JPS584050B2 - Method for producing modified polyisocyanurate foam - Google Patents
Method for producing modified polyisocyanurate foamInfo
- Publication number
- JPS584050B2 JPS584050B2 JP55078542A JP7854280A JPS584050B2 JP S584050 B2 JPS584050 B2 JP S584050B2 JP 55078542 A JP55078542 A JP 55078542A JP 7854280 A JP7854280 A JP 7854280A JP S584050 B2 JPS584050 B2 JP S584050B2
- Authority
- JP
- Japan
- Prior art keywords
- nitrogen
- alkali metal
- polyether polyol
- polyisocyanurate foam
- carboxylic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000006260 foam Substances 0.000 title claims description 25
- 238000004519 manufacturing process Methods 0.000 title claims description 22
- 229920000582 polyisocyanurate Polymers 0.000 title claims description 18
- 239000011495 polyisocyanurate Substances 0.000 title claims description 18
- -1 nitrogen-containing carboxylic acid Chemical class 0.000 claims description 52
- 150000003077 polyols Chemical class 0.000 claims description 46
- 229920005862 polyol Polymers 0.000 claims description 45
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 38
- 229920000570 polyether Polymers 0.000 claims description 38
- 229910052783 alkali metal Inorganic materials 0.000 claims description 21
- 239000003607 modifier Substances 0.000 claims description 14
- 238000005829 trimerization reaction Methods 0.000 claims description 14
- 150000001340 alkali metals Chemical class 0.000 claims description 11
- 239000012948 isocyanate Substances 0.000 claims description 11
- 150000002513 isocyanates Chemical class 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 208000005156 Dehydration Diseases 0.000 claims description 3
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 229920001228 polyisocyanate Polymers 0.000 description 8
- 239000005056 polyisocyanate Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 125000002947 alkylene group Chemical group 0.000 description 5
- 150000008064 anhydrides Chemical class 0.000 description 5
- 238000005187 foaming Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000004604 Blowing Agent Substances 0.000 description 4
- 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 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 2
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229920005830 Polyurethane Foam Polymers 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 150000002483 hydrogen compounds Chemical class 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000011496 polyurethane foam Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 230000003381 solubilizing effect Effects 0.000 description 2
- 229940014800 succinic anhydride Drugs 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 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 2
- 229940029284 trichlorofluoromethane Drugs 0.000 description 2
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 1
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- SUVPVVDTHJRFJI-UHFFFAOYSA-N 4-amino-n-quinoxalin-2-ylbenzenesulfonamide;4-hydroxy-3-(3-oxo-1-phenylbutyl)chromen-2-one Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=CN=C(C=CC=C2)C2=N1.OC=1C2=CC=CC=C2OC(=O)C=1C(CC(=O)C)C1=CC=CC=C1 SUVPVVDTHJRFJI-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- HTJDQJBWANPRPF-UHFFFAOYSA-N Cyclopropylamine Chemical compound NC1CC1 HTJDQJBWANPRPF-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- BWLUMTFWVZZZND-UHFFFAOYSA-N Dibenzylamine Chemical compound C=1C=CC=CC=1CNCC1=CC=CC=C1 BWLUMTFWVZZZND-UHFFFAOYSA-N 0.000 description 1
- 239000004338 Dichlorodifluoromethane Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 1
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 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
- 229930006000 Sucrose Natural products 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000003974 aralkylamines Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- UCMIRNVEIXFBKS-UHFFFAOYSA-N beta-alanine Chemical class NCCC(O)=O UCMIRNVEIXFBKS-UHFFFAOYSA-N 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001734 carboxylic acid salts Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical compound FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- KZZKOVLJUKWSKX-UHFFFAOYSA-N cyclobutanamine Chemical compound NC1CCC1 KZZKOVLJUKWSKX-UHFFFAOYSA-N 0.000 description 1
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 1
- 229940043276 diisopropanolamine Drugs 0.000 description 1
- 150000004656 dimethylamines Chemical class 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000004668 long chain fatty acids Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- MCSAJNNLRCFZED-UHFFFAOYSA-N nitroethane Chemical compound CC[N+]([O-])=O MCSAJNNLRCFZED-UHFFFAOYSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Description
【発明の詳細な説明】
本発明は分子製造中にイソシアヌレート環を有する耐熱
、耐炎性硬質発泡体の新規製造方法に関するものである
。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing heat-resistant, flame-resistant rigid foams having isocyanurate rings during molecular production.
更に詳しくは、イソシアネート三量化触媒活性を具備し
た変性剤の簡便、かつ安価な製造方法と該変性剤を用い
た変性ポリイソシアヌレートフォームの製造方法に関す
るものである。More specifically, the present invention relates to a simple and inexpensive method for producing a modifier having isocyanate trimerization catalytic activity and a method for producing a modified polyisocyanurate foam using the modifier.
変性ポリイソシアヌレートフォームの製造において、そ
の製造工程およびフォームの性能を支配する重要な要素
として、変性剤とイソシアネート三量化触媒の選択の問
題がある。In the production of modified polyisocyanurate foams, the selection of modifiers and isocyanate trimerization catalysts are important factors that govern the production process and the performance of the foams.
