CN1307230C - Polyol composition for rigid polyurethane foam and process for producing rigid polyurethane foam - Google Patents
Polyol composition for rigid polyurethane foam and process for producing rigid polyurethane foam Download PDFInfo
- Publication number
- CN1307230C CN1307230C CNB2004800035236A CN200480003523A CN1307230C CN 1307230 C CN1307230 C CN 1307230C CN B2004800035236 A CNB2004800035236 A CN B2004800035236A CN 200480003523 A CN200480003523 A CN 200480003523A CN 1307230 C CN1307230 C CN 1307230C
- Authority
- CN
- China
- Prior art keywords
- hfc
- polyol
- composition
- whipping agent
- rigid polyurethane
- 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 - Fee Related
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- 229920005862 polyol Polymers 0.000 title claims abstract description 70
- 239000000203 mixture Substances 0.000 title claims abstract description 67
- 229920005830 Polyurethane Foam Polymers 0.000 title claims abstract description 58
- 239000011496 polyurethane foam Substances 0.000 title claims abstract description 58
- 150000003077 polyols Chemical class 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims description 11
- -1 polyol compounds Chemical class 0.000 claims abstract description 64
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 claims abstract description 58
- 125000001302 tertiary amino group Chemical group 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 47
- 150000005846 sugar alcohols Polymers 0.000 claims description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 238000005187 foaming Methods 0.000 claims description 12
- 239000004094 surface-active agent Substances 0.000 claims description 10
- 239000012948 isocyanate Substances 0.000 claims description 9
- 150000002513 isocyanates Chemical class 0.000 claims description 7
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 claims description 4
- 238000007711 solidification Methods 0.000 claims description 3
- 230000008023 solidification Effects 0.000 claims description 3
- WZLFPVPRZGTCKP-UHFFFAOYSA-N 1,1,1,3,3-pentafluorobutane Chemical compound CC(F)(F)CC(F)(F)F WZLFPVPRZGTCKP-UHFFFAOYSA-N 0.000 abstract description 22
- YQQHEHMVPLLOKE-UHFFFAOYSA-N 1,1,2,2-tetrafluoro-1-methoxyethane Chemical compound COC(F)(F)C(F)F YQQHEHMVPLLOKE-UHFFFAOYSA-N 0.000 abstract description 20
- 239000004604 Blowing Agent Substances 0.000 abstract description 5
- 239000004615 ingredient Substances 0.000 abstract 2
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 abstract 1
- XEUCQOBUZPQUMQ-UHFFFAOYSA-N Glycolone Chemical compound COC1=C(CC=C(C)C)C(=O)NC2=C1C=CC=C2OC XEUCQOBUZPQUMQ-UHFFFAOYSA-N 0.000 abstract 1
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract 1
- FRCHKSNAZZFGCA-UHFFFAOYSA-N 1,1-dichloro-1-fluoroethane Chemical compound CC(F)(Cl)Cl FRCHKSNAZZFGCA-UHFFFAOYSA-N 0.000 description 15
- 239000006260 foam Substances 0.000 description 14
- 239000003063 flame retardant Substances 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 230000000704 physical effect Effects 0.000 description 10
- 239000004088 foaming agent Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 239000013056 hazardous product Substances 0.000 description 6
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 6
- 230000006837 decompression Effects 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- 229920001228 polyisocyanate Polymers 0.000 description 5
- 239000005056 polyisocyanate Substances 0.000 description 5
- 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 4
- 150000001412 amines Chemical class 0.000 description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000002924 oxiranes Chemical class 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 229940126062 Compound A Drugs 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000004902 Softening Agent Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000002483 hydrogen compounds Chemical class 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 150000002171 ethylene diamines Chemical class 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- RLEFZEWKMQQZOA-UHFFFAOYSA-M potassium;octanoate Chemical compound [K+].CCCCCCCC([O-])=O RLEFZEWKMQQZOA-UHFFFAOYSA-M 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- YACLCMMBHTUQON-UHFFFAOYSA-N 1-chloro-1-fluoroethane Chemical class CC(F)Cl YACLCMMBHTUQON-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 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
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-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
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 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
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-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
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-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
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 125000006226 butoxyethyl group Chemical group 0.000 description 1
- 210000004899 c-terminal region Anatomy 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical compound COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- XXUJMEYKYHETBZ-UHFFFAOYSA-N ethyl 4-nitrophenyl ethylphosphonate Chemical compound CCOP(=O)(CC)OC1=CC=C([N+]([O-])=O)C=C1 XXUJMEYKYHETBZ-UHFFFAOYSA-N 0.000 description 1
- 210000003746 feather Anatomy 0.000 description 1
- 244000144992 flock Species 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229940059574 pentaerithrityl Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N pentanoic acid group Chemical group C(CCCC)(=O)O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 150000003008 phosphonic acid esters Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000011493 spray foam Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 239000012970 tertiary amine catalyst Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 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
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- HQUQLFOMPYWACS-UHFFFAOYSA-N tris(2-chloroethyl) phosphate Chemical compound ClCCOP(=O)(OCCCl)OCCCl HQUQLFOMPYWACS-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/143—Halogen containing compounds
- C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
- C08J9/146—Halogen containing compounds containing carbon, halogen and hydrogen only only fluorine as halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0025—Foam properties rigid
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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Abstract
A polyol composition for rigid polyurethane foams, which is used in combination with HFC-245fa as a blowing agent at a reduced vapor pressure of the blowing agent. The blowing agent ingredient comprises 1,1,1,3,3-pentafluoropropan (HFC-245fa). The composition comprises diethylene glycol monoethyl ether acetate and one or more polyol compounds including a polyol compound having a tertiary amino group, wherein the content of nitrogen atoms assignable to the tertiary amino is 0.5 to 9 wt.% based on the polyol compounds. Use of the blowing agent ingredient which further includes HFC-365mfc or HFE-254pc is also preferable.
