CN114736364A - 反应型阻燃聚醚多元醇、聚异氰脲酸酯泡沫及其制备方法和应用 - Google Patents
反应型阻燃聚醚多元醇、聚异氰脲酸酯泡沫及其制备方法和应用 Download PDFInfo
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- CN114736364A CN114736364A CN202210344517.7A CN202210344517A CN114736364A CN 114736364 A CN114736364 A CN 114736364A CN 202210344517 A CN202210344517 A CN 202210344517A CN 114736364 A CN114736364 A CN 114736364A
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- Prior art keywords
- polyether polyol
- reactive flame
- retardant
- component
- catalyst
- 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.)
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 95
- 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 title claims abstract description 94
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 80
- 229920000570 polyether Polymers 0.000 title claims abstract description 80
- 150000003077 polyols Chemical class 0.000 title claims abstract description 75
- 229920005862 polyol Polymers 0.000 title claims abstract description 74
- 239000006260 foam Substances 0.000 title claims abstract description 53
- 229920000582 polyisocyanurate Polymers 0.000 title claims abstract description 40
- 239000011495 polyisocyanurate Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000004593 Epoxy Substances 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 239000003999 initiator Substances 0.000 claims abstract description 14
- 238000006757 chemical reactions by type Methods 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims description 41
- 238000002156 mixing Methods 0.000 claims description 28
- 239000000654 additive Substances 0.000 claims description 17
- 230000000996 additive effect Effects 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000004088 foaming agent Substances 0.000 claims description 12
- 239000012948 isocyanate Substances 0.000 claims description 12
- 150000002513 isocyanates Chemical group 0.000 claims description 12
- 229920005906 polyester polyol Polymers 0.000 claims description 12
- 239000004094 surface-active agent Substances 0.000 claims description 12
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 11
