CN111848531A - Rigid polyurethane foam - Google Patents
Rigid polyurethane foam Download PDFInfo
- Publication number
- CN111848531A CN111848531A CN201910359180.5A CN201910359180A CN111848531A CN 111848531 A CN111848531 A CN 111848531A CN 201910359180 A CN201910359180 A CN 201910359180A CN 111848531 A CN111848531 A CN 111848531A
- Authority
- CN
- China
- Prior art keywords
- poly
- isocyanurates
- reaction
- trimerization
- reaction system
- 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.)
- Pending
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- 229920005830 Polyurethane Foam Polymers 0.000 title abstract description 3
- 239000011496 polyurethane foam Substances 0.000 title abstract description 3
- 238000005829 trimerization reaction Methods 0.000 claims abstract description 59
- 239000012948 isocyanate Substances 0.000 claims abstract description 58
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 55
- 150000003254 radicals Chemical class 0.000 claims abstract description 46
- 239000003999 initiator Substances 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- -1 aromatic isocyanates Chemical class 0.000 claims description 59
- 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 claims description 31
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 27
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 25
- 229920005862 polyol Polymers 0.000 claims description 25
- 150000003077 polyols Chemical class 0.000 claims description 25
- 239000005056 polyisocyanate Substances 0.000 claims description 21
- 229920001228 polyisocyanate Polymers 0.000 claims description 21
- 230000008569 process Effects 0.000 claims description 18
- 150000002978 peroxides Chemical group 0.000 claims description 17
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 15
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 15
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 15
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 13
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 8
- 239000004604 Blowing Agent Substances 0.000 claims description 6
- 239000011810 insulating material Substances 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- 150000004978 peroxycarbonates Chemical class 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 39
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 description 31
- 229920005989 resin Polymers 0.000 description 22
- 239000011347 resin Substances 0.000 description 22
- 230000008859 change Effects 0.000 description 14
- 239000004721 Polyphenylene oxide Substances 0.000 description 11
- 229920000570 polyether Polymers 0.000 description 11
- 238000000354 decomposition reaction Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 239000004814 polyurethane Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229920005906 polyester polyol Polymers 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 229920002635 polyurethane Polymers 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920000515 polycarbonate Polymers 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000004088 foaming agent Substances 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- NVSXSBBVEDNGPY-UHFFFAOYSA-N 1,1,1,2,2-pentafluorobutane Chemical compound CCC(F)(F)C(F)(F)F NVSXSBBVEDNGPY-UHFFFAOYSA-N 0.000 description 2
- OYWRDHBGMCXGFY-UHFFFAOYSA-N 1,2,3-triazinane Chemical class C1CNNNC1 OYWRDHBGMCXGFY-UHFFFAOYSA-N 0.000 description 2
- 229940043375 1,5-pentanediol Drugs 0.000 description 2
- GEEGPFGTMRWCID-UHFFFAOYSA-N 1-n,1-n,1-n',1-n'-tetramethylbutane-1,1-diamine Chemical compound CCCC(N(C)C)N(C)C GEEGPFGTMRWCID-UHFFFAOYSA-N 0.000 description 2
- WMNWJTDAUWBXFJ-UHFFFAOYSA-N 3,3,4-trimethylheptane-2,2-diamine Chemical compound CCCC(C)C(C)(C)C(C)(N)N WMNWJTDAUWBXFJ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 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 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical class CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical class NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 2
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229930006000 Sucrose Natural products 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
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- XXKOQQBKBHUATC-UHFFFAOYSA-N cyclohexylmethylcyclohexane Chemical compound C1CCCCC1CC1CCCCC1 XXKOQQBKBHUATC-UHFFFAOYSA-N 0.000 description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical class CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 description 2
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- 229960004063 propylene glycol Drugs 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- HGXJDMCMYLEZMJ-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOOC(=O)C(C)(C)C HGXJDMCMYLEZMJ-UHFFFAOYSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- SXKNYNUXUHCUHX-UHFFFAOYSA-N 1,1,2,3,3,4-hexafluorobut-1-ene Chemical compound FCC(F)(F)C(F)=C(F)F SXKNYNUXUHCUHX-UHFFFAOYSA-N 0.000 description 1
- FRCHKSNAZZFGCA-UHFFFAOYSA-N 1,1-dichloro-1-fluoroethane Chemical compound CC(F)(Cl)Cl FRCHKSNAZZFGCA-UHFFFAOYSA-N 0.000 description 1
- NDKGUMMLYBINOC-UHFFFAOYSA-N 1,2-dichloro-1-fluoroethane Chemical compound FC(Cl)CCl NDKGUMMLYBINOC-UHFFFAOYSA-N 0.000 description 1
- 229940035437 1,3-propanediol Drugs 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 1
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 1
- LDTMPQQAWUMPKS-UHFFFAOYSA-N 1-chloro-3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)C=CCl LDTMPQQAWUMPKS-UHFFFAOYSA-N 0.000 description 1
- JIABEENURMZTTI-UHFFFAOYSA-N 1-isocyanato-2-[(2-isocyanatophenyl)methyl]benzene Chemical compound O=C=NC1=CC=CC=C1CC1=CC=CC=C1N=C=O JIABEENURMZTTI-UHFFFAOYSA-N 0.000 description 1
- LFSYUSUFCBOHGU-UHFFFAOYSA-N 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=CC=C1N=C=O LFSYUSUFCBOHGU-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical group [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