Description
Technical field
The present invention relates to a kind ofly contain 1,1,1,3,3-pentafluoropropane (HFC-245fa) is as the hard polyurethane foams polyhydric alcohol composition of the necessary principal constituent of whipping agent and use the manufacture method of HFC-245fa as the hard polyurethane foams of the main component of whipping agent.
Background technology
As the whipping agent of the hard polyurethane foams of the lagging material of excellence, use now be the broken ring system number of ozonosphere little 1,1-two chloro-1-fluoroethanes (HCFC-141b).Though HCFC-141b depletion of the ozone layer coefficient is little, be not zero, consider from the viewpoint of global environment protection, abrogated fully at the year ends 2003.
The whipping agent of HCFC-141b as an alternative, studying lower boiling hydrocarbons such as Skellysolve A or pentamethylene now, as the HFC-245fa or the HFC-365mfc of not chloride lower boiling halogenated hydrocarbon compound, also have the littler HFE-254pc of greenhouse effects of the earth coefficient.
; lower boiling hydrocarbons such as Skellysolve A or pentamethylene is flammable high compound; containing the manufacturing process of these compounds, using in the offal treatment operation etc. of waste of the manufacturing process of hard polyurethane foams of this polyhydric alcohol composition and this hard polyurethane foams of pulverization process as the polyhydric alcohol composition of whipping agent; existence must have serious fire to prevent countermeasure, be necessary to update the equipment in manufacturing works of in the past hard polyurethane foams etc., and the very huge such problem of cost of equipment.In addition, use the pentane class to compare as the product of whipping agent with use HCFC-141b in the past as the hard polyurethane foams of whipping agent, flame retardant resistance is bad, and to as the purposes that requires the material of construction of flame retardant resistance, it is very difficult intactly using.
HFC-365mfc, fire service law according to Japan, though be not confirmed to be inflammableness, but with German standard, flash-point is identified at-27 ℃, contains its polyhydric alcohol composition as whipping agent, and forming also to have according to it becomes the example that meets hazardous material the 4th class the 1st petroleum-type of stipulating in fire service law, and as hazardous material, exist with HCFC-141b as the polyhydric alcohol composition of whipping agent equal can not handle, store such problem.In addition, HFC-365mfc also exists and the such problem of intermiscibility difference as the polyvalent alcohol of the main component of polyhydric alcohol composition.
Though HFE-254pc still is in the whipping agent of development phase, do not study fully, as hazardous material, be the material close with HFC-365mfc, also there is same problem.
The danger relative therewith, that HFC-245fa does not catch fire be the whipping agent that there is no need as the hazardous material processing, but its boiling point is 15 ℃, vapour pressure height at normal temperatures.Therefore, if HFC-245fa is used as whipping agent, the gasoline that polyhydric alcohol composition is housed is irritated or container such as Oil Tank, particularly summer will produce expand such problem and when opening bolt because the gasification of whipping agent is spread ejection of polyhydric alcohol composition stoste or whipping agent volatilization, thereby its amount is reduced, can not obtain the problems such as foam of regulation density.
Summary of the invention
The object of the present invention is to provide a kind of use HFC-245fa as whipping agent, and the polyol composition for rigid polyurethane foam that is inhibited of its vapour pressure and the manufacture method of hard polyurethane foams.
Polyol composition for rigid polyurethane foam of the present invention, at least contain polyol compound, whipping agent, surfactant, catalyzer, and by mixing, and make it foamed solidification and can form hard polyurethane foams with the isocyanate prepolymer composition that contains isocyanate compound, it is characterized in that
The 1st whipping agent of the main component of above-mentioned whipping agent is 1,1,1,3,3-pentafluoropropane (HFC-245fa) is as the vapor pressure lowering agent, contain acetate ethyl carbitol ester, and above-mentioned HFC-245fa/ acetate ethyl carbitol ester=95/5～60/40 (weight ratio),
Above-mentioned polyol compound comprises the polyol compound with tertiary amino group, and is 0.5～9 weight % in the polyol compound based on the nitrogen of above-mentioned tertiary amino group.
By making the polyol composition for rigid polyurethane foam of above-mentioned composition, can reach purpose of the present invention.
Promptly, by using HFC-245fa as whipping agent, add simultaneously acetate ethyl carbitol ester (below, be abbreviated as CAc (abbreviation of Ethyl carbitol acetate ester)), the physical property of the hard polyurethane foams that has kept foaming character or obtained, thermal insulation etc., and can suppress the vapour pressure of HFC-245fa.
If the HFC-245fa/CAc weight ratio surpasses 95/5, then can not give full play to vapour pressure and reduce effect, the vapour pressure of polyol composition for rigid polyurethane foam is uprised.In addition, when HFC-245fa/CAc weight ratio less than 60/40, the ratio of CAc is too much, produces the situation that the foamy physical property reduces.
In addition because the intermiscibility of the polyol compound that contains tertiary amino group and HFC-245fa is than other polyol compound excellence, by and with the polyol compound that contains tertiary amino group, can obtain the vapour pressure reduction effect of excellent more HFC-245fa.By and with containing the polyol compound of tertiary amino group, the homogeneity that can also obtain the bubble of the hard polyurethane foams that the reactive behavior of polyhydric alcohol composition uprised, obtain simultaneously uprises, uprise such effect with the bonding strength of plane materiel.Based on 0.5 o'clock in the nitrogen hunger polyol compound of tertiary amino group, can not substantially improve vapour pressure reduce effect, bubble homogeneity, with the bonding strength of plane materiel, if surpass 9 weight %, the dimensional stability of the hard polyurethane foams that then obtains reduces.