- 238000005187 foaming Methods 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- -1 polyethylene terephthalate Polymers 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 4
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000005056 polyisocyanate Substances 0.000 claims description 4
- 229920001228 polyisocyanate Polymers 0.000 claims description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 4
- LDTMPQQAWUMPKS-OWOJBTEDSA-N (e)-1-chloro-3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)\C=C\Cl LDTMPQQAWUMPKS-OWOJBTEDSA-N 0.000 claims description 3
- FRCHKSNAZZFGCA-UHFFFAOYSA-N 1,1-dichloro-1-fluoroethane Chemical compound CC(F)(Cl)Cl FRCHKSNAZZFGCA-UHFFFAOYSA-N 0.000 claims description 3
- AATNZNJRDOVKDD-UHFFFAOYSA-N 1-[ethoxy(ethyl)phosphoryl]oxyethane Chemical compound CCOP(=O)(CC)OCC AATNZNJRDOVKDD-UHFFFAOYSA-N 0.000 claims description 3
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 claims description 3
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical compound COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 claims description 3
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- GTRSAMFYSUBAGN-UHFFFAOYSA-N tris(2-chloropropyl) phosphate Chemical compound CC(Cl)COP(=O)(OCC(C)Cl)OCC(C)Cl GTRSAMFYSUBAGN-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- YAOMHRRYSRRRKP-UHFFFAOYSA-N 1,2-dichloropropyl 2,3-dichloropropyl 3,3-dichloropropyl phosphate Chemical compound ClC(Cl)CCOP(=O)(OC(Cl)C(Cl)C)OCC(Cl)CCl YAOMHRRYSRRRKP-UHFFFAOYSA-N 0.000 claims description 2
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 claims description 2
- WAPWXMDDHHWKNM-UHFFFAOYSA-N 3-[2,3-bis[3-(dimethylamino)propyl]triazinan-1-yl]-n,n-dimethylpropan-1-amine Chemical compound CN(C)CCCN1CCCN(CCCN(C)C)N1CCCN(C)C WAPWXMDDHHWKNM-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- REIDAMBAPLIATC-UHFFFAOYSA-N 4-methoxycarbonylbenzoic acid Chemical compound COC(=O)C1=CC=C(C(O)=O)C=C1 REIDAMBAPLIATC-UHFFFAOYSA-N 0.000 claims description 2