従来より、イソシアネート三量化触媒の存在下に、ポリ
イソシアネートとポリオール(例えばポリエーテルやポ
リエステル等)とを反応させて、ウレタン変性ポリイソ
シアヌレートフォームを製造する方法はよく知られてい
る。BACKGROUND ART Conventionally, a method for producing a urethane-modified polyisocyanurate foam by reacting a polyisocyanate and a polyol (eg, polyether, polyester, etc.) in the presence of an isocyanate trimerization catalyst is well known.
(例えば特公昭46−2269、特公昭46−4238
6、特公昭47−28919等)また、インシアネート
三量化触媒についても各種知られている。(For example, Special Publication No. 46-2269, Special Publication No. 46-4238
6, Japanese Patent Publication No. 47-28919, etc.) Various incyanate trimerization catalysts are also known.
(例えば、特公昭35−2799、特公昭40−583
8、特公昭44−16669、特公昭46−13257
、特公昭46−15298、特公昭46−25017、
特公昭46−31531.特公昭46−33577、特
公昭46−37503、特公昭46−41393、特公
昭46−41610、特公昭47−36038、特公昭
4 8−3 5 7 2 0 、特開昭47−2949
1、特開昭48−49898、特開昭48−81996
等)これらの触媒の中で価格、触媒活性、臭気等の観点
からよく用いられるものに、カルボン酸塩類があるが、
これらは固体であるために使用に際しては液状化する必
要がある。(For example, Special Publication No. 35-2799, Special Publication No. 40-583
8, Special Publication No. 44-16669, Special Publication No. 46-13257
, Special Publication No. 46-15298, Special Publication No. 46-25017,
Special Publication Showa 46-31531. Special Publication No. 46-33577, Special Publication No. 46-37503, Special Publication No. 46-41393, Special Publication No. 46-41610, Special Publication No. 47-36038, Special Publication No. 48-35720, No. 47-2949
1. Japanese Patent Publication No. 48-49898, Japanese Patent Application Publication No. 48-81996
etc.) Among these catalysts, carboxylic acid salts are commonly used from the viewpoint of price, catalytic activity, odor, etc.
Since these are solids, they must be liquefied before use.
さらに変性ポリイソシアヌレートフォームの製造は、通
常、二分系として取り扱われるため、イソシアネート三
量化触媒は、変性剤、界面活性剤および発泡剤等と予め
混合され、均一な溶液とならなければいけない。Furthermore, since the production of modified polyisocyanurate foam is usually handled as a bipartite system, the isocyanate trimerization catalyst must be mixed with a modifier, a surfactant, a blowing agent, etc. in advance to form a homogeneous solution.
ところが、塩類は一般にポリオールには溶解し難く、発
泡剤(例えば、トリクロロプノレオロメタン等)には、
更に溶け難くほとんど溶解しない。However, salts are generally difficult to dissolve in polyols, and blowing agents (for example, trichloropunoleolomethane, etc.)
Furthermore, it is difficult to dissolve and hardly dissolves.
そこで、こうした問題点を改良する方法として、例えば
高分子量ポリオールと低分子グリコール類からなる混合
物中で長鎖脂肪酸と水酸化カリウムとを加熱化で反応せ
しめ、副生する水を減圧下で系外に留出せしめる方法(
特開昭48−39390)、酢酸カリウムを特定のポリ
オールによって可溶化する方法(特開昭48−8199
6)、β−アラニン誘導体のアルカリ金属塩を用いてポ
リオールに対する相溶性を高める方法(特開昭50−4
198)および粗性ポリオールを弱酸で中和して効率的
に可溶化する方法(特開昭51−6299)等が提案さ
れている。Therefore, as a method to improve these problems, for example, long-chain fatty acids and potassium hydroxide are reacted by heating in a mixture consisting of high-molecular-weight polyols and low-molecular-weight glycols, and the by-product water is removed from the system under reduced pressure. How to make it distillate (
JP-A-48-39390), a method for solubilizing potassium acetate with a specific polyol (JP-A-48-8199)
6), A method for increasing the compatibility with polyols using an alkali metal salt of a β-alanine derivative (Japanese Unexamined Patent Publication No. 50-4
198) and a method for efficiently solubilizing crude polyol by neutralizing it with a weak acid (Japanese Patent Application Laid-Open No. 51-6299).
しかし、これらの方法では製造工程が複雑化したり、使
用できるポリオール構造に制限を受けたり(したがって
、フォームの性能に制限を受ける)、触媒濃度の制限を
受ける等の不都合を避け得ない。However, these methods cannot avoid disadvantages such as complicating the manufacturing process, limiting the polyol structure that can be used (thereby limiting the performance of the foam), and limiting the catalyst concentration.
本発明者等は、上記したごとき欠点を改良するため鋭意
研究を重ねた結果、本発明を提供するに至ったものであ
る。The present inventors have conducted intensive research to improve the above-mentioned drawbacks, and as a result, they have provided the present invention.
