etylenoksyd delvis medkondenseres eller etterpå påkondenseres, skjønt de fremkomne polyhydroksyforbindelser ved lavere etylenok-sydinnhold ikke adskiller seg vesentlig fra de forannevnte polyhjyd/roksyforbindelser med hensyn til deres reaksjonsevne overfor polyisocyanater. Polyhydroksyforbindelser med sekundære hydroksylgrupper kan også fremstilles ved forestring av en eller flere av de foran nevnte polyalkoholer, som inneholder delvis sekundære hydroksylgrupper med underskuddmengder av de vanlige polykarbonsyrer som ravsyre, adipinsyre, sebacinsyre, di- og trimeriserte fettsyrer, ftalsyrer, maleinsyre eller fu-marsyrer, idet ved medanvendelse av aminoalkoholer samtidig tertiære nitrogenatomer eller karbonamidgrupper kan innbyg-ges i polyesteren. For carrying out the method according to the invention, polyhydroxy compounds are particularly suitable, which entirely or for the most part contain secondary hydroxyl groups. Examples include pure polymers of alkylene oxides such as propylene oxide, butylene oxides, styrene oxide, epichlorohydrin or also the addition products of these oxides to di- or polyhydric alcohols and phenols such as to ethylene glycol, polyethylene glycols, alkanediols and alkanetriols, alkenediols, alkynediols, pentaerythritol, trimethylolpropane . min, aniline, piperazine, to amino alcohols with at least two active hydrogen atoms such as ethanolamine, N-alkylethanolamines, diethanolamines, N-alkyldiethanolamines, triethanolamine, to polyesters that have at least two OH groups such as castor oil, but also to other compounds with more active hydrogen atoms such as to sugar. In the polycondensation of the oxy-sides, ethylene oxide can also be partially co-condensed or afterwards condensed, although the resulting polyhydroxy compounds at a lower ethylene oxide content do not differ significantly from the aforementioned polyhyd/roxy compounds with regard to their reactivity towards polyisocyanates. Polyhydroxy compounds with secondary hydroxyl groups can also be produced by esterification of one or more of the aforementioned polyalcohols, which partially contain secondary hydroxyl groups with deficit amounts of the usual polycarboxylic acids such as succinic acid, adipic acid, sebacic acid, di- and trimerized fatty acids, phthalic acids, maleic acid or fumaric acids , in that, by co-using amino alcohols, tertiary nitrogen atoms or carbonamide groups can be incorporated into the polyester at the same time.
Ved siden av de foretrukne egnede polyhydroksyforbindelser med sekundære hydroksylgrupper kan naturligvis også slike polyhydroksyforbindelser anvendes, hvis hydroksylgrupper er av primær natur. Slike polyhydroksyforbindelser kan f. eks. fås ved forestring av de ovennevnte primære polyalkoholer eller også aminoalkoholer med de allerede nevnte polykarbonsyrer. Videre regnes til denne gruppe dessuten de forskjelligste typer av polyetere, således som de avleder seg f. eks. fra etylenglykol, tetrahydrofuran eller også tiodiglykol eller også de forskjelligste polyacetaler. Alongside the preferred suitable polyhydroxy compounds with secondary hydroxyl groups, such polyhydroxy compounds can of course also be used, whose hydroxyl groups are of a primary nature. Such polyhydroxy compounds can, e.g. obtained by esterification of the above-mentioned primary polyalcohols or also amino alcohols with the already mentioned polycarboxylic acids. Furthermore, this group also includes the most diverse types of polyethers, such that they are derived from e.g. from ethylene glycol, tetrahydrofuran or also thiodiglycol or also the most diverse polyacetals.
De lineære eller forgrenede polyhydroksyforbindelser som anvendes for skumstoffremstillingen skal, hvis de avleder seg for polyestere, ha et syretall under 15. Samtlige typer skal ha en OH-ekvivalent på fortrinsvis 100—3 000, idet det med OH-ekvivalent skal forstås den mengde poly-hydroksyforbindelse i gram som inneholder et mol hydroksylgrupper. De anførte polyhydroksyforbindelser kan ved skumdannelsen dannes på vilkårlig måte, i tillegg kan dessuten også f. eks. de allerede nevnte lavmolekylære polyhydroksyforbindelser tilblandes, imidlertid må også da for blandingen OH-ekvivalenten ligge mellom 100 og 3 000. The linear or branched polyhydroxy compounds used for the foam preparation must, if they are derived from polyesters, have an acid number below 15. All types must have an OH equivalent of preferably 100-3,000, with OH equivalent being understood as the amount of poly -hydroxy compound in grams containing one mole of hydroxyl groups. The listed polyhydroxy compounds can be formed in any way during the foam formation, in addition, e.g. the already mentioned low molecular weight polyhydroxy compounds are mixed in, however the OH equivalent must also be between 100 and 3,000 for the mixture.
Som polyisocyanater kan det ved frem-gangsmåten ifølge oppfinnelsen finne anvendelse vilkårlig alifatiske, aralifatiske eller aromatiske flerverdige isocyanater som tetrametylendiisocyanat, heksametylendi-isocyanater, fenylendiisocyanat, toluylendi-isocyanater, 4, 4'-difenylmetandiisocyanat og flere andre, eller også addisjonsproduk-tene av disse flerverdige isocyanater til underskuddsmengder av laveremolekylære alkoholer som glycerin, trimetylolpropan, heksandioler og heksantrioler eller også til As polyisocyanates, in the method according to the invention, arbitrarily aliphatic, araliphatic or aromatic polyvalent isocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, phenylene diisocyanate, toluylene diisocyanate, 4,4'-diphenylmethane diisocyanate and several others can be used, or also the addition products of these polyhydric isocyanates to deficit amounts of lower molecular weight alcohols such as glycerin, trimethylolpropane, hexanediols and hexanetriols or also to
lavmolekulære polyestere som ricinusolje, low molecular weight polyesters such as castor oil,
såvelsom de f. eks. i de tyske utlegnings-skrifter nr. 1 022 789 og 1 027 394 nevnte isocyanatpolymerisater, idet selvsagt også i dette tilfellet vilkårlige blandinger kan as well as the e.g. isocyanate polymers mentioned in the German patent documents no. 1 022 789 and 1 027 394, since of course also in this case arbitrary mixtures can
anvendes. En videre anvendelse kan frem-gangsmåten også finne ved den ved hjelp are used. The method can also find a further application by means of it
av vanntilsetning bevirkede skumdannelse av det foraddisjonsprodukt som fås av of water addition caused foaming of the pre-addition product obtained from
ovennevnte polyhydroksyforbindelser og overskytende polyisocyanat. above-mentioned polyhydroxy compounds and excess polyisocyanate.
Ifølge oppfinnelsen anvendes det som katalysatorer ved skumdannelsen av reaksjonskomponentene tinnforbindelser med fireverdig tinn, hvorav hvert tinnatom er forbundet over minst en CvSn-binding med en organisk rest. Slike organiske rester kan være av alifatisk, aralifatisk cykloalifatisk eller aromatisk natur, f. eks. metyl-, etyl-, propyl-, butyl-, isobutyl-, amyl-, vinyl-, benzyl-, allyl eller fenylrester som også kan være substituert på vilkårlig ikkebasisk måte f. eks. ved halogenatomer, nitro-, alkoksy- eller karbalkoksygrupper. According to the invention, tin compounds with tetravalent tin are used as catalysts for the foaming of the reaction components, of which each tin atom is connected via at least one CvSn bond with an organic residue. Such organic residues can be of aliphatic, araliphatic, cycloaliphatic or aromatic nature, e.g. methyl, ethyl, propyl, butyl, isobutyl, amyl, vinyl, benzyl, allyl or phenyl residues which can also be substituted in any non-basic manner, e.g. by halogen atoms, nitro, alkoxy or carbolic oxy groups.
Så vidt tinnsalter av karbonsyrer kommer i betraktning, som minst inneholder et tertiært nitrogenatom i molekylet, kan det som mono- eller polykarbonsyrer eksempelvis nevnes: permetylerte eller generelt peralkylerte aminosyrer, f. eks. glycin, leucin, isoleucin, lysin, metionin, alanin, aminosmørsyrene, prolin, tryptofan, vali-nå glutaminsyre, asparginsyre, histidin, 6-aminokapronsyre, 11 -aminoundekansyre, mono- og polykarbonsyrene som fås av ammoniak eller aminer med akrylnitril ved addisjon og etterfølgende forsåping, videre også aromatiske aminokarbonsyrer, f. eks. permetylerte eller generelt peralkylerte aminobenzosyrer og aminoftalsyrer, såvel som benzylaminkarbonsyrer. Videre kan det nevnes pyridin-mono- og -polykarbonsyrer, kinolinkarbonsyrer og halvestrene av polykarbonsyrer med peralkylerte aminoalkoholer, f. eks. halvesteren av ftalsyre med dimetylaminoetanol. As far as tin salts of carboxylic acids are taken into account, which contain at least one tertiary nitrogen atom in the molecule, the following can be mentioned as mono- or polycarboxylic acids: permethylated or generally peralkylated amino acids, e.g. glycine, leucine, isoleucine, lysine, methionine, alanine, the aminobutyric acids, proline, tryptophan, valine-now glutamic acid, aspartic acid, histidine, 6-aminocaproic acid, 11-aminoundecanoic acid, the mono- and polycarboxylic acids obtained from ammonia or amines with acrylonitrile by addition and subsequent saponification, also aromatic aminocarbonic acids, e.g. permethylated or generally peralkylated aminobenzoic and aminophthalic acids, as well as benzylamine carboxylic acids. Furthermore, mention may be made of pyridine mono- and polycarboxylic acids, quinoline carboxylic acids and the half-esters of polycarboxylic acids with peralkylated amino alcohols, e.g. the half-ester of phthalic acid with dimethylaminoethanol.