- GESHUGMEDPDLNE-UHFFFAOYSA-N 6-[6-(dimethylamino)hexoxy]-n,n-dimethylhexan-1-amine Chemical compound CN(C)CCCCCCOCCCCCCN(C)C GESHUGMEDPDLNE-UHFFFAOYSA-N 0.000 claims 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 claims 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 claims description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 claims description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 125000005442 diisocyanate group Chemical group 0.000 claims description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 2
- UKACHOXRXFQJFN-UHFFFAOYSA-N heptafluoropropane Chemical compound FC(F)C(F)(F)C(F)(F)F UKACHOXRXFQJFN-UHFFFAOYSA-N 0.000 claims description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 2
- 238000006068 polycondensation reaction Methods 0.000 claims description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 2
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 2
- 235000011056 potassium acetate Nutrition 0.000 claims description 2
- RLEFZEWKMQQZOA-UHFFFAOYSA-M potassium;octanoate Chemical compound [K+].CCCCCCCC([O-])=O RLEFZEWKMQQZOA-UHFFFAOYSA-M 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
- 239000000600 sorbitol Substances 0.000 claims description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N terephthalic acid dimethyl ester Natural products COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 claims description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000005829 trimerization reaction Methods 0.000 claims description 2
- HQUQLFOMPYWACS-UHFFFAOYSA-N tris(2-chloroethyl) phosphate Chemical compound ClCCOP(=O)(OCCCl)OCCCl HQUQLFOMPYWACS-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims 1
- 239000012975 dibutyltin dilaurate Substances 0.000 claims 1
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- 229920005830 Polyurethane Foam Polymers 0.000 abstract description 3
- 239000011496 polyurethane foam Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
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- 239000000126 substance Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
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- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- YFMFNYKEUDLDTL-UHFFFAOYSA-N 1,1,1,2,3,3,3-heptafluoropropane Chemical compound FC(F)(F)C(F)C(F)(F)F YFMFNYKEUDLDTL-UHFFFAOYSA-N 0.000 description 1
