JP2004010812A - Polyether polyol and process for producing rigid polyurethane foam - Google Patents
Polyether polyol and process for producing rigid polyurethane foam Download PDFInfo
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- JP2004010812A JP2004010812A JP2002168221A JP2002168221A JP2004010812A JP 2004010812 A JP2004010812 A JP 2004010812A JP 2002168221 A JP2002168221 A JP 2002168221A JP 2002168221 A JP2002168221 A JP 2002168221A JP 2004010812 A JP2004010812 A JP 2004010812A
- Authority
- JP
- Japan
- Prior art keywords
- polyether polyol
- polyurethane foam
- hfc
- rigid polyurethane
- molecular weight
- 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.)
- Granted
Links
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 60
- 229920000570 polyether Polymers 0.000 title claims abstract description 60
- 229920005862 polyol Polymers 0.000 title claims abstract description 60
- 150000003077 polyols Chemical class 0.000 title claims abstract description 60
- 229920005830 Polyurethane Foam Polymers 0.000 title claims description 31
- 239000011496 polyurethane foam Substances 0.000 title claims description 31
- 238000000034 method Methods 0.000 title description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 34
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 25
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 20
- -1 amine compound Chemical class 0.000 claims abstract description 16
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims description 21
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 15
- 238000005187 foaming Methods 0.000 claims description 11
- 239000005056 polyisocyanate Substances 0.000 claims description 11
- 229920001228 polyisocyanate Polymers 0.000 claims description 11
- 239000006260 foam Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000004604 Blowing Agent Substances 0.000 claims description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000012948 isocyanate Substances 0.000 claims 1
- 150000002513 isocyanates Chemical class 0.000 claims 1
- 150000002989 phenols Chemical class 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 description 8
- 239000004088 foaming agent Substances 0.000 description 7
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000011810 insulating material Substances 0.000 description 5
- OHMHBGPWCHTMQE-UHFFFAOYSA-N 2,2-dichloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)C(Cl)Cl OHMHBGPWCHTMQE-UHFFFAOYSA-N 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 4
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000006683 Mannich reaction Methods 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- RXYPXQSKLGGKOL-UHFFFAOYSA-N 1,4-dimethylpiperazine Chemical compound CN1CCN(C)CC1 RXYPXQSKLGGKOL-UHFFFAOYSA-N 0.000 description 2
- GBAXGHVGQJHFQL-UHFFFAOYSA-N 1-(2-hydroxyethylamino)propan-2-ol Chemical compound CC(O)CNCCO GBAXGHVGQJHFQL-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- TUAMRELNJMMDMT-UHFFFAOYSA-N 3,5-xylenol Chemical compound CC1=CC(C)=CC(O)=C1 TUAMRELNJMMDMT-UHFFFAOYSA-N 0.000 description 2
- YQUQWHNMBPIWGK-UHFFFAOYSA-N 4-isopropylphenol Chemical compound CC(C)C1=CC=C(O)C=C1 YQUQWHNMBPIWGK-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 2
- 229940043276 diisopropanolamine Drugs 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 2
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011359 shock absorbing material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000004448 titration Methods 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