Fremstillingen av tinnsaltene kan foregå på kjent måte på forskjellige enkle måter, hvorav som eksempel omsetningen av et salt av syren med en tinnforbindelse med den generelle formel R„Sn(halogen) 4-n, eventuelt i et oppløsningsmiddel, omsetningen av alkyltinnoksyder med de frie syrer under azeotropisk fjernelse av det dannede vann, omestringen av tinnforbindelser med formel R„Sn(OCH3)4-n med de frie syrer ifølge amerikansk patentskrift nr. 2 727 917 eller omestringen av forbindelser med formelen RnSn(OCOR)4-n med de frie syrer, idet eventuelt tertiære aminer kan tilsettes for å oppfange de frie syrer. Ved egnet valg av komponenter og deres molforhold kan ifølge denne frem-gangsmåten såvel høyeremolekylære som også laveremolekylære lineære eller forgrenede tinnforbindelser fremstilles. Me-tallforbindelsene kan selvsagt også anvendes blandet på vilkårlig måte. The preparation of the tin salts can take place in a known manner in various simple ways, of which, for example, the reaction of a salt of the acid with a tin compound of the general formula R„Sn(halogen) 4-n, possibly in a solvent, the reaction of alkyl tin oxides with the free acids during the azeotropic removal of the water formed, the transesterification of tin compounds of the formula R„Sn(OCH3)4-n with the free acids according to US Patent No. 2,727,917 or the transesterification of compounds of the formula RnSn(OCOR)4-n with the free acids, as possibly tertiary amines can be added to capture the free acids. By suitable choice of components and their molar ratio, both higher molecular and lower molecular linear or branched tin compounds can be produced according to this method. The metal compounds can of course also be used mixed in any way.
Såvidt tinnalkoholater resp. tinnfenolater med fireverdig tinn av alkoholer resp. fenoler med minst et tertiært nitrogenatom i molekylet kommer i betraktning kan det nevnes som alkoholer resp. fenoler særskilt dialkyl- eller diaryletanolaminer, dialkylpropanolaminer, alkyl- eller aryl-dietanolaminer, dialkyl-amino-alkylenmo-no- eller -polyalkoholer, bis(-dialkylami-no)-alkanoler eller -alkandioler, omset-ningsprodukter av tertiære aminogruppe-holdige epoksyder, som f. eks. 3-dietylami-noepoksy-propan med mono- eller polyalkoholer, dialkylaminofenoler, bis-(dialkylamino)fenoler, peralkylerte benzylamino-fenoler som p-(dimetylaminometyl)-fenol eller 2, 4, 6-tris(dimetylaminometyl)-fenol trietanolamin, omsetningsproduktene av sekundære eller primære aminer med et eller to mol av et alkylenoksyd, som f. eks. propylenoksyd, reduksjonsprodukter av peralkylerte aminoketoner og aminokarbonsyrer, alkoholer av ringsystemer med tertiære nitrogenatomer som N, N'-di-(p- hy-droksyetyl)-perazin-pyridin og kinolinfor-bindelser med OH-grupper som f. eks. 8-oksykinolin. Aminoalkoholene resp. amino-fenolene kan ved siden av de tertiære ami-nogrupper ha vilkårlige andre substituen-ter f. eks. halogenatomer, nitrogrupper, alkoksy- og karbalkoksygrupper. Fremstillingen av disse aminoalkohol- resp. ami-nofenol-tinnforbindelser kan foregå på kjent måte ved omestring av en tinnforbindelse med formelen RnSn(OCH3)4-n med det angjeldende aminoalkohol ifølge U.S. patent nr. 2 727 917, idet ved valg av tilsvarende komponenter og mengdefor-hold såvel laveremolekylære som også høy-eremolekylære lineære eller forgrenede produkter kan fremstilles. Metallforbindel-sene kan selvsagt også blandes på vilkårlig måte. As far as tin alcoholates resp. tin phenolates with tetravalent tin of alcohols or phenols with at least one tertiary nitrogen atom in the molecule come into consideration, they can be mentioned as alcohols or phenols in particular dialkyl- or diarylethanolamines, dialkylpropanolamines, alkyl- or aryl-diethanolamines, dialkyl-amino-alkylene mono- or -polyalcohols, bis(-dialkylamino-no)-alkanols or -alkanediols, reaction products of tertiary amino group-containing epoxides , like for example. 3-diethylaminoepoxypropane with mono- or polyalcohols, dialkylaminophenols, bis-(dialkylamino)phenols, peralkylated benzylaminophenols such as p-(dimethylaminomethyl)phenol or 2,4,6-tris(dimethylaminomethyl)phenol triethanolamine, the reaction products of secondary or primary amines with one or two moles of an alkylene oxide, such as e.g. propylene oxide, reduction products of peralkylated aminoketones and aminocarboxylic acids, alcohols of ring systems with tertiary nitrogen atoms such as N,N'-di-(p-hydroxyethyl)-perazine-pyridine and quinoline compounds with OH groups such as e.g. 8-oxyquinoline. The amino alcohols resp. the amino-phenols can have arbitrary other substituents next to the tertiary amino groups, e.g. halogen atoms, nitro groups, alkyloxy and carbolicoxy groups. The production of these amino alcohol resp. Aminophenol-tin compounds can proceed in a known manner by transesterification of a tin compound with the formula RnSn(OCH3)4-n with the relevant amino alcohol according to U.S. patent no. 2 727 917, since by choosing corresponding components and quantity ratios both lower molecular and higher molecular linear or branched products can be produced. The metal compounds can of course also be mixed in any way.
Såvidt organiske kompleksforbindel-ser av det fireverdige tinn kommer i betraktning som minst inneholder et tertiært nitrogenatom i molekylet kan som kompleksdannende komponenter helt generelt slike stoffer nevnes som over en ho-ved- og bivalent binding danner en chelat-forbindelse med tinnet under dannelse av 5- og høyereleddede rigsystemer. Herved er selvsagt de forbindelser av tinnet be-gunstiget som inneholder to over Sn-C-binding forbundede organiske rester som da under oppnåelse av koordinasjonstallet 6 kan danne en avmettet molekylstruktur. Er tre organiske rester som beskrevet bundet til tinnatomet, så oppnås intermoleky-lært bare et koordinasjonstall på 5. Er der-imot bare en organisk rest på den nevnte måte bundet til tinn, så må en chelatdan-nende gruppering i sin bivalente deltagelse ikke tas i betraktning. Imidlertid lar også de siste stoffer seg anvende ifølge oppfinnelsen. As far as organic complex compounds of the tetravalent tin come into consideration which contain at least one tertiary nitrogen atom in the molecule, as complex-forming components quite generally such substances can be mentioned which over a main and bivalent bond form a chelate compound with the tin with the formation of 5 - and higher-level rig systems. Hereby, those compounds of tin are of course favored which contain two organic residues connected via Sn-C bonds which can then form a desaturated molecular structure when the coordination number 6 is achieved. If three organic residues as described are bound to the tin atom, then intermolecularly only a coordination number of 5 is achieved. If, on the other hand, only one organic residue is bound to tin in the aforementioned manner, then a chelating grouping in its bivalent participation must not be taken considering. However, the latter substances can also be used according to the invention.
Som chelatdannere som på vilkårlig, imidlertid kompleksdannelsen ikke umulig-gjørende måte kan være substituert og i alle tilfelle må inneholde tertiært nitrogenatom kan i detalj anføres: tertiære aminogrupperioldige (3-diketoner eller [3-ketokarbonsyreestere, som 7-dietylamino-heptandion-2,4 eller som de kan fås ved enkel omsetning av (3-diketoner eller (3-ketokarbonestere, som acetylaceton, 2-fu-royl-benzoyl-metan, 2-tenoyl-aceton, 2, 2'-ditenoylmetan, aceteddikester etc. med 1 mol av et halogenalkyl-dialkyl-amin over natriumforbindelsen, som f. eks. 3-(|3-dietyl-aminoetyl)-acetylaceton eller a-(|3-die-tylamino-etyl) -aceteddiksyreetylester, idet i det minste kompleksdannelsestendensen ikke bør være forhindret ved en fullstendig substituering ved det midtplaserte C-atom, videre omestringsproduktene av p-ketokar-bonsyreestere som aceteddikester eller cy-klopentanon-2-karbonsyreetylester i vann-fritt medium med egnede aminoalkoholer som f. eks. dimetyl-aminoetanol, dietyl-aminoetanol, dibutylaminoetanol, N-metyl-N-stearyl-etanolamin, tilleiringspro-dukter av alkylenoksyder som etylenoksyd, propylenoksyd til sekundære aminer, idet ved omestringen med polyfunksjonelle aminoalkoholer som N-alkyl-dietanolami-ner eller trietanolaminer på enkel måte polyfunksjonelle kompleksdannere med flere P-ketoesterkonfigurasjoner i molekylet kan fås. Det kan nevnes aceteddiksyre-(p-di-metylaminoetyl) -ester, aceteddiksyre-(P-dietylamino) -etylester, aceteddiksyre- (p-N-metyl-N-stearyl-aminetyl) -ester, cyklo-pentanon-2-karbonsyre- (p-dibutylamino - etyl) -ester, N-metyl-dietanolamin-bis- (aceteddiksyre)-ester. Videre aktuelle er basisk substituerte salicylaldehyder eller naf-taldehyder som p-dimetylaminosalicylal-dehyd som kompleksdanner. As chelating agents which can be substituted arbitrarily, but not in a way that makes complex formation impossible and must in all cases contain a tertiary nitrogen atom, the following can be listed in detail: 4 or as they can be obtained by simple reaction of (3-diketones or (3-ketocarbon esters, such as acetylacetone, 2-furoyl-benzoyl-methane, 2-thenoyl-acetone, 2, 2'-dithenoylmethane, acetated diester etc. with 1 mol of a haloalkyl-dialkyl-amine over the sodium compound, such as 3-(|3-diethylaminoethyl)-acetylacetone or α-(|3-diethylamino-ethyl)-acetoacetic acid ethyl ester, with at least the complexation tendency should not be prevented by a complete substitution at the centrally placed C atom, further the transesterification products of p-ketocarboxylic acid esters such as acetate diester or cyclopentanone-2-carboxylic acid ethyl ester in an anhydrous medium with suitable amino alcohols such as, for example, dimethylaminoethanol, diethyl aminoethanol, dibutylaminoethanol, N-methyl-N-stearyl-ethanolamine, addition products of alkylene oxides such as ethylene oxide, propylene oxide to secondary amines, whereby the transesterification with polyfunctional amino alcohols such as N-alkyl diethanolamines or triethanolamines in a simple way polyfunctional complex formers with several P- ketoester configurations in the molecule can be obtained. Mention may be made of acetoacetic acid-(p-dimethylaminoethyl)-ester, acetoacetic acid-(P-diethylamino)-ethyl ester, acetoacetic acid-(p-N-methyl-N-stearyl-amineethyl)-ester, cyclo-pentanone-2-carboxylic acid-( p-dibutylamino-ethyl)-ester, N-methyl-diethanolamine-bis-(acetoacetic acid)-ester. Also relevant are basic substituted salicylaldehydes or naphthalaldehydes such as p-dimethylaminosalicylicaldehyde as a complex former.