- QKKSKKMOIOGASY-UHFFFAOYSA-N 2,3-dibromobut-1-ene-1,1-diol Chemical compound CC(Br)C(Br)=C(O)O QKKSKKMOIOGASY-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- CWZPGMMKDANPKU-UHFFFAOYSA-L butyl-di(dodecanoyloxy)tin Chemical compound CCCC[Sn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O CWZPGMMKDANPKU-UHFFFAOYSA-L 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229950010007 dimantine Drugs 0.000 description 1
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- 238000006073 displacement reaction Methods 0.000 description 1
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- 239000006261 foam material Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
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- 238000002464 physical blending Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
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Classifications
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2639—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing elements other than oxygen, nitrogen or sulfur
-
- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
本发明涉及聚氨酯泡沫技术领域，具体涉及反应型阻燃聚醚多元醇、聚异氰脲酸酯泡沫及其制备方法和应用。本发明提供的反应型阻燃聚醚多元醇以3,4‑二溴‑3‑氯‑1,2‑二醇为起始剂。本发明提供的反应型阻燃聚醚多元醇，以3,4‑二溴‑3‑氯‑1,2‑二醇为起始剂，通过其与环氧化合物合成聚醚多元醇，将其应用到PIR泡沫中可有效提升泡沫的尺寸稳定性、压缩强度，同时还可提升泡沫韧性，降低材料热导性。
Description
技术领域
本发明涉及聚氨酯泡沫技术领域，具体涉及反应型阻燃聚醚多元醇、聚异氰脲酸酯泡沫及其制备方法和应用。
背景技术
近年来，国内外已发生多起聚氨酯硬泡火灾，使人们对聚氨酯保温材料望而却步。因此，解决聚氨酯材料的防火阻燃问题已然迫在眉睫。PIR(聚异氰脲酸酯)除具有传统的PUR分子结构及性能外，还具有异氰脲酸酯环，这种分子结构可提高泡沫的耐温性和耐燃性。此外，配方中加入添加型阻燃剂也可提高聚氨酯的阻燃性。添加型阻燃剂法操作相对简单，以物理共混的方式加入到发泡剂组合料中，阻燃效果好，但存在长期使用易迁移、阻燃效果变差等缺陷。同时由于添加型阻燃剂有增塑作用，添加量过多，会使泡沫变脆，严重时泡沫还会出现开裂现象。而反应型阻燃剂由于可将具有阻燃效用的基团或阻燃元素通过化学反应接入到聚合物分子链上，因此具有长效阻燃特性，受到了人们的青睐。
现有反应型阻燃剂主要有卤系反应型阻燃剂、磷系反应型阻燃剂和芳杂环反应型阻燃剂。和卤系反应型阻燃剂比较，市场上所见到的磷系反应型阻燃剂种类少、价格高；芳杂环反应型阻燃剂在其主链或侧链中引入芳环等阻燃基团以提高其阻燃性能，但其韧性较差。而现有卤系反应型阻燃剂虽具有较好的阻燃效果，但制得的泡沫尺寸稳定性、韧性不佳，压缩强度较低、导热性较高。
因此，急需开发一种尺寸稳定性、韧性更好，压缩强度高、导热性低的高阻燃PIR泡沫。
发明内容
本发明的目的在于克服现有PIR泡沫尺寸稳定性、韧性不佳，压缩强度较低、导热性较高的缺陷，进而提供一种反应型阻燃聚醚多元醇、聚异氰脲酸酯泡沫及其制备方法和应用。
为达到上述目的，本发明采用如下技术方案：
一种反应型阻燃聚醚多元醇，所述反应型阻燃聚醚多元醇以3,4-二溴-3-氯-1,2-二醇为起始剂。