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- RBFRSIRIVOFKDR-UHFFFAOYSA-N [C].[N].[O] Chemical compound [C].[N].[O] RBFRSIRIVOFKDR-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- MKUXAQIIEYXACX-UHFFFAOYSA-N aciclovir Chemical compound N1C(N)=NC(=O)C2=C1N(COCCO)C=N2 MKUXAQIIEYXACX-UHFFFAOYSA-N 0.000 description 1
- 229960004150 aciclovir Drugs 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
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- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- BLCKNMAZFRMCJJ-UHFFFAOYSA-N cyclohexyl cyclohexyloxycarbonyloxy carbonate Chemical compound C1CCCCC1OC(=O)OOC(=O)OC1CCCCC1 BLCKNMAZFRMCJJ-UHFFFAOYSA-N 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-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
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
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- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-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
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000012934 organic peroxide initiator Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- AUHHYELHRWCWEZ-UHFFFAOYSA-N tetrachlorophthalic anhydride Chemical compound ClC1=C(Cl)C(Cl)=C2C(=O)OC(=O)C2=C1Cl AUHHYELHRWCWEZ-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- SZHOJFHSIKHZHA-UHFFFAOYSA-N tridecanoic acid Chemical compound CCCCCCCCCCCCC(O)=O SZHOJFHSIKHZHA-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/30—Only oxygen atoms
- C07D251/34—Cyanuric or isocyanuric esters
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/794—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aromatic isocyanates or isothiocyanates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention relates to rigid polyurethane foams. The invention relates to a method for producing (poly) isocyanurates, to the (poly) isocyanurates produced by said method and to the use thereof. The method of the invention uses the free radical initiator as the trimerization catalyst, provides a trimerization catalytic reaction system with mild and controllable reaction rate, and can lead the trimerization reaction of the isocyanate to be carried out in a very mild way.
Description
Technical Field
The invention relates to a method for producing (poly) isocyanurates, to the (poly) isocyanurates produced by said method and to the use thereof.
Background
Trimerization of isocyanate functional groups is a curing cross-linking reaction commonly used in polyurethane reaction systems. The trimerization reaction typically occurs by polymerizing three isocyanate groups into an isocyanurate six-membered ring in the presence of one or more trimerization catalysts. However, the catalytic activity of the conventional trimerization catalyst is relatively high, so that the trimerization reaction speed is relatively high.
The trimerization catalytic reaction of isocyanate is a curing and crosslinking method commonly used in the application field of polyurethane materials. The isocyanurate six-membered ring rigid structure generated by trimerization can provide high crosslinking degree to enhance the mechanical strength of the cured polyurethane material, and meanwhile, due to the high carbon-nitrogen-oxygen content of the isocyanurate six-membered ring and the excellent flame retardance generated by the conjugated aromatic structure, the integral flame retardance of the polyurethane material can be improved. For these reasons, the trimerization of isocyanate functions is widely used in the field of polyurethane materials.
The trimerization of isocyanates takes place in the presence of a trimerization catalyst. The trimerization catalyst is generally a phosphorus-containing, amine-containing or metal salt-containing substance, or some suitable combination thereof. The trimerization reactions initiated by these catalysts are generally fast reactions and can occur rapidly in a short time, for example tens of seconds or minutes, to catalyze the trimerization reaction. A large amount of reaction heat is released along with the occurrence of the trimerization reaction, and since the polyurethane resin is a poor conductor of heat, the heat released from the trimerization reaction is difficult to be effectively released to the external environment in a short time, so that the heat released from the reaction is retained in the resin, thereby causing a significantly rapid increase in the temperature of the whole polyurethane resin reaction system. This temperature rise, in turn, further accelerates the isocyanate trimerization reaction and/or other polymerization reactions, thereby generating more heat which, in turn, continues to cause a temperature rise in the resin system. The circulation mode of ' heat release ' -temperature increase promotion ' -heat re-release ' -temperature increase re-promotion ' -belongs to a self-accelerated catalytic reaction mode, which can lead to the acceleration of the trimerization reaction of isocyanate and the poor controllability of the trimerization reaction. Especially when slow trimerization is required in certain applications, it is difficult to achieve the goal using these conventional trimerization catalysts.
CN101848951A discloses a process for the preparation of highly stable, liquid isocyanurate-modified PMDI compositions having higher viscosity and generally comparable functionality compared to conventional PMDI. It is characterized by comprising the following steps: (a) tri-polymerizing conventional PMDI having a viscosity of about 30 to about 300cps in the presence of a catalytically effective amount of a trimerization catalyst to produce isocyanurate-containing PMDI having a viscosity in the range of about 2,000mPas to about 200,000mPas at 25 ℃; (b) deactivating the trimerization catalyst with a catalyst deactivator to provide a mixture comprising isocyanurate-modified PMDI and deactivated trimerization catalyst; and (c) blending the mixture of step (b) with an amount of conventional PMDI sufficient to provide a blend having a viscosity in the range of from about 400mPas to about 20,000mPas at 25 ℃ and a free NCO content comparable to conventional PMDI.