すなわち、変性ポリイソシアヌレートフォームを製造す
る方法において、分子内にアミン性活性水素を1個以上
有する有機アミン化合物とジカルボン酸無水物とを反応
させて得られる含窒素カルボン酸を、末端水酸基の活性
水素の一部がアルカリ金属で置換されたポリエーテルポ
リオールで処理し、得られる含窒素カルボン酸アルカリ
金属塩とポリエーテルポリオールとの混合溶液を、イン
シアネート三量化触媒活性を具備した変性剤として使用
することを特徴とする変性ポリイソシアヌレートフォー
ムの製造方法、および変性ポリイソシアヌレートフォー
ムを製造する方法において、分子内にアミン性活性水素
を1個以上有する有機アミン化合物とジカルボン酸無水
物とを反応させて得られる含窒素カルボン酸を、末端水
酸基の活性水素の一部がアルカリ金属で置換されたポリ
エーテルポリオールとアルカリ金属水酸化物で処理し、
得られる含窒素カルボン酸アルカリ金属塩とポリエーテ
ルポリオールと水七の混合溶液をそのままで、または脱
水処理したのちインシアネート三量化触媒活性を具備し
た変性剤として使用することを特徴とする変性ポリイソ
シアヌレートフォームの製造方法である。That is, in a method for producing a modified polyisocyanurate foam, a nitrogen-containing carboxylic acid obtained by reacting an organic amine compound having one or more aminic active hydrogens in the molecule with a dicarboxylic acid anhydride is reacted with the activity of the terminal hydroxyl group. A mixed solution of a nitrogen-containing alkali metal carboxylic acid salt and a polyether polyol obtained by treatment with a polyether polyol in which a portion of hydrogen has been replaced with an alkali metal is used as a modifier with incyanate trimerization catalytic activity. A method for producing a modified polyisocyanurate foam, and a method for producing a modified polyisocyanurate foam, characterized in that an organic amine compound having one or more aminic active hydrogens in the molecule and a dicarboxylic acid anhydride are reacted. The nitrogen-containing carboxylic acid obtained is treated with a polyether polyol in which a portion of the active hydrogen of the terminal hydroxyl group has been replaced with an alkali metal and an alkali metal hydroxide,
A modified polyisocyanate characterized in that the resulting mixed solution of an alkali metal salt of a nitrogen-containing carboxylic acid, a polyether polyol, and water is used as it is or after dehydration treatment as a modifier having incyanate trimerization catalytic activity. This is a method for producing nurate foam.
本発明において用いられる分子内にアミン性活性水素を
1個以上有する有機アミン化合物(以下有機アミン化合
物という)としては、例えばメチンルアミン、エチルア
ミン、プロビルアミン、ブチルアミン等の脂肪族1級ア
ミン類、ジメチルアミン、ジエチルアミン、ジプロピル
アミン、ジブチルアミン等の脂肪族2級アミン、シクロ
プロピルアミン、シクロプチルアミン、シクロへキシル
アミン等の脂環族アミン類、アニリン、アミントルエン
、ナフチルアミン等の芳香族アミン類、ペンジルアミン
、ジベンジルアミン等のアラルキルアミン類、モルホリ
ン、ピロリジン ピペコリン等の複素環族アミン類、モ
ノエタノールアミン、ジエタノールアミン、モノイソプ
ロパノールアミン、ジイソプロパノールアミン等のアル
カノールアミン類、エチレンジアミン、プロピレンジア
ミン、プチレンジアミン、ヘキサメチレンジアミン、ジ
エチレントリアミン、トリエチレンテトラミン、ピペラ
ジン、N−アミノエチルピペラジン、フエニレンジアミ
ン、トルエンジアミン、シフエニルメタンジアミン等の
各種ポリアミン類および上記アミン類のアルキレンオキ
サイド付加物(ただし、アルキレンオキサイド付加量は
、分子内にアミン性活性水素1個以上存在する範囲内)
等が挙げられ、単独もしくは2種以上併用しても構わな
い。Examples of organic amine compounds having one or more aminic active hydrogens in the molecule (hereinafter referred to as organic amine compounds) used in the present invention include aliphatic primary amines such as methylinamine, ethylamine, probylamine, butylamine, dimethyl amines, aliphatic secondary amines such as diethylamine, dipropylamine, and dibutylamine; alicyclic amines such as cyclopropylamine, cyclobutylamine, and cyclohexylamine; aromatic amines such as aniline, amine toluene, and naphthylamine; Aralkylamines such as penzylamine and dibenzylamine, morpholine, pyrrolidine, heterocyclic amines such as pipecoline, alkanolamines such as monoethanolamine, diethanolamine, monoisopropanolamine, diisopropanolamine, ethylenediamine, propylene diamine, butylene diamine , hexamethylenediamine, diethylenetriamine, triethylenetetramine, piperazine, N-aminoethylpiperazine, phenylenediamine, toluenediamine, cyphenylmethanediamine, etc., and alkylene oxide adducts of the above amines (however, alkylene oxide adducts of the above amines) (The amount is within the range where one or more aminic active hydrogen atoms exist in the molecule)
etc., and may be used alone or in combination of two or more.
本発明において、使用されるジカルボン酸無水物として
は、例えば無水コハク酸、無水グルタル酸等の飽和脂肪
族ジカルボン酸無水物、無水フマル酸、無水マレイン酸
等の不飽和脂肪族ジカルボン酸無水物、無水フタル酸等
の芳香族ジカルボン酸無水物等が挙げられ単独もしくは
2種以上併用しても構わない。In the present invention, dicarboxylic acid anhydrides used include, for example, saturated aliphatic dicarboxylic anhydrides such as succinic anhydride and glutaric anhydride; unsaturated aliphatic dicarboxylic acid anhydrides such as fumaric anhydride and maleic anhydride; Aromatic dicarboxylic acid anhydrides such as phthalic anhydride may be used alone or in combination of two or more.
