NO127620B - - Google Patents
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- NO127620B NO127620B NO521868A NO521868A NO127620B NO 127620 B NO127620 B NO 127620B NO 521868 A NO521868 A NO 521868A NO 521868 A NO521868 A NO 521868A NO 127620 B NO127620 B NO 127620B
- Authority
- NO
- Norway
- Prior art keywords
- compounds
- mannich bases
- group
- reaction
- catalysts
- Prior art date
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 30
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 25
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 19
- 238000006116 polymerization reaction Methods 0.000 claims description 17
- RREANTFLPGEWEN-MBLPBCRHSA-N 7-[4-[[(3z)-3-[4-amino-5-[(3,4,5-trimethoxyphenyl)methyl]pyrimidin-2-yl]imino-5-fluoro-2-oxoindol-1-yl]methyl]piperazin-1-yl]-1-cyclopropyl-6-fluoro-4-oxoquinoline-3-carboxylic acid Chemical compound COC1=C(OC)C(OC)=CC(CC=2C(=NC(\N=C/3C4=CC(F)=CC=C4N(CN4CCN(CC4)C=4C(=CC=5C(=O)C(C(O)=O)=CN(C=5C=4)C4CC4)F)C\3=O)=NC=2)N)=C1 RREANTFLPGEWEN-MBLPBCRHSA-N 0.000 claims description 14
- 239000006260 foam Substances 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 150000002989 phenols Chemical class 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 239000004033 plastic Substances 0.000 claims description 11
- 229920003023 plastic Polymers 0.000 claims description 11
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 150000003335 secondary amines Chemical class 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000003380 propellant Substances 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 6
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims description 5
- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 230000006735 deficit Effects 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims description 3
- 238000010348 incorporation Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 description 33
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000005056 polyisocyanate Substances 0.000 description 15
- 229920001228 polyisocyanate Polymers 0.000 description 15
- 239000012948 isocyanate Substances 0.000 description 13
- 150000002513 isocyanates Chemical class 0.000 description 12
- -1 on the foam sector Chemical class 0.000 description 12
- 235000002639 sodium chloride Nutrition 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 8
- 150000001412 amines Chemical class 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 238000009833 condensation Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- 235000013824 polyphenols Nutrition 0.000 description 5
- 239000002966 varnish Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000007859 condensation product Substances 0.000 description 4
- 239000000123 paper Substances 0.000 description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 4
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 150000001414 amino alcohols Chemical class 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- DYDNPESBYVVLBO-UHFFFAOYSA-N formanilide Chemical compound O=CNC1=CC=CC=C1 DYDNPESBYVVLBO-UHFFFAOYSA-N 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical group SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- XWCDCDSDNJVCLO-UHFFFAOYSA-N Chlorofluoromethane Chemical class FCCl XWCDCDSDNJVCLO-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- SKZKKFZAGNVIMN-UHFFFAOYSA-N Salicilamide Chemical compound NC(=O)C1=CC=CC=C1O SKZKKFZAGNVIMN-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 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
- 239000000049 pigment Substances 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229920000582 polyisocyanurate Polymers 0.000 description 2
- 239000011495 polyisocyanurate Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229960000581 salicylamide Drugs 0.000 description 2
- 229960004889 salicylic acid Drugs 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- RSPCKAHMRANGJZ-UHFFFAOYSA-N thiohydroxylamine Chemical compound SN RSPCKAHMRANGJZ-UHFFFAOYSA-N 0.000 description 2
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- 229940113165 trimethylolpropane Drugs 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 1
- MTZUIIAIAKMWLI-UHFFFAOYSA-N 1,2-diisocyanatobenzene Chemical class O=C=NC1=CC=CC=C1N=C=O MTZUIIAIAKMWLI-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- BDQNKCYCTYYMAA-UHFFFAOYSA-N 1-isocyanatonaphthalene Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1 BDQNKCYCTYYMAA-UHFFFAOYSA-N 0.000 description 1
- DMAXMXPDVWTIRV-UHFFFAOYSA-N 2-(2-phenylethyl)phenol Chemical class OC1=CC=CC=C1CCC1=CC=CC=C1 DMAXMXPDVWTIRV-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- LJDSTRZHPWMDPG-UHFFFAOYSA-N 2-(butylamino)ethanol Chemical compound CCCCNCCO LJDSTRZHPWMDPG-UHFFFAOYSA-N 0.000 description 1
- MIJDSYMOBYNHOT-UHFFFAOYSA-N 2-(ethylamino)ethanol Chemical group CCNCCO MIJDSYMOBYNHOT-UHFFFAOYSA-N 0.000 description 1
- MVRPPTGLVPEMPI-UHFFFAOYSA-N 2-cyclohexylphenol Chemical class OC1=CC=CC=C1C1CCCCC1 MVRPPTGLVPEMPI-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- JSFITYFUKSFPBZ-UHFFFAOYSA-N 4-(7-methyloctyl)phenol Chemical compound CC(C)CCCCCCC1=CC=C(O)C=C1 JSFITYFUKSFPBZ-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical class CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- 238000006683 Mannich reaction Methods 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical group CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 1
- QORUGOXNWQUALA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 Chemical class N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 QORUGOXNWQUALA-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 125000005365 aminothiol group Chemical group 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 125000006222 dimethylaminomethyl group Chemical group [H]C([H])([H])N(C([H])([H])[H])C([H])([H])* 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000004872 foam stabilizing agent Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- TZMQHOJDDMFGQX-UHFFFAOYSA-N hexane-1,1,1-triol Chemical compound CCCCCC(O)(O)O TZMQHOJDDMFGQX-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- HVZWVEKIQMJYIK-UHFFFAOYSA-N nitryl chloride Chemical compound [O-][N+](Cl)=O HVZWVEKIQMJYIK-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 150000002888 oleic acid derivatives Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 125000004043 oxo group Chemical group O=* 0.000 description 1
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- CQRYARSYNCAZFO-UHFFFAOYSA-N salicyl alcohol Chemical compound OCC1=CC=CC=C1O CQRYARSYNCAZFO-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- HSVFKFNNMLUVEY-UHFFFAOYSA-N sulfuryl diazide Chemical class [N-]=[N+]=NS(=O)(=O)N=[N+]=[N-] HSVFKFNNMLUVEY-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 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 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
Description
Fremgangsmåte til fremstilling av isocyanurat- Process for the production of isocyanurate
gruppeholdig plast, spesielt skumplast. group-containing plastics, especially foam plastics.