CN108026232A discloses a process for preparing a PUR/PIR-rigid foam by reacting 1) an isocyanate component a comprising 1.1)15 to 25 wt.% isocyanurate groups, and 1.2)30 to 55 wt.% monomeric MDI, 1.3) an NCO-content of 23 to 30 wt.% (EN ISO 11909: 2007) each based on the total weight of the isocyanate component, and 2) a PUR/PIR system of polyol formulation (B) in the presence of the following components: 3) blowing agent (C), 4) catalyst (D), and 5) optionally further auxiliaries and additives (E) wherein isocyanate component a is prepared by a process comprising the steps of (i) preparing isocyanate blend a2 by partial trimerization of an isocyanate mixture a1 comprising oligomeric and monomeric MDI, wherein a1 prior to the trimerization has a total content of monomeric MDI of from-55 to 80% by weight, based on the total weight of a1, and-a viscosity at 25 ℃ of < 30mPas (DIN EN ISO 3219: 1994) (ii) a And (ii) optionally subsequently mixing the partially trimerized isocyanate blend A2 obtained in step (i) with further isocyanate (A3), preferably polymeric MDI, and wherein the system comprising components A to E has an isocyanate characteristic number of from 90 to 150.
Despite the above disclosures, there is still a great need in the industry for a process for the preparation of (poly) isocyanurates which is reaction-and slowly controllable.
Disclosure of Invention
In one aspect of the present invention, there is provided a process for preparing (poly) isocyanurates by reacting a reaction system comprising:
one or more polyisocyanates;
at least one free radical initiator.
Preferably, the isocyanate is selected from aromatic isocyanates, preferably diphenylmethane diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate or combinations thereof, particularly preferably diphenylmethane diisocyanate or (poly) diphenylmethane diisocyanate.
Preferably, the free radical initiator is present in an amount of from 0.1 to 5pbw, preferably from 0.2 to 4pbw, more preferably from 0.4 to 3pbw, based on the total weight of the reaction system.
Preferably, the radical initiator is selected from peroxides and/or azo compounds.
Preferably, the peroxide is selected from ketone peroxide, carbonate peroxide, acyl peroxide, peroxyester, hydrogen peroxide, alkyl peroxide or any combination thereof, preferably tert-butyl peroxybenzoate, benzoyl peroxide or any combination thereof.
Preferably, the azo compound is selected from azobisisobutyronitrile, azobisisoheptonitrile or any combination thereof.
Preferably, the reaction time of the reaction system is > 5 hours, preferably > 10 hours, particularly preferably > 24 hours.
Preferably, the temperature of the reaction system after the reaction is different from the temperature before the reaction by +/-2 ℃.
Through repeated experiments, we have surprisingly found that free radical initiators can catalyze the trimerization of isocyanates. Moreover, free radical initiators can provide a smooth and controlled polymerization reaction compared to conventional trimerization catalysts.
The method for preparing (poly) isocyanurate of the invention changes the conditions of violent reaction intensity and much temperature rise of trimerization reaction in the prior art. The isocyanate reaction system of the present invention has enough time for the heat released by the chemical reaction to diffuse to the external environment when the trimerization reaction occurs, rather than being retained in the resin system. Therefore, the temperature of the whole resin system is not increased by the part of heat, so that the trimerization reaction of the resin is not carried out, and the additional temperature change is not carried out at the same time, and the temperature of the whole resin is kept constant at a preset value, so that the chemical reaction of the resin system has better controllability.
In still another aspect of the present invention, there is provided a (poly) isocyanurate produced by the above-mentioned process for producing a (poly) isocyanurate according to the present invention.
In a further aspect of the present invention there is provided the use of a free radical initiator for catalysing the trimerisation of isocyanates to produce (poly) isocyanurates. The reaction system for the trimerization reaction comprises the following components:
one or more polyisocyanates;
at least one free radical initiator.
Preferably, the radical initiator is selected from peroxides and/or azo compounds.
Preferably, the peroxide is selected from ketone peroxide, carbonate peroxide, acyl peroxide, peroxyester, hydrogen peroxide, alkyl peroxide or any combination thereof, preferably tert-butyl peroxybenzoate, benzoyl peroxide or any combination thereof.
Preferably, the azo compound is selected from azobisisobutyronitrile, azobisisoheptonitrile or any combination thereof.
Preferably, the free radical initiator is present in an amount of from 0.1 to 5pbw, preferably from 0.2 to 4pbw, more preferably from 0.4 to 3pbw, based on the total weight of the reaction system.
In a further aspect of the present invention, there is provided a use of the (poly) isocyanurate obtained by the process for preparing (poly) isocyanurate of the present invention for thermal insulation.
In still another aspect of the present invention, there is provided a reaction system for preparing a polyurethane- (poly) isocyanurate compound, comprising:
(poly) isocyanurates produced by the aforementioned process of the present invention;
at least one polyol; and
optionally, at least one blowing agent.
The blowing agents which can be used according to the invention are preferably from 0.10 to 3.50% by weight, preferably from 0.5 to 2.8% by weight, particularly preferably from 1.5 to 2.6% by weight, of water, based on the total weight of the polyol.
Preferably, the reaction system of the present invention may further comprise at least one catalyst. Catalysts useful in the present invention preferably include blowing catalysts, gelling catalysts and trimerization catalysts. Wherein, the foaming catalyst is preferably selected from one, two or any mixture of more than two of pentamethyl diethylene triamine, bis-dimethyl aminoethyl ether, N, N, N ', N' -tetramethyl ethylene diamine, N, N, N ', N' -tetramethyl butane diamine and tetramethyl hexane diamine; the gel catalyst is preferably selected from one or any mixture of dimethylcyclohexylamine and dimethylbenzylamine; the trimerisation catalyst is preferably selected from one, two or any mixture of two or more of methylammonium salts, ethylammonium salts, octylamine salts or hexahydrotriazines and organometallic bases. The catalyst is preferably present in an amount of from 0.50 to 4.00pbw based on the total weight of the polyol component.