本発明において、有機アミン化合物とジカルボン酸無水
物とを反応させて得られる含窒素カルボン酸をカルボン
酸成分として用いる理由は次のとおりである。In the present invention, the reason why a nitrogen-containing carboxylic acid obtained by reacting an organic amine compound and a dicarboxylic anhydride is used as a carboxylic acid component is as follows.
有機アミン化合物のアミン性活性水素とカルボン酸無水
物との反応は、他の活性水素化合物、例えば水酸基の活
性水素との反応などと比較して、非常に反応が容易であ
り、かつ有機アアミン化合物の選択により種々のカルボ
ン酸が容易に得られること、および得られる含窒素カル
ボン酸アルカリ金属塩はアマイド性またはアミン性の窒
素原子の作用により、ポリエーテルポリオールおよび発
泡剤への相溶性が著しく増大することである。The reaction between the aminic active hydrogen of an organic amine compound and a carboxylic acid anhydride is very easy compared to the reaction of other active hydrogen compounds, such as the reaction of a hydroxyl group with active hydrogen, and Various carboxylic acids can be easily obtained by selecting , and the resulting alkali metal salts of nitrogen-containing carboxylic acids have significantly increased compatibility with polyether polyols and blowing agents due to the action of amide or amine nitrogen atoms. It is to be.
また、カルボン酸無水物としてジカルボン酸無水物を用
いる理由は、モノカルボン酸の無水物を用いるとアミン
化合物との反応時、モノカルボン酸自体が−同モル副生
ずるが、含窒素カルボン酸は得られず、ピロメリット酸
のような二無水物を用いるとアミン化合物の種類によっ
ては高分子化してしまうので本発明の目的に合致しない
からである。Furthermore, the reason for using dicarboxylic anhydride as the carboxylic anhydride is that when monocarboxylic acid anhydride is used, the same mole of monocarboxylic acid itself is produced as a by-product during the reaction with the amine compound, but nitrogen-containing carboxylic acid is not produced. This is because, if a dianhydride such as pyromellitic acid is used, the amine compound may become polymerized depending on the type of the amine compound, which does not meet the purpose of the present invention.
次に、本発明において用いられる末端水酸基の活性水素
の一部がアルカリ金属で置換されたポリエーテルポリオ
ールとしては、例えば少なくとも2個以上の活性水素有
する有機化合物(以下開始剤という)に触媒としてアル
カリ金属水酸化物を添加し、加熱減圧処理したのちアル
キレンオキサイドを付加重合することによって得られる
触媒を含有するポリエーテルポリオール(以下粗製ポリ
エーテルポリオールという)、粗製ポリエーテルポリオ
ールにさらにアルカリ金属水酸化物を追加添加したのち
、加熱減圧処理して得られるポリエーテルポリオール、
粗製ポリエーテルポリオールより触媒を精製処理して除
去したポリエーテルポリオール(以下精製ポリエーテル
ポリオールという)にアルカリ金属水酸化物を添加後、
加熱減圧処理して得られるポリエーテルポリオールおよ
びそれらの混合物が挙げられるが、最も好適なのは粗製
ポリエーテルポリオールである。Next, for the polyether polyol in which a part of the active hydrogen of the terminal hydroxyl group is substituted with an alkali metal used in the present invention, for example, an organic compound having at least two or more active hydrogens (hereinafter referred to as an initiator) is added with an alkali as a catalyst. A polyether polyol containing a catalyst (hereinafter referred to as crude polyether polyol) obtained by adding a metal hydroxide, heating and depressurizing it, and then addition-polymerizing an alkylene oxide; Polyether polyol obtained by heating and reducing pressure after additional addition of
After adding an alkali metal hydroxide to the polyether polyol (hereinafter referred to as purified polyether polyol) from which the catalyst has been purified and removed from the crude polyether polyol,
Examples include polyether polyols obtained by heat-reduction treatment and mixtures thereof, but crude polyether polyols are most preferred.
ポリエーテルポリオールの開始剤としては、例えばエチ
レシグリコール、プロピレングリコール、グリセリン、
トリメチロールプロパン、ペンタエリスリトール、ソル
ビトール、シュークローズ等の低分子多価アルコール、
モノエタノールアミン、ジエタノールナミン、トリエタ
ノールアミン等のアルカノールアミン、エチレンジアミ
ン、ジエチレントリアミン、トリエチレンテトラアミン
等の脂肪族ポリアミン、トリレンジアミン、4,4′一
ジフエニルメタンジアミン、フエニレンジアミン等の芳
香族ポリアミン、ビスフェノールA1 ノボラツク樹脂
等の芳香族多価アルコール等が挙げられる。Examples of initiators for polyether polyols include ethylene glycol, propylene glycol, glycerin,
Low-molecular polyhydric alcohols such as trimethylolpropane, pentaerythritol, sorbitol, and sucrose;
Alkanolamines such as monoethanolamine, diethanolanamine, and triethanolamine; aliphatic polyamines such as ethylenediamine, diethylenetriamine, and triethylenetetraamine; aromatic compounds such as tolylenediamine, 4,4'-diphenylmethanediamine, and phenylenediamine; Examples include aromatic polyhydric alcohols such as polyamines, bisphenol A1, and novolac resins.