Be more preferably 1.5～8.5 weight % in the polyol compound based on the nitrogen of tertiary amino group.
Above-mentioned hard polyaminoester also preferably contains 1 with polyhydric alcohol composition, 1,1,3,3-3-pentafluorobutane (HFC-365mfc) is as the 2nd whipping agent, and HFC-245fa/HFC-365mfc 〉=60/40, (HFC-245fa+HFC-365mfc)/CAc=95/5～60/40 (weight ratio).
The intermiscibility of HFC-365mfc and HFC-245fa is good, and comparing with HFC-245fa is the compound of high boiling point (40.2 ℃), therefore, by also using HFC-365mfc, the physical property of the hard polyurethane foams that has kept foaming character or obtained, thermal insulation etc. can also suppress the vapour pressure of HFC-245fa.
During HFC-245fa/HFC-365mfc weight ratio less than 60/40, the containing ratio of HFC-365mfc uprises, and the result makes flash-point reduce, even polyhydric alcohol composition among hazardous material the 4th class, also produces the situation that is identified as the high petroleum-type of inflammableness.In addition, if (HFC-245fa+HFC-365mfc)/the CAc weight ratio is above 95/5, and the ratio of CAc is very few, then become and to bring into play its additive effect fully, if this weight ratio is a less than 60/40, the ratio of CAc is too much, then produces the situation that the foamy physical property reduces.
(HFC-245fa+HFC-365mfc)/CAc weight ratio preferred 93/7～70/30.
Above-mentioned polyol composition for rigid polyurethane foam also preferably contains tetrafluoride methyl ethyl ether (HFE-254pc) as the 3rd whipping agent, and HFC-245fa/HFE-254pc 〉=50/50, (HFC-245fa+HFE-254pc)/CAc=95/5～60/40 (weight ratio).
By and use the HFE-254pc good and higher than HFC-245fa boiling point with the intermiscibility of HFC-245fa, the physical property of the hard polyurethane foams that has kept foaming character or obtained, thermal insulation etc., the vapour pressure that can also suppress HFC-245fa, and greenhouse effects of the earth prevented it also is effective.
During HFC-245fa/HFE-254pc weight ratio less than 50/50, the containing ratio of HFE-254pc uprises, and the result makes flash-point reduce, even polyhydric alcohol composition among hazardous material the 4th class, also produces the situation that is identified as the high petroleum-type of inflammableness.In addition, if (HFC-245fs+HFE-254pc)/the CAc weight ratio is above 95/5, and the ratio of CAc is very few, then become and to bring into play its additive effect fully, if this weight ratio is a less than 60/40, the ratio of CAc is too much, then produces the situation that the foamy physical property reduces.
(HFC-245fa+HFE-254pc)/CAc weight ratio preferred 93/7～70/30.
CAc can be pre-mixed as foaming agent composotion with HFC-245fa and HFC-365mfc or HFE-254pc and mix with polyol compound, also can add various compositions respectively, as long as the result makes them coexist, just pay no attention to its interpolation order, form in polyhydric alcohol composition.
We know, by CAc is used as a kind of composition of polyhydric alcohol composition, have also improved the bonding strength of hard polyurethane foams and plane materiel etc.Though its reason is not clear, but only with HFC-245fa or with HFC-245fa and HFC-365mfc or HFE-254pc during as whipping agent, because the intermiscibility of whipping agent and polyhydroxy reactant is bad, when the foaming stock solution composition that has mixed isocyanate prepolymer composition and polyhydric alcohol composition contacts with plane materiel etc., the temperature of contact surface reduces, the HFC-245fa frosting begins up to curing reaction, cause foamable reaction then, the foamy bubble of near interface is disorderly and unsystematic, can infer that its result is, with the binding property reduction of plane materiel.CAc is owing to have the effect of the intermiscibility that improves HFC-245fa and polyol compound, can think to improve the material of the bonding strength of hard polyurethane foams and plane materiel etc.
In addition, the present invention mixes isocyanate prepolymer composition and polyhydric alcohol composition and makes it to foam, solidify and become the manufacture method of the hard polyurethane foams of hard polyurethane foams, it is characterized in that, as polyhydric alcohol composition, use the polyol composition for rigid polyurethane foam of each record in the claim 1～3.
By this manufacture method, do not need to transform significantly fire Countermeasure, and use and use HCFC-141b as the same manufacturing installation of the occasion of whipping agent, just can make hard polyurethane foams.
Embodiment
Hard polyaminoester polyhydric alcohol composition of the present invention except that whipping agent, also contains polyol compound, surfactant and catalyzer at least.Polyol compound contains the polyol compound with tertiary amino group.
As polyol compound, unqualified, can use known hard polyurethane foams polyol compound.As such polyol compound, can enumerate the polyol compound that contains tertiary amino group, aliphatic polyol, aromatic polyol etc.
The polyol compound that contains tertiary amino group is to make epoxide with primary amine or secondary amine as initiator, particularly, a kind or more kinds of multi-functional polyvalent alcohol that carries out ring opening polyaddition and obtain of propylene oxide (PO), oxyethane (EO), phenyl ethylene oxide (SO), tetrahydrofuran (THF) etc.
Primary amine or secondary amine initiator as the initiator of the polyol compound that contains tertiary amino group, can enumerate Armeen such as ammonia, methylamine, ethamine or Zhong Yiyuan amine, quadrol, hexamethylene-diamine, N, alkanol amines such as aromatic series uncle such as aliphatics such as N '-dimethyl-ethylenediamine uncle or secondary polyamine, aniline, pentanoic, tolylene diamine, diphenylmethane diamine, methylphenylamine or Zhong Yiyuan or polynary amine, Monoethanolamine MEA BASF, diethanolamine.