The reaction system of the present invention preferably further comprises a surfactant. The surfactant, preferably a silicone oil, is present in an amount of from 0.1 to 5.0 wt.%, preferably from 0.5 to 4.0 wt.%, particularly preferably from 1.5 to 3.0 wt.%, based on the total weight of the polyol component.
In still another aspect of the present invention, there is provided a polyurethane- (poly) isocyanurate compound produced by the reaction system for producing a polyurethane- (poly) isocyanurate compound of the present invention.
In still another aspect of the present invention, there is provided a heat insulating material comprising the (poly) isocyanurate or the polyurethane- (poly) isocyanurate compound obtained by the method for preparing (poly) isocyanurate of the present invention.
Optionally, the heat insulating material is selected from the group consisting of heat insulating board, refrigerator wall, cold insulating pipe shell, refrigerator compartment side panel and vehicle-mounted refrigerator wall.
Drawings
The invention is illustrated below with reference to the accompanying drawings:
FIG. 1 shows infrared spectra of examples of the present invention and comparative examples. Wherein curve s1 in FIG. 1 represents the system spectrum for isocyanate 44V20 alone; the curve s2 in FIG. 1 shows that after 2% by weight of TBPB has been added to the isocyanate 44V20, the viscosity has not changed in the initial stage; curve s3 in FIG. 1 shows the spectrum after 56 days of addition of 2% by weight of TBPB in isocyanate 44V 20.
Detailed Description
The following terms used in the present invention have the following definitions or explanations.
pbw is the mass fraction of each component of the reaction system;
functionality, means according to the industry formula: a functionality of hydroxyl value (Mw/56100); wherein the molecular weight is determined by GPC high performance liquid chromatography;
isocyanate index, which means a value calculated by the following formula:
according to a first aspect of the present invention, a process for preparing (poly) isocyanurates, which is prepared by reacting a reaction system comprising:
one or more polyisocyanates;
at least one free radical initiator.
Any organic polyisocyanate may be used in the preparation of the above-described processes of the present invention, including aromatic, aliphatic and cycloaliphatic polyisocyanates and combinations thereof. The polyisocyanate can be represented by the general formula R (NCO) n, wherein R represents an aliphatic hydrocarbon group having 2 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 15 carbon atoms, an araliphatic hydrocarbon group having 8 to 15 carbon atoms, and n is 2 to 4.
Useful polyisocyanates include, but are not limited to, vinyl diisocyanate, tetramethylene 1, 4-diisocyanate, Hexamethylene Diisocyanate (HDI), dodecyl 1, 2-diisocyanate, cyclobutane 1, 3-diisocyanate, cyclohexane 1, 4-diisocyanate, 1-isocyanato 3, 3, 5-trimethyl 5-isocyanatomethylcyclohexane, hexahydrotoluene 2, 4-diisocyanate, hexahydrophenyl 1, 3-diisocyanate, hexahydrophenyl 1, 4-diisocyanate, perhydrodiphenylmethane 2, 4-diisocyanate, perhydrodiphenylmethane 4, 4-diisocyanate, phenylene 1, 3-diisocyanate, phenylene 1, 4-diisocyanate, stilbene 1, 4-diisocyanate, mixtures thereof, and mixtures thereof, 3, 3-dimethyl-4, 4-diphenyldiisocyanate, toluene-2, 4-diisocyanate (TDI), toluene-2, 6-diisocyanate (TDI), diphenylmethane-2, 4 ' -diisocyanate (MDI), diphenylmethane-2, 2 ' -diisocyanate (MDI), diphenylmethane-4, 4 ' -diisocyanate (MDI), mixtures of diphenylmethane diisocyanates and/or homologues of diphenylmethane diisocyanates having more rings, polyphenylmethane polyisocyanates (polymeric MDI), naphthylene-1, 5-diisocyanates (NDI), their isomers, and any mixtures thereof.
Useful polyisocyanates also include isocyanates modified with a carbonized diamine, allophanate, or isocyanate, preferably, but not limited to, diphenylmethane diisocyanate, carbonized diamine-modified diphenylmethane diisocyanate, isomers thereof, mixtures thereof with isomers thereof.
When used in the present invention, the polyisocyanate includes an isocyanate dimer, trimer, tetramer or a combination thereof.
In certain embodiments of the present invention, the isocyanate is selected from an aromatic isocyanate, preferably diphenylmethane diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate or a combination thereof, particularly preferably diphenylmethane diisocyanate or (poly) diphenylmethane diisocyanate.
In a preferred embodiment of the invention, the polyisocyanate component is selected from polymeric MDI.
The organic polyisocyanates of the invention have an NCO content of 20 to 33 wt.%, preferably 25 to 32 wt.%, particularly preferably 30 to 32 wt.%. The NCO content was determined by GB/T12009.4-2016.
The organic polyisocyanates can also be used in the form of polyisocyanate prepolymers. These polyisocyanate prepolymers can be obtained by reacting an excess of the above organic polyisocyanate with a compound having at least two isocyanate-reactive groups at a temperature of, for example, 30 to 100 ℃, preferably about 80 ℃. The polyisocyanate prepolymers of the present invention have an NCO content of 20 to 33 wt.%, preferably 25 to 32 wt.%. The NCO content was determined by GB/T12009.4-2016.
A free radical initiator refers to an agent capable of generating free radicals in a free radical reaction. Also known as free radical initiators. The process of generating free radicals becomes chain initiation. The radical initiator that can be used in the present invention includes, but is not limited to, peroxide initiators, organic peroxide initiators and inorganic peroxide initiators, azo initiators, redox initiators, and the like.