アルキレンオキサイドとしては、例えばエチレンオキサ
イド・プロピレンオキサイド・プチレンオキサイド等が
挙げられ、これらの単独もしくは2種以上を開始剤にラ
ンダムもしくはブロックコポリマーの形で付加重合させ
る。Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, etc., and one or more of these are added to an initiator in the form of a random or block copolymer.
本発明の末端水酸基の活性水素の一部がアルカリ金属で
置換されたポリエーテルポリオールは、通常水酸基価が
25〜1000、好ましくは100〜600である。The polyether polyol of the present invention in which a part of the active hydrogen of the terminal hydroxyl group is substituted with an alkali metal usually has a hydroxyl value of 25 to 1000, preferably 100 to 600.
また、アルカリ金属水酸化物としてはリチウム、ナトリ
ウム、カリウム等の水酸化物が挙げられる。Furthermore, examples of the alkali metal hydroxides include hydroxides of lithium, sodium, potassium, and the like.
含窒素カルボン酸へのアルカリ金属供給源として、末端
水酸基の活性水素の一部がアルカリ金属で置換されたポ
リエーテルポリオールを用いる理由は次のとおりである
。The reason for using a polyether polyol in which a part of the active hydrogen of the terminal hydroxyl group is substituted with an alkali metal as the alkali metal supply source to the nitrogen-containing carboxylic acid is as follows.
ポリエーテルポリオールの一般的な製造方法は上記粗製
ポリエーテルポリオールより触媒を精製処理して除去す
る方法であり、末端水酸基の活性水素の一部がアルカリ
金属で置換されたポリエーテルポリオールとして粗製ポ
リエーテルポリオールが好適に使用できることである。A general method for producing polyether polyol is to purify and remove the catalyst from the above-mentioned crude polyether polyol, and the crude polyether polyol is produced as a polyether polyol in which a portion of the active hydrogen of the terminal hydroxyl group has been replaced with an alkali metal. Polyol can be suitably used.
この粗製ポリエーテルポリオールと含窒素カルボン酸と
よりイソシアネート三量化触媒活性を具備した変性剤が
容易に得られることは、ポリエーテルポリオールの精製
工程を省略できる上に、従来、除去廃棄されてきたアル
キレンオキサイド重合触媒をイソシアネート三量化触媒
の必須成分として有効利用できるという一石二鳥の利点
がある。The fact that a modifier with isocyanate trimerization catalytic activity can be easily obtained from this crude polyether polyol and nitrogen-containing carboxylic acid means that the purification process of polyether polyol can be omitted, and alkylene, which has traditionally been removed and disposed of, can be easily obtained. This method has the advantage of killing two birds with one stone in that the oxide polymerization catalyst can be effectively used as an essential component of the isocyanate trimerization catalyst.
また、粗製ポリエーテルポリオール中に含まれるアルカ
リ金属の量では、不足な場合にはアルカリ金属水酸化物
もしくはアルカリ金属水酸化物の水溶液を必要量だけ追
加添加すればよい。Furthermore, if the amount of alkali metal contained in the crude polyether polyol is insufficient, a necessary amount of an alkali metal hydroxide or an aqueous solution of an alkali metal hydroxide may be added.
フォーム化に際し水分が存在しても構わない場合は、脱
水の必要はなく、そうでない場合は加熱減圧して水分を
除去すればよい。If it is acceptable for moisture to be present during foaming, there is no need for dehydration; otherwise, moisture may be removed by heating and reducing pressure.
本発明において用いられる有機アミン化合物とジカルボ
ン酸無水物との量的関係は、有機アミン化合物1モルに
対しジカルボン酸無水物1モル以上、かつ有機アミン化
合物中の1級および/または2級アミン1モルに対しジ
カルボン酸無水物1モル以下が好ましい。The quantitative relationship between the organic amine compound and the dicarboxylic anhydride used in the present invention is such that 1 mol or more of the dicarboxylic anhydride per 1 mol of the organic amine compound, and 1 mol or more of the primary and/or secondary amine in the organic amine compound. It is preferably 1 mol or less of dicarboxylic acid anhydride per mol.
含窒素カルボン酸が高粘度であったり、融点が高い場合
には、低粘度化剤として精製ポリエーテルポリオールの
共存下に反応してもかまわない。When the nitrogen-containing carboxylic acid has a high viscosity or a high melting point, the reaction may be carried out in the presence of a purified polyether polyol as a viscosity reducing agent.
反応条件は30〜150℃、好ましくは60〜120℃
で1〜3時間程度である。Reaction conditions are 30-150°C, preferably 60-120°C
It takes about 1 to 3 hours.
また、含窒素カルボン酸とアルカリ金属との量的関係は
アルカリ金属1モルに対し、カルボキシル基が0.1〜
1.5、好ましくは0.8〜1、2モルであり、加熱条
件は30〜150℃、好ましくは60〜120℃で1〜
3時間程度である。In addition, the quantitative relationship between nitrogen-containing carboxylic acid and alkali metal is that the carboxyl group is 0.1 to 1 mole of alkali metal.