Polymerisasjon av forbindelser med alifatiske og aromatiske isocyanatgrupper er kjent og omtalt i mange variasjoner. Vanligvis anvender man ved denne polymerisasjon alkaliske katalysatorer. Disse bevirker en omdannelse av NCO-gruppene i isocyanuratringer, idet denne reaksjon vanligvis i stoff resp. i oppløsning fører til definerte mengder av isocyanurat-ringholdige polymerer, de kan også føre til fullstendig utreaksjon av de tilstedeværende NCO-grupper. Ved anvendelse av forbindelser med mer enn en isocyanatgruppe i molekylet fører denne trimerisering vanligvis under ukon-trollerbare betingelser til et fullstendig nettdannet og sprøtt ma-teriale. En ytterligere vanskelighet ved polymerisasjonsreaksjonene er det faktum at vanligvis er det tilstede en inkubasjonstid som praktisk talt umuliggjør en reaksjonsbegynnelse til et definert tids-punkt. Båre ved anvendelse av meget aktive katalysatorer kan den ek-sotermt forløpende polymerisasjon av NCO-grupper allerede startes ved værelsestemperatur. Imidlertid er det da praktisk talt umulig å få reaksjonen under kontroll. Derfor gjennomføres slike polymeri-sasjonsreaksj oner vanligvis med svakt virksomme (basiske) åktivatorer ved forhøyede temperaturer. Det er allerede blit't beskrevet polymeri-sas jonsreaksjoner under anvendelse av fenoliske Mannichbaser som av-leder seg fra en eventuelt med halogen- eller C^-C^-alkylrester sub-stituert fenol eller tiofenol. Spesielt ble det anvendt 2,4,6-tris-dimetylaminometylfenol, idet sistnevnte spesielt skal anvendes sammen med et epoksyd for oppnåelse av en tilstrekkelig aktivitet. De derved dannede reaksjonsprodukter har imidlertid en sterk aminlukt som hind-rer en praktisk anvendelse. Dessuten fører de anvendte aminkomponent-er til et ujevnt forløp av polymerisasjonsreaksjonen og derved til et produkt som ikke er tilfredsstillende i teknisk henseende. Polymerization of compounds with aliphatic and aromatic isocyanate groups is known and discussed in many variations. Alkaline catalysts are usually used in this polymerization. These cause a conversion of the NCO groups into isocyanurate rings, as this reaction usually in substance or in solution leads to defined amounts of isocyanurate ring-containing polymers, they can also lead to complete reaction of the NCO groups present. When using compounds with more than one isocyanate group in the molecule, this trimerization usually leads under uncontrollable conditions to a completely networked and brittle material. A further difficulty with the polymerization reactions is the fact that usually there is an incubation time which practically makes it impossible to start the reaction at a defined point in time. Due to the use of highly active catalysts, the exothermic polymerization of NCO groups can already be started at room temperature. However, it is then practically impossible to get the reaction under control. Therefore, such polymerization reactions are usually carried out with weakly effective (basic) activators at elevated temperatures. Polymerization reactions have already been described using phenolic Mannich bases which are derived from a phenol or thiophenol optionally substituted with halogen or C₁-C₂ alkyl residues. In particular, 2,4,6-tris-dimethylaminomethylphenol was used, the latter in particular being used together with an epoxide to achieve sufficient activity. The resulting reaction products, however, have a strong amine smell which prevents practical use. In addition, the amine components used lead to an uneven course of the polymerization reaction and thereby to a product that is not satisfactory from a technical point of view.
Videre er det kjent å anvende alkoksylerte kondensasjonsprodukter av aminer, oksoforbindelser og fenoler med minst to frie o- og/eller p-stillinger som polyhydroksylforbindelser til omsetning med isocyanater, f.eks. på skumstoffsektoren, uten at det imidlertid i disse tilfeller kan iakttas en veséntlig polymerisasjons-reaksj on av isocyanatgruppene. Furthermore, it is known to use alkylated condensation products of amines, oxo compounds and phenols with at least two free o- and/or p-positions as polyhydroxyl compounds for reaction with isocyanates, e.g. on the foam sector, without, however, in these cases being able to observe a significant polymerization reaction of the isocyanate groups.
I de norske utlegningsskrifter nr. 126.025 og 126.026 omtales fremgangsmåter til fremstilling av isocyanuratgruppeholdige plaster, innbefattende skumstoffer, idet det som katalysatorer anvendes forbindelser av typen Mannichbaser. Disse katalysatorer har vist seg som virksomme forbindelser ved fremstilling av isocyanuratplaster. På grunn av de økende tekniske krav til polyisocyanurat-plaster, besto imidlertid det tekniske problem å finne slike høyvirk-somme katalysatorer som utmerker seg ved absolutt luktløshet (ingen aminlukt) og høyest mulig forenlighet med de øvrige reaksjonskomponenter. Overraskende har det vist seg at katalysatorene som anvendes ifølge foreliggende oppfinnelse oppfyller disse -krav. In the Norwegian explanatory documents no. 126,025 and 126,026, methods for the production of plasters containing isocyanurate groups, including foams, are described, with compounds of the Mannich base type being used as catalysts. These catalysts have proven to be effective compounds in the production of isocyanurate plasters. However, due to the increasing technical requirements for polyisocyanurate plastics, the technical problem was to find such highly effective catalysts which are distinguished by absolute odorlessness (no amine smell) and the highest possible compatibility with the other reaction components. Surprisingly, it has been shown that the catalysts used according to the present invention meet these requirements.