The general structural formula of the organic peroxide compound is R-O-O-H or R-O-O-R, wherein R is alkyl, acyl, carbonate and the like. It further comprises: acyl peroxides, for example: benzoyl peroxide, lauroyl peroxide; hydroperoxides, such as: cumene hydroperoxide, tert-butyl hydroperoxide; dialkyl peroxides, for example: di-tert-butyl peroxide, dicumyl peroxide; ester peroxides, tert-butyl peroxybenzoate, tert-butyl peroxypivalate; ketone peroxides, for example: methyl ethyl ketone peroxide and cyclohexanone peroxide; dicarbonate peroxides, for example: diisopropyl peroxydicarbonate and dicyclohexyl peroxydicarbonate. Generally, the order of activity of the organic peroxide is: dicarbonate peroxide > acyl peroxide > ester peroxide > dialkyl peroxide > hydroperoxide.
Azo initiators include azobisisobutyronitrile and azobisisoheptonitrile, which belong to low-activity initiators. Azodiisobutyronitrile is commonly used, the use temperature ranges from 50 ℃ to 65 ℃, the azodiisobutyronitrile is uniformly decomposed, only one free radical is formed, and other side reactions are avoided. Is relatively stable and can be safely stored in a pure state, but can be rapidly decomposed at 80-90 ℃. The disadvantage is the relatively low decomposition rate and the lack of dehydrogenation capability of the isobutyronitrile radicals formed, which cannot be used as initiators for graft polymerization.
In general, azobisisoheptonitrile has high activity and high initiation efficiency, and can be used for substituting azobisisobutyronitrile. The azodiisobutyrate dimethyl ester (AIBME) has moderate initiation activity, easy control of polymerization reaction, no residue in the polymerization process, high product conversion rate and harmless decomposition products, and is an optimal substitute of Azodiisobutyronitrile (AIBN). The decomposition temperature of the peroxide initiator and the azo initiator is high (50-100 ℃), so that the application of the low-temperature polymerization reaction is limited.
In the examples of the present invention, the free radical initiator is present in an amount of 0.1 to 5pbw, preferably 0.2 to 4pbw, more preferably 0.4 to 3pbw, based on the total weight of the reaction system.
Preferably, the radical initiator is selected from peroxides and/or azo compounds.
Preferably, the peroxide is selected from ketone peroxide, carbonate peroxide, acyl peroxide, peroxyester, hydrogen peroxide, alkyl peroxide or any combination thereof, more preferably tert-butyl peroxybenzoate, benzoyl peroxide or any combination thereof.
Preferably, the azo compound is selected from azobisisobutyronitrile, azobisisoheptonitrile or any combination thereof.
Preferably, the reaction time of the reaction system is > 5 hours, preferably > 10 hours, particularly preferably > 24 hours.
Preferably, the temperature of the reaction system after the reaction is different from the temperature before the reaction by +/-2 ℃.
By repeated experimentation, we have surprisingly found that free radical initiators can catalyse the trimerisation reaction of isocyanates. Many conventional free radical initiators can be slowly decomposed at normal temperature or under heating, and the free radicals obtained by decomposition can continuously catalyze the trimerization reaction of isocyanate. The rate of decomposition of these free radical initiators is slow and can be considered to proceed in a controlled manner, so that the trimerization reaction it catalyzes also occurs in a slow manner.
Therefore, the method provided by the invention can be used for trimerizing the isocyanate with good controllability. Thus, the present invention provides a mild and controlled process for the trimerization of isocyanates, and the isocyanate system is such that the heat released by the chemical reaction is allowed sufficient time to diffuse to the external environment, rather than being trapped in the resin system, as the trimerization reaction takes place. Therefore, the temperature of the whole resin system is not increased by the part of heat, so that the trimerization reaction of the resin is not carried out, and the additional temperature change is not carried out at the same time, and the temperature of the whole resin is kept constant at a preset value, so that the chemical reaction of the resin system has better controllability.
In still another aspect of the present invention, there is provided a (poly) isocyanurate produced by the above-mentioned process for producing a (poly) isocyanurate according to the present invention.
In a further aspect of the present invention there is provided the use of a free radical initiator for catalysing the trimerisation of isocyanates to produce (poly) isocyanurates. The reaction system for the trimerization reaction comprises the following components:
one or more polyisocyanates;
at least one free radical initiator.
Preferably, the free radical initiator is present in an amount of from 0.1 to 5pbw, preferably from 0.2 to 4pbw, more preferably from 0.4 to 3pbw, based on the total weight of the reaction system.
Preferably, the radical initiator is selected from peroxides and/or azo compounds.
Preferably, the peroxide is selected from ketone peroxide, carbonate peroxide, acyl peroxide, peroxyester, hydrogen peroxide, alkyl peroxide or a combination thereof, more preferably tert-butyl peroxybenzoate, benzoyl peroxide or any combination thereof.
Preferably, the azo compound is selected from azobisisobutyronitrile, azobisisoheptonitrile or a combination thereof.
In a further aspect of the present invention, there is provided a use of the (poly) isocyanurate obtained by the process for preparing (poly) isocyanurate of the present invention for thermal insulation.
In still another aspect of the present invention, there is provided a reaction system for preparing a polyurethane- (poly) isocyanurate compound, comprising:
(poly) isocyanurates produced by the process of the present invention;
at least one polyol; and
optionally, at least one blowing agent.
The reaction system for preparing a polyurethane- (poly) isocyanurate compound of the present invention may further include one or more polyisocyanates. Useful polyisocyanates are as previously described.