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 description 1
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 description 1
- YFMFNYKEUDLDTL-UHFFFAOYSA-N 1,1,1,2,3,3,3-heptafluoropropane Chemical compound FC(F)(F)C(F)C(F)(F)F YFMFNYKEUDLDTL-UHFFFAOYSA-N 0.000 description 1
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 1
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 description 1
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 description 1
- PCHXZXKMYCGVFA-UHFFFAOYSA-N 1,3-diazetidine-2,4-dione Chemical compound O=C1NC(=O)N1 PCHXZXKMYCGVFA-UHFFFAOYSA-N 0.000 description 1
- NZIGXAQHXJFYEW-UHFFFAOYSA-N 1-aminobutan-2-ol;ethanol Chemical compound CCO.CCC(O)CN NZIGXAQHXJFYEW-UHFFFAOYSA-N 0.000 description 1
- KYTMHUXSDFKSEO-UHFFFAOYSA-N 1-aminobutan-2-ol;propan-2-ol Chemical compound CC(C)O.CCC(O)CN KYTMHUXSDFKSEO-UHFFFAOYSA-N 0.000 description 1
- WHJWHBMJEOQRPH-UHFFFAOYSA-N 1-aminohexan-2-ol;ethanol Chemical compound CCO.CCCCC(O)CN WHJWHBMJEOQRPH-UHFFFAOYSA-N 0.000 description 1
- CEVWBJCREUNMRI-UHFFFAOYSA-N 1-aminohexan-2-ol;propan-2-ol Chemical compound CC(C)O.CCCCC(O)CN CEVWBJCREUNMRI-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- HOLHYSJJBXSLMV-UHFFFAOYSA-N 2,6-dichlorophenol Chemical compound OC1=C(Cl)C=CC=C1Cl HOLHYSJJBXSLMV-UHFFFAOYSA-N 0.000 description 1
- QHTUMQYGZQYEOZ-UHFFFAOYSA-N 2-(4-methylpiperazin-1-yl)ethanol Chemical compound CN1CCN(CCO)CC1 QHTUMQYGZQYEOZ-UHFFFAOYSA-N 0.000 description 1
- KKFDCBRMNNSAAW-UHFFFAOYSA-N 2-(morpholin-4-yl)ethanol Chemical compound OCCN1CCOCC1 KKFDCBRMNNSAAW-UHFFFAOYSA-N 0.000 description 1
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 description 1
- YSAANLSYLSUVHB-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]ethanol Chemical compound CN(C)CCOCCO YSAANLSYLSUVHB-UHFFFAOYSA-N 0.000 description 1
- BQBWUVWMUXGILF-UHFFFAOYSA-N 2-anthrol Chemical compound C1=CC=CC2=CC3=CC(O)=CC=C3C=C21 BQBWUVWMUXGILF-UHFFFAOYSA-N 0.000 description 1
- WRVIGSXNYQECJV-UHFFFAOYSA-N 2-bromo-6-cyclohexylphenol Chemical compound OC1=C(Br)C=CC=C1C1CCCCC1 WRVIGSXNYQECJV-UHFFFAOYSA-N 0.000 description 1
- VADKRMSMGWJZCF-UHFFFAOYSA-N 2-bromophenol Chemical compound OC1=CC=CC=C1Br VADKRMSMGWJZCF-UHFFFAOYSA-N 0.000 description 1
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 1
- AQDKZPFDOWHRDZ-UHFFFAOYSA-N 2-methyl-6-nitrophenol Chemical compound CC1=CC=CC([N+]([O-])=O)=C1O AQDKZPFDOWHRDZ-UHFFFAOYSA-N 0.000 description 1
- IIBOYMCHHLZIKC-UHFFFAOYSA-N 2-nitro-6-phenylphenol Chemical compound C1=CC=C([N+]([O-])=O)C(O)=C1C1=CC=CC=C1 IIBOYMCHHLZIKC-UHFFFAOYSA-N 0.000 description 1
- SYDNSSSQVSOXTN-UHFFFAOYSA-N 2-nitro-p-cresol Chemical compound CC1=CC=C(O)C([N+]([O-])=O)=C1 SYDNSSSQVSOXTN-UHFFFAOYSA-N 0.000 description 1
- KRPRVQWGKLEFKN-UHFFFAOYSA-N 3-(3-aminopropoxy)propan-1-amine Chemical compound NCCCOCCCN KRPRVQWGKLEFKN-UHFFFAOYSA-N 0.000 description 1
- FZQMJOOSLXFQSU-UHFFFAOYSA-N 3-[3,5-bis[3-(dimethylamino)propyl]-1,3,5-triazinan-1-yl]-n,n-dimethylpropan-1-amine Chemical compound CN(C)CCCN1CN(CCCN(C)C)CN(CCCN(C)C)C1 FZQMJOOSLXFQSU-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- FIBBSIRCVZWBML-UHFFFAOYSA-N 4-nitro-2-phenylphenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1C1=CC=CC=C1 FIBBSIRCVZWBML-UHFFFAOYSA-N 0.000 description 1
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- HEJMLGZFRLAQQJ-UHFFFAOYSA-N N=C=N.N=C=O.N=C=O.C(C1=CC=CC=C1)C1=CC=CC=C1 Chemical class N=C=N.N=C=O.N=C=O.C(C1=CC=CC=C1)C1=CC=CC=C1 HEJMLGZFRLAQQJ-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 230000000397 acetylating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 1