Katalysatorene som skal anvendes ifølge oppfinnelsen er innbyggbare i plaststrukturen. Ved reaksjon med polyisocyanatet bringes de i en slik form at det ikke mer kan iakttas noen forstyr-rende lukt og dessuten bringes ved innbyggbarheten, dvs. ved reaksjon med polyisocyanatet i en med de øvrige reaksjonskomponenter optimal forenlig form, således at i resultat forløper polymerisasjonsreaksjonen meget jevnt og fører til isocyanuratplaster, spesielt skumstoffer med fremragende jevn tetthetsfordeling. The catalysts to be used according to the invention can be built into the plastic structure. When reacting with the polyisocyanate, they are brought into such a form that no disturbing odor can be observed any more and are also brought into being by incorporation, i.e. by reaction with the polyisocyanate in a form that is optimally compatible with the other reaction components, so that as a result the polymerization reaction proceeds very evenly and leads to isocyanurate plasters, especially foams with excellent even density distribution.
Overraskende ble det nå funnet at man får plast med fordelaktige teknologiske egenskaper, på basis av polyisocyanater når man omsetter en forbindelse med mer enn en iaocyanatgruppe, eventuelt i nærvær av et drivmiddel og eventuelt med underskuddsmengder av forbindelser med aktive hydrogenatomer, eventuelt under tilsetning av stabilisatorer og vanlige hjelpemidler, med slike Mannichbaser av fenoler som katalysatorer som. utgjøres av innbygningsdyktige en- eller flerkjernede Mannichbaser av sekundære aminer, fortrinnsvis en blanding av dimetylamin og sekundære aminoalkoholer, formaldehyd og fenoler som i tillegg til den på fenolen substituerte aminometylgruppe og Surprisingly, it has now been found that plastics with advantageous technological properties are obtained on the basis of polyisocyanates when a compound with more than one iocyanate group is reacted, possibly in the presence of a propellant and possibly with deficit amounts of compounds with active hydrogen atoms, possibly with the addition of stabilizers and common auxiliaries, with such Mannich bases of phenols as catalysts as. consists of mono- or polynuclear Mannich bases capable of being incorporated into secondary amines, preferably a mixture of dimethylamine and secondary amino alcohols, formaldehyde and phenols which, in addition to the aminomethyl group substituted on the phenol and
den fenoliske OH-gruppe■minst inneholder en -0H, -SH, -COOH, -CONHg, -NH2 eller -NHR-gruppe hvor R er alkyl, cykloalkyl, aryl eller aralkyl. Ifølge oppfinnelsen anvendes altså katalysatorer som i molekylet inneholder frie 0H-, SH-, COOH-, CONH2-, -NH2~ eller -NHR-grupper,hvor R er alkyl, cykloalkyl, aryl eller aralkyl, og følgelig ved polymerisasjonsreaksjonen innbygges under samtidig reaksjon av • disse grupper i den polymere. Overfor de allerede tidligere omtalte katalysatorer utmerker de seg ved en vesentlig mindre lukt, såvel som også ved en helt igjennom høyere aktivitet. Denne betinges tydelig-vis ved det Jaktum at katalysatoren ved reaksjon med polyisocyanatet bringes i en med dette forenlig form, således at polymerisasjonsreaksjonen forløper jevnere. Sterkt hydrofile og uforenlige katalysatorer må anvendes til oppnåelse av optimal aktivitet sammen med emulgeringsmidler eller tilsvarende virkende midler. the phenolic OH group contains at least one -OH, -SH, -COOH, -CONHg, -NH2 or -NHR group where R is alkyl, cycloalkyl, aryl or aralkyl. According to the invention, catalysts are used which in the molecule contain free OH-, SH-, COOH-, CONH2-, -NH2~ or -NHR groups, where R is alkyl, cycloalkyl, aryl or aralkyl, and consequently in the polymerization reaction are incorporated during simultaneous reaction of • these groups in the polymer. Compared to the previously mentioned catalysts, they are distinguished by a significantly smaller smell, as well as by a completely higher activity. This is clearly conditioned by the fact that the catalyst is brought into a compatible form by reaction with the polyisocyanate, so that the polymerization reaction proceeds more smoothly. Strongly hydrophilic and incompatible catalysts must be used to achieve optimal activity together with emulsifiers or similar active agents.
De fra teknikkens stand kjente hydroksylgruppeholdige Mannichbaser av aminoalkoholer viser praktisk talt ingen aktivitet med hensyn til polymerisasjonsreaksjonen av NCO-gruppen, for hertil The hydroxyl group-containing Mannich bases of amino alcohols known from the state of the art show practically no activity with regard to the polymerization reaction of the NCO group, for
er det nødvendig med medanvendelsen av sekundære aminer som.fortrinnsvis dimetylamin. Spesielt virksomme katalysatorer fåes når de an-' vendte fenoler med minst to frie o- og/eller p-stillinger londenseres med omtrent like mengder av dimetylamin og en aminoalkohol, idet det til økning av katalysatorens begynnelsesforenlighet i polyisocyanatene er av spesiell betydning ekstra høyere alkyl-, cykloalkyl- eller aralkylrester. is the co-use of secondary amines such as preferably dimethylamine necessary. Particularly effective catalysts are obtained when the phenols used with at least two free o- and/or p-positions are condensed with approximately equal amounts of dimethylamine and an amino alcohol, since to increase the initial compatibility of the catalyst in the polyisocyanates extra higher alkyl is of particular importance -, cycloalkyl or aralkyl residues.