1.5, preferably 0.8 to 1,2 mol, and the heating conditions are 30 to 150°C, preferably 60 to 120°C, and 1 to 2 mol.
It takes about 3 hours.
本発明による含窒素カルボン酸アルカリ金属塩とポリエ
ーテルポリカールとの混合溶液をイソシアネート三量化
触媒活性を具備した変性剤として使用し、変性ポリイソ
シアヌレートフォームを製造する場合、一般に当量比2
以上のポリイソシアネートと反応させるのが好ましいが
、耐熱性、耐炎性などを厳しく要求されない場合には、
当量比2以下のポリイソシアネートと反応しても良好な
フォームが得られる。When producing a modified polyisocyanurate foam using the mixed solution of the nitrogen-containing alkali metal carboxylic acid salt and polyether polycal according to the present invention as a modifier having isocyanate trimerization catalytic activity, the equivalent ratio is generally 2.
It is preferable to react with the above polyisocyanate, but if heat resistance, flame resistance, etc. are not strictly required,
A good foam can be obtained even when reacting with a polyisocyanate having an equivalent ratio of 2 or less.
すなわち、当量比0.8〜1.2程度で反応する、いわ
ゆる硬質ウレタンフォーム用のウレタン化触媒活性を具
備したポリオールとして使用しても良好なフォームが得
られる。That is, a good foam can be obtained even when used as a polyol having urethanization catalyst activity for so-called rigid urethane foams, which reacts at an equivalent ratio of about 0.8 to 1.2.
当量比2以下でポリイソシアネートと反応する場合に、
本発明による変性剤の他に必要に応じて、さらにその他
の公知のイソシアネート三量化触媒やウレタン化触媒を
、さらにまた、変性剤として公知の各種の活性水素化合
物を併用することもできる。When reacting with polyisocyanate at an equivalent ratio of 2 or less,
In addition to the modifier according to the present invention, other known isocyanate trimerization catalysts and urethanization catalysts, and various known active hydrogen compounds as modifiers can also be used in combination, if necessary.
次に、本発明のポリイソシアヌレートフォームを製造す
るにおいて用いられるポリイソシアネートとしては、例
えば、4,4′−ジフエニルメタンジイソシアネート粗
製物(以下粗製MDIという)、ポリメチレンポリフェ
ニルイソシアネート(PAPI)、トリレンジイソシア
ネート粗製物(粗製TDM)、2,4−トリレンジイソ
シアネート、2.6−トリレンジイソシアネート、ナフ
タリンジイソシアネート、キシレンジイソシアネート、
ヘキサメチレンジイソシアネート、インホロンジイソシ
アネートなどのポリイソシアネートおよびこれらの混合
物、さらにこれらのポリイソシアネートとポリオ・−ル
のプレポリマー等が挙げられる。Next, as the polyisocyanate used in producing the polyisocyanurate foam of the present invention, for example, 4,4'-diphenylmethane diisocyanate crude product (hereinafter referred to as crude MDI), polymethylene polyphenylisocyanate (PAPI), Tolylene diisocyanate crude product (crude TDM), 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene diisocyanate, xylene diisocyanate,
Examples include polyisocyanates such as hexamethylene diisocyanate and inphorone diisocyanate, mixtures thereof, and prepolymers of these polyisocyanates and polyols.
発泡剤としては、例えばトリクロロモノフルオロメタン
(F−11)、ジクロロジフルオロメタン(F−12)
および塩化メチレンなどの低沸点有機溶媒、水、ニトロ
エタン、ホルムアミド、尿素、ホウ酸、ホウ砂等が挙げ
られる。As the blowing agent, for example, trichloromonofluoromethane (F-11), dichlorodifluoromethane (F-12)
and low-boiling organic solvents such as methylene chloride, water, nitroethane, formamide, urea, boric acid, borax, and the like.
また、界面活性剤としては、例えばシロキサンーオキシ
アルキレンコポリマー(以下シリコーン油という)、オ
ルガソボリシロキサン、オキシエチル化アルキルフェノ
ール、オキシエチル化高級アルコールおよびエチレンオ
キサイドープロピレンオキサイドブロツクポリマー等が
挙げられる。Further, examples of the surfactant include siloxane-oxyalkylene copolymer (hereinafter referred to as silicone oil), organosoborisiloxane, oxyethylated alkylphenol, oxyethylated higher alcohol, and ethylene oxide-propylene oxide block polymer.
その他の添加剤としては、必要により、公知の難燃剤、
充填剤および着色剤等も使用できる。Other additives include, if necessary, known flame retardants,
Fillers, colorants, etc. can also be used.
次に、変性ポリイソシアヌレートフォームの製造方法は
、スラブ発泡、注入発泡(コンベンショナルおよびクロ
ス法)、スプレー発泡および連続ラミネート発泡等の公
知の方法でワンショットモシくはプレポリマー法で行な
うものである。Next, the modified polyisocyanurate foam is produced by a one-shot molding method or a prepolymer method using known methods such as slab foaming, injection foaming (conventional and cross methods), spray foaming, and continuous lamination foaming. .