The polyol of the present invention may be a polyether polyol, a polyester polyol, a polycarbonate polyol and/or a mixture thereof.
The polyol of the present invention is preferably one or more polyether polyols, wherein at least one polyether polyol is an amine-initiated polyol. The polyether polyols have a functionality of from 2 to 8, preferably from 3 to 6, and a hydroxyl number of from 50 to 1200, preferably from 200 to 800.
Examples of polyether polyols which can be used in the present invention are aromatic amine-initiated polyether polyols, preferably propylene oxide-based polyether polyols initiated with diphenylmethanediamine.
In embodiments of the present invention, a portion of the polyether polyol is selected from sucrose, sorbitol initiated polyether polyols, more preferably, a portion of the polyether polyol is selected from sucrose, sorbitol initiated propylene oxide based polyether polyols.
The polyester polyol is prepared by reacting dicarboxylic acid or dicarboxylic anhydride with polyhydric alcohol. The dicarboxylic acid is preferably, but not limited to, aliphatic carboxylic acid containing 2 to 12 carbon atoms, such as: succinic acid, malonic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanecarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, and mixtures thereof. The dibasic acid anhydride is preferably, but not limited to, phthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, and mixtures thereof. The polyhydric alcohol is preferably, but not limited to, ethylene glycol, diethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, dipropylene glycol, 1, 3-methylpropylene glycol, 1, 4-butylene glycol, 1, 5-pentanediol, 1, 6-hexanediol, neopentyl glycol, 1, 10-decanediol, glycerol, trimethylolpropane, or a mixture thereof. The polyester polyol also comprises polyester polyol prepared from lactone. The polyester polyol prepared from lactone is preferably, but not limited to, a polyester polyol prepared from caprolactone.
The polycarbonate polyol is preferably, but not limited to, a polycarbonate diol. The polycarbonate diol may be prepared by reacting a diol with a dialkyl or diaryl carbonate or phosgene. The diol is preferably, but not limited to, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, diethylene glycol, trioxymethylene glycol, or a mixture thereof. The dialkyl or diaryl carbonate is preferably, but not limited to, diphenyl carbonate.
The foaming agent of the present invention may be selected from various physical foaming agents or chemical foaming agents.
Useful blowing agents include water, halogenated hydrocarbons, and the like. Useful halohydrocarbons are preferably pentafluorobutane, pentafluoropropane, chlorotrifluoropropene, hexafluorobutene, HCFC-141 b (monofluorodichloroethane), HFC-365 mfc (pentafluorobutane), HFC-245 fa (pentafluoropropane), or any mixture thereof. Useful hydrocarbon compounds include preferably butane, pentane, Cyclopentane (CP), hexane, cyclohexane, heptane and any mixture thereof.
The reaction system for producing a polyurethane- (poly) isocyanurate compound of the present invention may further include a catalyst. Catalysts useful in the present invention preferably include blowing catalysts, gelling catalysts and trimerization catalysts. Wherein, the foaming catalyst is preferably selected from one, two or any mixture of more than two of pentamethyl diethylene triamine, bis-dimethyl aminoethyl ether, N, N, N ', N' -tetramethyl ethylene diamine, N, N, N ', N' -tetramethyl butane diamine and tetramethyl hexane diamine; the gel catalyst is preferably selected from one or any mixture of dimethylcyclohexylamine and dimethylbenzylamine; the trimerisation catalyst is preferably selected from one, two or any mixture of two or more of methylammonium salts, ethylammonium salts, octylamine salts or hexahydrotriazines and organometallic bases. The catalyst is preferably present in an amount of from 0.50 to 4.00pbw based on the total weight of the polyol component.
The reaction system for producing a polyurethane- (poly) isocyanurate compound of the present invention may further include a surfactant. The surfactant is preferably a silicone oil, which is present in an amount of from 0.1 to 5.0% by weight, preferably from 0.5 to 4.0% by weight, particularly preferably from 1.5 to 3.0% by weight, based on the total weight of the polyol component.
In still another aspect of the present invention, there is provided a polyurethane- (poly) isocyanurate compound produced by the reaction system for producing a polyurethane- (poly) isocyanurate compound of the present invention.
In still another aspect of the present invention, there is provided a heat insulating material comprising the (poly) isocyanurate or the polyurethane- (poly) isocyanurate compound obtained by the method for preparing (poly) isocyanurate of the present invention.
Preferably, the heat insulating material of the present invention is selected from the group consisting of a heat insulating panel, a refrigerator wall, a cold insulating pipe case, a refrigerator compartment side panel, and a vehicle-mounted refrigerator wall.
Examples
Raw materials:
isocyanate 44V 20: NCO%: 30.5-32.5%, viscosity: 160-240mP.s @25oC, purchased from Corsik Polymer (China) Ltd;
tert-butyl peroxybenzoate (TBPB): purchased from acyclovir;
benzoyl Peroxide (BPO): purchased from Sigma-Aldrich;
Azobisisobutyronitrile (AIBN): purchased from Sigma-AIdrich;
DMP 30: trimerization catalyst, procured in air chemical industry;
TMR-2: trimerization catalyst, procured in air chemical industry;
PC-41: trimerization catalyst, procured in air chemical industry;
k15: trimerization catalyst, procured in air chemical industry;
1792: trimerization catalyst, procured in air chemical industry;
GTS-THP gel time determinator: purchased from Shanghai Senlan scientific instruments, Inc.