所述3,4-二溴-3-氯-1,2-二醇具有如下结构：
优选的，所述反应型阻燃聚醚多元醇是以3,4-二溴-3-氯-1,2-二醇为起始剂，和环氧化合物在第一催化剂的作用下反应制备得到。
优选的，所述反应型阻燃聚醚多元醇的羟值为120-300mgKOH/g，粘度为1800-6000mPa·s，优选的，所述反应型阻燃聚醚多元醇的羟值为200-250mgKOH/g，粘度为2000-3000mPa·s。
本发明还提供一种上述所述反应型阻燃聚醚多元醇的制备方法，包括如下步骤：
将3,4-二溴-3-氯-1,2-二醇和第一催化剂混合，然后加入环氧化合物，搅拌反应得到所述反应型阻燃聚醚多元醇。
优选的，所述第一催化剂用量为3,4-二溴-3-氯-1,2-二醇、第一催化剂、环氧化合物总用量的0.05wt％-1.5wt％；
所述反应温度为85-110℃，反应压力0.1-0.4MPa，反应时间为2-4h。
所述3,4-二溴-3-氯-1,2-二醇和环氧化合物的质量比为(0.4-3):1。
优选的，反应结束后还包括将反应混合物在真空条件下脱除未反应的环氧化合物单体的步骤。优选的，所述反应在氮气或者惰性气体氛围下进行。
优选的，
所述第一催化剂选自胺类催化剂、碱金属催化剂、双金属催化剂中的至少一种，优选的，所述催化剂选自碱金属催化剂、双金属催化剂中的至少一种；本发明所述胺类催化剂、碱金属催化剂、双金属催化剂均为本领域常规催化剂，包括但不限于氢氧化钠、氢氧化钾，二甲胺、二甲基乙醇胺、三甲胺、N,N-二甲基十八胺、双金属氰化物配位催化剂等。
所述环氧化合物选自环氧乙烷、环氧丙烷、环氧丁烷或环氧氯丙烷中的至少一种，优选的，所述环氧化合物为环氧乙烷、环氧丙烷中的至少一种。
本发明还提供上述所述反应型阻燃聚醚多元醇或上述所述制备方法制备得到的反应型阻燃聚醚多元醇在制备聚异氰脲酸酯泡沫中的应用。
本发明还提供一种聚异氰脲酸酯泡沫，其原料包括A组分和B组分，所述A组分包括如下重量份的原料：
第一聚醚多元醇10-100份，第二聚醚多元醇和/或聚酯多元醇0-90份，添加型阻燃剂0-30份，水0-2份，第二催化剂0.5–5份，有机硅表面活性剂1-3份，发泡剂10-30份；
所述第一聚醚多元醇为上述所述反应型阻燃聚醚多元醇或上述所述制备方法制备得到的反应型阻燃聚醚多元醇；
所述B组分为异氰酸酯。
优选的，所述A组分和B组分的质量比为1:(1.5-1.8)。
优选的，所述第二聚醚多元醇的官能度为2-8，羟值为50-750mgKOH/g；
所述聚酯多元醇的官能度为2-3，分子量为200-3000，羟值为50-400mgKOH/g，粘度为1000-15000mPa·s。
优选的，
所述第二聚醚多元醇是以甘油、三羟甲基丙烷、三乙醇胺、甲苯二胺、季戊四醇、山梨醇和蔗糖中的至少一种作为起始剂，和环氧乙烷、环氧丙烷中的至少一种反应制备得到。
所述聚酯多元醇是由二甘醇、三甘醇、乙二醇、丙二醇、丁二醇中的至少一种与丙二酸、己二酸、马来酸、邻苯二甲酸、对苯二甲酸甲酯、聚对苯二甲酸乙酯、聚对苯二甲酸丁酯中、苯酐中的至少一种通过缩聚反应制备得到，优选的，所述聚酯多元醇为芳香族二元酸多元醇，如聚酯PS-3152，PS-2412，3152。
优选的，
所述异氰酸酯为二异氰酸酯或多异氰酸酯，优选的，所述异氰酸酯选自甲苯二异氰酸酯，二苯基甲烷二异氰酸酯，多聚异氰酸酯，六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯，多亚甲基多苯基异氰酸酯中的至少一种；
所述添加型阻燃剂为三(2-氯乙基)磷酸酯(TCEP)，三(2-氯丙基)磷酸酯(TCPP)，三(二氯丙基)磷酸酯(TCDPP)，甲基膦酸二甲酯(DMMP)，乙基膦酸二乙酯(DEEP)，聚二溴苯醚(PBO)，三聚氰胺中的至少一种；
所述第二催化剂为N,N-二甲基环己胺(PC8)，五甲基二亚乙基三胺(PC5)，双(二甲氨基己基)醚(A1)，三亚乙基二胺(A33),三(二甲氨丙基)六氢三嗪(PC41)，二月桂酸而丁基锡(T12),2,4,6-三(二甲氨基甲基)苯酚(DMP-30)，TMR系列三聚催化剂，醋酸钾和辛酸钾中的至少一种；
所述有机硅表面活性剂为聚醚改性有机聚硅氧烷非离子共聚物，选自DC-193，B8450，B8486，AK-8872，AK-88108，M8805中的至少一种；进一步优选的，选自空气化工的DC-193，赢创特种化学的B8450，赢创特种化学的B8486，南京美思德新材料有限公司的AK-8872，南京美思德新材料有限公司的AK-88108，南京美思德新材料有限公司的M8805中的至少一种；
所述发泡剂为一氟二氯乙烷(HFC-141b)，五氟丙烷(HFC-245fa)，五氟丁烷(365mfc)，七氟丙烷(HFC-227ea)，反式-1-氯-3,3,3-三氟丙烯(HCFO-1233zd/LBA)，正戊烷，异戊烷，环戊烷和甲酸甲酯中的至少一种。
本发明还提供一种上述所述聚异氰脲酸酯泡沫的制备方法，包括如下步骤：