- 150000004074 biphenyls Chemical class 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000011521 glass Substances 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
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- TXXWBTOATXBWDR-UHFFFAOYSA-N n,n,n',n'-tetramethylhexane-1,6-diamine Chemical compound CN(C)CCCCCCN(C)C TXXWBTOATXBWDR-UHFFFAOYSA-N 0.000 description 1
- DMQSHEKGGUOYJS-UHFFFAOYSA-N n,n,n',n'-tetramethylpropane-1,3-diamine Chemical compound CN(C)CCCN(C)C DMQSHEKGGUOYJS-UHFFFAOYSA-N 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 description 1
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- RLEFZEWKMQQZOA-UHFFFAOYSA-M potassium;octanoate Chemical compound [K+].CCCCCCCC([O-])=O RLEFZEWKMQQZOA-UHFFFAOYSA-M 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011493 spray foam Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N tolylenediamine group Chemical group CC1=C(C=C(C=C1)N)N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Polyethers (AREA)
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、主として、ポリエーテルポリオールに関し、更に詳しくは、ヒドロフルオロカーボンの溶解度が高いポリエーテルポリオールに関する。
【０００２】
【従来の技術】
フェノール類とアミン化合物とホルマリンとをマンニッヒ化反応に供することによって得られる縮合物に、アルキレンオキサイドを付加して得られるポリエーテルポリオール（以下、マンニッヒ系ポリエーテルポリオールともいう）は、硬質ポリウレタンフォームを製造するのに、従来より、幅広く使用されている。
【０００３】
該硬質ポリウレタンフォームは、マンニッヒ系ポリエーテルポリオールに発泡剤を溶解し、これとポリイソシアネート化合物とを混合、発泡することによって得ている。該硬質ポリウレタンフォーム用の発泡剤として現在使用されているヒドロクロロフルオロカーボン（ＨＣＦＣ）は、マンニッヒ系ポリエーテルポリオールに対する溶解度が高く、硬質ポリウレタンフォームの所望の発泡度に合わせて発泡剤量を自由に調整することができる。
【０００４】
【発明が解決しようとする課題】
しかし、該ＨＣＦＣはオゾン層破壊係数及び地球温暖化係数が高く、２００３年末にはその使用が全面的に禁止される予定である。そこでこれに代えて、オゾン層破壊係数及び地球温暖化係数の低いヒドロフルオロカーボン（ＨＦＣ）の使用が検討されている。
【０００５】
ところがＨＦＣはＨＣＦＣに比べてマンニッヒ系ポリエーテルポリオールに対する溶解度が低く、必要とする量の発泡剤を使用すると、発泡剤がマンニッヒ系ポリエーテルポリオールに溶けきれずにそのまま残ってしまう場合があり、均質な硬質ポリウレタンフォームが得られない場合があるという問題がある。
【０００６】
本発明は、前記問題点に鑑み、ＨＦＣを十分に溶解することができるポリエーテルポリオールを提供することを課題とする。
【０００７】
【課題を解決するための手段】
前記課題を検討した結果、本発明者が初めて、水酸基価６００ｍｇＫＯＨ／ｇ以下、重量平均分子量５００以上のマンニッヒ系ポリエーテルポリオールの窒素含有率を４．５モル％以下に調整すると、ＨＦＣの溶解度を高くすることができることを発見し、本発明を完成した。
【０００８】
即ち本発明は、フェノール類とアミン化合物とのホルマリン縮合物にアルキレンオキサイドを付加することによって得られるポリエーテルポリオールであって、水酸基価が６００ｍｇＫＯＨ／ｇ以下、重量平均分子量が５００以上及び窒素含有率が４．５モル％以下であるポリエーテルポリオールに関する。
【０００９】
本発明のポリエーテルポリオールは、ＨＦＣの溶解度が高いので、多量のＨＦＣを混合しても、ＨＦＣは十分溶解し、均一なＨＦＣ含有ポリエーテルポリオールを得ることができる。
【００１０】
さらに本発明の硬質ポリウレタンフォームの製造方法は、フェノール類とアミン化合物とのホルマリン縮合物にアルキレンオキサイドを付加することによって得られるポリエーテルポリオールであって、水酸基価が６００ｍｇＫＯＨ／ｇ以下、重量平均分子量が５００以上及び窒素含有率が４．５モル％以下であるポリエーテルポリオールにヒドロフルオロカーボンを溶解し、これとポリイソシアネート化合物とを混合し、該混合物を発泡することを特徴とする。
【００１１】
本発明の硬質ポリウレタンフォームの製造方法によれば、ＨＦＣの溶解度が高いポリエーテルポリオールを使用しているので、ポリエーテルポリオールとポリイソシアネート化合物と反応させてポリウレタンフォームを製造する際、発泡剤として多量のＨＦＣをポリエーテルポリオールに溶解しても均一な溶液を得ることができ、したがって、均質な硬質ポリウレタンフォームを得ることができる。
【００１２】
【発明の実施の形態】
本発明のポリエーテルポリオールを製造するために使用されるフェノール類は、少なくとも１個のフェノール性ヒドロキシル基を有する化合物であって、該化合物は、単環式化合物であっても多環式化合物（ビフェニル類のような複数の環が別々になっている化合物、ナフタレン類のような縮合環化合物等）であってもよい。該フェノール類は、マンニッヒ化反応及びアルキレンオキサイドの付加反応、及びポリウレタン製造において、反応に悪影響を及ぼさない置換基によって置換されていてもよい。このような置換基として、アルキル基、アリール基、アルコキシ基、フェノキシ基、ハロゲン、ニトロ基等が挙げられる。好ましい置換基として、ハロゲン、特に好ましい置換基として塩素及びＣ１〜Ｃ１８アルキル基、その中でも好ましいものとしてＣ１〜Ｃ１２アルキル基が挙げられる。
【００１３】
このようなフェノール類として、例えば、フェノール、ｏ−、ｐ−、ｍ−クレゾール、エチルフェノール、ノニルフェノール、ドデシルフェノール、ｐ−フェニルフェノール、２，２−ビス（４−ヒドロキシフェニル）プロパン（ビスフェノールＡ）等のビスフェノール類、β−ナフトール、β−ヒドロキシアントラセン、ｐ−クロロフェノール、ｏ−ブロモフェノール、２，６−ジクロロフェノール、ｐ−ニトロフェノール、４−ニトロ−６−フェニルフェノール、２−ニトロ−６−フェニルフェノール、２−ニトロ−６−メチルフェノール、２−ニトロ−４−メチルフェノール、３，５−ジメチルフェノール、ｐ−イソプロピルフェノール、２−ブロモ−６−シクロヘキシルフェノール等が挙げられる。なかでも、フェノール及びモノアルキルフェノールが、特にフェノール及びＣ１−Ｃ１０パラアルキルフェノールが好ましい。入手が容易という点から、フェノール及びｐ−ｎ−ノニルフェノールがとりわけ好ましい。
【００１４】