Aliphatic polyol is as initiator with polyvalent alcohol, in aliphatics or alicyclic multi-functional active hydrogen compounds, make epoxide, particularly, a kind or more kinds of multi-functional oligopolymer that carries out ring opening polyaddition and obtain of cyclic ethers such as propylene oxide (PO), oxyethane (EO), phenyl ethylene oxide (SO), tetrahydrofuran (THF).
Polyol initiator as aliphatic polyol, can enumerate ethylene glycol, propylene glycol, 1,4-butyleneglycol, 1,3-butyleneglycol, 1, polyalcohols, water etc. such as 4 officials such as three alcohols such as glycolss such as 6-hexylene glycol, neopentyl glycol, TriMethylolPropane(TMP), glycerol, tetramethylolmethane energy alcohols, Sorbitol Powder, sucrose.
Can enumerate polyol compound of the ester that have in the multi-functional active hydrogen compounds of aromatic nucleus polyol compound that the method by the above-mentioned epoxide of addition obtains at intramolecularly, belongs to aromatic series polyprotonic acid and polyvalent alcohol etc. as aromatic polyol.
The polyol compound that obtains as the above-mentioned epoxide of addition in multi-functional active hydrogen compounds, can enumerate in quinhydrones, dihydroxyphenyl propane etc. open loop addition particularly PO, EO, SO at least a and the compound that obtains.
As the ester of aromatic series polyprotonic acid and polyvalent alcohol, can enumerate the ester polyol of terephthalic acid, phthalic acid, m-phthalic acid etc. and the C-terminal of ethylene glycol, Diethylene Glycol etc. particularly.
Above-mentioned polyol compound, preferred hydroxyl value 200～600mgKOH/g.In these polyol compounds, if use polyol compound, the aliphatic polyol contain tertiary amino group, the effect that can obtain making the viscosity of polyhydric alcohol composition to reduce.
As the catalyzer that in polyol composition for rigid polyurethane foam of the present invention, uses, unqualified, the known catalyzer that can use hard polyurethane foams to use.Particularly, as the urethane catalysts, can enumerate triethylenediamine, N-first for morpholine, N, N, N ', N '-Tetramethyl Ethylene Diamine, N, N, N ', metal species catalyzer such as tertiary amines, dibutyl tin laurate, dibutyltin diacetate, stannous octoate such as N '-tetramethyl-hexamethylene-diamine, DBU.
So-called hard polyurethane foams, the isocyanate groups that forms polymkeric substance can be a urethane bond, also can have urea key or tricarbimide ester bond.
As whipping agent, use a spot of water and the characteristic of improving the hard polyurethane foams that obtains is preferred mode.
In the structure of polyurethane molecular, the preferred catalyzer that is formed with the tricarbimide ester bond that helps to improve flame retardant resistance that uses can be enumerated, for example Potassium ethanoate, potassium octanoate.The material that promotes the chlorinated isocyanurates ring to form reaction is also arranged in the above-mentioned tertiary amine catalyst.And with promoting that catalyzer that the tricarbimide ester bond generates and the catalyzer that promotes urethane bond to generate are also no problem.
As surfactant, unqualified, the known surfactant that can use hard polyurethane foams to use.As surfactant, use the graft copolymer or the segmented copolymer of polydimethylsiloxane and polydimethylsiloxane and polyepoxide usually.As polyepoxide, can use the random copolymers or the segmented copolymer of polyethylene oxide, poly(propylene oxide), oxyethane and the propylene oxide of molecular-weight average 5000～8000.
In polyol composition for rigid polyurethane foam of the present invention, can also use fire retardant known to those skilled in the art, tinting material, oxidation inhibitor, antiscorch(ing) etc.
As fire retardant, can enumerate metallic compounds such as the compound that contains halogen, organophosphorus compounds, ANTIMONY TRIOXIDE SB 203 99.8 PCT, aluminium hydroxide.
These fire retardants, organophosphate for example, if excessive interpolation, the physical property of the hard polyurethane foams that then obtains reduces sometimes, in addition, if excessively add metal compound powders such as ANTIMONY TRIOXIDE SB 203 99.8 PCT, then exist to produce foamy foaming behavior is shown problems such as influence, its addition is limited in the scope that does not produce such problem.
In hard polyurethane foams of the present invention, the optionally suitable softening agent that uses.Such softening agent also preferably has the material that helps flame retardant resistance, can use halogenated alkyl ester, alkyl phosphate or aryl phosphate ester, the phosphonic acid ester etc. of phosphoric acid, particularly, can enumerate tris(2-chloroethyl)phosphate (CLP, big eight chemistry systems), tricresyl phosphate (β-chlorine propyl ester) (TMCPP, big eight chemistry systems), tricresyl phosphate (butoxy ethyl ester) (TBXP, big eight chemistry systems), tributyl phosphate, triethyl phosphate, phosphenylic acid tolyl ester, dimethyl methyl phosphonate etc., can use these a kind or more kinds of.The addition of softening agent, with respect to polyhydroxy reactant 100 weight parts, preferred 5～30 weight parts.If surpass this scope, then take place to obtain sufficient plasticization effect, or produce problem such as foamy physical property reduction.
Form the polyisocyanate compound of hard polyurethane foams as mixing, react with polyhydric alcohol composition, wait from physical property superiority, the low cost of the rapid degree of easiness, the reaction of operation, the hard polyurethane foams that obtains, use aqueous MDI.As aqueous MDI, can use the MDI (MillionateMTL that does not refine (rough) MDI (c-MDI) (44V-10,44V-20 etc. (SumitomoBayer Urethane Co., Ltd system)), contains ウ レ ト Application イ ミ Application; Japanese polyurethane industry system) etc.In these polyisocyanate compounds, from the physical property excellences such as physical strength of the hard polyurethane foams that forms, and these aspects of low price see that preferred especially the use refined (rough) MDI.