Examples the test methods are illustrated below:
the gel time is the time until the components of the reaction system start to be mixed until the viscosity reaches a certain value (for example, about 10000mPa. s). The gel time of the present invention is a time measured using a gel tester. The specific test method comprises the steps of uniformly mixing all components of the reaction system, placing the mixture in a gel tester, and recording the time from the pressing of an opening button to the stop of the gel tester, namely the gel time of the invention.
And (3) viscosity testing: tested according to GB/T12008.8-1992 standard.
Comparative examples 1 to 5 (trimerization of isocyanates with conventional trimerization catalysts)
100 parts by weight of the liquid isocyanate raw material 44V20 was added to a plastic cup, 2 parts by weight of the catalyst was added thereto, the mixture was rapidly stirred to be uniform, and then the viscosity change and the temperature change were monitored. The results are shown in Table 1.
TABLE 1 Experimental results of comparative examples 1 to 5
As can be seen from the data in Table 1, the reaction system using the conventional catalyst has a rapid temperature rise, a very short reaction time, and a difficult control of the reaction state.
Example 1
Adding 100 parts by weight of liquid isocyanate raw material 44V20 into a plastic cup, adding 2 parts by weight of TBPB, quickly stirring uniformly, then placing into an oven at 50 ℃, and monitoring the viscosity change and the temperature change of the mixture. At intervals, samples were removed, cooled to room temperature (25 degrees Celsius), and tested for viscosity and NCO content. The test results are shown in Table 2.
TABLE 2 test results of example 1
From table 2 it can be seen that the resin system changes greatly with time in the presence of the isocyanate together with the radical initiator: the NCO value is obviously reduced, the viscosity of the system is obviously increased until the system is solidified, and the occurrence of trimerization reaction is verified. It was demonstrated that the free radicals released by the initiator catalyze the trimerization of isocyanate groups, i.e. three NCO groups are consumed to form an isocyanurate group. This consumption leads to a decrease in the NCO value of the resin system. On the other hand, the formation of isocyanurate groups leads to an increase in the degree of crosslinking of the resin system, and thus to an increase in the viscosity of the system. Therefore, as time goes by, the trimerization reaction increases, more NCO groups are consumed, the NCO value of the resin gradually decreases, and the viscosity gradually increases. When the degree of crosslinking reaches a certain degree, the viscosity of the resin system can be greatly improved until the resin system becomes colloid or solid.
For comparison, the starting liquid isocyanate 44V20 (without added free radical initiator) was also placed in a 50 ℃ oven and monitored for viscosity change and temperature change. At intervals, samples were removed, cooled to room temperature (25 degrees Celsius), and tested for viscosity and NCO content. The test results are shown in Table 3.
TABLE 3 isocyanate Change (reference)
It can be seen from Table 3 that the isocyanate remains stable if it is present alone. At the same ambient temperature, the NCO value of the isocyanate is almost constant, and the viscosity change is small and slow.
The infrared spectrum of figure 1 also verifies these changes. Three characteristic peaks (1704.80 cm) were detected after 56 days for the isocyanate with the free radical initiator added, compared with the isocyanate without the free radical initiator added (1704.80 cm)-1，1409.60cm-1，758.36cm-1) The presence of isocyanurate groups was shown, confirming that trimerization occurred in the presence of free radicals, resulting in the formation of isocyanurate groups.
(Note: FIG. 1, curve s1 shows the spectrum for the system with only isocyanate 44V 20; FIG. 1, curve s2 shows that the viscosity has not changed in the initial stage after 2% by weight of TBPB has been added to isocyanate 44V 20; FIG. 1, curve s3 shows the spectrum after 56 days after 2% by weight of TBPB has been added to isocyanate 44V 20)
Example 2:
adding 100 parts by weight of liquid isocyanate raw material 44V20 into a plastic cup, adding 2 parts by weight of BPO, quickly stirring uniformly, then placing into an oven at 60 ℃, and monitoring the viscosity change and the temperature change of the mixture. At intervals, samples were removed, cooled to room temperature (25 degrees Celsius), and tested for viscosity and NCO content. The test results are shown in Table 4.
TABLE 4 test results of example 2
From Table 4 it can be seen that, similar to the results of Table 2 above, trimerisation occurs in the presence of an isocyanate in combination with the free radical initiator BPO. Since the rate of decomposition of BPO to generate free radicals is higher than the rate of decomposition of TBPB, BPO can catalyze the trimerization reaction to occur at a faster rate. Accordingly, the NCO value of the isocyanate decreases more rapidly, the viscosity thereof increases more rapidly, and the resin system reaches a solid state in a shorter time. However, since the rate of decomposition of BPO to form free radicals is still slowly controllable as a whole, the isocyanate trimerisation reaction catalysed by BPO is still carried out in a controlled manner and the temperature of the resin system remains constant at all times.
Example 3:
adding 100 parts by weight of liquid isocyanate raw material 44V20 into a plastic cup, adding 2 parts by weight of AIBN, quickly stirring uniformly, then placing into an oven with the temperature controlled at 60 ℃, and monitoring the viscosity change and the temperature change of the mixture. At intervals, samples were removed, cooled to room temperature (25 degrees Celsius), and tested for viscosity and NCO content. The test results are shown in Table 5.
TABLE 5 test results of example 3
From Table 5 it can be seen that, similarly to the results of tables 2 and 3 above, trimerization occurs in the presence of the isocyanate together with the free radical initiator AIBN. Since AIBN decomposes to form free radicals at a faster rate, it catalyzes the trimerization reaction to occur at a faster rate. Accordingly, the NCO value of the isocyanate decreases more rapidly, the viscosity thereof increases more rapidly, and the resin system reaches a solid state in a shorter time. However, since the rate of decomposition of AIBN to form free radicals is still slowly controllable as a whole, the isocyanate trimerisation reaction catalysed by it is still carried out in a controlled manner and the temperature of the resin system remains constant at all times.