1)将配方比例的第一聚醚多元醇、第二聚醚多元醇和/或聚酯多元醇、添加型阻燃剂、水、第二催化剂、有机硅表面活性剂进行混合，然后加入发泡剂，混合，得到A组分；
2)将A组分和B组分进行混合，发泡、熟化，得到所述聚异氰脲酸酯泡沫。
优选的，步骤2)中还包括控制A组分和B组分温度为20-22℃的步骤，发泡时搅拌转速3500-4000rpm，搅拌时间为5-7s，熟化温度为室温，熟化时间为40-55h。
本发明的有益效果：
1)本发明提供的反应型阻燃聚醚多元醇，以3,4-二溴-3-氯-1,2-二醇为起始剂，通过其与环氧化合物合成聚醚多元醇，其中含有特定结构的溴和氯，通过分子结构的设计，可大大提升溴和氯的含量，提升阻燃效果，同时该聚醚多元醇和添加型阻燃剂相比，在形成PIR块泡时会形成更多的闭孔，进而提升泡沫的尺寸稳定性、压缩强度，同时还可提升泡沫韧性，降低材料热导性。经测试，聚醚多元醇中溴的质量分数可高达30％，同时氯的质量分数可高达6％。
本发明提供的反应型阻燃聚醚多元醇，以3,4-二溴-3-氯-1,2-二醇为起始剂形成的聚醚多元醇，将其应用于PIR泡沫中时，可直接参与形成泡沫结构，没有迁移，由于其参与反应，将稳定地结合在聚氨酯基体中，不会在长期使用过程中析出而降低阻燃性能，阻燃效率高，并且其与常用的多元醇、磷酸酯类的阻燃添加剂共容，具有优异的稳定性。
本发明提供的反应型阻燃聚醚多元醇，将其应用在PIR泡沫中，替代或少用添加型的阻燃剂，使氧指数大于32，满足GB/T8624-2012中的B1级要求。并且该阻燃聚醚的羟值较低，在PIR体系中较普通硬泡聚醚更加适用。同时本发明中的反应型阻燃聚醚，黏度较低，在PIR块泡或间歇板材等流动性要求高的应用配方中，物料初始黏度低，流动性好。
2)本发明提供的聚异氰脲酸酯泡沫，使用本发明特定的反应型阻燃聚醚多元醇，同时配合其它组分，得到的聚异氰脲酸酯泡沫在具有高阻燃性能的同时，其泡沫材料还具有优异的尺寸稳定性、压缩强度、泡沫韧性，以及较低的材料热导性。
具体实施方式
提供下述实施例是为了更好地进一步理解本发明，并不局限于所述最佳实施方式，不对本发明的内容和保护范围构成限制，任何人在本发明的启示下或是将本发明与其他现有技术的特征进行组合而得出的任何与本发明相同或相近似的产品，均落在本发明的保护范围之内。
实施例中未注明具体实验步骤或条件者，按照本领域内的文献所描述的常规实验步骤的操作或条件即可进行。所用试剂或仪器未注明生产厂商者，均为可以通过市购获得的常规试剂产品。
本发明以下实施例和对比例中所用原料来源如下。
第二聚醚多元醇(4113)，是以蔗糖和甘油(两者质量比为65:35)为起始剂，和环氧丙烷反应制备得到，官能度为4.3，羟值为450mgKOH/g，购于佳化化学(抚顺)新材料有限公司。
聚酯多元醇3152，官能度为2，分子量为352，羟值为315mgKOH/g，粘度为2000-2500mPa·s，由斯泰潘公司生产。
有机硅表面活性剂(硅油)M8805，购自南京美思德新材料有限公司。
发泡剂HFC-141b(一氟二氯乙烷)，购自上海锐一环保科技有限公司。
异氰酸酯：多亚甲基多苯基异氰酸酯，粘度为200mpa.s，-NCO含量为30.5～32％，购于万华化学，型号PM200。
催化剂TMR-2，购自新典化学材料有限公司。
实施例1
本实施例提供一种反应型阻燃聚醚多元醇的制备方法，包括如下步骤：
将601g起始剂3,4-二溴-3-氯-1,2-二醇置于高压釜中，加入氢氧化钾6.0g，抽真空氮气置换3次，然后向釜中加入350g环氧丙烷，90℃下搅拌反应，反应压力为0.3MPa，反应时间为4h，反应结束后在90℃，-0.1MPa条件下真空脱去未反应的环氧丙烷，降温至50℃，放料，得到棕色透明的反应型阻燃聚醚多元醇，其羟值为245mgKOH/g，黏度为2700mPa·s。
实施例2
本实施例提供一种聚异氰脲酸酯泡沫，其制备方法包括如下步骤：
1)制备A组分：A组分的原料成分如下所示：
将上述反应型阻燃聚醚多元醇、第二聚醚多元醇、水、第二催化剂(PC8、PC41、TMR-2)、表面活性剂进行混合，然后加入发泡剂，混合均匀，得到A组分；
2)分别控制步骤1)得到的组分A和异氰酸酯PM200(232g，组分B)温度为22℃，然后将A组分和B组分进行混合，混合均匀后进行发泡(发泡时搅拌转速4000rpm，搅拌时间为6s)，熟化(熟化温度为室温，熟化时间为48h)，得到所述聚异氰脲酸酯泡沫。
实施例3
本实施例提供一种聚异氰脲酸酯泡沫，其制备方法包括如下步骤：
1)制备A组分：A组分的原料成分如下所示：
将上述反应型阻燃聚醚多元醇、第二聚醚多元醇、聚酯多元醇、添加型阻燃剂、水、第二催化剂(PC8、PC41、TMR-2)、表面活性剂进行混合，然后加入发泡剂，混合均匀，得到A组分；
2)分别控制步骤1)得到的组分A和异氰酸酯PM200(257g，组分B)温度为22℃，然后将A组分和B组分进行混合，混合均匀后进行发泡(搅拌转速为4000rpm，搅拌时间为6s)，熟化(熟化温度为室温，熟化时间为48h)，得到所述聚异氰脲酸酯泡沫。
对比例1