Fremstillingen av tinnkompleksforbin-delser kan foregå, på forskjellig måte. Således kan forbindelser med den generelle formel RnS-(OCH3)4-n med n = 1—3 iføl-ge U.S. patent nr. 2 727 917 omestres med de angjeldende kompleksdannere under av-spaltning av metanol. En ytterligere mu-lighet består i omsetningen av et haloge-nid R„Sn-(halo<g>en) 4-n med et salt av kompleksdanneren, f. eks. med natrium-salt. The production of tin complex compounds can take place in different ways. Thus, compounds with the general formula RnS-(OCH3)4-n with n = 1-3 according to the U.S. patent no. 2 727 917 is transesterified with the relevant complex formers while splitting off methanol. A further possibility consists in the reaction of a halide R„Sn-(halo<g>ene) 4-n with a salt of the complex former, e.g. with sodium salt.
Istedenfor tinnforbindelser med bare et fireverdig tinnatom i molekylet lar det seg likeså godt også anvende salter av stannoksaner med Sn-O-Sn-grupperinger i molekylet, idet igjen hvert tinnatom er forbundet med en organisk rest over minst en C-Sn-binding. Instead of tin compounds with only one tetravalent tin atom in the molecule, it is equally possible to use salts of stannoxanes with Sn-O-Sn groupings in the molecule, as each tin atom is again connected to an organic residue via at least one C-Sn bond.
Disse tinnforbindelser som skal anvendes ifølge oppfinnelsen er alt etter sin type faste amorfe, pastaformede eller også flytende og viskose produkter, som kan settes til reaksjonskomponentene, som skal forskummes, på forskjelligste måter. Således er de flytende tinnforbindelser vanligvis godt forenlige og kan med en gang settes til f. eks. polyeter eller polyesteren. Faste tinnforbindelser kan tilføres reak-sjonsblandingen som skal forskummes opp-løst i oppløsningsmidler som f .eks. i aceton, aromatiske kullvannstoffer, klorkullvann-stof f er, etere eller også i en av de beslektede reaksjonskomponenter, men endelig også i fast form, eventuelt tilpasset i polyhy-droksyforbindelsen. De nødvendige kataly-satormengder er meget forskjellige og av-henger naturligvis av typen og sammenset-ningen av den reaksjonsblanding som skal omdannes. På den annen side er det i det vesentlige virksomme Sn-innhold forskjellig, alt etter de anvendte tinnforbindelser. Generelt skulle imidlertid mellom 0,001— 5,0 vekt-%, referert til den samlede blanding som skal skumdannes, være fullstendig tilstrekkelig for å få et godt skumstoff. These tin compounds to be used according to the invention are, depending on their type, solid amorphous, pasty or also liquid and viscous products, which can be added to the reaction components, which are to be foamed, in a variety of ways. Thus, the liquid tin compounds are usually well compatible and can be immediately added to e.g. polyether or the polyester. Solid tin compounds can be added to the reaction mixture which is to be pre-foamed dissolved in solvents such as e.g. in acetone, aromatic hydrocarbons, chlorinated hydrocarbons, ethers or also in one of the related reaction components, but finally also in solid form, optionally adapted in the polyhydroxy compound. The required amounts of catalyst are very different and naturally depend on the type and composition of the reaction mixture to be converted. On the other hand, the essentially effective Sn content is different, depending on the tin compounds used. In general, however, between 0.001 and 5.0% by weight, referred to the total mixture to be foamed, should be completely sufficient to obtain a good foam.
Fremstillingen av skumstoffene fore-går forøvrig på i og for seg kjent måte ved samtidig intens blanding av komponente-ne (polyhydroksy- og/eller polykarboksyl-forbindelsene, polycyanat og eventuelt vann ved siden av ytterligere tilsetningsstoffer) hensiktsmessig ad maskinell vei, som det f. eks. er beskrevet i det franske patent nr. 1 074 713. Herunder kan også vannet anvendes i form av krystallvann-holdige salter. Det er allerede henvist til muligheten av å skumdanne isocyanatgruppeholdige foraddisjonsprodukter ved hjelp av vanntilsetning. The production of the foams is otherwise carried out in a manner known in and of itself by simultaneous intense mixing of the components (the polyhydroxy and/or polycarboxyl compounds, polycyanate and possibly water alongside further additives) appropriately by mechanical means, such as e.g. is described in the French patent no. 1 074 713. Here, the water can also be used in the form of salts containing crystal water. Reference has already been made to the possibility of foaming preaddition products containing isocyanate groups by means of water addition.
Ved reaksjonskomponentenes omsetning lar seg som bekjent de forskjelligste tilsetningsstoffer medanvende. Det kan eksempelvis nevnes emulgatorer som f. eks. sulfonert ricinusolje eller tilleiringsproduk-ter av etylenoksyd til hydrofobe forbindelser med reaktivt vannstoff, skumstabilisa-torer som f. eks. silikon-alkylenoksyd-kopolymere eller silikoner med basiske nitrogenatomer i molekylet, celleregulatorer som parafinoljer eller de forskjelligste silikon - oljer, fargestoffer, fyllstoffer, flammebe-skyttelsesmidler, mykningsmidler og flere andre. Blandt de tinnkatalysatorer som skal anvendes ifølge oppfinnelsen, kan i tillegg dessuten de kjente basiske påskyndingsmidler tilsettes f. eks. tertiære aminer som dimetylbenzylamin, l-alkoksy-3-dialkyl-aminopropan, endoetylenpiperazin i små mengder, permetylert N-etylamino-piperazin, dimetylalkylaminene eller også alkalisk reagerende metallforbindelser som alkalihydroksyder, -karbonater, -fenolater og -alkoholater. As is well known, a wide variety of additives can be used during the turnover of the reaction components. Emulsifiers such as e.g. sulphonated castor oil or addition products of ethylene oxide to hydrophobic compounds with reactive hydrogen, foam stabilizers such as e.g. silicone-alkylene oxide copolymers or silicones with basic nitrogen atoms in the molecule, cell regulators such as paraffin oils or the most diverse silicone oils, dyes, fillers, flame retardants, plasticizers and several others. Among the tin catalysts to be used according to the invention, the known basic accelerators can also be added, e.g. tertiary amines such as dimethylbenzylamine, 1-alkoxy-3-dialkylaminopropane, endoethylenepiperazine in small amounts, permethylated N-ethylaminopiperazine, the dimethylalkylamines or also alkaline-reacting metal compounds such as alkali hydroxides, carbonates, phenolates and alcoholates.
De fremkomne skumstoffer, hvis volumvekt som kjent kan modifiseres ved variasjon av polyisocyanat- og vannmeng-dene, utmerker seg ved fremragende mekaniske og fysikalske verdier. The resulting foams, whose volume weight, as is known, can be modified by varying the amounts of polyisocyanate and water, are distinguished by excellent mechanical and physical values.
Eksempel 1: Example 1:
blandes sammen maskinelt og den skum-mingsdyktige reaksjonsblanding fylles i form. Blandingen begynner straks å skumme opp og stivner hurtig til et elastisk skumstoff, som er fritt for revner og heller ikke skrumper sammen etter utherdingen. are mixed together mechanically and the foamable reaction mixture is filled into a mold. The mixture immediately begins to foam and hardens quickly into an elastic foam material, which is free from cracks and also does not shrink after curing.
Eksempel 2: Example 2:
sammenblandes maskinelt og den skum-mingsdyktige reaksjonsblanding fylles i form. Blandingen begynner straks å skumme opp og stivner hurtig til et elastisk skumstoff, som er fritt for revner og heller ikke skrumper sammen etter utherdingen. are mixed together mechanically and the foamable reaction mixture is filled into the mold. The mixture immediately begins to foam and hardens quickly into an elastic foam material, which is free from cracks and also does not shrink after curing.
Eksempel 3: Example 3:
blandes maskinelt og den skummingsdyk-tig reaksjonsblanding fylles i form. Blandingen begynner straks å skumme opp og stivner hurtig til et elastisk skumstoff, som er fritt for revner, og som heller ikke skrumper sammen etter utherdingen. are mixed mechanically and the foamable reaction mixture is filled into the mold. The mixture immediately begins to foam and hardens quickly into an elastic foam material, which is free from cracks, and which also does not shrink after curing.
Eksempel 4: Example 4:
sammenblandes maskinelt og den skum-mingsdyktige reaksjonsblanding fylles i form. Blandingen begynner straks å skumme opp og stivner hurtig til et elastisk skumstoff som er fritt for revner og heller ikke skrumper sammen ved utherdingen. are mixed together mechanically and the foamable reaction mixture is filled into the mold. The mixture immediately begins to foam and hardens quickly into an elastic foam that is free from cracks and does not shrink during curing.