アミン化合物としては、例えば、ジエタノールアミン、ジイソプロパノ−ルアミン、エタノールイソプロパノールアミン、エタノール−２−ヒドロキシブチルアミン、イソプロパノール−２−ヒドロキシブチルアミン、イソプロパノール−２−ヒドロキシヘキシルアミン、エタノール−２−ヒドロキシヘキシルアミン等のアルコールアミン、エチレンジアミン等のジアミン、ジエチレントリアミン等のトリアミン等、少なくとも一つの活性水素をホルマリン縮合物に与えうるアルキルアミンが挙げられる。中でもジエタノールアミン、ジイソプロパノールアミン及びエタノールイソプロパノールアミンが好ましい。
【００１５】
フェノール類とアミン化合物とのホルマリン縮合物に付加されるアルキレンオキサイドとして、エチレンオキサイド、プロピレンオキサイド、ブチレンオキサイド等が使用される。特にプロピレンオキサイド／エチレンオキサイドが１００／０〜３０／７０（モル比）の混合物が好ましい。
【００１６】
フェノール類とアミン化合物とのホルマリン縮合であるマンニッヒ化反応は、例えば、フェノール類１モルに対して１〜２モルのアミン化合物を混合し、これにフェノール類１モルに対して１．２５〜１．７５モルのホルムアルデヒドを添加し、５０〜１５０℃で行われる。該縮合反応終了後、反応混合物から水を除去し、これにアルキレンオキサイド、好ましくはプロピレンオキサイドとエチレンオキサイドの混合物（モル比１００／０〜３０／７０）を縮合反応物に加え、３０〜２００℃、１．０〜３．０ｋｇ／ｃｍ２Ｇで付加反応を行い、本発明のポリエーテルポリオールを得る。
【００１７】
本発明のポリエーテルポリオールは、重量平均分子量が５００以上、好ましくは５５０〜２０００である。該重量平均分子量が５００未満であれば、ＨＦＣの溶解度が低下し、均質な硬質ウレタンフォームが得られにくくなる。
なお、ポリエーテルポリオールの重量平均分子量の測定はＧＰＣ法で下記の条件で行う。
【００１８】
重量平均分子量測定（ＧＰＣ法）
ＧＰＣ本体として東ソー（株）製のＨＬＣ−８０２０を使用し、カラム温度４０℃、ポンプ流量０．６〜１．０ｍｌ／分、検出器としてＲＩ（ＧＰＣ本体に内蔵されている）を用いる。データ処理は、あらかじめ分子量が既知の標準ＰＰＧの検量線（分子量２５０以上での検量）を用いて、ＰＰＧ換算分子量より分子量を得る。
カラム：ＴＳＫｇｅｌ Ｇ６０００Ｈ ＨＲ ＋ Ｇ４０００Ｈ ＨＲ ＋Ｇ３０００Ｈ ＨＲ ＋ Ｇ２０００Ｈ ＨＲ （４本つないで使用）移動相：ＴＨＦ
注入量：８０μｌ
サンプル濃度：０．２％（ｗ／ｖ）
【００１９】
本発明のポリエーテルポリオールは、窒素含有率が４．５モル％以下、好ましくは１．５〜４．１モル％である。ポリエーテルポリオール中の窒素含有率が４．５モル％を超えると、ＨＦＣの該ポリエーテルポリオールに対する溶解度が低くなり、高発泡度を得るために必要な発泡剤の全量が溶解できなくなる場合がある。
前記窒素含有率が１．５〜４．１モル％の範囲であると、ＨＦＣの溶解度を極めて高くすることができる。
【００２０】
なお、窒素含有率は、下記式（Ｉ）によって計算される。
【００２１】
【数１】
本発明のポリエーテルポリオールは、水酸基価が６００ｍｇＫＯＨ／ｇ以下、好ましくは２００〜５００ｍｇＫＯＨ／ｇである。該水酸基価が６００ｍｇＫＯＨ／ｇを超えると、ＨＦＣの溶解度が低下し、均質な硬質ウレタンフォームが得られにくくなる。
なお水酸基価は、ポリエーテルポリオール１ｇをアセチル化するとき、水酸基と結合した酢酸を中和するのに要する水酸化カリウムのｍｇ数であり、ＪＩＳ Ｋ ００７０に規定する水酸基価の中和滴定法によって測定した値である。
【００２３】
本発明のポリエーテルポリオールを使用して硬質ポリウレタンフォームを製造する際、発泡剤として使用されるＨＦＣとして、例えば、１，１，１，３，３−ペンタフルオロプロパン（ＨＦＣ２４５ｆａ）、１，１，１，３，３−ペンタフルオロブタン（ＨＦＣ３６５ｍｆｃ）、１，１，１，２−テトラフルオロエタン（ＨＦＣ１３４ａ）、１，１，１，２，３，３，３、−ヘプタフルオロプロパン（ＨＦＣ２２７ｅａ）等が挙げられる。
またＨＦＣに併用してもよい発泡助剤として水が挙げられる。
【００２４】
硬質ポリウレタンフォームを製造する際に使用されるポリイソシアネート化合物として、芳香族ポリイソシアネート化合物、脂肪族ポリイソシアネート化合物、脂環族ポリイソシアネート化合物、これらの変性物、二量体、三量体等が挙げられ、これらは単独あるいは混合物として使用される。具体的には、例えば、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート（ＩＰＤＩ）、ジフェニルメタンジイソシアネート（ＭＤＩ）、トリレンジイソシアネート（ＴＤＩ）、キシリレンジイソシアネート（ＸＤＩ）、ジシクロヘキシルメタンジイソシアネート、ポリメチレンポリフェニルポリイソシアネート（ＭＤＩ−ＣＲ）、トリフェニルメチレントリイソシアネート、ウレチジオン、イソシアヌレート、変成（カルボジイミド）ジフェニルメタンジイソシアネート等が好ましく使用できる。
【００２５】
本発明の硬質ポリウレタンフォームの製造方法によれば、本発明のポリエーテルポリオール１００重量部にＨＦＣを３０〜１００重量部、好ましくは３０〜５０重量部溶解し、該ポリエーテルポリオールの水酸基に対して１．０〜２．０当量のポリイソシアネート化合物を加え、又、硬化触媒を必要に応じて加え、発泡させることによって硬質ポリウレタンフォームを得る。
【００２６】
前記硬化触媒として、アミン系触媒、有機金属触媒等が挙げられる。これらの硬化触媒は単独あるいは２種以上混合して使用される。
【００２７】
アミン系触媒として、例えば、トリエチルアミン、Ｎ，Ｎ−ジメチルシクロヘキシルアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルエチレンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルプロパン−１，３−ジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルヘキサン−１，６−ジアミン、Ｎ，Ｎ，Ｎ’，Ｎ”，Ｎ”−ペンタメチルジエチレントリアミン、Ｎ，Ｎ，Ｎ’，Ｎ”，Ｎ”−ペンタメチルジプロピレントリアミン、テトラメチルグアニジン、トリエチレンジアミン、Ｎ，Ｎ’−ジメチルピペラジン、Ｎ−メチル−Ｎ’−（２−ジメチルアミノ）−エチルピペラジン、Ｎ−メチルモルホリン、Ｎ−（Ｎ’，Ｎ’−ジメチルアミノエチル）−モルホリン、１，２−ジメチルイミダゾール、ジメチルアミノエタノール、ジメチルアミノエトキシエタノール、Ｎ，Ｎ，Ｎ’−トリメチルアミノエチル−エタノールアミン、Ｎ−メチル−Ｎ’−（２−ヒドロキシエチル）ピペラジン、Ｎ−（２−ヒドロキシエチル）モルホリン、ビス（２−ジメチルアミノエチル）エーテル、エチレングリコールビス（３−ジメチル）アミノプロピルエーテル等が挙げられる。
【００２８】
有機金属触媒として、例えば、ジブチルチンジアセテート、ジブチルチンジラウレート、オクチル酸カリウム等が挙げられる。
【００２９】
その他、整泡剤、充填剤、酸化防止剤、光安定剤、界面活性剤、難燃剤、防腐剤、防蟻剤、防黴剤等を添加してもよい。
【００３０】
得られた硬質ポリウレタンフォームは、好ましくは２０以上、更に好ましくは２０〜８０の硬度（タイプＣ型）をもつ。
ここで硬度は、スプリング式硬さ試験（ＪＩＳ Ｓ ６０５０に準じ、アスカーＣ型測定器（高分子計器（株）製）を使用）によって測定される。
【００３１】
該硬質ポリウレタンフォームは、例えば、冷蔵庫用断熱材、外壁用断熱材、ショーケース用断熱材、現場発泡用スプレーフォーム断熱材等の各種の断熱材、自動車用衝撃緩和材等の衝撃緩和材、道路盛土用材、擬木、ファブリック芯材等として使用される。
【００３２】
【実施例】
以下、本発明を実施例に基づいてさらに詳しく説明する。ただし本発明はこれらの実施例に限定されるものではない。
まず、以下に実施例、比較例で行った試験方法を記載する。
【００３３】
溶解度の測定