本对比例提供一种聚异氰脲酸酯泡沫，其制备方法包括如下步骤：
1)制备A组分：A组分的原料成分如下所示：
将第二聚醚多元醇、水、第二催化剂(PC8、PC41、TMR-2)、表面活性剂进行混合，然后加入发泡剂，混合均匀，得到A组分；
2)分别控制步骤1)得到的组分A和异氰酸酯PM200(232g，组分B)温度为22℃，然后将A组分和B组分进行混合，混合均匀后进行发泡(发泡时搅拌转速4000rpm，搅拌6s)，熟化(熟化温度为室温，熟化时间为48h)，得到所述聚异氰脲酸酯泡沫。
对比例2
本对比例提供一种聚异氰脲酸酯泡沫，其制备方法包括如下步骤：
1)制备A组分：A组分的原料成分如下所示：
将第二聚醚多元醇、聚酯多元醇、添加型阻燃剂、水、第二催化剂(PC8、PC41、TMR-2)、表面活性剂进行混合，然后加入发泡剂，混合均匀，得到A组分；
2)分别控制步骤1)得到的组分A和异氰酸酯PM200(257g，组分B)温度为22℃，然后将A组分和B组分进行混合，混合均匀后进行发泡(发泡时搅拌转速4000rpm，搅拌时间为6s)，熟化(熟化温度为室温，熟化时间为48h)，得到所述聚异氰脲酸酯泡沫。
对比例3
本对比例提供一种反应型阻燃聚醚多元醇的制备方法，包括如下步骤：
将601g起始剂二溴丁烯二醇置于高压釜中，加入氢氧化钾6.0g，抽真空氮气置换3次，然后向釜中加入522g环氧丙烷，90℃下搅拌反应，反应压力为0.3MPa，反应时间为4h，反应结束后在90℃，-0.1MPa条件下真空脱去未反应的环氧丙烷，降温至50℃，放料，得到棕色透明的反应型阻燃聚醚多元醇，其羟值为245mgKOH/g，黏度为2400mPa·s。
本对比例还提供一种聚异氰脲酸酯泡沫，其制备方法包括如下步骤：
1)制备A组分：A组分的原料成分如下所示：
将上述反应型阻燃聚醚多元醇、第二聚醚多元醇、聚酯多元醇、添加型阻燃剂、水、第二催化剂(PC8、PC41、TMR-2)、表面活性剂进行混合，然后加入发泡剂，混合均匀，得到A组分；
2)分别控制步骤1)得到的组分A和异氰酸酯PM200(257g，组分B)温度为22℃，然后将A组分和B组分进行混合，混合均匀后进行发泡(搅拌转速为4000rpm，搅拌时间为6s)，熟化(熟化温度为室温，熟化时间为48h)，得到所述聚异氰脲酸酯泡沫。
测试例
对上述实施例2-3和对比例1-3制备的聚异氰脲酸酯泡沫性能进行测试，测试结果如表1所示。
其中，
氧指数依据标准GB/T 8624-1997进行检测；
泡沫密度依据标准GB/T6343-2009进行检测；
压缩强度依据标准GB/T 10294-2008进行检测；
导热系数依据标准GB/T 8813-2008进行检测；
尺寸稳定性依据标准GB/T 8811-2008进行检测；
断裂伸长率依据标准GB/T 6344-1986进行检测。
表1泡沫性能测试结果
| 实施例2 | 实施例3 | 对比例1 | 对比例2 | 对比例3 | |
| 泡沫密度(kg/m<sup>3</sup>) | 31.3 | 33.7 | 34.1 | 35 | 33.4 |
| 氧指数/％ | 32 | 34 | 25.3 | 28 | 31 |
| 压缩强度/kPa | 190 | 172 | 170 | 154 | 162 |
| 导热系数/(mW/m·K) | 21.16 | 21.65 | 22.86 | 22.34 | 22.08 |
| 尺寸稳定性/％(70℃，48h) | -0.76 | -0.84 | -2.3 | -2 | -1.3 |
| 断裂伸长率/％ | 5.2 | 5.0 | 2.9 | 4.2 | 4.5 |
由表1中数据可知，本发明反应型阻燃聚醚代替部分普通的硬泡聚醚，可以明显降低泡沫密度，同时泡沫氧指数、压缩强度、尺寸稳定性和断裂伸长率也明显地提高。
显然，上述实施例仅仅是为清楚地说明所作的举例，而并非对实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引伸出的显而易见的变化或变动仍处于本发明创造的保护范围之中。
Claims (15)
1.一种反应型阻燃聚醚多元醇，其特征在于，所述反应型阻燃聚醚多元醇以3,4-二溴-3-氯-1,2-二醇为起始剂。
2.根据权利要求1所述的反应型阻燃聚醚多元醇，其特征在于，所述反应型阻燃聚醚多元醇是以3,4-二溴-3-氯-1,2-二醇为起始剂，和环氧化合物在第一催化剂的作用下反应制备得到。
3.根据权利要求1或2所述的反应型阻燃聚醚多元醇，其特征在于，所述反应型阻燃聚醚多元醇的羟值为120-300mgKOH/g，粘度为1800-6000mPa·s，优选的，所述反应型阻燃聚醚多元醇的羟值为200-250mgKOH/g，粘度为2000-3000mPa·s。
4.一种权利要求1-3任一项所述反应型阻燃聚醚多元醇的制备方法，其特征在于，包括如下步骤：
将3,4-二溴-3-氯-1,2-二醇和第一催化剂混合，然后加入环氧化合物，搅拌反应得到所述反应型阻燃聚醚多元醇。