本発明は断熱性の最も優れている硬質ポリウレタンフォ
ームに匹敵する断熱性を有し、かつ、硬質ポリウレタン
フォームの欠点である耐熱性、耐炎性を向上することの
できる変性ポリイソシアヌレートフォームの製造におい
て、重要なポイントとされているイソシアネート三量化
触媒と変性剤について、従来の方法における欠点、すな
わち、製造工程の複雑化、価格上昇、系の相溶性の悪さ
、臭気および変性剤の制限等を解決することにより、安
価で、製造工程の簡略化された、系の相溶性のよい臭気
のない、そして変性剤であるポリエーテルポリオールを
目的に応じてその分子構造を自由に選択できる変性ポリ
イソシアヌレートフォームを提供するものである。The present invention is directed to the production of modified polyisocyanurate foam, which has heat insulation properties comparable to rigid polyurethane foams, which have the best heat insulation properties, and can improve heat resistance and flame resistance, which are disadvantages of rigid polyurethane foams. Regarding isocyanate trimerization catalysts and modifiers, which are considered to be important points, we solved the drawbacks of conventional methods, such as complicating the manufacturing process, increasing costs, poor system compatibility, odor, and limitations on modifiers. The modified polyisocyanurate is inexpensive, has a simplified manufacturing process, has good system compatibility, is odorless, and allows the molecular structure of the modifying agent polyether polyol to be freely selected according to the purpose. It provides a form.
本発明をさらに具体的に説明するために、以下に実施例
を示すが、その要旨を越えない限り、以下の実施例に限
定されるものではない。In order to explain the present invention more specifically, Examples are shown below, but the present invention is not limited to the following Examples unless the gist thereof is exceeded.
実施例 1
合成グリセリン92重量部、85%水酸化カリウム5.
94重量部を窒素ガスで置換したオートクレープに仕込
み、130℃で5mmHgまで減圧した。Example 1 92 parts by weight of synthetic glycerin, 85% potassium hydroxide5.
94 parts by weight were charged into an autoclave purged with nitrogen gas, and the pressure was reduced to 5 mmHg at 130°C.
ついで、10.0〜110℃で195.7重量部のプロ
ピレンオキサイドを続いて48.9重量部のエチレンオ
キサイドを合計約3時間で反応させ、透明粘稠液体であ
る粗製ポリエーテルポリオールを得た。Next, 195.7 parts by weight of propylene oxide and then 48.9 parts by weight of ethylene oxide were reacted at 10.0 to 110°C for a total of about 3 hours to obtain a crude polyether polyol as a transparent viscous liquid. .
実施例 2
撹拌機、温度計、窒素導入管を装備した300cc四ツ
口フラスコに74重量部のジーn−ブチルアミンを仕込
み、窒素導入下50℃以下に保ちながら100重量部の
無水コハク酸を加えたのち90〜100℃で1時間加熱
撹拌し常温でワックス状の含窒素カルボン酸を得た。Example 2 74 parts by weight of di-n-butylamine was placed in a 300cc four-necked flask equipped with a stirrer, a thermometer, and a nitrogen inlet tube, and 100 parts by weight of succinic anhydride was added while introducing nitrogen and keeping the temperature below 50°C. Thereafter, the mixture was heated and stirred at 90 to 100° C. for 1 hour to obtain a nitrogen-containing carboxylic acid in the form of wax at room temperature.
ついで、別途撹拌機、温度計、窒素導入管を装備した5
00cc四ツロフラスコに含窒素カルボン酸の14重量
部と実施例−1で得た粗製ポリエーテルボリオールの3
00重量部を仕込み窒素導入下90〜100℃で1時間
反応させて淡黄色粘稠液体である含窒素カルボン酸アル
カリ金属塩とポリエーテルポリオールとの混合溶液を得
た。Next, a
14 parts by weight of nitrogen-containing carboxylic acid and 3 parts of the crude polyether polyol obtained in Example-1 were placed in a 00cc four-piece flask.
00 parts by weight was charged and reacted at 90 to 100° C. for 1 hour under nitrogen introduction to obtain a mixed solution of a nitrogen-containing alkali metal carboxylate and polyether polyol as a pale yellow viscous liquid.
実施例 3
実施例−2のジ−n−プチルアミンの代りに105重量
部のジエタノールアミンを用いて同様にして得られた淡
黄色粘稠液体である含窒素カルボン酸の16.5重量部
と実施例−1で得た籾製ポリエーテルポリオールの30
0重量部を撹拌機、温度計、窒素導入管を装備した50
0CC四ツ口フラスコに仕込み窒素導入下90〜100
℃で1時間反応させて淡黄色粘稠液体である含窒素カル
ボン酸アルカリ金属塩とポリエーテルポリオールとの混
合溶液を得た。Example 3 16.5 parts by weight of a nitrogen-containing carboxylic acid, which is a light yellow viscous liquid, obtained in the same manner as in Example 2 using 105 parts by weight of diethanolamine instead of di-n-butylamine and Example 3 30 of the rice-based polyether polyol obtained in -1
50 parts by weight equipped with a stirrer, thermometer, and nitrogen inlet tube
Pour into a 0CC four-necked flask and introduce nitrogen at 90 to 100
The mixture was reacted at .degree. C. for 1 hour to obtain a mixed solution of nitrogen-containing alkali metal carboxylic acid and polyether polyol as a pale yellow viscous liquid.