Oppfinnelsen vedrører en fremgangsmåte til fremstilling av isocyanuratgruppeholdig plast, spesielt skumplast, ved polymeri-sas jon av forbindelser med mer enn en isocyanatgruppe i molekylet i nærvær av Mannichbaser fremstilt av sekundære aminer, formaldehyd og fenoler, og eventuelt drivmidler, underskuddsmengder av forbindelser med aktive hydrogenatomer og stabilisatorer, idet fremgangsmåten er karakterisert ved at man som Mannichbaser anvender innbygningsdyktige en- eller flerkjernede Mannichbaser, som i tillegg til den på fenolen substituerte aminometylgruppe og den fenoliske OH-gruppe minst inneholder en -0H, -SH, -COOH, -CONH2~, -NHg- eller -NHR-gruppe, hvor R The invention relates to a method for producing plastics containing isocyanurate groups, in particular foam plastics, by polymerization of compounds with more than one isocyanate group in the molecule in the presence of Mannich bases produced from secondary amines, formaldehyde and phenols, and possibly propellants, deficit amounts of compounds with active hydrogen atoms and stabilizers, as the method is characterized by the use as Mannich bases of mononuclear or polynuclear Mannich bases, which in addition to the aminomethyl group substituted on the phenol and the phenolic OH group contain at least one -OH, -SH, -COOH, -CONH2~ , -NHg or -NHR group, where R
er alkyl, cykloalkyl, aryl eller aralkyl. is alkyl, cycloalkyl, aryl or aralkyl.
Som polyisocyanater kommer det på tale alifatiske og fortrinnsvis aromatiske flerverdige isocyanater, f.eks. alkylen-diisocyanater som tetra- og heksametylendiisocyanat, arylendiiso-cyanater og deres alkyleringsprodukter som fenylendiisocyanatene, naftylendiisocyanatene, difenylmetandiisocyanatene, toluylendiiso-cyanatene, di- og triisopropylbenzendiisocyanatene og trifenylmetan-triisocyanatene, p-isocyanatofenyl-tiofosforsyre-triestere, aralkyl-diisocyanater som l-(isocyanatofenyl)-etylisocyanat eller xylylen-diisocyanatene samt også de ved de forskjelligste substituenter som., alkoksy, nitro, klor eller brom substituerte polyisocyanater, videre med underskuddsmengder av polyhydroksylforbindelser som trimetylol-propan, heksantriol, glycerol, butandiol modifiserte polyisocyanater. Polyisocyanates include aliphatic and preferably aromatic multivalent isocyanates, e.g. alkylene diisocyanates such as tetra- and hexamethylene diisocyanate, arylene diisocyanates and their alkylation products such as the phenylene diisocyanates, the naphthylene diisocyanates, the diphenylmethane diisocyanates, the toluylene diisocyanates, the di- and triisopropylbenzene diisocyanates and the triphenylmethane triisocyanates, p-isocyanatophenylthiophosphoric acid triesters, aralkyl diisocyanates such as l-( isocyanatophenyl)-ethyl isocyanate or the xylylene diisocyanates as well as the polyisocyanates substituted by a wide variety of substituents such as, alkoxy, nitro, chlorine or bromine, further with deficit amounts of polyhydroxyl compounds such as trimethylol-propane, hexanetriol, glycerol, butanediol modified polyisocyanates.
Som foretrukket polyisocyanat skal det nevnes det ved anilin-formaldehyd-kondensasjon og etterfølgende fosgenering fremstillbare polyisocyanat. Videre skal det nevnes acetalmodifiserte isocyanater, polymeriserte isocyanater med isocyanuratringer, samt høyeremolekylære polyisocyanater som er fremstillbare ved omsetning av monomere polyisocyanater med høyeremolekylære forbindelser med reaksjonsdyktige hydrogenatomer, fortrinnsvis høyeremolekylære poly-hydroksylf orbindelser , polykarboksyl- og polyaminoforbindelser. Det kan selvsagt også anvendes blandinger av forskjellige isocyanater, idet det i dette tilfelle også kan medanvendes monoisocyanater som fenylisocyanat og naftylisocyanat. Preferred polyisocyanate should be mentioned the polyisocyanate that can be produced by aniline-formaldehyde condensation and subsequent phosgenation. Mention must also be made of acetal-modified isocyanates, polymerized isocyanates with isocyanurate rings, as well as higher molecular weight polyisocyanates that can be produced by reacting monomeric polyisocyanates with higher molecular weight compounds with reactive hydrogen atoms, preferably higher molecular weight polyhydroxyl compounds, polycarboxyl and polyamino compounds. Mixtures of different isocyanates can of course also be used, as in this case monoisocyanates such as phenyl isocyanate and naphthyl isocyanate can also be used.
Isocyanatforbindelsenes polymerisasjonsreaksjon kan foretas i nærvær av forbindelser med aktive hydrogenatomer. Ved anvendelse av vann, som fortrinnsvis anvendes, kan det herved oppnås en eventuelt ekstra driveffekt, forøvrig anvender man vanligvis organiske forbindelser med flere aktive hydrogenatomer. Det kommer her-på tale enkeltvis eller i blanding foruten polyaminer eller aminoalkoholer, fortrinnsvis lavere- og høyeremolekylære hydroksylforbindelser eller deres blandinger, slik de ofte er kjent til fremstilling av poly-uretaner, såvel som de vanlige mono- og polyalkoholer som butanol, cykloheksanol, benzylalkohol, etylenglykol, propylenglykol, glycerol,-trimetylolpropan resp. deres addukter med alkylenoksyder som etylen-og/eller propylenoksyd. Som polyfunksjonelle startere kommer det hertil også på tale kondensasjonsprodukter av ovennevnte polyalkoholer med polykarboksylsyrer som adipin-, sebacin-, malein-,. ftal- eller tereftalsyre. Tallrike slike forbindelser er omtalt i "Polyurethanes, Chemistry and Technology", bind I og II, Saunders-Frisch, Ihter-science Publishers 1962 og 1964 og i Kunststoffhandbuch, bind VII, Vieweg-Hochtlen, Carl-Hanser-Verlag, Munchen 1966-. The polymerization reaction of the isocyanate compounds can be carried out in the presence of compounds with active hydrogen atoms. When water is used, which is preferably used, an additional driving effect can be achieved, otherwise organic compounds with several active hydrogen atoms are usually used. In addition to polyamines or amino alcohols, preferably lower and higher molecular hydroxyl compounds or their mixtures, as they are often known for the production of polyurethanes, as well as the usual mono- and polyalcohols such as butanol, cyclohexanol, benzyl alcohol, ethylene glycol, propylene glycol, glycerol, trimethylolpropane or their adducts with alkylene oxides such as ethylene and/or propylene oxide. Polyfunctional starters also include condensation products of the above-mentioned polyalcohols with polycarboxylic acids such as adipic, sebacin, maleic, phthalic or terephthalic acid. Numerous such compounds are discussed in "Polyurethanes, Chemistry and Technology", Volumes I and II, Saunders-Frisch, Ihter-science Publishers 1962 and 1964 and in Kunststoffhandbuch, Volume VII, Vieweg-Hochtlen, Carl-Hanser-Verlag, Munchen 1966- .