Except aqueous MDI, can also and with other polyisocyanate compound.As such polyisocyanate compound, unqualified, can use in the technical field of urethane known two or polyisocyanate compound.
Polyol composition for rigid polyurethane foam of the present invention can be used for the manufacturing of the hard polyurethane foams demixing plate, spray foam (ス プ レ one Off オ one system) etc. of quantity-produced hard polyurethane foams, the injection forming of plate bearing (ス ラ Block ス ト Star Network) foam, demixing plate etc.
(embodiment)
Below, the embodiment that shows formation of the present invention and effect is particularly described.
The constituent material of polyhydric alcohol composition is shown in Table 1.
Table 1
| Composition | The supplier | Content | |
| Polyvalent alcohol | A | East nation physics and chemistry | The phthalic acid ester polyol (hydroxyl value=250) of birdsing of the same feather flock together |
| B | The military field of Mitsui chemistry | Ethylenediamines polyether polyol (hydroxyl value=760) | |
| C | Asahi Glass | Ethylenediamines polyether polyol (hydroxyl value=450) | |
| D | Asahi Glass | Dihydroxyphenyl propane class polyether polyol (hydroxyl value=280) | |
| Surfactant | SH-193 | Dow Coring Toray Co.，Ltd | Silicon class tensio-active agent |
| Fire retardant | TMCPP | Big eight chemical industry | The phosphoric acid ester fire retardant |
| Catalyzer | BELCAT9540 | Perron company | Potassium octanoate |
| Dabco-33L V | Air Products Japan | Amines catalyst (triethylenediamine 33%DPG solution) | |
| Isocyanic ester | 44V-20 | Sumitomo Bayer Urethane | Rough MDI (NCO=31.0 weight %) |
The composition of polyhydric alcohol composition and the addition of foaming agent composotion (weight part) are documented in table 2～4.Adjust the addition of foaming agent composotion so that the density of the hard polyurethane foams during free foaming reaches 25kg/m
3Foaming agent composotion is the composition that has added in advance in as HFC-245fa, the HFC-365mfc of whipping agent, HFE-254pc as the Ethyl carbitol acetate ester (CAc) of the additive of the vapour pressure that reduces whipping agent.
Hard polyurethane foams is according to the usual method manufacturing.Promptly, in the composition of table 1 record, mix the composition and the foaming agent composotion that stir except isocyanate prepolymer composition, and adjustment polyhydric alcohol composition, temperature is adjusted into 20 ℃, then temperature is adjusted into 20 ℃ polyhydroxy reactant and isocyanate prepolymer composition mixed in accordance with regulations and stirs, and make it foamed solidification and obtain hard polyurethane foams.
＜estimate
(vapour pressure evaluation)
50g is adjusted into regulation cooperates the polyhydric alcohol composition stoste of ratio to be encased in the SUS container made of capacity 100ml, make container be in airtight state fully, carry out the freezing degassing by liquid nitrogen after, be statically placed in 40 ℃ the thermostatic bath, measure absolute vapour pressure P.The decompression rate is calculated by following formula.P0 is the vapour pressure that whipping agent only uses 245fa (comparative example 2).
Decompression rate (%)=100 (P0-P)/P0
(compressive strength)
In container, cut out the cubes of 50mm * 50mm * 50mm, measure according to JISA9511 (expanded plastic lagging material) benchmark by the foam of free foaming.
(dimensional stability)
In container, cut out the cubes of 100mm * 100mm * 100mm, under-30 ℃ atmosphere, placed 24 hours the size up variable quantity by the foam of free foaming.Evaluation result is expressed as size changing rate (△ %).
(cementability)
On the kraft paper plane materiel, make the foam of free foaming, will introduce the recess of wide 5cm with the bonding plane materiel of foam from the inside then.Stripped end uses steelyard to stretch then, measures bonding strength (gf/5cm).
(bubble stability)
Foam by visual observation free foaming in container.Evaluation result is by following canonical representation.
Zero hole homogeneous and fine and closely woven is equal to HCFC-141b.
△ exists the hole defeated and dispersed, and is poorer slightly than HCFC-141b.
* hole is defeated and dispersed serious, and is bad for foaming.
＜evaluation result 〉
Evaluation result is shown in the hypomere of table 2～4.Foaming agent composotion shown in the table 2 is the composition that has been pre-mixed HFC-245fa and vapour pressure depressant CAc, and the foaming agent composotion shown in the table 3 is to be the composition that is made of 3 compositions that have been pre-mixed HFC-245fa, HFE-254pc and CAc by the foaming agent composotion shown in 3 compositions that have been pre-mixed HFC-245fa, HFC-365mfc and CAc, the table 4.Result from these tables, by making foaming agent composotion of the present invention, the vapour pressure of whipping agent significantly reduces, and with in the past use the equal operation of polyhydric alcohol composition of HCFC-141b become possibility, simultaneously, cementability, bubble stability with plane materiel have also been improved.But,, obtained following view for comparative example.For dimensional stability, having used HCFC-141b is-17.0% as the foam of whipping agent, and this is judged as benchmark.
A) be 55/45 o'clock at HFC-245fa/CAc, CAc is too much, its result, and dimensional stability is than the foam low (comparative example 3) that uses HCFC-141b as whipping agent.
B) HFC-245fa/HFC-365mfc is that 50/50 o'clock (comparative example 4), HFC-245fa/HFE-254pc are 40/60 o'clock (comparative example 7), the addition of HFC-365mfc or HFE-254pc is too much, its result, dimensional stability is lower as the foam of whipping agent than using HCFC-141b.