From the above experimental data, it can be seen that under the action of these free radicals, a trimerization reaction occurs at a slow and controllable rate, and the isocyanate groups are gradually consumed to form new isocyanurate groups.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (19)
1. A process for preparing (poly) isocyanurates by reacting a reaction system comprising:
A) one or more polyisocyanates;
B) at least one free radical initiator.
2. Process for the preparation of (poly) isocyanurates according to claim 1, wherein the isocyanate is selected from aromatic isocyanates, preferably diphenylmethane diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate or combinations thereof, more preferably diphenylmethane diisocyanate or (poly) diphenylmethane diisocyanate or combinations thereof.
3. Process for the preparation of (poly) isocyanurates according to claim 1 or 2, wherein the free-radical initiator is present in an amount of from 0.1 to 5pbw, preferably from 0.2 to 4pbw, more preferably from 0.4 to 3pbw, based on the total weight of the reaction system.
4. The process for producing (poly) isocyanurates according to claim 1 or 2, wherein the radical initiator is selected from peroxides and/or azo compounds.
5. The process for preparing (poly) isocyanurates according to claim 4, wherein the peroxide is selected from the group consisting of ketone peroxides, carbonate peroxides, acyl peroxides, peroxyesters, hydrogen peroxide, alkyl peroxides, and any combination thereof, preferably tert-butyl peroxybenzoate, benzoyl peroxide, and combinations thereof.
6. The process for producing (poly) isocyanurates according to claim 4, wherein said azo compound is selected from azobisisobutyronitrile, azobisisoheptonitrile, or any combination thereof.
7. The process for preparing (poly) isocyanurates according to claim 1 or 2, wherein the reaction system has a reaction time of > 5 hours, preferably > 10 hours, particularly preferably > 24 hours.
8. The process for producing (poly) isocyanurates according to claim 1 or 2, wherein the temperature of the reaction system after the reaction is within a range of ± 2 ℃ from the temperature before the reaction.
9. (poly) isocyanurates produced by the process for producing (poly) isocyanurates of any one of claims 1 to 8.
10. Use of a free radical initiator for catalyzing the trimerization of isocyanates to prepare (poly) isocyanurates.
11. Use according to claim 10, wherein the free radical initiator is present in an amount of 0.1 to 5pbw, preferably 0.2 to 4pbw, more preferably 0.4 to 3pbw, based on the total weight of the reaction system of the trimerization reaction.
12. Use according to claim 10 or 11, wherein the radical initiator is selected from peroxides and/or azo compounds.
13. Use according to claim 10 or 11, characterized in that the peroxide is selected from ketone peroxides, peroxycarbonates, peroxyacyl groups, peroxyesters, hydrogen peroxide, alkyl peroxides or combinations thereof, preferably tert-butyl peroxybenzoate, benzoyl peroxide or combinations thereof.
14. Use according to claim 10 or 11, wherein the azo compound is selected from azobisisobutyronitrile, azobisisoheptonitrile or a combination thereof.
15. Use of the (poly) isocyanurates obtained by the process for preparing (poly) isocyanurates according to any one of claims 1 to 8 for thermal insulation.
16. A reaction system for preparing a polyurethane- (poly) isocyanurate compound, comprising:
(poly) isocyanurates produced by the process for producing (poly) isocyanurates of any one of claims 1 to 8;
at least one polyol; and
optionally, at least one blowing agent.
17. A polyurethane- (poly) isocyanurate compound prepared from the reaction system of claim 16 for preparing a polyurethane- (poly) isocyanurate compound.
18. A heat insulating material comprising the (poly) isocyanurate produced by the process for producing (poly) isocyanurate as claimed in any one of claims 1 to 8.
19. The insulating material of claim 18, selected from the group consisting of insulation panels, refrigerator walls, insulation shells, refrigerator side panels, and vehicle refrigerator walls.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910359180.5A CN111848531A (en) | 2019-04-29 | 2019-04-29 | Rigid polyurethane foam |
| JP2021564382A JP2022531206A (en) | 2019-04-29 | 2020-04-24 | Rigid polyurethane foam |
| EP20720065.0A EP3962983A1 (en) | 2019-04-29 | 2020-04-24 | Rigid polyurethane foam |
| PCT/EP2020/061428 WO2020221662A1 (en) | 2019-04-29 | 2020-04-24 | Rigid polyurethane foam |
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| CN201910359180.5A CN111848531A (en) | 2019-04-29 | 2019-04-29 | Rigid polyurethane foam |
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| CN109312050A (en) * | 2016-06-17 | 2019-02-05 | 科思创德国股份有限公司 | The PUR/PIR hard foam for preparing the method for the composition containing isocyanate groups and isocyanurate group and being produced from it |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2358503A1 (en) * | 1972-11-24 | 1974-05-30 | Gen Tire & Rubber Co | HIGH-TEMPERATURE RIGID FOAMS AND THEIR PRODUCTION |
| US4072636A (en) * | 1975-03-07 | 1978-02-07 | Mitsubishi Chemical Industries Limited | Process for preparing smoke-retardant polyisocyanurate foam |
| US4129693A (en) * | 1976-12-20 | 1978-12-12 | Basf Wyandotte Corporation | Urethane-modified isocyanurate foams having enhanced physical properties |
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