実施例 4
実施例−2および−3の含窒素カルボン酸アルカリ金属
塩とポリエーテルポリオールとの混合溶液の各60重量
部、シリコーン油(DKSシリコーンD−332;第一
工業製薬社製)2重量部、トリクロロフルオロメタン(
ダイフロンR−11U;ダイキン工業社製)60重量
部を1lのポリエチレン製柄付ビーカーに秤り取り、2
0℃に調節した。Example 4 60 parts by weight of each mixed solution of the alkali metal salt of nitrogen-containing carboxylic acid and polyether polyol of Examples-2 and -3, 2 parts by weight of silicone oil (DKS Silicone D-332; manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) part, trichlorofluoromethane (
Weigh out 60 parts by weight of Daiflon R-11U (manufactured by Daikin Industries, Ltd.) into a 1 liter polyethylene handle beaker, and
The temperature was adjusted to 0°C.
ついで、予め20℃に調節された粗製MDI(ミリオネ
ートMR−100;日本ポリウレタン工業社製)の24
0重量部を素早く加え、ラボミキサーにて5秒間激しく
撹拌混合したのち、内側にポリエチレン製角袋をセット
した木箱の中へ注いだ。Then, 24° C. of crude MDI (Millionate MR-100; manufactured by Nippon Polyurethane Industries, Ltd.), which had been adjusted to 20° C.
After quickly adding 0 parts by weight and stirring and mixing vigorously for 5 seconds using a lab mixer, the mixture was poured into a wooden box with a polyethylene square bag set inside.
混合液はすみやかに発泡固化し、次のごとき性能の硬質
発泡体が得られた。The mixed liquid was rapidly foamed and solidified, and a rigid foam having the following properties was obtained.
Claims (1)
において、分子内にアミン性活性水素を1個以上有する
有機アミン化合物とジカルボン酸無水物とを反応させて
得られる含窒素カルボン酸を、末端水酸基の活性水素の
一部がアルカリ金属で置換されたポリエーテルポリオー
ルで処理し、得られる含窒素カルボン酸アルカリ金属塩
とポリエーテルポリオールとの混合溶液を、イソシアネ
ート三量化触媒活性を具備した変性剤として使用するこ
とを特徴とする変性ポリイソシアヌレートフォームの製
造方法。 2 変性ポリイソシアヌレートフォームを製造する方法
において、分子内にアミン性活性水素を1個以上有する
有機アミン化合物とジカルボン酸無水物とを反応させて
得られる含窒素カルボン酸を、末端水酸基の活性水素の
一部がアルカリ金属で置換されたポリエーテルポリオー
ルとアルカリ金属水酸化物で処理し、得られる含窒素カ
ルボン酸アルカリ金属塩とポリエーテルポリオールと水
との混合溶液をそのままで、または脱水処理したのちイ
ソシアネート三量化触媒活性を具備した変性剤として使
用することを特徴とする変性ポリイソシアヌレートフォ
ームの製造方法。 3 アルカリ金属水酸化物としてアルカリ金属水酸化物
水溶液を用いる特許請求の範囲第2項記載の変性ポリイ
ソシアヌレートフォームの製造方法。[Claims] 1. In a method for producing a modified polyisocyanurate foam, a nitrogen-containing carboxylic acid obtained by reacting an organic amine compound having one or more aminic active hydrogens in the molecule with a dicarboxylic acid anhydride is used. , a mixed solution of a nitrogen-containing alkali metal salt of a nitrogen-containing carboxylic acid and a polyether polyol was treated with a polyether polyol in which a part of the active hydrogen of the terminal hydroxyl group was substituted with an alkali metal, and the resulting mixed solution was treated with a polyether polyol having an isocyanate trimerization catalytic activity. A method for producing a modified polyisocyanurate foam, characterized in that it is used as a modifier. 2. In the method for producing modified polyisocyanurate foam, a nitrogen-containing carboxylic acid obtained by reacting an organic amine compound having one or more aminic active hydrogens in the molecule with a dicarboxylic acid anhydride, A mixed solution of a nitrogen-containing alkali metal salt of a nitrogen-containing carboxylic acid, a polyether polyol, and water is treated as it is or after dehydration treatment. A method for producing a modified polyisocyanurate foam, which is subsequently used as a modifier having isocyanate trimerization catalytic activity. 3. The method for producing a modified polyisocyanurate foam according to claim 2, wherein an aqueous alkali metal hydroxide solution is used as the alkali metal hydroxide.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP55078542A JPS584050B2 (en) | 1980-06-10 | 1980-06-10 | Method for producing modified polyisocyanurate foam |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP55078542A JPS584050B2 (en) | 1980-06-10 | 1980-06-10 | Method for producing modified polyisocyanurate foam |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS573811A JPS573811A (en) | 1982-01-09 |
JPS584050B2 true JPS584050B2 (en) | 1983-01-24 |
Family
ID=13664794
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP55078542A Expired JPS584050B2 (en) | 1980-06-10 | 1980-06-10 | Method for producing modified polyisocyanurate foam |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS584050B2 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100852925B1 (en) | 2005-01-17 | 2008-08-19 | 혼다 기켄 고교 가부시키가이샤 | Bobbin-less coil and method of manufacturing the same |
-
1980
- 1980-06-10 JP JP55078542A patent/JPS584050B2/en not_active Expired
Also Published As
Publication number | Publication date |
---|---|
JPS573811A (en) | 1982-01-09 |
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