Eksempel 5: Example 5:
blandes sammen maskinelt og den skum-mingsdyktige reaksjonsblanding fylles i form. Blandingen begynner straks å skumme opp og stivner hurtig til et elastisk skumstoff som er fritt for revner og som heller ikke etter utherdingen skrumper sammen. are mixed together mechanically and the foamable reaction mixture is filled into a mold. The mixture immediately begins to foam and hardens quickly into an elastic foam that is free from cracks and does not shrink after curing either.
Eksempel 6: Example 6:
a) 0,5 mol CH3-0-[Sn(C4Ho)20]„CH:t med n = 1,5 omestres med 1 mol a-(p-dietylaminoetyl) -aceteddiksyreetylester ved maks. 130° C i vannstrålevakuum under utelukkelse av fuktighet og under avdes-tillasjon av den beregnede mengde metanol. Herved får man i beregnet mengde en gul viskos olje. b) 100 vektsdeler av et lineært polypropylenglykol med et OH-tall på 51, 43 a) 0.5 mol CH3-0-[Sn(C4Ho)20]„CH:t with n = 1.5 is transesterified with 1 mol a-(p-diethylaminoethyl)-acetoacetic acid ethyl ester at max. 130° C. in a water jet vacuum while excluding moisture and during distillation of the calculated amount of methanol. This results in a yellow viscous oil in the calculated amount. b) 100 parts by weight of a linear polypropylene glycol with an OH number of 51.43
vektsdeler av et toluylendiisocyanat som inneholder 2,4- og 2,6-isomere i forholdet 80 : 20, 1,5 vektsdeler av en vannoppløselig silikonforbindelse, 1,0 vektsdeler av den ifølge eksempel 6a erholdte tinnkom-pleksforbindelse og 3,5 vektsdeler vann, blandes på vanlig måte med hverandre og gir etter fylling i en form et hurtig avbindende skumstoff med gode elastiske egenskaper og uten skrumpningstendens. parts by weight of a toluylene diisocyanate containing 2,4- and 2,6-isomers in the ratio 80:20, 1.5 parts by weight of a water-soluble silicone compound, 1.0 parts by weight of the tin complex compound obtained according to example 6a and 3.5 parts by weight of water , are mixed with each other in the usual way and, after filling in a form, give a fast setting foam material with good elastic properties and no tendency to shrink.
Eksempel 7: Example 7:
a) 130 vektsdeler aceteddikester og 117 vektsdeler N, N-dietyl-etanolamin omestres a) 130 parts by weight of acetic acid ester and 117 parts by weight of N,N-diethyl-ethanolamine transester
under utelukkelse av fuktighet på en ko-lonne, idet den beregnede mengde etanol fås ved siden av små mengder aceton. Re-siduet gir ved destillasjonen ved oljepum-pe ca. 110 vektsdeler med kokepunkt 83— while excluding moisture on a column, the calculated amount of ethanol being obtained alongside small amounts of acetone. The residue yields approx. 110 parts by weight with boiling point 83—
20 87°C og n D : 1,4500, som gir de beregnede analyseverdier. 20 87°C and n D : 1.4500, which gives the calculated analysis values.
b) 75 vektsdeler av den ifølge a) fremkomne aceteddiksyre ((3-dietylaminoetyl) b) 75 parts by weight of the acetoacetic acid obtained according to a) ((3-diethylaminoethyl)
ester og 55,4 vektsdeler dibutyldimetoksytinn omestres under utelukkelse av fuktighet og til maks. 130° C, til slutt i vakuum ved 20 mm. Herunder avdestilleres den teoretiske metanolmengde og man får et gult viskost produkt med en brytningsin-20 ester and 55.4 parts by weight of dibutyldimethoxytin are transesterified under the exclusion of moisture and to max. 130° C, finally in vacuum at 20 mm. Below this, the theoretical amount of methanol is distilled off and a yellow viscous product is obtained with a refractive index of 20
deks på n D : 1,5008. dex of n D : 1.5008.
c) 100 vektsdeler av en polyester av adipinsyre, dietylenglykol og heksantriol c) 100 parts by weight of a polyester of adipic acid, diethylene glycol and hexanetriol
med et OH-tall på 56, et syretall på 1,3 og en viskositet på 18 000 cP ved 25° C, 43 vektsdeler toluylendiisocyanat som inneholder 2, 4- og 2, 6-isomere i forholdet 65 : 35, 0,5 vektsdeler av det ifølge eks. 7b) fremkomne tinnkomplekssalt, 1,5 vektsdeler av en 50 %-ig vandig oppløsning av natriumsaltet av sulfonert ricinusolje, 1,5 vektsdeler av en 50 %ig vandig oppløsning av natriumsaltet av den sulfonerte ricinol-syre og 2,0 vektsdeler H2O sammenblandes med hverandre på vanlig måte og gir etter uthelling et i to minutter stigende skum, som i 15—20 minutter avbindes og har fremragende elastiske egenskaper. with an OH number of 56, an acid number of 1.3 and a viscosity of 18,000 cP at 25° C, 43 parts by weight of toluylene diisocyanate containing 2,4- and 2,6-isomers in the ratio 65 : 35, 0.5 parts by weight of it according to e.g. 7b) resulting tin complex salt, 1.5 parts by weight of a 50% aqueous solution of the sodium salt of sulphonated castor oil, 1.5 parts by weight of a 50% aqueous solution of the sodium salt of sulphonated ricinoleic acid and 2.0 parts by weight of H2O are mixed with each other in the usual way and after pouring produces a foam that rises for two minutes, which sets in 15-20 minutes and has excellent elastic properties.
Eksempel 8: Example 8:
a) 380 vektsdeler a((3-dietylaminoetyl) aceteddiksyreetylester og 250 vektsdeler dibutyldimetoksytinn omestres ifølge eksempel 7b) og gir i kvantitativt utbytte et tinnkomplekssalt med en brytningsin-20 a) 380 parts by weight of a((3-diethylaminoethyl)acetoacetic acid ethyl ester and 250 parts by weight of dibutyldimethoxytin are transesterified according to example 7b) and give in quantitative yield a tin complex salt with a refractive index of 20
deks på n n : 1,4932. dex of n n : 1.4932.
b) 100 vektsdeler av et polypropylenglykol som er fremkommet ved tilleiring b) 100 parts by weight of a polypropylene glycol which has been produced by addition of clay
av propylenoksyd til trimetylolpropan med et OH-tall på 55,8, 42 vektsdeler toluylendiisocyanat ifølge eksempel 6, 1,5 vektsdeler av en silikonolje ifølge eksempel 6b), 1,5 vektsdeler av et komplekssalt ifølge eks. 8a) og 3,3 vektsdeler vann gir ved skumdannelse ifølge fransk patent nr. 1 074 713 et etter ca. 30 minutter avbindende skumstoff med fremragende elastiske egenskaper. of propylene oxide to trimethylolpropane with an OH number of 55.8, 42 parts by weight of toluylene diisocyanate according to example 6, 1.5 parts by weight of a silicone oil according to example 6b), 1.5 parts by weight of a complex salt according to ex. 8a) and 3.3 parts by weight of water give when foaming according to French patent no. 1 074 713 et after approx. 30-minute curing foam with excellent elastic properties.
Eksempel 9: Example 9:
Ved anvendelse av 1,5 vektsdeler av en basisk silikonolje, H2N-CH2-CH2-0-[Si (CH:1)20]11CH2-CH2-NH2, som det fremkom ved omestring av den tilsvarende die-toksyforbindelse, C2H50-[Si(CH3)20]„C2H5 (molekylvekt 700) med 2 mol etanolamin, istedenfor silikonoljen ifølge eksempel 8b) kunne analoge resultater fås. Using 1.5 parts by weight of a basic silicone oil, H2N-CH2-CH2-0-[Si (CH:1)20]11CH2-CH2-NH2, which was obtained by transesterification of the corresponding diethoxy compound, C2H50-[ Si(CH3)20]„C2H5 (molecular weight 700) with 2 mol of ethanolamine, instead of the silicone oil according to example 8b) analogous results could be obtained.
Eksempel 10: Example 10:
a) 52 vektsdeler aceteddiksyreetylester og 130,8 vektsdeler N-metyl-N-stearyl-etanolamin omestres under fuktighetsuteluk-kelse ved 120° C, til slutt i vakuum, idet den teoretiske mengde etanol avdestilleres. Deretter tilsetter man 59 vektsdeler dibutyldimetoksytinn og omestrer på nytt ved 140° C, til slutt i vakuum, den teoretiske mengde metanol. Man får 207 vektsdeler av en langsomt stivnende olje med en bryt-20 a) 52 parts by weight of acetoacetic acid ethyl ester and 130.8 parts by weight of N-methyl-N-stearyl-ethanolamine are transesterified under moisture exclusion at 120° C, finally in vacuum, the theoretical amount of ethanol being distilled off. 59 parts by weight of dibutyldimethoxytin are then added and re-esterified at 140° C, finally in vacuum, with the theoretical amount of methanol. You get 207 parts by weight of a slowly solidifying oil with a break-20
ningsindeks n D : 1,4862. ning index n D : 1.4862.
b) 100 vektsdeler av et polyeterisocyanat med et NCO-innhold på 8,1 % og en b) 100 parts by weight of a polyetherisocyanate with an NCO content of 8.1% and a
viskositet på 8 000 cP ved 25° C, som det fremkom ved reaksjon av 70 vektsdeler av et lineært polypropylenglykol med et OH-tall på 54,6 og 30 vektsdeler av et polypropylenglykol ifølge eksempel 8b) med 34,4 viscosity of 8,000 cP at 25° C, which was obtained by reacting 70 parts by weight of a linear polypropylene glycol with an OH number of 54.6 and 30 parts by weight of a polypropylene glycol according to example 8b) with 34.4
vektsdeler toluylendiisocyanat ifølge eksempel 6b), 0,1 vektsdel silikonolje ifølge parts by weight toluylene diisocyanate according to example 6b), 0.1 parts by weight silicone oil according to
eksempel 9, 1,8 vektsdeler vann og 0,8 vekts-* deler av et tinnkompleks ifølge eksempel 10a) gir ved sammenrøring og uthelling et skum med en stigetid på 90 sek. og som har gode elastiske verdier og høy rivefast-het. example 9, 1.8 parts by weight of water and 0.8 parts by weight of a tin complex according to example 10a) gives, when mixed and poured, a foam with a rise time of 90 sec. and which have good elastic values and high tear resistance.