Ved fremgangsmåten kan det fåes homogene faste legemer, lakk, overtrekk, skum og cellelegemer. Fremstillingen av skumstoffer er foretrukket. Homogeneous solid bodies, varnishes, coatings, foams and cellular bodies can be obtained by the method. The production of foams is preferred.
En drivreaksjon for fremstilling av skumstoffer gjennom-føres ved anvendelse av vann eller av ekstra drivmiddel. Som drivmidler kan finne anvendelse ved siden av de forbindelser "som spalter seg under avspaltning av gasser, eksempelvis a<y> nitrogen, f.eks. azoforbindelser eller sulfonylazider, spesielt laverekokende hydro-karboner og deres halogeneringsprodukter, f.eks. halogenerte metaner eller etaner, klorfluormetaner, etylendiklorid, vinylidenklorid. A propellant reaction for the production of foams is carried out using water or an additional propellant. As propellants can be used alongside the compounds "which split during the evolution of gases, for example a<y> nitrogen, e.g. azo compounds or sulfonyl azides, especially lower-boiling hydrocarbons and their halogenation products, e.g. halogenated methane or ethanes, chlorofluoromethanes, ethylene dichloride, vinylidene chloride.
Som tilsetningsmiddel anvendes for å lette sammenbland-ings- og skumdannelsesreaksjonen de vanlige emulgatorer og skumsta-bilisatorer, f.eks. høyere alkyl- resp. arylsulfonsyrer og deres salter, svovelsyreestere av.ricinusolje eller ricinolsyre og deres salter,- olje- eller stearinsyresalter, basisk gruppeholdig silikon-olje, siloksan- og alkylenoksyd-delholdige blandingskondensasjons-produkter. The usual emulsifiers and foam stabilizers, e.g. higher alkyl resp. arylsulphonic acids and their salts, sulfuric acid esters of castor oil or ricinoleic acid and their salts, oleic or stearic acid salts, silicone oil containing basic groups, mixed condensation products containing siloxane and alkylene oxide parts.
Som katalysatorer anvendes generelt slike innbygningsdyktige en- eller flerkjernede Mannichbaser av sekundære aminer, formaldehyd og fenoler som i tillegg til den på fenolen substituerte aminometylgruppe og den fenoliske OH-gruppe dessuten inneholder minst en 0H-, -SH, -COOH, -CONH2, -NH2 eller -NHR-gruppe, hvor R er alkyl., cykloalkyl, aryl eller aralkyl. Disse inneholder i forhold til isocyanater reaksjonsdyktige hydrogenatomer. Catalysts are generally used such embedding-capable mononuclear or multinuclear Mannich bases of secondary amines, formaldehyde and phenols which, in addition to the aminomethyl group substituted on the phenol and the phenolic OH group, also contain at least one OH-, -SH, -COOH, -CONH2, - NH 2 or -NHR group, where R is alkyl., cycloalkyl, aryl or aralkyl. Compared to isocyanates, these contain reactive hydrogen atoms.
Som katalysatorer anvendes fortrinnsvis i henhold til oppfinnelsen f.eks. Mannichbaser av fenoler med minst to kondensa-sj onsdyktige o- og/eller p-stillinger, formaldehyd og blandinger av dimetylamin og sekundære' aminoalkoholer. Catalysts are preferably used according to the invention, e.g. Mannich bases of phenols with at least two condensable o- and/or p-positions, formaldehyde and mixtures of dimethylamine and secondary amino alcohols.
'Som eksempler på katalysatorer som kan anvendes ifølge oppfinnelsen skal det angis følgende: As examples of catalysts that can be used according to the invention, the following shall be stated:
Som fenoler kommer det for fremstilling av katalysatorene på tale: fenol, kresoler, xylenoler, isooktyl-,. isononyl-, isododecyl- og cykloheksylfenoler med substituentene i o-, fortrinnsvis p-stilling, de ved omsetning av fenpl med styren dannede fenetyl-fenoler, videre polyfenoler som hydrochinon, 4,4'-dihydroksy-difenyl-metan, salicylsyre resp. dens salter, hydroksyalkylester av salicylsyre, salicylsyreamid, saligenin-hydroksyalkyleter. The following phenols are used for the production of the catalysts: phenol, cresols, xylenols, isooctyl-,. isononyl, isododecyl and cyclohexylphenols with the substituents in the o-, preferably p-position, the phenethylphenols formed by reacting phenpl with styrene, further polyphenols such as hydroquinone, 4,4'-dihydroxy-diphenyl-methane, salicylic acid or its salts, hydroxyalkyl esters of salicylic acid, salicylic acid amide, saligenin hydroxyalkyl ether.