C) though whipping agent form within the scope of the invention, when in the polyol compound total amount based on the nitrogen concentration less than 0.5 weight % of tertiary amino group the time, bubble stability reduces, and also reduces (comparative example 5,8) with the bonding strength of plane materiel.If the nitrogen concentration based on tertiary amino group surpasses 9 weight %, the dimensional stability of the hard polyurethane foams that obtains reduces (comparative example 6,9).
Table 2
| Embodiment | Comparative example | |||||||
| 1 | 2 | 3 | 1 | 2 | 3 | |||
| Polyol compound | A | 45 | 45 | 45 | 50 | 50 | 50 | |
| B | 45 | 45 | 45 | 40 | 40 | 40 | ||
| C | ||||||||
| D | 10 | 10 | 10 | 10 | 10 | 10 | ||
| Whipping agent | HFC-245fa | 50.0 | 55.0 | 59.0 | 50.0 | 62.0 | ||
| HFC-365mfc | ||||||||
| HCFC-141b | 46.0 | |||||||
| Vapor pressure lowering agent CAc | 5.6 | 14.3 | 25.3 | - | - | 50.7 | ||
| Catalyzer | Perron9540 | 4.0 | 4.0 | 4.0 | 4.0 | 4.0 | 4.0 | |
| Dabco-33LV | 4.0 | 4.0 | 4.0 | 4.0 | 4.0 | 4.0 | ||
| Fire retardant TMCPP | 15 | 15 | 15 | 15 | 15 | 15 | ||
| Surfactant SH-193 | 2.0 | 2.0 | 2.0 | 2.0 | 2.0 | 2.0 | ||
| Nitrogen in the polyol compound (wt%) | 4.3 | 4.3 | 4.3 | 3.8 | 3.8 | 3.8 | ||
| [HFC total amount]/[CAc] | 90/10 | 80/20 | 70/30 | - | 100/0 | 55/45 | ||
| The vapour pressure evaluation result | Absolute vapour pressure (40 ℃ of kPa at) | 186 | 177 | 165 | 203 | 158 | ||
| Decompression rate (%) | 8 | 13 | 19 | 0 | 21 | |||
| The foam evaluation result | Dimensional stability (△ %) | -1.1 | -3.4 | -7.4 | -17.0 | -2.0 | -21.3 | |
| Compressive strength (kPa) | 162 | 157 | 156 | 145 | 186 | 139 | ||
| Cohesive strength (gf/5cm) | 1600 | 1500 | 1550 | 1800 | 400 | 1500 | ||
| Bubble stability | ○～△ | ○ | ○ | ○ | × | ○ | ||
Table 3
| Embodiment | Comparative example | |||||||||
| 4 | 5 | 6 | 7 | B | 4 | 5 | 6 | |||
| Polyol compound | A | 60 | 60 | 50 | 45 | 15 | 45 | 73 | ||
| B | 20 | 20 | 40 | 45 | 85 | 45 | 100 | |||
| C | 7 | |||||||||
| D | 20 | 20 | 10 | 10 | 10 | 20 | ||||
| Whipping agent | HFC-245fa | 40.0 | 49.9 | 38.0 | 32.4 | 43.2 | 27.5 | 43.0 | 43.0 | |
| HFC-365mfc | 10.0 | 12.5 | 16.2 | 21.6 | 10.8 | 27.5 | 10.8 | 10.8 | ||
| HCFC-141b | ||||||||||
| Vapor pressure lowering agent CAc | 5.6 | 41.6 | 6.0 | 6.0 | 13.5 | 6.1 | 13.5 | 13.5 | ||
| Catalyzer | Pcrron9540 | 4.0 | 4.0 | 4.0 | 4.0 | 4.0 | 4.0 | 4.0 | 4.0 | |
| DabCo-33LV | 4.0 | 4.0 | 4.0 | 4.0 | 4.0 | 4.0 | 4.0 | 4.0 | ||
| Fire retardant TMCPP | 15 | 15 | 15 | 15 | 15 | 15 | 15 | 15 | ||
| Surfactant SH-193 | 2.0 | 2.0 | 2.0 | 2.0 | 2.0 | 2.0 | 2.0 | 2.0 | ||
| Nitrogen in the polyol compound (wt%) | 1.9 | 1.9 | 3.8 | 4.3 | 8.2 | 4.3 | 0.4 | 10.0 | ||
| [HFC-245fa]/[HFc-365mfc] | 80/20 | 80/20 | 70/30 | 60/40 | 80/20 | 50/50 | 80/20 | 80/20 | ||
| [HFC total amount]/[CAc] | 90/10 | 60/40 | 90/10 | 90/10 | 80/20 | 90/10 | 80/20 | 80/20 | ||
| The vapour pressure evaluation result | Absolute vapour pressure (40 ℃ of kPa at) | 165 | 134 | 155 | 156 | 158 | 148 | 168 | 159 | |
| Decompression rate (%) | 18 | 34 | 24 | 24 | 21 | 27 | 17 | 21 | ||
| The foam evaluation result | Dimensional stability (△ %) | -1.9 | -10.9 | -7.2 | -10.6 | -16.3 | -20.6 | -11.0 | -25.6 | |
| Compressive strength (kPa) | 161 | 146 | 179 | 171 | 151 | 137 | 174 | 132 | ||
| Cohesive strength (gf/5cm) | 1200 | 1350 | 1200 | 1000 | 1700 | 800 | 500 | 1750 | ||
| Bubble stability | ○ | ○ | ○ | ○ | ○ | △ | × | ○ | ||
Table 4
| Embodiment | Comparative example | ||||||||||||
| 9 | 10 | 11 | 12 | 13 | 14 | 15 | 7 | 8 | 9 | ||||
| Polyol compound | A | 45 | 45 | 45 | 60 | 60 | 50 | 50 | 50 | 73 | |||
| B | 45 | 45 | 45 | 20 | 20 | 40 | 40 | 40 | 100 | ||||