Eksempel 11: Example 11:
100 vektsdeler av et halvforgrenet polypropylenglykol som ble fremstilt ved tilleiring av propylenoksyd til en blanding av heksantriol og propandiol-1,2 i molforhol-det 1:1 og hadde et OH-tall på 56, 35,5 volumdeler tolmlendiisocyanat ifølge eksempel 6b), 3,0 vektsdeler vann, 1,5 vektsdeler av en vannoppløselig silikonolje iføl-ge eksempel 6b) og 1,0 vektsdeler av et tinnkomplekssalt ifølge eksempel 10a) blandes maskinelt i et apparat ifølge fransk patent nr. 1 074 713 og gir et hurtig stigende skum med en avbindingstid på 20 minutter, som har gode elastiske egenskaper. 100 parts by weight of a semi-branched polypropylene glycol which was produced by adding propylene oxide to a mixture of hexanetriol and propanediol-1,2 in the molar ratio 1:1 and had an OH number of 56, 35.5 parts by volume of tolmlenediisocyanate according to example 6b), 3.0 parts by weight of water, 1.5 parts by weight of a water-soluble silicone oil according to example 6b) and 1.0 parts by weight of a tin complex salt according to example 10a) are mechanically mixed in an apparatus according to French patent no. 1 074 713 and give a rapidly rising foam with a setting time of 20 minutes, which has good elastic properties.
Fysikalske verdier: Physical values:
Eksempel 12: Example 12:
100 vektsdeler av et forgrenet polypropylenglykol, som fremkom ved tilleiring av propylenoksyd til heksantriol (OH-tall 55), 38 vektsdeler toluylendiisocyanat, som in-neholdt 2,4- og 2,6-isomere i forholdet 80 : 20, 1,5 vektsdeler av en vannoppløselig po-liysiloksan-alkylenoksyd-kopolymer, 2,9 vektsdeler vann og 1,0 vektsdel dibutyltinn-bis-(rø-dimetylamino-kaproat), som det fremkom ved azeotropisk forestring av 159 vektsdeler av den frie syre og 125 vektsdeler dibutyl-tinnoksyd under medanvendelse av toluol som bæremiddel i viskos 20 form og med en brytmgsmdeks n D = 1,4900, ga ved skumdannelse i et apparat ifølge det franske patent nr. 7 074 713 et høy elastisk skumstoff med en stigetid 1,5 minutter, som avbinder i løpet av kort tid. 100 parts by weight of a branched polypropylene glycol, which was obtained by adding propylene oxide to hexanetriol (OH number 55), 38 parts by weight of toluylene diisocyanate, which contained 2,4- and 2,6-isomers in the ratio 80:20, 1.5 parts by weight of a water-soluble polysiloxane-alkylene oxide copolymer, 2.9 parts by weight of water and 1.0 part by weight of dibutyltin bis-(red-dimethylamino-caproate), which was obtained by azeotropic esterification of 159 parts by weight of the free acid and 125 parts by weight of dibutyl -tin oxide with the co-use of toluene as a carrier in viscose form and with a volume index n D = 1.4900, when foaming in an apparatus according to French patent no. 7 074 713 gave a highly elastic foam with a rise time of 1.5 minutes, which dissolves within a short time.
Eksempel 13: Example 13:
100 vektsdeler av et lineært polypropylenglykol (OH-tall 56), 39 vektsdeler av et toluyendiisocyanat ifølge eksempel 12, 0,2 vektsdeler endoetylenpiperazin, 3,0 vektsdeler vann, 1,3 vektsdeler av et omes-tringsprodukt av 1 mol C2H50-[Si(OHs)20] 100 parts by weight of a linear polypropylene glycol (OH number 56), 39 parts by weight of a toluene diisocyanate according to example 12, 0.2 parts by weight of endoethylene piperazine, 3.0 parts by weight of water, 1.3 parts by weight of a transesterification product of 1 mol of C2H50-[Si (OHs)20]
-C2H5 med 2 mol etanolamin og 0,6 vekts- -C2H5 with 2 mol ethanolamine and 0.6 wt-
deler dibutyltinn-bis- (a-dimetylamino-acetat), som fremkom ved azeotrop forestring ifølge eksempel 12 i viskos med en parts dibutyltin-bis-(α-dimethylamino-acetate), which was obtained by azeotropic esterification according to example 12 in viscose with a
20 20
brytningsindeks n D = 1,5086, gir ved sammenrøring et hurtig stigende skumstoff med gode elastiske verdier. refractive index n D = 1.5086, when mixed, produces a rapidly rising foam with good elastic values.
Eksempel 14: Example 14:
100 vektsdeler av et polypropylenglykol ifølge eksempel 12, 38 vektsdeler toluyendiisocyanat ifølge eksempel 12, 1,5 vektsdeler av et polysiloksan ifølge eksempel 12, 2,6 vektsdeler vann og 1,0 vektsdel dioktyltinn-bis- (æ-dimetylamino-kaproat), som fremkom ved omestring av den frie syre med dioktyldimetoksytinn og har en bryt-20 nmgsindeks på n D = 1,4738, gir ved den maskinelle sammenblanding et hurtig stigende avbindende skumstoff med følgende fysikalske verdier: 100 parts by weight of a polypropylene glycol according to Example 12, 38 parts by weight of toluene diisocyanate according to Example 12, 1.5 parts by weight of a polysiloxane according to Example 12, 2.6 parts by weight of water and 1.0 part by weight of dioctyltin-bis-(ε-dimethylamino-caproate), which was obtained by transesterification of the free acid with dioctyldimethoxytin and has a refractive index of n D = 1.4738, when mechanically mixed it gives a rapidly rising debinding foam with the following physical values:
Eksempel 15: Example 15:
100 vektsdeler polypropylenglykol iføl-ge eksempel 12, 38 vektsdeler toluylendiisocyanat ifølge eksempel 12, 1,5 vektsdeler av et polysiloksan ifølge eksempel 12, 2,8 vektsdeler vann, 1,0 vektsdel l-etoksy-3-dimetylaminopropan og 1,0 vektsdel diben-zyltinn-bis-(oo-dimetylaminokaproat), som fremkom ved omestring av den frie syre med dibenzyldimetoksytinn ved maks. 130° 100 parts by weight polypropylene glycol according to example 12, 38 parts by weight toluylene diisocyanate according to example 12, 1.5 parts by weight of a polysiloxane according to example 12, 2.8 parts by weight water, 1.0 parts by weight 1-ethoxy-3-dimethylaminopropane and 1.0 parts by weight dibene -zyltin-bis-(oo-dimethylaminocaproate), which was obtained by transesterification of the free acid with dibenzyldimethoxytin at max. 130°
20 20
C og som har en brytmgsindeks n D = C and which has a bending index n D =
1,5520, ga ved sammenblanding et godt 1.5520, when combined gave a good
skumstoff med en volumvekt på 42 kg/m'<1>foam material with a volume weight of 42 kg/m'<1>
og en støtelastisitet på 46 %. and an impact elasticity of 46%.
Eksempel 16: Example 16:
100 vektsdeler av et forgrenet polypropylenglykol ifølge eksempel 12, 38 vektsdeler toluylendiisocyanat som inneholder 2,4- og 2,6-isomere i forholdet 65 : 35, 1,0 vektsdel av et polysiloksan ifølge eksempel 12, 2,6 vektsdeler vann og 0,3 vektsdeler av et tinnsalt med formelen 100 parts by weight of a branched polypropylene glycol according to example 12, 38 parts by weight of toluylene diisocyanate containing 2,4- and 2,6-isomers in the ratio 65:35, 1.0 parts by weight of a polysiloxane according to example 12, 2.6 parts by weight of water and 0, 3 parts by weight of a tin salt with the formula
med n = 1,5, som fremkom ved omestring av det tilsvarende dimetoksystannoksan med 2 mol oa-dimetylaminokapronsyre og with n = 1.5, which was obtained by transesterification of the corresponding dimethoxystannoxane with 2 mol o-dimethylaminocaproic acid and
20 20
hadde en brytingsindeks n D = 1,4865, had a refractive index n D = 1.4865,
ga ved skumdannelse et hurtig stigende gave, when foaming, a rapid rise
skumstoff med en volumvekt på 34 kg/m<3>, en støtelastisitet på 44 %, en rivfasthet på 1,1 kp/cm<2> og en bruddutvidelse på 220 %. foam material with a bulk density of 34 kg/m<3>, an impact elasticity of 44%, a tear resistance of 1.1 kp/cm<2> and an expansion at break of 220%.