Som sekundære aminer kommer det spesielt på tale dial-kanolaminer som dietanol- eller dipropanolamin såvel som N-alkylalka-nolaminer som N-metyl-, N-etyl- eller N-butyletanolamin. Til kondensasjon med fenolene kommer også på tale aminokarboksylsyrer som alanin (eller dens salter) eller aminer som 1,3-propylendiamin, dietylentriamin eller aminotioler. Secondary amines include dialkanolamines such as diethanolamine or dipropanolamine as well as N-alkylalkanolamines such as N-methyl-, N-ethyl- or N-butylethanolamine. Condensation with the phenols also includes aminocarboxylic acids such as alanine (or its salts) or amines such as 1,3-propylenediamine, diethylenetriamine or aminothiols.
Mengdeforholdet mellom den sekundære aminoalkohol, The quantity ratio between the secondary amino alcohol,
resp. aminokarboksylsyre (eller dens salt), resp. polyamin, resp. aminotiol og dimetylamin innstiller man fortrinnsvis således at pr. molekyl innføres minst en katalytisk.virksom dimetylaminometylgruppe og minst en innbygningsdyktig gruppe med i forhold til isocyanater reaktive hydrogenatomer. Dette oppnår man ved monosubstituerte fenoler ved anvendelse av like molekylære mengder av dimetylamin og sekundær aminoalkohol resp. av aminokarboksylsyre (eller dens salt), resp. diamin, resp. aminotiol, mens man ved anvendelse eller med anvendelse av fenol skulle anvende 33-66 mol% dimetylamin. Katalysatorer med andre funksjonelle grupper, f.eks. avledet .av salicylsyreamid, fremstilles på analog måte ved Mannichreaksjon med formaldehyd og det sekundære amin, spesielt dimetylamin.. respectively aminocarboxylic acid (or its salt), resp. polyamine, resp. aminothiol and dimethylamine is preferably set so that per molecule, at least one catalytically active dimethylaminomethyl group and at least one incorporation-capable group with hydrogen atoms reactive in relation to isocyanates are introduced. This is achieved with monosubstituted phenols by using equal molecular amounts of dimethylamine and secondary amino alcohol or of aminocarboxylic acid (or its salt), resp. diamine, resp. aminothiol, while when using or with the use of phenol, 33-66 mol% dimethylamine should be used. Catalysts with other functional groups, e.g. derived from salicylic acid amide, is prepared in an analogous way by the Mannich reaction with formaldehyde and the secondary amine, especially dimethylamine..
De for fremstilling av katalysatoren anvendte fenol- The phenols used for the production of the catalyst
og andre komponenter kan selvsagt hver gang anvendes i form av deres blandinger, idet for blandinger av monosubstituerte fenoler og usub-stituert fenol skal det på samme måte anvendes ovennevnte mengdefor-hold. Mengden av formaldehyd bestemmes ved de kondensasjonsdyktige grupperinger i det anvendte fenol. Hvis formaldehydmengden tilsvarer aminmengden fåes enkje.rnede Mannichbaser, mens ved høyere formalde-hydmengder kan det fremstilles ved tilsvarende reduksjon av aminmengden også 'flerkjernede katalysatorer. Eksempelvis oppstår av to mol p-isononylfenol, et mol dimetylamin og 1 mol dietanolamin med tre mol formaldehyd et statistisk tokjernet oppbygget kondensasjonsprodukt. and other components can of course be used each time in the form of their mixtures, since for mixtures of monosubstituted phenols and unsubstituted phenol the above-mentioned ratio of quantities must be used in the same way. The amount of formaldehyde is determined by the condensable groups in the phenol used. If the amount of formaldehyde corresponds to the amount of amine, mononuclear Mannich bases are obtained, while with higher amounts of formaldehyde, polynuclear catalysts can also be produced by correspondingly reducing the amount of amine. For example, two moles of p-isononylphenol, one mole of dimethylamine and 1 mole of diethanolamine with three moles of formaldehyde give rise to a statistically dinuclear condensation product.
Kondensasjonen av fenol, sekundært amin og formaldehyd foregår f.eks. etter den lære som fremgår av US-patenter nr. 2.033.092 og 2.220.834. The condensation of phenol, secondary amine and formaldehyde takes place e.g. according to the teachings of US Patent Nos. 2,033,092 and 2,220,834.
Ved:siden av katalysatorene som skal anvendes ifølge oppfinnelsen kan det også medanvendes de vanlige i isocyanat-kjemien kjente katalysatorer, f.eks. organiske metallforbindelser som Pb-eller Sn-salter, uorganiske og organiske flerbasiske metallsalter såvel som tertiære aminer som dimetylbenzylamin eller endoetylen-piperazin. Ytterligere enkeltheter over emulgatorer, katalysatorer etc. kan finnes f.eks. i "Polyurethanes, Chemistry and Technology", bind I og II, Saunders-Prisch, Interscience Publishers, 1962 og 1964. In addition to the catalysts to be used according to the invention, the usual catalysts known in isocyanate chemistry can also be used, e.g. organic metal compounds such as Pb or Sn salts, inorganic and organic polybasic metal salts as well as tertiary amines such as dimethylbenzylamine or endoethylene piperazine. Further details on emulsifiers, catalysts etc. can be found e.g. in "Polyurethanes, Chemistry and Technology", Volumes I and II, Saunders-Prisch, Interscience Publishers, 1962 and 1964.