密閉できるガラス製容器に得られたポリエーテルポリオール１００ｇを秤量して入れ、１０℃に調整した。ここへ、ＨＦＣとしてＨＦＣ２４５ｆａ又はＨＦＣ３６５ｍｆｃを添加し、ディスパー攪拌器（特殊機化工業社製）ＴＫホモディスパーｆ）で混合した。この時ＨＦＣの飛散量を補正しながら混合攪拌を行った。均一な溶液になった時点で密封し、１０℃の恒温槽中で約２４時間静置した後、内容物を肉眼で観察して、ＨＦＣとポリエーテルポリオールが分離しているか否か、あるいは溶液が白濁しているか否かをチェックした。
表１中の数字は、ＨＦＣ５ｇの使用から始めて１ｇづつ増やしていき、分離あるいは白濁が観察されるまで行い、これらが観察されない最大のＨＦＣ量を溶解度として示したものである。
【００３４】
重量平均分子量測定（ＧＰＣ法）
前記したＧＰＣ法により測定した。
【００３５】
窒素含有率（モル％）の計算
式（Ｉ）によって計算した。
【００３６】
水酸基価の測定
ＪＩＳ Ｋ ００７０に規定される中和滴定法によって測定した。
【００３７】
硬度の測定
スプリング式硬さ試験によって測定した。
【００３８】
セル数
ＰＥＡＫ社製ＷＩＤＥ ＳＲＡＮＤ ＭＩＣＲＯ顕微鏡で１０倍の倍率で観察し、１ｍｍの間に存在するセルの個数を数えた。数字が大きいほどセルは細かい。
【００３９】
実施例１
温度及び圧力調整ができる攪拌器、真空脱水装置を付帯する５ｌの高圧反応容器にノニルフェノール４５０ｇとジエタノールアミン４２０ｇとを仕込み、攪拌混合を開始し、続いて３７重量％ホルマリン水溶液２４３ｇを３回に分けて添加した。その後混合液を１２０℃まで約３０分かけて昇温し、１２０℃に保ちながら、１時間縮合反応を行った。反応終了後、反応混合物の温度を１１０〜１１５℃まで冷却し、反応混合物を２０ｍｍＨｇの減圧下で脱水した。次に減圧下でプロピレンオキサイド／エチレンオキサイドのモル比が８０／２０になるようにプロピレンオキサイド４２０ｇ、エチレンオキサイド８０ｇを加え、１１５℃、２．５ｋｇ／ｃｍ２Ｇで付加反応を２時間行い、所望のポリエーテルポリオールを得た。
【００４０】
得られたポリエーテルポリオールの重量平均分子量（ＧＰＣ法）、窒素含有率、水酸基価、及びＨＦＣ２４５ｆａ及びＨＦＣ３６５ｍｆｃの溶解度を測定した。
結果を表１に示す。
【００４１】
【表１】
得られたポリエーテルポリオールにＨＦＣ２４５ｆａあるいはＨＦＣ３６５ｍｆｃを表２、３に示す量加えてディスパー攪拌器で攪拌した。該混合物に粗ＭＤＩ（ジフェニルメタンジイソシアネートの構造異性体混合物）を加え、整泡剤としてＳＺ１６０５（日本ユニカー製）をポリエーテルポリオール１００ｇに対し１ｇ加え、トヨキャットＴＲＣ（アミン系硬化触媒、東ソー製）を表２、３に示す量加え、発泡を行った。得られたポリウレタンフォームの密度、硬度及びセル数を表２、３に示す。
【００４３】
【表２】
【表３】
実施例２、３及び比較例１、２、５
表１に示す成分及び配合量を用いて、実施例１と同様にしてポリエーテルポリオールを得た。得られたポリエーテルポリオールの重量平均分子量（ＧＰＣ法）、窒素含有率、及び水酸基価、ＨＦＣ２４５ｆａ及びＨＦＣ３６５ｍｆｃの溶解度を測定した。
結果を表１に示す。
【００４６】
実施例１と同様にして、得られたポリエーテルポリオールとＨＦＣとの混合物を得て該混合物の外観を観察し、また該混合物を使用してポリウレタンフォームを得た。前記混合物の外観及びポリウレタンフォームの密度、硬度及びセル数を表２、３に示す。
【００４７】
比較例３
ＧＲ−４６（水酸基価が４５０ｍｇＫＯＨ／ｇのトリレンジアミン系ポリエーテルポリオール、三井武田ケミカル（株）製）に対するＨＦＣ２４５ｆａ及びＨＦＣ３６５ｍｆｃの溶解度を測定した。結果を表１に示す。
【００４８】
実施例１と同様にして、該ポリエーテルポリオールとＨＦＣとの混合物を得て該混合物の外観を観察し、また該混合物を使用してポリウレタンフォームを得た。前記混合物の外観及びポリウレタンフォームの密度、硬度及びセル数を表２、３に示す。
【００４９】
比較例４
ノニルフェノール、３７％ホルマリン水溶液及びアミン化合物として表１に示す成分及び配合量を用い、またアルキレンオキサイドの代わりにポリエポキシ化合物（デナコールＥＸ６１１、長瀬産業（株）製）を８００ｇ用い、実施例１と同様にしてポリエーテルポリオールを得た。得られたポリエーテルポリオールの重量平均分子量（ＧＰＣ法）、窒素含有率、水酸基価、ＨＦＣ２４５ｆａ及びＨＦＣ３６５ｍｆｃの溶解度を測定した。
結果を表１に示す。
【００５０】
実施例１と同様にして、得られたポリエーテルポリオールとＨＦＣとの混合物を得て該混合物の外観を観察し、また該混合物を使用してポリウレタンフォームを得た。前記ポリウレタンフォームの外観及びポリウレタンフォームの密度、硬度及びセル数を表２、３に示す。
【００５１】
表１から明らかなように、フェノール類とアミン化合物とのホルマリン縮合物から得られるポリエーテルポリオールであって、水酸基価が６００ｍｇＫＯＨ／ｇ以下、重量平均分子量が５００以上、窒素含有率が４．５モル％以下であるポリエーテルポリオールは、ＨＦＣ２４５ｆａを、ポリエーテルポリオール１００ｇに対して５０ｇ以上、ＨＦＣ３６５ｍｆｃを４０ｇ以上溶解した。
これに対して、水酸基価、重量平均分子量、窒素含有率のいずれかが上記範囲外の値をもつポリエーテルポリオールについては、ＨＦＣ２４５ｆａもＨＦＣ３６５ｍｆｃも高い溶解度を示さなかった。
また、実施例１〜３のポリウレタンフォームは密度が小さく、従って発泡剤の発泡効率が高かったことがわかる。またセルの細かい均質なポリウレタンフォームであった。一方、比較例１〜５のポリウレタンフォームは、実施例１〜３のポリウレタンフォームに比べ密度が高く、発泡効率が低かったことがわかる。
【００５２】
【発明の効果】
本発明のポリエーテルポリオールは、ＨＦＣを十分に溶解することができる。特にポリエーテルポリオール中に発泡剤としてＨＦＣが溶解され、該溶液とポリイソシアネート化合物とを混合して発泡させる硬質ポリウレタンフォームの製造方法において、均質な硬質ポリウレタンフォームを提供することができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates mainly to polyether polyols, and more particularly to polyether polyols having high hydrofluorocarbon solubility.
[0002]
[Prior art]
A polyether polyol obtained by adding an alkylene oxide to a condensate obtained by subjecting a phenol, an amine compound and formalin to a Mannich reaction (hereinafter, also referred to as a Mannich-based polyether polyol) is a rigid polyurethane foam. It has been widely used for manufacturing.
[0003]
The rigid polyurethane foam is obtained by dissolving a foaming agent in a Mannich-based polyether polyol, mixing this with a polyisocyanate compound, and foaming. Hydrochlorofluorocarbon (HCFC), which is currently used as a foaming agent for the rigid polyurethane foam, has a high solubility in Mannich-based polyether polyols, and the amount of the foaming agent can be freely adjusted according to the desired degree of foaming of the rigid polyurethane foam. can do.