Eksempel 17: Example 17:
100 vektsdeler av et polypropylenglykol ifølge eksempel 12, 38 vektsdeler toluy-lendiisocyant ifølge eksempel 12, 1,0 vektsdel polysiloksan ifølge eksempel 12, 2,6 . vektsdeler vann og 0,5 vektsdeler av en basisk stannoksanforbindelse med formelen 100 parts by weight of a polypropylene glycol according to example 12, 38 parts by weight toluene diisocyanate according to example 12, 1.0 parts by weight polysiloxane according to example 12, 2.6 . parts by weight of water and 0.5 parts by weight of a basic stannoxane compound of the formula
som fremkom ved azeotrop forestring av 1 mol dibutyltinnoksyd med 1 mol co-dime-tylamino-kapronsyre under medanvendelse av toluol og med en brytningsindeks which was obtained by the azeotropic esterification of 1 mol of dibutyltin oxide with 1 mol of co-dimethylamino-caproic acid with the co-use of toluene and with a refractive index
20 20
n D = 1,4867, ga ved skumdannelsen hurtig avbindende skumstoff med en volumvekt på 35 kg/m<8>, en strekkfasthet på 1,3 kp/cm<2>, en bruddutvidelse på 275 % og en støtelastisitet på 45 %. n D = 1.4867, upon foaming gave rapid setting foam with a bulk weight of 35 kg/m<8>, a tensile strength of 1.3 kp/cm<2>, an expansion at break of 275% and an impact elasticity of 45%.
Eksempel 18: Example 18:
100 vektsdeler polypropylenglykol iføl-ge eksempel 12, 38 vektsdeler toluylendiisocyanat ifølge eksempel 12, 1,0 vektsdel polysiloksan ifølge eksempel 12, 2,6 vektsdeler vann, 0,5 vektsdeler l-etoksy-3-dim-etylamino-propan og 1,6 vektsdeler av en 50 %ig aceton-oppløsning av et basisk tinnsalt med den teoretiske formel 100 parts by weight polypropylene glycol according to example 12, 38 parts by weight toluylene diisocyanate according to example 12, 1.0 parts by weight polysiloxane according to example 12, 2.6 parts by weight water, 0.5 parts by weight 1-ethoxy-3-dimethylamino-propane and 1.6 parts by weight of a 50% acetone solution of a basic tin salt with the theoretical formula
som det fremkom ved azeotropisk forestring av 2 mol av den tilsvarende syre med 1 mol dibutyltinnoksyd, gir ved skumdannelse på maskinell måte et hurtig stigende og avbindende skumstoff med en volumvekt på 35 kg/m<K>, en strekkfasthet på 1,3 kp/ cm<2>, en bruddutvidelse på 255 %, en støte-lastisitet på 45 % og en varig deformering på 14 % . which was obtained by azeotropic esterification of 2 mol of the corresponding acid with 1 mol of dibutyltin oxide, when foaming in a mechanical way gives a rapidly rising and setting foam with a volume weight of 35 kg/m<K>, a tensile strength of 1.3 kp/ cm<2>, a fracture elongation of 255%, an impact elasticity of 45% and a permanent deformation of 14%.
Eksempel 19: Katalysatorens fremstilling: Ved omestring av 70 vektsdeler trietylmetoksytinn med 47,7 vektsdeler co-dimetylamino-ka-pronsyre ved maksimalt 130° C, får man i kvantitativt utbytte trietyltinn-co-dime-tylamino-kaproat, smeltepunkt 65° C (fra aceton). Example 19: Preparation of the catalyst: By transesterification of 70 parts by weight of triethylmethoxytin with 47.7 parts by weight of co-dimethylamino-caproic acid at a maximum of 130° C, triethyltin-co-dimethylamino-caproate is obtained in quantitative yield, melting point 65° C ( from acetone).
100 vektsdeler polypropylenglykol iføl-ge eksempel 12, 38 vektsdeler toluylendiisocyanat ifølge eksempel 12, 1,0 vektsdeler polysiloksan ifølge eksempel 12, 2,6 vektsdeler av tinnsaltet fremstilt som nevnt ovenfor, oppløst i 1 ml aceton, gir etter maskinell utrøring i 1,5 minutter stigende og i 10 minutter avbindende skumstoff med en volumvekt på 34 kg/m<s>, en strekkfasthet på 0,8 kp/cm<2>, en bruddutvidelse på 215 % og en støtelastisitet på 37 %. 100 parts by weight polypropylene glycol according to example 12, 38 parts by weight toluylene diisocyanate according to example 12, 1.0 parts by weight polysiloxane according to example 12, 2.6 parts by weight of the tin salt prepared as mentioned above, dissolved in 1 ml of acetone, gives after mechanical stirring for 1.5 minutes rising and 10 minutes setting foam with a bulk density of 34 kg/m<s>, a tensile strength of 0.8 kp/cm<2>, a breaking expansion of 215% and an impact elasticity of 37%.
Eksempel 20: Example 20:
100 vektsdeler av et polyeterisocyanat (isocyanatinnhold 9 %), som det fremkom ved omsetning av 100 vektsdeler polypropylenglykol ifølge eksempel 13 med 37,3 vektsdeler toluylendiisocyanat ifølge eksempel 16, 1,0 vektsdel polydimetylsil-oksan, 1,9 vektsdeler vann og 1,0 vektsdel dibutyltinn-bis- (co-dimetylaminokap-roat) gir ved maskinell sammenblanding et hurtig avbindende skumstoff med gode mekaniske verdier. 100 parts by weight of a polyetherisocyanate (isocyanate content 9%), which was obtained by reacting 100 parts by weight polypropylene glycol according to example 13 with 37.3 parts by weight toluylene diisocyanate according to example 16, 1.0 parts by weight polydimethylsiloxane, 1.9 parts by weight water and 1.0 part by weight of dibutyltin-bis-(co-dimethylaminocaproate) gives, by mechanical mixing, a fast setting foam with good mechanical values.
Eksempel 21: Example 21:
100 vektsdeler av en polyester av adipinsyre, dietylenglykol og trimetylolpropan (OH-tall 58,0, syretall 1,3, viskositet 18 500 cP/25° C), 38 vektsdeler toluylendiisocyanat, som inneholder 2,4- og 2,6-isomere i forholdet 65 : 35, 2,5 vektsdeler vann, såvelsom en oppløsning av 2 ml toluol og 1,0 vektsdel av et tinnsalt, som fremkom ved omestring av 1 mol dibutyldimetoksytinn med 2 mol 8-oksykinolin og smel-tet ved 150—154° C, ga ved sammenblanding et hurtig stigende og utherdende, noe gulgrønt farget skumstoff med gode elastiske verdier. 100 parts by weight of a polyester of adipic acid, diethylene glycol and trimethylolpropane (OH number 58.0, acid number 1.3, viscosity 18,500 cP/25° C), 38 parts by weight toluylene diisocyanate, containing 2,4- and 2,6-isomers in the ratio 65:35, 2.5 parts by weight of water, as well as a solution of 2 ml of toluene and 1.0 part by weight of a tin salt, which was obtained by transesterification of 1 mol of dibutyldimethoxytin with 2 mol of 8-oxyquinoline and melted at 150-154 ° C, when mixed together gave a rapidly rising and hardening, slightly yellow-green colored foam with good elastic values.
Eksempel 22: Example 22:
100 vektsdeler av et svakt forgrenet polypropylenglykol, som fremkom ved addisjon av propylenoksyd til en blanding av propandiol-1,2 og trimetylolpropan i mol-forholdet 1 : 1 (OH-tall 56), 40 vektsdeler av et toluylendiisocyanat, som inneholder 2,4- og 2,6-isomere i forhold 80 : 20, 1,5 vektsdeler av et vannoppløselig polysiloksan-alkylenoksyd-kopolymer, 2,9 vektsdeler vann og 0,5 vektsdeler av et basisk tinnfenolat, som fremkom ved omestring av 1 mol dibutyldimetoksytinn med 2 mol 2, 4, 6-tris-(dimetylaminometyl)-fenol ved maks. 130° C i vakuum og hadde en bryt-20 nmgsindeks n D = 1,5370, sammenblandes i et skumdannelsesapparatur ifølge det franske patent nr. 1 074 713. Skumstoffet steg i løpet av 1 minutt og er avbundet etter 10 minutter 100 parts by weight of a weakly branched polypropylene glycol, which was obtained by adding propylene oxide to a mixture of propanediol-1,2 and trimethylolpropane in the molar ratio 1:1 (OH number 56), 40 parts by weight of a toluylene diisocyanate, which contains 2.4 - and 2,6-isomers in a ratio of 80:20, 1.5 parts by weight of a water-soluble polysiloxane-alkylene oxide copolymer, 2.9 parts by weight of water and 0.5 parts by weight of a basic tin phenolate, which was obtained by transesterification of 1 mol of dibutyldimethoxytin with 2 mol 2, 4, 6-tris-(dimethylaminomethyl)-phenol at max. 130° C in vacuum and had a break-20 nmg index n D = 1.5370, is mixed in a foaming apparatus according to the French patent No. 1 074 713. The foam material rose within 1 minute and is debonded after 10 minutes
Under anvendelse av 0,25 vektsdeler av det basiske tinnfenolat ved ellers uforandrede blandingsbestanddeler fås ved en stigetid på 1,3 minutter et skumstoff med følgende fysikalske verdier: Using 0.25 parts by weight of the basic tin phenolate with otherwise unchanged mixture components, a foam with the following physical values is obtained with a rise time of 1.3 minutes:
Eksempel 23: Example 23:
100 vektsdeler polypropylenglykol iføl-ge eksempel 22, 38 vektsdeler toluylendiisocyanat ifølge eksempel 22, 1,5 vektsdeler polysiloksan ifølge eksempel 22, 2,9 vektsdeler vann og 1,0 vektsdel av et basisk tinnfenolat, som fremkom ved omestring av 1 mol dibutyldimetoksytinn med 2 mol rå dimetylaminometylfenol ved maks. 130° C i vakuum og hadde en brytningsin-20 deks på n D = 1,5470, ga ved skumdannelse ifølge eksempel 22 et skumstoff med følgende fysikalske verdier: 100 parts by weight of polypropylene glycol according to example 22, 38 parts by weight of toluylene diisocyanate according to example 22, 1.5 parts by weight of polysiloxane according to example 22, 2.9 parts by weight of water and 1.0 parts by weight of a basic tin phenolate, which was obtained by transesterification of 1 mol of dibutyldimethoxytin with 2 mol crude dimethylaminomethylphenol at max. 130° C in vacuum and had a refractive index of 20 dex of n D = 1.5470, when foaming according to example 22 gave a foam with the following physical values:
Anvendes istedenfor 1,0 vektsdel av det basiske tinnfenolat en blanding av 0,8 vektsdeler av det basiske tinnfenolat og 0,2 vektsdeler permetylert N-aminoetyl-piperazin ved ellers uforandrede blandingsbestanddeler, så får man et skumstoff med følgende verdier: If instead of 1.0 parts by weight of the basic tin phenolate, a mixture of 0.8 parts by weight of the basic tin phenolate and 0.2 parts by weight of permethylated N-aminoethyl piperazine is used with otherwise unchanged mixture components, then a foam material with the following values is obtained:
Eksempel 24: Example 24:
100 vektsdeler av et lineært polypropylenglykol (OH-tall 56), 38 vektsdeler toluylendiisocyanat ifølge eksempel 22, 1,5 vektsdeler siv en basisk silikonolje som fremkom ved omestring av 1 mol C2H5O-[Si(CH3)20-]nC2H5 med 2 mol etanolamin, 2,9 vektsdeler vann og 1,5 vektsdel av et tinnaminoalkoholat (C4H9)2Sn- (O-CH2CH2 100 parts by weight of a linear polypropylene glycol (OH number 56), 38 parts by weight of toluylene diisocyanate according to example 22, 1.5 parts by weight of a basic silicone oil obtained by transesterification of 1 mol of C2H5O-[Si(CH3)20-]nC2H5 with 2 mol of ethanolamine , 2.9 parts by weight of water and 1.5 parts by weight of a stannous aminoalcoholate (C4H9)2Sn-(O-CH2CH2
-N-CH2CH20H)2, som fås ved omestring av 1 mol dibutyldimetoksytinn med 2 mol -N-CH2CH20H)2, which is obtained by transesterification of 1 mol of dibutyldimethoxytin with 2 mol
N-metyldietanolamin ved maks. 130° C, ga ved maskinell omdannelse et hurtig stigende og avbindende skumstoff med gode egenskaper. N-methyldiethanolamine at max. 130° C, by mechanical conversion gave a rapidly rising and binding foam with good properties.