Fremstillingen av skumstoffer foregår på den vanlige og generelt kjente måte, fortrinnsvis på maskinell måte, ved reak-sjonskomponentenes sammenblanding og uthelling i en tilsvarende form-innretning. Drivmiddelmengdene bestemmes herved ved den ønskede volumvekt. Man bringer vanligvis til anvendelse mellom 1 og 100, fortrinnsvis mellom 5 og 50 vektdeler av et fluorklormetan eller en tilsvarende mengde av et annet drivmiddel, referert til isocyanatkomponentene. Vanligvis tilstrebes volumvekter mellom 15 og 200 eller også høyere, fortrinnsvis mellom 20 og 200 kg/m^. The production of foam substances takes place in the usual and generally known way, preferably in a mechanical way, by mixing the reaction components and pouring them into a corresponding molding device. The propellant quantities are determined by the desired volume weight. Between 1 and 100, preferably between 5 and 50 parts by weight of a fluorochloromethane or a corresponding amount of another propellant, referred to the isocyanate components, are usually used. Volume weights between 15 and 200 or even higher, preferably between 20 and 200 kg/m^, are usually aimed for.
Mengden av forbindelser med reaktive hydrogenatomer innstiller man vanligvis således at det dessuten står til disposisjon en tilstrekkelig mengde av frie isocyanat-grupper for polymerisasjonsreaksjonen. Fortrinnsvis dimensjonerer man imidlertid mengdene således å minst 50%, fortrinnsvis over 70%, av den tilsammen anvendte isocyanatmengde står til disposisjon for polymerisasjonsreaksjonen. Katalysatormengden bestemmes i det vesentlige ved dens oppbygning, idet det ikke mer inntrer noen relasjon mellom nitrogenmengden og dens aktivitet. Et visst mål angir den i det følgende omtalte aktivitets-prøve. Vanligvis kan man anvende mellom 0,5 og 15 vekt% av kataly-satorkomponenter, referert til isocyanatkomponentene. The amount of compounds with reactive hydrogen atoms is usually set so that there is also a sufficient amount of free isocyanate groups available for the polymerization reaction. Preferably, however, the quantities are sized so that at least 50%, preferably more than 70%, of the total amount of isocyanate used is available for the polymerization reaction. The amount of catalyst is essentially determined by its structure, as there is no longer any relationship between the amount of nitrogen and its activity. The activity test mentioned below sets a certain goal. Generally, one can use between 0.5 and 15% by weight of catalyst components, referred to the isocyanate components.
I tillegg til de ved plastfremstillingen anvendte komponenter kan det tilblandes de vanlige hjelpemidler som pigmenter, fargestoffer, mykningsmidler, flammebeskyttelsesmidler som antimon-, fosfor- eller halogenforbindelser. In addition to the components used in plastic production, the usual auxiliaries such as pigments, dyes, softeners, flame retardants such as antimony, phosphorus or halogen compounds can be mixed.
På samme måte foregår fremstillingen av lakker og faste stoffer etter prinsippielt kjente metoder. Lakkene påføres under med-anvendelse av oppløsningsmidler, eventuelt etter tilsetning av vanlige lakkhjelpemidler og pigmenter på de forskjelligste substrater som tre, glass, metall eller papir. Kondensasjonen kan også føres til av-slutning ved forhøyet temperatur. Faste stoffer fremstilles ved inn-helling av den med katalysatoren blandede polyisocyanat(blanding) i former, eventuelt under avkjøling eller etteroppvarmning. In the same way, the production of varnishes and solids takes place according to known methods in principle. The varnishes are applied with the use of solvents, possibly after the addition of common varnish auxiliaries and pigments on a wide variety of substrates such as wood, glass, metal or paper. Condensation can also be brought to completion at an elevated temperature. Solid substances are produced by pouring the polyisocyanate (mixture) mixed with the catalyst into molds, possibly during cooling or post-heating.
En IR-spektroskopisk undersøkelse av de oppnådde plaster, lakker, overtrekk og skumstoffer viser høye mengder av isocyanuratringer ved siden av mindre mengder av karbodiimidgrupper. • An IR spectroscopic examination of the obtained plasters, varnishes, coatings and foams shows high amounts of isocyanurate rings next to smaller amounts of carbodiimide groups. •
A) Aktivitetsbestemmelse: A) Activity determination:
25 vektdeler toluylen-2,4-diisocyanat bringes til 25 parts by weight of toluylene-2,4-diisocyanate are added
20°C og blandes deretter under rysting med 0,1 ml av en (vanligvis flytende) katalysator. Man ryster ennå i 5 sekunder og bestemmer deretter temperaturen i avhengighet av tiden. Som karakteristiske størrelser tas den tid ifølge hvilken blandingen har nådd en temperatur fra 50 og 75°C. I denne aktivitetsprøve bringer 2,4,6-trisdi-metylaminometylfenol en verdi på 50°C'etter 175 sekunder og 75°C étter 200 sekunder. 20°C and then mixed with shaking with 0.1 ml of a (usually liquid) catalyst. One still shakes for 5 seconds and then determines the temperature as a function of time. The time according to which the mixture has reached a temperature of 50 and 75°C is taken as characteristic values. In this activity test, 2,4,6-trisdimethylaminomethylphenol brings a value of 50°C after 175 seconds and 75°C after 200 seconds.
B) Fremstilling av katalysatoren som skal anvendes: B) Preparation of the catalyst to be used:
Generell arbeidsforskrift: Fenolet med dimetylamin-mengden, sistnevnte i form av en 25#-ig vandig oppløsning og alkanol-aminmengden has sammen ved ca. 25°C og deretter tildryppes i løpet av 30 min. den nødvendige formaldehydmengde, vanligvis i form av den 40$-ige vandige oppløsning. Man oppvarmer ennå ca. 1 time ved 30°C og øker deretter temperaturen i løpet av ytterligere 2 timer til 80°C. Etter 2 timer ved 80°C skiller man ved tilsetning av kokesalt organisk og vandig fase og inndamper den organiske fase ved 70°C7 12 torr, eventuelt må den organiske fase etter inndampning ved fil-trering befris for uorganiske deler. Likeledes er det mulig å unnlate adskillelsen av den vandige fase ved kokesalttilsetning og å inndampe kombinasjonen direkte ved 70 - 80°C/12 torr. General work instructions: The phenol with the amount of dimethylamine, the latter in the form of a 25% aqueous solution, and the alkanol-amine amount are combined at approx. 25°C and then added drop by drop over the course of 30 min. the required amount of formaldehyde, usually in the form of the 40% aqueous solution. It is still heated approx. 1 hour at 30°C and then increase the temperature during a further 2 hours to 80°C. After 2 hours at 80°C, the organic and aqueous phases are separated by adding common salt and the organic phase is evaporated at 70°C7 12 torr, if necessary the organic phase after evaporation must be freed of inorganic parts by filtration. Likewise, it is possible to omit the separation of the aqueous phase by adding common salt and to evaporate the combination directly at 70 - 80°C/12 torr.