[0004]
[Problems to be solved by the invention]
However, the HCFC has a high ozone depletion potential and a high global warming potential, and its use will be completely banned by the end of 2003. Therefore, use of hydrofluorocarbons (HFCs) having a low ozone depletion potential and a low global warming potential has been studied instead.
[0005]
However, HFC has a lower solubility in Mannich-based polyether polyol than HCFC, and when a required amount of a blowing agent is used, the blowing agent may not be completely dissolved in the Mannich-based polyether polyol and may remain as it is. There is a problem that a rigid polyurethane foam may not be obtained.
[0006]
In view of the above problems, an object of the present invention is to provide a polyether polyol capable of sufficiently dissolving HFC.
[0007]
[Means for Solving the Problems]
As a result of examining the above-mentioned problems, the present inventor for the first time adjusted the nitrogen content of a Mannich-based polyether polyol having a hydroxyl value of 600 mgKOH / g or less and a weight average molecular weight of 500 or more to 4.5 mol% or less. They discovered that they could be higher and completed the present invention.
[0008]
That is, the present invention relates to a polyether polyol obtained by adding an alkylene oxide to a formalin condensate of a phenol and an amine compound, which has a hydroxyl value of 600 mgKOH / g or less, a weight average molecular weight of 500 or more, and a nitrogen content. Is 4.5 mol% or less.
[0009]
Since the polyether polyol of the present invention has a high solubility of HFC, even if a large amount of HFC is mixed, the HFC is sufficiently dissolved and a uniform HFC-containing polyether polyol can be obtained.
[0010]
Furthermore, the method for producing a rigid polyurethane foam of the present invention is a polyether polyol obtained by adding an alkylene oxide to a formalin condensate of a phenol and an amine compound, wherein the hydroxyl value is 600 mgKOH / g or less, and the weight average molecular weight is Is characterized by dissolving a hydrofluorocarbon in a polyether polyol having a nitrogen content of not less than 500 and a nitrogen content of not more than 4.5 mol%, mixing this with a polyisocyanate compound, and foaming the mixture.
[0011]
According to the method for producing a rigid polyurethane foam of the present invention, since a polyether polyol having a high HFC solubility is used, when producing a polyurethane foam by reacting the polyether polyol with a polyisocyanate compound, a large amount of a foaming agent is used. A homogeneous solution can be obtained even if the HFC is dissolved in a polyether polyol, and thus a homogeneous rigid polyurethane foam can be obtained.
[0012]
BEST MODE FOR CARRYING OUT THE INVENTION
The phenol used for producing the polyether polyol of the present invention is a compound having at least one phenolic hydroxyl group. The compound may be a monocyclic compound or a polycyclic compound ( Compounds in which a plurality of rings are separate such as biphenyls, and condensed ring compounds such as naphthalenes) may be used. The phenols may be substituted by a substituent that does not adversely affect the reaction in the Mannich reaction and the addition reaction of alkylene oxide, and in the production of polyurethane. Examples of such a substituent include an alkyl group, an aryl group, an alkoxy group, a phenoxy group, a halogen, a nitro group, and the like. Preferred substituents include halogen, particularly preferred substituents are chlorine and C 1 -C 18 alkyl groups, and among them, preferred are C 1 -C 12 alkyl groups.
[0013]
Examples of such phenols include phenol, o-, p-, m-cresol, ethylphenol, nonylphenol, dodecylphenol, p-phenylphenol, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) Bisphenols such as β-naphthol, β-hydroxyanthracene, p-chlorophenol, o-bromophenol, 2,6-dichlorophenol, p-nitrophenol, 4-nitro-6-phenylphenol, and 2-nitro-6 -Phenylphenol, 2-nitro-6-methylphenol, 2-nitro-4-methylphenol, 3,5-dimethylphenol, p-isopropylphenol, 2-bromo-6-cyclohexylphenol and the like. Among them, phenol and monoalkyl phenol, especially phenol and C 1 -C 10 para alkylphenol is preferred. Phenol and pn-nonylphenol are particularly preferred in that they are easily available.
[0014]
Examples of the amine compound include alcohol amines such as diethanolamine, diisopropanolamine, ethanolisopropanolamine, ethanol-2-hydroxybutylamine, isopropanol-2-hydroxybutylamine, isopropanol-2-hydroxyhexylamine, and ethanol-2-hydroxyhexylamine. And alkylamines that can provide at least one active hydrogen to the formalin condensate, such as diamines such as ethylenediamine and triamines such as diethylenetriamine. Among them, diethanolamine, diisopropanolamine and ethanolisopropanolamine are preferred.
[0015]
As the alkylene oxide added to the formalin condensate of a phenol and an amine compound, ethylene oxide, propylene oxide, butylene oxide and the like are used. In particular, a mixture of propylene oxide / ethylene oxide in a molar ratio of 100/0 to 30/70 is preferable.
[0016]
In the Mannich reaction, which is a formalin condensation of a phenol and an amine compound, for example, 1 to 2 mol of an amine compound is mixed with respect to 1 mol of a phenol, and 1.25 to 1 mol is mixed with 1 mol of the phenol. .75 mol of formaldehyde are added and the reaction is carried out at 50-150 ° C. After completion of the condensation reaction, water is removed from the reaction mixture, and an alkylene oxide, preferably a mixture of propylene oxide and ethylene oxide (molar ratio 100/0 to 30/70) is added to the condensation reaction product. , 1.0-3.0 kg / cm 2 G to obtain the polyether polyol of the present invention.
[0017]
The polyether polyol of the present invention has a weight average molecular weight of 500 or more, preferably 550 to 2,000. If the weight average molecular weight is less than 500, the solubility of HFC is reduced, and it is difficult to obtain a homogeneous rigid urethane foam.
The weight average molecular weight of the polyether polyol is measured by the GPC method under the following conditions.
[0018]
Weight average molecular weight measurement (GPC method)
The HPC-8020 manufactured by Tosoh Corporation is used as the GPC main body, the column temperature is 40 ° C., the pump flow rate is 0.6 to 1.0 ml / min, and the RI (built in the GPC main body) is used as the detector. In the data processing, a molecular weight is obtained from a PPG-converted molecular weight using a calibration curve of a standard PPG having a known molecular weight in advance (calibration at a molecular weight of 250 or more).
Column: TSKgel G6000H HR + G4000H HR + G3000H HR + G2000H HR (use four connected) Mobile phase: THF
Injection volume: 80 μl
Sample concentration: 0.2% (w / v)
[0019]
The polyether polyol of the present invention has a nitrogen content of 4.5 mol% or less, preferably 1.5 to 4.1 mol%. If the nitrogen content in the polyether polyol exceeds 4.5 mol%, the solubility of HFC in the polyether polyol becomes low, and the entire amount of the blowing agent required to obtain a high degree of foaming may not be dissolved. .