| C | 7 | ||||||||||||
| D | 10 | 10 | 10 | 20 | 20 | 10 | 10 | 10 | 20 | ||||
| Whipping agent | HPC-245fa | 48.6 | 50.0 | 40.0 | 35.0 | 38.0 | 30.0 | 25.0 | 20.0 | 40.0 | 40.0 | ||
| HFE-254pc | 5.4 | 5.6 | 10.0 | 15.0 | 16.0 | 20.0 | 25.0 | 30.0 | 10.0 | 10.0 | |||
| HCFC-141b | |||||||||||||
| Vapor pressure lowering agent CAc | 6.0 | 23.8 | 12.0 | 5.6 | 23.0 | 5.6 | 5.6 | 5.6 | 12.0 | 12.0 | |||
| Catalyzer | Perron9540 | 4.0 | 4.0 | 4.0 | 4.0 | 4.0 | 4.0 | 4.0 | 4.0 | 4.0 | 4.0 | ||
| Dabco-33LV | 4.0 | 4.0 | 4.0 | 4.0 | 4.0 | 4.0 | 4.0 | 4.0 | 4.0 | 4.0 | |||
| Fire retardant TMCPP | 15 | 15 | 15 | 15 | 15 | 15 | 15 | 15 | 15 | 15 | |||
| Surfactant SH-193 | 2.0 | 2.0 | 2.0 | 2.0 | 2.0 | 2.0 | 2.0 | 2.0 | 2.0 | 2.0 | |||
| Nitrogen in the polyol compound (wt%) | 4.3 | 4.3 | 4.3 | 1.9 | 1.9 | 3.8 | 3.8 | 3.8 | 0.4 | 10.0 | |||
| [HFC-245fa]/[HFE-254pc] | 90/10 | 90/10 | 80/20 | 70/30 | 70/30 | 60/40 | 50/50 | 40/60 | 80/20 | 80/20 | |||
| [HFC-245fa+HFE-254pc]/[CAc] | 90/10 | 70/30 | 80/20 | 90/10 | 70/30 | 90/10 | 90/10 | 90/10 | 80/20 | 80/20 | |||
| The vapour pressure evaluation result | Absolute vapour pressure (40 ℃ of kPa at) | 178 | 162 | 159 | 167 | 148 | 153 | 147 | 139 | 160 | 158 | ||
| Decompression rate (%) | 13 | 20 | 22 | 18 | 27 | 25 | 28 | 32 | 21 | 22 | |||
| The foam evaluation result | Dimensional stability (△ %) | -1.5 | -2.2 | -3.2 | -5.4 | -10.4 | -17.0 | -17.0 | -22.8 | -11.0 | -26.3 | ||
| Compressive strength (kPa) | 183 | 181 | 180 | 194 | 152 | 178 | 162 | 135 | 170 | 146 | |||
| Cohesive strength (gf/5cm) | 1200 | 1500 | 1300 | 1100 | 1300 | 1000 | 1000 | 1200 | 600 | 1750 | |||
| Bubble stability | ○～△ | ○ | ○～△ | ○～△ | ○～△ | △ | △ | △ | × | ○ | |||
Industrial applicibility
As described above, according to formation of the present invention, provide use HFC-245fa as blowing agent, suppressed simultaneously the manufacture method of polyol composition for rigid polyurethane foam and the hard polyurethane foams of its vapour pressure. Therefore, the present invention is industrial significant.
Claims (4)
1. polyol composition for rigid polyurethane foam, it contains polyol compound, whipping agent, surfactant, catalyzer at least, and by mixing with the isocyanate prepolymer composition that contains isocyanate compound, and makes it foamed solidification and form hard polyurethane foams, it is characterized in that
The 1st whipping agent of the main component of above-mentioned whipping agent is 1,1,1,3, and the 3-pentafluoropropane as the vapor pressure lowering agent, contains acetate ethyl carbitol ester, and above-mentioned 1,1,1,3,3-pentafluoropropane/acetate ethyl carbitol ester=95/5～60/40 weight ratio,
Above-mentioned polyol compound comprises the polyol compound with tertiary amine group, and is 0.5～9 weight % in the polyol compound based on the nitrogen of above-mentioned tertiary amine group.
2. according to the polyol composition for rigid polyurethane foam of claim 1 record, it is characterized in that, further contain as 1,1 of the 2nd whipping agent, 1,3, the 3-3-pentafluorobutane, and 1,1,1,3,3-pentafluoropropane/1,1,1,3,3-3-pentafluorobutane 〉=60/40, (1,1,1,3,3-pentafluoropropane+1,1,1,3, the 3-3-pentafluorobutane)/acetate ethyl carbitol ester=95/5～60/40 weight ratio.
3. according to the polyol composition for rigid polyurethane foam of claim 1 record, it is characterized in that, further contain tetrafluoride methyl ethyl ether as the 3rd whipping agent, and 1,1,1,3,3-pentafluoropropane/tetrafluoride methyl ethyl ether 〉=50/50, (1,1,1,3,3-pentafluoropropane+tetrafluoride methyl ethyl ether)/acetate ethyl carbitol ester=95/5～60/40 weight ratio.