Istedenfor N-metyldietanolamin kan ved omestringen av tinnforbindelsen, såvel ved den etterfølgende skumdannelse med samme resultat anvendes det ikkesubsti-tuerte dietanolamin. Instead of N-methyldiethanolamine, unsubstituted diethanolamine can be used in the transesterification of the tin compound, as well as in the subsequent foam formation with the same result.
Eksempel 25: Example 25:
100 vektsdeler polypropylenglykol iføl-ge eksempel 22, 38 vektsdeler toluylendiisocyanat ifølge eksempel 22, 1,5 vektsdeler polysiloksan ifølge eksempel 22, 2,61 vektsdeler vann og 0,9 vektsdeler dioktyltinn-bis- (5-dietylamino-pentylat-2), som fås ved omestring av 1 mol dioktyldimetoksytinn med 2 mol 1-dietylamino-penta-20 nol-4 og har en brytingsindeks på n D 100 parts by weight polypropylene glycol according to example 22, 38 parts by weight toluylene diisocyanate according to example 22, 1.5 parts by weight polysiloxane according to example 22, 2.61 parts by weight water and 0.9 parts by weight dioctyltin-bis-(5-diethylamino-pentylate-2), which is obtained by transesterification of 1 mol of dioctyldimethoxytin with 2 mol of 1-diethylamino-penta-20-nol-4 and has a refractive index of n D
= 1,4700, gir ved den maskinelle sammenblanding et skumstoff med en volumvekt på 39 kg/m<:i>, en støtelastisitet på 35 %, en strekkfasthet på 1,1 kp/cm<2> og en bruddutvidelse på 240 % ved gode stige- og av-bindingstider. = 1.4700, the mechanical mixing gives a foam material with a bulk weight of 39 kg/m<:i>, an impact elasticity of 35%, a tensile strength of 1.1 kp/cm<2> and a breaking expansion of 240% at good rise and release times.
Eksempel 26: Example 26:
100 vektsdeler polypropylenglykol iføl-ge eksempel 22, 38 vektsdeler toluylendiisocyanat ifølge eksempel 22, 1,0 vektsdel polysiloksan ifølge eksempel 22, 2,8 vekts- 100 parts by weight polypropylene glycol according to example 22, 38 parts by weight toluylene diisocyanate according to example 22, 1.0 parts by weight polysiloxane according to example 22, 2.8 parts by weight
deler vann, 0,2 vektsdeler endoetylenpipe- parts water, 0.2 parts by weight endoethylene pipe-
razin såvelsom 3 vektsdeler av en 33 %ig acetonoppløsning av et basisk dibenzyl- razin as well as 3 parts by weight of a 33% acetone solution of a basic dibenzyl
fenolat som fremkom ved omsetning av 1 phenolate which emerged from reaction of 1
mol dibenzyltinndiklorid med 2 mol av natriumforbindelsen av 2, 4, 6-tris-(dimetyla-minometyl)-f enol (råproduktets smelte- mol of dibenzyltin dichloride with 2 mol of the sodium compound of 2, 4, 6-tris-(dimethylaminomethyl)-phenol (the crude product's melting
punkt = 55 — 60° C), gir ved sammenblan- point = 55 — 60° C), gives when combined
ding et skumstoff med gode stigetider og gode egenskaper. ding a foam material with good rise times and good properties.
i Eksempel 27: in Example 27:
100 vektsdeler polypropylenglykol iføl- 100 parts by weight polypropylene glycol in
ge eksempel 22, 38 vektsdeler toluylendiisocyanat ifølge eksempel 22, 1,0 vektsdel polysiloksan ifølge eksempel 22, 2,8 vekts- give example 22, 38 parts by weight toluylene diisocyanate according to example 22, 1.0 parts by weight polysiloxane according to example 22, 2.8 parts by weight
deler vann og 1,0 vektsdel av et basisk trie-tyltinnfenolat som fremkom ved omestring av 1 mol trietylmetoksytinn med 1 mol 2, parts water and 1.0 part by weight of a basic triethyltin phenolate which was obtained by transesterification of 1 mol of triethylmethoxytin with 1 mol of 2,
4, 6-tris-(dimetylaminometyl)-fenol og har 4, 6-tris-(dimethylaminomethyl)-phenol and has
20 20
en brytningsindeks på n D = 1,5208, gir ved maskinell sammenblanding et hurtig stigende og avbindende skumstoff med en volumvekt på 37 kg/m<3>, en støtelastisitet på 34 %, en bruddutvidelse på 210 % såvel som en strekkfasthet på 1,0 kp/cm<2>. a refractive index of n D = 1.5208, upon mechanical mixing, gives a rapidly rising and setting foam with a volume weight of 37 kg/m<3>, an impact elasticity of 34%, an elongation at break of 210% as well as a tensile strength of 1, 0 kp/cm<2>.
Eksempel 28: Example 28:
100 vektsdeler av et polyeterisocyanat (isocyanatinnhold 9 %), som fremkom ved omsetning av 100 vektsdeler av et lineært polypropylenglykol ifølge eksempel 24 med 37,3 vektsdeler toluylendiisocyanat ifølge eksempel 21, 0,8 vektsdeler polydimetylsl-loksan, 0,2 vektsdeler av et basisk dibutyl-tinnfenolat ifølge eksempel 22 og 1,9 vekts- 100 parts by weight of a polyetherisocyanate (isocyanate content 9%), which was obtained by reacting 100 parts by weight of a linear polypropylene glycol according to example 24 with 37.3 parts by weight of toluylene diisocyanate according to example 21, 0.8 parts by weight of polydimethylsiloxane, 0.2 parts by weight of a basic dibutyl tin phenolate according to example 22 and 1.9 wt.
deler vann, gir ved skumdannelse et hurtig stigende og avbindende skumstoff med go- divides water, when foaming produces a rapidly rising and binding foam with go-
de mekaniske verdier. the mechanical values.
Eksempel 29: Example 29:
100 vektsdeler av et polypropylenglykol 100 parts by weight of a polypropylene glycol
ifølge eksempel 11, 38 vektsdeler toluylendiisocyanat ifølge eksempel 6, 1,5 vekts- according to example 11, 38 parts by weight of toluylene diisocyanate according to example 6, 1.5 parts by weight
deler polysiloksan ifølge eksempel 6, 2,9 vektsdeler vann og 1,0 vektsdel av et dibutyl-tinn-bis (aceteddiksyre-|3-dietylamino-etylester)-kompleks ifølge eksempel 7 gir ved maskinell sammenblanding i en appa- parts polysiloxane according to example 6, 2.9 parts by weight of water and 1.0 parts by weight of a dibutyl-tin-bis (acetoacetic acid-|3-diethylamino-ethyl ester) complex according to example 7 gives by mechanical mixing in an appa-
ratur ifølge det franske patent nr. 1 074 713 rature according to French Patent No. 1,074,713
et i 1,5 minutter stigende skumstoff, som er avbundet etter 10 minutter og har en volumvekt på 36 kg/m<3>, en strekkfasthet på 1,1 kp/cm<2>, en bruddutvidelse på 385 a foam that rises for 1.5 minutes, which is debonded after 10 minutes and has a bulk weight of 36 kg/m<3>, a tensile strength of 1.1 kp/cm<2>, a breaking expansion of 385
%, en støtelastisitet på 51 % og en varig deformering (22 timer ved 70° C, bestemt etter y2 time) på 14 %. %, an impact elasticity of 51% and a permanent deformation (22 hours at 70° C, determined after y2 hours) of 14%.