When the nitrogen content is in the range of 1.5 to 4.1 mol%, the solubility of HFC can be extremely increased.
[0020]
The nitrogen content is calculated by the following equation (I).
[0021]
(Equation 1)
The polyether polyol of the present invention has a hydroxyl value of 600 mgKOH / g or less, preferably 200 to 500 mgKOH / g. When the hydroxyl value exceeds 600 mgKOH / g, the solubility of HFC decreases, and it becomes difficult to obtain a uniform rigid urethane foam.
The hydroxyl value is the number of mg of potassium hydroxide required to neutralize acetic acid bonded to the hydroxyl group when acetylating 1 g of polyether polyol, and is determined by a neutralization titration method for hydroxyl value specified in JIS K 0070. It is a measured value.
[0023]
When producing a rigid polyurethane foam using the polyether polyol of the present invention, examples of HFC used as a foaming agent include 1,1,1,3,3-pentafluoropropane (HFC245fa), 1,1,1 1,3,3-pentafluorobutane (HFC365mfc), 1,1,1,2-tetrafluoroethane (HFC134a), 1,1,1,2,3,3,3-heptafluoropropane (HFC227ea), etc. Is mentioned.
Water may be used as a foaming aid that may be used in combination with the HFC.
[0024]
Examples of the polyisocyanate compound used in producing the rigid polyurethane foam include an aromatic polyisocyanate compound, an aliphatic polyisocyanate compound, an alicyclic polyisocyanate compound, a modified product thereof, a dimer, and a trimer. These are used alone or as a mixture. Specifically, for example, hexamethylene diisocyanate, isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), dicyclohexyl methane diisocyanate, polymethylene polyphenyl polyisocyanate (MDI- CR), triphenylmethylene triisocyanate, uretdione, isocyanurate, modified (carbodiimide) diphenylmethane diisocyanate and the like can be preferably used.
[0025]
According to the method for producing a rigid polyurethane foam of the present invention, 30 to 100 parts by weight, preferably 30 to 50 parts by weight, of HFC is dissolved in 100 parts by weight of the polyether polyol of the present invention, and based on the hydroxyl groups of the polyether polyol. A rigid polyurethane foam is obtained by adding 1.0 to 2.0 equivalents of a polyisocyanate compound and, if necessary, adding a curing catalyst, followed by foaming.
[0026]
Examples of the curing catalyst include an amine catalyst and an organometallic catalyst. These curing catalysts are used alone or in combination of two or more.
[0027]
Examples of the amine catalyst include triethylamine, N, N-dimethylcyclohexylamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethylpropane-1,3-diamine , N, N, N ', N'-tetramethylhexane-1,6-diamine, N, N, N', N ", N" -pentamethyldiethylenetriamine, N, N, N ', N ", N" -Pentamethyldipropylenetriamine, tetramethylguanidine, triethylenediamine, N, N'-dimethylpiperazine, N-methyl-N '-(2-dimethylamino) -ethylpiperazine, N-methylmorpholine, N- (N', N′-dimethylaminoethyl) -morpholine, 1,2-dimethylimidazole, dimethylaminoethanol, dimethylaminoethoxyethanol, N, , N'-trimethylaminoethyl-ethanolamine, N-methyl-N '-(2-hydroxyethyl) piperazine, N- (2-hydroxyethyl) morpholine, bis (2-dimethylaminoethyl) ether, ethylene glycol bis ( 3-dimethyl) aminopropyl ether and the like.
[0028]
Examples of the organic metal catalyst include dibutyltin diacetate, dibutyltin dilaurate, potassium octylate and the like.
[0029]
In addition, a foam stabilizer, a filler, an antioxidant, a light stabilizer, a surfactant, a flame retardant, a preservative, an ant-proofing agent, a fungicide, and the like may be added.
[0030]
The obtained rigid polyurethane foam preferably has a hardness (Type C type) of 20 or more, more preferably 20 to 80.
Here, the hardness is measured by a spring-type hardness test (using an Asker C-type measuring device (manufactured by Kobunshi Keiki Co., Ltd.) according to JIS S 6050).
[0031]
The rigid polyurethane foam includes, for example, various heat insulating materials such as a heat insulating material for refrigerators, a heat insulating material for an outer wall, a heat insulating material for a showcase, a spray foam heat insulating material for foaming on site, a shock absorbing material such as an automobile shock absorbing material, and a road. Used as embankment material, artificial wood, fabric core material, etc.
[0032]
【Example】
Hereinafter, the present invention will be described in more detail based on examples. However, the present invention is not limited to these examples.
First, test methods performed in Examples and Comparative Examples are described below.
[0033]
Measurement of Solubility 100 g of the obtained polyether polyol was weighed into a hermetically sealable glass container and adjusted to 10 ° C. To this, HFC245fa or HFC365mfc was added as HFC, and mixed with a disper stirrer (TK homodisper f, manufactured by Tokushu Kika Kogyo Co., Ltd.). At this time, the mixture was stirred while correcting the amount of HFC scattered. When the solution became homogeneous, it was sealed, and allowed to stand in a constant temperature bath at 10 ° C. for about 24 hours. Then, the contents were visually observed to determine whether HFC and polyether polyol had separated, or Was checked for cloudiness.
The numbers in Table 1 are shown starting from the use of 5 g of HFC and increasing in increments of 1 g until separation or turbidity is observed.
[0034]
Weight average molecular weight measurement (GPC method)
It was measured by the GPC method described above.
[0035]
The nitrogen content (mol%) was calculated by the formula (I).
[0036]
Measurement of hydroxyl value The hydroxyl value was measured by a neutralization titration method specified in JIS K0070.
[0037]
The hardness was measured by a spring hardness test.
[0038]
The number of cells was observed at a magnification of 10 times with a WIDE SRAND MICRO microscope manufactured by PEAK, and the number of cells existing within 1 mm was counted. The higher the number, the finer the cell.