4. the manufacture method of a hard polyurethane foams, it mixes isocyanate prepolymer composition with polyhydric alcohol composition, and make it foaming, solidify and become hard polyurethane foams, it is characterized in that, as polyhydric alcohol composition, use the polyol composition for rigid polyurethane foam of each record in the claim 1～3.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29407/2003 | 2003-02-06 | ||
| JP2003029407A JP3902143B2 (en) | 2003-02-06 | 2003-02-06 | Polyol composition for rigid polyurethane foam and method for producing rigid polyurethane foam |
Publications (2)
| Publication Number | Publication Date |
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| CN1747978A CN1747978A (en) | 2006-03-15 |
| CN1307230C true CN1307230C (en) | 2007-03-28 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB2004800035236A Expired - Fee Related CN1307230C (en) | 2003-02-06 | 2004-02-05 | Polyol composition for rigid polyurethane foam and process for producing rigid polyurethane foam |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JP3902143B2 (en) |
| KR (1) | KR100982430B1 (en) |
| CN (1) | CN1307230C (en) |
| HK (1) | HK1085494A1 (en) |
| TW (1) | TW200418897A (en) |
| WO (1) | WO2004069891A1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2646990C (en) * | 2006-03-21 | 2018-02-20 | Honeywell International Inc. | Foaming agents containing fluorine substituted unsaturated olefins |
| JP5109556B2 (en) * | 2006-11-01 | 2012-12-26 | セントラル硝子株式会社 | Azeotropic and azeotrope-like compositions comprising 1,1,2,2-tetrafluoro-1-methoxyethane |
| KR101321258B1 (en) * | 2011-07-04 | 2013-10-28 | 삼성중공업 주식회사 | Polyurethane Form Having Improved Insulating Property by Eco-Friendly Foaming Agent |
| CN102604022A (en) * | 2012-03-08 | 2012-07-25 | 巨化集团公司 | Hard polyurethane foam polyalcohol composite for refrigerating industry |
| JP6764664B2 (en) * | 2016-02-29 | 2020-10-07 | 三洋化成工業株式会社 | Method for producing (polyoxyalkylene) polyol and method for producing rigid polyurethane foam |
| CN109438664B (en) * | 2018-09-30 | 2021-06-18 | 山东一诺威新材料有限公司 | Flame-retardant rigid foam polyurethane material for household appliances and preparation method thereof |
| KR102140285B1 (en) * | 2018-12-07 | 2020-07-31 | 서울시립대학교 산학협력단 | Polyurethane foam and manufacturing method of the same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1142513A (en) * | 1995-03-14 | 1997-02-12 | 三菱化成陶氏株式会社 | Process for preparing open-cellular rigid polyurethane foam |
| CN1244878A (en) * | 1997-01-30 | 2000-02-16 | 国际壳牌研究有限公司 | Use of polyol mixtures in rigid and semi rigid polyurethane foams |
| US6043291A (en) * | 1997-06-03 | 2000-03-28 | Asahi Glass Company Ltd. | Method for producing foamed synthetic resin |
| US6080799A (en) * | 1996-12-17 | 2000-06-27 | Solvay Fluor Und Derivate Gmbh | Mixtures containing 1,1,1,3,3 pentafluorobutane |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3909536B2 (en) * | 1997-06-03 | 2007-04-25 | 旭硝子株式会社 | Manufacturing method of rigid foam synthetic resin |
| JP2001247645A (en) | 1999-12-28 | 2001-09-11 | Bridgestone Corp | Rigid polyurethane foam and method for producing the same |
| JP2003535157A (en) * | 2000-03-16 | 2003-11-25 | アライドシグナル インコーポレイテッド | Foam under foamed hydrofluorocarbon and method for producing the same |
| JP3894326B2 (en) * | 2001-11-13 | 2007-03-22 | ダイキン工業株式会社 | Method for producing synthetic resin foam |
| JP4215553B2 (en) * | 2002-06-28 | 2009-01-28 | セントラル硝子株式会社 | Foaming agent composition, premix for the preparation of rigid polyurethane foam or polyisocyanurate and process for producing said foam |
| JP3952185B2 (en) * | 2002-07-16 | 2007-08-01 | ダイキン工業株式会社 | Method for producing foaming agent, premix and foam having low vapor pressure |
-
2003
- 2003-02-06 JP JP2003029407A patent/JP3902143B2/en not_active Expired - Fee Related
-
2004
- 2004-02-05 CN CNB2004800035236A patent/CN1307230C/en not_active Expired - Fee Related
- 2004-02-05 KR KR1020057014419A patent/KR100982430B1/en not_active IP Right Cessation
- 2004-02-05 WO PCT/JP2004/001196 patent/WO2004069891A1/en active Application Filing
- 2004-02-06 TW TW093102814A patent/TW200418897A/en not_active IP Right Cessation
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2006
- 2006-05-15 HK HK06105579A patent/HK1085494A1/en not_active IP Right Cessation
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1142513A (en) * | 1995-03-14 | 1997-02-12 | 三菱化成陶氏株式会社 | Process for preparing open-cellular rigid polyurethane foam |
| US6080799A (en) * | 1996-12-17 | 2000-06-27 | Solvay Fluor Und Derivate Gmbh | Mixtures containing 1,1,1,3,3 pentafluorobutane |
| CN1244878A (en) * | 1997-01-30 | 2000-02-16 | 国际壳牌研究有限公司 | Use of polyol mixtures in rigid and semi rigid polyurethane foams |
| US6043291A (en) * | 1997-06-03 | 2000-03-28 | Asahi Glass Company Ltd. | Method for producing foamed synthetic resin |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3902143B2 (en) | 2007-04-04 |
| TWI332959B (en) | 2010-11-11 |
| CN1747978A (en) | 2006-03-15 |
| KR100982430B1 (en) | 2010-09-15 |
| HK1085494A1 (en) | 2006-08-25 |
| KR20050121199A (en) | 2005-12-26 |
| TW200418897A (en) | 2004-10-01 |
| JP2004262967A (en) | 2004-09-24 |
| WO2004069891A1 (en) | 2004-08-19 |
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