Enkeltheter over de anvendte mengder, utbytter...og egenskaper av reaksjonsproduktene fremgår av følgende tabell: Details of the quantities used, yields... and properties of the reaction products appear in the following table:
Eksempel 1- 4. Example 1-4.
Generelle arbeidsforskrifter. General work regulations.
100 vektdeler ved hjelp av anilin-formaldehydkondensa-sjon og etterfølgende fosgenering dannet polyaryl-polymetylen-polyisocyanat settes til en blanding av 6,0 vektdeler katalysator, 15j0 vektdeler monofluortriklormetan og 1,0 vektdeler av et poly-siloksan-polyeter-kopolymerisat, blandes godt med en elektrisk drevet rører og helles i forberedte pakkpapirfårmer. 100 parts by weight of polyaryl-polymethylene-polyisocyanate formed by aniline-formaldehyde condensation and subsequent phosgenation are added to a mixture of 6.0 parts by weight of catalyst, 15j0 parts by weight of monofluorotrichloromethane and 1.0 parts by weight of a poly-siloxane-polyether copolymer, mixed well with an electrically powered stirrer and poured into prepared wrapping paper forms.
I tabell 2 er det angitt reaksjonstider og egenskaper av de dannede polyisocyanurat-skumstoffer. Table 2 shows the reaction times and properties of the polyisocyanurate foams formed.
Eksempel 5~ 8. Example 5~8.
100,0 vektdeler ved hjelp av anilin-formaldehydkon-densasjon og etterfølgende fosgenering dannet polyaryl-polymetylen-polyisocyanat utrører man med en blanding av 6 vektdeler katalysator, 15 vektdeler monofluortriklormetan, 1 vektdel av et polysiloksan-polyeterkopolymerisat og 10 vektdeler av en sukrose/propylenoksyd-polyeter med OH-tall 380. Deretter fylles reaksjonsmassen i papir-former.. 100.0 parts by weight by means of aniline-formaldehyde condensation and subsequent phosgenation formed polyaryl-polymethylene-polyisocyanate is stirred with a mixture of 6 parts by weight of catalyst, 15 parts by weight of monofluorotrichloromethane, 1 part by weight of a polysiloxane-polyether copolymer and 10 parts by weight of a sucrose/propylene oxide -polyether with an OH number of 380. The reaction mass is then filled into paper forms.
De dannede skumstoffers reaksjonstider og egenskaper er angitt i tabell 3. The reaction times and properties of the foams formed are given in table 3.
Eksempel 9 . Example 9.
50 vektdeler av det i eksempel 1 omtalte isocyanat blandes med 1 vektdel av den ifølge B 2 dannede katalysator, utkoh-denseres i en lukket form under trykk til et homogent formlegeme (reaksjonen fullstendiggjøres ved 2 timers etteroppvarmning ved 80°C). Man får et praktisk talt ubrennbart plast med høy fasthet. 50 parts by weight of the isocyanate mentioned in example 1 are mixed with 1 part by weight of the catalyst formed according to B 2, condensed in a closed mold under pressure to a homogeneous molded body (the reaction is completed by 2 hours post-heating at 80°C). You get a practically non-flammable plastic with high strength.
Eksempel 10. Example 10.
25 vektdeler av det av 3 mol heksametylendiisocyanat 25 parts by weight of that of 3 moles of hexamethylene diisocyanate
og 1 mol vann dannede biuretdiisocyanat blandes etter oppløsning i and 1 mol of water formed biuret diisocyanate are mixed after dissolution in
25 vektdeler av en oppløsningsmiddelkombinasjon av like deler etyl-acetat, butylacetat og glykolmonometyleteracetat med 2 vektdeler av den ifølge B 3 dannede katalysator og påføres på glass, papir og vevnad. Etter etteroppvarmning ved 80°C (2 timer) føres reaksjonen til avslitning. Man får et praktisk talt ubrennbart overtrekk. 25 parts by weight of a solvent combination of equal parts ethyl acetate, butyl acetate and glycol monomethyl ether acetate with 2 parts by weight of the catalyst formed according to B 3 and applied to glass, paper and fabric. After reheating at 80°C (2 hours), the reaction is brought to wear. You get a practically non-combustible covering.
Claims (2)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19681720768 DE1720768A1 (en) | 1968-01-02 | 1968-01-02 | Isocyanate-based plastics and processes for their manufacture |
Publications (1)
Publication Number | Publication Date |
---|---|
NO127620B true NO127620B (en) | 1973-07-23 |
Family
ID=5689848
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
NO521868A NO127620B (en) | 1968-01-02 | 1968-12-28 |
Country Status (3)
Country | Link |
---|---|
AT (1) | AT286633B (en) |
DK (1) | DK130470B (en) |
NO (1) | NO127620B (en) |
-
1968
- 1968-12-20 DK DK629568A patent/DK130470B/en unknown
- 1968-12-28 NO NO521868A patent/NO127620B/no unknown
-
1969
- 1969-01-02 AT AT1269A patent/AT286633B/en not_active IP Right Cessation
Also Published As
Publication number | Publication date |
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DK130470C (en) | 1975-07-21 |
AT286633B (en) | 1970-12-10 |
DK130470B (en) | 1975-02-24 |
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