[0039]
Example 1
Nonylphenol (450 g) and diethanolamine (420 g) were charged into a 5-liter high-pressure reaction vessel equipped with a stirrer and a vacuum dehydrator capable of adjusting the temperature and pressure, and stirring and mixing were started. Was added. Thereafter, the temperature of the mixture was raised to 120 ° C. over about 30 minutes, and a condensation reaction was performed for 1 hour while maintaining the temperature at 120 ° C. After completion of the reaction, the temperature of the reaction mixture was cooled to 110 to 115 ° C, and the reaction mixture was dehydrated under a reduced pressure of 20 mmHg. Next, 420 g of propylene oxide and 80 g of ethylene oxide are added under reduced pressure so that the molar ratio of propylene oxide / ethylene oxide becomes 80/20, and an addition reaction is performed at 115 ° C. and 2.5 kg / cm 2 G for 2 hours to obtain a desired product. Was obtained.
[0040]
The weight average molecular weight (GPC method), nitrogen content, hydroxyl value, and solubility of HFC245fa and HFC365mfc of the obtained polyether polyol were measured.
Table 1 shows the results.
[0041]
[Table 1]
HFC245fa or HFC365mfc was added to the obtained polyether polyol in an amount shown in Tables 2 and 3, and the mixture was stirred with a disper stirrer. Crude MDI (mixture of structural isomers of diphenylmethane diisocyanate) was added to the mixture, SZ1605 (manufactured by Nippon Unicar) was added as a foam stabilizer at 1 g per 100 g of polyether polyol, and Toyocat TRC (amine-based curing catalyst, manufactured by Tosoh) was added. Foaming was performed in addition to the amounts shown in Tables 2 and 3. Tables 2 and 3 show the density, hardness and cell number of the obtained polyurethane foam.
[0043]
[Table 2]
[Table 3]
Examples 2, 3 and Comparative Examples 1, 2, 5
Using the components and amounts shown in Table 1, a polyether polyol was obtained in the same manner as in Example 1. The weight average molecular weight (GPC method), nitrogen content, hydroxyl value, and solubility of HFC245fa and HFC365mfc of the obtained polyether polyol were measured.
Table 1 shows the results.
[0046]
In the same manner as in Example 1, a mixture of the obtained polyether polyol and HFC was obtained, the appearance of the mixture was observed, and a polyurethane foam was obtained using the mixture. Tables 2 and 3 show the appearance of the mixture and the density, hardness and cell number of the polyurethane foam.
[0047]
Comparative Example 3
The solubility of HFC245fa and HFC365mfc in GR-46 (tolylenediamine-based polyether polyol having a hydroxyl value of 450 mgKOH / g, manufactured by Mitsui Takeda Chemical Co., Ltd.) was measured. Table 1 shows the results.
[0048]
In the same manner as in Example 1, a mixture of the polyether polyol and HFC was obtained, the appearance of the mixture was observed, and a polyurethane foam was obtained using the mixture. Tables 2 and 3 show the appearance of the mixture and the density, hardness and cell number of the polyurethane foam.
[0049]
Comparative Example 4
Nonylphenol, 37% formalin aqueous solution, and the components and amounts shown in Table 1 were used as the amine compound, and 800 g of a polyepoxy compound (Denacol EX611, manufactured by Nagase Sangyo Co., Ltd.) was used instead of the alkylene oxide. To obtain a polyether polyol. The weight average molecular weight (GPC method), nitrogen content, hydroxyl value, solubility of HFC245fa and HFC365mfc of the obtained polyether polyol were measured.
Table 1 shows the results.
[0050]
In the same manner as in Example 1, a mixture of the obtained polyether polyol and HFC was obtained, the appearance of the mixture was observed, and a polyurethane foam was obtained using the mixture. Tables 2 and 3 show the appearance of the polyurethane foam and the density, hardness and number of cells of the polyurethane foam.
[0051]
As is clear from Table 1, a polyether polyol obtained from a formalin condensate of a phenol and an amine compound has a hydroxyl value of 600 mgKOH / g or less, a weight average molecular weight of 500 or more, and a nitrogen content of 4.5. The mol% or less polyether polyol dissolved 50 g or more of HFC245fa and 100 g of HFC365mfc in 100 g of the polyether polyol.
On the other hand, as for the polyether polyol having any one of the hydroxyl value, the weight average molecular weight and the nitrogen content outside the above-mentioned ranges, neither HFC245fa nor HFC365mfc showed high solubility.
Further, it can be seen that the polyurethane foams of Examples 1 to 3 had a low density, and thus the foaming efficiency of the foaming agent was high. It was a homogeneous polyurethane foam with fine cells. On the other hand, it can be seen that the polyurethane foams of Comparative Examples 1 to 5 had higher density and lower foaming efficiency than the polyurethane foams of Examples 1 to 3.
[0052]
【The invention's effect】
The polyether polyol of the present invention can sufficiently dissolve HFC. In particular, in a method for producing a rigid polyurethane foam in which HFC is dissolved as a foaming agent in a polyether polyol, and the solution is mixed with a polyisocyanate compound to foam the foam, a homogeneous rigid polyurethane foam can be provided.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005206819A (en) * | 2003-12-22 | 2005-08-04 | Asahi Glass Co Ltd | Method of manufacturing hard foam synthetic resin |
| WO2010147091A1 (en) | 2009-06-16 | 2010-12-23 | 旭硝子株式会社 | Process for producing polyether polyol and process for producing rigid foamed synthetic resin using same |
| JP2011017027A (en) * | 2003-12-22 | 2011-01-27 | Asahi Glass Co Ltd | Process for producing rigid foam synthetic resin |
| JP2012184446A (en) * | 2005-11-01 | 2012-09-27 | E I Du Pont De Nemours & Co | Method for making foam using blowing agent comprising unsaturated fluorocarbon |
-
2002
- 2002-06-10 JP JP2002168221A patent/JP3774680B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005206819A (en) * | 2003-12-22 | 2005-08-04 | Asahi Glass Co Ltd | Method of manufacturing hard foam synthetic resin |
| JP2011017027A (en) * | 2003-12-22 | 2011-01-27 | Asahi Glass Co Ltd | Process for producing rigid foam synthetic resin |
| JP4654678B2 (en) * | 2003-12-22 | 2011-03-23 | 旭硝子株式会社 | Manufacturing method of rigid foam synthetic resin |
| JP2012184446A (en) * | 2005-11-01 | 2012-09-27 | E I Du Pont De Nemours & Co | Method for making foam using blowing agent comprising unsaturated fluorocarbon |
| WO2010147091A1 (en) | 2009-06-16 | 2010-12-23 | 旭硝子株式会社 | Process for producing polyether polyol and process for producing rigid foamed synthetic resin using same |
| US8623933B2 (en) | 2009-06-16 | 2014-01-07 | Asahi Glass Company, Limited | Process for producing polyether polyol and process for producing rigid foamed synthetic resin using same |
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| JP3774680B2 (en) | 2006-05-17 |
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