5.根据权利要求4所述反应型阻燃聚醚多元醇的制备方法，其特征在于，所述第一催化剂用量为3,4-二溴-3-氯-1,2-二醇、第一催化剂、环氧化合物总用量的0.05wt％-1.5wt％；
所述3,4-二溴-3-氯-1,2-二醇和环氧化合物的质量比为(0.4-3):1。
6.根据权利要求4或5所述反应型阻燃聚醚多元醇的制备方法，其特征在于，所述反应温度为85-110℃，反应压力0.1-0.4MPa，反应时间为2-4h。
7.根据权利要求4-6任一项所述反应型阻燃聚醚多元醇的制备方法，其特征在于，反应结束后还包括将反应混合物在真空条件下脱除未反应的环氧化合物单体的步骤。
8.根据权利要求4-7任一项所述反应型阻燃聚醚多元醇的制备方法，其特征在于，
所述第一催化剂选自胺类催化剂、碱金属催化剂、双金属催化剂中的至少一种，优选的，所述催化剂选自碱金属催化剂、双金属催化剂中的至少一种；
所述环氧化合物选自环氧乙烷、环氧丙烷、环氧丁烷或环氧氯丙烷中的至少一种，优选的，所述环氧化合物为环氧乙烷、环氧丙烷中的至少一种。
9.权利要求1-3任一项所述反应型阻燃聚醚多元醇或权利要求4-8任一项所述制备方法制备得到的反应型阻燃聚醚多元醇在制备聚异氰脲酸酯泡沫中的应用。
10.一种聚异氰脲酸酯泡沫，其特征在于，其原料包括A组分和B组分，所述A组分包括如下重量份的原料：
第一聚醚多元醇10-100份，第二聚醚多元醇和/或聚酯多元醇0-90份，添加型阻燃剂0-30份，水0-2份，第二催化剂0.5–5份，有机硅表面活性剂1-3份，发泡剂10-30份；
所述第一聚醚多元醇为权利要求1-3任一项所述反应型阻燃聚醚多元醇或权利要求4-8任一项所述制备方法制备得到的反应型阻燃聚醚多元醇；
所述B组分为异氰酸酯。
11.根据权利要求10所述的聚异氰脲酸酯泡沫，其特征在于，所述A组分和B组分的质量比为1:(1.5-1.8)。
12.根据权利要求10或11所述的聚异氰脲酸酯泡沫，其特征在于，所述第二聚醚多元醇的官能度为2-8，羟值为50-750mgKOH/g；
所述聚酯多元醇的官能度为2-3，分子量为200-3000，羟值为50-400mgKOH/g，粘度为1000-15000mPa·s。
13.根据权利要求10-12任一项所述的聚异氰脲酸酯泡沫，其特征在于，
所述第二聚醚多元醇是以甘油、三羟甲基丙烷、三乙醇胺、甲苯二胺、季戊四醇、山梨醇和蔗糖中的至少一种作为起始剂，和环氧乙烷、环氧丙烷中的至少一种反应制备得到；
所述聚酯多元醇是由二甘醇、三甘醇、乙二醇、丙二醇、丁二醇中的至少一种与丙二酸、己二酸、马来酸、邻苯二甲酸、对苯二甲酸甲酯、聚对苯二甲酸乙酯、聚对苯二甲酸丁酯中、苯酐中的至少一种通过缩聚反应制备得到。
14.根据权利要求10-13任一项所述的聚异氰脲酸酯泡沫，其特征在于，
所述异氰酸酯为二异氰酸酯或多异氰酸酯，优选的，所述异氰酸酯选自甲苯二异氰酸酯，二苯基甲烷二异氰酸酯，聚异氰酸酯，六亚甲基二异氰酸酯，异佛尔酮二异氰酸酯，多亚甲基多苯基异氰酸酯中的至少一种；
所述添加型阻燃剂为三(2-氯乙基)磷酸酯、三(2-氯丙基)磷酸酯、三(二氯丙基)磷酸酯、甲基膦酸二甲酯、乙基膦酸二乙酯、聚二溴苯醚、三聚氰胺中的至少一种；
所述第二催化剂为N,N-二甲基环己胺、五甲基二亚乙基三胺、双(二甲氨基己基)醚、三亚乙基二胺、三(二甲氨丙基)六氢三嗪、二月桂酸二丁基锡、2,4,6-三(二甲氨基甲基)苯酚、TMR系列三聚催化剂、醋酸钾和辛酸钾中的至少一种；
所述有机硅表面活性剂为聚醚改性有机聚硅氧烷非离子共聚物；
所述发泡剂为一氟二氯乙烷、五氟丙烷、五氟丁烷、七氟丙烷、反式-1-氯-3,3,3-三氟丙烯、正戊烷、异戊烷、环戊烷和甲酸甲酯中的至少一种。
15.一种权利要求10-14任一项所述聚异氰脲酸酯泡沫的制备方法，其特征在于，包括如下步骤：
1)将配方比例的第一聚醚多元醇、第二聚醚多元醇和/或聚酯多元醇、添加型阻燃剂、水、第二催化剂、有机硅表面活性剂进行混合，然后加入发泡剂，混合，得到A组分；
2)将A组分和B组分进行混合，发泡、熟化，得到所述聚异氰脲酸酯泡沫。
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| CN112552503A (zh) * | 2020-12-15 | 2021-03-26 | 句容宁武新材料股份有限公司 | 一种溴硝醇反应型阻燃聚醚多元醇的制备方法 |
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| CN116284649B (zh) * | 2023-04-10 | 2024-04-05 | 上海玓墨节能科技有限公司 | 一种防火封堵聚氨酯泡沫及其制备方法和应用 |
| CN118005882A (zh) * | 2024-03-07 | 2024-05-10 | 江苏三旌科技材料有限公司 | 一种高阻燃的聚氨酯硬泡保温材料及其制备方法 |
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