Eksempel 30: Example 30:
100 vektsdeler polypropylenglykol iføl- 100 parts by weight polypropylene glycol in
ge eksempel 11, 38 vektsdeler toluylendiisocyanat ifølge eksempel 6, 1,0 vektsdel polysiloksan ifølge eksempel 6, 2,8 vekts- give example 11, 38 parts by weight of toluylene diisocyanate according to example 6, 1.0 parts by weight of polysiloxane according to example 6, 2.8 parts by weight
deler vann og 1,2 vektsdeler av et basisk dioktyltinn-kompleks, som det fremkom ved omestring av 13 vektsdeler aceteddik- parts of water and 1.2 parts by weight of a basic dioctyltin complex, which was obtained by transesterification of 13 parts by weight of acetic acetic
ester, 31,3 vektsdeler N-metyl-N-stearyl-etanolamin og 20,5 vektsdeler dioktyldimetoksytinn ved maks. 130° C med en bryt- ester, 31.3 parts by weight of N-methyl-N-stearyl-ethanolamine and 20.5 parts by weight of dioctyldimethoxytin at max. 130° C with a switch
20 20
ingsindeks n D = 1,4823, gir ved sammenblanding en hurtig avbindende revne- ing index n D = 1.4823, when mixed together, gives a fast binding crack-
og skrumpingsfast skumstoff med gode elastiske egenskaper. and shrink-resistant foam material with good elastic properties.
Eksempel 31: Example 31:
100 vektsdeler polypropylenglykol iføl- 100 parts by weight polypropylene glycol in
ge eksempel 11, 38 vektsdeler toluylendiisocyanat ifølge eksempel 6, 1,0 vektsdel polysiloksan ifølge eksempel 6, 2,8 vekts- give example 11, 38 parts by weight of toluylene diisocyanate according to example 6, 1.0 parts by weight of polysiloxane according to example 6, 2.8 parts by weight
deler vann, 0,5 vektsdeler N-etylmorfolin og 2,0 vektsdeler av et dibenzyltinn-kompleks, som det fremkom ved omestring av 31,3 vektsdeler N-metyl-N-stearyl-etanolamin med 13 vektsdeler aceteddikester og 18,2 vektsdeler dibenzyldimetoksy-tinn ved maks. 130° C, med en brytningsindeks 20 parts of water, 0.5 parts by weight of N-ethylmorpholine and 2.0 parts by weight of a dibenzyltin complex, which was obtained by transesterification of 31.3 parts by weight of N-methyl-N-stearyl-ethanolamine with 13 parts by weight of acetaldehyde and 18.2 parts by weight of dibenzyldimethoxy - tin at max. 130° C, with a refractive index of 20
n — 1.5095 gir ved maskinell sammenblanding et uklanderlig og hurtig avbindende skumstoff. n — 1.5095 gives, when mechanically mixed, an impeccable and fast setting foam material.
Anvendelsen av 2 mol trietylmetoksy- The use of 2 moles of triethylmethoxy-
tinn istedenfor 1 mol dibenzyl-dimetoksy- tin instead of 1 mol of dibenzyl-dimethoxy-
tinn ved fremstillingen av det beskrevne komplekssalt såvel som dets etterfølgende anvendelse ved skumfremstillingen fører til et tilsvarende skumstoff. tin in the preparation of the described complex salt as well as its subsequent use in the production of foam leads to a corresponding foam substance.
Claims (6)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US17070971A | 1971-08-11 | 1971-08-11 |
Publications (2)
Publication Number | Publication Date |
---|---|
NO134469B true NO134469B (en) | 1976-07-05 |
NO134469C NO134469C (en) | 1976-10-13 |
Family
ID=22620945
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
NO2840/72A NO134469C (en) | 1971-08-11 | 1972-08-09 |
Country Status (4)
Country | Link |
---|---|
US (1) | US3713499A (en) |
CA (1) | CA965047A (en) |
GB (1) | GB1359775A (en) |
NO (1) | NO134469C (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1985005118A1 (en) * | 1984-05-09 | 1985-11-21 | Otto Farstad | Drilling fluid |
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CA1047243A (en) * | 1973-06-28 | 1979-01-30 | Irwin Fox | Porous fe304 drilling mud additive |
US3964557A (en) * | 1974-10-11 | 1976-06-22 | Gulf Research & Development Company | Treatment of weighted drilling mud |
US4474254A (en) * | 1982-11-05 | 1984-10-02 | Etter Russell W | Portable drilling mud system |
US4725362A (en) * | 1985-11-18 | 1988-02-16 | Dugat John W | Treatment techniques for drill fluids, cuttings and other oil field wastes |
US4696353A (en) * | 1986-05-16 | 1987-09-29 | W. S. Tyler, Incorporated | Drilling mud cleaning system |
US4790933A (en) * | 1986-11-18 | 1988-12-13 | Mobil Oil Corporation | Dynamic filtration unit and process of use |
US4872949A (en) * | 1988-03-08 | 1989-10-10 | Wilwerding Carl M | Process for treatment of drilling mud |
NO164219C (en) * | 1988-03-25 | 1990-09-12 | Steinar E Mellgren | PROCEDURE AND PLANT FOR TREATMENT OF RETURNED BORESLAM. |
FR2636669B3 (en) * | 1988-09-19 | 1991-03-29 | Guillaume Jean Paul | MOBILE DRILLING SLUDGE REGENERATOR UNIT |
US5090498A (en) * | 1989-11-10 | 1992-02-25 | M-I Drilling Fluids Company | Water wash/oil wash cyclonic column tank separation system |
NO175412C (en) * | 1990-11-28 | 1994-10-12 | Norske Stats Oljeselskap | Process for treating waste materials for injection into underground formations |
US5344570A (en) * | 1993-01-14 | 1994-09-06 | James E. McLachlan | Method and apparatus for removing solids from a liquid |
AU6417694A (en) * | 1993-03-26 | 1994-10-24 | Western Atlas International, Inc. | Method and apparatus for determining depth of drill cuttings |
FR2704455B1 (en) * | 1993-04-28 | 1995-07-21 | Stratech International | Process for recovering sludge from sawing, cutting and polishing granite blocks. |
US5944195A (en) * | 1995-07-05 | 1999-08-31 | Exxon Production Research Company | Method for separation of solids from drilling fluids by magnetic separation and centrifugation |
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US6932169B2 (en) * | 2002-07-23 | 2005-08-23 | Halliburton Energy Services, Inc. | System and method for developing and recycling drilling fluids |
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US20090200080A1 (en) * | 2003-04-16 | 2009-08-13 | Tibbitts Gordon A | Impact excavation system and method with particle separation |
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US7867399B2 (en) | 2008-11-24 | 2011-01-11 | Arkansas Reclamation Company, Llc | Method for treating waste drilling mud |
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US8925653B2 (en) | 2011-02-28 | 2015-01-06 | TD Tools, Inc. | Apparatus and method for high pressure abrasive fluid injection |
MX2014002993A (en) | 2011-09-19 | 2014-08-22 | Fp Marangoni Inc | Three-phase separation system for drilling fluids and drill cuttings. |
US9334699B2 (en) | 2012-04-02 | 2016-05-10 | Beitzel Corporation | Drill cuttings conveyance systems |
US8950510B2 (en) | 2012-04-02 | 2015-02-10 | Beitzel Corporation | Drill cuttings conveyance systems |
US9896918B2 (en) | 2012-07-27 | 2018-02-20 | Mbl Water Partners, Llc | Use of ionized water in hydraulic fracturing |
US10036217B2 (en) | 2012-07-27 | 2018-07-31 | Mbl Partners, Llc | Separation of drilling fluid |
US8997562B2 (en) | 2013-01-21 | 2015-04-07 | Halliburton Energy Services, Inc. | Drilling fluid sampling system and sampling heat exchanger |
US9254453B2 (en) | 2013-03-06 | 2016-02-09 | Halliburton Energy Services, Inc. | Economical method for scavenging hydrogen sulfide in fluids |
US9617811B2 (en) | 2014-05-13 | 2017-04-11 | National Oilwell Varco, L.P. | Drilling mud cooling system |
US10041314B2 (en) | 2014-07-08 | 2018-08-07 | National Oilwell Varco, L.P. | Closed loop drilling mud cooling system for land-based drilling operations |
US10081994B2 (en) | 2015-01-30 | 2018-09-25 | Fp Marangoni Inc. | Screened enclosure with vacuum ports for use in a vacuum-based drilling fluid recovery system |
CN105134080A (en) * | 2015-07-09 | 2015-12-09 | 四川川庆石油钻采科技有限公司 | Particle drilling method |
US10486920B2 (en) | 2016-09-12 | 2019-11-26 | Vermeer Manufacturing Company | Transfer systems for receiving and conveying material |
CN110668669B (en) * | 2019-09-26 | 2022-03-08 | 浙江中卓环境科技有限公司 | Mud-water separation system |
CN110566143A (en) * | 2019-10-28 | 2019-12-13 | 平煤建工集团特殊凿井工程有限公司 | Forced drilling slag-liquid separator |
NL2026757B1 (en) | 2020-10-23 | 2022-06-17 | Stichting Canopus Intellectueel Eigendom | Device and method for concentrating particles within a stream |
-
1971
- 1971-08-11 US US00170709A patent/US3713499A/en not_active Expired - Lifetime
-
1972
- 1972-06-02 CA CA143,687A patent/CA965047A/en not_active Expired
- 1972-08-01 GB GB3587472A patent/GB1359775A/en not_active Expired
- 1972-08-09 NO NO2840/72A patent/NO134469C/no unknown
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1985005118A1 (en) * | 1984-05-09 | 1985-11-21 | Otto Farstad | Drilling fluid |
Also Published As
Publication number | Publication date |
---|---|
CA965047A (en) | 1975-03-25 |
GB1359775A (en) | 1974-07-10 |
NO134469C (en) | 1976-10-13 |
US3713499A (en) | 1973-01-30 |
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